WO2014050941A1 - Processing fluid supply device, substrate processing device, processing fluid supply method, substrate processing method, processing fluid processing device, and processing fluid processing method - Google Patents

Processing fluid supply device, substrate processing device, processing fluid supply method, substrate processing method, processing fluid processing device, and processing fluid processing method Download PDF

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Publication number
WO2014050941A1
WO2014050941A1 PCT/JP2013/076006 JP2013076006W WO2014050941A1 WO 2014050941 A1 WO2014050941 A1 WO 2014050941A1 JP 2013076006 W JP2013076006 W JP 2013076006W WO 2014050941 A1 WO2014050941 A1 WO 2014050941A1
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WO
WIPO (PCT)
Prior art keywords
substrate
processing
liquid
processing liquid
pipe
Prior art date
Application number
PCT/JP2013/076006
Other languages
French (fr)
Japanese (ja)
Inventor
宮城　雅宏
荒木　浩之
政典 鈴木
朋且 佐藤
川瀬　信雄
Original Assignee
大日本スクリーン製造株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012215294A external-priority patent/JP6044951B2/en
Priority claimed from JP2013194293A external-priority patent/JP6212818B2/en
Application filed by 大日本スクリーン製造株式会社 filed Critical 大日本スクリーン製造株式会社
Priority to KR1020157006772A priority Critical patent/KR20150046148A/en
Priority to US14/431,992 priority patent/US10133173B2/en
Priority to CN201380047457.1A priority patent/CN104662644B/en
Publication of WO2014050941A1 publication Critical patent/WO2014050941A1/en
Priority to US16/008,710 priority patent/US10761422B2/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • H01L21/67057—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing with the semiconductor substrates being dipped in baths or vessels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H01L21/67739—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations into and out of processing chamber
    • H01L21/6776—Continuous loading and unloading into and out of a processing chamber, e.g. transporting belts within processing chambers
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K5/00—Irradiation devices

Definitions

  • the present invention relates to a processing liquid supply apparatus, a substrate processing apparatus, a processing liquid supply method, a substrate processing method, a processing liquid processing apparatus, and a processing liquid processing method.
  • the processing object using the processing liquid includes a substrate, a container, an optical component, and the like.
  • Substrates used as objects to be processed include, for example, semiconductor wafers, glass substrates for liquid crystal display devices, substrates for plasma displays, substrates for FED (Field Emission Display), substrates for OLED (organic electroluminescence), substrates for optical disks, and magnetism.
  • Substrates such as a disk substrate, a magneto-optical disk substrate, a photomask substrate, a ceramic substrate, and a solar cell substrate are included.
  • a treatment liquid is supplied to the surface of a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display panel, and the surface of the substrate is washed with the treatment liquid.
  • a substrate processing apparatus that performs a single wafer cleaning process that processes substrates one by one, a spin chuck that rotates the substrate while holding the substrate substantially horizontally with a plurality of chuck pins, and the spin chuck And a processing liquid nozzle for supplying a processing liquid to the surface of the substrate rotated by.
  • the substrate is rotated by the spin chuck. Then, the chemical solution is supplied from the nozzle to the surface of the rotating substrate. The chemical solution supplied onto the surface of the substrate flows on the surface of the substrate toward the peripheral edge under the centrifugal force due to the rotation of the substrate. As a result, the chemical solution spreads over the entire surface of the substrate, and the treatment of the substrate surface with the chemical solution is achieved. And after the process by this chemical
  • pure water is supplied from the treatment liquid nozzle to the surface of the substrate rotated by the spin chuck, and the pure water spreads by receiving the centrifugal force due to the rotation of the substrate, so that the chemical solution adhered to the surface of the substrate Is washed away.
  • the rotation speed of the substrate by the spin chuck is increased, and spin dry treatment is performed in which pure water adhering to the substrate is shaken off and dried (see Patent Document 1 below).
  • the substrate may be fluidly charged.
  • the substrate is a glass substrate or a silicon wafer
  • the substrate is positively charged. If the substrate is charged, there is a risk of destruction of devices formed on the surface of the substrate when the discharge of the charge occurs.
  • a batch type substrate processing apparatus that processes a plurality of substrates at once is also used.
  • the batch-type substrate processing apparatus includes, for example, a plurality of processing tanks including a chemical processing tank storing a chemical and a rinsing processing tank storing water. When processing is performed on a plurality of substrates at once, the substrates are sequentially immersed in the chemical solution processing tank and the rinse processing tank.
  • the substrate is charged during the rinsing process in the rinsing tank.
  • the substrate is a silicon wafer or a glass substrate
  • the substrate is positively charged. If the substrate after a series of treatments is charged, there is a risk that the device formed on the surface of the substrate will be destroyed when the discharge of the charge occurs.
  • the same problem may occur when the object to be treated is charged before being carried into the treatment tank. Therefore, it is required to perform a rinsing process (a process using a processing liquid) while preventing the substrate from being charged and eliminating the charge.
  • Antistatic and neutralization in processing using a processing solution are not limited to the case where the processing target is a substrate, but are common issues when the processing target is a container or other optical component.
  • an object of the present invention is to provide a processing liquid supply apparatus and a processing liquid supply method capable of supplying a processing liquid to the processing object while preventing or neutralizing the processing object.
  • Another object of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of performing processing using a processing liquid on the substrate while preventing or eliminating the charge of the substrate.
  • Another object of the present invention is to provide a processing liquid processing apparatus and a processing liquid processing method capable of performing processing using a processing liquid on a processing object while preventing or neutralizing the processing object. It is.
  • a first aspect of the present invention is a processing liquid supply device for discharging a processing liquid from a discharge port and supplying the processing liquid to a processing object, and a first pipe through which the processing liquid can circulate
  • the processing liquid supply apparatus includes: a first pipe whose inside communicates with the discharge port; and an X-ray irradiation unit that irradiates the processing liquid existing in the first pipe with X-rays. .
  • the processing liquid existing in the first pipe is irradiated with X-rays. Further, the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the processing object.
  • irradiation portion of the treatment liquid In the portion of the treatment liquid that is irradiated with X-rays (hereinafter referred to as “irradiation portion of the treatment liquid”), electrons are emitted from the water molecules by excitation of the water molecules, and as a result, positive ions and electrons of the water molecules Is formed in a plasma state.
  • the processing liquid discharged from the discharge port is supplied to the processing object and comes into contact with the processing object.
  • the case where the processing liquid discharged from the discharge port is connected to the liquid state between the discharge port and the processing target will be considered.
  • the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the processing object can be neutralized through the processing liquid connected to the liquid state according to the principle described above.
  • the treatment liquid can be supplied to the treatment object while preventing the charge of the treatment object or eliminating the charge.
  • X-ray means an electromagnetic wave having a wavelength of about 0.001 nm to 10 nm, “soft X-ray” having a relatively long wavelength (about 0.1 nm to 10 nm), This includes “hard X-rays” (about 0.001 nm to 0.1 nm) having a relatively short wavelength.
  • processing object includes a substrate, a container, an optical component, and the like.
  • the first pipe has an opening in its pipe wall, and the opening is closed by a window member formed using a material that can transmit X-rays.
  • the X-ray irradiation unit irradiates the processing liquid existing in the first pipe with X-rays through the window member.
  • the window member is formed using a material capable of transmitting X-rays. And the X-ray irradiated from the X-ray irradiation means is irradiated to the process liquid which exists in the said 1st piping through a window member. Thereby, the plasma state in which positive ions of water molecules and electrons are mixed can be satisfactorily formed in the irradiated portion of the treatment liquid.
  • the window member may be formed using beryllium or polyimide resin.
  • the substance has a small atomic weight such as beryllium, X-rays with low penetrating power can be transmitted. Therefore, by forming the window member using beryllium, X-rays can pass through the window member.
  • the window member when the window member is formed using polyimide resin, X-rays can pass through the window member. Moreover, since the polyimide resin is excellent in chemical stability, the window member can be used over a long period of time.
  • the wall surface of the window member on the side where the treatment liquid exists is hydrophilic. In this case, it is possible to suppress or prevent air bubbles from being mixed between the wall surface and the treatment liquid. Thereby, X-ray
  • the wall surface of the window member on the side where the treatment liquid is present may be coated with a film. Thereby, an irradiation window can be protected.
  • the window member when the window member is formed using beryllium having poor acid resistance, the window member can be well protected from the acidic treatment liquid.
  • This film is preferably formed using a hydrophilic material. In this case, it is possible to suppress or prevent air bubbles from being mixed between the film and the treatment liquid. Thereby, X-ray
  • the film may be a film containing one or more materials of polyimide resin, diamond-like carbon, fluorine resin, and hydrocarbon resin.
  • the X-ray irradiation means may include an X-ray generator that has an irradiation window disposed to face the window member, generates X-rays, and irradiates the generated X-rays from the irradiation window. Good.
  • the X-ray generated by the X-ray generator is irradiated from the irradiation window of the X-ray generator to the processing liquid flowing in the first pipe.
  • the X-ray irradiation means may further include a cover surrounding the X-ray generator with a space from the X-ray generator, and a gas supply means for supplying a gas to the inside of the cover. .
  • the X-ray generator generates heat by driving the X-ray generator.
  • the X-ray generator can be cooled, and the temperature rise in the ambient atmosphere of the X-ray generator can be suppressed.
  • the first pipe includes a processing liquid pipe through which a processing liquid flows toward the discharge port, and the X-ray irradiating means is a process that circulates in the first pipe.
  • the liquid may be irradiated with the X-ray.
  • the apparatus further includes a processing liquid pipe through which the processing liquid flows toward the discharge port, and the first pipe includes a branch pipe branched from the processing liquid pipe. Also good. In this case, the X-ray is irradiated to the processing liquid present in the branch pipe.
  • the processing liquid discharged from the discharge port flows along the fibrous substance, even when the discharge flow rate of the processing liquid from the discharge port is a small flow rate, the processing liquid discharged from the discharge port An aspect can be made into the continuous flow form connected to both the said discharge outlet and the said process target object. Therefore, it is possible to connect the processing object and the irradiated portion of the processing liquid through the processing liquid with a simple configuration.
  • the tip of the fibrous substance may be in contact with the liquid film of the processing liquid or the processing object.
  • the mode of the processing liquid discharged from the discharge port is easily maintained in the continuous flow as described above.
  • the electrode may further include an electrode disposed downstream of the X-ray irradiation position in the first pipe in the treatment liquid flow direction and a power source for applying a voltage to the electrode.
  • the power supply applies a voltage to the electrodes in conjunction with the X-ray irradiation to the treatment liquid existing in the first pipe.
  • a voltage to the electrode By applying a voltage to the electrode, a positive charge or a negative charge can be generated in the electrode.
  • the electrode may be disposed at the tip of the first pipe.
  • the electrode is arrange
  • the processing liquid supply device includes a processing liquid detection means for detecting the presence or absence of a processing liquid at the irradiation position of the X-ray in the first pipe, and when the processing liquid is present at the irradiation position, the X-ray An X-ray irradiation control unit that performs X-ray irradiation by the irradiation unit and that does not perform X-ray irradiation by the X-ray irradiation unit when the treatment liquid is not present at the irradiation position may be further included.
  • the X-rays may leak out of the first pipe.
  • 1st aspect of this invention provides the substrate processing apparatus which contains the board
  • X-rays are irradiated to the processing liquid existing in the first pipe of the processing liquid supply apparatus.
  • the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the main surface of the substrate.
  • electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
  • the processing liquid discharged from the discharge port is supplied to the main surface of the substrate and comes into contact with the main surface of the substrate.
  • a case where the processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the main surface of the substrate will be considered.
  • the main surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the processing liquid in which electrons from the irradiated portion of the processing liquid are in contact with the substrate due to a potential difference between the irradiated portion of the processing liquid and the positively charged substrate Toward the liquid, it moves along the processing liquid connected to the liquid state. As a result, since the processing liquid in contact with the substrate has a large amount of electrons, the positively charged substrate is neutralized.
  • the object to be treated can be neutralized through the treatment liquid connected to the liquid according to the principle described above. As a result, it is possible to prevent device destruction due to charging of the substrate.
  • the substrate can be treated with the treatment liquid while preventing or eliminating the charge of the substrate.
  • the substrate holding unit includes a substrate holding and rotating unit that rotates a substrate around a predetermined rotation axis while holding the substrate in a horizontal posture
  • the substrate processing apparatus includes the substrate holding and rotating unit.
  • a cylindrical liquid receiving member surrounding the periphery of the means; and the processing liquid supply device further includes a processing liquid pipe through which the processing liquid flows toward the discharge port, and the processing liquid supply device includes:
  • the first pipe includes a branch pipe branched from the processing liquid pipe, and the branch pipe has a liquid receiving outlet for discharging the processing liquid toward the liquid receiving member.
  • the X-ray irradiation means irradiates the processing liquid flowing through the branch pipe while discharging the processing liquid from the liquid receiving discharge port toward the liquid receiving member.
  • a plasma state in which positive ions of water molecules and electrons are mixed is formed in the irradiated portion of the treatment liquid in the branch pipe.
  • the processing liquid discharged from the liquid receiving discharge port is supplied to the liquid receiving member and comes into contact with the liquid receiving member.
  • the processing liquid discharged from the liquid receiving discharge port is connected in a liquid state between the liquid receiving discharge port and the liquid receiving member, the liquid receiving member and the irradiated portion of the processing liquid receive the processing liquid. Connected through.
  • the liquid receiving member is positively charged, electrons from the irradiated portion of the processing liquid are received by the potential difference between the irradiated portion of the processing liquid and the positively charged liquid receiving member. It moves along the treatment liquid connected to the liquid toward the treatment liquid in contact with the member. As a result, since the processing liquid in contact with the liquid receiving member has a large amount of electrons, the positively charged liquid receiving member is neutralized.
  • the substrate holding means includes substrate holding rotating means for rotating the substrate around a predetermined vertical rotation axis while holding the substrate in a horizontal posture
  • the substrate holding rotating means includes the substrate A support member that is in contact with at least a part of the lower surface of the substrate and supports the substrate in a horizontal posture, the support member is formed using a porous material, and the processing liquid discharged from the discharge port Supplied to the support member.
  • the processing liquid supplied to the support member is impregnated inside the support member.
  • the treatment liquid impregnated inside the support member oozes out from the support member and forms a liquid film of the treatment liquid on the support member.
  • the liquid film of the processing liquid comes into contact with the lower surface of the substrate, the lower surface of the substrate is processed.
  • the discharge port is connected to the discharge port through the processing liquid impregnated inside the support member.
  • the lower surface of the substrate is connected in a liquid state, and therefore, the lower surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the treatment using the treatment liquid can be performed on the lower surface of the substrate while preventing the charge of the substrate and eliminating the charge.
  • the substrate holding means may include substrate holding and conveying means for conveying the substrate in a predetermined conveying direction while holding the substrate.
  • the processing liquid discharged from the discharge port is supplied to the main surface (upper surface) of the substrate transported by the substrate holding transport means, and comes into contact with the main surface (upper surface) of the substrate.
  • the processing liquid in which electrons from the irradiated portion of the processing liquid are in contact with the substrate due to a potential difference between the irradiated portion of the processing liquid and the positively charged substrate Toward the liquid, it moves along the processing liquid connected to the liquid state. As a result, since the processing liquid in contact with the substrate has a large amount of electrons, the positively charged substrate is neutralized.
  • the substrate holding and transporting means is transported while holding the substrate in a posture that is inclined along the transport direction and with respect to a horizontal plane.
  • the processing liquid discharged from the discharge port flows on the substrate along the inclined surface. Therefore, since the processing liquid does not stay on the substrate, it is possible to prevent or suppress the load from being concentrated on a predetermined portion of the substrate due to the weight of the processing liquid. Further, since the processing liquid flows smoothly on the substrate, a liquid film of the processing liquid spreading over a wide range can be formed on the upper surface of the substrate. As a result, it is possible to prevent charge and eliminate static electricity over a wide range of the substrate.
  • 1st aspect of this invention is a processing liquid supply method which discharges a processing liquid from the discharge outlet of a processing liquid supply apparatus, and supplies this processing liquid to a process target object, Comprising: The said discharge outlet is set to the said process target object.
  • the X-ray irradiation step of irradiating the X-ray to the treatment liquid existing inside the first pipe communicating with the discharge port, And a processing liquid discharge step for discharging the processing liquid from the discharge port.
  • a processing liquid supply method is provided in which the processing liquid is in a liquid state between the discharge port and the processing object. To do.
  • the processing liquid existing in the first pipe is irradiated with X-rays. Further, the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the processing object. In the portion of the treatment liquid that is irradiated with X-rays, electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
  • the processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the object to be processed.
  • the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the processing object can be neutralized through the processing liquid connected to the liquid state according to the principle described above.
  • the treatment liquid can be supplied to the treatment object while preventing the charge of the treatment object or eliminating the charge.
  • the processing liquid discharged from the discharge port has a continuous flow shape connected to both the discharge port and the processing object.
  • the processing object and the irradiated portion of the processing liquid can be easily connected via the processing liquid.
  • the processing object may be a second pipe through which liquid flows, or a container for storing articles.
  • 1st aspect of this invention is a substrate processing method which processes a board
  • a processing liquid discharge step of discharging a processing liquid from the discharge port, and in the processing liquid discharge step, the processing liquid is connected in a liquid state between the discharge port and the main surface of the substrate.
  • the processing liquid existing in the first pipe is irradiated with X-rays.
  • the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the main surface of the substrate.
  • electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
  • the processing liquid discharged from the discharge port is supplied to the upper surface of the substrate and comes into contact with the upper surface of the substrate.
  • the processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the main surface of the substrate. In this case, the main surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the processing liquid in which electrons from the irradiated portion of the processing liquid are in contact with the substrate due to a potential difference between the irradiated portion of the processing liquid and the positively charged substrate Toward the liquid, it moves along the processing liquid connected to the liquid state. As a result, since the processing liquid in contact with the substrate has a large amount of electrons, the positively charged substrate is neutralized.
  • the object to be treated can be neutralized through the treatment liquid connected to the liquid according to the principle described above. As a result, it is possible to prevent device destruction due to charging of the substrate.
  • the substrate can be treated with the treatment liquid while preventing or eliminating the charge of the substrate.
  • the processing liquid discharged from the discharge port has a continuous flow shape connected to both the discharge port and the main surface of the substrate.
  • substrate and the irradiation part of a process liquid can be connected easily via a process liquid.
  • the substrate is held in a horizontal posture by the substrate holding means, and the opposing arrangement step is such that the discharge port faces the upper surface of the substrate held by the substrate holding means.
  • the processing liquid discharged from the discharge port is supplied to the upper surface of the substrate and comes into contact with the upper surface of the substrate.
  • the processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the upper surface of the substrate, and the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the substrate is held in a horizontal posture by the substrate holding means, and the opposing arrangement step is such that the discharge port is placed on the lower surface of the substrate held by the substrate holding means.
  • the substrate processing method is executed in parallel with the processing liquid discharge step, and rotates the substrate about a predetermined vertical rotation axis, and the processing liquid
  • an upper surface processing liquid supply step for supplying a processing liquid to the upper surface of the substrate is further included.
  • the processing liquid discharged from the discharge port is supplied to the lower surface of the substrate and comes into contact with the lower surface of the substrate.
  • the processing liquid in contact with the lower surface of the substrate spreads to the peripheral edge along the lower surface of the substrate, and a liquid film of the processing liquid is formed over the entire lower surface of the substrate.
  • the processing liquid that reaches the peripheral edge of the lower surface of the substrate goes around the peripheral end surface of the substrate and reaches the peripheral edge of the upper surface of the substrate.
  • the processing liquid is supplied to the upper surface of the substrate.
  • the processing liquid supplied to the substrate receives a centrifugal force due to the rotation of the substrate and spreads the upper surface of the substrate toward the peripheral portion, thereby forming a liquid film of the processing liquid over the entire upper surface of the substrate.
  • the processing liquid that has come around from the lower surface side of the substrate merges with the liquid film of the processing liquid on the upper surface side of the substrate, and as a result, the liquid film of the processing liquid on the upper surface side of the substrate and the liquid film of the processing liquid on the lower surface side of the substrate. Will be connected.
  • both the upper surface of the substrate and the lower surface of the substrate connect the irradiated portions of the processing liquid via the processing liquid. Therefore, it is possible to prevent charging and charge removal on both the upper and lower surfaces of the substrate.
  • the process may further include a second X-ray irradiation process that is performed in parallel with the liquid draining process or the drying process that is performed after the processing liquid discharge process is completed and that irradiates the main surface of the substrate with X-rays.
  • the processing liquid is removed from the main surface of the substrate by the liquid draining process or the drying process.
  • X-rays are irradiated to the main surface of the substrate immediately after the treatment liquid is removed.
  • it is possible to more reliably achieve prevention of static charge and neutralization of the substrate.
  • a substrate holding means for holding a substrate, an X-ray irradiation means for irradiating the surface of the substrate held by the substrate holding means with X-rays, and the substrate holding means.
  • the processing liquid supply means for supplying the processing liquid to the surface of the substrate, and the X-ray irradiation means and the processing liquid supply means so that the supply of the processing liquid to the surface of the substrate and the X-ray irradiation are performed in parallel.
  • a control means for controlling the substrate.
  • the liquid film of the processing liquid that contacts the surface is formed on the surface of the substrate.
  • X-rays are irradiated to the liquid film of the processing liquid.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules coexist as a result of electrons being emitted from the water molecules by excitation of water molecules. Is formed.
  • electrons generated in the processing liquid due to X-ray irradiation are generated on the substrate through the liquid film of the processing liquid.
  • the X-ray irradiation means includes an irradiation window, and includes an X-ray generator that generates X-rays and irradiates the generated X-rays from the irradiation window.
  • the surface of the substrate is irradiated with X-rays generated by the X-ray generator from the irradiation window of the X-ray generator.
  • the substrate processing apparatus further includes a cover that surrounds the X-ray generator with a space therebetween, and an opening is formed in the cover at a portion facing the irradiation window.
  • the periphery of the X-ray generator is covered with a cover.
  • the cover has an opening at a portion facing the irradiation window, and X-rays from the irradiation window are guided to the surface of the substrate through the opening.
  • the substrate processing apparatus further includes a gas supply unit that supplies a gas into the cover.
  • a gas supply unit that supplies a gas into the cover.
  • the gas supplied from the gas supply means to the inside of the cover include CDA (low humidity clean air) and nitrogen gas.
  • the gas supply means may supply a gas having a temperature higher than room temperature.
  • the high-temperature gas supplied into the cover reaches the outer surface of the irradiation window through the space between the X-ray generator and the cover.
  • the high-temperature gas water droplets adhering to the outer surface of the irradiation window can be removed by evaporation, thereby suppressing or preventing fogging of the irradiation window.
  • the outer surface of the irradiation window may be coated with a film. Thereby, an irradiation window can be protected.
  • the irradiation window is formed using beryllium having poor acid resistance, the irradiation window can be well protected from the acidic treatment liquid.
  • This film is preferably formed using a water-repellent material.
  • moisture is prevented from precipitating in the form of a film over the entire irradiation window, and the moisture is made into fine water droplets.
  • Water droplets adhering to the outer surface of the irradiation window are in a state where they can easily move on the outer surface. Therefore, it is possible to easily remove water droplets from the outer surface of the irradiation window, thereby suppressing or preventing the irradiation window from being fogged.
  • the substrate processing apparatus preferably includes both the coating by the film on the outer surface of the irradiation window and the gas supply means. Since the water droplets adhering to the outer surface of the irradiation window are in a state of being easily moved on the outer surface, the water droplets adhering to the outer surface of the irradiation window move by receiving the air flow formed in the space. Thereby, water droplets can be favorably removed from the outer surface of the irradiation window, and the irradiation window can be reliably prevented from being fogged.
  • the film may be a polyimide resin film.
  • the film may be a diamond-like carbon film.
  • the film may be an amorphous fluororesin film.
  • a heating member is disposed around the opening of the cover and at least one of the irradiation window.
  • the periphery of the irradiation window of the X-ray generator is heated by the heat generating member. Therefore, water droplets adhering to the outer surface of the irradiation window can be removed by evaporation, thereby suppressing or preventing fogging of the irradiation window.
  • the substrate processing apparatus may further include a shielding member that is disposed to face the surface of the substrate held by the substrate holding means and shields a space on the surface of the substrate from the periphery thereof.
  • the shielding member is for keeping X-rays irradiated from the irradiation window in a space on the surface of the substrate.
  • the shielding member may be provided so as to be movable together with the cover.
  • the substrate processing apparatus further includes moving means for moving the X-ray irradiation means along the surface of the substrate held by the substrate holding means.
  • the X-ray irradiation means is moved along the surface of the substrate while the X-ray irradiation means is irradiated with the X-ray while the X-ray irradiation means is opposed to the surface of the substrate.
  • the ionized processing liquid can be supplied to the entire surface of the substrate.
  • the substrate can be neutralized over the entire area of the substrate.
  • the treatment liquid may be water.
  • a processing liquid supply step for supplying a processing liquid to the surface of the substrate held by the substrate holding means, and a substrate held by the substrate holding means in parallel with the processing liquid supply step.
  • An X-ray irradiation step of irradiating the surface of the substrate with X-rays is provided.
  • a liquid film of the processing liquid that contacts the surface is formed on the surface of the substrate.
  • X-rays are irradiated to the liquid film of the processing liquid.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules coexist as a result of electrons being emitted from the water molecules by excitation of water molecules. Is formed.
  • electrons generated in the processing liquid due to X-ray irradiation are generated on the substrate through the liquid film of the processing liquid.
  • a third aspect of the present invention is a processing liquid processing apparatus that performs processing by immersing a processing object in the processing liquid, storing the processing liquid and immersing the processing object in the processing liquid. And the processing liquid stored in the processing tank or a pipe through which the processing liquid can flow, and the processing liquid existing in the pipe communicating with the processing tank is irradiated with X-rays
  • a processing liquid processing apparatus including X-ray irradiation means.
  • X-rays are irradiated to the processing liquid stored in the processing tank or the processing liquid existing inside the pipe communicating with the processing tank.
  • treatment liquid irradiation portion In a portion of the treatment liquid that is irradiated with X-rays (treatment liquid irradiation portion), electrons are emitted from the water molecules by excitation of water molecules, and as a result, plasma in which positive ions and electrons of water molecules are mixed. A state is formed.
  • the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected through the processing solution.
  • the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object positively charged. It moves through the processing liquid stored in the processing tank. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized.
  • the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected via the processing liquid which has been processed and the processing liquid in the pipe.
  • the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object that is positively charged. It moves through the processing liquid stored in the processing tank and the processing liquid in the pipe. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized.
  • the treatment object is treated via the treatment liquid in the treatment tank or the treatment liquid in the pipe according to the principle described above. Can neutralize things.
  • the pipe wall of the pipe or the wall of the processing tank has an opening, and the opening is closed by a window member formed using a material that can transmit X-rays.
  • the X-ray irradiation means irradiates X-rays through the window member.
  • the window member is formed using a material capable of transmitting X-rays. And the X-ray irradiated from the X-ray irradiation means is irradiated to the process liquid which exists in the said piping through a window member. Thereby, the plasma state in which positive ions of water molecules and electrons are mixed can be satisfactorily formed in the irradiated portion of the treatment liquid.
  • the window member may be formed using beryllium or polyimide resin.
  • the substance has a small atomic weight such as beryllium, X-rays with low penetrating power can be transmitted. Therefore, by forming the window member using beryllium, X-rays can pass through the window member.
  • the window member when the window member is formed using a polyimide resin, X-rays can be transmitted through the window member. Moreover, since the polyimide resin is excellent in chemical stability, the window member can be used over a long period of time.
  • the wall surface of the window member on the side where the treatment liquid exists is hydrophilic. In this case, it is possible to suppress or prevent air bubbles from being mixed between the wall surface and the treatment liquid. Thereby, it is possible to satisfactorily irradiate X-rays to the processing liquid existing in the pipe.
  • the wall surface of the window member on the side where the treatment liquid is present may be coated with a film. Thereby, an irradiation window can be protected.
  • the window member when the window member is formed using beryllium having poor acid resistance, the window member can be well protected from the acidic treatment liquid.
  • This film is preferably formed using a hydrophilic material. In this case, it is possible to suppress or prevent air bubbles from being mixed between the film and the treatment liquid. Thereby, it is possible to satisfactorily irradiate X-rays to the processing liquid existing in the pipe.
  • the film may be a film containing one or more materials of polyimide resin, diamond-like carbon, fluorine resin, and hydrocarbon resin.
  • the X-ray irradiation means may include an X-ray generator that has an irradiation window disposed to face the window member, generates X-rays, and irradiates the generated X-rays from the irradiation window. Good.
  • the X-ray generated by the X-ray generator is irradiated to the processing liquid flowing in the pipe from the irradiation window of the X-ray generator.
  • the X-ray irradiation means may further include a cover surrounding the X-ray generator with a space from the X-ray generator, and a gas supply means for supplying a gas to the inside of the cover. .
  • the X-ray generator generates heat by driving the X-ray generator.
  • the X-ray generator can be cooled, and the temperature rise in the ambient atmosphere of the X-ray generator can be suppressed.
  • the pipe includes a processing liquid supply pipe that communicates with the inside of the processing tank and supplies a processing liquid into the processing tank, and the X-ray irradiation means includes the processing liquid supply You may irradiate the said process liquid currently distribute
  • the said processing tank stores the processing liquid
  • the inner tank which immerses a process target object in the processing liquid
  • the outer tank which collect
  • the pipe includes an overflow pipe through which the processing liquid collected in the outer tank flows, and the X-ray irradiation means irradiates the processing liquid flowing through the overflow pipe with the X-ray. Also good.
  • the treatment tank includes an inner tank for storing the treatment liquid and immersing the treatment object in the treatment liquid, and an outer tank for recovering the treatment liquid overflowing from the inner tank.
  • the X-ray irradiation means may irradiate the X-ray to the processing liquid stored in the inner tank.
  • the treatment tank includes an inner tank for storing the treatment liquid and immersing the treatment object in the treatment liquid, and an outer tank for recovering the treatment liquid overflowing from the inner tank.
  • the pipe may include a pipe that communicates with the inside of the inner tank.
  • the third aspect of the present invention is stored in the processing tank in parallel with the processing object immersion step for immersing the processing object in the processing liquid stored in the processing tank and the processing object immersion step.
  • X-rays are irradiated to the processing liquid stored in the processing tank or the processing liquid existing inside the piping communicating with the processing tank.
  • treatment liquid irradiation portion In a portion of the treatment liquid that is irradiated with X-rays (treatment liquid irradiation portion), electrons are emitted from the water molecules by excitation of water molecules, and as a result, plasma in which positive ions and electrons of water molecules are mixed. A state is formed.
  • the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected through the processing solution.
  • the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object positively charged. It moves through the processing liquid stored in the processing tank. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized.
  • the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected via the processing liquid which has been processed and the processing liquid in the pipe.
  • the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object that is positively charged. It moves through the processing liquid stored in the processing tank and the processing liquid in the pipe. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized.
  • the treatment object is treated via the treatment liquid in the treatment tank or the treatment liquid in the pipe according to the principle described above. Can neutralize things.
  • 4th aspect of this invention is the processing liquid processing method for immersing a process target object in the processing liquid stored by the processing tank, and processing, Comprising: In the processing liquid stored by the said processing tank A treatment object immersion step for immersing the treatment object, a treatment liquid discharge step for discharging treatment liquid from a discharge port toward the inside of the treatment tank, and the treatment liquid discharge step in parallel with the treatment object immersion step.
  • the X-ray irradiation step of irradiating the processing liquid existing inside the pipe communicating with the discharge port with X-rays is stored in the discharge port and the processing tank in the processing liquid discharge step.
  • This is a processing liquid processing method in which the processing liquid is connected to the liquid surface of the processing liquid.
  • X-rays are irradiated to the processing liquid existing in the pipe. Further, the processing liquid discharged from the discharge port communicating with the inside of the pipe is supplied to the processing object. In the portion of the treatment liquid that is irradiated with X-rays, electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
  • the processing liquid discharged from the discharge port is connected in liquid form with the liquid surface of the processing liquid.
  • the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
  • the treatment object can be treated with the treatment liquid while preventing or removing the charge of the treatment object.
  • FIG. 2 is a schematic longitudinal sectional view of the integrated head shown in FIG. 1. It is a block diagram which shows the electric constitution of the substrate processing apparatus shown in FIG. It is process drawing which shows the process example performed in the substrate processing apparatus shown in FIG. It is an illustration sectional view showing the irradiation state of soft X-rays in the water nozzle. It is a figure which shows the state which has performed the rinse process to the board
  • substrate. 6 is a flowchart for explaining a modification of the processing example shown in FIG. 4. It is a figure which shows typically the structure of the integrated head which concerns on 2nd Embodiment of this invention.
  • FIG. 9 is a cross-sectional view taken along section line IX-IX in FIG. It is a figure for demonstrating the structure of the integrated head which concerns on 3rd Embodiment of this invention. It is a figure which shows the structure of the substrate processing apparatus which concerns on 4th Embodiment of this invention. It is a figure which shows the structure of the substrate processing apparatus which concerns on 5th Embodiment of this invention. It is a figure explaining discharge of the processing liquid in a 5th embodiment of the present invention. It is a figure which shows the structure of the substrate processing apparatus which concerns on 6th Embodiment of this invention. It is a figure which shows the structure of the substrate processing apparatus which concerns on 7th Embodiment of this invention.
  • FIG. 18 it is a figure which shows the flow of DIW at the time of a rinse process. It is a figure which shows the structure of the substrate processing apparatus which concerns on 11th Embodiment of this invention. It is a figure which shows the state which the water supply unit shown in FIG. 20 is supplying DIW to the inclination part of the cup upper part.
  • FIG. 25 is a cross-sectional view showing a state in which the soft X-ray irradiation apparatus shown in FIG.
  • FIG. 32 is a schematic longitudinal sectional view of the soft X-ray irradiation head shown in FIG. 31.
  • FIG. 32 is a plan view showing movement of the soft X-ray irradiation head shown in FIG. 31.
  • FIG. 32 is a block diagram showing an electrical configuration of the substrate processing apparatus shown in FIG. 31.
  • FIG. 32 is a process diagram showing an example of processing executed in the substrate processing apparatus shown in FIG. 31. It is an illustration figure for demonstrating a rinse process. It is an illustration figure which shows the state of the surface vicinity of the board
  • FIG. 45 is a schematic cross-sectional view illustrating a configuration of a branch pipe and a soft X-ray irradiation unit illustrated in FIG. 44.
  • FIG. 45 is a process diagram illustrating an example of a substrate process performed in the substrate processing apparatus illustrated in FIG. 44. It is an illustration figure which shows the irradiation state of the soft X-ray to the branch piping shown in FIG. It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 20th Embodiment of this invention was applied.
  • FIG. 1 is a diagram showing a configuration of a substrate processing apparatus 1 according to the first embodiment of the present invention.
  • the substrate processing apparatus 1 is a single wafer used for processing a surface (processing target surface) of a circular semiconductor wafer (silicon wafer) as an example of a substrate (processing target) W with a processing solution (chemical solution and water). Device.
  • a processing solution chemical solution and water
  • water is used for rinsing the substrate W performed after the chemical treatment.
  • the substrate processing apparatus 1 includes a spin chuck (substrate holding rotating means) 4 for rotating the substrate W in a horizontal posture in a processing chamber 3 partitioned by a partition wall (not shown), and an upper surface (upper side) of the substrate W.
  • Water supply unit treatment liquid supply
  • DIW deionized water
  • a chemical nozzle 7 for supplying a chemical to the upper surface of the substrate W held by the spin chuck 4.
  • the spin chuck 4 includes a spin motor 8, a spin shaft 9 integrated with a drive shaft of the spin motor 8, and a disk-shaped spin base attached substantially horizontally to the upper end of the spin shaft 9. 10 and a plurality of clamping members 11 provided at a plurality of positions on the peripheral edge of the spin base 10 at substantially equal intervals.
  • the spin chuck 4 rotates the spin base 10 by the rotational driving force of the spin motor 8 in a state where the substrate W is sandwiched by the plurality of sandwiching members 11 so that the substrate W is placed in a substantially horizontal posture. In this state, it can be rotated around the vertical rotation axis C together with the spin base 10.
  • the spin chuck 4 is not limited to a sandwiching type, and for example, by vacuum-sucking the back surface of the substrate W, the substrate W is held in a horizontal posture and further rotated around a vertical rotation axis in that state.
  • a vacuum chucking type vacuum chuck
  • a vacuum chuck that can rotate the held substrate W may be employed.
  • the spin chuck 4 is accommodated in a cup (liquid receiving member) 17.
  • the cup 17 includes a cup lower part 18 and a cup upper part 19 provided so as to be movable up and down above the cup lower part 18.
  • the cup lower part 18 has a bottomed cylindrical shape whose center axis coincides with the rotation axis C.
  • An exhaust port (not shown) is formed on the bottom surface of the cup lower portion 18, and the atmosphere in the cup 17 is always exhausted from the exhaust port while the substrate processing apparatus 1 is in operation.
  • the cup upper portion 19 includes a cylindrical cylindrical portion 20 having a central axis common to the cup lower portion 18, and an inclined portion 21 that is inclined so as to increase from the upper end of the cylindrical portion 20 toward the central axis of the cylindrical portion 20. Integrated.
  • a cup elevating unit 22 for moving the cup upper portion 19 up and down (moving up and down) is coupled to the cup upper portion 19. By the cup lifting / lowering unit 22, the cup upper portion 19 is moved to a position where the cylindrical portion 20 is disposed on the side of the spin base 10 and a position where the upper end of the inclined portion 21 is disposed below the spin base 10.
  • the cup upper portion 19 and the cup lower portion 18 are each formed using a resin material (for example, PTFE (polytetrafluoroethylene)).
  • a resin material for example, PTFE (polytetrafluoroethylene)
  • the chemical nozzle 7 is, for example, a straight nozzle that discharges chemical liquid in a continuous flow state, and is fixedly disposed above the spin chuck 4 with its discharge port directed toward the rotation center of the substrate W.
  • a chemical liquid supply pipe 15 to which a chemical liquid from a chemical liquid supply source is supplied is connected to the chemical liquid nozzle 7.
  • a chemical solution valve 16 for switching supply / stop of supply of the chemical solution from the chemical solution nozzle 7 is interposed in the middle portion of the chemical solution supply pipe 15.
  • the chemical nozzle 7 does not need to be fixedly arranged with respect to the spin chuck 4.
  • the chemical nozzle 7 is attached to an arm that can swing in a horizontal plane above the cup 17, and the substrate is moved by the swing of the arm.
  • a so-called scan nozzle configuration in which the position where the chemical liquid is deposited on the surface of W is scanned may be employed.
  • a liquid according to the content of the treatment for the surface of the substrate W is used.
  • APM ammonia-hydrogen peroxide mixture
  • TMAH tetramethylammonium hydroxide aqueous solution
  • SPM sulfuric acid / A resist stripping solution and a polymer removing solution such as hydrogen peroxide mixture (sulfuric acid / hydrogen peroxide mixture) and APM (ammonia-hydrogen peroxide mixture) are used.
  • Cleaning treatment to remove metal contaminants includes hydrofluoric acid, HPM (hydrochloric acid / hydrogen peroxide mixture) and SPM (sulfuric acid / hydrogen peroxide mixture). Is used.
  • the water supply unit 100 has an integrated head 6 disposed so as to face the upper side of the spin chuck 4.
  • the integrated head 6 includes a water nozzle (treatment liquid nozzle) 61 for discharging DIW as an example of water, and a soft X-ray irradiation unit (for irradiating soft X-rays to water flowing through the water nozzle 61).
  • X-ray irradiation means) 62 is integrally provided.
  • the soft X-ray irradiation unit 62 is attached to the water nozzle 61.
  • the water nozzle 61 is, for example, a straight nozzle that discharges a chemical solution in a continuous flow state, and is disposed with its discharge port 53 facing downward.
  • the water nozzle 61 is connected to a water supply pipe 13 to which DIW from a DIW supply source is supplied.
  • a water valve 14 for switching supply / stop of supply of DIW from the water nozzle 61 is interposed in the middle of the water supply pipe 13.
  • the soft X-ray irradiation unit 62 will be described later.
  • FIG. 2 is a schematic longitudinal sectional view of the integrated head 6.
  • the water nozzle 61 of the integrated head 6 has a first nozzle pipe 51 having a round tubular shape (cylindrical shape) extending in the vertical direction.
  • the first nozzle pipe 51 is formed using, for example, a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). ing.
  • a round discharge port 53 is opened at the front end (lower end) of the first nozzle pipe 51.
  • a circular first opening 52 is formed in the middle pipe wall.
  • a soft X-ray irradiation unit 62 is attached to the first nozzle pipe 51 so as to close the first opening 52.
  • the integrated head 6 is fixedly disposed above the rotation axis C of the substrate W by the spin chuck 4 with its discharge port 53 directed downward (near the rotation center of the substrate W).
  • An annular electrode 56 is fitted and fixed to the tip of the first nozzle pipe 51.
  • a voltage with respect to the apparatus ground is applied to the electrode 56 by a power source 57 (see FIG. 3), whereby an electric field is applied to the processing liquid passing near the electrode 56.
  • the soft X-ray irradiation unit 62 includes a soft X-ray generator (X-ray generator) 25, a cover 26 made of, for example, polyvinyl-chloride covering the periphery of the soft X-ray generator 25, A gas nozzle (gas supply means) 27 for supplying a gas to the inside of the cover 26 is provided, and soft X-rays are irradiated sideways.
  • the cover 26 has a horizontally long rectangular box shape surrounding the soft X-ray generator 25 with a space from the soft X-ray generator 25.
  • a circular second opening 28 having the same diameter as the first opening 52 is formed in a portion facing the irradiation window 35 described next.
  • the soft X-ray irradiation unit 62 includes a nozzle pipe so that the second opening 28 of the cover 26 coincides with the first opening 52 of the first nozzle pipe 51 and the lateral wall 26A is in close contact with the outer periphery of the first nozzle pipe 51. 51 is attached.
  • the second opening 28 is closed by a disk-shaped window member 71.
  • the window member 71 closes the second opening 28 from the inside of the cover 26.
  • the window member 71 closes not only the second opening 28 but also the first opening 52.
  • a substance having a small atomic weight is used so that soft X-rays having a low penetrating power are easily transmitted.
  • beryllium (Be) is adopted as the material of the window member 71.
  • the thickness of the window member 71 is set to about 0.3 mm, for example.
  • the soft X-ray generator 25 emits (radiates) soft X-rays used to ionize the processing liquid passing through the first nozzle pipe 51.
  • the soft X-ray generator 25 includes a case body 29, a soft X-ray tube 30 that is long to generate soft X-rays, and a high voltage unit 31 that supplies a high voltage to the soft X-ray tube 30. Yes.
  • the case body 29 is in the shape of a horizontally long rectangular tube that accommodates the soft X-ray tube 30 and the high voltage unit 31, and is made of a material having conductivity and heat conductivity (for example, a metal material such as aluminum). It is formed using.
  • the high voltage unit 31 inputs a drive voltage having a high potential of ⁇ 9.5 kV, for example, to the soft X-ray tube 30.
  • the high voltage unit 31 is supplied with a voltage from a power source (not shown) through a feed line 43 drawn out of the cover 26 through a through hole 42 formed in the cover 26.
  • the soft X-ray tube 30 is made of a glass or metal cylindrical vacuum tube, and is arranged so that the tube direction is horizontal. One end (opening end, left end shown in FIG. 2) of the soft X-ray tube 30 forms a circular opening 41. The other end of the soft X-ray tube 30 (the right end shown in FIG. 2) is closed and serves as a stem 32.
  • a filament 33 serving as a cathode and a target 36 serving as an anode are disposed so as to face each other.
  • the soft X-ray tube 30 houses a filament 33 and a focus 34. Specifically, a filament 33 as a cathode is disposed on the stem 32.
  • the filament 33 is electrically connected to the high voltage unit 31.
  • the filament 33 is surrounded by a cylindrical focus 34.
  • the open end of the soft X-ray tube 30 is closed by a plate-shaped irradiation window 35 having a vertical posture.
  • the irradiation window 35 has a disk shape, for example, and is fixed to the wall surface of the open end of the soft X-ray tube 30 by silver brazing.
  • As the material of the irradiation window 35 a substance having a small atomic weight is used so that soft X-rays having a low transmission power can be easily transmitted. For example, beryllium (Be) is adopted.
  • the thickness of the irradiation window 35 is set to about 0.3 mm, for example.
  • the irradiation window 35 faces the inner surface 71 ⁇ / b> A of the window member 71 and is arranged at a minute distance from the window member 71.
  • a metal target 36 is formed on the inner surface 35A of the irradiation window 35 by vapor deposition.
  • a metal having a high atomic weight and a high melting point such as tungsten (W) or tantalum (Ta) is used.
  • the filament 33 When the drive voltage from the high voltage unit 31 is applied to the filament 33 which is a cathode, the filament 33 emits electrons. The electrons emitted from the filament 33 are converged by the focus 34 to become an electron beam and collide with the target 36 to generate soft X-rays. The generated soft X-rays are emitted (radiated) from the irradiation window 35 in the lateral direction (leftward in FIG. 2), and irradiate the inside of the first nozzle pipe 51 through the window member 71 and the first opening 52.
  • the soft X-ray irradiation angle (irradiation range) from the irradiation window 35 is a wide angle (for example, 130 °) as shown in FIG. Soft X-rays irradiated from the irradiation window 35 into the first nozzle pipe 51 have a wavelength of, for example, 0.13 to 0.4 nm.
  • the entire outer surface of the window member 71 (the wall surface on the side where the treatment liquid flows in the closed window) 71B is covered with a hydrophilic film (film) 38.
  • the hydrophilic film 38 is, for example, a polyimide resin film.
  • the reason why the outer surface 71B of the window member 71 is covered with the hydrophilic film 38 is to protect the window member 71 made of beryllium having poor acid resistance from an acid contained in a treatment liquid such as water.
  • the film thickness of the hydrophilic film 38 is 50 ⁇ m or less, and preferably about 10 ⁇ m. Since the hydrophilic film 38 has hydrophilicity, it is possible to suppress or prevent air bubbles from being mixed between the film 38 and DIW. Thereby, the soft X-rays from the irradiation window 35 can be favorably irradiated to the DIW flowing through the first nozzle pipe 51.
  • the discharge port of the gas nozzle 27 opens in the horizontal wall of the cover 26.
  • Gas from a gas supply source (not shown) is supplied to the gas nozzle 27 via a gas valve (gas supply means) 37.
  • the gas discharged from the gas nozzle 27 include CDA (clean air with low humidity) and inert gas such as nitrogen gas.
  • the gas discharged from the gas nozzle 27 is supplied into the cover 26.
  • the soft X-ray generator 25 generates heat by driving the soft X-ray generator 25.
  • the soft X-ray generator 25 is cooled to generate soft X-rays. The temperature rise in the ambient atmosphere of the vessel 25 can be suppressed.
  • FIG. 3 is a block diagram showing an electrical configuration of the substrate processing apparatus 1.
  • the substrate processing apparatus 1 further includes a control device (X-ray irradiation control means) 40 having a configuration including a microcomputer.
  • the control device 40 is connected with a cup lifting unit 22, a spin motor 8, a high voltage unit 31, a chemical liquid valve 16, a water valve 14, a power source 57, a gas valve 37, and the like as control targets.
  • gas valve 37 is always open while the substrate processing apparatus 1 is powered on in order to release the heat in the cover 26.
  • FIG. 4 is a process diagram showing a processing example of the substrate W executed in the substrate processing apparatus 1.
  • the rinse process is performed after the chemical process.
  • the processing of the substrate W in the substrate processing apparatus 1 will be described with reference to FIGS. 1, 3, and 4.
  • an unprocessed substrate W is carried into the processing chamber 3 by a transfer robot (not shown) (step S1), and is transferred to the spin chuck 4 with its surface facing upward.
  • the control device 40 controls the spin motor 8 to start the rotation of the substrate W by the spin chuck 4 (step S2).
  • the rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
  • the control device 40 opens the chemical liquid valve 16 and discharges the chemical liquid from the chemical liquid nozzle 7 toward the rotation center of the upper surface of the substrate W.
  • the chemical solution supplied to the upper surface of the substrate upper surface W receives centrifugal force due to the rotation of the substrate W and flows toward the periphery of the substrate W (spreads over the entire area of the substrate W). Thereby, the process by a chemical
  • control device 40 closes the chemical solution valve 16 and stops the supply of the chemical solution from the chemical solution nozzle 7.
  • control device 40 opens the water valve 14 and discharges DIW from the water nozzle 61 of the integrated head 6 toward the rotation center of the upper surface of the substrate W in a rotating state (step S4).
  • the soft X-ray irradiation timing comes.
  • the predetermined time is provided so that soft X-ray irradiation is started after DIW is sufficiently filled in the first nozzle pipe 51.
  • the control device 40 controls the high voltage unit 31 to generate soft X-rays in the soft X-ray generator 25 of the soft X-ray irradiation unit 62 and irradiates the soft X-rays. Irradiation from the window 35 to the inside of the first nozzle pipe 51 through the window member 71 (step S5). Thereby, soft X-rays are irradiated to DIW which distribute
  • FIG. 5 is a schematic cross-sectional view showing a state of soft X-ray irradiation into the water nozzle 61.
  • the soft X-rays are irradiated to the DIW flowing through the first nozzle pipe 51 of the water nozzle 61. Further, the processing liquid discharged from the discharge port 53 is supplied to the upper surface of the substrate W.
  • the part irradiated with soft X-rays (the part facing the first opening 52 in the first nozzle pipe 51. The shaded part shown in FIG. 5. 54 "), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 54 of DIW.
  • FIG. 6 is a diagram showing a state where the substrate W is rinsed.
  • the DIW supplied to the upper surface of the substrate W receives centrifugal force due to the rotation of the substrate W and flows toward the peripheral edge of the substrate W (spreads over the entire area of the substrate W).
  • a DIW liquid film 63 in contact with the upper surface is formed over the entire upper surface of the substrate W.
  • the chemical solution adhering to the upper surface of the substrate W is washed away by the liquid film 63 of DIW.
  • the DIW supply flow rate to the water nozzle 61 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the form of DIW discharged from the discharge port 53 of the water nozzle 61 forms a continuous flow connected to both the discharge port 53 and the DIW liquid film 63 on the upper surface of the substrate W, and the first nozzle In the pipe 51, DIW is in a liquid-tight state. At this time, the DIW liquid film 63 and the DIW irradiated portion 54 are connected via the DIW.
  • the substrate W can be subjected to the rinsing process while preventing or eliminating the charge of the substrate W.
  • liquid property of DIW does not change by irradiation with soft X-rays, unlike the case where the substrate W is processed using an acidic processing solution such as carbonated water, there is no possibility of adversely affecting the devices on the substrate W. .
  • the electrode 56 of the power source 57 is applied to the electrode 56 of the power source 57.
  • the electrode 56 is preferably charged to a positive charge.
  • the electrons generated in the DIW irradiated portion 54 due to the soft X-ray irradiation due to the positive charge of the electrode 56 are pulled toward the electrode 56, and the first nozzle pipe 51 (water nozzle 61) with the electrode 56 is provided. It moves to the tip. That is, a large amount of electrons can be pulled toward the discharge port 53 of the water nozzle 61. Thereby, the movement of the electrons to the substrate W side can be promoted.
  • the control device 40 closes the water valve 14 to stop supplying DIW (step S6), and the high voltage
  • the unit 31 is controlled to stop the soft X-ray irradiation from the irradiation window 35 of the soft X-ray irradiation unit 62 (step S7).
  • the control device 40 also stops the application of the electric field to the electrode 56 in conjunction with the stop of the soft X-ray irradiation from the soft X-ray irradiation unit 62.
  • control device 40 controls the spin motor 8 to increase the rotation speed of the substrate W to a spin dry rotation speed (for example, 2500 rpm).
  • a spin dry rotation speed for example, 2500 rpm.
  • step S9 When the spin drying is performed for a predetermined drying time, the rotation of the spin chuck 4 is stopped. Thereafter, the processed substrate W is unloaded from the processing chamber 3 by a transfer robot (not shown) (step S9).
  • soft X-rays are irradiated to the DIW flowing through the first nozzle pipe 51 of the water nozzle 61.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 54 of DIW.
  • These electrons travel along the continuous flow DIW and move to the DIW liquid film 63, and as a result, the DIW liquid film 63 has a large amount of electrons.
  • charging of the substrate W due to contact separation with DIW does not occur. Therefore, charging of the substrate W during the rinsing process can be prevented.
  • the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
  • liquid property of DIW does not change by irradiation with soft X-rays, unlike the case where the substrate W is processed using an acidic processing solution such as carbonated water, there is no possibility of adversely affecting the devices on the substrate W. .
  • FIG. 7 is a flowchart for explaining a modification of the processing example shown in FIG.
  • the water supply unit 100 detects the presence / absence of DIW in the first nozzle pipe 51 at the predetermined water detection position 102 in the first nozzle pipe 51 of the water nozzle 61.
  • a liquid detection sensor (processing liquid detection means) 101 is disposed.
  • the water detection position 102 is set to the same position as the first opening (opening, soft X-ray irradiation position) 52 (see FIG. 2) or a position close to the first opening 52 with respect to the flow direction of the first nozzle pipe 51. ing.
  • the liquid detection sensor 101 is constituted by, for example, a capacitance type sensor, and is directly attached to or arranged close to the outer peripheral wall (not shown) of the first nozzle pipe 51.
  • the liquid detection sensor 101 detects the presence or absence of DIW in the first nozzle pipe 51 around the water detection position 102 and outputs a signal corresponding to the detection result.
  • DIW is present near the first opening 52 of the first nozzle pipe 51
  • DIW is detected.
  • DIW is not present near the first opening 52 of the first nozzle pipe 51
  • DIW is not detected. .
  • liquid detection sensor 101 an optical sensor (for example, a combination of a light emitting diode and a light receiving element and using a difference in refractive index between gas and liquid) or a conductivity sensor may be employed.
  • an optical sensor for example, a combination of a light emitting diode and a light receiving element and using a difference in refractive index between gas and liquid
  • a conductivity sensor may be employed.
  • the control device 40 refers to the detection output of the liquid detection sensor 101 to determine whether there is DIW near the first opening 52 (with liquid). Whether or not there is liquid is checked (step S12). If there is DIW near the first opening 52 (YES in step S12), the control device 40 starts X-ray irradiation by the soft X-ray irradiation unit 62 (step S13).
  • the liquid detection sensor 101 is also used in water supply units 230, 250, and 600 (see FIGS. 15A, 15B, 16, and 28) in which the same configuration as the water supply unit 100 is adopted. Is possible. In this case, the process shown in FIG. 7 can be executed.
  • FIG. 8 is a diagram schematically showing the configuration of an integrated head 6A according to the second embodiment of the present invention.
  • FIG. 9 is a cross-sectional view taken along section line IX-IX in FIG.
  • the integrated head 6A parts common to the integrated head 6 according to the first embodiment are denoted by the same reference numerals as in FIGS. 1 to 6, and description thereof is omitted.
  • the main point that the integrated head 6A differs from the integrated head 6 is that a first nozzle pipe 51A having a flat tip is used for the water nozzle 61. Similar to the first nozzle pipe 51, the first nozzle pipe 51 ⁇ / b> A in the region excluding the tip has a round tubular shape (cylindrical shape).
  • the first nozzle pipe 51A extends in the vertical direction, and also includes polyvinyl-chloride, PTFE (polytetrafluorofluoroethylene), PFA (perfluoro-alkylvinyl-ether-tetrafluoro). -ethlene-copolymer) and the like.
  • a flat portion 151 having a substantially rectangular cross section is formed at the tip of the first nozzle pipe 51A.
  • the flat portion 151 is obtained by deforming a round tube by thermoforming.
  • a width W1 between the pair of flat wall portions 152 and 153 is set to about 5 to 10 mm, for example.
  • a circular third opening (opening, X-ray irradiation position) 52A is formed in the middle of the first nozzle pipe 51A.
  • a soft X-ray irradiation unit 62 is attached to the first nozzle pipe 51A so as to close the third opening 52A.
  • the second opening 28 of the cover 26A coincides with the third opening 52A of the first nozzle pipe 51A, and the lateral wall 26A is in close contact with the outer periphery of the first nozzle pipe 51A. Thus, it is attached to the first nozzle pipe 51A.
  • the width W1 of the flat portion 151 is such that soft X-rays irradiated from the irradiation window 35 of the soft X-ray irradiation unit 62 reach the other flat wall portion 153 in a state where the flat portion 151 is filled with DIW.
  • the width is set. Therefore, the soft X-rays from the soft X-ray irradiation unit 62 are irradiated to all the DIWs that flow through the flat portion 151 of the first nozzle pipe 51A.
  • the irradiation part 54 of DIW can be maintained in a wide range, the amount of electrons contained in the DIW liquid film 63 on the upper surface of the substrate W can be further increased. As a result, the occurrence of charging of the substrate W due to contact separation with DIW can be more reliably suppressed, and even if the substrate W is charged before the rinsing process, the substrate W can be more reliably discharged.
  • FIG. 10 (a) and 10 (b) are diagrams for explaining the configuration of an integrated head 6B according to a third embodiment of the present invention.
  • FIG. 10A is a cross-sectional view of the main part of the integrated head 6B during the rinsing process
  • FIG. 10B is a view of FIG. 10A viewed from below.
  • a fiber bundle (fibrous substance) 65 configured by bundling a large number of string-like fibers is attached to the discharge port 53 of the first nozzle pipe 51 of the water nozzle 61.
  • the fiber bundle 65 has a cylindrical shape having a central axis along the longitudinal direction of the first nozzle pipe 51.
  • the protruding length of the fiber bundle 65 from the discharge port 53 of the first nozzle pipe 51 is set to be approximately the same as the interval between the substrate W held by the spin chuck 4 and the discharge port 53.
  • DIW discharged from the discharge port 53 of the first nozzle pipe 51 flows downward along a large number of fibers included in the fiber bundle 65.
  • the tip of the fiber bundle 65 is in contact with the DIW liquid film 63 formed on the upper surface of the substrate W, and floats in the liquid film 63. Since the fiber bundle 65 leads the DIW well from the discharge port 53 to the DIW liquid film 63, the DIW mode discharged from the discharge port 53 is a continuous flow that connects both the discharge port 53 and the DIW liquid film 63. Easy to maintain.
  • the mode of DIW discharged from the discharge port 53 can be maintained in the above-described continuous flow state. Accordingly, it is possible to prevent the substrate W from being charged and to remove the charge from the substrate W while reducing the consumption of DIW.
  • the tip of the fiber bundle 65 may be in contact with the upper surface of the substrate W in addition to the liquid film 63 during the rinsing process.
  • the fiber bundle 65 at the tip of the first nozzle pipe 51A (see FIG. 8). Further, in the water supply units 230, 250, and 600 (see FIGS. 15A, 15B, 16 and 28) in which the same configuration as the water supply unit 100 is adopted, the tip of the first nozzle pipe 51 is used. It is also possible to provide a fiber bundle 65 in the part.
  • the fibrous substance attached to the discharge port 53 of the first nozzle pipe 51 of the water nozzle 61 the fiber bundle 65 configured by bundling a large number of string-like fibers has been described as an example.
  • the fibrous substance is not limited to a structure in which a large number of string-like fibers are bundled.
  • the fibrous substance may be constituted by a single thick string-like fiber, or a cloth-like material instead of a string-like material. You may be comprised with the fiber.
  • FIG. 11 is a diagram showing a configuration of a substrate processing apparatus 201 according to the fourth embodiment of the present invention.
  • a water supply unit 200 in which a nozzle and a soft X-ray irradiation unit are separately provided is provided. Is provided.
  • the water supply unit 200 exists in the water nozzle 202, a water supply pipe (treatment liquid pipe) 204 that supplies DIW (an example of water) from the DIW supply source to the water nozzle 202, and the water supply pipe 204.
  • a soft X-ray irradiation unit (X-ray irradiation means) 203 for irradiating the DIW with soft X-rays.
  • the soft X-ray irradiation unit 203 is attached to the water supply pipe 204.
  • the water nozzle 202 has a round tubular (cylindrical) nozzle pipe, and is attached to the tip of the water supply pipe 204.
  • the water nozzle 202 is configured by a straight nozzle that discharges liquid in a continuous flow state, and the water nozzle 202 is fixedly disposed in the processing chamber 3 with the discharge port 202A directed toward the center of the upper surface of the substrate W. ing.
  • the water nozzle 202 has the same configuration as the water nozzle 61 (see FIG. 2) of the first embodiment except that the first opening 52 (see FIG. 2) is not formed. That is, an annular electrode 56 is fitted and fixed to the tip of the nozzle pipe of the water nozzle 202, and a voltage with respect to the apparatus ground is applied to the electrode 56 by a power source 57 (see FIG. 3). It has become.
  • the water supply pipe 204 has a round tubular shape (cylindrical shape).
  • the water supply pipe 204 is formed using a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • An opening (not shown) is formed in the tube wall in the middle of the water supply pipe 204.
  • the soft X-ray irradiation unit 203 adopts the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment.
  • the soft X-ray irradiation unit 203 is attached to the water supply pipe 204 so as to close the opening of the water supply pipe 204.
  • the opening of the cover of the soft X-ray irradiation unit 203 (the opening corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is the opening of the water supply pipe 204.
  • the wall surface of the cover of the soft X-ray irradiation unit 203 (corresponding to the lateral wall 26A (see FIG.
  • the high voltage unit of the soft X-ray irradiation unit 203 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
  • the water supply pipe 204 is provided with a water valve 205 for opening and closing the water supply pipe 204.
  • a water valve 205 for opening and closing the water supply pipe 204.
  • DIW is supplied from the water supply pipe 204 to the water nozzle 202, and when the water valve 205 is closed, the supply of DIW from the water supply pipe 204 to the water nozzle 202 is stopped.
  • the water valve 205 is connected to the control device 40 (see FIG. 3).
  • the control device 40 opens the water valve 205. Thereby, DIW flowing through the water supply pipe 204 is supplied to the water nozzle 202. DIW is discharged from the discharge port 202A of the water nozzle 202 toward the rotation center of the upper surface of the substrate W in a rotating state.
  • the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 203 so that the soft X-ray irradiation unit 203 has a soft X-ray irradiation timing.
  • a soft X-ray is generated in a X-ray generator (corresponding to the soft X-ray generator 25 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment), and the soft X-ray is supplied to the water supply pipe 204. Irradiate the inside. Thereby, soft X-rays are irradiated to DIW which distribute
  • the DIW supplied to the upper surface of the substrate W receives a centrifugal force due to the rotation of the substrate W and flows toward the periphery of the substrate W (spreads over the entire area of the substrate W). As a result, a DIW liquid film is formed over the entire upper surface of the substrate W. The chemical liquid adhering to the upper surface of the substrate W is washed away by the liquid film of DIW.
  • the DIW supply flow rate to the water nozzle 202 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 202A of the water nozzle 202 is a continuous flow mode connected to both the discharge port 202A and the DIW liquid film on the upper surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 202 and the water supply pipe 204.
  • the DIW irradiated portion in the water supply pipe 204 (shown in FIG. 5 of the DIW according to the first embodiment) In a portion equivalent to the irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water supply pipe 204.
  • the DIW irradiated portion is connected to the DIW liquid film formed on the upper surface of the substrate W via the DIW.
  • FIG. 12 is a diagram showing a configuration of a substrate processing apparatus 211 according to the fifth embodiment of the present invention.
  • Parts common to the substrate processing apparatus 201 according to the fourth embodiment are denoted by the same reference numerals as those in FIG.
  • the difference between the substrate processing apparatus 211 and the substrate processing apparatus 201 is that a water nozzle 212 having a plurality of discharge ports 216 is provided instead of the water nozzle 202 (see FIG. 11).
  • the water nozzle 212 includes a main body 213 formed of a round tubular (cylindrical) nozzle pipe, and a plurality of (for example, three in FIG. 12) discharge port portions arranged in the horizontal direction at the tip of the main body 213. 215 and a communication part 214 that communicates the internal space of the main body part 213 and the internal space of each discharge port part 215. Each discharge port portion 215 has a discharge port 216. Each discharge port portion 215 is configured by a straight nozzle that discharges liquid in a continuous flow state. An electrode 56 is fitted and fixed to each discharge port portion 215. The water nozzle 212 is fixedly disposed in the processing chamber 3 with the plurality of discharge ports 216 directed toward the center of the upper surface of the substrate W. A water supply pipe 204 is connected to the main body 213 of the water nozzle 212.
  • DIW an example of water
  • DIW is supplied to the water nozzle 212, and DIW is discharged from each discharge port 216 of the water nozzle 212.
  • a DIW liquid film is formed over the entire upper surface of the substrate W.
  • the DIW mode discharged from the individual discharge ports 216 is a continuous flow that leads to both the discharge port 216 and the DIW liquid film on the upper surface of the substrate W.
  • the aspect is made. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 212 and the water supply pipe 204.
  • the substrate processing apparatus 211 if the aspect of DIW discharged from at least one discharge port 216 has a continuous flow shape connected to both the discharge port 216 and the DIW liquid film on the upper surface of the substrate W. Good.
  • the nozzle pipe of the water nozzle 212 and the DIW liquid film on the upper surface of the substrate W need only be connected by at least one continuous flow 64A (see FIG. 13).
  • one discharge port 216A has a continuous flow shape connected to both the discharge port 216 and the DIW liquid film on the upper surface of the substrate W.
  • the other discharge ports 216B and 216C do not form a continuous flow.
  • DIW is ejected in the form of droplets from the ejection port 216B and the ejection port 216C, or DIW is not ejected.
  • the nozzle pipe of the water nozzle 212 and the DIW liquid film on the upper surface of the substrate W are connected by at least one continuous flow 64A. Therefore, when the substrate W is positively charged, electrons from the DIW irradiated portion in the water supply pipe 204 move along the single continuous flow 64A toward the DIW liquid film 63 on the upper surface of the substrate W. To do. As a result, it is possible to prevent the substrate W from being charged and to neutralize the substrate W.
  • FIG. 14 is a diagram showing a configuration of a substrate processing apparatus 221 according to the sixth embodiment of the present invention.
  • a water supply unit (processing liquid supply apparatus) 220 is provided instead of the water supply unit 200.
  • the water supply unit 220 includes a water nozzle 202, a water supply pipe 204, a first branch pipe (branch pipe) 222 that branches from the middle of the water supply pipe 204, and a DIW present in the first branch pipe 222.
  • the soft X-ray irradiation unit 223 is attached to the first branch pipe 222. That is, in the water supply unit 220, the soft X-ray irradiation unit 223 is attached to the first branch pipe 222 instead of the water supply pipe 204.
  • the first branch pipe 222 branches from the upstream side of the water valve 205 in the water supply pipe 204.
  • the first branch pipe 222 is a round tube (cylindrical), such as poly-vinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer), etc. These resin materials are used.
  • a branch valve 225 for opening and closing the first branch pipe 222 is interposed in the middle of the first branch pipe 222.
  • the branch valve 225 is connected to the control device 40 (see FIG. 3).
  • an opening (not shown) is formed in a predetermined portion of the pipe wall upstream of the branch valve 225.
  • a first cup nozzle 224 is attached to the downstream end of the first branch pipe 222.
  • the first cup nozzle 224 is constituted by a straight nozzle that discharges liquid in a continuous flow state.
  • the discharge port (liquid receiving discharge port) 224A is connected to the outer wall of the cup upper portion 19 (for example, the upper surface of the inclined portion 21). ) And is fixedly disposed above the cup upper portion 19 in the processing chamber 3.
  • the soft X-ray irradiation unit 223 employs the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment.
  • the soft X-ray irradiation unit 223 is attached to the first branch pipe 222 so as to close the opening of the first branch pipe 222.
  • the opening of the cover of the soft X-ray irradiation unit 223 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is aligned with the opening of the first branch pipe 222.
  • the wall surface of the cover of the soft X-ray irradiation unit 223 (corresponding to the lateral wall 26A of the cover 26 of the soft X-ray irradiation unit 62 (see FIG. 2)) is in close contact with the outer periphery of the first branch pipe 222.
  • the high voltage unit of the soft X-ray irradiation unit 223 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
  • the cup 17 since the cup upper part 19 is moved up and down by the cup elevating unit 22, the cup 17 (particularly the cup upper part 19) may be charged. For this reason, it is necessary to neutralize the cup upper portion 19 prior to executing the processing on the substrate W.
  • the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 223 to control the soft X-ray generator (the soft X-ray irradiation unit 62 according to the first embodiment) of the soft X-ray irradiation unit 223.
  • the soft X-ray generator 25 (refer to FIG. 2) generates soft X-rays and irradiates the soft X-rays toward the inside of the first branch pipe 222. Thereby, soft X-rays are irradiated to DIW existing in the first branch pipe 222.
  • control device 40 opens the branch valve 225 while closing the water valve 205. Accordingly, DIW flowing through the first branch pipe 222 is supplied to the first cup nozzle 224. DIW is discharged from the discharge port 224A of the first cup nozzle 224 toward the upper surface of the inclined portion 21 of the cup upper portion 19. The supplied DIW flows downward along the upper surface of the inclined portion 21. Therefore, a DIW liquid film is formed on the upper surface of the inclined portion 21. At this time, the supply flow rate of DIW to the first cup nozzle 224 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min).
  • the DIW mode discharged from the discharge port 224A of the first cup nozzle 224 has a continuous flow mode connected to both the discharge port 224A and the DIW liquid film on the upper surface of the inclined portion 21. Further, DIW is in a liquid-tight state in the nozzle pipe of the first cup nozzle 224 and in the first branch pipe 222.
  • the potential difference between the DIW irradiation portion in the first branch pipe 222 and the positively charged cup upper portion 19 causes the DIW in the first branch pipe 222 to be positive. Electrons from the irradiated portion move toward the DIW liquid film on the upper surface of the inclined portion 21 along the continuous flow DIW. As a result, the DIW liquid film on the upper surface of the inclined portion 21 has a large amount of electrons, so that the portion of the positively charged cup upper portion 19 that is in contact with the DIW liquid film is neutralized.
  • the unprocessed substrate W is carried into the processing chamber 3 and delivered to the spin chuck 4.
  • the control device 40 controls the spin motor 8 to start the rotation of the substrate W by the spin chuck 4 (step S2 in FIG. 4).
  • the rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
  • control device 40 opens the water valve 205 while closing the branch valve 225.
  • the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 223 to control the soft X-ray irradiation unit 223.
  • Soft X-rays are generated in the line generator, and the soft X-rays are irradiated toward the inside of the first branch pipe 222. Thereby, soft X-rays are irradiated to DIW which distribute
  • DIW is discharged from the discharge port 202A of the water nozzle 202 toward the rotation center of the upper surface of the substrate W in a rotating state. During the rinsing process, a DIW liquid film is formed over the entire upper surface of the substrate W.
  • the mode of DIW discharged from the discharge port 202A of the water nozzle 202 is a continuous flow mode connected to both the discharge port 202A and the DIW liquid film on the upper surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 202, the water supply pipe 204, and the first branch pipe 222.
  • the DIW irradiated portion in the first branch pipe 222 (according to the first embodiment shown in FIG. 5).
  • the DIW irradiated portion 54 electrons are emitted from the water molecules by excitation of the water molecules.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the first branch pipe 222.
  • the DIW irradiated portion is connected to the DIW liquid film formed on the upper surface of the substrate W via the DIW.
  • the hydrophilic film (corresponding to the hydrophilic film 38 (see FIG. 2)) is peeled off from the outer surface of the window member of the X-ray irradiation unit 223 (corresponding to the outer surface 71B (see FIG. 2) of the window member 71), There is a risk that beryllium contained in the window member dissolves into a processing solution such as DIW. Even in such a case, since the X-ray irradiation unit 223 is provided in the first branch pipe 222, the DIW containing such beryllium is supplied to the first cup nozzle 224 instead of the water nozzle 202. The Thereby, it is possible to reliably prevent the DIW containing beryllium from being supplied to the substrate W.
  • DIW an example of water
  • 202 is used to remove static electricity from the second nozzle pipes (second pipes) 232 and 262 through which the processing liquid flows using DIW (an example of water).
  • DIW an example of water
  • 15 (a) and 15 (b) are diagrams showing the configuration of the substrate processing apparatus 231 according to the seventh embodiment of the present invention.
  • the substrate processing apparatus 231 is different from the substrate processing apparatus 1 according to the first embodiment in that the substrate processing apparatus 231 includes a second nozzle pipe 232 for supplying a processing liquid to the substrate W held on the spin chuck 4.
  • the point is that DIW as an example of water is supplied to the second nozzle pipe 232 by the water supply unit 230. Since the water supply unit 230 employs a configuration equivalent to that of the water supply unit 100 (see FIG. 1), the same reference numerals as those in the case of the water supply unit 100 are attached and description thereof is omitted. In FIGS. 15A and 15B, only the configuration related to the water supply unit 230 is described, and the other portions are not shown. FIG.
  • FIG. 15A is a cross-sectional view showing a state in which the second nozzle pipe 232 is accommodated in the standby pod 237 described below
  • FIG. 15B is a cross-sectional line B-- in FIG. It is sectional drawing seen from B.
  • FIG. 15A is a cross-sectional view showing a state in which the second nozzle pipe 232 is accommodated in the standby pod 237 described below
  • FIG. 15B is a cross-sectional line B-- in FIG. It is sectional drawing seen from B.
  • the second nozzle pipe 232 is integrally provided with a cylindrical horizontal portion 233 extending in the horizontal direction and a cylindrical hanging portion 234 hanging from the tip of the horizontal portion 233.
  • the second nozzle pipe 232 is made of a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a processing liquid flow passage 235 is formed inside the second nozzle pipe 232.
  • the processing liquid flow passage 235 is opened in a circular shape as the discharge port 236 at the lower end of the hanging part 234.
  • a processing liquid (chemical solution or water) from a processing liquid supply source is supplied to the second nozzle pipe 232 via a processing liquid valve (not shown). When the processing liquid valve is opened, the processing liquid is supplied to the upstream end of the horizontal portion 233 of the second nozzle pipe 232.
  • the processing liquid introduced into the second nozzle pipe 232 is discharged from the discharge port 236 after flowing through the processing liquid flow passage 235.
  • the second nozzle pipe 232 is supported by a support shaft (not shown) extending substantially vertically on the side of the cup 17 (see FIG. 1), and rotational force is input to the support shaft to rotate the support shaft. By moving it, the second nozzle pipe 232 can be swung above the spin chuck 4 (see FIG. 1). That is, the second nozzle pipe 232 has a form as a scan nozzle.
  • the processing liquid is not supplied to the substrate W (see FIG. 1)
  • the second nozzle pipe 232 is retracted to the home position installed on the side of the cup 17 (see FIG. 1).
  • the second nozzle pipe 232 is moved above the substrate W.
  • the substrate processing apparatus 231 includes a bowl-shaped standby pod 237 for accommodating the second nozzle pipe 232 at the home position.
  • the standby pod 237 has a pod body 238 having a substantially rectangular cross section along the longitudinal direction of the second nozzle pipe 232.
  • a liquid storage groove 239 extending along the longitudinal direction of the second nozzle pipe 232 is formed on the upper surface of the pod body 238.
  • the liquid reservoir groove 239 is formed over the entire area in the longitudinal direction except for both ends in the longitudinal direction.
  • the liquid reservoir groove 239 has a substantially U-shaped cross section. The width and depth of the liquid reservoir groove 239 are set to a size that can accommodate the second nozzle pipe 232.
  • End walls 240 are provided at both ends of the pod main body 238 in the longitudinal direction. Each end wall 240 is formed with an insertion hole 241 formed of a round hole substantially aligned with the second nozzle pipe 232.
  • a waste liquid pipe 242 is connected to the bottom of the liquid reservoir groove 239. In the middle of the waste liquid pipe 242, a waste liquid valve 243 for opening and closing the waste liquid pipe 242 is interposed.
  • the second nozzle pipe 232 is at the home position, the second nozzle pipe 232 is accommodated in the liquid storage groove 239. At this time, the second nozzle pipe 232 is inserted through the insertion holes 241 of both end walls 240.
  • the water nozzle 61 of the water supply unit 230 has a second nozzle pipe 232 fixedly disposed above the standby pod 237 with the discharge port 53 directed to the liquid storage groove 239.
  • the second nozzle pipe 232 is disposed at the home position.
  • DIW is discharged from the water nozzle 61 of the water supply unit 230.
  • DIW is stored in the liquid storage groove 239 of the standby pod 237.
  • the entire area in the circumferential direction of the second nozzle pipe 232 (the horizontal portion 233 thereof) is immersed by the DIW stored in the liquid storage groove 239.
  • the DIW discharged from the water nozzle 61 is continued.
  • the supply flow rate of DIW to the water nozzle 61 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 53 of the water nozzle 61 is a continuous flow mode connected to both the discharge port 53 and the DIW stored in the liquid storage groove 239. That is, DIW discharged from the discharge port 53 is connected in a liquid state between the discharge port 53 and the outer peripheral wall of the second nozzle pipe 232. In the first nozzle pipe 51, DIW is in a liquid-tight state.
  • the soft X-rays from the soft X-ray irradiation unit 62 are irradiated inside the water nozzle 61 (first nozzle pipe 51).
  • the irradiated portion 54 see FIG. 5 of the DIW.
  • a plasma state is formed.
  • the DIW irradiation portion 54 and the DIW in contact with the outer peripheral wall of the second nozzle pipe 232 are connected via the DIW.
  • the processing liquid remains inside the second nozzle pipe 232 (particularly the horizontal portion 233).
  • the outer peripheral wall of the second nozzle pipe 232 is positively or negatively charged, the residual processing liquid in the second nozzle pipe 232 may be positively or negatively charged due to induction charging.
  • the processing liquid in such a charged state is supplied to the substrate W, even the substrate W is charged, and when the charge is discharged, the device formed on the upper surface of the substrate W is destroyed. May occur.
  • DIW irradiation is caused by a potential difference between the DIW irradiation portion 54 (see FIG. 5) and the outer peripheral wall of the positively charged second nozzle pipe 232. Electrons from the portion 54 (see FIG. 5) move toward the outer peripheral wall of the second nozzle pipe 232 through the continuous flow DIW and the DIW stored in the liquid storage groove 239. As a result, the outer peripheral wall of the second nozzle pipe 232 that is positively charged is removed.
  • FIG. 16 is a diagram showing a configuration of a substrate processing apparatus 251 according to the eighth embodiment of the present invention.
  • the substrate processing apparatus 251 is different from the substrate processing apparatus 231 according to the seventh embodiment (see FIGS. 15A and 15B) in that the second nozzle pipe 232 is connected to the DIW stored in the liquid storage groove 239.
  • the DIW from the discharge port 53 of the water nozzle 61 of the water supply unit (processing liquid supply device) 250 is directly supplied to the outer peripheral wall of the second nozzle pipe 232, thereby immersing the second nozzle pipe 232. This is the point of eliminating static electricity.
  • the water supply unit 250 employs a configuration equivalent to that of the water supply unit 100 (see FIG. 1) except for the configuration of the moving unit 252 described below. Therefore, the same reference numerals as those in the case of the water supply unit 100 are attached, and the description is omitted.
  • a moving unit 252 for moving the integrated head 6 in the horizontal direction is coupled to the integrated head 6.
  • the moving unit 252 is configured using a ball nut or a motor, and is connected to the control device 40 (see FIG. 3) as a control target.
  • the control device 40 supplies DIW (an example of water) to the water nozzle 61 (first nozzle pipe 51) and at the same time the water nozzle 61 (first The soft X-rays from the soft X-ray irradiation unit 62 are irradiated inside the one nozzle pipe 51). DIW discharged from the water nozzle 61 of the integrated head 6 is supplied to the outer peripheral wall of the second nozzle pipe 232 and flows down along the outer peripheral wall of the second nozzle pipe 232.
  • DIW an example of water
  • the supply flow rate of DIW to the water nozzle 61 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 53 of the water nozzle 61 is a continuous flow mode connected to both the discharge port 53 and the outer peripheral wall of the second nozzle pipe 232. In the first nozzle pipe 51, DIW is in a liquid-tight state.
  • the soft X-rays from the soft X-ray irradiation unit 62 are irradiated inside the water nozzle 61 (first nozzle pipe 51).
  • the irradiated portion 54 see FIG. 5 of the DIW.
  • a plasma state is formed.
  • the DIW irradiation portion 54 and the DIW in contact with the outer peripheral wall of the second nozzle pipe 232 are connected via the DIW.
  • the control device 40 controls the moving unit 252 to move the DIW liquid landing site on the outer peripheral wall of the second nozzle pipe 232 (horizontal portion 233) in one direction along the longitudinal direction of the second nozzle pipe 232. Or reciprocate. Accordingly, the position of the second nozzle pipe 232 to be neutralized can be moved along the longitudinal direction of the second nozzle pipe 232 (horizontal portion 233). Therefore, the second nozzle pipe 232 (horizontal portion 233) It is possible to remove static electricity in a substantially entire area of the outer peripheral wall.
  • 17 (a) and 17 (b) are diagrams showing the configuration of the substrate processing apparatus 261 according to the ninth embodiment of the present invention.
  • the substrate processing apparatus 261 includes a water supply unit (processing liquid supply apparatus) 260 instead of the water supply unit 100 (see FIG. 1) according to the first embodiment, and the substrate processing apparatus 1 according to the first embodiment (
  • the other configuration is the same as that of the substrate processing apparatus 1.
  • 17 (a) and 17 (b) show only the configuration related to the water supply unit 260, and the other parts are not shown.
  • FIG. 17A is a longitudinal sectional view of a second nozzle pipe 262 and a third nozzle pipe 272 to be described next, and FIG. 17B is viewed from a cutting plane line B1-B1 in FIG. 17A. It is sectional drawing.
  • the water supply unit 260 includes a second nozzle pipe 262 and a third nozzle pipe 272.
  • the second nozzle pipe 262 and the third nozzle pipe 272 form a double pipe structure by inserting the second nozzle pipe 262 into the third nozzle pipe 272.
  • the second nozzle pipe 262 is integrally provided with a cylindrical horizontal portion 263 extending in the horizontal direction and a cylindrical hanging portion 264 that hangs down from the tip of the horizontal portion 263.
  • the second nozzle pipe 262 is formed of a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a processing liquid flow passage 265 is formed inside the second nozzle pipe 262.
  • the processing liquid flow passage 265 opens in a circular shape as the discharge port 266 at the lower end of the hanging part 264.
  • a processing liquid (chemical solution or water) from a processing liquid supply source is supplied to the second nozzle pipe 262 via a processing liquid valve (not shown).
  • the water supply unit 260 includes a part of the configuration of the water supply unit 200 (see FIG. 11) according to the fourth embodiment. That is, the water supply unit 260 includes a water supply pipe 204, a soft X-ray irradiation unit 203, and a water valve 205.
  • the soft X-ray irradiation unit 203 and the water supply pipe 204 are described in the fourth embodiment except that the water supply pipe 204 supplies DIW (an example of water) from the DIW supply source to the third nozzle pipe 272. Since it is the structure as it was, detailed description is abbreviate
  • the third nozzle pipe 272 is integrally provided with a cylindrical horizontal portion 273 extending in the horizontal direction and a cylindrical hanging portion 274 depending from the tip of the horizontal portion 273.
  • the third nozzle pipe 272 is formed of a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • the horizontal portion 263 of the second nozzle pipe 262 passes through the horizontal portion 273 of the third nozzle pipe 272, passes through the wall of the drooping portion 274 of the third nozzle pipe 272, and the downstream end thereof is the second nozzle pipe.
  • a water flow passage 275 is formed in a space between the inner wall of the third nozzle pipe 272 and the outer wall of the second nozzle pipe 262.
  • the water flow passage 275 opens in an annular shape as a discharge port 276 at the lower end of the hanging portion 274.
  • the processing liquid valve When performing the processing liquid processing using the processing liquid on the substrate W, the processing liquid valve is opened.
  • the processing liquid valve is opened, the processing liquid is supplied to the upstream end of the horizontal portion 263 of the second nozzle pipe 262.
  • the processing liquid introduced into the second nozzle pipe 262 is discharged from the discharge port 266 after flowing through the processing liquid flow passage 265.
  • the processing liquid valve is closed, but then the processing liquid remains inside the second nozzle pipe 262 (particularly the horizontal portion 263).
  • the water valve 205 When supplying DIW to the substrate W, the water valve 205 is opened. DIW is supplied to the upstream end of the water flow passage 275 of the third nozzle pipe 272. DIW introduced into the third nozzle pipe 272 is discharged from the discharge port 276 after flowing through the water flow passage 275. When the DIW supply stop timing is reached, the water valve 205 is closed, but DIW remains in the space between the inner wall of the third nozzle pipe 272 and the outer wall of the second nozzle pipe 262 thereafter.
  • the residual processing liquid in the second nozzle pipe 262 may be positively or negatively charged due to induction charging.
  • the processing liquid in such a charged state is supplied to the substrate W, even the substrate W is charged, and when the charge is discharged, the device formed on the upper surface of the substrate W is destroyed. May occur.
  • the outer peripheral wall of the third nozzle pipe 272 is charged first, and then the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272. It is conceivable that the outer peripheral wall of the second nozzle pipe 262 is charged through the residual DIW between the first nozzle pipe 262 and the second nozzle pipe 262.
  • the soft X-ray irradiation unit 203 softens the water supply pipe 204. X-ray irradiation continues.
  • DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272 and DIW existing in the water supply pipe 204 are in a liquid-tight state (in a continuous flow form). )It is connected.
  • the potential difference between the DIW irradiated portion in the water supply pipe 204 and the positively charged third nozzle pipe 272 causes a difference in the water supply pipe 204. Electrons from the irradiated portion of DIW travel through DIW in the water supply pipe 204 and DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272 toward the third nozzle pipe 272. Move. As a result, the positively charged third nozzle pipe 272 is neutralized.
  • the third nozzle pipe 272 when the third nozzle pipe 272 is negatively charged, the electrons from the third nozzle pipe 272 are directed toward the positive ions at the DIW irradiated portion in the water supply pipe 204, and the DIW in the water supply pipe 204.
  • the second nozzle pipe 262 moves along the DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272. As a result, the third nozzle pipe 272 is neutralized.
  • the second nozzle pipe 262 is positively charged, electrons from the DIW irradiated portion in the water supply pipe 204 are transferred to the DIW in the water supply pipe 204 and the outer wall of the second nozzle pipe 262. The residual DIW is transferred to the inner wall of the three-nozzle pipe 272 and moves toward the second nozzle pipe 262. If the second nozzle pipe 262 is negatively charged, the electrons from the second nozzle pipe 262 are directed toward the positive ions at the DIW irradiated portion in the water supply pipe 204, and the DIW in the water supply pipe 204. The second nozzle pipe 262 moves along the DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272. That is, even if the second nozzle pipe 262 is charged, the charge removal of the second nozzle pipe 262 can be achieved in this way.
  • FIG. 18 is a diagram showing a configuration of a substrate processing apparatus 301 according to the tenth embodiment of the present invention.
  • the substrate processing apparatus 301 includes a water supply unit (treatment liquid supply apparatus) 300 for supplying DIW (an example of water) to the lower surface of the substrate W, and the water supply unit 100 with respect to the upper surface of the substrate W. It differs from the substrate processing apparatus 1 (refer FIG. 1) which concerns on 1st Embodiment in the point which replaces (refer FIG. 1) and supplies DIW (an example of water) with the water nozzle 302 mainly.
  • DIW an example of water
  • the water nozzle 302 is constituted by a straight nozzle that discharges liquid in a continuous flow state, and the water nozzle 302 is fixedly disposed in the processing chamber 3 with the discharge port directed toward the center of the upper surface of the substrate W. Yes.
  • a water supply pipe 303 to which DIW is supplied from a DIW supply source is connected to the water nozzle 302.
  • the water supply pipe 303 is provided with a water valve 304 for opening and closing the water supply pipe 303.
  • the spin shaft 9 is a hollow shaft.
  • a lower processing liquid supply pipe 305 is inserted into the spin shaft 9 in a non-contact state.
  • the water supply unit 300 supplies DIW from the DIW supply source to the lower processing liquid supply pipe 305, the lower surface nozzle 306 attached to the upper end of the lower processing liquid supply pipe 305, and the lower processing liquid supply pipe 305.
  • a water supply pipe (treatment liquid pipe) 307 to be supplied and a soft X-ray irradiation unit (X-ray irradiation means) 309 for irradiating the DIW existing in the water supply pipe 307 with soft X-rays are included.
  • the soft X-ray irradiation unit 309 is attached to the water supply pipe 307.
  • the lower surface nozzle 306 is disposed so that its discharge port 306A (see FIG. 19) is close to the center of the lower surface of the substrate W supported by the sandwiching member 11.
  • a water supply pipe 307 is connected to the lower processing liquid supply pipe 305.
  • DIW can be supplied from the lower processing liquid supply pipe 305 to the lower surface nozzle 306 and discharged from the discharge port 306A (see FIG. 19) of the lower surface nozzle 306 toward the center of the lower surface of the substrate W. .
  • the water supply pipe 307 has a round tubular shape (cylindrical shape).
  • the water supply pipe 307 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer).
  • a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer).
  • An opening (not shown) is formed in the tube wall in the middle of the water supply pipe 307.
  • the soft X-ray irradiation unit 309 employs the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment.
  • the soft X-ray irradiation unit 309 is attached to the water supply pipe 307 so as to close the opening of the water supply pipe 307.
  • the opening of the cover of the soft X-ray irradiation unit 309 corresponds with the opening of the water supply pipe 307.
  • the wall surface of the cover of the soft X-ray irradiation unit 309 (corresponding to the lateral wall 26A (see FIG.
  • the high voltage unit of the soft X-ray irradiation unit 309 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
  • the water supply pipe 307 is provided with a water valve 308 for opening and closing the water supply pipe 307.
  • the water valve 308 is connected to the control device 40 (see FIG. 3).
  • the same processing as in the processing example shown in FIG. 4 is performed.
  • the control device 40 opens the water valve 304. Thereby, DIW is discharged from the water nozzle 302 toward the center of the upper surface of the substrate W.
  • the control device 40 opens the water valve 308.
  • DIW flowing through the water supply pipe 307 is supplied to the lower surface nozzle 306. DIW is discharged upward from the discharge port 306A of the lower surface nozzle 306 toward the center of the lower surface of the substrate W.
  • the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 309 to generate soft X-rays of the soft X-ray irradiation unit 309.
  • a soft X-ray is generated in a vessel (corresponding to the soft X-ray generator 25 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment), and this soft X-ray is generated inside the water supply pipe 307. Irradiate toward Thereby, soft X-rays are irradiated to DIW which distribute
  • FIG. 19 is a diagram showing a DIW flow of the rinsing process in the substrate processing apparatus 301.
  • the DIW supplied to the central portion of the upper surface of the substrate W receives a centrifugal force due to the rotation of the substrate W, and spreads on the upper surface of the substrate W from the central portion toward the peripheral portion. As a result, a DIW liquid film is formed over the entire upper surface of the substrate W. The chemical liquid adhering to the upper surface of the substrate W is washed away by the liquid film of DIW.
  • DIW supplied to the central portion of the lower surface of the substrate W receives a centrifugal force due to the rotation of the substrate W, propagates along the lower surface of the substrate W to the outer side of the rotation radius, and reaches the lower peripheral edge 321 of the substrate W It reaches. Therefore, a DIW liquid film is formed on the entire lower surface of the substrate W.
  • DIW that has reached the lower surface peripheral portion 321 goes around the peripheral end surface 322 of the substrate W and reaches the upper surface peripheral portion 323 of the substrate W.
  • the DIW that has passed through the upper surface of the substrate W and the DIW that has come around from the peripheral end surface 322 of the substrate W come to merge at the upper peripheral edge 323 of the substrate W as shown in FIG. Therefore, the DIW liquid film formed on the upper surface of the substrate W and the DIW liquid film formed on the lower surface of the substrate W are connected to each other.
  • the supply flow rate of DIW to the lower surface nozzle 306 during the rinsing process is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 306A of the lower surface nozzle 306 is a continuous flow mode connected to both the discharge port 306A and the liquid film of DIW formed on the lower surface of the substrate W.
  • the DIW discharged from the discharge port 306A is Not only the DIW liquid film formed on the lower surface but also the DIW liquid film formed on the upper surface of the substrate W are connected in liquid form. Further, DIW is in a liquid-tight state in the nozzle pipe of the lower surface nozzle 306, the lower processing liquid supply pipe 305, and the water supply pipe 307.
  • the DIW irradiated portion in the water supply pipe 307 (shown in FIG. 5 of the DIW according to the first embodiment)
  • electrons are emitted from the water molecules by excitation of the water molecules.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water supply pipe 307.
  • the DIW irradiated portion is connected to the DIW liquid film formed on the lower surface of the substrate W and the DIW liquid film formed on the upper surface of the substrate W via the DIW.
  • the potential difference between the DIW irradiated portion in the water supply pipe 307 and the positively charged substrate W is different from the DIW irradiated portion in the water supply pipe 307. Electrons move along the lower processing liquid supply pipe 305, the water supply pipe 307, and the continuous flow DIW toward the DIW liquid films on the upper surface and the lower surface of the substrate W. Thereby, the liquid films of DIW formed on the lower surface and the upper surface of the substrate W each have a large amount of electrons.
  • the substrate W when simultaneous rinsing processing is performed on both the upper and lower surfaces of the substrate W, even if DIW is supplied to the upper and lower surfaces of the rotating substrate W, the substrate W is not charged by contact separation with the DIW. The charging of the substrate W at the time can be prevented. Further, even if the substrate W is charged before the rinsing process, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
  • FIG. 20 is a diagram showing a configuration of a substrate processing apparatus 311 according to the eleventh embodiment of the present invention.
  • a water supply unit (processing liquid supply apparatus) 310 is provided instead of the water supply unit 300 (see FIG. 18).
  • a soft X-ray irradiation device 314 is disposed in the processing chamber 3. In the eleventh embodiment, these points are different from the tenth embodiment.
  • the water supply unit 310 includes a lower processing liquid supply pipe 305, a lower surface nozzle 306, a water supply pipe 307, a second branch pipe (branch pipe) 312 that branches from a middle portion of the water supply pipe 307, and a second branch. And a soft X-ray irradiation unit (X-ray irradiation means) 319 for irradiating DIW (an example of water) existing in the pipe 312 with soft X-rays.
  • the soft X-ray irradiation unit 319 is attached to the second branch pipe 312.
  • the second branch pipe 312 branches from a portion upstream of the water valve 308 in the water supply pipe 307.
  • the second branch pipe 312 has a round tubular shape (cylindrical shape), such as poly-vinyl-chloride, PTFE (polytetrafluoroethylene), PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer), etc. These resin materials are used.
  • a branch valve 318 for opening and closing the second branch pipe 312 is interposed in the middle of the second branch pipe 312.
  • the branch valve 318 is connected to the control device 40 (see FIG. 3).
  • the second branch pipe 312 has an opening (not shown) in a predetermined portion of the pipe wall upstream of the branch valve 318.
  • a second cup nozzle 313 is attached to the downstream end of the second branch pipe 312.
  • the second cup nozzle 313 is constituted by a straight nozzle that discharges liquid in a continuous flow state, and the discharge port 313A (see FIG. 21. liquid receiving discharge port) is connected to the inner wall (for example, inclined) of the cup upper portion 19. In a state facing the lower surface of the portion 21, for example, it is fixedly disposed on the outer wall of the spin chuck 4.
  • the soft X-ray irradiation unit 319 employs the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment.
  • the soft X-ray irradiation unit 319 is attached to the second branch pipe 312 so as to close the opening of the second branch pipe 312.
  • the opening of the cover of the soft X-ray irradiation unit 319 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is equal to the opening of the second branch pipe 312.
  • the wall surface of the cover of the soft X-ray irradiation unit 319 (corresponding to the lateral wall 26A (see FIG.
  • the high voltage unit of the soft X-ray irradiation unit 319 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
  • DIW is supplied from the water supply pipe 307 to the lower surface nozzle 306 via the lower processing liquid supply pipe 305 and is discharged from the discharge port 306A of the lower surface nozzle 306. DIW is discharged.
  • the branch valve 318 is opened with the water valve 308 closed, DIW is supplied from the second branch pipe 312 to the second cup nozzle 313, and DIW is discharged from the discharge port 313A of the second cup nozzle 313.
  • the soft X-ray irradiation device 314 includes a soft X-ray generator 315 having an irradiation window 316.
  • Soft X-rays generated in the irradiation window 316 are emitted (radiated) outside the soft X-ray irradiation device 314.
  • the irradiation angle (irradiation range) of soft X-rays from the irradiation window 316 is, for example, 130 °, and the soft X-rays irradiated from the irradiation window 316 have a wavelength of, for example, 0.13 to 0.41 nm.
  • the soft X-ray generator 315 adopts the same configuration as the soft X-ray generator 25 (see FIG.
  • the soft X-ray irradiation device 314 is disposed above the cup upper portion 19 so that the irradiation window 316 faces the upper surface of the inclined portion 21 of the cup upper portion 19.
  • the same processing as in the processing example shown in FIG. 4 is performed. However, before the substrate W is loaded in step S 1 of FIG.
  • the eleventh embodiment is common to the sixth embodiment in that the cup 17 is subjected to charge removal.
  • the eleventh embodiment is not limited to supplying DIW to the cup upper portion 19 but also softening in parallel with the supply of DIW. It differs from the case of 6th Embodiment by the point which soft X-rays are irradiated from the X-ray irradiation apparatus 314, and the cup 17 is neutralized.
  • the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 319, and the soft X-ray generator of the soft X-ray irradiation unit 319 (the soft X-ray irradiation unit 62 according to the first embodiment).
  • the soft X-ray generator 25 (refer to FIG. 2) generates soft X-rays and irradiates the soft X-rays toward the inside of the second branch pipe 312. Further, the control device 40 opens the branch valve 318 while closing the water valve 308. Thereby, DIW which circulated through the 2nd branch piping 312 is discharged from discharge port 313A (refer to Drawing 21) of nozzle 313 for the 2nd cup.
  • FIG. 21 is a view showing a state where the water supply unit 310 shown in FIG. 20 supplies DIW to the inclined portion 21 of the cup upper portion 19.
  • DIW discharged from the discharge port 313A is supplied to the lower surface of the inclined portion 21 of the cup upper portion 19 and flows downward along the lower surface of the inclined portion 21. Therefore, a DIW liquid film is formed on the lower surface of the inclined portion 21.
  • the supply flow rate of DIW to the second cup nozzle 313 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 313A of the second cup nozzle 313 has a continuous flow mode connected to both the discharge port 313A and the DIW liquid film on the lower surface of the inclined portion 21. Further, DIW is in a liquid-tight state in the nozzle pipe of the second cup nozzle 313 and in the second branch pipe 312.
  • the potential difference between the DIW irradiated portion in the second branch pipe 312 and the positively charged cup upper portion 19 causes the DIW in the second branch pipe 312 to be positive. Electrons from the irradiated portion move along the continuous flow DIW toward the DIW liquid film on the lower surface of the inclined portion 21. As a result, the DIW liquid film on the lower surface of the inclined portion 21 has a large amount of electrons, so that a portion of the positively charged cup upper portion 19 that is in contact with the DIW liquid film is discharged.
  • the cup upper portion 19 when the cup upper portion 19 is negatively charged, the electrons from the cup upper portion 19 move along the continuous flow treatment liquid toward the positive ions in the DIW irradiated portion in the second branch pipe 312. To do. Therefore, the portion of the cup upper portion 19 that is negatively charged and in contact with the DIW liquid film is neutralized.
  • control device 40 controls the high voltage unit of the soft X-ray irradiation device 314 to generate soft X-rays in the soft X-ray generator 315 of the soft X-ray irradiation device 314, Irradiate the upper surface of the inclined portion 21 of the cup upper portion 19.
  • the inclined portion 21 of the cup upper portion 19 is a member that is disposed around the substrate W during processing. However, by applying soft X-rays from the soft X-ray irradiation device 314, the inclined portion 21 can be prevented from being charged and discharged. .
  • the unprocessed substrate W is carried into the processing chamber 3 and delivered to the spin chuck 4.
  • the control device 40 controls the spin motor 8 to start the rotation of the substrate W by the spin chuck 4 (step S2 in FIG. 4).
  • the rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
  • the control device 40 In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 308 while closing the branch valve 318. In addition, when a predetermined time elapses after the opening of the water valve 308 and the soft X-ray irradiation timing is reached, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 319 so that the soft X-ray irradiation unit 319 has a soft X-ray irradiation timing. Soft X-rays are generated in the line generator, and the soft X-rays are irradiated toward the inside of the second branch pipe 312. Thus, DIW is discharged from the lower surface nozzle 306 toward the center of the lower surface of the substrate W.
  • the DIW supplied to the central portion of the lower surface of the substrate W spreads to the outer side of the rotation radius along the lower surface of the substrate W, as in the case of the tenth embodiment, and the peripheral end surface 322 (see FIG. 19) of the substrate W. It goes around and reaches the peripheral edge of the upper surface of the substrate W. Then, the DIW that has traveled along the upper surface of the substrate W and the DIW that has circulated from the peripheral end surface 322 of the substrate W merge at the peripheral edge of the upper surface of the substrate W, and as a result, the DIW formed over the entire upper surface of the substrate W. And the DIW liquid film formed over the entire lower surface of the substrate W are connected to each other.
  • the mode of DIW discharged from the discharge port 306A of the lower surface nozzle 306 is a continuous flow mode connected to both the discharge port 306A and the liquid film of DIW formed on the lower surface of the substrate W. Since the DIW liquid film formed on the upper surface of the substrate W and the DIW liquid film formed on the lower surface of the substrate W are connected to each other, the DIW discharged from the discharge port 306A is formed on the lower surface of the substrate W. In addition to the DIW liquid film, the DIW liquid film formed on the upper surface of the substrate W is connected in liquid form. Further, DIW is in a liquid-tight state in the nozzle pipe of the lower surface nozzle 306, the lower processing liquid supply pipe 305, the water supply pipe 307, and the second branch pipe 312.
  • the DIW irradiated portion in the second branch pipe 312 When the DIW existing in the second branch pipe 312 is irradiated with soft X-rays during the rinsing process, the DIW irradiated portion in the second branch pipe 312 (according to the first embodiment shown in FIG. 5). In the DIW irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the second branch pipe 312. The DIW irradiated portion is connected to the DIW liquid film formed on the lower surface of the substrate W and the DIW liquid film formed on the upper surface of the substrate W via the DIW.
  • step S8 soft X-ray irradiation by the soft X-ray irradiation apparatus 314 may be performed prior to the loading of the substrate W, but not only before the loading of the substrate W but also spin dry (FIG. 4).
  • step S8 soft X-ray irradiation by the soft X-ray irradiation apparatus 314 may be performed.
  • the surface of the substrate W immediately after the treatment liquid is shaken off is irradiated with soft X-rays. Prevention and static elimination can be achieved more reliably.
  • two water supply units 310 and a soft X-ray irradiation device 314 having a configuration including the second cup nozzle 313 are provided.
  • only one of the water supply unit 310 and the soft X-ray irradiation device 314 may be provided.
  • FIG. 22 is a diagram showing a configuration of a substrate processing apparatus 401 according to the twelfth embodiment of the present invention.
  • the substrate processing apparatus 401 mainly includes a spin chuck (substrate holding and rotating means) 402 instead of the spin chuck 4 and supplies DIW (an example of water) to the lower surface of the substrate W via the spin chuck 402. Two points are different from the substrate processing apparatus 301 (see FIG. 18) according to the tenth embodiment.
  • the substrate processing apparatus 401 includes a water supply unit (processing liquid supply apparatus) 400.
  • the spin chuck 402 is a sandwich type. Specifically, the spin chuck 402 includes a spin motor 403, a spin shaft (support member) 404 integrated with a drive shaft of the spin motor 403, and a disc attached substantially horizontally to the upper end of the spin shaft 404.
  • a spin base (support member) 405 having a plurality of shapes, and a plurality of sandwiching members 406 provided at substantially equal intervals at a plurality of positions on the peripheral edge of the spin base 405 are provided.
  • the spin shaft 404 includes an inner shaft portion 407 formed using a resin, steel, or the like, and an outer cylinder portion 408 formed using a porous material, and the inner shaft portion 407 is inserted into the outer cylinder portion 408. It is integrated in the state. That is, the outer periphery of the inner shaft portion 407 is surrounded by the outer cylinder portion 408 in a close contact state.
  • the spin base 405 is formed using a porous material.
  • An upper end surface of the outer cylinder portion 408 is connected to the lower surface 405B of the spin base 405 in a close contact state.
  • the clamping member 406 is formed using a steel material or the like. In a state where the substrate W is sandwiched by the plurality of sandwiching members 406, the specifications of the sandwiching member 406 and the thickness in the height direction of the spin base 405 are such that the entire lower surface of the substrate W is in contact with the upper surface of the spin base 405. , Each is set.
  • the porous material that is the material of the outer cylindrical portion 408 of the spin shaft 404 and the spin base 405 is, for example, a sponge made of PVA (polyvinyl alcohol) and has a large number of pores.
  • the pores of the porous material have a size (for example, a diameter of 0.05 to 100 ⁇ m) through which DIW (an example of water) can pass. Therefore, it is possible to pass the DIW through the pores of the porous material. Therefore, it is possible to move the DIW in the outer cylinder portion 408 or the spin base 405.
  • urethane resin as a raw material of the porous material, urethane resin, fluorine resin (PTFE (polytetrafluoroethylene)), PEEK (polyether-ether-ketone), PVC (polyvinyl chloride), and
  • PTFE polytetrafluoroethylene
  • PEEK polyether-ether-ketone
  • PVC polyvinyl chloride
  • PFA perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer
  • the water supply unit 400 exists in the water nozzle 409, a water supply pipe (treatment liquid pipe) 410 that supplies DIW (an example of water) from a DIW supply source to the water nozzle 409, and the water supply pipe 410.
  • a soft X-ray irradiation unit (X-ray irradiation means) 412 for irradiating the DIW with soft X-rays.
  • the soft X-ray irradiation unit 412 is attached to the water supply pipe 410.
  • the water nozzle 409 has a round tubular (cylindrical) nozzle pipe and is attached to the tip of the water supply pipe 410.
  • the water nozzle 409 is configured by a straight nozzle that discharges liquid in a continuous flow state, and the discharge port 409A is fixed in the processing chamber 3 with the discharge port 409A facing the outer cylindrical portion 408 of the spin shaft 404. Has been placed.
  • the water supply pipe 410 has a round tubular shape (cylindrical shape).
  • the water supply pipe 410 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • An opening (not shown) is formed in the tube wall in the middle of the water supply pipe 410.
  • the soft X-ray irradiation unit 412 adopts the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment.
  • the soft X-ray irradiation unit 412 is attached to the water supply pipe 410 so as to close the opening of the water supply pipe 410.
  • the opening of the cover of the soft X-ray irradiation unit 412 corresponds with the opening of the water supply pipe 410.
  • the wall surface of the cover of the soft X-ray irradiation unit 412 (corresponding to the lateral wall 26A (see FIG.
  • a high voltage unit of the soft X-ray irradiation unit 412 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
  • a water valve 411 for opening and closing the water supply pipe 410 is interposed in the water supply pipe 410.
  • the water valve 411 is connected to the control device 40 (see FIG. 3).
  • the control device 40 see FIG. 3
  • DIW is supplied from the water supply pipe 410 to the water nozzle 409, and when the water valve 411 is closed, the supply of DIW to the water nozzle 409 is stopped.
  • FIG. 23 is a diagram illustrating a state in which the water supply unit 400 is supplying DIW to the outer cylinder portion 408.
  • the same processing as in the processing example shown in FIG. 4 is performed.
  • the control device 40 opens the water valve 304. Accordingly, DIW is discharged from the discharge port 302A of the water nozzle 302 toward the center of the upper surface of the substrate W.
  • the DIW supplied to the central portion of the upper surface of the substrate W receives a centrifugal force due to the rotation of the substrate W and spreads on the upper surface of the substrate W from the central portion toward the peripheral portion. As a result, a DIW liquid film is formed over the entire upper surface of the substrate W. The chemical liquid adhering to the upper surface of the substrate W is washed away by the liquid film of DIW.
  • the control device 40 opens the water valve 411 in conjunction with the opening of the water valve 304.
  • DIW flowing through the water supply pipe 410 is supplied to the water nozzle 409. DIW is discharged laterally from the discharge port 409A of the water nozzle 409 toward the outer cylinder portion 408 of the spin shaft 404.
  • DIW supplied to the outer peripheral surface of the outer cylinder portion 408 penetrates into the outer cylinder portion 408, passes through the outer cylinder portion 408, and is supplied to the lower surface 405B of the spin base 405.
  • the DIW supplied to the lower surface 405B of the spin base 405 penetrates into the spin base 405, passes through the outer cylindrical portion 408, and is supplied to the upper surface 405A of the spin base 405.
  • the DIW impregnated in the spin base 405 oozes out from the upper surface 405A, and as shown in FIG. 23, a DIW liquid film is formed on the upper surface 405A.
  • the DIW liquid film is in contact with the lower surface of the substrate W, the chemical liquid adhering to the lower surface of the substrate W is washed away by the DIW. Thereby, the rinsing process can be performed on the entire lower surface of the substrate W.
  • the water nozzle 409 has a discharge port 409A disposed at a small distance S1 from the outer peripheral surface of the outer tube portion 408. Further, the DIW supply flow rate to the water nozzle 61 during the rinsing process is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the form of DIW discharged from the discharge port 409A of the water nozzle 409 forms a continuous flow that is connected to both the discharge port 409A and the outer peripheral surface of the outer cylindrical portion 408 of the spin shaft 404. Therefore, the DIW discharged from the discharge port 409A is connected in liquid form to the DIW liquid film formed on the lower surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 409 and the water supply pipe 410.
  • the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 412 to generate soft X-rays of the soft X-ray irradiation unit 412.
  • a soft X-ray is generated in a vessel (corresponding to the soft X-ray generator 25 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment), and the soft X-ray is generated inside the water supply pipe 410. Irradiate toward Thereby, soft X-rays are irradiated to DIW circulating in the water supply pipe 410.
  • the DIW irradiated portion in the water supply pipe 410 (shown in FIG. 5 of the DIW according to the first embodiment) In the same manner as the irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water supply pipe 410.
  • the DIW irradiated portion is connected to the DIW liquid film formed on the lower surface of the substrate W via the DIW.
  • the DIW in the water supply pipe 410 is determined by the potential difference between the DIW irradiated portion in the water supply pipe 410 and the lower surface of the positively charged substrate W. Electrons from the irradiated portion move toward the DIW liquid film in contact with the lower surface of the substrate W along the continuous flow DIW. As a result, the liquid film of DIW in contact with the lower surface of the substrate W has a large amount of electrons.
  • the present invention is based on the single wafer processing apparatus 1,201, 211, 221, 231, 251, 261, 301, 311, 401 for processing the circular substrate W.
  • the present invention can also be applied to a substrate transport type substrate processing apparatus for processing a square (sheet-like) substrate.
  • FIG. 24 is an illustrative perspective view showing the configuration of the substrate processing apparatus 501 according to the thirteenth embodiment of the present invention.
  • the substrate processing apparatus 501 is an apparatus used for cleaning the surface (surface to be processed) of a square glass substrate for a liquid crystal display device as an example of the substrate W using a processing liquid such as water.
  • the length of one side of the square substrate W to be processed is, for example, in the range of several tens of cm to 2 m, and the plate thickness is in the range of about 0.5 to 1.2 mm.
  • the horizontal direction along the transport direction of the substrate W which will be described below, is defined as the X direction
  • the horizontal direction orthogonal to the X direction is defined as the Y direction
  • the vertical direction is defined as the Z direction.
  • the substrate processing apparatus 501 includes a roller transport unit 504 (substrate holding and transporting unit) for transporting the substrate W along the X direction, and DIW (treatment liquid) on the surface of the substrate W transported by the roller transport unit 504.
  • a water supply unit (processing liquid supply device) 500 for supplying water (an example of water), a gas knife nozzle 519 for blowing nitrogen gas as an example of an inert gas onto the surface of the substrate W being transferred by the roller transfer unit 504, And a soft X-ray irradiation device 512 that irradiates the surface of the substrate W transported by the roller transport unit 504 with soft X-rays.
  • the substrate processing apparatus 501 supplies DIW to the surface of the substrate W and performs a cleaning process chamber 502 for cleaning the surface of the substrate W, and a liquid draining process for draining DIW adhering to the surface of the substrate W.
  • the cleaning processing chamber 502 and the liquid draining chamber 503 are disposed adjacent to each other.
  • a supply unit 500 is disposed above the roller transport unit 504 in the cleaning processing chamber 502.
  • a gas knife nozzle 519 and a soft X-ray irradiation device 512 are arranged in this order in the transport direction above the roller transport unit 504.
  • the roller transport unit 504 is arranged in a state extending in the left-right direction so as to straddle between the internal space of the cleaning processing chamber 502 and the internal space of the liquid draining chamber 503.
  • the substrate W carried in from the substrate carry-in port 523 formed on the upstream side wall of the cleaning processing chamber 502 is transported by the roller transport unit 504, and is supplied to the partition wall 521 that partitions the cleaning processing chamber 502 and the liquid draining chamber 503. It is transferred to the liquid draining chamber 503 through the formed substrate passage port 522. Then, the inside of the liquid draining chamber 503 is transported by the roller transport unit 504, and unloaded from the substrate unloading port 524 formed on the side wall on the downstream side of the liquid draining chamber 503.
  • the substrate W is placed on the roller transport unit 504 with its surface facing upward.
  • the surface of the substrate W is sequentially scanned by the water supply position P1 and the inert gas injection position P2.
  • DIW is first supplied on the surface of the substrate W, and then nitrogen gas is injected after a predetermined time delay.
  • FIG. 25 is a perspective view showing the configuration of the roller transport unit 504.
  • the conveyance rollers 505 are arranged in parallel at substantially equal pitches in the X direction. Each transport roller 505 is synchronously rotated in the same direction by driving of a drive unit (not shown).
  • Each conveyance roller 505 includes a roller shaft 515 that is inclined with respect to a horizontal plane in a plane (YZ plane) orthogonal to the X direction. Therefore, the conveyance path realized by the roller conveyance unit 504 is entirely inclined in the Y direction with respect to the horizontal plane.
  • the substrate W is transported while maintaining an inclined posture.
  • the inclination angle ⁇ (see FIG. 26) of the substrate W with respect to the horizontal plane is set to about 5 °, for example.
  • Each conveying roller 505 includes, for example, a pair of left and right side rollers 516 that are fitted on the left and right sides of the roller shaft 515 so as to be able to rotate together with the roller shaft 515, and a center roller 517 provided at the center of the roller shaft 515. Is a so-called partially supported transport roller.
  • Each individual side roller 516 has a flange 516A provided integrally with the side roller 516 on the outer side.
  • the flange 516A prevents the substrate W to be transported from being laterally displaced, and prevents the substrate W from sliding along the inclined surface by the lower flange 516A.
  • an O-ring (not shown) made of rubber or the like is externally fitted to each of the rollers 516 and 517, and the sliding of the O-ring prevents the substrate W from falling down more reliably.
  • the water supply unit 500 is for supplying DIW to a plurality (for example, three in FIG. 24) of water nozzles 531 disposed in the cleaning processing chamber 502 and to each of the water nozzles 531.
  • a water supply pipe (treatment liquid pipe) 533 and a water collecting pipe 532 to which the upstream ends of the individual water supply pipes 533 are connected are included.
  • the plurality of water nozzles 531 are arranged, for example, at equal intervals along the X direction.
  • Each water nozzle 531 is fixedly arranged with its discharge port 531A facing downward at a position facing the upper portion of the substrate W transported by the roller transport unit 504.
  • the water collecting pipe 532 is a pipe for supplying DIW (an example of water) from the DIW supply source to the plurality of water supply pipes 533.
  • An annular electrode 56 is fitted and fixed to the tip of each water nozzle 531, and a voltage with respect to the apparatus ground is applied to the electrode 56 by a power source 57 (see FIG. 3). .
  • the water supply unit 500 further includes a soft X-ray irradiation unit (X-ray irradiation means) 534 for irradiating the DIW existing in the water collecting pipe 532 with soft X-rays.
  • the soft X-ray irradiation unit 534 is attached to the water collecting pipe 532.
  • the water collecting pipe 532 has a round tubular shape (cylindrical shape), and is formed using, for example, polyvinyl-chloride.
  • a collecting valve 535 for opening and closing the water collecting pipe 532 is interposed in the middle of the water collecting pipe 532.
  • an opening (not shown) is formed in a predetermined portion of the pipe wall downstream of the collecting.
  • the soft X-ray irradiation unit 534 has the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment.
  • the soft X-ray irradiation unit 534 is attached to the water collecting pipe 532 so as to close the opening of the water collecting pipe 532.
  • the opening of the cover of the soft X-ray irradiation unit 534 corresponds with the opening of the water collecting pipe 532.
  • the wall surface of the cover of the soft X-ray irradiation unit 534 (corresponding to the lateral wall 26A (see FIG.
  • the high voltage unit of the soft X-ray irradiation unit 534 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
  • the collecting valve 535 is opened, DIW is supplied from the water collecting pipe 532 to each water supply pipe 533, and DIW is discharged from the discharge port 531A of each water nozzle 531.
  • the gas knife nozzle 519 has a nitrogen gas as an example of an inert gas on the upper surface of the substrate W transported by the roller transport unit 504 in order to blow off DIW adhering to the upper surface of the substrate W. It is a nozzle for injecting. Another example of the inert gas is CDA (clean air with low humidity).
  • the gas knife nozzle 519 has a slit injection port 519 ⁇ / b> A that is long in the Y direction, and can supply nitrogen gas over the entire width in the Y direction of the substrate W transported by the roller transport unit 504.
  • the gas knife nozzle 519 is fixedly disposed in the liquid draining chamber 503 so that the slit injection port 519A faces the upper surface of the substrate W with a minute gap.
  • Nitrogen gas from a nitrogen gas supply source is supplied to the gas knife nozzle 519 via an inert gas valve 511.
  • the gas knife nozzle 519 injects nitrogen gas in a strip shape along the Y direction.
  • the blowing direction of the inert gas from the slit injection port 519A of the gas knife nozzle 519 with respect to the upper surface of the substrate W is inclined in the direction opposite to the transport direction of the substrate W (left side shown in FIG. 24) with respect to the vertical direction. Yes.
  • the inclination angle ⁇ (see FIG. 27) is in the range of 20 ° to 70 °, for example. *
  • the soft X-ray irradiation apparatus 512 has a built-in soft X-ray generator 513 having an irradiation window 514. Soft X-rays generated in the irradiation window 514 are emitted (radiated) outside the soft X-ray irradiation apparatus 512.
  • the irradiation angle (irradiation range) of soft X-rays from the irradiation window 514 is, for example, 130 °, and the soft X-rays irradiated from the irradiation window 514 have a wavelength of, for example, 0.13 to 0.41 nm.
  • the soft X-ray generator 513 has the same configuration as the soft X-ray generator 25 (see FIG. 2) included in the soft X-ray irradiation unit 534, and the irradiation window 514 is the irradiation window 35 (see FIG. 2). It corresponds to.
  • the soft X-ray irradiation device 512 is disposed on the downstream side of the gas knife nozzle 519 above the substrate W transported by the roller transport unit 504. Specifically, the soft X-ray irradiation apparatus 512 is disposed so that the irradiation window 514 faces the inert gas injection position P2.
  • FIG. 26 is a cross-sectional view showing a state where the water supply unit 500 supplies DIW to the substrate W.
  • FIG. 27 is a cross-sectional view showing a state where the soft X-ray irradiation apparatus 512 irradiates the upper surface of the substrate W with soft X-rays.
  • DIW discharged from each discharge port 531A is supplied to the water supply position P1 on the upper surface of the substrate W, and flows along the inclined surface on the upper surface of the substrate W. As a result, a liquid film of DIW is formed on the upper surface of the substrate W.
  • the DIW supply flow rate to each water nozzle 531 is set to a relatively large flow rate (for example, 1 to several tens L / min depending on the size of the glass substrate and the degree of cleaning). Therefore, the DIW discharged from each of the discharge ports 531A is in a continuous flow mode connected to both the discharge port 531A of the water nozzle 531 and the DIW liquid film on the upper surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 531, the water collecting pipe 532, and the water supply pipe 533.
  • soft X-rays from the soft X-ray irradiation unit 534 are irradiated into the water collecting pipe 532.
  • the DIW irradiated portion in the water collecting pipe 532 (equivalent to the DIW irradiated portion 54 according to the first embodiment shown in FIG. 5). )
  • Electrons are emitted from the water molecules by excitation of the water molecules.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water collecting pipe 532.
  • the DIW irradiated portion is connected to the DIW liquid film formed on the upper surface of the substrate W via the DIW.
  • the electrons from the DIW irradiated portion in the water collecting pipe 532 are converted into a substrate by the potential difference between the DIW irradiated portion in the water collecting pipe 532 and the positively charged substrate W. It moves along the continuous flow of DIW toward the liquid film of DIW on the upper surface of W. Thus, the DIW liquid film on the upper surface of the substrate W has a large amount of electrons.
  • the nitrogen gas from the slit injection port 519A of the gas knife nozzle 519 is connected to the discharge port 531A via a DIW liquid film (DIW continuous flow) formed on the upper surface of the substrate W. Sprayed on the liquid film).
  • DIW liquid film DIW continuous flow
  • the upper surface of the substrate W is irradiated with soft X-rays generated by the soft X-ray generator 513 of the soft X-ray irradiation apparatus 512.
  • the case where the substrate W is processed using water (for example, DIW) in the cleaning processing chamber 502 has been described as an example.
  • processing using a chemical solution and water is used in the cleaning processing chamber 502.
  • the substrate W can be processed.
  • the chemical liquid nozzle 506 is arranged on the upstream side of the water supply unit 500.
  • a chemical solution from a chemical solution supply source is supplied to the chemical solution nozzle 506 via a chemical solution valve 508. That is, the chemical solution supply position P0 is set upstream of the water supply position P1.
  • roller transport unit 504 that transports the substrate W in an inclined posture has been described as an example, but the roller transport unit 504 may transport the substrate W while maintaining the horizontal posture.
  • the substrate processing apparatus 501 has been described by taking as an example an apparatus that cleans the upper surface (upper main surface) of the substrate W.
  • the substrate processing apparatus 501 is a type of substrate processing apparatus that performs a cleaning process on both surfaces of the substrate.
  • the present invention can be applied.
  • the water supply unit 500 and the gas knife nozzle 519 are also arranged below the roller transport unit 504, respectively, and the water supply unit on the lower side at the water supply position P1. DIW is supplied to the lower surface of the substrate W by 500, and nitrogen gas is injected to the lower surface of the substrate W by the lower gas knife nozzle 519 at the inert gas injection position P2.
  • 200, 220, 230, 250, 260, 300, 310, 400, 500 have been described as examples, but the present invention can also be applied to processing units other than the substrate W as processing objects.
  • the processing object is a substrate container (container) 602, and a container cleaning device 601 for cleaning the processing object using a cleaning liquid (processing liquid) will be described as an example.
  • FIG. 28 is a diagram showing a configuration of an article cleaning apparatus 601 according to the fourteenth embodiment of the present invention.
  • FIG. 29 is a perspective view showing the configuration of the substrate container 602.
  • the substrate container 602 is a container that accommodates the substrate W in a sealed state.
  • An example of the substrate container 602 is FOSB (Front Opening Shipping Box).
  • the FOSB is exclusively used to deliver the substrate W from the semiconductor wafer manufacturer to the semiconductor device manufacturer.
  • the FOSB accommodates a plurality of unprocessed substrates W and prevents damage to the substrates W while maintaining the cleanliness of these substrates W.
  • the article cleaning apparatus 601 includes a mounting table 607 for mounting the container main body 603 of the substrate container 602, and water for supplying DIW as an example of a cleaning liquid to the substrate container 602.
  • a supply unit (processing liquid supply device) 600 is provided.
  • the water supply unit 600 employs the same configuration as the water supply unit 100 (see FIG. 1) according to the first embodiment. Therefore, the same reference numerals are given to FIG. 28 and the description is omitted.
  • the water nozzle 61 of the water supply unit 600 is disposed above the container main body 603 mounted on the mounting table 607 with its discharge port 53 facing downward.
  • the substrate container 602 includes a bottomed box-shaped container body 603 having an opening 603A on the side, and a lid 604 for opening and closing the opening 603A of the container body 603 (FIG. 28 shows a closed state of the lid 604).
  • a multi-stage container support shelf 606 attached to the inner wall of the container body 603, and a multi-stage lid support shelf 605 attached to the lid 604.
  • the substrate W is put in and out of the container main body 603 through the opening 603A.
  • the container body 603 and the lid 604 are each formed using a resin material such as polyvinyl-chloride.
  • the container main body 603 has a substantially cubic outer shape, and as shown in FIG. 28, the opening side may have a slightly larger diameter than the bottom side. In this case, the upper surface of the container body 603 has an inclined surface.
  • DIW is supplied from the water supply unit 600 to the outer wall of the container body 603 of the substrate container 602. Specifically, the water valve 14 is opened, and DIW flowing through the water supply pipe 13 is supplied to the water nozzle 61. Accordingly, DIW is discharged downward from the discharge port 53 of the water nozzle 61 toward the upper surface of the outer wall of the container body 603.
  • the control device 40 generates soft X-rays in the soft X-ray generator 25 (see FIG. 2) and irradiates the soft X-rays toward the inside of the first nozzle pipe 51 of the water nozzle 61. Thereby, soft X-rays are irradiated to DIW which distribute
  • the DIW supplied to the upper side surface of the outer wall of the container main body 603 flows down along the upper side surface and the bottom surface formed of inclined surfaces. As a result, a DIW liquid film is formed on the outer wall of the container body 603. By this liquid film, dirt or dust adhering to the outer wall of the container body 603 is washed away.
  • the DIW supply flow rate to the water nozzle 61 is set to a relatively large flow rate (for example, 1 to 10 L / min depending on the size of the substrate container 602). Therefore, the mode of DIW discharged from the discharge port 53 of the water nozzle 61 is a continuous flow mode connected to both the discharge port 53 and the outer wall of the container body 603. Therefore, a DIW liquid film is formed on the outer wall of the container body 603. By this liquid film, the liquid film 63 formed on the outer wall of the container body 603 and the DIW irradiation portion 54 are connected via the DIW. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 61.
  • the potential difference between the DIW irradiation portion 54 and the outer wall of the container main body 603 that is positively charged causes an electron from the DIW irradiation portion 54.
  • it moves along the continuous flow DIW toward the DIW liquid film in contact with the outer wall of the container body 603.
  • the DIW liquid film in contact with the outer wall of the container body 603 has a large amount of electrons.
  • the DIW liquid film 63 and the DIW irradiated portion 54 are connected via the DIW.
  • charging of the container body 603 during the cleaning process can be prevented. Moreover, even if the container main body 603 is charged before the cleaning process, the charge on the container main body 603 can be removed (that is, static elimination).
  • the case where the container main body 603 is cleaned has been described as an example.
  • the cleaning method is similarly adopted.
  • the lid 604 and the support shelves 605 and 606 can be subjected to a cleaning process while removing electricity from the lid 604 and the support shelves 605 and 606.
  • the FOSB has been described as an example of the substrate container 602
  • the FOUP Front-Opening-Unified
  • the substrate container 602 other types of substrate containers such as FOUP (Front Opening Unified Unified Pod), SMIF (Standard Mechanical Interface) pod, OC (Open Cassette) can be exemplified.
  • the container is not limited to the one that accommodates the substrate W.
  • a medium container that accommodates a disk-shaped medium such as a CD, a DVD, or a blue disk, or an optical component such as a lens, a mirror, or a diffraction grating.
  • the component container which accommodates can be made into a process target object.
  • a static elimination test is performed to confirm that the processing object such as a silicon wafer, a glass substrate, and a container can be eliminated by supplying DIW (an example of water) from a water supply unit containing a soft X-ray irradiation unit. went.
  • DIW an example of water
  • FIG. 30 is a diagram for explaining a test apparatus 651 used in the static elimination test.
  • the test apparatus 651 includes a resin-made bottomed container 652, a charged body holding base 653 that holds the charged body E in the container 652, and the charged body E that is held by the charged body holding base 653.
  • a water supply unit 654 for supplying the treatment liquid a charging plate monitor 655 for measuring the charge amount of the charging body E while charging the charging body E held on the charging body holding base 653,
  • the charging plate monitor 655 has a metal plate 671 that is electrically connected to the charged body E.
  • An example of the charging plate monitor 655 is CPM210 manufactured by Ion Systems, Inc.
  • an example of the recorder 656 is HIOKI8841 manufactured by Hioki Electric Co., Ltd.
  • the water supply unit 654 includes a water nozzle 661, a soft X-ray irradiation unit 662 for irradiating the DIW (an example of water) flowing through the water nozzle 661 with soft X-rays, and a DIW tank 670 for the water nozzle 661. And a water supply pipe 663 for supplying DIW.
  • the soft X-ray irradiation unit 662 is attached to the water supply pipe 663.
  • the water supply pipe 663 is provided with a valve 664 for adjusting the opening / closing and opening of the water supply pipe 663.
  • the water nozzle 661 includes an ionization chamber 665, an inlet portion 666 having an inlet 666A for allowing DIW to flow into the ionization chamber 665, and an outlet portion 667 having an outlet 667A of DIW flowing through the ionization chamber 665.
  • the ionization chamber 665 is formed in a rectangular flat shape, and the internal space of the ionization chamber 665 is set to a rectangular space having a length of about 100 mm in the flow direction, a width of about 5 mm in the flow direction, and a depth of about 60 mm in the flow direction. .
  • the soft X-ray irradiation unit 662 adopts the same configuration as the soft X-ray irradiation unit 62 according to the first embodiment.
  • the soft X-ray irradiation unit 662 has a soft X-ray generator corresponding to the soft X-ray generator 25 (see FIG. 2) according to the first embodiment.
  • An example of the soft X-ray generator is a soft X-ray ionizer (L9490, manufactured by Hamamatsu Photonics).
  • the diameter of the round opening corresponding to the second opening 28 is, for example, 17 mm.
  • a rectangular metal plate (130 mm ⁇ 93 mm ⁇ thickness 1 mm) is used as the charged body E to be measured.
  • the substrate holding table 653 holds the charged body E in an inclined posture inclined at a predetermined angle with respect to the horizontal plane.
  • the charged body E is insulated from the container 652 by a block 668 made of PTFE (polytetrafluoroethylene) contained in the substrate holding table 653.
  • the distance between the upper end of the charged body E and the outlet 667A is, for example, 55 mm.
  • Second step Adjusting the valve 664, DIW (conductivity: 1 ⁇ S / cm or less in this case) is dropped in the form of droplets (discontinuous flow) from the outlet 667A of the water nozzle 661.
  • a droplet form means a state where a droplet is not connected to the next droplet.
  • Second step The charged body E is charged via the metal plate 671 of the charging plate monitor 655, and the soft X-ray generator of the soft X-ray irradiation unit 662 is turned on / off.
  • Table 1 shows the experimental results when DIW was dropped into droplets. As shown in Table 1, the time (static elimination time) during which the potential of the charged body E decays from +/ ⁇ 4.5 kV to +/ ⁇ 3.0 kV is almost constant regardless of whether the soft X-ray generator is on or off. It was. From the experimental results shown in Table 1, it can be seen that when DIW is dropped into droplets, the charged body E is hardly neutralized.
  • Table 2 shows the experimental results when DIW was allowed to flow down continuously. As shown in Table 2, when the DIW flow rate is 0.774 L / min and 0.08 L / min, the potential of the charged body E is +/- 1 kV ⁇ +/ ⁇ when the soft X-ray generator is turned on. Time to decay to 0.1kV (static elimination time) has been shortened. The static elimination time in this case is just over 1 second. From the experimental results shown in Table 2, it can be seen that when DIW is allowed to flow down in a continuous flow, the charge removal performance is improved.
  • Table 3 shows the experimental results when the distance from the outlet of the water nozzle 661 to the charged body E is changed while allowing DIW to flow down in a continuous flow.
  • Table 3 shows the experimental results when the distance from the outlet of the water nozzle 661 to the charged body E is changed while allowing DIW to flow down in a continuous flow.
  • this distance is 3000 mm, the charge can be removed in 1 to 2 seconds. From this, it can be seen that the distance from the outlet of the water nozzle 661 to the charged body E does not significantly affect the charge removal performance.
  • the principle of static elimination that neutralizes the processing object by supplying DIW from the water supply unit incorporating the soft X-ray irradiation unit is estimated as follows. That is, electrons are emitted from water molecules excited by soft X-ray irradiation, and this irradiated portion is in a plasma state in which positive ions and electrons of water molecules excited by soft X-rays are mixed.
  • the potential difference between the DIW irradiated part and the charged object to be processed is directed toward the object to be charged which is positively charged with electrons in the DIW irradiated part.
  • the object to be processed which is moved and positively charged is neutralized.
  • electrons move from the charged object to be processed toward positive ions in the irradiated part of the DIW, and the object to be negatively charged is neutralized.
  • FIG. 31 is a diagram showing a configuration of a substrate processing apparatus 701 according to the fifteenth embodiment of the present invention.
  • the substrate processing apparatus 701 is a single-wafer type apparatus used for processing a surface (processing target surface) of a circular semiconductor wafer (silicon wafer) as an example of the substrate W with a processing liquid (chemical solution and water). .
  • a processing liquid chemical solution and water.
  • water is used for rinsing the substrate W performed after the chemical treatment.
  • an oxide film or the like is formed on the surface of the substrate W to be processed.
  • a substrate processing apparatus 701 includes a spin chuck (substrate holding means) 704 that rotates a substrate W held in a horizontal posture in a processing chamber 703 partitioned by a partition wall 702, and a substrate W held by the spin chuck 704.
  • Soft X-rays are applied to the surface of a substrate W held by a spin nozzle 704 and a water nozzle (water supply means) 705 for discharging DIW (deionized water, pure water) as an example of water onto the surface (upper surface).
  • DIW deionized water, pure water
  • the spin chuck 704 for example, a sandwich type is adopted.
  • the spin chuck 704 includes a spin motor 708, a spin shaft 709 integrated with a drive shaft of the spin motor 708, and a disk-shaped spin base attached substantially horizontally to the upper end of the spin shaft 709. 710 and a plurality of clamping members 711 provided at a plurality of positions on the peripheral edge of the spin base 710 at substantially equal intervals.
  • the spin chuck 704 rotates the spin base 710 by the rotational driving force of the spin motor 708 in a state where the substrate W is sandwiched by the plurality of sandwiching members 711, so that the substrate W is placed in a substantially horizontal posture. In this state, it can be rotated around the rotation axis C together with the spin base 710.
  • the spin chuck 704 is not limited to a sandwich type, and for example, the back surface of the substrate W is vacuum-sucked to hold the substrate W in a horizontal posture and further rotate around the vertical rotation axis C in that state.
  • a vacuum chucking type vacuum chuck capable of rotating the held substrate W may be employed.
  • the water nozzle 705 is, for example, a straight nozzle that discharges DIW in a continuous flow state, and is fixedly disposed above the spin chuck 704 so that the discharge port faces the vicinity of the rotation center of the substrate W.
  • a water supply pipe 713 to which DIW from a DIW supply source is supplied is connected to the water nozzle 705.
  • a water valve (water supply means) 714 for switching supply / stop of supply of DIW from the water nozzle 705 is interposed in the middle of the water supply pipe 713.
  • the chemical nozzle 707 is, for example, a straight nozzle that discharges the chemical in a continuous flow state, and is fixedly disposed above the spin chuck 704 with its discharge port directed toward the vicinity of the rotation center of the substrate W.
  • a chemical solution supply pipe 715 to which a chemical solution from a chemical solution supply source is supplied is connected to the chemical solution nozzle 707.
  • a chemical solution valve 716 for switching supply / stop of supply of the chemical solution from the chemical solution nozzle 707 is interposed in the middle of the chemical solution supply pipe 715.
  • the chemical nozzle 707 does not need to be fixedly arranged with respect to the spin chuck 704.
  • the chemical nozzle 707 is attached to an arm that can be swung in a horizontal plane above the spin chuck 704, and the arm is swung.
  • a so-called scan nozzle form in which the position of the chemical solution on the surface of the substrate W is scanned may be employed.
  • a support shaft 717 extending in the vertical direction is disposed on the side of the spin chuck 704.
  • An arm 718 extending in the horizontal direction is coupled to the upper end of the support shaft 717, and a soft X-ray irradiation head 706 is attached to the tip of the arm 718.
  • the support shaft 717 includes a swing drive mechanism (moving means) 719 for rotating the support shaft 717 around the axis, and a lift drive mechanism (for moving the support shaft 717 up and down along the axial direction). Moving means) 720.
  • the arm 718 By inputting a driving force from the swing drive mechanism 719 to the support shaft 717 and rotating the support shaft 717 within a predetermined angular range, the arm 718 is moved above the substrate W held by the spin chuck 704.
  • the support shaft 717 is swung as a fulcrum.
  • the soft X-ray irradiation head 706 is moved to a position including the rotation axis C of the substrate W (a position facing the rotation center of the substrate W) and a home position set to the side of the spin chuck 704. Can be moved between.
  • the soft X-ray irradiation head 706 is brought close to the surface of the substrate W held by the spin chuck 704 by inputting a driving force to the support shaft 717 from the lifting drive mechanism 720 and moving the support shaft 717 up and down. It is moved up and down between a position (a position indicated by a two-dot chain line in FIG. 31) and a retreat position (a position indicated by a solid line in FIG. 31) for retreating above the substrate W.
  • the proximity position is a predetermined distance (for example, the distance between the surface of the substrate W held by the spin chuck 704 and the lower surface of the soft X-ray irradiation head 706 (the lower surface of the lower wall 726A) is 1 to 30 mm (for example, It is set to a position that will be about 10mm).
  • An opening 721 for carrying the substrate W in and out of the processing chamber 703 is formed on the side wall (one of the plurality of side walls) of the partition wall 702.
  • a transfer robot (not shown) facing the opening 721 outside the processing chamber 703 accesses the hand into the processing chamber 703 through the opening 721.
  • the unprocessed substrate W can be placed on the spin chuck 704, or the processed substrate W can be removed from the spin chuck 704.
  • the opening 721 is opened and closed by a shutter 722.
  • the shutter 722 has a closed position (shown by a solid line in FIG. 31) covering the opening 721 and an open position (open by a two-dot chain line in FIG. 31) covering the opening 721 by a shutter lifting mechanism (not shown) coupled to the shutter 722. As shown).
  • FIG. 32 is a schematic cross-sectional view of the soft X-ray irradiation head 706.
  • the soft X-ray irradiation head 706 includes an X-ray generator 725, a cover 726 made of, for example, polyvinyl chloride (PVC) covering the periphery of the X-ray generator 725, and a gas for supplying gas to the inside of the cover 726. And a nozzle (gas supply means) 727.
  • the cover 726 is in the shape of a vertically long rectangular box that surrounds the X-ray generator 725 with a space from the X-ray generator 725.
  • the cover 726 has a horizontal plate-like lower wall 726A next to the X-ray generator 725. For example, a circular opening 728 is formed in a portion facing the irradiation window 735 described above.
  • the X-ray generator 725 emits (radiates) soft X-rays used to ionize DIW on the substrate W.
  • the X-ray generator 725 includes a case body 729, a vertically long X-ray tube 730 for generating X-rays, and a high voltage unit 731 that supplies a high voltage to the X-ray tube 730.
  • the case body 729 is a vertically long rectangular tube that accommodates the X-ray tube 730 and the high voltage unit 731 and is made of a material having conductivity and thermal conductivity (for example, a metal material such as aluminum). Is formed.
  • the high voltage unit 731 inputs, for example, a high potential drive voltage of ⁇ 9.5 kV to the X-ray tube 730.
  • the high voltage unit 731 is supplied with a voltage from a power source (not shown) through a feed line 743 drawn out of the cover 726 through a through hole 742 formed in the cover 726.
  • the X-ray tube 730 is made of a glass or metal cylindrical vacuum tube, and is arranged so that the tube direction is vertical. A lower end portion (opening end portion) of the X-ray tube 730 is opened to form a circular opening 741. The upper end portion of the X-ray tube 730 is closed and serves as a stem 732.
  • a filament 733 serving as a cathode and a target 736 serving as an anode are disposed so as to face each other.
  • the X-ray tube 730 contains a filament 733 and a focus 734. Specifically, a filament 733 as a cathode is disposed on the stem 732. The filament 733 is electrically connected to the high voltage unit 731. The filament 733 is surrounded by a cylindrical focus 734.
  • the open end of the X-ray tube 730 is closed by a plate-shaped irradiation window 735 that has a vertical posture.
  • the irradiation window 735 has a disk shape, for example, and is fixed to the wall surface of the open end of the X-ray tube 730 by silver brazing.
  • As the material of the irradiation window 735 a substance having a small atomic weight that is easy to transmit soft X-rays having a low transmission power is used, and beryllium (Be) is employed in this embodiment.
  • the thickness of the irradiation window 735 is set to about 0.3 mm, for example.
  • a metal target 736 is formed on the inner surface 735A of the irradiation window 735 by vapor deposition.
  • a metal having a high atomic weight and a high melting point such as tungsten (W) or tantalum (Ta) is used.
  • the filament 733 When the drive voltage from the high voltage unit 731 is applied to the filament 733 that is a cathode, the filament 733 emits electrons. The electrons emitted from the filament 733 are converged at the focus 734 to become an electron beam, and soft X-rays are generated by colliding with the target 736. The generated soft X-rays are emitted (radiated) downward from the irradiation window 735.
  • the irradiation angle (irradiation range) of soft X-rays from the irradiation window 735 is a wide angle (for example, 130 °) as shown in FIG.
  • the wavelength of soft X-rays irradiated from the irradiation window 735 to the outside of the soft X-ray irradiation head 706 is, for example, 0.13 to 0.41 nm.
  • the irradiation window 735 is a generation source that generates soft X-rays. Therefore, if the irradiation window 735 is clouded due to adhesion of water droplets or the like to the outer surface 735B, there is a possibility that the irradiation of soft X-rays from the irradiation window 735 may be hindered.
  • the entire outer surface 735B of the irradiation window 735 is covered with a polyimide resin film 738 having water repellency.
  • the reason why the outer surface 735B of the irradiation window 735 is covered with the film 738 is to protect the irradiation window 735 made of beryllium having poor acid resistance from an acid contained in a treatment liquid such as water.
  • the polyimide resin film 738 has a polyamic acid type polyimide resin.
  • the film thickness of the polyimide resin film 738 is 50 ⁇ m or less, and preferably about 10 ⁇ m. Since the film 738 has water repellency, moisture can be excluded from the outer surface 735B of the irradiation window 735.
  • the polyimide resin film 738 has high chemical stability, the outer surface 735B of the irradiation window 735 can be protected for a long period of time.
  • the reason why the X-ray generator 725 is covered with the cover 726 is to protect the X-ray generator 725 from moisture. Since the X-ray generator 725 includes the high voltage unit 731 as described above, if the atmosphere around the X-ray generator 725 contains a large amount of moisture, a high voltage is generated when soft X-rays are generated. May leak. Therefore, the X-ray generator 725 is covered with a cover 726 in order to prevent moisture from entering the X-ray generator 725.
  • the discharge port of the gas nozzle 727 opens on the upper wall of the cover 726.
  • Gas from a gas supply source (not shown) is supplied to the gas nozzle 727 via a gas valve (gas supply means) 737.
  • the gas nozzle 727 is supplied with a gas having a temperature higher than room temperature (for example, 25 ° C.) (for example, 60 ° C.). Therefore, the gas nozzle 727 discharges a gas having a high temperature (for example, 60 ° C.).
  • Examples of the gas discharged from the gas nozzle 727 include CDA (clean air with low humidity) and inert gas such as nitrogen gas.
  • the gas discharged from the gas nozzle 727 is supplied into the cover 726.
  • the lower wall 726A of the cover 726 is formed with an opening 728 for transmitting soft X-rays from the irradiation window 735. Therefore, in combination with the supply of gas into the cover 726, that is, in the space between the cover 726 and the outer wall of the X-ray generator 725, an air flow toward the opening 728 is formed. Therefore, the atmosphere outside the cover 726 can be suppressed or prevented from entering the cover 726 through the opening 728, and moisture can be further prevented from entering the atmosphere around the X-ray generator 725. be able to.
  • the water repellent coating 738 is formed on the outer surface 735B of the irradiation window 735. Therefore, moisture is not deposited in the form of a film on the front surface of the irradiation window 735, but becomes fine water droplets. Since the water droplets adhering to the outer surface 735B of the irradiation window 735 are in contact with the outer surface 735B at a high contact angle, it can be said that the water droplets easily move on the outer surface 735B.
  • the gas supplied into the cover 726 reaches the outer surface of the irradiation window 735 through the space 739 between the X-ray generator 725 and the cover 726.
  • the water droplets adhering to the outer surface 735B of the irradiation window 735 move in response to the airflow formed in the space 739. Thereby, water droplets can be favorably eliminated from the outer surface 735B of the irradiation window 735, and the irradiation window 735 can be reliably prevented from being fogged. Further, since the gas supplied into the cover 726 is at a high temperature, water droplets adhering to the outer surface 735B of the irradiation window 735 can be removed by evaporation, so that the irradiation window 735 can be further clouded. It can be surely prevented.
  • a sheet-like heater (heating member) 744 is disposed in the vicinity of the periphery of the opening 728 on the lower wall 726A of the cover 726.
  • the heater 744 is formed by printing a resistor on a sheet.
  • the heater 744 is heated by energization of the heater 744, the surrounding members are warmed, and the irradiation window 735 is also warmed. Therefore, water droplets adhering to the outer surface 735B of the irradiation window 735 can also be removed by evaporation, and thereby the irradiation window 735 can be more reliably prevented from being fogged.
  • FIG. 33 is a plan view showing an arrangement position of the soft X-ray irradiation head 706.
  • the soft X-ray irradiation head 706 draws an arc-shaped locus intersecting the rotation direction of the substrate W on the surface of the substrate W held by the spin chuck 704. It is provided to be movable. When the soft X-ray irradiation head 706 irradiates the surface of the substrate W with soft X-rays, the soft X-ray irradiation head 706 is disposed at a close position. And, during irradiation with soft X-rays, it remains arranged in the proximity position. The arrangement position of the soft X-ray irradiation head 706 shown by a solid line in FIG.
  • the arrangement position of the soft X-ray irradiation head 706 indicated by a two-dot chain line in FIG. 33 is the edge proximity position, and the proximity position including the peripheral edge of the surface of the substrate W in the irradiation area from the irradiation window 735 of the soft X-ray irradiation head 706. It is.
  • FIG. 34 is a block diagram showing an electrical configuration of the substrate processing apparatus 701.
  • the substrate processing apparatus 701 further includes a control device (control means) 740 having a configuration including a microcomputer.
  • a spin motor 708, a high voltage unit 731, a swing drive mechanism 719, a lift drive mechanism 720, a chemical solution valve 716, a water valve 714, a gas valve 737, a heater 744, and the like are connected to the control device 740 as control targets.
  • the gas valve 737 is always opened and the heater 744 is driven while the substrate processing apparatus 701 is powered on.
  • the heater 744 is heated and raised to about 100 ° C., for example.
  • FIG. 35 is a process diagram showing a processing example of the substrate W executed in the substrate processing apparatus 701.
  • the rinse process is performed after the chemical process.
  • the surface of the substrate W is irradiated with soft X-rays from the soft X-ray irradiation head 706.
  • the shutter 722 When processing the substrate W, the shutter 722 is changed from the closed state to the open state. Thereby, the opening 721 is opened. Thereafter, an unprocessed substrate W is carried into the processing chamber 703 through the opening 721 by a transfer robot (not shown) (step S701), and delivered to the spin chuck 704 with the surface thereof facing upward. . At this time, the soft X-ray irradiation head 706 is disposed at the home position so as not to hinder the loading of the substrate W. After the hand of the transfer robot has retreated from the processing chamber 703, the shutter 722 is closed.
  • the control device 740 controls the spin motor 708 to start the rotation of the substrate W by the spin chuck 704 (step S702).
  • the rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
  • the controller 740 opens the chemical liquid valve 716 and discharges the chemical liquid from the chemical liquid nozzle 707 toward the rotation center of the surface of the substrate W (S703: supply of chemical liquid).
  • the chemical solution supplied to the surface of the substrate W receives a centrifugal force due to the rotation of the substrate W and flows toward the periphery of the substrate W (spreads over the entire area of the substrate W). As a result, the entire surface of the substrate W is treated with the chemical solution.
  • control device 740 closes the chemical solution valve 716 and stops the supply of the chemical solution from the chemical solution nozzle 707.
  • control device 740 opens the water valve 714 and discharges DIW from the water nozzle 705 toward the rotation center of the surface of the substrate W in a rotating state (step S704). Further, the control device 740 controls the swing drive mechanism 719 to move the soft X-ray irradiation head 706 from the home position set on the side of the spin chuck 704 to above the spin chuck 704 and then drive it up and down. By controlling the mechanism 720, the soft X-ray irradiation head 706 is disposed at a close position close to the surface of the substrate W.
  • control device 740 controls the high voltage unit 731 to generate soft X-rays in the X-ray generator 725 of the soft X-ray irradiation head 706 and irradiate downward from the irradiation window 735 (step S704). .
  • the DIW supplied to the surface of the substrate W flows toward the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W (spreads over the entire area of the substrate W). Thereby, the chemical solution adhering to the surface of the substrate W is washed away by DIW (rinsing process).
  • FIG. 36 is an illustrative view for explaining the rinsing process.
  • the soft X-ray irradiation by the soft X-ray irradiation head 706 is continuously executed in parallel with the supply of DIW to the substrate W.
  • the soft X-ray irradiation head 706 is reciprocated between the center proximity position and the edge proximity position.
  • the irradiation position on the surface of the substrate W to which the soft X-rays from the soft X-ray irradiation head 706 are guided crosses the rotation direction of the substrate W within a range from the rotation center of the substrate W to the peripheral edge of the substrate W. It moves back and forth while drawing an arcuate trajectory. As a result, soft X-rays can be irradiated over the entire surface of the substrate W.
  • FIG. 37 is an illustrative view showing a state in the vicinity of the surface of the substrate W in the rinsing process.
  • the surface of the substrate W is irradiated with soft X-rays while DIW is supplied to the surface of the substrate W.
  • the soft X-rays are applied to the DIW flowing toward the periphery of the surface of the substrate W.
  • DIW flowing on the surface of the substrate W forms a liquid film of DIW in contact with the surface on the surface of the substrate W.
  • the surface portion of this liquid film (the portion shaded in FIG. 37) ) Is irradiated with soft X-rays.
  • the control device 740 closes the water valve 714 and stops supplying DIW (step S705). Thereby, the rinsing process ends.
  • the control device 740 controls the high voltage unit 731 to stop the soft X-ray irradiation from the irradiation window 735 of the soft X-ray irradiation head 706 (step S706). . In addition, the control device 740 controls the swing drive mechanism 719 and the lift drive mechanism 720 to return the soft X-ray irradiation head 706 to the home position. It should be noted that the X-ray irradiation on the surface of the substrate W by the soft X-ray irradiation head 706 is executed until immediately before the start of the spin dry described below.
  • the control device 740 controls the spin motor 708 to increase the rotation speed of the substrate W to a spin dry rotation speed (for example, 2500 rpm).
  • a spin dry rotation speed for example, 2500 rpm.
  • the rotation of the spin chuck 704 is stopped. Thereafter, the shutter 722 is changed from the closed state to the open state, and the opening 721 is opened. Then, the processed substrate W is unloaded by the transfer robot (not shown) through the opening 721 (step S708).
  • the liquid film of DIW formed on the surface of the substrate W is irradiated with soft X-ray X-rays.
  • the DIW liquid film irradiated with soft X-rays electrons are emitted from the water molecules by excitation of the water molecules, resulting in a plasma state in which a large amount of electrons and a large amount of positive ions of the water molecules coexist. Is formed.
  • FIG. 38 is a cross-sectional view for explaining a test apparatus 902 used for these tests.
  • the test apparatus 902 has a rectangular box-shaped water tank 903 for storing DIW and an X-ray irradiation for irradiating soft X-rays to the DIW attached to the water tank 903 from above and stored in the water tank 903.
  • the water tank 903 has a width of 100 mm, a depth of 100 mm, and a height of 100 mm.
  • the bottom wall, the four side walls, and the top wall of the water tank 903 are each made of a PVC plate having a thickness of 5 mm.
  • the X-ray irradiation head 904 is a soft X-ray ionizer (manufactured by Hamamatsu Photonics) having a configuration equivalent to that of the X-ray generator 725 shown in FIG. 32 and the like, and is arranged with the irradiation window 735 facing downward. .
  • An opening 905 is formed in the upper wall of the water tank 903, and the lower end portion of the soft X-ray irradiation head 904 including the irradiation window 735 enters the water tank through the opening 905.
  • the lower surface of the irradiation window of the soft X-ray irradiation head 904 is located 5 mm below the lower surface of the upper wall of the water tank 903.
  • a silicon rubber packing 906 is fitted in a gap between the side edge of the opening 905 on the upper wall of the water tank 903 and the lower end of the soft X-ray irradiation head 904, and thereby the soft X-ray irradiation head 904 is fixed to the upper wall of the water tank 903.
  • a stainless steel square (80 cm ⁇ 80 cm) mesh 911, 912 (having a lattice shape and forming a plate shape as a whole) is used as a measurement object in place of a substrate such as a silicon wafer or a glass substrate.
  • Two meshes 911 and 912 are attached to the water tank 903 in a horizontal posture with a space in the vertical direction.
  • the distance between the upper mesh 911 and the outer surface 735B of the irradiation window 735 of the soft X-ray irradiation head 904 is, for example, 10 mm.
  • the distance between the lower mesh 912 and the outer surface 735B of the irradiation window 735 of the soft X-ray irradiation head 904 is, for example, 25 mm.
  • a drain nipple 907 and a water injection nipple 908 are attached to the side wall of the water tank 903.
  • the nipples 907 and 908 respectively penetrate the inside and outside of the side wall of the water tank 903.
  • the drain nipple 907 is disposed at a position 20 mm from the lower surface of the upper wall of the water tank 903 (that is, a position 5 mm below the upper mesh 911 and 10 mm above the lower mesh 912).
  • the water injection nipple 908 is disposed below the lower mesh 912 with a large gap.
  • a water injection hose (not shown) is connected to the water injection nipple 908, and a water discharge hose (not shown) is connected to the water discharge nipple 907. Water is supplied to the water tank 903 via the water injection hose and discharged through the drainage nipple 907 and the drainage hose.
  • the lower mesh 912 is connected to a metal plate (not shown) of a charged plate monitor CPM (CPM210, manufactured by Ion Systems Inc., USA) with a high voltage cable.
  • CPM charged plate monitor
  • the charge removal time when charged to +/- 1 kV was within 1 second, and the charge removal time when charged to +/- 5 kV was about 2 seconds.
  • This static elimination test shows that the charged body (lower mesh 912) in the DIW can be satisfactorily eliminated by irradiating the DIW with soft X-rays.
  • (2) Ionization test A superinsulation resistance meter (Model 4329A manufactured by Yokogawa Hewlett-Packard Co., Ltd.) was connected between the upper and lower meshes 911, 912, and two meshes 911, 912 depending on the presence or absence of soft X-ray irradiation. The change in electrical resistance was measured.
  • DIW is accumulated in the water tank 903 up to the height of the nipple 907 for drainage. Then, with the soft X-ray irradiation head 904 turned off, a voltage of 10 V was applied to the lower mesh 912, and the electrical resistance between the two meshes 911 and 912 was measured. Next, while applying a voltage of 10 V to the lower mesh 912, the soft X-ray irradiation head 904 is turned on, and the DIW stored in the water tank 903 is irradiated with soft X-rays, and between the two meshes 911, 912 The electrical resistance was measured.
  • the electrical resistance during soft X-ray irradiation decreased from 1 ⁇ 10 11 ( ⁇ ) before soft X-ray irradiation to 1 ⁇ 10 9 ( ⁇ ).
  • This ionization test shows that DIW can be ionized by irradiating DIW with soft X-rays.
  • DIW can be ionized by irradiating DIW with soft X-rays. It can be seen that due to the ionization of the IW, the charged body in contact with the DIW can be well discharged.
  • FIG. 39 is a diagram schematically showing the configuration of the substrate processing apparatus 820 according to the sixteenth embodiment of the present invention. Parts common to the substrate processing apparatus 820 according to the fifteenth embodiment are denoted by the same reference numerals as in FIGS. 31 to 37, and description thereof is omitted.
  • the main difference between the substrate processing apparatus 820 and the substrate processing apparatus 701 is that a water nozzle (water supply means) 821 adopting a scan nozzle form is provided in place of the fixed water nozzle 705.
  • the water nozzle 821 is, for example, a straight nozzle that discharges DIW in a continuous flow state.
  • the water nozzle 821 is attached to the tip of a water arm 823 that extends substantially horizontally with its discharge port facing downward.
  • a water supply pipe 713 is connected to the water nozzle 821.
  • the water arm 823 is provided so as to be able to turn around a predetermined swing axis extending in the vertical direction.
  • the water arm 823 is coupled to a water arm swing drive mechanism 822 for swinging the water arm 823 within a predetermined angle range.
  • the water nozzle 821 is positioned between the position on the rotation axis C of the substrate W (position facing the rotation center of the substrate W) and the home position set to the side of the spin chuck 704. It is moved with.
  • the water arm swing driving mechanism 822 is controlled, and the water nozzle 821 is reciprocated between the rotation center of the substrate W and the peripheral edge.
  • the supply position on the surface of the substrate W to which DIW from the water nozzle 821 is guided is an arc shape that intersects the rotation direction of the substrate W within a range from the rotation center of the substrate W to the peripheral edge of the substrate W.
  • the swing positions of the water nozzle 821 and the soft X-ray irradiation head 706 are controlled so that the water nozzle 821 and the soft X-ray irradiation head 706 do not interfere with each other.
  • FIG. 40 is a diagram schematically showing the configuration of the substrate processing apparatus 830 according to the seventeenth embodiment of the present invention. Portions common to the substrate processing apparatus 701 according to the fifteenth embodiment are denoted by the same reference numerals as in FIGS. 31 to 37, and description thereof is omitted.
  • the main difference between the substrate processing apparatus 830 and the substrate processing apparatus 701 is that an integrated head 831 having a water nozzle and a soft X-ray irradiation head is provided.
  • the integrated head 831 includes a water nozzle (water supply means) 833 having a configuration equivalent to that of the water nozzle 821 of the second embodiment and a soft X-ray having a configuration equivalent to that of the soft X-ray irradiation head 706 of the first embodiment.
  • An irradiation unit (X-ray irradiation means) 834 and a holder 835 for holding a water nozzle 833 and a soft X-ray irradiation unit 834 are provided.
  • the integrated head 831 is attached to the tip of an arm 832 that extends substantially horizontally.
  • the arm 832 is provided so as to be able to turn around a predetermined swing axis extending in the vertical direction. By swinging the arm 832, the integrated head 831 moves between a position on the rotation axis C of the substrate W (a position facing the rotation center of the substrate W) and a home position set to the side of the spin chuck 704. It is moved with.
  • the integrated head 831 is reciprocated between the rotation center of the substrate W and the peripheral edge.
  • the supply position on the surface of the substrate W to which DIW from the water nozzle 833 is guided and the irradiation position on the surface of the substrate W to which soft X-rays from the soft X-ray irradiation unit 834 are guided are the rotation center of the substrate W.
  • FIG. 41 is a diagram schematically showing the configuration of the substrate processing apparatus 840 according to the eighteenth embodiment of the present invention.
  • the substrate processing apparatus 840 includes a soft X-ray irradiation head (X-ray irradiation means) 841 instead of the soft X-ray irradiation head 706 of the first embodiment.
  • the main difference between the soft X-ray irradiation head 841 and the soft X-ray irradiation head 706 is that it projects outward from the lower edge of the side wall of the cover 726 in the horizontal direction (projects from the cover 726 to the side). This is a point provided with a shielding plate portion (shielding member) 842.
  • the shielding plate portion 842 has a square ring plate shape, and the lower surface thereof has a horizontal plane continuous with the lower wall 726A of the cover 726. During the rinsing process, the shielding plate portion 842 is disposed to face the surface of the substrate W held by the spin chuck 704. Soft X-rays emitted from the irradiation window 735 are placed in the space between the substrate W and the shielding plate 842 by the shielding plate 842. Therefore, it is possible to suppress or prevent the soft X-rays irradiated from the irradiation window 735 from being scattered around the substrate W, and thus the safety of the substrate processing apparatus 840 can be improved.
  • FIG. 44 is a diagram showing a configuration of a substrate processing apparatus 1001 to which the processing liquid processing apparatus according to the nineteenth embodiment of the present invention is applied.
  • the substrate processing apparatus 1001 is, for example, a batch type substrate processing apparatus that collectively performs processing liquid processing (cleaning processing) on a plurality of substrates W.
  • the substrate processing apparatus 1001 includes a processing tank 1002 for storing a processing liquid, a processing liquid nozzle 1003 for supplying the processing liquid to the processing tank 1002, and a lifter 1004 for immersing the substrate W in the processing liquid stored in the processing tank 1002.
  • a circulation mechanism 1005 that circulates the treatment liquid stored in the treatment tank 1002 and a control device 1006 that controls each device and valve provided in the substrate treatment apparatus 1001 are included.
  • the treatment tank 1002 has a double tank structure including an inner tank 1007 and an outer tank 1008 having an upper opening opened upward.
  • the inner tank 1007 is configured to store the processing liquid and accommodate a plurality of substrates W.
  • the outer tub 1008 is provided on the outer surface of the upper opening of the inner tub 1007, and the height of its upper edge is set higher than the height of the upper edge of the inner tub 1007.
  • a drain valve 1020 is interposed on the bottom wall of the inner tank 1007.
  • the drainage valve 1020 is a so-called piston valve that opens and closes a part of the bottom wall of the inner tank 1007 by moving a piston (not shown) forward and backward. Due to the retreat of the piston (not shown), a part of the bottom surface of the inner tank 1007 is detached and a drain port is formed on the bottom surface of the inner tank 1007, whereby the processing liquid is quickly drained. Yes. That is, the processing tank 1002 has a QDR (Quick Dump Rinse) function. The processing liquid discharged from the bottom of the inner tank 1007 is sent to a waste liquid device for processing.
  • QDR Quality Dump Rinse
  • the processing liquid nozzle 1003 is connected to a processing liquid pipe 1010 in which a processing liquid valve 1009 is interposed.
  • the processing liquid nozzle 1003 has a large number of fine discharge ports (not shown), and is constituted by, for example, a shower nozzle that discharges liquid in the form of droplets.
  • the control device 1006 opens the processing liquid valve 1009, the processing liquid discharged from the processing liquid nozzle 1003 in a shower shape is supplied into the inner tank 1007.
  • the overflowing processing liquid is received by the outer tank 1008 and collected.
  • Water or diluted chemical is used as the treatment liquid.
  • any of DIW (deionized water), carbonated water, electrolytic ionic water, hydrogen water, ozone water, and dilute concentration (for example, about 10 ppm to 100 ppm) hydrochloric acid water can be employed.
  • Diluent solutions include hydrofluoric acid diluted to a predetermined concentration, BHF (BufferdPMHF), APM (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide aqueous solution), aqueous ammonia, HPM (hydrochloric acid / hydrogen / peroxide mixture) can be used. The same applies to not only this embodiment (19th embodiment) but also the 19th to 27th embodiments.
  • the substrate W held by the lifter 1004 is immersed in the processing liquid stored in the inner tank 1007.
  • the lifter 1004 includes a plurality of holding bars 1011 extending horizontally.
  • the plurality of substrates W are held in an upright position (vertical posture) with the lower edges of the substrates W being brought into contact with each other by the plurality of holding rods 1011 in a state where the plurality of substrates W are aligned in the frontward direction of the drawing.
  • Lifter 1004 includes an elevating mechanism 1022.
  • the lifting mechanism 1022 includes a processing position where the substrate W held by the lifter 1004 is positioned in the inner tank 1007 (position shown in FIG. 44), and the substrate W held by the lifter 1004 is positioned above the inner tank 1007.
  • the lifter 1004 is moved up and down between the retracted position (not shown). Accordingly, when the lifter 1004 is moved to the processing position by the lifting mechanism 1022, a plurality of substrates W held by the lifter 1004 are immersed in the processing liquid. Thereby, the process using the process liquid with respect to the board
  • the circulation mechanism 1005 includes a circulation pipe 1012 that guides the treatment liquid discharged from the treatment tank 1002 to the treatment tank 1002 again, a plurality of circulation nozzles 1013 connected to the downstream end of the circulation pipe 1012, and the circulation pipe 1012. And a circulation pump 1014 for sending the processing liquid to the circulation nozzle 1013.
  • the circulation pipe 1012 includes a return pipe (overflow pipe) 1019 having an upstream end connected to the bottom of the outer tank 1008, and a branch pipe (treatment liquid supply pipe) branched into a plurality from the downstream end of the return pipe 1019. ) 1016.
  • a circulation nozzle 1013 is attached to the tip of each branch pipe 1016.
  • Each circulation nozzle 1013 has one or a plurality of discharge ports, and discharges the processing liquid into the inner tank 1007.
  • a circulation pump 1014, a filter 1015, and a circulation valve 1021 are interposed in this order from the upstream side.
  • the filter 1015 is a filter 1015 for filtering the processing liquid flowing through the circulation pipe 1012
  • the circulation valve 1021 is a valve for opening and closing the return pipe 1019.
  • a soft X-ray irradiation unit (X-ray irradiation means) 1017 is attached to at least one of the plurality of branch pipes 1016 (one in this embodiment).
  • the soft X-ray irradiation unit 1017 is a unit for irradiating the processing liquid existing in the branch pipe 1016 with soft X-rays.
  • FIG. 45A is a schematic cross-sectional view showing the configuration of the branch pipe 1016 and the soft X-ray irradiation unit 1017, respectively.
  • the branch pipe 1016 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a circular first opening 1052 is formed in the middle pipe wall.
  • a soft X-ray irradiation unit 1017 is attached to the branch pipe 1016 so as to close the first opening 1052.
  • the soft X-ray irradiation unit 1017 includes a soft X-ray generator (X-ray generator) 1025, a cover 1026 made of, for example, polyvinyl-chloride covering the periphery of the soft X-ray generator 1025, A gas nozzle (gas supply means) 1027 for supplying a gas to the inside of the cover 1026 is provided, and soft X-rays are irradiated sideways.
  • the cover 1026 is in the shape of a horizontally long rectangular box surrounding the soft X-ray generator 1025 with a space from the soft X-ray generator 1025, and the soft X-ray generator 1025 is formed on the vertical plate-shaped horizontal wall 1026A.
  • a circular second opening 1028 having the same diameter as the first opening 1052 is formed in a portion facing the irradiation window 1035 described next.
  • the soft X-ray irradiation unit 1017 is attached to the branch pipe 1016 so that the second opening 1028 of the cover 1026 coincides with the first opening 1052 of the branch pipe 1016 and the lateral wall 1026A is in close contact with the outer periphery of the branch pipe 1016.
  • the second opening 1028 is closed by a disk-shaped window member 1071.
  • the window member 1071 closes the second opening 1028 from the inside of the cover 1026.
  • the window member 1071 closes not only the second opening 1028 but also the first opening 1052.
  • a substance having a small atomic weight is used so that soft X-rays having a low penetrating power are easily transmitted.
  • beryllium (Be) is adopted as the material of the window member 1071.
  • the thickness of the window member 1071 is set to about 0.3 mm, for example.
  • Soft X-ray generator 1025 emits (radiates) soft X-rays used to ionize the processing liquid passing through the branch pipe 1016.
  • the soft X-ray generator 1025 includes a case body 1029, a soft X-ray tube 1030 that is long to generate soft X-rays, and a high voltage unit 1031 that supplies a high voltage to the soft X-ray tube 1030.
  • the case body 1029 is a horizontally long rectangular tube housing the soft X-ray tube 1030 and the high voltage unit 1031 therein, and is made of a material having conductivity and heat conductivity (for example, a metal material such as aluminum). It is formed using.
  • the high voltage unit 1031 inputs a driving voltage having a high potential of ⁇ 9.5 kV, for example, to the soft X-ray tube 1030.
  • the high voltage unit 1031 is supplied with a voltage from a power source (not shown) through a feed line 1043 drawn out of the cover 1026 through a through hole 1042 formed in the cover 1026.
  • the soft X-ray tube 1030 is made of a glass or metal cylindrical vacuum tube, and is arranged so that the tube direction is horizontal. One end (opening end, left end shown in FIG. 45A) of the soft X-ray tube 1030 forms a circular opening 1041. The other end of the soft X-ray tube 1030 (the right end shown in FIG. 45A) is closed and serves as a stem 1032.
  • a filament 1033 serving as a cathode and a target 1036 serving as an anode are disposed so as to face each other.
  • the soft X-ray tube 1030 contains a filament 1033 and a focus 1034. Specifically, a filament 1033 as a cathode is disposed on the stem 1032. The filament 1033 is electrically connected to the high voltage unit 1031. Filament 1033 is surrounded by a cylindrical focus 1034.
  • the open end of the soft X-ray tube 1030 is closed by a plate-shaped irradiation window 1035 having a vertical posture.
  • the irradiation window 1035 has a disk shape, for example, and is fixed to the wall surface of the open end of the soft X-ray tube 1030 by silver brazing.
  • a material of the irradiation window 1035 a substance having a small atomic weight is used so that soft X-rays having a low transmission power can be easily transmitted.
  • beryllium (Be) is adopted.
  • the thickness of the irradiation window 1035 is set to about 0.3 mm, for example.
  • the irradiation window 1035 faces the inner surface 1071A of the window member 1071 and is arranged with a small gap from the window member 1071.
  • a metal target 1036 is formed on the inner surface 1035A of the irradiation window 1035 by vapor deposition.
  • a metal having a high atomic weight and a high melting point such as tungsten (W) or tantalum (Ta) is used.
  • the filament 1033 When the driving voltage from the high voltage unit 1031 is applied to the filament 1033 which is a cathode, the filament 1033 emits electrons. The electrons emitted from the filament 1033 are converged at the focus 1034 to become an electron beam, and soft X-rays are generated by colliding with the target 1036. The generated soft X-rays are emitted (radiated) from the irradiation window 1035 in the lateral direction (leftward in FIG. 45A), and irradiate the inside of the branch pipe 1016 through the window member 1071 and the first opening 1052.
  • the irradiation angle (irradiation range) of soft X-rays from the irradiation window 1035 is a wide angle (for example, 130 °) as shown in FIG.
  • the wavelength of the soft X-ray irradiated from the irradiation window 1035 to the inside of the branch pipe 1016 is, for example, 0.13 to 0.4 nm.
  • the entire outer surface of the window member 1071 (wall surface on the side where the treatment liquid flows in the closed window) 1071B is covered with a hydrophilic film (film) 1038.
  • the hydrophilic film 1038 is, for example, a polyimide resin film.
  • the reason why the outer surface 1071B of the window member 1071 is covered with the hydrophilic film 1038 is to protect the beryllium-made window member 1071 having poor acid resistance from acid contained in the treatment liquid such as water.
  • the film thickness of the hydrophilic film 1038 is 50 ⁇ m or less, and preferably about 10 ⁇ m. Since the hydrophilic film 1038 has hydrophilicity, it is possible to suppress or prevent air bubbles from being mixed between the film 1038 and the treatment liquid. Thereby, the soft X-rays from the irradiation window 1035 can be satisfactorily irradiated to the processing liquid flowing through the branch pipe 1016.
  • the discharge port of the gas nozzle 1027 opens in the upper wall of the cover 1026.
  • Gas from a gas supply source (not shown) is supplied to the gas nozzle 1027 via a gas valve (gas supply means) 1037.
  • the gas discharged from the gas nozzle 1027 include CDA (clean air with low humidity) and an inert gas such as nitrogen gas.
  • the gas discharged from the gas nozzle 1027 is supplied into the cover 1026.
  • the soft X-ray generator 1025 may be heated by driving the soft X-ray generator 1025, supplying the gas into the cover 1026 cools the soft X-ray generator 1025 and generates soft X-rays. The temperature increase in the ambient atmosphere of the vessel 1025 can be suppressed.
  • the control device 1006 has a configuration including a microcomputer, and controls operations of the elevating mechanism 1022 and the circulation pump 1014 according to a predetermined program. Further, the control device 1006 controls opening / closing operations of the processing liquid valve 1009, the drain valve 1020, and the like.
  • FIG. 45B is a process diagram illustrating a processing example of substrate processing executed in the substrate processing apparatus 1001. An example of substrate processing will be described with reference to FIGS. 44, 45A, and 45B.
  • the circulation of the processing liquid is continuously performed in the circulation mechanism 1005. That is, except for specific situations such as replacement of processing liquid and apparatus maintenance, the processing liquid is always stored in the processing tank 1002, and the processing liquid does not stay in the processing tank 1002 and passes through the circulation pipe 1012. It is circulating. During such circulation, the circulation valve 1021 is opened. As a result, the processing liquid flowing out from the outer tank 1008 passes through the circulation pipe 1012 and is supplied from the circulation nozzle 1013 to the inside of the inner tank 1007.
  • the processing liquid When the processing liquid is further supplied from the circulation nozzle 1013 while the inside of the inner tank 1007 is filled with the processing liquid, the surplus processing liquid overflows from the upper end of the inner tank 1007 and flows into the outer tank 1008. . Then, the processing liquid that has flowed out of the outer tank 1008 passes through the circulation pipe 1012 and is supplied from the circulation nozzle 1013 to the inside of the inner tank 1007.
  • the circulation valve 1021 is closed and the circulation pump 1014 is stopped, and the drain valve 1020 is opened, so that the treatment liquid stored in the inner tank 1007 is rapidly drained. Liquid is applied (step S1001).
  • the control device 1006 controls the lifter 1004 to receive the plurality of substrates W received at the delivery position into the inner tank 1007. To the processing position inside. As a result, the substrate W is put into the processing bath 1002 (step S1002). The substrate W is held inside an empty inner tank 1007.
  • the control device 1006 opens the processing liquid valve 1009 and discharges the processing liquid from the processing liquid nozzle 1003 in a shower shape. (Step S1003). At this time, the drainage valve 1020 remains open and the drainage port (not shown) is opened, so that the treatment liquid containing the contaminant cannot be stored.
  • the control device 1006 closes the drain valve 1020. At this time, since the discharge of the processing liquid from the processing liquid nozzle 1003 is continued, the processing liquid is stored in the inner tank 1007. Thereby, the board
  • the control device 1006 closes the processing liquid valve 1009 and stops the discharge of the processing liquid from the processing liquid nozzle 1003.
  • the control device 1006 starts driving the circulation pump 1014 and opens the circulation valve 1021.
  • the treatment liquid does not stay in the treatment tank 1002 and circulates through the circulation pipe 1012 (step S1004).
  • the processing liquid flowing out from the outer tank 1008 is supplied to the inside of the inner tank 1007 from the circulation nozzle 1013 through the circulation pipe 1012.
  • the surplus processing liquid overflows from the upper end of the inner tank 1007 and flows into the outer tank 1008. .
  • the processing liquid that has flowed out of the outer tank 1008 passes through the circulation pipe 1012 and is supplied from the circulation nozzle 1013 to the inside of the inner tank 1007.
  • Contaminants such as particles are removed when the circulating processing liquid passes through the filter 1015.
  • a clean processing liquid from which contaminants have been removed is discharged from the circulation nozzle 1013 toward the inner tank 1007.
  • the processing liquid is in a liquid-tight state in the nozzle pipe and the branch pipe 1016 of the circulation nozzle 1013.
  • control device 1006 controls the high voltage unit 1031 (see FIG. 45A) to generate soft X-rays in the soft X-ray generator 1025 (see FIG. 45A) of the soft X-ray irradiation unit 1017.
  • X-rays are irradiated from the irradiation window 1035 (see FIG. 45A) through the window member 1071 toward the inside of the branch pipe 1016 (step S1005). Thereby, soft X-rays are irradiated to the processing liquid flowing through the branch pipe 1016.
  • FIG. 46 is an illustrative view showing a state of irradiation of soft X-rays into the branch pipe 1016 shown in FIG.
  • processing liquid flowing through the branch pipe 1016 is irradiated with soft X-rays.
  • the part irradiated with soft X-rays (the part facing the first opening 1052 in the branch pipe 1016.
  • the shaded part shown in FIG. 46 (hereinafter referred to as “processing liquid irradiation part 1054”).
  • electrons are emitted from the water molecules by excitation of the water molecules.
  • a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 1054 of the processing liquid.
  • the processing liquid is liquid-tight in the nozzle pipe and the branch pipe 1016 of the circulation nozzle 1013 as described above, the substrate W and the processing liquid immersed in the processing liquid stored in the inner tank 1007 are used.
  • the irradiation portion 1054 is connected to the processing liquid stored in the inner tank 1007 and the processing liquid in the branch pipe 1016.
  • electrons from the irradiation portion 1054 of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion 1054 of the processing liquid and the positively charged substrate W. It moves through the processing liquid stored in the inner tank 1007 and the processing liquid in the branch pipe 1016. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
  • the substrate W is positively charged before being immersed in the processing liquid, the substrate W is transferred via the processing liquid in the inner tank 1007 or the processing liquid in the branch pipe 1016 according to the same principle. Static neutralization is possible.
  • the control device 1006 stops the soft X-ray irradiation from the soft X-ray irradiation unit 1017 (step S1006).
  • the processed substrate W is unloaded from the inner tank 1007 (step S1007).
  • the unloading of the substrates W is performed by lifting the lifter 1004 that collectively holds the plurality of substrates W from the processing position inside the inner tank 1007 to the upper delivery position. A lot consisting of a plurality of substrates W raised to the delivery position is transferred to the processing tank of the next process.
  • step S1001 If there is a subsequent substrate W to be processed subsequently, the process returns to step S1001 and the above-described series of processing is repeatedly executed.
  • the substrate W can be prevented from being charged during the immersion treatment of the treatment liquid. Further, even if the substrate W is charged before the immersion treatment, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
  • FIG. 47 is a diagram showing a configuration of a substrate processing apparatus 1201 to which the processing liquid processing apparatus according to the twentieth embodiment of the present invention is applied.
  • the substrate processing apparatus 1201 according to the twentieth embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that the soft X-ray irradiation unit (X-ray irradiation means) 1217 is more than the circulation pump 1014 in the return pipe 1019. Is also located upstream.
  • the soft X-ray irradiation unit 1217 is attached to the return pipe 1019.
  • the return pipe 1019 has a round tubular shape (cylindrical shape), such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer), etc. These resin materials are used.
  • PTFE polytetrafluoroethylene
  • PFA perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer
  • the soft X-ray irradiation unit 1217 adopts the same configuration as the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment.
  • the soft X-ray irradiation unit 1217 is attached to the return pipe 1019 so as to close the opening of the return pipe 1019.
  • the opening of the cover of the soft X-ray irradiation unit 1217 matches the opening of the return pipe 1019.
  • the wall surface of the cover of the soft X-ray irradiation unit 1217 (corresponding to the lateral wall 1026A of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) is in close contact with the outer periphery of the return pipe 1019.
  • a high voltage unit of the soft X-ray irradiation unit 1217 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
  • the same processing as in the processing example shown in FIG. 45B is performed.
  • the processing liquid does not stay in the processing tank 1002 and circulates through the circulation pipe 1012.
  • the processing liquid is further supplied from the circulation nozzle 1013 while the inside of the inner tank 1007 is filled with the processing liquid, the excess processing liquid overflows (overflows) from the upper end of the inner tank 1007. Flows into 1008.
  • FIG. 48 is a schematic cross-sectional view showing a state where the processing liquid has overflowed from the upper end of the inner tank 1007.
  • the outer tank 1008 has an annular plate-shaped bottom wall 1081 that surrounds the outer periphery of the inner tank 1007, and a rising wall 1082 that rises vertically upward from the outer peripheral edge of the bottom wall 1081.
  • An overflow port 1083 formed of a through-hole penetrating the bottom wall 1081 in the thickness direction is formed at, for example, one place in the circumferential direction of the bottom wall 1081.
  • the upstream end of the return pipe 1019 is connected to the overflow port 1083.
  • the supply of the processing liquid from the circulation nozzle 1013 is intermittently continued, so that the inside of the return pipe 1019 is made liquid-tight with the processing liquid. Further, as shown in FIG. 48, the state where the liquid mass 1080 of the processing liquid gets over the upper end of the inner tank 1007 always continues, so that the processing liquid stored in the inner tank 1007 and the processing stored in the outer tank 1008 are performed. The liquid is always connected by such a liquid mass 1080 of the processing liquid.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1217 to the processing liquid circulating in the return pipe 1019 (step S1005 in FIG. 45B).
  • the portion irradiated with soft X-rays (treatment liquid irradiation portion.
  • the portion equivalent to the treatment liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is a water molecule. Electrons are emitted from the water molecules by excitation of. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
  • the processing liquid is liquid-tight in the return pipe 1019, and the processing liquid stored in the inner tank 1007 and the processing liquid stored in the outer tank 1008 are a liquid mass of the processing liquid. Since it is always connected by 1080, the substrate W immersed in the processing liquid stored in the inner tank 1007 and the irradiated portion of the processing liquid are stored in the processing liquid stored in the inner tank 1007 and the outer tank 1008. And the processing liquid in the return pipe 1019.
  • the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W, and the inner tank It moves through the processing liquid stored in 1007 and the processing liquid in the return pipe 1019. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
  • FIG. 49 is a diagram showing a configuration of a substrate processing apparatus 1301 to which the processing liquid processing apparatus according to the twenty-first embodiment of the present invention is applied.
  • the substrate processing apparatus 1301 according to the twenty-first embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that an inner tank 1307 having a substantially box-shaped first bulging portion 1318 instead of the inner tank 1007. And a soft X-ray irradiation unit (X-ray irradiation means) 1317 is attached to the wall of the first bulging portion 1318.
  • X-ray irradiation means X-ray irradiation means
  • the first bulging portion 1318 bulges outward from the cylindrical peripheral wall 1307A of the inner tank 1307 along the horizontal direction, and is formed integrally with the peripheral wall 1307A of the inner tank 1307.
  • An opening 1321 is formed in the upper wall or lower wall (upper surface in FIG. 49) of the first bulging portion 1318.
  • the soft X-ray irradiation unit 1317 employs a configuration equivalent to that of the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment.
  • the soft X-ray irradiation unit 1317 is attached so as to close the opening 1321 of the first bulging portion 1318.
  • the opening of the cover of the soft X-ray irradiation unit 1317 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) is the opening 1321 of the first bulging portion 1318.
  • a high voltage unit of the soft X-ray irradiation unit 1317 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
  • the same processing as in the processing example shown in FIG. 45B is performed.
  • the processing liquid is stored in the inner tank 1307, and thereby the inside of the first bulging portion 1318 becomes liquid-tight with the processing liquid.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1317 to the processing liquid in the first bulging portion 1318 (step S1005 in FIG. 45B).
  • the portion irradiated with soft X-rays (the processing liquid irradiation portion; a portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46). Electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
  • the substrate W immersed in the processing liquid stored in the inner tank 1307 and the irradiated portion of the processing liquid are connected via the processing liquid stored in the inner tank 1307.
  • the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W, and the inner tank It moves through the processing liquid stored in 1307.
  • the positively charged substrate W is neutralized.
  • FIG. 50 is a diagram showing a configuration of a substrate processing apparatus 1401 to which the processing liquid processing apparatus according to the twenty-second embodiment of the present invention is applied.
  • the substrate processing apparatus 1401 according to the twenty-second embodiment differs from the substrate processing apparatus 1001 according to the nineteenth embodiment in that it has a substantially box-shaped second bulging portion 1418 at the bottom instead of the inner tank 1007.
  • the substrate processing apparatus 1401 includes a circulation mechanism having the same configuration as the circulation mechanism 1005 (see FIG. 44), but the illustration thereof is omitted.
  • the second bulging portion 1418 bulges outward from the bottom wall 1407A of the inner tank 1407 along the horizontal, and is formed integrally with the bottom wall 1407A of the inner tank 1407.
  • a drainage valve 1420 is interposed at a predetermined position on the lower wall of the second bulging portion 1418.
  • the drainage valve 1420 has the same configuration as the drainage valve 1020 (see FIG. 44). That is, the second bulging portion 1418 is a portion for installing a QDR (Quick Dump Rinse).
  • QDR Quality Dump Rinse
  • One end of a pipe 1423 is connected to the upper wall of the second bulging portion 1418, for example.
  • the inside of the pipe 1423 communicates with the inside of the second bulging portion 1418.
  • the connection position of the pipe 1423 in the second bulging portion 1418 is desirably a position different from the arrangement position of the drainage valve 1420 in the second bulging portion 1418 in plan view.
  • the pipe 1423 has a round tubular shape (cylindrical shape), such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). It is formed using a resin material. An opening 1421 is formed in the middle of the pipe 1423.
  • the soft X-ray irradiation unit 1417 employs a configuration equivalent to that of the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment.
  • the soft X-ray irradiation unit 1417 is attached to the pipe 1423 so as to close the opening 1421 of the pipe 1423.
  • the opening of the cover of the soft X-ray irradiation unit 1417 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG.
  • the wall surface of the cover of the soft X-ray irradiation unit 1417 (corresponding to the lateral wall 1026A of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) is in close contact with the outer periphery of the pipe 1423.
  • the high voltage unit of the soft X-ray irradiation unit 1417 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
  • the same processing as in the processing example shown in FIG. 45B is performed.
  • the processing liquid is stored in the inner tank 1407, and the second bulging portion 1418 and the pipe 1423 are also made liquid-tight by the processing liquid.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1417 to the processing liquid circulating in the pipe 1423 (step S1005 in FIG. 45B).
  • the portion irradiated with soft X-rays contains water molecules. Electrons are emitted from the water molecules by excitation. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
  • the processing liquid is in a liquid-tight state in the pipe 1423 and the second bulging portion 1418 is also liquid-tight with the processing liquid, so that the processing liquid stored in the inner tank 1407 is stored.
  • the substrate W immersed in the substrate and the irradiated portion of the processing liquid are connected via the processing liquid stored in the inner tank 1407 (including the second bulging portion 1418) and the processing liquid in the pipe 1423.
  • the electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W, and the pipe 1423. It moves through the inner processing liquid and the processing liquid stored in the inner tank 1407. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
  • FIG. 51 is a diagram showing a configuration of a substrate processing apparatus 1501 to which the processing liquid processing apparatus according to the twenty-third embodiment of the present invention is applied.
  • the substrate processing apparatus 1501 according to the twenty-third embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that the processing liquid flowing out from the outer tank 1008 is not provided with the circulation mechanism 1005 (see FIG. 44). In other words, waste liquid is collected or collected through the drain pipe 1519, and a treatment liquid nozzle 1561 is provided instead of the treatment liquid nozzle 1003 (see FIG. 44).
  • a soft X-ray irradiation unit 1562 for irradiating the processing liquid flowing through the processing liquid nozzle 1561 with soft X-rays is attached to the processing liquid nozzle 1561.
  • the treatment liquid nozzle 1561 is, for example, a straight nozzle that discharges liquid in a continuous flow state, and is disposed with the discharge port 1553 facing the inside of the inner tank 1007.
  • a processing liquid pipe 1513 to which a processing liquid from a processing liquid supply source is supplied is connected to the processing liquid nozzle 1561.
  • a processing liquid valve 1514 for switching supply / stop of processing liquid from the processing liquid nozzle 1561 is interposed in the middle of the processing liquid pipe 1513.
  • the treatment liquid nozzle 1561 has a round tubular (cylindrical) nozzle pipe 1551 extending in the vertical direction.
  • the nozzle pipe 1551 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer).
  • a round discharge port 1553 is opened at the front end (lower end) of the nozzle pipe 1551.
  • a circular opening 1552 is formed in the middle pipe wall.
  • the soft X-ray irradiation unit 1562 adopts the same configuration as the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment.
  • the soft X-ray irradiation unit 1562 is attached to the nozzle pipe 1551 so as to close the opening 1552 of the nozzle pipe 1551.
  • the opening of the cover of the soft X-ray irradiation unit 1562 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG.
  • the wall surface of the cover of the X-ray irradiation unit 1562 (corresponding to the lateral wall 1026A (see FIG. 45A) of the cover 1026 of the soft X-ray irradiation unit 1017) is in close contact with the outer periphery of the nozzle pipe 1551.
  • the high voltage unit of the soft X-ray irradiation unit 1562 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
  • the substrate processing apparatus 1501 After the processing liquid is stored in the processing tank 1502, the substrates W are collectively put into the processing tank 1502 by the lifter 1004. Thereafter, substrate immersion processing (steps S1004 to S1006 in FIG. 45B) is performed.
  • the substrate processing apparatus 1501 since the substrate processing apparatus 1501 is not provided with the circulation mechanism 1005 (see FIG. 44), the processing liquid stored in the processing tank 1502 is not circulated in the substrate immersion processing. Instead, the supply of the processing liquid from the processing liquid nozzle 1561 is continued intermittently during the substrate immersion process.
  • the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007.
  • the processing liquid in the nozzle pipe 1551 of the processing liquid nozzle 1561, the processing liquid is in a liquid-tight state.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B).
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007. Therefore, the substrate W immersed in the processing liquid stored in the inner tank 1007 and the irradiated portion of the processing liquid are stored in the inner tank 1007. Are connected through the processing liquid in the continuous flow state and the processing liquid in the nozzle pipe 1551. At this time, if the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W. It moves through the processing liquid in 1551, the above-described continuous flow processing liquid, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
  • a soft X-ray irradiation unit 1562 may be provided in a pipe that communicates, and the processing liquid flowing through the pipe may be irradiated with soft X-rays from the soft X-ray irradiation unit 1562.
  • FIG. 52 is a diagram showing a configuration of a substrate processing apparatus 1601 to which the processing liquid processing apparatus according to the twenty-fourth embodiment of the present invention is applied.
  • the substrate processing apparatus 1601 according to the twenty-fourth embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that the processing liquid flowing out from the outer tank 1008 is not provided with the circulation mechanism 1005 (see FIG. 44). This is a point where waste liquid is collected or collected through the drain pipe 1519 and a processing liquid nozzle 1561 for discharging the processing liquid toward the outer tank 1008 is provided.
  • the treatment liquid nozzle 1561 is, for example, a straight nozzle that discharges liquid in a continuous flow state, and is disposed with its discharge port 1553 facing the inside of the outer tank 1008.
  • a soft X-ray irradiation unit 1562 for irradiating the processing liquid flowing through the processing liquid nozzle 1561 with soft X-rays is attached to the processing liquid nozzle 1561. Since a series of configurations related to the treatment liquid nozzle 1561 and the soft X-ray irradiation unit 1562 are the same as those in the twenty-third embodiment, the same reference numerals as those in the twenty-third embodiment are attached and description thereof is omitted.
  • the same processing as in the processing example shown in FIG. 45B is performed.
  • the substrate processing apparatus 1601 since the substrate processing apparatus 1601 is not provided with the circulation mechanism 1005 (see FIG. 44), the processing liquid stored in the processing tank 1502 is circulated during the substrate immersion processing (steps S1004 to S1006 in FIG. 45B). Not. Instead, the supply of the processing liquid from the processing liquid nozzle 1003 is intermittently continued during the substrate immersion process.
  • the processing liquid is further supplied from the processing liquid nozzle 1003 while the inside of the inner tank 1007 is filled with the processing liquid, the surplus processing liquid overflows (overflows) from the upper end of the inner tank 1007. It flows into the tank 1008.
  • the processing liquid valve 1514 is opened, and the processing liquid is discharged from the discharge port 1553 of the processing liquid nozzle 1561 toward the inside of the outer tank 1008.
  • the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 has a continuous flow mode connected to both the discharge port 1553 and the liquid level of the processing liquid stored in the outer tank 1008. At this time, the processing liquid is in a liquid-tight state in the nozzle pipe 1551 of the processing liquid nozzle 1561.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B).
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the mode of the processing liquid discharged from the discharge port 1553 is both the discharge port 1553 and the liquid level of the processing liquid stored in the outer tank 1008. Since the processing liquid stored in the inner tank 1007 and the processing liquid stored in the outer tank 1008 are always connected by the liquid mass of the processing liquid, the inner tank The substrate W immersed in the processing liquid stored in 1007 and the irradiated portion of the processing liquid are the processing liquid stored in the inner tank 1007, the processing liquid stored in the outer tank 1008, and the continuous flow Are connected to each other via a treatment liquid in the nozzle pipe 1551.
  • the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W. It moves through the processing liquid in 1551, the above-described continuous flow processing liquid, the processing liquid stored in the outer tank 1008, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
  • the hydrophilic film (corresponding to the hydrophilic film 1038 (refer to FIG. 45)) is peeled off from the outer surface of the window member of the soft X-ray irradiation unit 1562 (corresponding to the outer surface 71B (refer to FIG. 45A) of the window member 1071).
  • the beryllium contained in the window member may be dissolved in the treatment liquid. Even in such a case, since the processing liquid containing beryllium is drained through the drain pipe 1519, this reliably prevents the processing liquid containing beryllium from being supplied to the substrate W. it can.
  • FIG. 53 is a diagram showing a configuration of a substrate processing apparatus 1701 to which the processing liquid processing apparatus according to the twenty-fifth embodiment of the present invention is applied.
  • the substrate processing apparatus 1701 according to the twenty-fifth embodiment is different from the substrate processing apparatus 1501 according to the twenty-third embodiment in that a plurality of substrates W are handled together with a cassette 1702 that holds a plurality of substrates W collectively. This is a point immersed in 1502.
  • the substrate processing apparatus 1701 is provided with configurations such as a lifter 1004 and an elevating mechanism 1022 of the twenty-third embodiment. The lifter 1004 holds and raises the cassette 1702 in which a plurality of substrates W are held together.
  • the cassette 1702 is formed using a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
  • substrate processing apparatus 1701 After the processing liquid is stored in the processing tank 1502, a plurality of substrates W and cassettes 1702 are put into the processing tank 1502. Thereafter, substrate immersion processing (steps S1004 to S1006 in FIG. 45B) is performed.
  • the supply of the processing liquid from the processing liquid nozzle 1561 is continued intermittently as in the case of the twenty-third embodiment.
  • the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007.
  • the processing liquid is in a liquid-tight state.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B).
  • the portion irradiated with soft X-rays (the processing liquid irradiation portion.
  • the portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is described above.
  • a plasma state is formed in the irradiated portion of the processing liquid.
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007.
  • the substrate W immersed in the processing liquid stored in the inner tank 1007 and the cassette 1702 and the irradiation portion of the processing liquid are included in the inner surface 1007.
  • the processing liquid stored in the tank 1007, the continuous flow processing liquid, and the processing liquid in the nozzle pipe 1551 are connected.
  • the cassette 1702 may be negatively charged.
  • electrons from the cassette 1702 are treated with the treatment liquid stored in the inner tank 1007, and the continuous flow treatment described above. It moves toward the positive ions at the irradiated portion of the processing liquid via the processing liquid in the nozzle pipe 1551. As a result, electrons are removed from the cassette 1702, and as a result, the negatively charged cassette 1702 is discharged.
  • the present invention is applied to the substrate processing apparatuses 1001, 1201, 1301, 1401, 1501, 1601 in which the processing object is the substrate W has been described.
  • the present invention can also be applied to a processing liquid processing apparatus (article cleaning apparatus) that treats as a processing object.
  • FIG. 54 is a diagram showing a configuration of an article cleaning apparatus 1801 to which the processing liquid processing apparatus according to the twenty-sixth embodiment of the present invention is applied.
  • the article cleaning apparatus 1801 is an apparatus for cleaning an optical component using a processing liquid (cleaning liquid), for example, using an optical component such as a lens L as a processing target.
  • the article cleaning apparatus 1801 cleans the lens L by immersing the lens L in the treatment tank 1502.
  • a plurality of lenses L are immersed in the processing tank 1502 in a state where they are collectively accommodated in the cassette 1802.
  • the article cleaning apparatus 1801 is provided with an ultrasonic generator (not shown) that generates ultrasonic vibrations in the processing liquid stored in the processing tank 1502.
  • the general configuration of the article cleaning apparatus 1801 is the same as that of the substrate processing apparatus 1701 according to the 25th embodiment except that an ultrasonic generator (not shown) is provided. Portions common to the embodiment are denoted by the same reference numerals as in FIG. 53, and description thereof is omitted.
  • the processing liquid is stored in the processing tank 1502. Accordingly, the lens L and the cassette 1802 are immersed in the processing liquid, and the lens L is cleaned by continuing such immersion processing for a predetermined period.
  • the supply of the processing liquid from the processing liquid nozzle 1561 is continued intermittently as in the case of the twenty-third embodiment.
  • the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007.
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551 of the processing liquid nozzle 1561.
  • the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B).
  • the portion irradiated with soft X-rays (the processing liquid irradiation portion.
  • the portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is described above.
  • a plasma state is formed in the irradiated portion of the processing liquid.
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007.
  • the lens L and the cassette 1802 immersed in the processing liquid stored in the inner tank 1007 and the irradiation portion of the processing liquid are included.
  • the processing liquid stored in the tank 1007, the continuous flow processing liquid, and the processing liquid in the nozzle pipe 1551 are connected.
  • the lens L or the cassette 1802 is positively charged, the electrons from the irradiation portion of the processing liquid are converted into the lens L by the potential difference between the irradiation portion of the processing liquid and the positively charged lens L or the cassette 1802. And move toward the cassette 1802 through the processing liquid in the nozzle pipe 1551, the above-described continuous flow processing liquid, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged lens L is neutralized.
  • the cassette 1802 may be negatively charged depending on the material of the cassette 1802, the cassette 1802 may be negatively charged.
  • electrons from the cassette 1802 are treated with the treatment liquid stored in the inner tank 1007 and the continuous flow treatment. It moves toward the positive ions at the irradiated portion of the processing liquid via the processing liquid in the nozzle pipe 1551.
  • electrons are removed from the cassette 1802, and as a result, the negatively charged cassette 1802 is discharged.
  • the lens L can be prevented from being charged during the immersion treatment of the treatment liquid. Further, even if the lens L is charged before the immersion treatment, the charge on the lens L can be removed (that is, static elimination).
  • lens L has been described as an example of the optical component
  • a component container that accommodates an optical component such as a mirror or a diffraction grating can be processed.
  • Parts other than the optical parts can also be set as objects to be cleaned (processing objects).
  • the same configuration as that of the 19th to 22nd and 24th embodiments may be adopted.
  • processing similar to that described in the nineteenth to twenty-second and twenty-fourth embodiments is performed. That is, parts such as an optical component (lens L) are immersed in the processing liquid stored in the processing tank 1502, and in parallel therewith, the processing liquid stored in the processing tank 1502 or the inside is stored in the processing tank 1502.
  • Soft X-rays from the soft X-ray units 1017, 1217, 1317, and 1417 are irradiated to the processing liquid existing in the pipes 1016, 1019, and 1423 that communicate with each other.
  • FIG. 55 is a diagram showing a configuration of an article cleaning apparatus 1901 to which the processing liquid processing apparatus according to the twenty-seventh embodiment of the present invention is applied.
  • the article cleaning apparatus 1901 is an apparatus for cleaning the substrate container 1602 using a processing liquid (cleaning liquid), for example, using the substrate container (container) 1602 as an object to be processed.
  • the article cleaning apparatus 1901 cleans the substrate container 1602 by immersing the substrate container 1602 in the treatment tank 1502.
  • FIG. 56 is a perspective view showing the configuration of the substrate container 1602.
  • the substrate container 1602 is a container that accommodates the substrate W in a sealed state.
  • An example of the substrate container 1602 is FOSB (Front Opening Shipping Shipping Box).
  • the FOSB is exclusively used to deliver the substrate W from the semiconductor wafer manufacturer to the semiconductor device manufacturer.
  • the FOSB accommodates a plurality of unprocessed substrates W and prevents damage to the substrates W while maintaining the cleanliness of these substrates W.
  • the substrate container 1602 is attached to a bottomed box-shaped container body 1603 having an opening 1603A on the side, a lid 1604 for opening and closing the opening 1603A of the container body 1603, and an inner wall of the container body 1603.
  • a multi-stage container support shelf 1606 and a multi-stage lid support shelf 1605 attached to the lid 1604 are included.
  • the substrate W is taken in and out of the container main body 1603 through the opening 1603A.
  • Container body 1603 and lid 1604 are each formed using a resin material such as polyvinyl-chloride.
  • the schematic configuration of the article cleaning apparatus 1901 is the same as the configuration of the substrate processing apparatus 1701 according to the 25th embodiment. Therefore, in the 27th embodiment, the parts common to the 25th embodiment include The same reference numerals as those in FIG.
  • the substrate processing apparatus 1901 After the substrate container 1602 (container body 1603) is put into the processing tank 1502, the processing liquid is stored in the processing tank 1502. Accordingly, the substrate container 1602 is immersed in the processing liquid, and the substrate container 1602 is cleaned by continuing such immersion processing for a predetermined period.
  • the supply of the treatment liquid from the treatment liquid nozzle 1561 is continued intermittently as in the case of the twenty-fifth embodiment.
  • the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007.
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551 of the processing liquid nozzle 1561.
  • soft X-rays are irradiated from the soft X-ray irradiation unit 1562 to the processing liquid flowing in the nozzle pipe 1551 (step S5 in FIG. 45B).
  • the portion irradiated with soft X-rays (the processing liquid irradiation portion.
  • the portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is described above.
  • a plasma state is formed in the irradiated portion of the processing liquid.
  • the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007.
  • the substrate container 1602 immersed in the processing liquid stored in the inner tank 1007 and the irradiated portion of the processing liquid are in the inner tank.
  • the processing liquid stored in 1007, the above-described continuous flow processing liquid, and the processing liquid in the nozzle pipe 1551 are connected.
  • the substrate container 1602 is positively charged, electrons from the irradiated part of the processing liquid are transferred to the substrate container 1602 due to a potential difference between the irradiation part of the processing liquid and the positively charged substrate container 1602.
  • the processing liquid in the nozzle pipe 1551, the processing liquid in the continuous flow state, and the processing liquid stored in the inner tank 1007 are moved. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate container 1602 (container body 1603) is neutralized.
  • the substrate container 1602 may be negatively charged.
  • electrons from the substrate container 1602 are stored in the inner tank 1007, It moves toward the positive ions at the irradiated portion of the processing liquid through the continuous flow processing liquid and the processing liquid in the nozzle pipe 1551.
  • the electrons are removed from the substrate container 1602, and as a result, the negatively charged substrate container 1602 is neutralized.
  • the substrate container 1602 can be prevented from being charged during the immersion treatment of the processing liquid. Further, even if the substrate container 1602 is charged before the immersion treatment, the charge on the substrate container 1602 can be removed (that is, static elimination).
  • the lid 1604 and the support shelves 1605 and 1606 can be subjected to a cleaning process while removing electricity from the lid 1604 and the support shelves 1605 and 1606.
  • the FOSB has been described as an example of the substrate container 1602
  • the FOUP Front-Opening-Unified
  • the substrate container 1602 include other types of substrate containers such as a SMIF (Standard Mechanical Interface) pod and OC (Open Cassette).
  • the container is not limited to the one that accommodates the substrate W, but a medium container that accommodates a disk-shaped medium such as a CD, a DVD, or a blue disk, a lens L (see FIG. 54), a mirror, a diffraction grating, or the like.
  • a component container that accommodates an optical component can be a processing target.
  • the same configuration as in the 19th to 22nd and 24th embodiments may be adopted.
  • processing similar to that described in the nineteenth to twenty-second and twenty-fourth embodiments is performed. That is, a container such as the substrate container 1602 is immersed in the processing liquid stored in the processing tank 1002, and the processing liquid stored in the processing tank 1002 or the inside communicates with the inside of the processing tank 1002 in parallel therewith.
  • the soft X-rays from the soft X-ray units 1017, 1217, 1317, and 1417 are irradiated to the processing liquid existing in the pipes 1016, 1019, and 1423.
  • electrodes 56 (FIGS. 1, 8, 10 (a), 11, 12, 14, 15 (a), FIG. 16, FIG. 24, and FIG. 28) are described as being provided, but a configuration in which the electrode 56 is not provided in the nozzle pipe may be employed. In this case, the power source 57 (see FIG. 3) is also omitted.
  • an electrode 56 is provided at the tip of the water nozzle 409 of the twelfth embodiment and the tips of the cup nozzles 224 and 313 of the sixth and eleventh embodiments, and the electrode 56 is powered by a power source 57 (see FIG. 3). A voltage with respect to the device ground may be applied.
  • the water supply pipes 204, 307, and 410 of the fourth, tenth, twelfth, and thirteenth embodiments are used.
  • 533 and the branch pipes 222 and 312 of the sixth and eleventh embodiments may be provided with a liquid detection sensor (treatment liquid detection means) 101.
  • the liquid detection sensor 101 is a sensor for detecting the presence or absence of DIW at a predetermined water detection position 102 in the water supply pipes 204, 307, 410, 533 and the branch pipes 222, 312.
  • the water detection position 102 is set at the same position as or close to the opening (opening to which soft X-rays are irradiated) formed in the water supply pipes 204, 307, 410, 533 and the branch pipes 222, 312. Yes.
  • a process equivalent to the process of FIG. 7 can also be executed.
  • the discharge ports 202A, 216, 409A and 531A of the water nozzles 202, 212, 409 and 531 and the cup nozzle 224 of the sixth and eleventh embodiments are used.
  • the fibrous substances according to the third embodiment can be provided in the discharge ports 224A and 313A of 313, respectively.
  • the cup 17 is neutralized using DIW from the nozzles 224 and 313 provided at the ends of the branch pipes 222 and 312.
  • the DIW of the second nozzle pipe 232 may be used for static elimination.
  • the soft X-ray irradiation units 223 and 319 are disposed in the branch pipes 222 and 312. However, the soft X-ray irradiation units 223 and 319 are provided in the water supply pipes 204 and 307, respectively. It may be arranged.
  • water supply units 230, 250, and 600 according to the seventh, eighth, and fourteenth embodiments have been described as adopting the same configuration as the water supply unit 100 according to the first embodiment, but the fourth embodiment.
  • the structure equivalent to the water supply unit 200 (refer FIG. 1) which concerns on, and the water supply unit 220 which concerns on 5th Embodiment is also employable.
  • the water supply unit 100 according to the first to third embodiments ( 1), a water supply unit 200 according to the fourth embodiment (see FIG. 11), and a water supply unit 220 according to the fifth embodiment may be employed.
  • the case where the substrate W is rinsed on both sides has been described as an example.
  • only the lower surface of the substrate W may be rinsed. Good.
  • the soft X-ray irradiation apparatus 314 can be arranged in the processing chamber 3 in the first to tenth and twelfth embodiments.
  • soft X-rays from the soft X-ray irradiation device 314 may be irradiated to the cup upper portion 19.
  • DIW water
  • a processing object substrate W, substrate container 602, second nozzle pipe 2302.
  • the DIW is supplied from a plurality of nozzles.
  • the upstream ends of a plurality of water supply pipes for supplying DIW to the nozzles 61, 202, 212, 306, 409 are connected to the water collecting pipe.
  • the DIW existing in the water collecting pipe is irradiated with soft X-rays from the soft X-ray irradiation unit.
  • a hydrophilic film 38 covering the outer surface 71B of the window member 71 for example, a hydrophilic DLC (Diamond Like Carbon) film, a hydrophilic fluororesin film, carbonized A hydrogen resin film or the like can be used.
  • a hydrophilic DLC (Diamond Like Carbon) film for example, a hydrophilic fluororesin film, carbonized A hydrogen resin film or the like can be used.
  • the window member 71 can be formed using polyimide resin. In this case, soft X-rays can be transmitted through the window member 71. Moreover, since the polyimide resin is excellent in chemical stability, the window member 71 can be continuously used for a long time. In this case, it is not necessary to cover the outer surface 71B with the hydrophilic film 38.
  • DIW has been exemplified as an example of water that is irradiated with soft X-rays and discharged from the discharge port.
  • the present invention is not limited to DIW, but carbonated water, electrolytic ionic water, hydrogen-dissolved water.
  • ozone-dissolved water and dilute concentration for example, about 10 ppm to 100 ppm
  • hydrochloric acid water can also be employed.
  • a chemical solution (diluted chemical solution) can be adopted as a processing solution irradiated with soft X-rays and discharged from the discharge port.
  • a chemical solution hydrofluoric acid diluted to a predetermined concentration, BHF (Bufferd HF), APM (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide aqueous solution), ammonia Water, HPM (hydrochloric acid / hydrogen-peroxide mixture), etc.
  • BHF Bufferd HF
  • APM ammonia-hydrogen peroxide mixture
  • TMAH tetramethylammonium hydroxide aqueous solution
  • HPM hydrochloric acid / hydrogen-peroxide mixture
  • the inside of the first pipe is performed in parallel with the supply of the processing liquid. It is also possible to irradiate soft X-rays to the processing solution that is distributed.
  • other films can be used as the water-repellent film formed on the outer surface 735B of the irradiation window 735 and covering the outer surface 735B.
  • a water-repellent DLC (Diamond-Like Carbon) film 851 (diamond-like carbon film) can be employed.
  • the film thickness of the DLC film 851 is 10 ⁇ m or less, and preferably about 1 to 2 ⁇ m.
  • silicon (Si) ions are implanted into the outer surface 735B of the irradiation window 735 by ion implantation or the like, and then carbon (C) is implanted into the outer surface 735B of the irradiation window 735 by sputtering or the like.
  • Ions are implanted.
  • the outer surface 735B of the irradiation window 735 is modified.
  • a deposited film of DLC is formed on the outer surface 735B of the irradiation window 735 by plasma CVD or the like, whereby a DLC film 851 is formed.
  • Silicon (Si) ion implantation, carbon (C) ion implantation, and DLC deposition are performed in a low temperature environment of room temperature to 150 ° C.
  • DLC film 851 formed by such a method has water repellency.
  • plasma ion assist method has water repellency.
  • water-repellent DLC film 851 is formed on the outer surface 735B of the irradiation window 735, water droplets can be prevented from adhering to the outer surface 735B of the irradiation window 735. As a result, clouding of the irradiation window 735 can be suppressed or prevented.
  • the DLC film 851 has high adhesion even under a high temperature environment. Therefore, it is possible to reliably prevent the peeled DLC from contaminating the irradiation window 735.
  • the DLC is deposited in a low temperature environment, the temperature drop after the deposition is small, and the stress hardly remains in the DLC film 851. Thereby, it is possible to form a film that is difficult to break (high durability).
  • an amorphous fluororesin film 861 having water repellency can be adopted as the water repellent film.
  • the amorphous fluororesin film 861 is made of amorphous fluorine made of, for example, Cytop resin (trade name).
  • the film thickness of the amorphous fluororesin film 861 is 50 ⁇ m or less, and preferably about 5 to 10 ⁇ m.
  • the coating In the fifteenth to eighteenth embodiments, embodiments of DLC and amorphous fluororesin were described as the coating.
  • the present coating is easy to transmit soft X-rays and has heat resistance of about several hundred degrees Celsius.
  • the shielding member may be provided integrally with the soft X-ray irradiation head 841.
  • the shielding member may be provided separately from the irradiation head 841. In this case, it may be attached to an arm that can be swung in a horizontal plane above the spin chuck 704 so as to be movable on the spin chuck 704 by the swing of this arm.
  • the X-ray irradiation from the soft X-ray irradiation heads 706 and 841 and the X-ray irradiation unit 834 is stopped. It may be.
  • the gas nozzle 727 has been described as ejecting a gas having a temperature higher than normal temperature, but normal temperature gas may be ejected from the gas nozzle 727.
  • the configuration in which the sheet-like heater 744 as the heat generating member is arranged is adopted, but another heat source may be provided as the heat generating member.
  • the irradiation window 735 may be provided without being limited to the periphery of the opening 728 such as the lower wall 726 ⁇ / b> A of the cover 726.
  • the structure provided in both the lower wall 726A of the cover 726 and the irradiation window 735 may be sufficient.
  • a configuration in which a heating member such as the heater 744 is not provided around the irradiation window 735 may be employed.
  • the movable soft X-ray irradiation heads 706 and 841 and the movable X-ray irradiation unit 834 are provided as X-ray irradiation means.
  • the X-ray irradiation means may be disposed so as to be fixedly opposed to the substrate W held by the spin chuck 704. In this case, it is necessary that the soft X-rays irradiated from the fixed X-ray irradiation unit are irradiated to the entire area of the substrate W.
  • DIW is given as an example of water supplied to the substrate W in parallel with the soft X-ray irradiation.
  • the water is not limited to DIW, but carbonated water, electrolytic ionic water, hydrogen dissolved. Any of water, ozone-dissolved water and hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm) can also be employed.
  • the case where soft X-rays are applied to the surface of the substrate W in parallel with the supply of water for the rinsing process has been described as an example.
  • the supply of a chemical solution diluted chemical solution
  • soft X-ray irradiation can be performed.
  • the chemical solution hydrofluoric acid diluted to a predetermined concentration, BHF (BufferdAHF), APM (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide aqueous solution) ), Ammonia water, HPM (hydrochloric acid / hydrogen peroxide mixture).
  • the inside of the first pipe is performed in parallel with the supply of the processing liquid. It is also possible to irradiate soft X-rays to the processing solution that is distributed.
  • the soft X-rays are applied to the surface of the substrate W in parallel with the supply of water. Can also be irradiated.
  • the case where the processing is performed on the substrate W on which the oxide film is formed is taken as an example. ) May be performed on the substrate W on which is formed.
  • all the processing liquid in the processing tank 1002 may be discharged after the substrate immersion processing, and the post-processing shower rinsing may be performed from the processing liquid nozzle 1003 to the substrate W.
  • the contaminants that remain attached to the substrate W even after the immersion treatment can be washed away, and are prevented from reattaching to the substrate W.
  • the heater 25 for heating may be interposed.
  • the circulation mechanism 1005 (see FIG. 44) may be omitted.
  • the processing liquid stored in the processing tanks 1002 and 1502 is not circulated, and the processing liquid recovered in the outer tank 1008 is waste liquid or recovered.
  • a configuration in which a circulation mechanism 1005 (see FIG. 44) is provided may be employed.
  • the processing liquid stored in the processing tank 1502 is circulated, and the processing liquid recovered in the outer tank 1008 is supplied again into the processing tank 1502.
  • the process of rubbing and cleaning the processing object immersed in the processing liquid with a brush can be executed in parallel.
  • the outer tub 1008 is not essential.
  • the configuration of the outer tank 1008 can be omitted.
  • hydrophilic film 1038 covering the outer surface 71B of the window member 1071 for example, a hydrophilic DLC (Diamond Like Carbon) film, a hydrophilic fluororesin film, or carbonized A hydrogen resin film or the like can be used.
  • a hydrophilic DLC (Diamond Like Carbon) film for example, a hydrophilic fluororesin film, or carbonized A hydrogen resin film or the like can be used.
  • the window member 1071 can also be formed using a polyimide resin. In this case, soft X-rays can be transmitted through the window member 1071. In addition, since the polyimide resin is excellent in chemical stability, the window member 1071 can be used for a long time. In this case, it is not necessary to cover the outer surface 71B with the hydrophilic film 1038.
  • a voltage may be applied from the power source 1557 to the electrode 1556 in conjunction with the soft X-ray irradiation by the soft X-ray irradiation unit 1562.
  • the electrode 1556 is preferably charged to a positive charge.
  • the electrons generated in the irradiated portion of the treatment liquid by the soft X-ray irradiation due to the positive charge of the electrode 1556 are pulled toward the electrode 1556 and moved to the tip of the nozzle pipe 1551 where the electrode 1556 is provided. Become. That is, a large amount of electrons can be pulled toward the discharge port 1553 of the processing liquid nozzle 1561. Thereby, the movement of the electrons to the substrate W side can be promoted.
  • X-rays that emit “soft X-rays” having a relatively long wavelength are used as the X-ray irradiating means.
  • Short “hard X-rays” (0.001 nm to 0.1 nm) can also be used.
  • a surface of the apparatus operator side is covered with a lead plate having a considerable thickness, for example, a shielding structure for shielding leakage of X-rays to the outside of the apparatus is provided, Alternatively, it is desirable to take measures such as prohibiting an operator from entering the periphery of the apparatus during X-ray irradiation.
  • the substrate W has been described by taking a semiconductor wafer or a glass substrate for a liquid crystal display device as an example.
  • the substrate W can also be a plasma display substrate, a FED (Field Emission Display) substrate, an OLED (organic electroluminescence).
  • SiC, quartz, sapphire, a plastic, a ceramic, etc. other than silicon and glass can be illustrated.

Abstract

A processing fluid supply device (100) is a processing fluid supply device (100) for discharging processing fluid from a discharge opening (53) and supplying this processing liquid to an article (W) being processed. The device includes: a first pipe (51) that is a first pipe (51) within which processing fluid can flow and the inside thereof is connected to the discharge opening (53); and an x-ray irradiation means (62) that irradiates the processing fluid present within the first pipe (51) with x-rays. The first pipe (53) has an opening (52) in the pipe wall thereof, and the opening (52) is closed with a window member (71) formed using materials through which x-rays can pass. The x-ray irradiation means (62) irradiates x-rays through the window member (71) into the processing fluid present within the first pipe (51).

Description

処理液供給装置、基板処理装置、処理液供給方法、基板処理方法、処理液処理装置および処理液処理方法Processing liquid supply apparatus, substrate processing apparatus, processing liquid supply method, substrate processing method, processing liquid processing apparatus, and processing liquid processing method
　この発明は、処理液供給装置、基板処理装置、処理液供給方法、基板処理方法、処理液処理装置および処理液処理方法に関する。処理液を用いた処理の処理対象物には、基板や収容器、光学部品等が含まれる。処理対象物として用いられる基板には、たとえば、半導体ウエハ、液晶表示装置用ガラス基板、プラズマディスプレイ用基板、ＦＥＤ(Field Emission Display)用基板、OLED（有機エレクトロルミネッセンス）用基板、光ディスク用基板、磁気ディスク用基板、光磁気ディスク用基板、フォトマスク用基板、セラミック基板、太陽電池用基板などの基板が含まれる。 The present invention relates to a processing liquid supply apparatus, a substrate processing apparatus, a processing liquid supply method, a substrate processing method, a processing liquid processing apparatus, and a processing liquid processing method. The processing object using the processing liquid includes a substrate, a container, an optical component, and the like. Substrates used as objects to be processed include, for example, semiconductor wafers, glass substrates for liquid crystal display devices, substrates for plasma displays, substrates for FED (Field Emission Display), substrates for OLED (organic electroluminescence), substrates for optical disks, and magnetism. Substrates such as a disk substrate, a magneto-optical disk substrate, a photomask substrate, a ceramic substrate, and a solar cell substrate are included.
　半導体装置や液晶表示装置の製造工程では、半導体ウエハや液晶表示パネル用ガラス基板などの基板の表面に処理液を供給して、その基板の表面を処理液で洗浄する処理などが行われる。 In the manufacturing process of a semiconductor device or a liquid crystal display device, a treatment liquid is supplied to the surface of a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display panel, and the surface of the substrate is washed with the treatment liquid.
　たとえば、基板を１枚ずつ処理する枚葉式の洗浄処理を実施する基板処理装置は、複数本のチャックピンで基板をほぼ水平に保持しつつ、その基板を回転させるスピンチャックと、このスピンチャックによって回転される基板の表面に処理液を供給するための処理液ノズルとを備えている。 For example, a substrate processing apparatus that performs a single wafer cleaning process that processes substrates one by one, a spin chuck that rotates the substrate while holding the substrate substantially horizontally with a plurality of chuck pins, and the spin chuck And a processing liquid nozzle for supplying a processing liquid to the surface of the substrate rotated by.
　基板の処理に際しては、スピンチャックによって基板が回転される。そして、ノズルから回転中の基板の表面に薬液が供給される。基板の表面上に供給された薬液は、基板の回転による遠心力を受けて、基板の表面上を周縁に向けて流れる。これによって、基板の表面の全域に薬液が行き渡り、基板の表面に対する薬液による処理が達成される。そして、この薬液による処理後には、基板に付着した薬液を純水で洗い流すためのリンス処理が行われる。すなわち、処理液ノズルからスピンチャックによって回転されている基板の表面に純水が供給されて、その純水が基板の回転による遠心力を受けて拡がることにより、基板の表面に付着している薬液が洗い流される。このリンス処理後は、スピンチャックによる基板の回転速度が上昇されて、基板に付着している純水を振り切って乾燥させるスピンドライ処理が行われる（下記特許文献１参照）。 When the substrate is processed, the substrate is rotated by the spin chuck. Then, the chemical solution is supplied from the nozzle to the surface of the rotating substrate. The chemical solution supplied onto the surface of the substrate flows on the surface of the substrate toward the peripheral edge under the centrifugal force due to the rotation of the substrate. As a result, the chemical solution spreads over the entire surface of the substrate, and the treatment of the substrate surface with the chemical solution is achieved. And after the process by this chemical | medical solution, the rinse process for washing away the chemical | medical solution adhering to a board | substrate with a pure water is performed. That is, pure water is supplied from the treatment liquid nozzle to the surface of the substrate rotated by the spin chuck, and the pure water spreads by receiving the centrifugal force due to the rotation of the substrate, so that the chemical solution adhered to the surface of the substrate Is washed away. After this rinse treatment, the rotation speed of the substrate by the spin chuck is increased, and spin dry treatment is performed in which pure water adhering to the substrate is shaken off and dried (see Patent Document 1 below).
特開２００５－１９１５１１号公報JP 2005-191511 A
　ところが、このような従来の基板処理装置では、リンス処理時に、回転状態の基板の表面と純水との間に接触分離が生じ、基板が流動帯電することがあった。基板がガラス基板やシリコンウエハである場合には、基板が正に帯電する。基板が電荷を帯びると、その電荷の放電が生じたときに、基板の表面に形成されるデバイスの破壊を生じるおそれがある。 However, in such a conventional substrate processing apparatus, contact separation occurs between the surface of the rotating substrate and pure water during the rinsing process, and the substrate may be fluidly charged. When the substrate is a glass substrate or a silicon wafer, the substrate is positively charged. If the substrate is charged, there is a risk of destruction of devices formed on the surface of the substrate when the discharge of the charge occurs.
　また、半導体装置や液晶表示装置などの製造工程では、複数枚の基板に対して一括して処理を施すバッチ式の基板処理装置も用いられる。バッチ型の基板処理装置は、たとえば、薬液が貯留された薬液処理槽および水が貯留されたリンス処理槽を含む複数の処理槽を備えている。複数枚の基板に対して一括して処理が行われる場合には、薬液処理槽およびリンス処理槽に基板が順次浸漬されていく。 In addition, in a manufacturing process of a semiconductor device, a liquid crystal display device, or the like, a batch type substrate processing apparatus that processes a plurality of substrates at once is also used. The batch-type substrate processing apparatus includes, for example, a plurality of processing tanks including a chemical processing tank storing a chemical and a rinsing processing tank storing water. When processing is performed on a plurality of substrates at once, the substrates are sequentially immersed in the chemical solution processing tank and the rinse processing tank.
　リンス処理槽におけるリンス処理において基板に帯電が生じるおそれがある。基板がシリコンウエハやガラス基板である場合には、基板が正に帯電する。一連の処理後の基板が電荷を帯びていると、その電荷の放電が生じたときに、基板の表面に形成されるデバイスの破壊を生じるおそれがある。また、処理槽への搬入前から処理対象物が帯電している場合にも、同様の問題が生じるおそれがある。したがって、基板の帯電防止および除電を図りつつリンス処理（処理液を用いた処理）を行うことが求められている。 There is a possibility that the substrate is charged during the rinsing process in the rinsing tank. When the substrate is a silicon wafer or a glass substrate, the substrate is positively charged. If the substrate after a series of treatments is charged, there is a risk that the device formed on the surface of the substrate will be destroyed when the discharge of the charge occurs. In addition, the same problem may occur when the object to be treated is charged before being carried into the treatment tank. Therefore, it is required to perform a rinsing process (a process using a processing liquid) while preventing the substrate from being charged and eliminating the charge.
　処理液を用いた処理における帯電防止および除電は、処理対象物が基板である場合に限られず、処理対象が収容器や他の光学部品等である場合にも共通する課題である。 Antistatic and neutralization in processing using a processing solution are not limited to the case where the processing target is a substrate, but are common issues when the processing target is a container or other optical component.
 
　そこで、この発明の目的は、処理対象物の帯電防止または除電を図りつつ、当該処理対象物に処理液を供給できる処理液供給装置および処理液供給方法を提供することである。
Accordingly, an object of the present invention is to provide a processing liquid supply apparatus and a processing liquid supply method capable of supplying a processing liquid to the processing object while preventing or neutralizing the processing object.
　また、この発明の他の目的は、基板の帯電防止または除電を図りつつ、当該基板に、処理液を用いた処理を施すことができる基板処理装置および基板処理方法を提供することである。 Another object of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of performing processing using a processing liquid on the substrate while preventing or eliminating the charge of the substrate.
　この発明の他の目的は、処理対象物の帯電防止または除電を図りつつ、当該処理対象物に、処理液を用いた処理を施すことができる処理液処理装置および処理液処理方法を提供することである。 Another object of the present invention is to provide a processing liquid processing apparatus and a processing liquid processing method capable of performing processing using a processing liquid on a processing object while preventing or neutralizing the processing object. It is.
　この発明の第１の局面は、吐出口から処理液を吐出して、この処理液を処理対象物に供給するための処理液供給装置であって、処理液が内部を流通可能な第１配管であって、当該内部が前記吐出口に連通する第１配管と、前記第１配管内に存在する処理液に、Ｘ線を照射するＸ線照射手段とを含む、処理液供給装置を提供する。 A first aspect of the present invention is a processing liquid supply device for discharging a processing liquid from a discharge port and supplying the processing liquid to a processing object, and a first pipe through which the processing liquid can circulate The processing liquid supply apparatus includes: a first pipe whose inside communicates with the discharge port; and an X-ray irradiation unit that irradiates the processing liquid existing in the first pipe with X-rays. .
　この構成によれば、第１配管内に存在している処理液にＸ線が照射される。また、第１配管の内部に連通する吐出口から吐出された処理液が処理対象物に供給される。処理液のうちＸ線が照射される部分（以下、「処理液の照射部分」という。）では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this configuration, the processing liquid existing in the first pipe is irradiated with X-rays. Further, the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the processing object. In the portion of the treatment liquid that is irradiated with X-rays (hereinafter referred to as “irradiation portion of the treatment liquid”), electrons are emitted from the water molecules by excitation of the water molecules, and as a result, positive ions and electrons of the water molecules Is formed in a plasma state.
　吐出口から吐出された処理液は、処理対象物に供給され、当該処理対象物に接液する。以下、吐出口から吐出される処理液が、吐出口と処理対象物との間で液状に繋がっている場合について考える。この場合、処理対象物と処理液の照射部分とが、処理液を介して繋がっている。 The processing liquid discharged from the discharge port is supplied to the processing object and comes into contact with the processing object. Hereinafter, the case where the processing liquid discharged from the discharge port is connected to the liquid state between the discharge port and the processing target will be considered. In this case, the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
　このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が、処理対象物に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、処理対象物に接液している処理液が多量の電子を有するようになるので、正に帯電している処理対象物が除電される。 At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid come into contact with the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object positively charged. It moves along the processing liquid connected to the liquid toward the processing liquid that is liquid. As a result, since the processing liquid in contact with the processing object has a large amount of electrons, the positively charged processing object is neutralized.
　一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、液状に繋がっている処理液を伝って移動する。これにより、負に帯電している処理対象物が除電される。 On the other hand, when the object to be processed is negatively charged, electrons from the object to be processed move toward the positive ions in the irradiated portion of the process liquid through the process liquid connected to the liquid state. As a result, the object that is negatively charged is neutralized.
　したがって、処理液の供給時における処理対象物の帯電の発生を防止できる。 Therefore, it is possible to prevent the processing object from being charged when the processing liquid is supplied.
　また、処理液の供給前から処理対象物が正または負に帯電している場合にも、前述した原理により、液状に繋がっている処理液を介して、当該処理対象物を除電できる。 In addition, even when the processing object is positively or negatively charged before the processing liquid is supplied, the processing object can be neutralized through the processing liquid connected to the liquid state according to the principle described above.
　以上により、処理対象物の帯電防止または除電を図りつつ、当該処理対象物に処理液を供給することができる。 As described above, the treatment liquid can be supplied to the treatment object while preventing the charge of the treatment object or eliminating the charge.
　なお、本明細書および請求の範囲において「Ｘ線」とは０．００１nm～１０nm程度の波長を有する電磁波をいい、波長が比較的長い「軟Ｘ線」（０．１nm～１０nm程度）と、波長が比較的短い「硬Ｘ線」（０．００１nm～０．１nm程度）とを含む趣旨である。 In the present specification and claims, “X-ray” means an electromagnetic wave having a wavelength of about 0.001 nm to 10 nm, “soft X-ray” having a relatively long wavelength (about 0.1 nm to 10 nm), This includes “hard X-rays” (about 0.001 nm to 0.1 nm) having a relatively short wavelength.
　また、本明細書および請求の範囲において「処理対象物」には、基板、収容器、光学部品等が含まれる。 In addition, in the present specification and claims, “processing object” includes a substrate, a container, an optical component, and the like.
　この発明の一実施形態では、前記第１配管は、その管壁に開口を有し、前記開口は、Ｘ線が透過可能な材料を用いて形成された窓部材にて閉塞されており、前記Ｘ線照射手段は、前記第１配管内に存在している処理液に、前記窓部材を介してＸ線を照射する。 In one embodiment of the present invention, the first pipe has an opening in its pipe wall, and the opening is closed by a window member formed using a material that can transmit X-rays. The X-ray irradiation unit irradiates the processing liquid existing in the first pipe with X-rays through the window member.
　この構成によれば、Ｘ線が透過可能な材料を用いて、窓部材が形成されている。そして、Ｘ線照射手段から照射されたＸ線は、窓部材を介して、前記第１配管内に存在する処理液に照射される。これにより、処理液の照射部分において、水分子の正イオンと電子とが混在するプラズマ状態を、良好に形成できる。 According to this configuration, the window member is formed using a material capable of transmitting X-rays. And the X-ray irradiated from the X-ray irradiation means is irradiated to the process liquid which exists in the said 1st piping through a window member. Thereby, the plasma state in which positive ions of water molecules and electrons are mixed can be satisfactorily formed in the irradiated portion of the treatment liquid.
　この場合、前記窓部材は、ベリリウムまたはポリイミド樹脂を用いて形成されていてもよい。 In this case, the window member may be formed using beryllium or polyimide resin.
　ベリリウムのような原子量の小さい物質であれば、透過力の弱いＸ線でも透過できる。したがって、ベリリウムを用いて窓部材を形成することにより、Ｘ線が窓部材を透過することが可能である。 If the substance has a small atomic weight such as beryllium, X-rays with low penetrating power can be transmitted. Therefore, by forming the window member using beryllium, X-rays can pass through the window member.
　また、窓部材がポリイミド樹脂を用いて形成される場合、Ｘ線が窓部材を透過することが可能である。また、ポリイミド樹脂は化学安定性に優れているので、窓部材の長期にわたる使用が可能である。 Also, when the window member is formed using polyimide resin, X-rays can pass through the window member. Moreover, since the polyimide resin is excellent in chemical stability, the window member can be used over a long period of time.
　また、窓部材における処理液が存在する側の壁面は、親水性であることが好ましい。この場合、当該壁面と処理液との間に気泡が混入するのを、抑制または防止することができる。これにより、第１配管に存在する処理液に対してＸ線を良好に照射することができる。 Moreover, it is preferable that the wall surface of the window member on the side where the treatment liquid exists is hydrophilic. In this case, it is possible to suppress or prevent air bubbles from being mixed between the wall surface and the treatment liquid. Thereby, X-ray | X_line can be favorably irradiated with respect to the process liquid which exists in 1st piping.
　前記窓部材における処理液が存在する側の壁面は、皮膜によりコーティングされていてもよい。これにより、照射窓を保護することができる。とくに、窓部材が耐酸性の劣るベリリウムを用いて形成されている場合、窓部材を酸性の処理液から良好に守ることができる。 The wall surface of the window member on the side where the treatment liquid is present may be coated with a film. Thereby, an irradiation window can be protected. In particular, when the window member is formed using beryllium having poor acid resistance, the window member can be well protected from the acidic treatment liquid.
　この皮膜は、親水性材料を用いて形成されていることが好ましい。この場合、当該皮膜と処理液との間に気泡が混入するのを、抑制または防止することができる。これにより、第１配管に存在する処理液に対してＸ線を良好に照射することができる。 This film is preferably formed using a hydrophilic material. In this case, it is possible to suppress or prevent air bubbles from being mixed between the film and the treatment liquid. Thereby, X-ray | X_line can be favorably irradiated with respect to the process liquid which exists in 1st piping.
　この場合、前記皮膜は、ポリイミド樹脂、ダイヤモンドライクカーボン、フッ素樹脂および炭化水素樹脂のうちの１つ以上の材質を含む皮膜であってもよい。 In this case, the film may be a film containing one or more materials of polyimide resin, diamond-like carbon, fluorine resin, and hydrocarbon resin.
　前記Ｘ線照射手段は、前記窓部材に対向して配置される照射窓を有し、Ｘ線を発生するとともに、発生したＸ線を前記照射窓から照射するＸ線発生器を含んでいてもよい。 The X-ray irradiation means may include an X-ray generator that has an irradiation window disposed to face the window member, generates X-rays, and irradiates the generated X-rays from the irradiation window. Good.
　この構成によれば、Ｘ線発生器によって発生されたＸ線が、Ｘ線発生器の照射窓から第１配管内を流通している処理液に照射される。 According to this configuration, the X-ray generated by the X-ray generator is irradiated from the irradiation window of the X-ray generator to the processing liquid flowing in the first pipe.
　前記Ｘ線照射手段は、前記Ｘ線発生器の周囲を、当該Ｘ線発生器と間隔を空けて取り囲むカバーと、前記カバーの内部に気体を供給する気体供給手段とをさらに含んでいてもよい。 The X-ray irradiation means may further include a cover surrounding the X-ray generator with a space from the X-ray generator, and a gas supply means for supplying a gas to the inside of the cover. .
　この構成によれば、Ｘ線発生器の駆動により当該Ｘ線発生器が発熱するおそれがある。カバー内に気体を供給することにより、Ｘ線発生器を冷却し、Ｘ線発生器の周囲雰囲気の昇温を抑制することができる。 According to this configuration, there is a possibility that the X-ray generator generates heat by driving the X-ray generator. By supplying the gas into the cover, the X-ray generator can be cooled, and the temperature rise in the ambient atmosphere of the X-ray generator can be suppressed.
　この発明の一実施形態では前記第１配管は、前記吐出口に向けて処理液が内部を流通する処理液配管を含み、前記Ｘ線照射手段は、前記第１配管内を流通している処理液に前記Ｘ線を照射していてもよい。 In one embodiment of the present invention, the first pipe includes a processing liquid pipe through which a processing liquid flows toward the discharge port, and the X-ray irradiating means is a process that circulates in the first pipe. The liquid may be irradiated with the X-ray.
　また、この発明の別の実施形態では、前記吐出口に向けて処理液が内部を流通する処理液配管をさらに含み、前記第１配管は、前記処理液配管から分岐する分岐配管を含んでいてもよい。この場合、分岐配管に存在する処理液に前記Ｘ線が照射される。 Further, in another embodiment of the present invention, the apparatus further includes a processing liquid pipe through which the processing liquid flows toward the discharge port, and the first pipe includes a branch pipe branched from the processing liquid pipe. Also good. In this case, the X-ray is irradiated to the processing liquid present in the branch pipe.
　前記吐出口に配置され、当該吐出口から吐出される処理液が伝って流れることが可能な繊維状物質をさらに含むことが好ましい。 It is preferable to further include a fibrous substance that is disposed at the discharge port and through which the processing liquid discharged from the discharge port can flow.
　この構成によれば、吐出口から吐出される処理液が繊維状物質を伝って流れるので、吐出口からの処理液の吐出流量が少流量である場合でも、吐出口から吐出される処理液の態様を、当該吐出口と前記処理対象物との双方に繋がる連続流状とすることができる。したがって、簡単な構成で、処理対象物と処理液の照射部分とを処理液を介して繋げることができる。 According to this configuration, since the processing liquid discharged from the discharge port flows along the fibrous substance, even when the discharge flow rate of the processing liquid from the discharge port is a small flow rate, the processing liquid discharged from the discharge port An aspect can be made into the continuous flow form connected to both the said discharge outlet and the said process target object. Therefore, it is possible to connect the processing object and the irradiated portion of the processing liquid through the processing liquid with a simple configuration.
　吐出口からの処理液の吐出により、処理対象物に処理液の液膜が形成される場合、繊維状物質の先端は、当該処理液の液膜または処理対象物に接触していてもよい。この場合、吐出口から吐出される処理液の態様を、前記のような連続流状に維持し易い。 When the liquid film of the processing liquid is formed on the processing object by discharging the processing liquid from the discharge port, the tip of the fibrous substance may be in contact with the liquid film of the processing liquid or the processing object. In this case, the mode of the processing liquid discharged from the discharge port is easily maintained in the continuous flow as described above.
　前記第１配管における前記Ｘ線の照射位置よりも、処理液流通方向の下流側に配置された電極と、前記電極に対して電圧を印加する電源とをさらに含んでいてもよい。 The electrode may further include an electrode disposed downstream of the X-ray irradiation position in the first pipe in the treatment liquid flow direction and a power source for applying a voltage to the electrode.
　この構成によれば、第１配管内に存在している処理液に対するＸ線の照射に併せて、電源が電極に対し電圧を印加する。電極への電圧の印加により、電極に、正電荷や負電荷を発生させることができる。 According to this configuration, the power supply applies a voltage to the electrodes in conjunction with the X-ray irradiation to the treatment liquid existing in the first pipe. By applying a voltage to the electrode, a positive charge or a negative charge can be generated in the electrode.
　電極に正電荷を発生させることにより、処理液の照射部分（プラズマ状態）に存在する電子が、電極の正電荷に引っ張られて電極に向けて移動する。これにより、基板側に向かう電子の移動を促進させることができる。 By generating a positive charge on the electrode, electrons existing in the irradiated portion (plasma state) of the treatment liquid are pulled by the positive charge of the electrode and move toward the electrode. Thereby, the movement of the electrons toward the substrate side can be promoted.
　前記電極は、前記第１配管の先端部に配置されていてもよい。この構成によれば、電極が第１配管の先端部に配置されている。そのため、処理液の照射部分（プラズマ状態）に存在する電子が、電極の正電荷に引っ張られて、第１配管の先端部まで移動する。すなわち、多量の電子を、第１配管の先端部まで引っ張ることができる。これにより、基板側に向かう電子の移動をより一層促進させることができる。 The electrode may be disposed at the tip of the first pipe. According to this structure, the electrode is arrange | positioned at the front-end | tip part of 1st piping. Therefore, electrons existing in the irradiated portion (plasma state) of the processing liquid are pulled by the positive charge of the electrode and move to the tip of the first pipe. That is, a large amount of electrons can be pulled to the tip of the first pipe. Thereby, the movement of the electrons toward the substrate side can be further promoted.
　前記処理液供給装置は、前記第１配管において、前記Ｘ線の前記照射位置における処理液の有無を検出するための処理液検出手段と、前記照射位置に処理液が存在するときには、前記Ｘ線照射手段によるＸ線の照射を実行するとともに、前記照射位置に処理液が存在しないときには、前記Ｘ線照射手段によるＸ線の照射を行わないＸ線照射制御手段とをさらに含んでいてもよい。 The processing liquid supply device includes a processing liquid detection means for detecting the presence or absence of a processing liquid at the irradiation position of the X-ray in the first pipe, and when the processing liquid is present at the irradiation position, the X-ray An X-ray irradiation control unit that performs X-ray irradiation by the irradiation unit and that does not perform X-ray irradiation by the X-ray irradiation unit when the treatment liquid is not present at the irradiation position may be further included.
　第１配管におけるＸ線の照射位置に処理液が存在しない状態でＸ線が照射されると、当該Ｘ線が第１配管外に漏れるおそれがある。 If X-rays are irradiated in the state where the treatment liquid does not exist at the X-ray irradiation position in the first pipe, the X-rays may leak out of the first pipe.
　この構成によれば、第１配管におけるＸ線の照射位置に処理液が存在しないときには、当該Ｘ線の照射位置に対するＸ線の照射が禁止される。これにより、第１配管外へのＸ線の漏れを抑制または防止できる。 According to this configuration, when there is no processing liquid at the X-ray irradiation position in the first pipe, X-ray irradiation to the X-ray irradiation position is prohibited. Thereby, the leakage of X-rays outside the first pipe can be suppressed or prevented.
　この発明の第１局面は、基板を保持する基板保持手段と、前記処理液供給装置とを含み、前記吐出口から吐出された処理液を前記基板の主面に供給する、基板処理装置を提供する。 1st aspect of this invention provides the substrate processing apparatus which contains the board | substrate holding means holding the board | substrate, and the said process liquid supply apparatus, and supplies the process liquid discharged from the said discharge outlet to the main surface of the said board | substrate. To do.
　この構成によれば、処理液供給装置の第１配管内に存在している処理液にＸ線が照射される。また、第１配管の内部に連通する吐出口から吐出された処理液が基板の主面に供給される。処理液の照射部分では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this configuration, X-rays are irradiated to the processing liquid existing in the first pipe of the processing liquid supply apparatus. In addition, the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the main surface of the substrate. In the irradiated portion of the treatment liquid, electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
　吐出口から吐出された処理液は、基板の主面に供給され、当該基板の主面に接液する。以下、吐出口から吐出される処理液が、吐出口と基板の主面との間で液状に繋がっている場合について考える。この場合、基板の主面と処理液の照射部分とが、処理液を介して繋がっている。 The processing liquid discharged from the discharge port is supplied to the main surface of the substrate and comes into contact with the main surface of the substrate. Hereinafter, a case where the processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the main surface of the substrate will be considered. In this case, the main surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
　このとき、基板が正に帯電すると、処理液の照射部分と、正に帯電している基板との間の電位差で、処理液の照射部分からの電子が、基板に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、基板に接液している処理液が多量の電子を有するようになるので、正に帯電している基板が除電される。 At this time, when the substrate is positively charged, the processing liquid in which electrons from the irradiated portion of the processing liquid are in contact with the substrate due to a potential difference between the irradiated portion of the processing liquid and the positively charged substrate. Toward the liquid, it moves along the processing liquid connected to the liquid state. As a result, since the processing liquid in contact with the substrate has a large amount of electrons, the positively charged substrate is neutralized.
　これにより、処理液との接触分離による基板の帯電を生じない。したがって、処理液の供給時における基板の帯電の発生を防止できる。 This prevents charging of the substrate due to contact separation with the processing solution. Therefore, it is possible to prevent the substrate from being charged when the processing liquid is supplied.
　また、処理液の供給前から基板が正に帯電している場合にも、前述した原理により、液状に繋がっている処理液を介して、当該処理対象物を除電できる。その結果、基板の帯電に起因するデバイス破壊を防止できる。 Further, even when the substrate is positively charged before the treatment liquid is supplied, the object to be treated can be neutralized through the treatment liquid connected to the liquid according to the principle described above. As a result, it is possible to prevent device destruction due to charging of the substrate.
　以上により、基板の帯電防止または除電を図りつつ、当該基板に、処理液を用いた処理を施すことができる。 As described above, the substrate can be treated with the treatment liquid while preventing or eliminating the charge of the substrate.
　この発明の一実施形態では、前記基板保持手段は、基板を水平姿勢に保持しつつ、鉛直な所定の回転軸線周りに回転させる基板保持回転手段を含み、前記基板処理装置は、前記基板保持回転手段の周囲を包囲する筒状の液受け部材をさらに含み、前記処理液供給装置は、前記吐出口に向けて処理液が内部を流通する処理液配管をさらに含み、前記処理液供給装置の前記第１配管は、前記処理液配管から分岐する分岐配管を含み、前記分岐配管は、前記液受け部材に向けて処理液を吐出するための液受け用吐出口を有する。 In one embodiment of the present invention, the substrate holding unit includes a substrate holding and rotating unit that rotates a substrate around a predetermined rotation axis while holding the substrate in a horizontal posture, and the substrate processing apparatus includes the substrate holding and rotating unit. A cylindrical liquid receiving member surrounding the periphery of the means; and the processing liquid supply device further includes a processing liquid pipe through which the processing liquid flows toward the discharge port, and the processing liquid supply device includes: The first pipe includes a branch pipe branched from the processing liquid pipe, and the branch pipe has a liquid receiving outlet for discharging the processing liquid toward the liquid receiving member.
　この構成によれば、液受け用吐出口から液受け部材に向けて処理液を吐出させながら、分岐配管内を流通している処理液に対し、Ｘ線照射手段からＸ線を照射させる。分岐配管内における処理液の照射部分では、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this configuration, the X-ray irradiation means irradiates the processing liquid flowing through the branch pipe while discharging the processing liquid from the liquid receiving discharge port toward the liquid receiving member. A plasma state in which positive ions of water molecules and electrons are mixed is formed in the irradiated portion of the treatment liquid in the branch pipe.
　液受け用吐出口から吐出された処理液は、液受け部材に供給され、当該液受け部材に接液する。液受け用吐出口から吐出される処理液が、液受け用吐出口と液受け部材との間で液状に繋がっている場合には、液受け部材と処理液の照射部分とが、処理液を介して繋がっている。 The processing liquid discharged from the liquid receiving discharge port is supplied to the liquid receiving member and comes into contact with the liquid receiving member. When the processing liquid discharged from the liquid receiving discharge port is connected in a liquid state between the liquid receiving discharge port and the liquid receiving member, the liquid receiving member and the irradiated portion of the processing liquid receive the processing liquid. Connected through.
　このとき、液受け部材が正に帯電していると、処理液の照射部分と、正に帯電している液受け部材との間の電位差で、処理液の照射部分からの電子が、液受け部材に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、液受け部材に接液している処理液が多量の電子を有するようになるので、正に帯電している液受け部材が除電される。 At this time, if the liquid receiving member is positively charged, electrons from the irradiated portion of the processing liquid are received by the potential difference between the irradiated portion of the processing liquid and the positively charged liquid receiving member. It moves along the treatment liquid connected to the liquid toward the treatment liquid in contact with the member. As a result, since the processing liquid in contact with the liquid receiving member has a large amount of electrons, the positively charged liquid receiving member is neutralized.
　一方、液受け部材が負に帯電していると、液受け部材からの電子が、処理液の照射部分の正イオンに向けて、液状に繋がっている処理液を伝って移動する。これにより、負に帯電している液受け部材が除電される。 On the other hand, when the liquid receiving member is negatively charged, electrons from the liquid receiving member move through the processing liquid connected to the liquid toward the positive ions in the irradiated portion of the processing liquid. Thereby, the negatively charged liquid receiving member is neutralized.
　したがって、基板の帯電防止や除電だけではなく、液受け部材の帯電の発生防止を図ることができる。 Therefore, it is possible not only to prevent the substrate from being charged and to remove static electricity, but also to prevent the liquid receiving member from being charged.
　この発明の別の実施形態では、前記基板保持手段は、基板を水平姿勢に保持しつつ、鉛直な所定の回転軸線周りに回転させる基板保持回転手段を含み、前記基板保持回転手段は、前記基板の下面の少なくとも一部と接触して、当該基板を水平姿勢に支持する支持部材を有し、前記支持部材は多孔質材料を用いて形成されており、前記吐出口から吐出された処理液が前記支持部材に供給される。 In another embodiment of the present invention, the substrate holding means includes substrate holding rotating means for rotating the substrate around a predetermined vertical rotation axis while holding the substrate in a horizontal posture, and the substrate holding rotating means includes the substrate A support member that is in contact with at least a part of the lower surface of the substrate and supports the substrate in a horizontal posture, the support member is formed using a porous material, and the processing liquid discharged from the discharge port Supplied to the support member.
　この構成によれば、支持部材に供給された処理液は、当該支持部材の内部に含浸される。支持部材の内部に含浸されている処理液が、支持部材から染み出して、支持部材上に処理液の液膜を形成する。この処理液の液膜が基板の下面に接液することにより、基板の下面が処理される。 According to this configuration, the processing liquid supplied to the support member is impregnated inside the support member. The treatment liquid impregnated inside the support member oozes out from the support member and forms a liquid film of the treatment liquid on the support member. When the liquid film of the processing liquid comes into contact with the lower surface of the substrate, the lower surface of the substrate is processed.
　このとき、吐出口から吐出される処理液が、当該吐出口と支持部材との双方に繋がる連続流状をなしている場合、支持部材の内部に含浸されている処理液を介して吐出口と基板の下面とが液状に繋がっており、そのため、基板の下面と処理液の照射部分とが、処理液を介して繋がっている。 At this time, when the processing liquid discharged from the discharge port has a continuous flow connected to both of the discharge port and the support member, the discharge port is connected to the discharge port through the processing liquid impregnated inside the support member. The lower surface of the substrate is connected in a liquid state, and therefore, the lower surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
　これにより、基板の帯電防止や除電を図りつつ、当該基板の下面に処理液を用いた処理を施すことができる。 Thereby, the treatment using the treatment liquid can be performed on the lower surface of the substrate while preventing the charge of the substrate and eliminating the charge.
　また、前記基板保持手段は、前記基板を保持しながら、当該基板を所定の搬送方向に向けて搬送する基板保持搬送手段を含んでいてもよい。この構成によれば、吐出口から吐出された処理液が、基板保持搬送手段によって搬送される基板の主面（上面）に供給され、当該基板の主面（上面）に接液する。 Further, the substrate holding means may include substrate holding and conveying means for conveying the substrate in a predetermined conveying direction while holding the substrate. According to this configuration, the processing liquid discharged from the discharge port is supplied to the main surface (upper surface) of the substrate transported by the substrate holding transport means, and comes into contact with the main surface (upper surface) of the substrate.
　吐出口から吐出される処理液が、吐出口と基板の主面との間で液状に繋がっている場合について考える。この場合、基板の主面と処理液の照射部分とが、処理液を介して繋がっている。 Consider the case where the processing liquid discharged from the discharge port is connected to the liquid state between the discharge port and the main surface of the substrate. In this case, the main surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
　このとき、基板が正に帯電すると、処理液の照射部分と、正に帯電している基板との間の電位差で、処理液の照射部分からの電子が、基板に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、基板に接液している処理液が多量の電子を有するようになるので、正に帯電している基板が除電される。 At this time, when the substrate is positively charged, the processing liquid in which electrons from the irradiated portion of the processing liquid are in contact with the substrate due to a potential difference between the irradiated portion of the processing liquid and the positively charged substrate. Toward the liquid, it moves along the processing liquid connected to the liquid state. As a result, since the processing liquid in contact with the substrate has a large amount of electrons, the positively charged substrate is neutralized.
　この場合、前記基板保持搬送手段は、前記基板を、前記搬送方向に沿い、かつ水平面に対し傾斜する姿勢に保持しつつ搬送されていることが好ましい。 In this case, it is preferable that the substrate holding and transporting means is transported while holding the substrate in a posture that is inclined along the transport direction and with respect to a horizontal plane.
　この構成によれば、基板が傾斜姿勢に保持されているので、吐出口から吐出された処理液は基板上を傾斜面に沿って流れる。そのため、処理液が基板上に滞留することがないから、処理液の重量によって、基板の所定の一箇所に荷重が集中するのを防止または抑制できる。また、処理液は基板上をスムーズに流れるから、広範囲に広がる処理液の液膜を基板の上面に形成することができる。これにより、基板の広範囲において、帯電防止や除電を図ることができる。 According to this configuration, since the substrate is held in an inclined posture, the processing liquid discharged from the discharge port flows on the substrate along the inclined surface. Therefore, since the processing liquid does not stay on the substrate, it is possible to prevent or suppress the load from being concentrated on a predetermined portion of the substrate due to the weight of the processing liquid. Further, since the processing liquid flows smoothly on the substrate, a liquid film of the processing liquid spreading over a wide range can be formed on the upper surface of the substrate. As a result, it is possible to prevent charge and eliminate static electricity over a wide range of the substrate.
　この発明の第１の局面は、処理液供給装置の吐出口から処理液を吐出させ、この処理液を処理対象物に供給する処理液供給方法であって、前記吐出口を、前記処理対象物に対向して配置する対向配置工程と、前記吐出口に連通する第１配管の内部に存在する処理液にＸ線を照射するＸ線照射工程と、前記Ｘ線照射工程と並行して、前記吐出口から処理液を吐出させる処理液吐出工程とを含み、前記処理液吐出工程では、前記吐出口と前記処理対象物との間で処理液が液状に繋がっている、処理液供給方法を提供する。 1st aspect of this invention is a processing liquid supply method which discharges a processing liquid from the discharge outlet of a processing liquid supply apparatus, and supplies this processing liquid to a process target object, Comprising: The said discharge outlet is set to the said process target object. In parallel with the X-ray irradiation step, the X-ray irradiation step of irradiating the X-ray to the treatment liquid existing inside the first pipe communicating with the discharge port, And a processing liquid discharge step for discharging the processing liquid from the discharge port. In the processing liquid discharge step, a processing liquid supply method is provided in which the processing liquid is in a liquid state between the discharge port and the processing object. To do.
　この方法によれば、第１配管内に存在している処理液にＸ線が照射される。また、第１配管の内部に連通する吐出口から吐出された処理液が処理対象物に供給される。処理液のうちＸ線が照射される部分では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this method, the processing liquid existing in the first pipe is irradiated with X-rays. Further, the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the processing object. In the portion of the treatment liquid that is irradiated with X-rays, electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
　吐出口から吐出される処理液は、吐出口と処理対象物との間で液状に繋がっている。この場合、処理対象物と処理液の照射部分とが、処理液を介して繋がっている。 The processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the object to be processed. In this case, the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
　このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が、処理対象物に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、処理対象物に接液している処理液が多量の電子を有するようになるので、正に帯電している処理対象物が除電される。 At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid come into contact with the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object positively charged. It moves along the processing liquid connected to the liquid toward the processing liquid that is liquid. As a result, since the processing liquid in contact with the processing object has a large amount of electrons, the positively charged processing object is neutralized.
　一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、液状に繋がっている処理液を伝って移動する。これにより、負に帯電している処理対象物が除電される。 On the other hand, when the object to be processed is negatively charged, electrons from the object to be processed move toward the positive ions in the irradiated portion of the process liquid through the process liquid connected to the liquid state. As a result, the object that is negatively charged is neutralized.
　したがって、処理液の供給時における処理対象物の帯電の発生を防止できる。 Therefore, it is possible to prevent the processing object from being charged when the processing liquid is supplied.
　また、処理液の供給前から処理対象物が正または負に帯電している場合にも、前述した原理により、液状に繋がっている処理液を介して、当該処理対象物を除電できる。 In addition, even when the processing object is positively or negatively charged before the processing liquid is supplied, the processing object can be neutralized through the processing liquid connected to the liquid state according to the principle described above.
　以上により、処理対象物の帯電防止または除電を図りつつ、当該処理対象物に処理液を供給することができる。 As described above, the treatment liquid can be supplied to the treatment object while preventing the charge of the treatment object or eliminating the charge.
　この場合、前記処理液吐出工程では、前記吐出口から吐出される処理液が、当該吐出口と前記処理対象物との双方に繋がる連続流状をなしていることが好ましい。この場合、処理対象物と処理液の照射部分とを処理液を介して、簡単に繋げることができる。 In this case, in the processing liquid discharge step, it is preferable that the processing liquid discharged from the discharge port has a continuous flow shape connected to both the discharge port and the processing object. In this case, the processing object and the irradiated portion of the processing liquid can be easily connected via the processing liquid.
　前記処理対象物は、内部を液が流通する第２配管であってもよいし、物品を収容するための収容器であってもよい。 The processing object may be a second pipe through which liquid flows, or a container for storing articles.
　この発明の第１の局面は、処理液供給装置の吐出口から吐出される処理液を用いて基板を処理する基板処理方法であって、前記吐出口を、基板保持手段に保持されている基板の主面に対向して配置する対向配置工程と、前記吐出口に連通する第１配管の内部に存在する処理液にＸ線を照射するＸ線照射工程と、前記Ｘ線照射工程と並行して、前記吐出口から処理液を吐出させる処理液吐出工程とを含み、前記処理液吐出工程では、前記吐出口と前記基板の主面との間で処理液が液状に繋がっている、基板処理方法を提供する。 1st aspect of this invention is a substrate processing method which processes a board | substrate using the process liquid discharged from the discharge outlet of a process liquid supply apparatus, Comprising: The said board | substrate hold | maintained at the board | substrate holding means In parallel with the X-ray irradiation step, an opposing arrangement step of opposing the main surface, an X-ray irradiation step of irradiating the processing liquid existing inside the first pipe communicating with the discharge port with X-rays, and the X-ray irradiation step And a processing liquid discharge step of discharging a processing liquid from the discharge port, and in the processing liquid discharge step, the processing liquid is connected in a liquid state between the discharge port and the main surface of the substrate. Provide a method.
　この方法によれば、第１配管内に存在している処理液にＸ線が照射される。また、第１配管の内部に連通する吐出口から吐出された処理液が基板の主面に供給される。処理液のうちＸ線が照射される部分では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this method, the processing liquid existing in the first pipe is irradiated with X-rays. In addition, the processing liquid discharged from the discharge port communicating with the inside of the first pipe is supplied to the main surface of the substrate. In the portion of the treatment liquid that is irradiated with X-rays, electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
　吐出口から吐出された処理液は、基板の上面に供給され、当該基板の上面に接液する。吐出口から吐出される処理液は、吐出口と基板の主面との間で液状に繋がっている。この場合、基板の主面と処理液の照射部分とが、処理液を介して繋がっている。 The processing liquid discharged from the discharge port is supplied to the upper surface of the substrate and comes into contact with the upper surface of the substrate. The processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the main surface of the substrate. In this case, the main surface of the substrate and the irradiated portion of the processing liquid are connected via the processing liquid.
　このとき、基板が正に帯電すると、処理液の照射部分と、正に帯電している基板との間の電位差で、処理液の照射部分からの電子が、基板に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、基板に接液している処理液が多量の電子を有するようになるので、正に帯電している基板が除電される。 At this time, when the substrate is positively charged, the processing liquid in which electrons from the irradiated portion of the processing liquid are in contact with the substrate due to a potential difference between the irradiated portion of the processing liquid and the positively charged substrate. Toward the liquid, it moves along the processing liquid connected to the liquid state. As a result, since the processing liquid in contact with the substrate has a large amount of electrons, the positively charged substrate is neutralized.
　これにより、処理液との接触分離による基板の帯電を生じない。したがって、処理液の供給時における基板の帯電の発生を防止できる。 This prevents charging of the substrate due to contact separation with the processing solution. Therefore, it is possible to prevent the substrate from being charged when the processing liquid is supplied.
　また、処理液の供給前から基板が正に帯電している場合にも、前述した原理により、液状に繋がっている処理液を介して、当該処理対象物を除電できる。その結果、基板の帯電に起因するデバイス破壊を防止できる。 Further, even when the substrate is positively charged before the treatment liquid is supplied, the object to be treated can be neutralized through the treatment liquid connected to the liquid according to the principle described above. As a result, it is possible to prevent device destruction due to charging of the substrate.
　以上により、基板の帯電防止または除電を図りつつ、当該基板に、処理液を用いた処理を施すことができる。 As described above, the substrate can be treated with the treatment liquid while preventing or eliminating the charge of the substrate.
　この場合、前記処理液吐出工程では、前記吐出口から吐出される処理液が、当該吐出口と前記基板の主面との双方に繋がる連続流状をなしていることが好ましい。これにより、基板の主面と処理液の照射部分とを処理液を介して、簡単に繋げることができる。 In this case, in the processing liquid discharge step, it is preferable that the processing liquid discharged from the discharge port has a continuous flow shape connected to both the discharge port and the main surface of the substrate. Thereby, the main surface of a board | substrate and the irradiation part of a process liquid can be connected easily via a process liquid.
　この発明の一実施形態では、前記基板は、前記基板保持手段によって水平姿勢に保持されており、前記対向配置工程は、前記吐出口を、前記基板保持手段に保持されている基板の上面に対向するように配置する工程を含む
　この方法によれば、吐出口から吐出された処理液は、基板の上面に供給され、当該基板の上面に接液する。吐出口から吐出される処理液が、吐出口と基板上面との間で液状に繋がっており、処理対象物と処理液の照射部分とが、処理液を介して繋がっている。そのため、基板の上面が正に帯電すると、処理液の照射部分と、正に帯電している基板の上面との間の電位差で、処理液の照射部分からの電子が、基板の上面に接液している処理液に向けて、液状に繋がっている処理液を伝って移動する。これにより、基板の上面に接液している処理液が多量の電子を有するようになるので、正に帯電している基板の上面を除電できる。 In one embodiment of the present invention, the substrate is held in a horizontal posture by the substrate holding means, and the opposing arrangement step is such that the discharge port faces the upper surface of the substrate held by the substrate holding means. According to this method, the processing liquid discharged from the discharge port is supplied to the upper surface of the substrate and comes into contact with the upper surface of the substrate. The processing liquid discharged from the discharge port is connected in a liquid state between the discharge port and the upper surface of the substrate, and the processing object and the irradiated portion of the processing liquid are connected via the processing liquid. Therefore, when the upper surface of the substrate is positively charged, electrons from the irradiated portion of the processing liquid are in contact with the upper surface of the substrate due to a potential difference between the irradiated portion of the processing liquid and the upper surface of the positively charged substrate. It moves along the processing liquid connected to the liquid toward the processing liquid. As a result, the processing liquid in contact with the upper surface of the substrate has a large amount of electrons, so that the upper surface of the positively charged substrate can be neutralized.
　この発明の別の実施形態では、前記基板は、前記基板保持手段によって水平姿勢に保持されており、前記対向配置工程は、前記吐出口を、前記基板保持手段に保持されている基板の下面に対向するように配置する工程を含み、前記基板処理方法は、前記処理液吐出工程に並行して実行され、前記基板を、鉛直な所定の回転軸線まわりに回転させる基板回転工程と、前記処理液吐出工程および前記基板回転工程に並行して、前記基板の上面に処理液を供給する上面処理液供給工程とをさらに含む。 In another embodiment of the present invention, the substrate is held in a horizontal posture by the substrate holding means, and the opposing arrangement step is such that the discharge port is placed on the lower surface of the substrate held by the substrate holding means. Including a step of arranging the substrates so as to face each other, and the substrate processing method is executed in parallel with the processing liquid discharge step, and rotates the substrate about a predetermined vertical rotation axis, and the processing liquid In parallel with the discharging step and the substrate rotating step, an upper surface processing liquid supply step for supplying a processing liquid to the upper surface of the substrate is further included.
　この方法によれば、吐出口から吐出された処理液は、基板の下面に供給され、当該基板の下面に接液する。基板の下面に接液した処理液は、基板の下面を伝って周縁部へと拡がり、基板の下面の全域に処理液の液膜が形成される。基板の下面の周縁部に至った処理液は、基板の周端面を回り込んで基板の上面の周縁部に至る。 According to this method, the processing liquid discharged from the discharge port is supplied to the lower surface of the substrate and comes into contact with the lower surface of the substrate. The processing liquid in contact with the lower surface of the substrate spreads to the peripheral edge along the lower surface of the substrate, and a liquid film of the processing liquid is formed over the entire lower surface of the substrate. The processing liquid that reaches the peripheral edge of the lower surface of the substrate goes around the peripheral end surface of the substrate and reaches the peripheral edge of the upper surface of the substrate.
　また、基板の上面に処理液が供給される。基板に供給された処理液は、基板の回転による遠心力を受けて、基板の上面を周縁部に向けて拡がり、これにより、基板の上面の全域に処理液の液膜が形成される。そして、基板下面側から回り込んできた処理液が、基板上面側の処理液の液膜に合流し、その結果、基板上面側の処理液の液膜と、基板下面側の処理液の液膜とが繋がるようになる。 Also, the processing liquid is supplied to the upper surface of the substrate. The processing liquid supplied to the substrate receives a centrifugal force due to the rotation of the substrate and spreads the upper surface of the substrate toward the peripheral portion, thereby forming a liquid film of the processing liquid over the entire upper surface of the substrate. Then, the processing liquid that has come around from the lower surface side of the substrate merges with the liquid film of the processing liquid on the upper surface side of the substrate, and as a result, the liquid film of the processing liquid on the upper surface side of the substrate and the liquid film of the processing liquid on the lower surface side of the substrate. Will be connected.
　これにより、基板の上面と基板の下面の双方が、処理液の照射部分を処理液を介して繋がるようになる。ゆえに、基板の上下両面の帯電防止や除電を図ることができる。 Thereby, both the upper surface of the substrate and the lower surface of the substrate connect the irradiated portions of the processing liquid via the processing liquid. Therefore, it is possible to prevent charging and charge removal on both the upper and lower surfaces of the substrate.
　前記処理液吐出工程の終了後に実行される液切り処理または乾燥処理に並行して実行され、前記基板の主面にＸ線を照射する第２Ｘ線照射工程をさらに含んでいてもよい。 The process may further include a second X-ray irradiation process that is performed in parallel with the liquid draining process or the drying process that is performed after the processing liquid discharge process is completed and that irradiates the main surface of the substrate with X-rays.
　この方法によれば、液切り処理または乾燥処理により、基板の主面から処理液が除去される。処理液が除去された直後の基板の主面にＸ線が照射される。これにより、基板の帯電防止および除電を、より一層確実に達成できる。 According to this method, the processing liquid is removed from the main surface of the substrate by the liquid draining process or the drying process. X-rays are irradiated to the main surface of the substrate immediately after the treatment liquid is removed. As a result, it is possible to more reliably achieve prevention of static charge and neutralization of the substrate.
　この発明の第２の局面は、基板を保持する基板保持手段と、前記基板保持手段に保持されている基板の表面にＸ線を照射するＸ線照射手段と、前記基板保持手段に保持されている基板の表面に処理液を供給する処理液供給手段と、基板の表面に対する処理液の供給とＸ線の照射とが並行して行われるように、前記Ｘ線照射手段および前記処理液供給手段を制御する制御手段とを含む、基板処理装置を提供する。 According to a second aspect of the present invention, a substrate holding means for holding a substrate, an X-ray irradiation means for irradiating the surface of the substrate held by the substrate holding means with X-rays, and the substrate holding means. The processing liquid supply means for supplying the processing liquid to the surface of the substrate, and the X-ray irradiation means and the processing liquid supply means so that the supply of the processing liquid to the surface of the substrate and the X-ray irradiation are performed in parallel. And a control means for controlling the substrate.
　この構成によれば、基板の表面には、当該表面に接液する処理液の液膜が形成される。処理液の液膜にＸ線が照射される。処理液の液膜のうちＸ線が照射される部分では、水分子の励起により当該水分子から電子が放出される結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が形成される。これにより、処理液との接触分離により基板に正電荷が生じた場合であっても、Ｘ線の照射により処理液中に発生した電子が、処理液の液膜を介して、基板に発生した正電荷に引っ張られて移動し、当該電荷を打ち消すように作用する。これにより、基板の帯電を抑制することができる。また、リンス処理前から基板が帯電していても、基板の表面に接液する処理液の液膜によって、その帯電した基板を除電することができる。その結果、基板の帯電に起因するデバイス破壊を防止することができる。 According to this configuration, the liquid film of the processing liquid that contacts the surface is formed on the surface of the substrate. X-rays are irradiated to the liquid film of the processing liquid. In the portion of the liquid film of the treatment liquid that is irradiated with X-rays, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules coexist as a result of electrons being emitted from the water molecules by excitation of water molecules. Is formed. As a result, even when a positive charge is generated on the substrate due to contact separation with the processing liquid, electrons generated in the processing liquid due to X-ray irradiation are generated on the substrate through the liquid film of the processing liquid. It moves by being pulled by a positive charge and acts to cancel the charge. Thereby, charging of the substrate can be suppressed. Further, even if the substrate is charged before the rinsing process, the charged substrate can be neutralized by the liquid film of the processing liquid in contact with the surface of the substrate. As a result, it is possible to prevent device destruction due to the charging of the substrate.
　また、Ｘ線の照射によって処理液の液性は変化しないので、炭酸水等の酸性の処理液を用いて基板を処理する場合とは異なり、デバイスに悪影響を与えるおそれがない。 In addition, since the liquidity of the treatment liquid does not change due to the X-ray irradiation, unlike the case where the substrate is treated with an acidic treatment liquid such as carbonated water, there is no possibility of adversely affecting the device.
　この発明の一実施形態では、前記Ｘ線照射手段は、照射窓を有し、Ｘ線を発生させるとともに、発生したＸ線を前記照射窓から照射するＸ線発生器を備えている。 In one embodiment of the present invention, the X-ray irradiation means includes an irradiation window, and includes an X-ray generator that generates X-rays and irradiates the generated X-rays from the irradiation window.
　この構成によれば、Ｘ線発生器によって発生されたＸ線が、Ｘ線発生器の照射窓から基板の表面に照射される。 According to this configuration, the surface of the substrate is irradiated with X-rays generated by the X-ray generator from the irradiation window of the X-ray generator.
　前記基板処理装置は、前記Ｘ線発生器の周囲を、間隔を空けて取り囲むカバーをさらに含み、前記カバーには、前記照射窓に対向する部分に開口が形成されている。 The substrate processing apparatus further includes a cover that surrounds the X-ray generator with a space therebetween, and an opening is formed in the cover at a portion facing the irradiation window.
　この構成によれば、Ｘ線発生器の周囲の雰囲気に水分が多く含まれていると、Ｘ線を発生させる際に高電圧がリークするおそれがある。そのため、Ｘ線発生器の周囲に水分が侵入するのを防止するために、Ｘ線発生器の周囲をカバーで覆っている。この場合、カバーにおける照射窓と対向する部分に開口を有し、照射窓からのＸ線を、開口を介して基板の表面に導いている。これにより、Ｘ線発生器からのＸ線の照射を阻害することなく、Ｘ線発生器の周囲の雰囲気に水分が進入するのを抑制することができる。 According to this configuration, if the atmosphere around the X-ray generator contains a lot of moisture, a high voltage may leak when generating X-rays. Therefore, in order to prevent moisture from entering the periphery of the X-ray generator, the periphery of the X-ray generator is covered with a cover. In this case, the cover has an opening at a portion facing the irradiation window, and X-rays from the irradiation window are guided to the surface of the substrate through the opening. Thereby, it can suppress that a water | moisture content penetrate | invades into the atmosphere around an X-ray generator, without inhibiting the irradiation of the X-ray from an X-ray generator.
　この場合、前記基板処理装置は、前記カバーの内部に気体を供給する気体供給手段をさらに含むことが好ましい。カバーに開口が形成されていると、水分を多く含む、カバー外の雰囲気が、開口を介してカバー内に進入するおそれがある。 In this case, it is preferable that the substrate processing apparatus further includes a gas supply unit that supplies a gas into the cover. When the opening is formed in the cover, an atmosphere outside the cover containing a lot of moisture may enter the cover through the opening.
　この構成によれば、カバー内に気体が供給されることにより、Ｘ線発生器とカバーとの間の空間に、開口に至る気流が形成される。そのため、カバー外の雰囲気が、開口を介してカバー内に進入するのを抑制または防止することができる。気体供給手段からカバーの内部に供給される気体は、たとえばＣＤＡ（低湿度の清浄空気）や窒素ガスがある。 According to this configuration, when the gas is supplied into the cover, an air flow reaching the opening is formed in the space between the X-ray generator and the cover. Therefore, the atmosphere outside the cover can be suppressed or prevented from entering the cover through the opening. Examples of the gas supplied from the gas supply means to the inside of the cover include CDA (low humidity clean air) and nitrogen gas.
　前記気体供給手段は、常温よりも高温の気体を供給してもよい。 The gas supply means may supply a gas having a temperature higher than room temperature.
　この構成によれば、カバー内に供給される高温の気体は、Ｘ線発生器とカバーとの間の空間を通って照射窓の外表面に達する。高温の気体により、照射窓の外表面に付着する水滴を蒸発により除去することができ、これにより、照射窓が曇るのを抑制または防止することができる。 According to this configuration, the high-temperature gas supplied into the cover reaches the outer surface of the irradiation window through the space between the X-ray generator and the cover. With the high-temperature gas, water droplets adhering to the outer surface of the irradiation window can be removed by evaporation, thereby suppressing or preventing fogging of the irradiation window.
　前記照射窓の外表面は、皮膜によりコーティングされていてもよい。これにより、照射窓を保護することができる。とくに、耐酸性の劣るベリリウムを用いて照射窓が形成されている場合、この照射窓を酸性の処理液から良好に守ることができる。 The outer surface of the irradiation window may be coated with a film. Thereby, an irradiation window can be protected. In particular, when the irradiation window is formed using beryllium having poor acid resistance, the irradiation window can be well protected from the acidic treatment liquid.
　この皮膜は、撥水性材料を用いて形成されていることが好ましい。この場合、照射窓全面に水分が膜状に析出するのを防止して水分を微細な水滴にする。照射窓の外表面に付着する水滴は、当該外表面を移動し易い状態である。そのため、照射窓の外表面から水滴を容易に排除させることができ、これにより、照射窓が曇るのを抑制または防止することができる。 This film is preferably formed using a water-repellent material. In this case, moisture is prevented from precipitating in the form of a film over the entire irradiation window, and the moisture is made into fine water droplets. Water droplets adhering to the outer surface of the irradiation window are in a state where they can easily move on the outer surface. Therefore, it is possible to easily remove water droplets from the outer surface of the irradiation window, thereby suppressing or preventing the irradiation window from being fogged.
　とくに、前記基板処理装置は、前記照射窓の外表面による前記皮膜によるコーティングと、前記気体供給手段との双方を含むことが好ましい。照射窓の外表面に付着する水滴は当該外表面を移動し易い状態であるので、照射窓の外表面に付着している水滴は、当該空間に形成された気流を受けて移動する。これにより、照射窓の外表面から良好に水滴を排除することができ、照射窓が曇るのを確実に防止することができる。 In particular, the substrate processing apparatus preferably includes both the coating by the film on the outer surface of the irradiation window and the gas supply means. Since the water droplets adhering to the outer surface of the irradiation window are in a state of being easily moved on the outer surface, the water droplets adhering to the outer surface of the irradiation window move by receiving the air flow formed in the space. Thereby, water droplets can be favorably removed from the outer surface of the irradiation window, and the irradiation window can be reliably prevented from being fogged.
　前記皮膜は、ポリイミド樹脂の皮膜であってもよい。 The film may be a polyimide resin film.
　また、前記皮膜は、ダイヤモンドライクカーボンの皮膜であってもよい。 The film may be a diamond-like carbon film.
　さらに、前記皮膜は、アモルファスフッ素樹脂の皮膜であってもよい。 Furthermore, the film may be an amorphous fluororesin film.
　前記カバーにおける前記開口の周囲および前記照射窓の少なくとも一方に、発熱部材が配設されていることが好ましい。 It is preferable that a heating member is disposed around the opening of the cover and at least one of the irradiation window.
　この構成によれば、発熱部材により、Ｘ線発生器の照射窓の周囲が加熱される。そのため、照射窓の外表面に付着する水滴を蒸発により除去することができ、これにより、照射窓が曇るのを抑制または防止することができる。 According to this configuration, the periphery of the irradiation window of the X-ray generator is heated by the heat generating member. Therefore, water droplets adhering to the outer surface of the irradiation window can be removed by evaporation, thereby suppressing or preventing fogging of the irradiation window.
　前記基板処理装置は、前記基板保持手段に保持される基板の表面に対向配置され、当該基板の表面上の空間をその周囲から遮蔽するための遮蔽部材をさらに含んでいてもよい。前記遮蔽部材は、前記照射窓から照射されたＸ線を当該基板の表面上の空間に留めておくためのものである。 The substrate processing apparatus may further include a shielding member that is disposed to face the surface of the substrate held by the substrate holding means and shields a space on the surface of the substrate from the periphery thereof. The shielding member is for keeping X-rays irradiated from the irradiation window in a space on the surface of the substrate.
　この構成によれば、照射窓から照射されたＸ線が、基板の表面上の空間に留められる。そのため、照射窓から照射されたＸ線が基板の周囲に散乱するのを抑制または防止することができる。これにより、基板処理装置の安全性を高めることができる。 According to this configuration, X-rays irradiated from the irradiation window are retained in the space on the surface of the substrate. Therefore, it is possible to suppress or prevent the X-rays irradiated from the irradiation window from being scattered around the substrate. Thereby, the safety | security of a substrate processing apparatus can be improved.
　前記遮蔽部材は、前記カバーと一体移動可能に設けられていてもよい。 The shielding member may be provided so as to be movable together with the cover.
　前記基板処理装置は、前記Ｘ線照射手段を、前記基板保持手段によって保持された基板の表面に沿って移動させる移動手段をさらに含む。 The substrate processing apparatus further includes moving means for moving the X-ray irradiation means along the surface of the substrate held by the substrate holding means.
　この構成によれば、Ｘ線照射手段を基板の表面に対向させつつ、Ｘ線照射手段からＸ線を照射するとともに、Ｘ線照射手段を基板の表面に沿って移動させる。これにより、電離された処理液を基板の表面の全域に供給することができる。これにより、基板の全域で、基板を除電することができる。 According to this configuration, the X-ray irradiation means is moved along the surface of the substrate while the X-ray irradiation means is irradiated with the X-ray while the X-ray irradiation means is opposed to the surface of the substrate. Thereby, the ionized processing liquid can be supplied to the entire surface of the substrate. As a result, the substrate can be neutralized over the entire area of the substrate.
　また、前記処理液は水であってもよい。 Further, the treatment liquid may be water.
　この発明の第２の局面は、基板保持手段に保持された基板の表面に処理液を供給する処理液供給工程と、前記処理液供給工程と並行して、前記基板保持手段に保持された基板の表面にＸ線を照射するＸ線照射工程とを含む、基板処理方法を提供する。 According to a second aspect of the present invention, there is provided a processing liquid supply step for supplying a processing liquid to the surface of the substrate held by the substrate holding means, and a substrate held by the substrate holding means in parallel with the processing liquid supply step. An X-ray irradiation step of irradiating the surface of the substrate with X-rays is provided.
　この発明の方法によれば、基板の表面には、当該表面に接液する処理液の液膜が形成される。処理液の液膜にＸ線が照射される。処理液の液膜のうちＸ線が照射される部分では、水分子の励起により当該水分子から電子が放出される結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が形成される。これにより、処理液との接触分離により基板に正電荷が生じた場合であっても、Ｘ線の照射により処理液中に発生した電子が、処理液の液膜を介して、基板に発生した正電荷に引っ張られて移動し、当該電荷を打ち消すように作用する。これにより、基板の帯電を抑制することができる。また、リンス処理前から基板が帯電していても、基板の表面に接液する処理液の液膜によって、その帯電した基板を除電することができる。その結果、基板の帯電に起因するデバイス破壊を防止することができる。 According to the method of the present invention, a liquid film of the processing liquid that contacts the surface is formed on the surface of the substrate. X-rays are irradiated to the liquid film of the processing liquid. In the portion of the liquid film of the treatment liquid that is irradiated with X-rays, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules coexist as a result of electrons being emitted from the water molecules by excitation of water molecules. Is formed. As a result, even when a positive charge is generated on the substrate due to contact separation with the processing liquid, electrons generated in the processing liquid due to X-ray irradiation are generated on the substrate through the liquid film of the processing liquid. It moves by being pulled by a positive charge and acts to cancel the charge. Thereby, charging of the substrate can be suppressed. Further, even if the substrate is charged before the rinsing process, the charged substrate can be neutralized by the liquid film of the processing liquid in contact with the surface of the substrate. As a result, it is possible to prevent device destruction due to the charging of the substrate.
　この発明の第３の局面は、処理液中に処理対象物を浸漬して処理を行う処理液処理装置であって、処理液を貯留し、その処理液中に処理対象物を浸漬させる処理槽と、前記処理槽に貯留された処理液、または処理液が内部を流通可能な配管であって、当該内部が前記処理槽内に連通する配管内に存在する処理液に、Ｘ線を照射するＸ線照射手段とを含む、処理液処理装置である。 A third aspect of the present invention is a processing liquid processing apparatus that performs processing by immersing a processing object in the processing liquid, storing the processing liquid and immersing the processing object in the processing liquid. And the processing liquid stored in the processing tank or a pipe through which the processing liquid can flow, and the processing liquid existing in the pipe communicating with the processing tank is irradiated with X-rays A processing liquid processing apparatus including X-ray irradiation means.
　この構成によれば、処理槽に貯留されている処理液、または内部が前記処理槽内に連通する配管内に存在している処理液にＸ線が照射される。当該処理液のうちＸ線が照射される部分（処理液の照射部分）では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this configuration, X-rays are irradiated to the processing liquid stored in the processing tank or the processing liquid existing inside the pipe communicating with the processing tank. In a portion of the treatment liquid that is irradiated with X-rays (treatment liquid irradiation portion), electrons are emitted from the water molecules by excitation of water molecules, and as a result, plasma in which positive ions and electrons of water molecules are mixed. A state is formed.
　処理槽に貯留されている処理液にＸ線が照射される場合、処理槽に貯留されている処理液に浸漬されている処理対象物と処理液の照射部分とが、処理槽に貯留されている処理液を介して繋がっている。このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が処理対象物に向けて、処理槽に貯留されている処理液を介して移動する。これにより、処理対象物に多量の電子が供給される結果、正に帯電している処理対象物が除電される。一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、処理槽に貯留されている処理液を介して移動する。これにより、処理対象物から電子が除去される結果、負に帯電している処理対象物が除電される。 When the processing liquid stored in the processing tank is irradiated with X-rays, the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected through the processing solution. At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object positively charged. It moves through the processing liquid stored in the processing tank. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized. On the other hand, when the processing object is negatively charged, electrons from the processing object move toward the positive ions in the irradiated portion of the processing liquid through the processing liquid stored in the processing tank. Thereby, as a result of removing electrons from the processing object, the processing object that is negatively charged is neutralized.
　また、配管内に存在している処理液にＸ線が照射される場合、処理槽に貯留されている処理液に浸漬されている処理対象物と処理液の照射部分とが、処理槽に貯留されている処理液および配管内の処理液を介して繋がっている。このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が処理対象物に向けて、処理槽に貯留されている処理液および配管内の処理液を介して移動する。これにより、処理対象物に多量の電子が供給される結果、正に帯電している処理対象物が除電される。一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、処理槽に貯留されている処理液および配管内の処理液を介して移動する。これにより、処理対象物から電子が除去される結果、負に帯電している処理対象物が除電される。 Further, when X-rays are irradiated to the processing liquid existing in the pipe, the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected via the processing liquid which has been processed and the processing liquid in the pipe. At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object that is positively charged. It moves through the processing liquid stored in the processing tank and the processing liquid in the pipe. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized. On the other hand, when the object to be processed is negatively charged, electrons from the object to be processed move toward the positive ions in the irradiated portion of the processing liquid through the processing liquid stored in the processing tank and the processing liquid in the pipe. To do. Thereby, as a result of removing electrons from the processing object, the processing object that is negatively charged is neutralized.
　また、処理液への浸漬の前から処理対象物が正または負に帯電している場合にも、前述した原理により、処理槽内の処理液や配管内の処理液を介して、当該処理対象物を除電できる。 In addition, even when the object to be treated is positively or negatively charged before being immersed in the treatment liquid, the treatment object is treated via the treatment liquid in the treatment tank or the treatment liquid in the pipe according to the principle described above. Can neutralize things.
　この発明の一実施形態では、前記配管の管壁または前記処理槽の壁は、開口を有し、前記開口は、Ｘ線が透過可能な材料を用いて形成された窓部材にて閉塞されており、前記Ｘ線照射手段は、前記窓部材を介してＸ線を照射する。 In one embodiment of the present invention, the pipe wall of the pipe or the wall of the processing tank has an opening, and the opening is closed by a window member formed using a material that can transmit X-rays. The X-ray irradiation means irradiates X-rays through the window member.
　この構成によれば、Ｘ線が透過可能な材料を用いて、窓部材が形成されている。そして、Ｘ線照射手段から照射されたＸ線は、窓部材を介して、前記配管内に存在する処理液に照射される。これにより、処理液の照射部分において、水分子の正イオンと電子とが混在するプラズマ状態を、良好に形成できる。 According to this configuration, the window member is formed using a material capable of transmitting X-rays. And the X-ray irradiated from the X-ray irradiation means is irradiated to the process liquid which exists in the said piping through a window member. Thereby, the plasma state in which positive ions of water molecules and electrons are mixed can be satisfactorily formed in the irradiated portion of the treatment liquid.
　この場合、前記窓部材は、ベリリウムまたはポリイミド樹脂を用いて形成されていてもよい。 In this case, the window member may be formed using beryllium or polyimide resin.
　ベリリウムのような原子量の小さい物質であれば、透過力の弱いＸ線でも透過できる。したがって、ベリリウムを用いて窓部材を形成することにより、Ｘ線が窓部材を透過することが可能である。 If the substance has a small atomic weight such as beryllium, X-rays with low penetrating power can be transmitted. Therefore, by forming the window member using beryllium, X-rays can pass through the window member.
　また、窓部材がポリイミド樹脂を用いて形成される場合、窓部材にＸ線を透過させることができる。また、ポリイミド樹脂は化学安定性に優れているので、窓部材の長期にわたる使用が可能である。 In addition, when the window member is formed using a polyimide resin, X-rays can be transmitted through the window member. Moreover, since the polyimide resin is excellent in chemical stability, the window member can be used over a long period of time.
　また、窓部材における処理液が存在する側の壁面は、親水性であることが好ましい。この場合、当該壁面と処理液との間に気泡が混入するのを、抑制または防止することができる。これにより、配管に存在する処理液に対してＸ線を良好に照射することができる。 Moreover, it is preferable that the wall surface of the window member on the side where the treatment liquid exists is hydrophilic. In this case, it is possible to suppress or prevent air bubbles from being mixed between the wall surface and the treatment liquid. Thereby, it is possible to satisfactorily irradiate X-rays to the processing liquid existing in the pipe.
　前記窓部材における処理液が存在する側の壁面は、皮膜によりコーティングされていてもよい。これにより、照射窓を保護することができる。とくに、窓部材が耐酸性の劣るベリリウムを用いて形成されている場合、窓部材を酸性の処理液から良好に守ることができる。 The wall surface of the window member on the side where the treatment liquid is present may be coated with a film. Thereby, an irradiation window can be protected. In particular, when the window member is formed using beryllium having poor acid resistance, the window member can be well protected from the acidic treatment liquid.
　この皮膜は、親水性材料を用いて形成されていることが好ましい。この場合、当該皮膜と処理液との間に気泡が混入するのを、抑制または防止することができる。これにより、配管に存在する処理液に対してＸ線を良好に照射することができる。 This film is preferably formed using a hydrophilic material. In this case, it is possible to suppress or prevent air bubbles from being mixed between the film and the treatment liquid. Thereby, it is possible to satisfactorily irradiate X-rays to the processing liquid existing in the pipe.
　この場合、前記皮膜は、ポリイミド樹脂、ダイヤモンドライクカーボン、フッ素樹脂および炭化水素樹脂のうちの１つ以上の材質を含む皮膜であってもよい。 In this case, the film may be a film containing one or more materials of polyimide resin, diamond-like carbon, fluorine resin, and hydrocarbon resin.
　前記Ｘ線照射手段は、前記窓部材に対向して配置される照射窓を有し、Ｘ線を発生するとともに、発生したＸ線を前記照射窓から照射するＸ線発生器を含んでいてもよい。 The X-ray irradiation means may include an X-ray generator that has an irradiation window disposed to face the window member, generates X-rays, and irradiates the generated X-rays from the irradiation window. Good.
　この構成によれば、Ｘ線発生器によって発生されたＸ線が、Ｘ線発生器の照射窓から配管内を流通している処理液に照射される。 According to this configuration, the X-ray generated by the X-ray generator is irradiated to the processing liquid flowing in the pipe from the irradiation window of the X-ray generator.
　前記Ｘ線照射手段は、前記Ｘ線発生器の周囲を、当該Ｘ線発生器と間隔を空けて取り囲むカバーと、前記カバーの内部に気体を供給する気体供給手段とをさらに含んでいてもよい。 The X-ray irradiation means may further include a cover surrounding the X-ray generator with a space from the X-ray generator, and a gas supply means for supplying a gas to the inside of the cover. .
　この構成によれば、Ｘ線発生器の駆動により当該Ｘ線発生器が発熱するおそれがある。カバー内に気体を供給することにより、Ｘ線発生器を冷却し、Ｘ線発生器の周囲雰囲気の昇温を抑制することができる。 According to this configuration, there is a possibility that the X-ray generator generates heat by driving the X-ray generator. By supplying the gas into the cover, the X-ray generator can be cooled, and the temperature rise in the ambient atmosphere of the X-ray generator can be suppressed.
　この発明の一実施形態では、前記配管は、前記処理槽内と連通し、前記処理槽内に処理液を供給するための処理液供給配管を含み、前記Ｘ線照射手段は、前記処理液供給配管を流通している処理液に前記Ｘ線を照射してもよい。 In one embodiment of the present invention, the pipe includes a processing liquid supply pipe that communicates with the inside of the processing tank and supplies a processing liquid into the processing tank, and the X-ray irradiation means includes the processing liquid supply You may irradiate the said process liquid currently distribute | circulating piping.
　また、この発明の別の実施形態では、前記処理槽は、処理液を貯留し、その処理液中に処理対象物を浸漬させる内槽と、前記内槽から溢れる処理液を回収する外槽とを含み、前記配管は、前記外槽に回収された処理液が流通するオーバーフロー配管を含み、前記Ｘ線照射手段は、前記オーバーフロー配管内を流通している処理液に前記Ｘ線を照射してもよい。 Moreover, in another embodiment of this invention, the said processing tank stores the processing liquid, the inner tank which immerses a process target object in the processing liquid, and the outer tank which collect | recovers the processing liquid overflowing from the said inner tank, And the pipe includes an overflow pipe through which the processing liquid collected in the outer tank flows, and the X-ray irradiation means irradiates the processing liquid flowing through the overflow pipe with the X-ray. Also good.
　この発明のさらに別の実施形態では、前記処理槽は、処理液を貯留し、その処理液中に処理対象物を浸漬させる内槽と、前記内槽から溢れる処理液を回収する外槽とを含み、前記Ｘ線照射手段は、前記内槽に貯留されている処理液に前記Ｘ線を照射してもよい。 In still another embodiment of the present invention, the treatment tank includes an inner tank for storing the treatment liquid and immersing the treatment object in the treatment liquid, and an outer tank for recovering the treatment liquid overflowing from the inner tank. In addition, the X-ray irradiation means may irradiate the X-ray to the processing liquid stored in the inner tank.
　この発明のさらに別の実施形態では、前記処理槽は、処理液を貯留し、その処理液中に処理対象物を浸漬させる内槽と、前記内槽から溢れる処理液を回収する外槽とを含み、前記配管は、前記内槽内に内部が連通する配管を含んでいてもよい。 In still another embodiment of the present invention, the treatment tank includes an inner tank for storing the treatment liquid and immersing the treatment object in the treatment liquid, and an outer tank for recovering the treatment liquid overflowing from the inner tank. The pipe may include a pipe that communicates with the inside of the inner tank.
　この発明の第３の局面は、処理槽に貯留された処理液中に処理対象物を浸漬させる処理対象物浸漬工程と、前記処理対象物浸漬工程に並行して、前記処理槽に貯留された処理液、または処理液が内部を流通可能な配管であって、当該内部が前記処理槽内に連通する配管内に存在する処理液に、Ｘ線を照射するＸ線照射工程とを含む、処理液処理方法である。 The third aspect of the present invention is stored in the processing tank in parallel with the processing object immersion step for immersing the processing object in the processing liquid stored in the processing tank and the processing object immersion step. A treatment liquid, or a pipe through which the treatment liquid can flow, and an X-ray irradiation step of irradiating the treatment liquid existing in the pipe communicating with the inside of the treatment tank with X-rays It is a liquid processing method.
　この方法によれば、処理槽に貯留されている処理液、または内部が前記処理槽内に連通する配管内に存在している処理液にＸ線が照射される。当該処理液のうちＸ線が照射される部分（処理液の照射部分）では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this method, X-rays are irradiated to the processing liquid stored in the processing tank or the processing liquid existing inside the piping communicating with the processing tank. In a portion of the treatment liquid that is irradiated with X-rays (treatment liquid irradiation portion), electrons are emitted from the water molecules by excitation of water molecules, and as a result, plasma in which positive ions and electrons of water molecules are mixed. A state is formed.
　処理槽に貯留されている処理液にＸ線が照射される場合、処理槽に貯留されている処理液に浸漬されている処理対象物と処理液の照射部分とが、処理槽に貯留されている処理液を介して繋がっている。このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が処理対象物に向けて、処理槽に貯留されている処理液を介して移動する。これにより、処理対象物に多量の電子が供給される結果、正に帯電している処理対象物が除電される。一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、処理槽に貯留されている処理液を介して移動する。これにより、処理対象物から電子が除去される結果、負に帯電している処理対象物が除電される。 When the processing liquid stored in the processing tank is irradiated with X-rays, the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected through the processing solution. At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object positively charged. It moves through the processing liquid stored in the processing tank. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized. On the other hand, when the processing object is negatively charged, electrons from the processing object move toward the positive ions in the irradiated portion of the processing liquid through the processing liquid stored in the processing tank. Thereby, as a result of removing electrons from the processing object, the processing object that is negatively charged is neutralized.
　また、配管内に存在している処理液にＸ線が照射される場合、処理槽に貯留されている処理液に浸漬されている処理対象物と処理液の照射部分とが、処理槽に貯留されている処理液および配管内の処理液を介して繋がっている。このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が処理対象物に向けて、処理槽に貯留されている処理液および配管内の処理液を介して移動する。これにより、処理対象物に多量の電子が供給される結果、正に帯電している処理対象物が除電される。一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、処理槽に貯留されている処理液および配管内の処理液を介して移動する。これにより、処理対象物から電子が除去される結果、負に帯電している処理対象物が除電される。 Further, when X-rays are irradiated to the processing liquid existing in the pipe, the processing object immersed in the processing liquid stored in the processing tank and the irradiated portion of the processing liquid are stored in the processing tank. It is connected via the processing liquid which has been processed and the processing liquid in the pipe. At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object that is positively charged. It moves through the processing liquid stored in the processing tank and the processing liquid in the pipe. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized. On the other hand, when the object to be processed is negatively charged, electrons from the object to be processed move toward the positive ions in the irradiated portion of the processing liquid through the processing liquid stored in the processing tank and the processing liquid in the pipe. To do. Thereby, as a result of removing electrons from the processing object, the processing object that is negatively charged is neutralized.
　また、処理液への浸漬の前から処理対象物が正または負に帯電している場合にも、前述した原理により、処理槽内の処理液や配管内の処理液を介して、当該処理対象物を除電できる。 In addition, even when the object to be treated is positively or negatively charged before being immersed in the treatment liquid, the treatment object is treated via the treatment liquid in the treatment tank or the treatment liquid in the pipe according to the principle described above. Can neutralize things.
　この発明の第４の局面は、処理槽に貯留された処理液中に処理対象物を浸漬して処理を行うための処理液処理方法であって、前記処理槽に貯留された処理液中に処理対象物を浸漬させる処理対象物浸漬工程と、前記処理対象物浸漬工程に並行して、前記処理槽内に向けて吐出口から処理液を吐出させる処理液吐出工程と、前記処理液吐出工程に並行して、前記吐出口に連通する配管の内部に存在する処理液にＸ線を照射するＸ線照射工程とを含み、前記処理液吐出工程では、前記吐出口と前記処理槽に溜められている処理液の液面との間で処理液が液状に繋がっている、処理液処理方法である。 4th aspect of this invention is the processing liquid processing method for immersing a process target object in the processing liquid stored by the processing tank, and processing, Comprising: In the processing liquid stored by the said processing tank A treatment object immersion step for immersing the treatment object, a treatment liquid discharge step for discharging treatment liquid from a discharge port toward the inside of the treatment tank, and the treatment liquid discharge step in parallel with the treatment object immersion step. In parallel, the X-ray irradiation step of irradiating the processing liquid existing inside the pipe communicating with the discharge port with X-rays is stored in the discharge port and the processing tank in the processing liquid discharge step. This is a processing liquid processing method in which the processing liquid is connected to the liquid surface of the processing liquid.
　この方法によれば、配管内に存在している処理液にＸ線が照射される。また、配管の内部に連通する吐出口から吐出された処理液が処理対象物に供給される。処理液のうちＸ線が照射される部分では、水分子の励起により当該水分子から電子が放出され、その結果、水分子の正イオンと電子とが混在するプラズマ状態が形成される。 According to this method, X-rays are irradiated to the processing liquid existing in the pipe. Further, the processing liquid discharged from the discharge port communicating with the inside of the pipe is supplied to the processing object. In the portion of the treatment liquid that is irradiated with X-rays, electrons are emitted from the water molecules by excitation of the water molecules, and as a result, a plasma state in which positive ions and electrons of the water molecules are mixed is formed.
　吐出口から吐出される処理液は、処理液の液面との間で液状に繋がっている。この場合、処理対象物と処理液の照射部分とが、処理液を介して繋がるようになる。 The processing liquid discharged from the discharge port is connected in liquid form with the liquid surface of the processing liquid. In this case, the processing object and the irradiated portion of the processing liquid are connected via the processing liquid.
　このとき、処理対象物が正に帯電すると、処理液の照射部分と、正に帯電している処理対象物との間の電位差で、処理液の照射部分からの電子が処理対象物に向けて、液状に繋がっている処理液および処理槽に貯留されている処理液を介して移動する。これにより、処理対象物に多量の電子が供給される結果、正に帯電している処理対象物が除電される。一方、処理対象物が負に帯電すると、処理対象物からの電子が、処理液の照射部分の正イオンに向けて、液状に繋がっている処理液および処理槽に貯留されている処理液を介して移動する。これにより、処理対象物から電子が除去される結果、負に帯電している処理対象物が除電される。 At this time, when the processing object is positively charged, electrons from the irradiation part of the processing liquid are directed toward the processing object due to a potential difference between the irradiation part of the processing liquid and the processing object that is positively charged. It moves through the treatment liquid connected to the liquid and the treatment liquid stored in the treatment tank. Thereby, as a result of supplying a large amount of electrons to the processing target, the positively charged processing target is neutralized. On the other hand, when the processing object is negatively charged, electrons from the processing object are directed to the positive ions in the irradiated portion of the processing liquid through the processing liquid connected to the liquid and the processing liquid stored in the processing tank. Move. Thereby, as a result of removing electrons from the processing object, the processing object that is negatively charged is neutralized.
　以上により、処理対象物の帯電防止または除電を図りつつ、当該処理対象物に、処理液を用いた処理を施すことができる。 As described above, the treatment object can be treated with the treatment liquid while preventing or removing the charge of the treatment object.
　本発明における前述の、またはさらに他の目的、特徴および効果は、添付図面を参照して次に述べる実施形態の説明により明らかにされる。 The above-described or other objects, features, and effects of the present invention will be clarified by the following description of embodiments with reference to the accompanying drawings.
本発明の第１実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 1st Embodiment of this invention. 図１に示す一体型ヘッドの図解的な縦断面図である。FIG. 2 is a schematic longitudinal sectional view of the integrated head shown in FIG. 1. 図１に示す基板処理装置の電気的構成を示すブロック図である。It is a block diagram which shows the electric constitution of the substrate processing apparatus shown in FIG. 図１に示す基板処理装置において実行される処理例を示す工程図である。It is process drawing which shows the process example performed in the substrate processing apparatus shown in FIG. 水ノズル内への軟Ｘ線の照射状態を示す図解的な断面図である。It is an illustration sectional view showing the irradiation state of soft X-rays in the water nozzle. 基板にリンス処理を施している状態を示す図である。It is a figure which shows the state which has performed the rinse process to the board | substrate. 図４に示す処理例の変形例を説明するためのフローチャートである。6 is a flowchart for explaining a modification of the processing example shown in FIG. 4. 本発明の第２実施形態に係る一体型ヘッドの構成を模式的に示す図である。It is a figure which shows typically the structure of the integrated head which concerns on 2nd Embodiment of this invention. 図８の切断面線IX－IXから見た断面図である。FIG. 9 is a cross-sectional view taken along section line IX-IX in FIG. 本発明の第３実施形態に係る一体型ヘッドの構成を説明するための図である。It is a figure for demonstrating the structure of the integrated head which concerns on 3rd Embodiment of this invention. 本発明の第４実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 4th Embodiment of this invention. 本発明の第５実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 5th Embodiment of this invention. 本発明の第５実施形態における処理液の吐出について説明する図である。It is a figure explaining discharge of the processing liquid in a 5th embodiment of the present invention. 本発明の第６実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 6th Embodiment of this invention. 本発明の第７実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 7th Embodiment of this invention. 本発明の第８実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 8th Embodiment of this invention. 本発明の第９実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 9th Embodiment of this invention. 本発明の第１０実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 10th Embodiment of this invention. 図１８に示す基板処理装置において、リンス処理時のＤＩＷの流れを示す図である。In the substrate processing apparatus shown in FIG. 18, it is a figure which shows the flow of DIW at the time of a rinse process. 本発明の第１１実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 11th Embodiment of this invention. 図２０に示す水供給ユニットがカップ上部の傾斜部にＤＩＷを供給している状態を示す図である。It is a figure which shows the state which the water supply unit shown in FIG. 20 is supplying DIW to the inclination part of the cup upper part. 本発明の第１２実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 12th Embodiment of this invention. 図２２に示す水供給ユニットが外筒部にＤＩＷを供給している状態を示す図である。It is a figure which shows the state in which the water supply unit shown in FIG. 22 is supplying DIW to an outer cylinder part. 本発明の第１３実施形態に係る基板処理装置の構成を示す図解的な斜視図である。It is a schematic perspective view which shows the structure of the substrate processing apparatus which concerns on 13th Embodiment of this invention. 図２４に示すコロ搬送ユニットの構成を示す斜視図である。It is a perspective view which shows the structure of the roller conveyance unit shown in FIG. 図２４に示す水供給ユニットが基板にＤＩＷを供給している状態を示す断面図である。It is sectional drawing which shows the state in which the water supply unit shown in FIG. 24 is supplying DIW to a board | substrate. 図２４に示す軟Ｘ線照射装置が、基板の上面に軟Ｘ線を照射している状態を示す断面図である。FIG. 25 is a cross-sectional view showing a state in which the soft X-ray irradiation apparatus shown in FIG. 本発明の第１４実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 14th Embodiment of this invention. 図２８に示す基板収容器の構成を示す斜視図である。It is a perspective view which shows the structure of the board | substrate container shown in FIG. 除電試験に用いられる試験装置を説明するための図である。It is a figure for demonstrating the test apparatus used for a static elimination test. 本発明の第１５実施形態に係る基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus which concerns on 15th Embodiment of this invention. 図３１に示す軟Ｘ線照射ヘッドの図解的な縦断面図である。FIG. 32 is a schematic longitudinal sectional view of the soft X-ray irradiation head shown in FIG. 31. 図３１に示す軟Ｘ線照射ヘッドの移動を示す平面図である。FIG. 32 is a plan view showing movement of the soft X-ray irradiation head shown in FIG. 31. 図３１に示す基板処理装置の電気的構成を示すブロック図である。FIG. 32 is a block diagram showing an electrical configuration of the substrate processing apparatus shown in FIG. 31. 図３１に示す基板処理装置において実行される処理例を示す工程図である。FIG. 32 is a process diagram showing an example of processing executed in the substrate processing apparatus shown in FIG. 31. リンス処理を説明するための図解的な図である。It is an illustration figure for demonstrating a rinse process. リンス処理における基板の表面近傍の状態を示す図解的な図である。It is an illustration figure which shows the state of the surface vicinity of the board | substrate in the rinse process. 試験に用いられる試験装置を説明するための図である。It is a figure for demonstrating the testing apparatus used for a test. 本発明の第１６実施形態に係る基板処理装置の構成を模式的に示す図である。It is a figure which shows typically the structure of the substrate processing apparatus which concerns on 16th Embodiment of this invention. 本発明の第１７実施形態に係る基板処理装置の構成を模式的に示す図である。It is a figure which shows typically the structure of the substrate processing apparatus which concerns on 17th Embodiment of this invention. 本発明の第１８実施形態に係る基板処理装置の構成を模式的に示す図である。It is a figure which shows typically the structure of the substrate processing apparatus which concerns on 18th Embodiment of this invention. 本発明の変形例を示す図である（その１）。It is a figure which shows the modification of this invention (the 1). 本発明の変形例を示す図である（その２）。It is a figure which shows the modification of this invention (the 2). 本発明の第１９実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 19th Embodiment of this invention was applied. 図４４に示す分岐配管および軟Ｘ線照射ユニットの構成をそれぞれ示す図解的な断面図である。FIG. 45 is a schematic cross-sectional view illustrating a configuration of a branch pipe and a soft X-ray irradiation unit illustrated in FIG. 44. 図４４に示す基板処理装置において実行される基板処理の処理例を示す工程図である。FIG. 45 is a process diagram illustrating an example of a substrate process performed in the substrate processing apparatus illustrated in FIG. 44. 図４４に示す分岐配管内への軟Ｘ線の照射状態を示す図解図である。It is an illustration figure which shows the irradiation state of the soft X-ray to the branch piping shown in FIG. 本発明の第２０実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 20th Embodiment of this invention was applied. 処理液が内槽の上端部からオーバーフローしている状態を示す模式的な断面図である。It is typical sectional drawing which shows the state which the process liquid has overflowed from the upper end part of the inner tank. 本発明の第２１実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 21st Embodiment of this invention was applied. 本発明の第２２実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 22nd Embodiment of this invention was applied. 本発明の第２３実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 23rd Embodiment of this invention was applied. 本発明の第２４実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 24th Embodiment of this invention was applied. 本発明の第２５実施形態に係る処理液処理装置が適用された基板処理装置の構成を示す図である。It is a figure which shows the structure of the substrate processing apparatus with which the processing liquid processing apparatus which concerns on 25th Embodiment of this invention was applied. 本発明の第２６実施形態に係る処理液処理装置が適用された物品洗浄装置の構成を示す図である。It is a figure which shows the structure of the articles | goods washing apparatus with which the process liquid processing apparatus concerning 26th Embodiment of this invention was applied. 本発明の第２７実施形態に係る処理液処理装置が適用された物品洗浄装置の構成を示す図である。It is a figure which shows the structure of the articles | goods washing apparatus with which the process liquid processing apparatus concerning 27th Embodiment of this invention was applied. 図５５に示す基板収容器の構成を示す斜視図である。It is a perspective view which shows the structure of the board | substrate container shown in FIG.
　図１は、本発明の第１実施形態に係る基板処理装置１の構成を示す図である。 FIG. 1 is a diagram showing a configuration of a substrate processing apparatus 1 according to the first embodiment of the present invention.
　基板処理装置１は、基板（処理対象物）Ｗの一例としての円形の半導体ウエハ（シリコンウエハ）の表面（処理対象面）に処理液（薬液および水）による処理を施すために用いられる枚葉式の装置である。この実施形態では、薬液処理後に行われる基板Ｗのリンスのために水が用いられる。 The substrate processing apparatus 1 is a single wafer used for processing a surface (processing target surface) of a circular semiconductor wafer (silicon wafer) as an example of a substrate (processing target) W with a processing solution (chemical solution and water). Device. In this embodiment, water is used for rinsing the substrate W performed after the chemical treatment.
　基板処理装置１は、隔壁（図示しない）により区画された処理室３内に、基板Ｗを水平姿勢に保持して回転させるスピンチャック（基板保持回転手段）４と、基板Ｗの上面（上側の主面。表面）に、水の一例としてのＤＩＷ（脱イオン水：deionized water）を供給し、かつ基板Ｗに供給する前のＤＩＷに軟Ｘ線を照射するための水供給ユニット（処理液供給装置）１００と、スピンチャック４に保持されている基板Ｗの上面に薬液を供給するための薬液ノズル７とを備えている。 The substrate processing apparatus 1 includes a spin chuck (substrate holding rotating means) 4 for rotating the substrate W in a horizontal posture in a processing chamber 3 partitioned by a partition wall (not shown), and an upper surface (upper side) of the substrate W. Water supply unit (treatment liquid supply) for supplying DIW (deionized water) as an example of water to the main surface and the surface and irradiating the DIW with soft X-rays before being supplied to the substrate W Apparatus) 100 and a chemical nozzle 7 for supplying a chemical to the upper surface of the substrate W held by the spin chuck 4.
　スピンチャック４として、たとえば挟持式のものが採用されている。具体的には、スピンチャック４は、スピンモータ８と、このスピンモータ８の駆動軸と一体化されたスピン軸９と、スピン軸９の上端にほぼ水平に取り付けられた円板状のスピンベース１０と、スピンベース１０の周縁部の複数箇所にほぼ等間隔で設けられた複数個の挟持部材１１とを備えている。これにより、スピンチャック４は、複数個の挟持部材１１によって基板Ｗを挟持した状態で、スピンモータ８の回転駆動力によってスピンベース１０を回転させることにより、その基板Ｗを、ほぼ水平な姿勢を保った状態で、スピンベース１０とともに鉛直な回転軸線Ｃまわりに回転させることができる。 For example, a pinch type is used as the spin chuck 4. Specifically, the spin chuck 4 includes a spin motor 8, a spin shaft 9 integrated with a drive shaft of the spin motor 8, and a disk-shaped spin base attached substantially horizontally to the upper end of the spin shaft 9. 10 and a plurality of clamping members 11 provided at a plurality of positions on the peripheral edge of the spin base 10 at substantially equal intervals. As a result, the spin chuck 4 rotates the spin base 10 by the rotational driving force of the spin motor 8 in a state where the substrate W is sandwiched by the plurality of sandwiching members 11 so that the substrate W is placed in a substantially horizontal posture. In this state, it can be rotated around the vertical rotation axis C together with the spin base 10.
　なお、スピンチャック４としては、挟持式のものに限らず、たとえば基板Ｗの裏面を真空吸着することにより、基板Ｗを水平な姿勢で保持し、さらにその状態で鉛直な回転軸線まわりに回転することにより、その保持した基板Ｗを回転させることができる真空吸着式のもの（バキュームチャック）が採用されてもよい。 Note that the spin chuck 4 is not limited to a sandwiching type, and for example, by vacuum-sucking the back surface of the substrate W, the substrate W is held in a horizontal posture and further rotated around a vertical rotation axis in that state. Thus, a vacuum chucking type (vacuum chuck) that can rotate the held substrate W may be employed.
　スピンチャック４は、カップ（液受け部材）１７内に収容されている。カップ１７は、カップ下部１８と、カップ下部１８の上方に昇降可能に設けられたカップ上部１９とを備えている。 The spin chuck 4 is accommodated in a cup (liquid receiving member) 17. The cup 17 includes a cup lower part 18 and a cup upper part 19 provided so as to be movable up and down above the cup lower part 18.
　カップ下部１８は、中心軸線が回転軸線Ｃと一致する有底円筒状をなしている。カップ下部１８の底面には、排気口（図示しない）が形成されており、基板処理装置１の稼働中は、常時、カップ１７内の雰囲気が排気口から排気されている。 The cup lower part 18 has a bottomed cylindrical shape whose center axis coincides with the rotation axis C. An exhaust port (not shown) is formed on the bottom surface of the cup lower portion 18, and the atmosphere in the cup 17 is always exhausted from the exhaust port while the substrate processing apparatus 1 is in operation.
　カップ上部１９は、カップ下部１８と中心軸線を共通とする円筒状の円筒部２０と、この円筒部２０の上端から円筒部２０の中心軸線に近づくほど高くなるように傾斜する傾斜部２１とを一体的に備えている。カップ上部１９には、カップ上部１９を昇降（上下動）させるためのカップ昇降ユニット２２が結合されている。カップ昇降ユニット２２により、カップ上部１９は、円筒部２０がスピンベース１０の側方に配置される位置と、傾斜部２１の上端がスピンベース１０の下方に配置される位置とに移動される。 The cup upper portion 19 includes a cylindrical cylindrical portion 20 having a central axis common to the cup lower portion 18, and an inclined portion 21 that is inclined so as to increase from the upper end of the cylindrical portion 20 toward the central axis of the cylindrical portion 20. Integrated. A cup elevating unit 22 for moving the cup upper portion 19 up and down (moving up and down) is coupled to the cup upper portion 19. By the cup lifting / lowering unit 22, the cup upper portion 19 is moved to a position where the cylindrical portion 20 is disposed on the side of the spin base 10 and a position where the upper end of the inclined portion 21 is disposed below the spin base 10.
　カップ上部１９およびカップ下部１８は、それぞれ、樹脂材料（たとえばＰＴＦＥ（poly tetra-fluoro ethylene））を用いて形成されている。 The cup upper portion 19 and the cup lower portion 18 are each formed using a resin material (for example, PTFE (polytetrafluoroethylene)).
　薬液ノズル７は、たとえば、連続流の状態で薬液を吐出するストレートノズルであり、スピンチャック４の上方で、その吐出口を基板Ｗの回転中心付近に向けて固定的に配置されている。薬液ノズル７には、薬液供給源からの薬液が供給される薬液供給管１５が接続されている。薬液供給管１５の途中部には、薬液ノズル７からの薬液の供給／供給停止を切り換えるための薬液バルブ１６が介装されている。 The chemical nozzle 7 is, for example, a straight nozzle that discharges chemical liquid in a continuous flow state, and is fixedly disposed above the spin chuck 4 with its discharge port directed toward the rotation center of the substrate W. A chemical liquid supply pipe 15 to which a chemical liquid from a chemical liquid supply source is supplied is connected to the chemical liquid nozzle 7. A chemical solution valve 16 for switching supply / stop of supply of the chemical solution from the chemical solution nozzle 7 is interposed in the middle portion of the chemical solution supply pipe 15.
　また、薬液ノズル７は、スピンチャック４に対して固定的に配置されている必要はなく、たとえば、カップ１７上方において水平面内で揺動可能なアームに取り付けられて、このアームの揺動により基板Ｗの表面における薬液の着液位置がスキャンされる、いわゆるスキャンノズルの形態が採用されてもよい。 The chemical nozzle 7 does not need to be fixedly arranged with respect to the spin chuck 4. For example, the chemical nozzle 7 is attached to an arm that can swing in a horizontal plane above the cup 17, and the substrate is moved by the swing of the arm. A so-called scan nozzle configuration in which the position where the chemical liquid is deposited on the surface of W is scanned may be employed.
　なお、薬液としては、基板Ｗの表面に対する処理の内容に応じたものが用いられる。たとえば、基板Ｗの表面からパーティクルを除去するための洗浄処理を行うときは、ＡＰＭ（ammonia-hydrogen peroxide mixture：アンモニア過酸化水素水混合液）などが用いられる。また、基板Ｗの表面から酸化膜などをエッチングするための洗浄処理を行うときは、フッ酸やBHF（Bufferd HF）、ＴＭＡＨ（水酸化テトラメチルアンモニウム水溶液）などが用いられ、基板Ｗの表面に形成されたレジスト膜を剥離するレジスト剥離処理や、レジスト剥離後の基板Ｗの表面にポリマーとなって残留しているレジスト残渣を除去するためのポリマー除去処理を行うときは、ＳＰＭ（sulfuric acid/hydrogen peroxide mixture：硫酸過酸化水素水混合液）やＡＰＭ（ammonia-hydrogen peroxide mixture：アンモニア過酸化水素水混合液）などのレジスト剥離液やポリマー除去液が用いられる。金属汚染物を除去する洗浄処理には、フッ酸やＨＰＭ（hydrochloric acid/hydrogen peroxide mixture：塩酸過酸化水素水混合液）やＳＰＭ（sulfuric acid/hydrogen peroxide mixture：硫酸過酸化水素水混合液）などが用いられる。 In addition, as the chemical solution, a liquid according to the content of the treatment for the surface of the substrate W is used. For example, when performing a cleaning process for removing particles from the surface of the substrate W, APM (ammonia-hydrogen peroxide mixture) is used. In addition, when performing a cleaning process for etching an oxide film or the like from the surface of the substrate W, hydrofluoric acid, BHF (Bufferd HF), TMAH (tetramethylammonium hydroxide aqueous solution), or the like is used. When performing a resist removal process for removing the formed resist film or a polymer removal process for removing a resist residue remaining as a polymer on the surface of the substrate W after the resist is removed, SPM (sulfuric acid / A resist stripping solution and a polymer removing solution such as hydrogen peroxide mixture (sulfuric acid / hydrogen peroxide mixture) and APM (ammonia-hydrogen peroxide mixture) are used. Cleaning treatment to remove metal contaminants includes hydrofluoric acid, HPM (hydrochloric acid / hydrogen peroxide mixture) and SPM (sulfuric acid / hydrogen peroxide mixture). Is used.
　水供給ユニット１００は、スピンチャック４の上方に対向して配置された一体型ヘッド６を有している。一体型ヘッド６は、水の一例としてのＤＩＷを吐出するための水ノズル（処理液ノズル）６１と、水ノズル６１内を流通する水に軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）６２とを一体的に備えた構成である。軟Ｘ線照射ユニット６２は、水ノズル６１に取り付けられている。水ノズル６１は、たとえば、連続流の状態で薬液を吐出するストレートノズルであり、その吐出口５３を下方に向けた状態で配置されている。水ノズル６１には、ＤＩＷ供給源からのＤＩＷが供給される水供給配管１３が接続されている。水供給配管１３の途中部には、水ノズル６１からのＤＩＷの供給／供給停止を切り換えるための水バルブ１４が介装されている。軟Ｘ線照射ユニット６２については後述する。 The water supply unit 100 has an integrated head 6 disposed so as to face the upper side of the spin chuck 4. The integrated head 6 includes a water nozzle (treatment liquid nozzle) 61 for discharging DIW as an example of water, and a soft X-ray irradiation unit (for irradiating soft X-rays to water flowing through the water nozzle 61). X-ray irradiation means) 62 is integrally provided. The soft X-ray irradiation unit 62 is attached to the water nozzle 61. The water nozzle 61 is, for example, a straight nozzle that discharges a chemical solution in a continuous flow state, and is disposed with its discharge port 53 facing downward. The water nozzle 61 is connected to a water supply pipe 13 to which DIW from a DIW supply source is supplied. A water valve 14 for switching supply / stop of supply of DIW from the water nozzle 61 is interposed in the middle of the water supply pipe 13. The soft X-ray irradiation unit 62 will be described later.
　図２は、一体型ヘッド６の図解的な縦断面図である。 FIG. 2 is a schematic longitudinal sectional view of the integrated head 6.
　一体型ヘッド６の水ノズル６１は、鉛直方向に延びる丸管状（円筒状）の第１ノズル配管５１を有している。第１ノズル配管５１は、たとえば塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。第１ノズル配管５１の先端部（下端部）には、丸型の吐出口５３が開口している。第１ノズル配管５１には、途中部の管壁に、たとえば円形の第１開口５２が形成されている。第１ノズル配管５１には、第１開口５２を塞ぐように軟Ｘ線照射ユニット６２が取り付けられている。一体型ヘッド６は、スピンチャック４による基板Ｗの回転軸線Ｃの上方で、その吐出口５３を下方（基板Ｗの回転中心付近）に向けて固定的に配置されている。 The water nozzle 61 of the integrated head 6 has a first nozzle pipe 51 having a round tubular shape (cylindrical shape) extending in the vertical direction. The first nozzle pipe 51 is formed using, for example, a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). ing. A round discharge port 53 is opened at the front end (lower end) of the first nozzle pipe 51. In the first nozzle pipe 51, for example, a circular first opening 52 is formed in the middle pipe wall. A soft X-ray irradiation unit 62 is attached to the first nozzle pipe 51 so as to close the first opening 52. The integrated head 6 is fixedly disposed above the rotation axis C of the substrate W by the spin chuck 4 with its discharge port 53 directed downward (near the rotation center of the substrate W).
　第１ノズル配管５１の先端部には、円環状の電極５６が外嵌固定されている。この電極５６には、電源５７（図３参照）によって装置グラウンドに対する電圧が印加され、これによって電極５６付近を通過する処理液に対して電界が印加されるようになっている。 An annular electrode 56 is fitted and fixed to the tip of the first nozzle pipe 51. A voltage with respect to the apparatus ground is applied to the electrode 56 by a power source 57 (see FIG. 3), whereby an electric field is applied to the processing liquid passing near the electrode 56.
　軟Ｘ線照射ユニット６２は、軟Ｘ線発生器（Ｘ線発生器）２５と、軟Ｘ線発生器２５の周囲を取り囲むように覆うたとえば塩ビ(poly-vinyl-chloride)製のカバー２６と、カバー２６の内部に気体を供給するための気体ノズル（気体供給手段）２７とを備え、横向きに軟Ｘ線を照射する。カバー２６は、軟Ｘ線発生器２５の周囲を、軟Ｘ線発生器２５と間隔を空けて取り囲む横長の矩形箱状のものであり、鉛直板状の横壁２６Ａにおいて、軟Ｘ線発生器２５の次に述べる照射窓３５に対向する部分に、第１開口５２と同径を有するたとえば円形の第２開口２８を形成している。軟Ｘ線照射ユニット６２は、カバー２６の第２開口２８が、第１ノズル配管５１の第１開口５２に一致し、かつ横壁２６Ａが第１ノズル配管５１の外周に密着するように、ノズル配管５１に取り付けられる。 The soft X-ray irradiation unit 62 includes a soft X-ray generator (X-ray generator) 25, a cover 26 made of, for example, polyvinyl-chloride covering the periphery of the soft X-ray generator 25, A gas nozzle (gas supply means) 27 for supplying a gas to the inside of the cover 26 is provided, and soft X-rays are irradiated sideways. The cover 26 has a horizontally long rectangular box shape surrounding the soft X-ray generator 25 with a space from the soft X-ray generator 25. For example, a circular second opening 28 having the same diameter as the first opening 52 is formed in a portion facing the irradiation window 35 described next. The soft X-ray irradiation unit 62 includes a nozzle pipe so that the second opening 28 of the cover 26 coincides with the first opening 52 of the first nozzle pipe 51 and the lateral wall 26A is in close contact with the outer periphery of the first nozzle pipe 51. 51 is attached.
　第２開口２８は、円板状の窓部材７１によって閉塞されている。窓部材７１は、カバー２６の内側から第２開口２８を閉塞する。窓部材７１により、第２開口２８だけでなく、第１開口５２も閉塞される。窓部材７１の材料として、透過力の弱い軟Ｘ線が透過し易いように原子量の小さい物質が使用され、たとえばベリリウム（Ｂｅ）が採用されている。窓部材７１の厚みは、たとえば0.3mm程度に設定されている。 The second opening 28 is closed by a disk-shaped window member 71. The window member 71 closes the second opening 28 from the inside of the cover 26. The window member 71 closes not only the second opening 28 but also the first opening 52. As the material of the window member 71, a substance having a small atomic weight is used so that soft X-rays having a low penetrating power are easily transmitted. For example, beryllium (Be) is adopted. The thickness of the window member 71 is set to about 0.3 mm, for example.
　軟Ｘ線発生器２５は、第１ノズル配管５１を通る処理液を電離させるために用いられる軟Ｘ線を射出（放射）する。軟Ｘ線発生器２５は、ケース体２９と、軟Ｘ線を発生させるための左右に長い軟Ｘ線管３０と、軟Ｘ線管３０に高電圧を供給する高電圧ユニット３１とを備えている。ケース体２９は、その内部に、軟Ｘ線管３０および高電圧ユニット３１を収容する横長の矩形筒状のものであり、導電性および熱伝導性を有する材料（たとえばアルミニウム等の金属材料）を用いて形成されている。 The soft X-ray generator 25 emits (radiates) soft X-rays used to ionize the processing liquid passing through the first nozzle pipe 51. The soft X-ray generator 25 includes a case body 29, a soft X-ray tube 30 that is long to generate soft X-rays, and a high voltage unit 31 that supplies a high voltage to the soft X-ray tube 30. Yes. The case body 29 is in the shape of a horizontally long rectangular tube that accommodates the soft X-ray tube 30 and the high voltage unit 31, and is made of a material having conductivity and heat conductivity (for example, a metal material such as aluminum). It is formed using.
　高電圧ユニット３１は、たとえば-9.5kVという高電位の駆動電圧を軟Ｘ線管３０に入力する。高電圧ユニット３１には、カバー２６に形成された貫通孔４２を通してカバー２６外に引き出された給電線４３を介して電源（図示しない）からの電圧が供給されている。 The high voltage unit 31 inputs a drive voltage having a high potential of −9.5 kV, for example, to the soft X-ray tube 30. The high voltage unit 31 is supplied with a voltage from a power source (not shown) through a feed line 43 drawn out of the cover 26 through a through hole 42 formed in the cover 26.
　軟Ｘ線管３０は、ガラス製または金属製の円筒形状の真空管からなり、管方向が水平となるように配置されている。軟Ｘ線管３０の一端部（開口端部。図２に示す左端部）は円形開口４１を形成している。軟Ｘ線管３０の他端部（図２に示す右端部）は閉じており、ステム３２となっている。軟Ｘ線管３０内には、陰極であるフィラメント３３と、陽極であるターゲット３６とが対向するように配置されている。軟Ｘ線管３０は、フィラメント３３およびフォーカス３４を収容している。具体的には、ステム３２に、カソードとしてのフィラメント３３が配置されている。フィラメント３３は、高電圧ユニット３１と電気的に接続されている。フィラメント３３は円筒状のフォーカス３４によって取り囲まれている。 The soft X-ray tube 30 is made of a glass or metal cylindrical vacuum tube, and is arranged so that the tube direction is horizontal. One end (opening end, left end shown in FIG. 2) of the soft X-ray tube 30 forms a circular opening 41. The other end of the soft X-ray tube 30 (the right end shown in FIG. 2) is closed and serves as a stem 32. In the soft X-ray tube 30, a filament 33 serving as a cathode and a target 36 serving as an anode are disposed so as to face each other. The soft X-ray tube 30 houses a filament 33 and a focus 34. Specifically, a filament 33 as a cathode is disposed on the stem 32. The filament 33 is electrically connected to the high voltage unit 31. The filament 33 is surrounded by a cylindrical focus 34.
　軟Ｘ線管３０の開口端部は、鉛直姿勢をなす板状の照射窓３５によって閉塞されている。照射窓３５はたとえば円板状をなし、銀ロウ付けによって軟Ｘ線管３０の開口端部の壁面に固定されている。照射窓３５の材料として、透過力の弱い軟Ｘ線が透過し易いように原子量の小さい物質が使用され、たとえばベリリウム（Ｂｅ）が採用されている。照射窓３５の厚みは、たとえば0.3mm程度に設定されている。照射窓３５は、窓部材７１の内面７１Ａに対向して、当該窓部材７１と微小の間隔を空けて配置されている。 The open end of the soft X-ray tube 30 is closed by a plate-shaped irradiation window 35 having a vertical posture. The irradiation window 35 has a disk shape, for example, and is fixed to the wall surface of the open end of the soft X-ray tube 30 by silver brazing. As the material of the irradiation window 35, a substance having a small atomic weight is used so that soft X-rays having a low transmission power can be easily transmitted. For example, beryllium (Be) is adopted. The thickness of the irradiation window 35 is set to about 0.3 mm, for example. The irradiation window 35 faces the inner surface 71 </ b> A of the window member 71 and is arranged at a minute distance from the window member 71.
　照射窓３５の内面３５Ａには、金属製のターゲット３６が蒸着によって形成されている。ターゲット３６には、タングステン（Ｗ）やタンタル（Ｔａ）等の原子量の大きく融点の高い金属が用いられる。 A metal target 36 is formed on the inner surface 35A of the irradiation window 35 by vapor deposition. For the target 36, a metal having a high atomic weight and a high melting point such as tungsten (W) or tantalum (Ta) is used.
　高電圧ユニット３１からの駆動電圧が陰極であるフィラメント３３に印加されることにより、フィラメント３３が電子を放出する。フィラメント３３から放出された電子は、フォーカス３４で収束されて電子ビームとなり、ターゲット３６に衝突することによって軟Ｘ線が発生する。発生した軟Ｘ線は照射窓３５から横方向（図２に示す左方）に向けて射出（放射）され、窓部材７１および第１開口５２を通して第１ノズル配管５１の内部を照射する。照射窓３５からの軟Ｘ線の照射角（照射範囲）は、図５に示すように広角（たとえば130°）である。照射窓３５から第１ノズル配管５１の内部に照射される軟Ｘ線は、その波長がたとえば0.13～0.4nmである。 When the drive voltage from the high voltage unit 31 is applied to the filament 33 which is a cathode, the filament 33 emits electrons. The electrons emitted from the filament 33 are converged by the focus 34 to become an electron beam and collide with the target 36 to generate soft X-rays. The generated soft X-rays are emitted (radiated) from the irradiation window 35 in the lateral direction (leftward in FIG. 2), and irradiate the inside of the first nozzle pipe 51 through the window member 71 and the first opening 52. The soft X-ray irradiation angle (irradiation range) from the irradiation window 35 is a wide angle (for example, 130 °) as shown in FIG. Soft X-rays irradiated from the irradiation window 35 into the first nozzle pipe 51 have a wavelength of, for example, 0.13 to 0.4 nm.
　窓部材７１の外表面（閉塞窓における処理液が流通する側の壁面）７１Ｂの全域は、親水性皮膜（皮膜）３８によって被覆されている。親水性皮膜３８は、たとえばポリイミド樹脂皮膜である。窓部材７１の外表面７１Ｂを親水性皮膜３８で覆ったのは、耐酸性の劣るベリリウム製の窓部材７１を、水等の処理液に含まれる酸から守るためのものである。親水性皮膜３８の膜厚は、50μm以下であり、とくに10μm程度であることが好ましい。親水性皮膜３８が親水性を有しているので、皮膜３８とＤＩＷとの間に気泡が混入するのを、抑制または防止することができる。これにより、照射窓３５からの軟Ｘ線を、第１ノズル配管５１を流通しているＤＩＷに対して良好に照射できる。 The entire outer surface of the window member 71 (the wall surface on the side where the treatment liquid flows in the closed window) 71B is covered with a hydrophilic film (film) 38. The hydrophilic film 38 is, for example, a polyimide resin film. The reason why the outer surface 71B of the window member 71 is covered with the hydrophilic film 38 is to protect the window member 71 made of beryllium having poor acid resistance from an acid contained in a treatment liquid such as water. The film thickness of the hydrophilic film 38 is 50 μm or less, and preferably about 10 μm. Since the hydrophilic film 38 has hydrophilicity, it is possible to suppress or prevent air bubbles from being mixed between the film 38 and DIW. Thereby, the soft X-rays from the irradiation window 35 can be favorably irradiated to the DIW flowing through the first nozzle pipe 51.
　気体ノズル２７の吐出口は、カバー２６の横壁に開口している。気体ノズル２７には気体バルブ（気体供給手段）３７を介して気体供給源（図示しない）からの気体が供給されている。気体ノズル２７が吐出する気体として、ＣＤＡ（低湿度の清浄空気）や窒素ガス等の不活性ガスを例示できる。気体ノズル２７から吐出された気体は、カバー２６の内部に供給される。軟Ｘ線発生器２５の駆動により当該軟Ｘ線発生器２５が発熱するおそれがあるが、カバー２６の内部に気体を供給することにより、軟Ｘ線発生器２５を冷却し、軟Ｘ線発生器２５の周囲雰囲気の昇温を抑制できる。 The discharge port of the gas nozzle 27 opens in the horizontal wall of the cover 26. Gas from a gas supply source (not shown) is supplied to the gas nozzle 27 via a gas valve (gas supply means) 37. Examples of the gas discharged from the gas nozzle 27 include CDA (clean air with low humidity) and inert gas such as nitrogen gas. The gas discharged from the gas nozzle 27 is supplied into the cover 26. There is a possibility that the soft X-ray generator 25 generates heat by driving the soft X-ray generator 25. However, by supplying gas into the cover 26, the soft X-ray generator 25 is cooled to generate soft X-rays. The temperature rise in the ambient atmosphere of the vessel 25 can be suppressed.
　図３は、基板処理装置１の電気的構成を示すブロック図である。基板処理装置１は、さらに、マイクロコンピュータを含む構成の制御装置（Ｘ線照射制御手段）４０を備えている。制御装置４０には、カップ昇降ユニット２２、スピンモータ８、高電圧ユニット３１、薬液バルブ１６、水バルブ１４、電源５７ 、気体バルブ３７等が制御対象として接続されている。 FIG. 3 is a block diagram showing an electrical configuration of the substrate processing apparatus 1. The substrate processing apparatus 1 further includes a control device (X-ray irradiation control means) 40 having a configuration including a microcomputer. The control device 40 is connected with a cup lifting unit 22, a spin motor 8, a high voltage unit 31, a chemical liquid valve 16, a water valve 14, a power source 57, a gas valve 37, and the like as control targets.
　なお、カバー２６内の熱を逃がすために、基板処理装置１に電源が投入されている間、気体バルブ３７は常に開放されている。 Note that the gas valve 37 is always open while the substrate processing apparatus 1 is powered on in order to release the heat in the cover 26.
　図４は、基板処理装置１において実行される基板Ｗの処理例を示す工程図である。この処理例では、薬液処理の実行後、リンス処理が実行される。図１、図３および図４を参照しながら、基板処理装置１における基板Ｗの処理について説明する。 FIG. 4 is a process diagram showing a processing example of the substrate W executed in the substrate processing apparatus 1. In this process example, the rinse process is performed after the chemical process. The processing of the substrate W in the substrate processing apparatus 1 will be described with reference to FIGS. 1, 3, and 4.
　基板Ｗの処理に際して、搬送ロボット（図示しない）によって、未処理の基板Ｗが処理室３内に搬入されて（ステップＳ１）、その表面を上方に向けた状態でスピンチャック４に受け渡される。 When processing the substrate W, an unprocessed substrate W is carried into the processing chamber 3 by a transfer robot (not shown) (step S1), and is transferred to the spin chuck 4 with its surface facing upward.
　スピンチャック４に基板Ｗが保持された後、制御装置４０はスピンモータ８を制御して、スピンチャック４による基板Ｗの回転を開始させる（ステップＳ２）。基板Ｗの回転速度が所定の液処理速度（たとえば500rpm）まで上げられ、その後、その液処理速度に維持される。 After the substrate W is held on the spin chuck 4, the control device 40 controls the spin motor 8 to start the rotation of the substrate W by the spin chuck 4 (step S2). The rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
　基板Ｗの回転速度が液処理速度に達すると、制御装置４０は薬液バルブ１６を開いて、薬液ノズル７から基板Ｗの上面の回転中心に向けて薬液を吐出する。基板上面Ｗの上面に供給された薬液は、基板Ｗの回転による遠心力を受けて、基板Ｗの周縁に向けて流れる（基板Ｗの全域へと拡がる）。これにより、基板Ｗの表面の全域に薬液による処理が施される（Ｓ３：薬液処理）。 When the rotation speed of the substrate W reaches the liquid processing speed, the control device 40 opens the chemical liquid valve 16 and discharges the chemical liquid from the chemical liquid nozzle 7 toward the rotation center of the upper surface of the substrate W. The chemical solution supplied to the upper surface of the substrate upper surface W receives centrifugal force due to the rotation of the substrate W and flows toward the periphery of the substrate W (spreads over the entire area of the substrate W). Thereby, the process by a chemical | medical solution is given to the whole surface of the board | substrate W (S3: Chemical process).
　薬液の供給開始から所定の薬液処理時間が経過すると、制御装置４０は薬液バルブ１６が閉じ、薬液ノズル７からの薬液の供給を停止する。 When a predetermined chemical solution processing time has elapsed from the start of the supply of the chemical solution, the control device 40 closes the chemical solution valve 16 and stops the supply of the chemical solution from the chemical solution nozzle 7.
　また、制御装置４０は水バルブ１４を開いて、回転状態にある基板Ｗの上面の回転中心に向けて、一体型ヘッド６の水ノズル６１からＤＩＷを吐出する（ステップＳ４）。 Further, the control device 40 opens the water valve 14 and discharges DIW from the water nozzle 61 of the integrated head 6 toward the rotation center of the upper surface of the substrate W in a rotating state (step S4).
　水バルブ１４を開成してから所定時間（たとえば２秒間）経過すると、軟Ｘ線照射タイミングになる。この所定時間は、第１ノズル配管５１の内部に十分にＤＩＷが充たされてから、軟Ｘ線の照射が開始されるように設けられている。軟Ｘ線照射タイミングになると、制御装置４０は高電圧ユニット３１を制御して、軟Ｘ線照射ユニット６２の軟Ｘ線発生器２５に軟Ｘ線を発生させて、この軟Ｘ線を、照射窓３５から窓部材７１を介して、第１ノズル配管５１の内部に向けて照射させる（ステップＳ５）。これにより、第１ノズル配管５１内を流通しているＤＩＷに、軟Ｘ線が照射される。 When a predetermined time (for example, 2 seconds) elapses after the water valve 14 is opened, the soft X-ray irradiation timing comes. The predetermined time is provided so that soft X-ray irradiation is started after DIW is sufficiently filled in the first nozzle pipe 51. When the soft X-ray irradiation timing comes, the control device 40 controls the high voltage unit 31 to generate soft X-rays in the soft X-ray generator 25 of the soft X-ray irradiation unit 62 and irradiates the soft X-rays. Irradiation from the window 35 to the inside of the first nozzle pipe 51 through the window member 71 (step S5). Thereby, soft X-rays are irradiated to DIW which distribute | circulates the inside of the 1st nozzle piping 51. FIG.
　図５は、水ノズル６１内への軟Ｘ線の照射状態を示す図解的な断面図である。 FIG. 5 is a schematic cross-sectional view showing a state of soft X-ray irradiation into the water nozzle 61.
　リンス処理中は、水ノズル６１の第１ノズル配管５１内を流通しているＤＩＷに軟Ｘ線が照射される。また、吐出口５３から吐出された処理液が基板Ｗの上面に供給される。第１ノズル配管５１内のＤＩＷのうち軟Ｘ線が照射される部分（第１ノズル配管５１内の第１開口５２に対向する部分。図５に示す網掛け部分。以下、「ＤＩＷの照射部分５４」という。）では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、ＤＩＷの照射部分５４に形成される。 During the rinsing process, the soft X-rays are irradiated to the DIW flowing through the first nozzle pipe 51 of the water nozzle 61. Further, the processing liquid discharged from the discharge port 53 is supplied to the upper surface of the substrate W. Of the DIW in the first nozzle pipe 51, the part irradiated with soft X-rays (the part facing the first opening 52 in the first nozzle pipe 51. The shaded part shown in FIG. 5. 54 "), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 54 of DIW.
　図６は、基板Ｗにリンス処理を施している状態を示す図である。 FIG. 6 is a diagram showing a state where the substrate W is rinsed.
　基板Ｗの上面に供給されたＤＩＷは、基板Ｗの回転による遠心力を受けて、基板Ｗの周縁部に向けて流れる（基板Ｗの全域へと拡がる）。これにより、基板Ｗの上面の全域に、当該上面に接液するＤＩＷの液膜６３が形成される。ＤＩＷの液膜６３によって、基板Ｗの上面に付着している薬液が洗い流される。 The DIW supplied to the upper surface of the substrate W receives centrifugal force due to the rotation of the substrate W and flows toward the peripheral edge of the substrate W (spreads over the entire area of the substrate W). Thus, a DIW liquid film 63 in contact with the upper surface is formed over the entire upper surface of the substrate W. The chemical solution adhering to the upper surface of the substrate W is washed away by the liquid film 63 of DIW.
　リンス処理中における、水ノズル６１に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、水ノズル６１の吐出口５３から吐出されるＤＩＷの態様が、吐出口５３と基板Ｗの上面のＤＩＷの液膜６３との双方に繋がる連続流状をなしており、また、第１ノズル配管５１内では、ＤＩＷが液密状態にある。このとき、ＤＩＷの液膜６３とＤＩＷの照射部分５４とが、ＤＩＷを介して繋がっている。 During the rinsing process, the DIW supply flow rate to the water nozzle 61 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the form of DIW discharged from the discharge port 53 of the water nozzle 61 forms a continuous flow connected to both the discharge port 53 and the DIW liquid film 63 on the upper surface of the substrate W, and the first nozzle In the pipe 51, DIW is in a liquid-tight state. At this time, the DIW liquid film 63 and the DIW irradiated portion 54 are connected via the DIW.
　図５および図６に示すように、基板Ｗが正に帯電すると、ＤＩＷの照射部分５４と、正に帯電している基板Ｗとの間の電位差で、ＤＩＷの照射部分５４からの電子が、基板Ｗの上面のＤＩＷの液膜６３に向けて、連続流状のＤＩＷを伝って移動する。これにより、基板Ｗの上面のＤＩＷの液膜６３が多量の電子を有するようになるので、正に帯電している基板Ｗが除電される。 As shown in FIGS. 5 and 6, when the substrate W is positively charged, electrons from the DIW irradiated portion 54 are caused by a potential difference between the DIW irradiated portion 54 and the positively charged substrate W. It moves along the continuous flow of DIW toward the DIW liquid film 63 on the upper surface of the substrate W. As a result, the DIW liquid film 63 on the upper surface of the substrate W has a large amount of electrons, so that the positively charged substrate W is discharged.
　これにより、回転状態の基板ＷにＤＩＷが供給されても、処理液との接触分離による基板の帯電を生じない。したがって、リンス処理時における基板Ｗの帯電を防止できる。また、リンス処理前から基板Ｗが帯電していても、その基板Ｗに帯びた電荷を除去（すなわち、除電）できる。その結果、基板Ｗの帯電に起因するデバイス破壊を防止できる。 Thereby, even if DIW is supplied to the rotating substrate W, the substrate is not charged by contact separation with the processing liquid. Therefore, charging of the substrate W during the rinsing process can be prevented. Further, even if the substrate W is charged before the rinsing process, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
　以上により、基板Ｗの帯電防止または除電を図りつつ、当該基板Ｗにリンス処理を施すことができる。 As described above, the substrate W can be subjected to the rinsing process while preventing or eliminating the charge of the substrate W.
　また、軟Ｘ線の照射によってＤＩＷの液性は変化しないので、炭酸水等の酸性の処理液を用いて基板Ｗを処理する場合とは異なり、基板Ｗ上のデバイスに悪影響を与えるおそれがない。 Moreover, since the liquid property of DIW does not change by irradiation with soft X-rays, unlike the case where the substrate W is processed using an acidic processing solution such as carbonated water, there is no possibility of adversely affecting the devices on the substrate W. .
　また、軟Ｘ線照射ユニット６２による軟Ｘ線の照射に併せて、電源５７の電極５６に対し印加する。この場合、電極５６は正電荷に帯電されることが好ましい。この場合、電極５６の正電荷によって、軟Ｘ線の照射によりＤＩＷの照射部分５４中に発生した電子は、電極５６側に引っ張られ、電極５６のある第１ノズル配管５１（水ノズル６１）の先端部まで移動するようになる。すなわち、多量の電子を、水ノズル６１の吐出口５３に向けて引っ張ることができる。これにより、基板Ｗ側への電子の移動を促進させることができる。 Also, in conjunction with the soft X-ray irradiation by the soft X-ray irradiation unit 62, it is applied to the electrode 56 of the power source 57. In this case, the electrode 56 is preferably charged to a positive charge. In this case, the electrons generated in the DIW irradiated portion 54 due to the soft X-ray irradiation due to the positive charge of the electrode 56 are pulled toward the electrode 56, and the first nozzle pipe 51 (water nozzle 61) with the electrode 56 is provided. It moves to the tip. That is, a large amount of electrons can be pulled toward the discharge port 53 of the water nozzle 61. Thereby, the movement of the electrons to the substrate W side can be promoted.
　図１、図３および図４に示すように、ＤＩＷの供給開始から所定のリンス時間が経過すると、制御装置４０は、水バルブ１４を閉じてＤＩＷを供給停止し（ステップＳ６）、かつ高電圧ユニット３１を制御して、軟Ｘ線照射ユニット６２の照射窓３５からの軟Ｘ線の照射を停止させる（ステップＳ７）。また、制御装置４０は、軟Ｘ線照射ユニット６２からの軟Ｘ線の照射停止に併せて、電極５６への電界の印加も停止する。 As shown in FIG. 1, FIG. 3, and FIG. 4, when a predetermined rinsing time has elapsed from the start of DIW supply, the control device 40 closes the water valve 14 to stop supplying DIW (step S6), and the high voltage The unit 31 is controlled to stop the soft X-ray irradiation from the irradiation window 35 of the soft X-ray irradiation unit 62 (step S7). The control device 40 also stops the application of the electric field to the electrode 56 in conjunction with the stop of the soft X-ray irradiation from the soft X-ray irradiation unit 62.
　その後、制御装置４０は、スピンモータ８を制御して、基板Ｗの回転速度をスピンドライ回転速度（たとえば2500rpm）に上昇させる。これにより、リンス処理後の基板Ｗの上面に付着しているＤＩＷが遠心力で振り切られて乾燥される（Ｓ８：スピンドライ（乾燥処理））。 Thereafter, the control device 40 controls the spin motor 8 to increase the rotation speed of the substrate W to a spin dry rotation speed (for example, 2500 rpm). Thereby, DIW adhering to the upper surface of the substrate W after the rinsing process is shaken off by the centrifugal force and dried (S8: spin dry (drying process)).
　スピンドライが所定の乾燥時間にわたって行われると、スピンチャック４の回転が停止される。その後、処理済の基板Ｗが搬送ロボット（図示しない）によって処理室３から搬出される（ステップＳ９）。 When the spin drying is performed for a predetermined drying time, the rotation of the spin chuck 4 is stopped. Thereafter, the processed substrate W is unloaded from the processing chamber 3 by a transfer robot (not shown) (step S9).
　以上により第１実施形態によれば、水ノズル６１の第１ノズル配管５１内を流通しているＤＩＷに軟Ｘ線が照射される。これにより、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、ＤＩＷの照射部分５４に形成される。これらの電子が、連続流状のＤＩＷを伝ってＤＩＷの液膜６３に移動し、その結果、当該ＤＩＷの液膜６３が多量の電子を有するようになる。そのため、回転状態の基板ＷにＤＩＷが供給されても、ＤＩＷとの接触分離による基板Ｗの帯電を生じない。したがって、リンス処理時における基板Ｗの帯電を防止できる。また、リンス処理前から基板Ｗが帯電していても、その基板Ｗに帯びた電荷を除去（すなわち、除電）できる。その結果、基板Ｗの帯電に起因するデバイス破壊を防止できる。 As described above, according to the first embodiment, soft X-rays are irradiated to the DIW flowing through the first nozzle pipe 51 of the water nozzle 61. Thereby, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 54 of DIW. These electrons travel along the continuous flow DIW and move to the DIW liquid film 63, and as a result, the DIW liquid film 63 has a large amount of electrons. For this reason, even if DIW is supplied to the rotating substrate W, charging of the substrate W due to contact separation with DIW does not occur. Therefore, charging of the substrate W during the rinsing process can be prevented. Further, even if the substrate W is charged before the rinsing process, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
　また、軟Ｘ線の照射によってＤＩＷの液性は変化しないので、炭酸水等の酸性の処理液を用いて基板Ｗを処理する場合とは異なり、基板Ｗ上のデバイスに悪影響を与えるおそれがない。 Moreover, since the liquid property of DIW does not change by irradiation with soft X-rays, unlike the case where the substrate W is processed using an acidic processing solution such as carbonated water, there is no possibility of adversely affecting the devices on the substrate W. .
　図７は、図４に示す処理例の変形例を説明するためのフローチャートである。 FIG. 7 is a flowchart for explaining a modification of the processing example shown in FIG.
　図７に示す変形例では、前述の軟Ｘ線照射タイミングになったとき、第１ノズル配管５１の第１開口５２付近にＤＩＷが存在するときには、軟Ｘ線照射ユニット６２による軟Ｘ線の照射を実行し、第１ノズル配管５１の第１開口５２付近にＤＩＷが存在しないときには、軟Ｘ線照射ユニット６２による軟Ｘ線の照射を行わない。以下、具体的に説明する。 In the modification shown in FIG. 7, when the soft X-ray irradiation timing is reached and the DIW exists in the vicinity of the first opening 52 of the first nozzle pipe 51, soft X-ray irradiation by the soft X-ray irradiation unit 62 is performed. When the DIW is not present near the first opening 52 of the first nozzle pipe 51, the soft X-ray irradiation by the soft X-ray irradiation unit 62 is not performed. This will be specifically described below.
　図１に二点鎖線で示すように、水供給ユニット１００では、水ノズル６１の第１ノズル配管５１に、第１ノズル配管５１内のＤＩＷの存否を所定の水検出位置１０２で検出するための液検出センサ（処理液検出手段）１０１が配置されている。水検出位置１０２は、第１ノズル配管５１の流通方向に関し、第１開口（開口、軟Ｘ線の照射位置）５２（図２参照）と同じ位置かあるいは第１開口５２に近い位置に設定されている。 As shown by a two-dot chain line in FIG. 1, the water supply unit 100 detects the presence / absence of DIW in the first nozzle pipe 51 at the predetermined water detection position 102 in the first nozzle pipe 51 of the water nozzle 61. A liquid detection sensor (processing liquid detection means) 101 is disposed. The water detection position 102 is set to the same position as the first opening (opening, soft X-ray irradiation position) 52 (see FIG. 2) or a position close to the first opening 52 with respect to the flow direction of the first nozzle pipe 51. ing.
　液検出センサ１０１は、たとえば静電容量型のセンサによって構成されており、第１ノズル配管５１の外周壁（図示しない）に直付け配置または近接配置されている。液検出センサ１０１は、水検出位置１０２の周囲の第１ノズル配管５１内のＤＩＷの存否を検出し、その検出結果に応じた信号を出力するものである。第１ノズル配管５１の第１開口５２付近にＤＩＷが存在するとき、ＤＩＷが検出され、一方、第１ノズル配管５１の第１開口５２付近にＤＩＷが存在しないとき、ＤＩＷが検出されないことになる。 The liquid detection sensor 101 is constituted by, for example, a capacitance type sensor, and is directly attached to or arranged close to the outer peripheral wall (not shown) of the first nozzle pipe 51. The liquid detection sensor 101 detects the presence or absence of DIW in the first nozzle pipe 51 around the water detection position 102 and outputs a signal corresponding to the detection result. When DIW is present near the first opening 52 of the first nozzle pipe 51, DIW is detected. On the other hand, when DIW is not present near the first opening 52 of the first nozzle pipe 51, DIW is not detected. .
　また、液検出センサ１０１として、光学式（例えば発光ダイオードと受光素子を組み合わせ、気体と液体の屈折率差を利用した）センサや導電率センサが採用されても良い。 Further, as the liquid detection sensor 101, an optical sensor (for example, a combination of a light emitting diode and a light receiving element and using a difference in refractive index between gas and liquid) or a conductivity sensor may be employed.
　前述の軟Ｘ線照射タイミングになったとき（ステップＳ１１でＹＥＳ）、制御装置４０は、液検出センサ１０１の検出出力を参照して、第１開口５２付近にＤＩＷがあるか否か（液ありか液なしか）を調べる（ステップＳ１２）。第１開口５２付近にＤＩＷがある場合には（ステップＳ１２でＹＥＳ）、制御装置４０は、軟Ｘ線照射ユニット６２によるＸ線照射を開始する（ステップＳ１３）。一方、第１開口５２付近にＤＩＷが存在しない場合（ステップＳ１２でＮＯ）や、軟Ｘ線照射タイミングになっていない場合（ステップＳ１１でＮＯ）には、軟Ｘ線照射ユニット６２によるＸ線照射が開始されないまま、その後図７の処理がリターンされる。 When the soft X-ray irradiation timing is reached (YES in step S11), the control device 40 refers to the detection output of the liquid detection sensor 101 to determine whether there is DIW near the first opening 52 (with liquid). Whether or not there is liquid is checked (step S12). If there is DIW near the first opening 52 (YES in step S12), the control device 40 starts X-ray irradiation by the soft X-ray irradiation unit 62 (step S13). On the other hand, when DIW is not present near the first opening 52 (NO in step S12) or when the soft X-ray irradiation timing is not reached (NO in step S11), X-ray irradiation by the soft X-ray irradiation unit 62 is performed. Then, the process of FIG. 7 is returned.
　この場合、第１開口５２付近にＤＩＷが存在しないときには、第１開口５２に対する軟Ｘ線の照射が禁止される。これにより、第１ノズル配管５１外への軟Ｘ線の漏れを抑制または防止できる。 In this case, when there is no DIW near the first opening 52, the soft X-ray irradiation to the first opening 52 is prohibited. Thereby, the leakage of the soft X-rays to the outside of the first nozzle pipe 51 can be suppressed or prevented.
　なお、液検出センサ１０１は、水供給ユニット１００と同等の構成が採用される水供給ユニット２３０，２５０，６００（図１５（ａ），１５（ｂ）、図１６、図２８参照）においても採用可能である。この場合、図７に示す処理を実行できる。 The liquid detection sensor 101 is also used in water supply units 230, 250, and 600 (see FIGS. 15A, 15B, 16, and 28) in which the same configuration as the water supply unit 100 is adopted. Is possible. In this case, the process shown in FIG. 7 can be executed.
　図８は、本発明の第２実施形態に係る一体型ヘッド６Ａの構成を模式的に示す図である。図９は、図８の切断面線IX－IXから見た断面図である。 FIG. 8 is a diagram schematically showing the configuration of an integrated head 6A according to the second embodiment of the present invention. FIG. 9 is a cross-sectional view taken along section line IX-IX in FIG.
　一体型ヘッド６Ａが、第１実施形態に係る一体型ヘッド６と共通する部分には、図１～図６の場合と同一の参照符号を付し説明を省略する。一体型ヘッド６Ａが一体型ヘッド６と相違する主たる点は、水ノズル６１に、先端部が扁平状をなす第１ノズル配管５１Ａを用いた点である。先端部を除く領域の第１ノズル配管５１Ａは、第１ノズル配管５１と同様、丸管状（円筒状）を有している。また、第１ノズル配管５１Ａは第１ノズル配管５１と同様、鉛直方向に延び、また塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。 In the integrated head 6A, parts common to the integrated head 6 according to the first embodiment are denoted by the same reference numerals as in FIGS. 1 to 6, and description thereof is omitted. The main point that the integrated head 6A differs from the integrated head 6 is that a first nozzle pipe 51A having a flat tip is used for the water nozzle 61. Similar to the first nozzle pipe 51, the first nozzle pipe 51 </ b> A in the region excluding the tip has a round tubular shape (cylindrical shape). Similarly to the first nozzle pipe 51, the first nozzle pipe 51A extends in the vertical direction, and also includes polyvinyl-chloride, PTFE (polytetrafluorofluoroethylene), PFA (perfluoro-alkylvinyl-ether-tetrafluoro). -ethlene-copolymer) and the like.
　第１ノズル配管５１Ａの先端部には、その断面略長方形の扁平部１５１が形成されている。扁平部１５１は、丸管を熱成形により変形させたものである。一対の平坦壁部１５２，１５３間の幅Ｗ１はたとえば5～10mm程度に設定されている。一方の平坦壁部１５２には、第１ノズル配管５１Ａの途中部には、たとえば円形の第３開口（開口、Ｘ線の照射位置）５２Ａが形成されている。第１ノズル配管５１Ａには、第３開口５２Ａを塞ぐように軟Ｘ線照射ユニット６２が取り付けられている。具体的には、軟Ｘ線照射ユニット６２は、カバー２６Ａの第２開口２８が、第１ノズル配管５１Ａの第３開口５２Ａに一致し、かつ横壁２６Ａが第１ノズル配管５１Ａの外周に密着するように、第１ノズル配管５１Ａに取り付けられている。 A flat portion 151 having a substantially rectangular cross section is formed at the tip of the first nozzle pipe 51A. The flat portion 151 is obtained by deforming a round tube by thermoforming. A width W1 between the pair of flat wall portions 152 and 153 is set to about 5 to 10 mm, for example. In one flat wall portion 152, for example, a circular third opening (opening, X-ray irradiation position) 52A is formed in the middle of the first nozzle pipe 51A. A soft X-ray irradiation unit 62 is attached to the first nozzle pipe 51A so as to close the third opening 52A. Specifically, in the soft X-ray irradiation unit 62, the second opening 28 of the cover 26A coincides with the third opening 52A of the first nozzle pipe 51A, and the lateral wall 26A is in close contact with the outer periphery of the first nozzle pipe 51A. Thus, it is attached to the first nozzle pipe 51A.
　扁平部１５１の幅Ｗ１は、扁平部１５１にＤＩＷが満たされている状態で、軟Ｘ線照射ユニット６２の照射窓３５から照射される軟Ｘ線が、他方の平坦壁部１５３まで届く程度の幅に設定されている。そのため、軟Ｘ線照射ユニット６２からの軟Ｘ線が、第１ノズル配管５１Ａの扁平部１５１を流通するＤＩＷの全てに照射される。これにより、ＤＩＷの照射部分５４を広範囲に保つことができるから、基板Ｗの上面のＤＩＷの液膜６３に含まれる電子の量を、より一層増やすことができる。これにより、ＤＩＷとの接触分離による基板Ｗの帯電の発生をより確実に抑制することができ、また、リンス処理前から基板Ｗが帯電していても、その基板Ｗをより確実に除電できる。 The width W1 of the flat portion 151 is such that soft X-rays irradiated from the irradiation window 35 of the soft X-ray irradiation unit 62 reach the other flat wall portion 153 in a state where the flat portion 151 is filled with DIW. The width is set. Therefore, the soft X-rays from the soft X-ray irradiation unit 62 are irradiated to all the DIWs that flow through the flat portion 151 of the first nozzle pipe 51A. Thereby, since the irradiation part 54 of DIW can be maintained in a wide range, the amount of electrons contained in the DIW liquid film 63 on the upper surface of the substrate W can be further increased. As a result, the occurrence of charging of the substrate W due to contact separation with DIW can be more reliably suppressed, and even if the substrate W is charged before the rinsing process, the substrate W can be more reliably discharged.
　図１０（ａ），１０（ｂ）は、本発明の第３実施形態に係る一体型ヘッド６Ｂの構成を説明するための図である。図１０（ａ）は、リンス処理中における一体型ヘッド６Ｂの要部の断面図を示し、図１０（ｂ）は、図１０（ａ）を下方から見た図である。 10 (a) and 10 (b) are diagrams for explaining the configuration of an integrated head 6B according to a third embodiment of the present invention. FIG. 10A is a cross-sectional view of the main part of the integrated head 6B during the rinsing process, and FIG. 10B is a view of FIG. 10A viewed from below.
　一体型ヘッド６Ｂでは、水ノズル６１の第１ノズル配管５１の吐出口５３に
、多数本の紐状繊維を束ねて構成した繊維束（繊維状物質）６５が取り付けられている。繊維束６５は、第１ノズル配管５１の長手方向に沿う中心軸線を有する円柱状をなしている。第１ノズル配管５１の吐出口５３からの繊維束６５の突出長さは、スピンチャック４に保持された基板Ｗと吐出口５３との間の間隔と同程度に設定されている。 In the integrated head 6 </ b> B, a fiber bundle (fibrous substance) 65 configured by bundling a large number of string-like fibers is attached to the discharge port 53 of the first nozzle pipe 51 of the water nozzle 61. The fiber bundle 65 has a cylindrical shape having a central axis along the longitudinal direction of the first nozzle pipe 51. The protruding length of the fiber bundle 65 from the discharge port 53 of the first nozzle pipe 51 is set to be approximately the same as the interval between the substrate W held by the spin chuck 4 and the discharge port 53.
　リンス処理時には、第１ノズル配管５１の吐出口５３から吐出されるＤＩＷは、繊維束６５に含まれる多数本の繊維を伝って下方に向けて流れる。繊維束６５の先端は、基板Ｗの上面に形成されるＤＩＷの液膜６３に接触し、当該液膜６３中を漂っている。繊維束６５が、吐出口５３からＤＩＷの液膜６３までＤＩＷを良好に導くので、吐出口５３から吐出されるＤＩＷの態様を、吐出口５３とＤＩＷの液膜６３との双方に繋がる連続流状に維持し易い。 During the rinsing process, DIW discharged from the discharge port 53 of the first nozzle pipe 51 flows downward along a large number of fibers included in the fiber bundle 65. The tip of the fiber bundle 65 is in contact with the DIW liquid film 63 formed on the upper surface of the substrate W, and floats in the liquid film 63. Since the fiber bundle 65 leads the DIW well from the discharge port 53 to the DIW liquid film 63, the DIW mode discharged from the discharge port 53 is a continuous flow that connects both the discharge port 53 and the DIW liquid film 63. Easy to maintain.
　そして、吐出口５３からのＤＩＷの吐出流量が少流量である場合でも、吐出口５３から吐出されるＤＩＷの態様を、前記の連続流状に維持できる。これにより、ＤＩＷの消費量を低減しつつ、基板Ｗの帯電防止や基板Ｗの除電を図ることができる。なお、リンス処理時において、繊維束６５の先端が、液膜６３だけでなく、基板Ｗの上面に接触していてもよい。 And even when the discharge flow rate of DIW from the discharge port 53 is a small flow rate, the mode of DIW discharged from the discharge port 53 can be maintained in the above-described continuous flow state. Accordingly, it is possible to prevent the substrate W from being charged and to remove the charge from the substrate W while reducing the consumption of DIW. Note that the tip of the fiber bundle 65 may be in contact with the upper surface of the substrate W in addition to the liquid film 63 during the rinsing process.
　なお、第１ノズル配管５１Ａ（図８参照）の先端部に、繊維束６５を設けることも可能である。また、水供給ユニット１００と同等の構成が採用される水供給ユニット２３０，２５０，６００（図１５（ａ），１５（ｂ）、図１６、図２８参照）において、第１ノズル配管５１の先端部に、繊維束６５を設けることも可能である。 In addition, it is also possible to provide the fiber bundle 65 at the tip of the first nozzle pipe 51A (see FIG. 8). Further, in the water supply units 230, 250, and 600 (see FIGS. 15A, 15B, 16 and 28) in which the same configuration as the water supply unit 100 is adopted, the tip of the first nozzle pipe 51 is used. It is also possible to provide a fiber bundle 65 in the part.
　また、第３実施形態において、水ノズル６１の第１ノズル配管５１の吐出口５３に取り付けられる繊維状物質として、多数本の紐状繊維を束ねて構成した繊維束６５を例に挙げて説明したが、繊維状物質は、多数本の紐状繊維を束ねて構成するものに限られるものではなく、たとえば１本の太い紐状繊維から構成されていてもよいし、紐状ではなく布状の繊維によって構成されていてもよい。 Further, in the third embodiment, as the fibrous material attached to the discharge port 53 of the first nozzle pipe 51 of the water nozzle 61, the fiber bundle 65 configured by bundling a large number of string-like fibers has been described as an example. However, the fibrous substance is not limited to a structure in which a large number of string-like fibers are bundled. For example, the fibrous substance may be constituted by a single thick string-like fiber, or a cloth-like material instead of a string-like material. You may be comprised with the fiber.
　図１１は、本発明の第４実施形態に係る基板処理装置２０１の構成を示す図である。 FIG. 11 is a diagram showing a configuration of a substrate processing apparatus 201 according to the fourth embodiment of the present invention.
　第４実施形態において、第１実施形態と共通する部分には、図１～図６の場合と同一の参照符号を付し説明を省略する。基板処理装置２０１では、第１実施形態に係る水供給ユニット１００（図１参照）に代えて、ノズルと軟Ｘ線照射ユニットとが別個に設けられた水供給ユニット（処理液供給装置）２００が設けられている。 In the fourth embodiment, parts common to the first embodiment are denoted by the same reference numerals as those in FIGS. 1 to 6 and description thereof is omitted. In the substrate processing apparatus 201, instead of the water supply unit 100 (see FIG. 1) according to the first embodiment, a water supply unit (processing liquid supply apparatus) 200 in which a nozzle and a soft X-ray irradiation unit are separately provided is provided. Is provided.
　水供給ユニット２００は、水ノズル２０２と、水ノズル２０２に対し、ＤＩＷ供給源からのＤＩＷ（水の一例）を供給する水供給配管（処理液配管）２０４と、水供給配管２０４内に存在しているＤＩＷに軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）２０３とを含む。軟Ｘ線照射ユニット２０３は、水供給配管２０４に取り付けられている。 The water supply unit 200 exists in the water nozzle 202, a water supply pipe (treatment liquid pipe) 204 that supplies DIW (an example of water) from the DIW supply source to the water nozzle 202, and the water supply pipe 204. And a soft X-ray irradiation unit (X-ray irradiation means) 203 for irradiating the DIW with soft X-rays. The soft X-ray irradiation unit 203 is attached to the water supply pipe 204.
　水ノズル２０２は、丸管状（円筒状）のノズル配管を有しており、水供給配管２０４の先端に取り付けられている。水ノズル２０２は、連続流の状態で液を吐出するストレートノズルによって構成されていて、その吐出口２０２Ａを、基板Ｗの上面中央部に向けた状態で、処理室３内に固定的に配置されている。水ノズル２０２は、第１開口５２（図２参照）が形成されていない点を除いて、第１実施形態の水ノズル６１（図２参照）と同等の構成を採用している。すなわち、水ノズル２０２のノズル配管の先端部には、円環状の電極５６が外嵌固定されており、かつ電極５６には、電源５７（図３参照）によって装置グラウンドに対する電圧が印加されるようになっている。 The water nozzle 202 has a round tubular (cylindrical) nozzle pipe, and is attached to the tip of the water supply pipe 204. The water nozzle 202 is configured by a straight nozzle that discharges liquid in a continuous flow state, and the water nozzle 202 is fixedly disposed in the processing chamber 3 with the discharge port 202A directed toward the center of the upper surface of the substrate W. ing. The water nozzle 202 has the same configuration as the water nozzle 61 (see FIG. 2) of the first embodiment except that the first opening 52 (see FIG. 2) is not formed. That is, an annular electrode 56 is fitted and fixed to the tip of the nozzle pipe of the water nozzle 202, and a voltage with respect to the apparatus ground is applied to the electrode 56 by a power source 57 (see FIG. 3). It has become.
　水供給配管２０４は、丸管状（円筒状）をなしている。水供給配管２０４は、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。水供給配管２０４の途中部の管壁には、開口（図示しない）が形成されている。 The water supply pipe 204 has a round tubular shape (cylindrical shape). The water supply pipe 204 is formed using a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). . An opening (not shown) is formed in the tube wall in the middle of the water supply pipe 204.
　軟Ｘ線照射ユニット２０３は、第１実施形態に係る軟Ｘ線照射ユニット６２（図２参照）と同等の構成を採用している。軟Ｘ線照射ユニット２０３は、水供給配管２０４の開口を塞ぐように水供給配管２０４に取り付けられている。具体的には、軟Ｘ線照射ユニット２０３のカバーの開口（軟Ｘ線照射ユニット６２のカバー２６の第２開口２８（図２参照）に相当する開口）が水供給配管２０４の前記の開口に一致し、かつ軟Ｘ線照射ユニット２０３のカバーの壁面（軟Ｘ線照射ユニット６２のカバー２６の横壁２６Ａ（図２参照）に相当）が水供給配管２０４の外周に密着している。軟Ｘ線照射ユニット２０３の高電圧ユニット（第１実施形態に係る軟Ｘ線照射ユニット６２の高電圧ユニット３１（図２参照）に相当）は、制御装置４０（図３参照）に接続されている。 The soft X-ray irradiation unit 203 adopts the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment. The soft X-ray irradiation unit 203 is attached to the water supply pipe 204 so as to close the opening of the water supply pipe 204. Specifically, the opening of the cover of the soft X-ray irradiation unit 203 (the opening corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is the opening of the water supply pipe 204. The wall surface of the cover of the soft X-ray irradiation unit 203 (corresponding to the lateral wall 26A (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is in close contact with the outer periphery of the water supply pipe 204. The high voltage unit of the soft X-ray irradiation unit 203 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
　水供給配管２０４には、水供給配管２０４を開閉するための水バルブ２０５が介装されている。水バルブ２０５が開かれると、水供給配管２０４から水ノズル２０２にＤＩＷが供給され、また、水バルブ２０５が閉じられると、水供給配管２０４から水ノズル２０２へのＤＩＷの供給が停止される。水バルブ２０５は、制御装置４０（図３参照）に接続されている。 The water supply pipe 204 is provided with a water valve 205 for opening and closing the water supply pipe 204. When the water valve 205 is opened, DIW is supplied from the water supply pipe 204 to the water nozzle 202, and when the water valve 205 is closed, the supply of DIW from the water supply pipe 204 to the water nozzle 202 is stopped. The water valve 205 is connected to the control device 40 (see FIG. 3).
　基板処理装置２０１では、図４に示す処理例の場合と同様の処理が実施される。リンス処理（図４のステップＳ４～Ｓ６）では、制御装置４０（図３参照）は、水バルブ２０５を開く。これにより、水供給配管２０４を流通するＤＩＷが水ノズル２０２に供給される。水ノズル２０２の吐出口２０２Ａから、回転状態にある基板Ｗの上面の回転中心に向けて、ＤＩＷが吐出される。 In the substrate processing apparatus 201, the same processing as in the processing example shown in FIG. 4 is performed. In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 205. Thereby, DIW flowing through the water supply pipe 204 is supplied to the water nozzle 202. DIW is discharged from the discharge port 202A of the water nozzle 202 toward the rotation center of the upper surface of the substrate W in a rotating state.
　また、水バルブ２０５の開成後所定時間経過して軟Ｘ線照射タイミングになると、制御装置４０は、軟Ｘ線照射ユニット２０３の高電圧ユニットを制御して、軟Ｘ線照射ユニット２０３の軟Ｘ線発生器（第１実施形態に係る軟Ｘ線照射ユニット６２の軟Ｘ線発生器２５（図２参照）に相当）に軟Ｘ線を発生させて、この軟Ｘ線を、水供給配管２０４の内部に向けて照射させる。これにより、水供給配管２０４内を流通しているＤＩＷに、軟Ｘ線が照射される。 In addition, when a predetermined time elapses after the opening of the water valve 205 and the soft X-ray irradiation timing is reached, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 203 so that the soft X-ray irradiation unit 203 has a soft X-ray irradiation timing. A soft X-ray is generated in a X-ray generator (corresponding to the soft X-ray generator 25 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment), and the soft X-ray is supplied to the water supply pipe 204. Irradiate the inside. Thereby, soft X-rays are irradiated to DIW which distribute | circulates the inside of the water supply piping 204. FIG.
　基板Ｗの上面に供給されたＤＩＷは、基板Ｗの回転による遠心力を受けて、基板Ｗの周縁に向けて流れる（基板Ｗの全域へと拡がる）。これにより、基板Ｗの上面の全域にＤＩＷの液膜が形成される。ＤＩＷの液膜によって、基板Ｗの上面に付着している薬液が洗い流される。 The DIW supplied to the upper surface of the substrate W receives a centrifugal force due to the rotation of the substrate W and flows toward the periphery of the substrate W (spreads over the entire area of the substrate W). As a result, a DIW liquid film is formed over the entire upper surface of the substrate W. The chemical liquid adhering to the upper surface of the substrate W is washed away by the liquid film of DIW.
　リンス処理中における、水ノズル２０２に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、水ノズル２０２の吐出口２０２Ａから吐出されるＤＩＷの態様が、吐出口２０２Ａと基板Ｗの上面のＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。また、水ノズル２０２のノズル配管内および水供給配管２０４内では、ＤＩＷが液密状態にある。 During the rinsing process, the DIW supply flow rate to the water nozzle 202 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 202A of the water nozzle 202 is a continuous flow mode connected to both the discharge port 202A and the DIW liquid film on the upper surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 202 and the water supply pipe 204.
　リンス処理中に、水供給配管２０４内を流通しているＤＩＷに軟Ｘ線が照射されると、水供給配管２０４内におけるＤＩＷの照射部分（図５に示す、第１実施形態に係るＤＩＷの照射部分５４と同等の部分）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、水供給配管２０４内におけるＤＩＷの照射部分に形成される。ＤＩＷの照射部分は、基板Ｗの上面に形成されたＤＩＷの液膜と、ＤＩＷを介して繋がっている。 During the rinsing process, when soft X-rays are irradiated to the DIW flowing through the water supply pipe 204, the DIW irradiated portion in the water supply pipe 204 (shown in FIG. 5 of the DIW according to the first embodiment) In a portion equivalent to the irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water supply pipe 204. The DIW irradiated portion is connected to the DIW liquid film formed on the upper surface of the substrate W via the DIW.
　基板Ｗが正に帯電すると、水供給配管２０４内におけるＤＩＷの照射部分と、正に帯電している基板Ｗとの間の電位差で、水供給配管２０４内におけるＤＩＷの照射部分からの電子が、基板Ｗの上面のＤＩＷの液膜に向けて、連続流状のＤＩＷを伝って移動する。これにより、基板Ｗの上面のＤＩＷの液膜が多量の電子を有するようになる。 When the substrate W is positively charged, electrons from the DIW irradiated portion in the water supply pipe 204 are caused by a potential difference between the DIW irradiated portion in the water supply pipe 204 and the positively charged substrate W. It moves along the continuous flow DIW toward the DIW liquid film on the upper surface of the substrate W. Thus, the DIW liquid film on the upper surface of the substrate W has a large amount of electrons.
　以上により、第４実施形態においても、第１実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, also in the fourth embodiment, the same effects as those described in the first embodiment can be obtained.
　図１２は、本発明の第５実施形態に係る基板処理装置２１１の構成を示す図である。 FIG. 12 is a diagram showing a configuration of a substrate processing apparatus 211 according to the fifth embodiment of the present invention.
　基板処理装置２１１が、第４実施形態に係る基板処理装置２０１と共通する部分には、図１１の場合と同一の参照符号を付し説明を省略する。基板処理装置２１１が基板処理装置２０１と相違する点は、水ノズル２０２（図１１参照）に代えて、複数の吐出口２１６を有する水ノズル２１２を設けた点である。 Parts common to the substrate processing apparatus 201 according to the fourth embodiment are denoted by the same reference numerals as those in FIG. The difference between the substrate processing apparatus 211 and the substrate processing apparatus 201 is that a water nozzle 212 having a plurality of discharge ports 216 is provided instead of the water nozzle 202 (see FIG. 11).
　水ノズル２１２は、丸管状（円筒状）のノズル配管からなる本体部２１３と、本体部２１３の先端部に、水平方向に並んで配置された複数（図１２ではたとえば３つ）の吐出口部２１５と、本体部２１３の内部空間と個々の吐出口部２１５の内部空間とを連通する連通部２１４とを含む。個々の吐出口部２１５は、吐出口２１６を有している。個々の吐出口部２１５は、連続流の状態で液を吐出するストレートノズルによって構成されている。各吐出口部２１５には、電極５６が外嵌固定されている。水ノズル２１２は、複数の吐出口２１６を、基板Ｗの上面中央部に向けた状態で、処理室３内に固定的に配置されている。水ノズル２１２の本体部２１３に、水供給配管２０４が接続されている。 The water nozzle 212 includes a main body 213 formed of a round tubular (cylindrical) nozzle pipe, and a plurality of (for example, three in FIG. 12) discharge port portions arranged in the horizontal direction at the tip of the main body 213. 215 and a communication part 214 that communicates the internal space of the main body part 213 and the internal space of each discharge port part 215. Each discharge port portion 215 has a discharge port 216. Each discharge port portion 215 is configured by a straight nozzle that discharges liquid in a continuous flow state. An electrode 56 is fitted and fixed to each discharge port portion 215. The water nozzle 212 is fixedly disposed in the processing chamber 3 with the plurality of discharge ports 216 directed toward the center of the upper surface of the substrate W. A water supply pipe 204 is connected to the main body 213 of the water nozzle 212.
　リンス処理中は、水ノズル２１２にＤＩＷ（水の一例）が供給され、水ノズル２１２の各吐出口２１６から、ＤＩＷが吐出される。リンス処理中には、基板Ｗの上面の全域にＤＩＷの液膜が形成される。また、リンス処理中には、図１２に示すように、個々の吐出口２１６から吐出されるＤＩＷの態様が、吐出口２１６と基板Ｗの上面のＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。また、水ノズル２１２のノズル配管内および水供給配管２０４内では、ＤＩＷが液密状態にある。 During the rinsing process, DIW (an example of water) is supplied to the water nozzle 212, and DIW is discharged from each discharge port 216 of the water nozzle 212. During the rinsing process, a DIW liquid film is formed over the entire upper surface of the substrate W. Further, during the rinsing process, as shown in FIG. 12, the DIW mode discharged from the individual discharge ports 216 is a continuous flow that leads to both the discharge port 216 and the DIW liquid film on the upper surface of the substrate W. The aspect is made. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 212 and the water supply pipe 204.
　ところで、基板処理装置２１１では、少なくとも１つの吐出口２１６から吐出されるＤＩＷの態様が、当該吐出口２１６と基板Ｗの上面のＤＩＷの液膜との双方に繋がる連続流状をなしていればよい。換言すると、水ノズル２１２のノズル配管内と、基板Ｗの上面のＤＩＷの液膜とが、少なくとも１本の連続流６４Ａ（図１３参照）によって繋がっていればよい。 By the way, in the substrate processing apparatus 211, if the aspect of DIW discharged from at least one discharge port 216 has a continuous flow shape connected to both the discharge port 216 and the DIW liquid film on the upper surface of the substrate W. Good. In other words, the nozzle pipe of the water nozzle 212 and the DIW liquid film on the upper surface of the substrate W need only be connected by at least one continuous flow 64A (see FIG. 13).
　具体的には、図１３に示すように、複数の吐出口２１６のうち１つの吐出口２１６Ａにおいて、当該吐出口２１６と基板Ｗの上面のＤＩＷの液膜との双方に繋がる連続流状をなしているが、その他の吐出口２１６Ｂ，２１６Ｃでは連続流状をなしていない場合を考える。このとき、吐出口２１６Ｂや吐出口２１６Ｃからは、ＤＩＷが液滴の態様で吐出されているか、あるいはＤＩＷが吐出されていない。 Specifically, as shown in FIG. 13, in one of the plurality of discharge ports 216, one discharge port 216A has a continuous flow shape connected to both the discharge port 216 and the DIW liquid film on the upper surface of the substrate W. However, let us consider a case where the other discharge ports 216B and 216C do not form a continuous flow. At this time, DIW is ejected in the form of droplets from the ejection port 216B and the ejection port 216C, or DIW is not ejected.
　図１３に示すような場合であっても、水ノズル２１２のノズル配管内と、基板Ｗの上面のＤＩＷの液膜とが、少なくとも１本の連続流６４Ａによって繋がっている。そのため、基板Ｗが正に帯電すると、水供給配管２０４内におけるＤＩＷの照射部分からの電子が、基板Ｗの上面のＤＩＷの液膜６３に向けて、この１本の連続流６４Ａを伝って移動する。これにより、基板Ｗの帯電防止や基板Ｗの除電を図ることができる。 Even in the case shown in FIG. 13, the nozzle pipe of the water nozzle 212 and the DIW liquid film on the upper surface of the substrate W are connected by at least one continuous flow 64A. Therefore, when the substrate W is positively charged, electrons from the DIW irradiated portion in the water supply pipe 204 move along the single continuous flow 64A toward the DIW liquid film 63 on the upper surface of the substrate W. To do. As a result, it is possible to prevent the substrate W from being charged and to neutralize the substrate W.
　図１４は、本発明の第６実施形態に係る基板処理装置２２１の構成を示す図である。 FIG. 14 is a diagram showing a configuration of a substrate processing apparatus 221 according to the sixth embodiment of the present invention.
　基板処理装置２２１が、第４実施形態に係る基板処理装置２０１と共通する部分には、図１１の場合と同一の参照符号を付し説明を省略する。基板処理装置２２１では、水供給ユニット２００に代えて、水供給ユニット（処理液供給装置）２２０が設けられている。 The parts common to the substrate processing apparatus 201 according to the fourth embodiment are denoted by the same reference numerals as those in FIG. In the substrate processing apparatus 221, a water supply unit (processing liquid supply apparatus) 220 is provided instead of the water supply unit 200.
　水供給ユニット２２０は、水ノズル２０２と、水供給配管２０４と、水供給配管２０４の途中部から分岐する第１分岐配管（分岐配管）２２２と、第１分岐配管２２２内に存在しているＤＩＷ（水の一例）に軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）２２３とを含む。軟Ｘ線照射ユニット２２３は、第１分岐配管２２２に取り付けられている。すなわち、水供給ユニット２２０では、水供給配管２０４ではなく第１分岐配管２２２に、軟Ｘ線照射ユニット２２３が取り付けられている。 The water supply unit 220 includes a water nozzle 202, a water supply pipe 204, a first branch pipe (branch pipe) 222 that branches from the middle of the water supply pipe 204, and a DIW present in the first branch pipe 222. (An example of water) includes a soft X-ray irradiation unit (X-ray irradiation means) 223 for irradiating soft X-rays. The soft X-ray irradiation unit 223 is attached to the first branch pipe 222. That is, in the water supply unit 220, the soft X-ray irradiation unit 223 is attached to the first branch pipe 222 instead of the water supply pipe 204.
　第１分岐配管２２２は、水供給配管２０４において水バルブ２０５よりも上流側の部分から分岐している。第１分岐配管２２２は、丸管状（円筒状）をなし、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。第１分岐配管２２２の途中部には、第１分岐配管２２２を開閉するための分岐バルブ２２５が介装されている。分岐バルブ２２５は、制御装置４０（図３参照）に接続されている。第１分岐配管２２２には、分岐バルブ２２５よりも上流側の所定部分の管壁に開口（図示しない）が形成されている。 The first branch pipe 222 branches from the upstream side of the water valve 205 in the water supply pipe 204. The first branch pipe 222 is a round tube (cylindrical), such as poly-vinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer), etc. These resin materials are used. A branch valve 225 for opening and closing the first branch pipe 222 is interposed in the middle of the first branch pipe 222. The branch valve 225 is connected to the control device 40 (see FIG. 3). In the first branch pipe 222, an opening (not shown) is formed in a predetermined portion of the pipe wall upstream of the branch valve 225.
　第１分岐配管２２２の下流端には、第１カップ用ノズル２２４が取り付けられている。第１カップ用ノズル２２４は、連続流の状態で液を吐出するストレートノズルによって構成されていて、その吐出口（液受け用吐出口）２２４Ａを、カップ上部１９の外壁（たとえば傾斜部２１の上面）に向けた状態で、処理室３内におけるカップ上部１９の上方に、固定的に配置されている。 A first cup nozzle 224 is attached to the downstream end of the first branch pipe 222. The first cup nozzle 224 is constituted by a straight nozzle that discharges liquid in a continuous flow state. The discharge port (liquid receiving discharge port) 224A is connected to the outer wall of the cup upper portion 19 (for example, the upper surface of the inclined portion 21). ) And is fixedly disposed above the cup upper portion 19 in the processing chamber 3.
　軟Ｘ線照射ユニット２２３は、第１実施形態に係る軟Ｘ線照射ユニット６２（図２参照）と同等の構成を採用している。軟Ｘ線照射ユニット２２３は、第１分岐配管２２２の開口を塞ぐように第１分岐配管２２２に取り付けられている。具体的には、軟Ｘ線照射ユニット２２３のカバーの開口（軟Ｘ線照射ユニット６２のカバー２６の第２開口２８（図２参照）に相当）が第１分岐配管２２２の前記の開口に一致し、かつ軟Ｘ線照射ユニット２２３のカバーの壁面（軟Ｘ線照射ユニット６２のカバー２６の横壁２６Ａ（図２参照）に相当）が第１分岐配管２２２の外周に密着している。軟Ｘ線照射ユニット２２３の高電圧ユニット（第１実施形態に係る軟Ｘ線照射ユニット６２の高電圧ユニット３１（図２参照）に相当）は、制御装置４０（図３参照）に接続されている。 The soft X-ray irradiation unit 223 employs the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment. The soft X-ray irradiation unit 223 is attached to the first branch pipe 222 so as to close the opening of the first branch pipe 222. Specifically, the opening of the cover of the soft X-ray irradiation unit 223 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is aligned with the opening of the first branch pipe 222. In addition, the wall surface of the cover of the soft X-ray irradiation unit 223 (corresponding to the lateral wall 26A of the cover 26 of the soft X-ray irradiation unit 62 (see FIG. 2)) is in close contact with the outer periphery of the first branch pipe 222. The high voltage unit of the soft X-ray irradiation unit 223 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
　分岐バルブ２２５が閉じられた状態で水バルブ２０５を開くと、水供給配管２０４から水ノズル２０２にＤＩＷが供給されて、水ノズル２０２の吐出口２０２ＡからＤＩＷが吐出される。水バルブ２０５が閉じられた状態で分岐バルブ２２５を開くと、第１分岐配管２２２から第１カップ用ノズル２２４にＤＩＷが供給されて、第１カップ用ノズル２２４の吐出口２２４ＡからＤＩＷが吐出される。 When the water valve 205 is opened while the branch valve 225 is closed, DIW is supplied from the water supply pipe 204 to the water nozzle 202, and DIW is discharged from the discharge port 202A of the water nozzle 202. When the branch valve 225 is opened with the water valve 205 closed, DIW is supplied from the first branch pipe 222 to the first cup nozzle 224, and DIW is discharged from the discharge port 224A of the first cup nozzle 224. The
　ところで、カップ昇降ユニット２２によりカップ上部１９が昇降するため、カップ１７（とくにカップ上部１９）が帯電していることが考えられる。そのため、基板Ｗに対する処理の実行に先立って、カップ上部１９を除電する必要がある。 Incidentally, since the cup upper part 19 is moved up and down by the cup elevating unit 22, the cup 17 (particularly the cup upper part 19) may be charged. For this reason, it is necessary to neutralize the cup upper portion 19 prior to executing the processing on the substrate W.
　基板処理装置２２１では、図４に示す処理例の場合と同様の処理が実施されるが、図４のステップＳ１の基板Ｗの搬入に先立って、カップ１７に対して除電が行われる。具体的には、制御装置４０は、軟Ｘ線照射ユニット２２３の高電圧ユニットを制御して、軟Ｘ線照射ユニット２２３の軟Ｘ線発生器（第１実施形態に係る軟Ｘ線照射ユニット６２の軟Ｘ線発生器２５（図２参照）に相当）に軟Ｘ線を発生させて、この軟Ｘ線を、第１分岐配管２２２の内部に向けて照射させる。これにより、第１分岐配管２２２に存在しているＤＩＷに、軟Ｘ線が照射される。 In the substrate processing apparatus 221, the same processing as that in the processing example shown in FIG. 4 is performed, but before the substrate W is loaded in step S1 in FIG. Specifically, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 223 to control the soft X-ray generator (the soft X-ray irradiation unit 62 according to the first embodiment) of the soft X-ray irradiation unit 223. The soft X-ray generator 25 (refer to FIG. 2) generates soft X-rays and irradiates the soft X-rays toward the inside of the first branch pipe 222. Thereby, soft X-rays are irradiated to DIW existing in the first branch pipe 222.
　また、制御装置４０は、水バルブ２０５を閉じながら分岐バルブ２２５を開く。これにより、第１分岐配管２２２を流通するＤＩＷは第１カップ用ノズル２２４に供給される。第１カップ用ノズル２２４の吐出口２２４Ａから、カップ上部１９の傾斜部２１の上面に向けてＤＩＷが吐出される。供給されたＤＩＷは、傾斜部２１の上面を伝って下方に向けて流れる。そのため、傾斜部２１の上面には、ＤＩＷの液膜が形成される。このとき、第１カップ用ノズル２２４に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、第１カップ用ノズル２２４の吐出口２２４Ａから吐出されるＤＩＷの態様が、吐出口２２４Ａと傾斜部２１の上面のＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。また、第１カップ用ノズル２２４のノズル配管内および第１分岐配管２２２内では、ＤＩＷが液密状態にある。 Further, the control device 40 opens the branch valve 225 while closing the water valve 205. Accordingly, DIW flowing through the first branch pipe 222 is supplied to the first cup nozzle 224. DIW is discharged from the discharge port 224A of the first cup nozzle 224 toward the upper surface of the inclined portion 21 of the cup upper portion 19. The supplied DIW flows downward along the upper surface of the inclined portion 21. Therefore, a DIW liquid film is formed on the upper surface of the inclined portion 21. At this time, the supply flow rate of DIW to the first cup nozzle 224 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the DIW mode discharged from the discharge port 224A of the first cup nozzle 224 has a continuous flow mode connected to both the discharge port 224A and the DIW liquid film on the upper surface of the inclined portion 21. Further, DIW is in a liquid-tight state in the nozzle pipe of the first cup nozzle 224 and in the first branch pipe 222.
　カップ上部１９が正に帯電しているときには、第１分岐配管２２２内におけるＤＩＷの照射部分と、正に帯電しているカップ上部１９との間の電位差で、第１分岐配管２２２内におけるＤＩＷの照射部分からの電子が、傾斜部２１の上面のＤＩＷの液膜に向けて、連続流状のＤＩＷを伝って移動する。これにより、傾斜部２１の上面のＤＩＷの液膜が多量の電子を有するようになるので、正に帯電しているカップ上部１９のうち、ＤＩＷの液膜に接する部分が除電される。 When the cup upper portion 19 is positively charged, the potential difference between the DIW irradiation portion in the first branch pipe 222 and the positively charged cup upper portion 19 causes the DIW in the first branch pipe 222 to be positive. Electrons from the irradiated portion move toward the DIW liquid film on the upper surface of the inclined portion 21 along the continuous flow DIW. As a result, the DIW liquid film on the upper surface of the inclined portion 21 has a large amount of electrons, so that the portion of the positively charged cup upper portion 19 that is in contact with the DIW liquid film is neutralized.
　一方、カップ上部１９が負に帯電しているときには、カップ上部１９からの電子が、第１分岐配管２２２内におけるＤＩＷの照射部分の正イオンに向けて、連続流状のＤＩＷを伝って移動する。そのため、負に帯電しているカップ上部１９のうち、ＤＩＷの液膜に接する部分が除電される。 On the other hand, when the cup upper portion 19 is negatively charged, electrons from the cup upper portion 19 move along the continuous flow DIW toward the positive ions in the DIW irradiated portion in the first branch pipe 222. . Therefore, the portion of the cup upper portion 19 that is negatively charged and in contact with the DIW liquid film is neutralized.
　カップ上部１９に対する除電が行われた後、未処理の基板Ｗが処理室３に搬入され、スピンチャック４に受け渡される。 After the static electricity is removed from the cup upper part 19, the unprocessed substrate W is carried into the processing chamber 3 and delivered to the spin chuck 4.
　スピンチャック４に基板Ｗが保持された後、制御装置４０はスピンモータ８を制御して、スピンチャック４による基板Ｗの回転を開始させる（図４のステップＳ２）。基板Ｗの回転速度が所定の液処理速度（たとえば500rpm）まで上げられ、その後、その液処理速度に維持される。 After the substrate W is held on the spin chuck 4, the control device 40 controls the spin motor 8 to start the rotation of the substrate W by the spin chuck 4 (step S2 in FIG. 4). The rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
　リンス処理（図４のステップＳ４～Ｓ６）では、制御装置４０（図３参照）は、分岐バルブ２２５を閉じつつ水バルブ２０５を開く。 In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 205 while closing the branch valve 225.
　また、水バルブ２０５の開成後所定時間経過して軟Ｘ線照射タイミングになると、制御装置４０は、軟Ｘ線照射ユニット２２３の高電圧ユニットを制御して、軟Ｘ線照射ユニット２２３の軟Ｘ線発生器に軟Ｘ線を発生させて、この軟Ｘ線を、第１分岐配管２２２の内部に向けて照射させる。これにより、第１分岐配管２２２内を流通しているＤＩＷに、軟Ｘ線が照射される。 In addition, when a predetermined time elapses after the opening of the water valve 205 and the soft X-ray irradiation timing is reached, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 223 to control the soft X-ray irradiation unit 223. Soft X-rays are generated in the line generator, and the soft X-rays are irradiated toward the inside of the first branch pipe 222. Thereby, soft X-rays are irradiated to DIW which distribute | circulates the inside of the 1st branch piping 222. FIG.
　水ノズル２０２の吐出口２０２Ａから、回転状態にある基板Ｗの上面の回転中心に向けて、ＤＩＷが吐出される。リンス処理中には、基板Ｗの上面の全域にＤＩＷの液膜が形成される。水ノズル２０２の吐出口２０２Ａから吐出されるＤＩＷの態様が、吐出口２０２Ａと基板Ｗの上面のＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。また、水ノズル２０２のノズル配管内、水供給配管２０４内および第１分岐配管２２２内では、ＤＩＷが液密状態にある。 DIW is discharged from the discharge port 202A of the water nozzle 202 toward the rotation center of the upper surface of the substrate W in a rotating state. During the rinsing process, a DIW liquid film is formed over the entire upper surface of the substrate W. The mode of DIW discharged from the discharge port 202A of the water nozzle 202 is a continuous flow mode connected to both the discharge port 202A and the DIW liquid film on the upper surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 202, the water supply pipe 204, and the first branch pipe 222.
　リンス処理中に、第１分岐配管２２２内に存在しているＤＩＷに軟Ｘ線が照射されると、第１分岐配管２２２内におけるＤＩＷの照射部分（図５に示す、第１実施形態に係るＤＩＷの照射部分５４と同等）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、第１分岐配管２２２内におけるＤＩＷの照射部分に形成される。ＤＩＷの照射部分は、基板Ｗの上面に形成されたＤＩＷの液膜と、ＤＩＷを介して繋がっている。 When the DIW existing in the first branch pipe 222 is irradiated with soft X-rays during the rinsing process, the DIW irradiated portion in the first branch pipe 222 (according to the first embodiment shown in FIG. 5). In the DIW irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the first branch pipe 222. The DIW irradiated portion is connected to the DIW liquid film formed on the upper surface of the substrate W via the DIW.
　基板Ｗが正に帯電すると、第１分岐配管２２２内におけるＤＩＷの照射部分と、正に帯電している基板Ｗとの間の電位差で、第１分岐配管２２２内におけるＤＩＷの照射部分からの電子が、基板Ｗの上面のＤＩＷの液膜に向けて、水供給配管２０４および連続流状のＤＩＷの双方を伝って移動する。これにより、基板Ｗの上面のＤＩＷの液膜が多量の電子を有するようになる。 When the substrate W is positively charged, electrons from the DIW irradiated portion in the first branch pipe 222 are caused by a potential difference between the DIW irradiated portion in the first branch pipe 222 and the positively charged substrate W. However, it moves through both the water supply pipe 204 and the continuous flow DIW toward the DIW liquid film on the upper surface of the substrate W. Thus, the DIW liquid film on the upper surface of the substrate W has a large amount of electrons.
　以上により、第６実施形態では、第１実施形態で述べた作用効果と同等の作用効果に加えて、カップ上部１９の除電を良好に行える作用効果を奏することができる。 As described above, in the sixth embodiment, in addition to the operational effects equivalent to the operational effects described in the first embodiment, it is possible to achieve an operational effect that can satisfactorily eliminate the charge on the cup upper portion 19.
　また、Ｘ線照射ユニット２２３の窓部材の外表面（窓部材７１の外表面７１Ｂ（図２参照）に相当）から親水性皮膜（親水性皮膜３８（図２参照）に相当）が剥がれると、当該窓部材に含まれるベリリウムがＤＩＷ等の処理液に溶け出すおそれがある。このような場合であっても、Ｘ線照射ユニット２２３が第１分岐配管２２２に設けられているので、そのようなベリリウムを含むＤＩＷは、水ノズル２０２ではなく第１カップ用ノズル２２４に供給される。これにより、ベリリウムを含むＤＩＷが基板Ｗに供給されるのを、確実に防止できる。 Further, when the hydrophilic film (corresponding to the hydrophilic film 38 (see FIG. 2)) is peeled off from the outer surface of the window member of the X-ray irradiation unit 223 (corresponding to the outer surface 71B (see FIG. 2) of the window member 71), There is a risk that beryllium contained in the window member dissolves into a processing solution such as DIW. Even in such a case, since the X-ray irradiation unit 223 is provided in the first branch pipe 222, the DIW containing such beryllium is supplied to the first cup nozzle 224 instead of the water nozzle 202. The Thereby, it is possible to reliably prevent the DIW containing beryllium from being supplied to the substrate W.
　第１～第６実施形態では、水ノズル６１，２０２から吐出されるＤＩＷ（水の一例）を用いて、リンス処理時における基板Ｗの帯電防止や除電を図る場合を説明したが、水ノズル６１，２０２から吐出されるＤＩＷ（水の一例）を用いて、内部を処理液が流通する第２ノズル配管（第２配管）２３２，２６２の除電を図る場合を、次に述べる第７～第９実施形態に係る基板処理装置２３１，２５１，２６１において説明する。 In the first to sixth embodiments, a case has been described in which DIW (an example of water) discharged from the water nozzles 61 and 202 is used to prevent charging or charge removal of the substrate W during the rinsing process. , 202 is used to remove static electricity from the second nozzle pipes (second pipes) 232 and 262 through which the processing liquid flows using DIW (an example of water). The substrate processing apparatuses 231, 251, 261 according to the embodiment will be described.
　図１５（ａ），１５（ｂ）は、本発明の第７実施形態に係る基板処理装置２３１の構成を示す図である。 15 (a) and 15 (b) are diagrams showing the configuration of the substrate processing apparatus 231 according to the seventh embodiment of the present invention.
　基板処理装置２３１が、第１実施形態に係る基板処理装置１と相違する点は、スピンチャック４に保持されている基板Ｗに処理液を供給するための第２ノズル配管２３２を備える点、および水供給ユニット２３０によって第２ノズル配管２３２に水の一例としてのＤＩＷを供給する点である。水供給ユニット２３０は、水供給ユニット１００（図１参照）と同等の構成を採用しているので、水供給ユニット１００の場合と同一の参照符号を付して説明を省略している。図１５（ａ），１５（ｂ）には、水供給ユニット２３０に関連する構成のみを記載し、その他の部分の図示は省略する。図１５（ａ）は、第２ノズル配管２３２が、次に述べる待機ポッド２３７に収容された状態を示す断面図であり、図１５（ｂ）は、図１５（ａ）の切断面線Ｂ－Ｂから見た断面図である。 The substrate processing apparatus 231 is different from the substrate processing apparatus 1 according to the first embodiment in that the substrate processing apparatus 231 includes a second nozzle pipe 232 for supplying a processing liquid to the substrate W held on the spin chuck 4. The point is that DIW as an example of water is supplied to the second nozzle pipe 232 by the water supply unit 230. Since the water supply unit 230 employs a configuration equivalent to that of the water supply unit 100 (see FIG. 1), the same reference numerals as those in the case of the water supply unit 100 are attached and description thereof is omitted. In FIGS. 15A and 15B, only the configuration related to the water supply unit 230 is described, and the other portions are not shown. FIG. 15A is a cross-sectional view showing a state in which the second nozzle pipe 232 is accommodated in the standby pod 237 described below, and FIG. 15B is a cross-sectional line B-- in FIG. It is sectional drawing seen from B. FIG.
　第２ノズル配管２３２は、水平方向に延びる円筒状の水平部２３３と、この水平部２３３の先端から垂下する円筒状の垂下部２３４とを一体的に備えている。第２ノズル配管２３２は、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料によって形成されている。 The second nozzle pipe 232 is integrally provided with a cylindrical horizontal portion 233 extending in the horizontal direction and a cylindrical hanging portion 234 hanging from the tip of the horizontal portion 233. The second nozzle pipe 232 is made of a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
　第２ノズル配管２３２の内部には処理液流通路２３５が形成されている。処理液流通路２３５は、垂下部２３４の下端において、吐出口２３６として円形状に開口している。第２ノズル配管２３２には、処理液供給源からの処理液（薬液や水）が、処理液バルブ（図示しない）を介して供給されている。この処理液バルブが開かれると、第２ノズル配管２３２の水平部２３３の上流端に処理液が供給される。第２ノズル配管２３２に導入された処理液は、処理液流通路２３５を流通した後、吐出口２３６から吐出される。 A processing liquid flow passage 235 is formed inside the second nozzle pipe 232. The processing liquid flow passage 235 is opened in a circular shape as the discharge port 236 at the lower end of the hanging part 234. A processing liquid (chemical solution or water) from a processing liquid supply source is supplied to the second nozzle pipe 232 via a processing liquid valve (not shown). When the processing liquid valve is opened, the processing liquid is supplied to the upstream end of the horizontal portion 233 of the second nozzle pipe 232. The processing liquid introduced into the second nozzle pipe 232 is discharged from the discharge port 236 after flowing through the processing liquid flow passage 235.
　第２ノズル配管２３２は、カップ１７（図１参照）の側方でほぼ鉛直に延びた支持軸（図示しない）によって支持されており、この支持軸に回転力を入力して当該支持軸を回動させることにより、スピンチャック４（図１参照）の上方で第２ノズル配管２３２を揺動させることができる。すなわち、第２ノズル配管２３２は、スキャンノズルとしての形態を有している。基板Ｗ（図１参照）に対する処理液の供給が行われないときには、第２ノズル配管２３２は、カップ１７（図１参照）の側方に設置されたホームポジションに退避している。基板Ｗ（図１参照）に対する処理液の供給時には、第２ノズル配管２３２は、基板Ｗの上方へと移動させられる。 The second nozzle pipe 232 is supported by a support shaft (not shown) extending substantially vertically on the side of the cup 17 (see FIG. 1), and rotational force is input to the support shaft to rotate the support shaft. By moving it, the second nozzle pipe 232 can be swung above the spin chuck 4 (see FIG. 1). That is, the second nozzle pipe 232 has a form as a scan nozzle. When the processing liquid is not supplied to the substrate W (see FIG. 1), the second nozzle pipe 232 is retracted to the home position installed on the side of the cup 17 (see FIG. 1). When the processing liquid is supplied to the substrate W (see FIG. 1), the second nozzle pipe 232 is moved above the substrate W.
　図１５（ａ），１５（ｂ）に示すように、基板処理装置２３１は、ホームポジションにある第２ノズル配管２３２を収容するための樋状の待機ポッド２３７を含む。待機ポッド２３７は、第２ノズル配管２３２の長手方向に沿う断面略矩形のポッド本体２３８を有している。ポッド本体２３８の上面には、第２ノズル配管２３２の長手方向に沿って延びる液溜め溝２３９が形成されている。液溜め溝２３９は、長手方向の両端を除く、長手方向の全域に亘って形成されている。液溜め溝２３９は、断面略Ｕ字状をなしている。液溜め溝２３９の幅および深さは、第２ノズル配管２３２を収容可能なサイズに設定されている。 As shown in FIGS. 15A and 15B, the substrate processing apparatus 231 includes a bowl-shaped standby pod 237 for accommodating the second nozzle pipe 232 at the home position. The standby pod 237 has a pod body 238 having a substantially rectangular cross section along the longitudinal direction of the second nozzle pipe 232. A liquid storage groove 239 extending along the longitudinal direction of the second nozzle pipe 232 is formed on the upper surface of the pod body 238. The liquid reservoir groove 239 is formed over the entire area in the longitudinal direction except for both ends in the longitudinal direction. The liquid reservoir groove 239 has a substantially U-shaped cross section. The width and depth of the liquid reservoir groove 239 are set to a size that can accommodate the second nozzle pipe 232.
　ポッド本体２３８の長手方向の両端には、それぞれ端壁２４０が設けられている。各端壁２４０には、第２ノズル配管２３２とほぼ整合する丸孔からなる挿通孔２４１が形成されている。液溜め溝２３９の底部には、廃液配管２４２が接続されている。廃液配管２４２の途中部には、廃液配管２４２を開閉するための廃液バルブ２４３が介装されている。第２ノズル配管２３２がホームポジションにあるときには、第２ノズル配管２３２が液溜め溝２３９に収容配置される。このとき、第２ノズル配管２３２は、両方の端壁２４０の挿通孔２４１を挿通している。 End walls 240 are provided at both ends of the pod main body 238 in the longitudinal direction. Each end wall 240 is formed with an insertion hole 241 formed of a round hole substantially aligned with the second nozzle pipe 232. A waste liquid pipe 242 is connected to the bottom of the liquid reservoir groove 239. In the middle of the waste liquid pipe 242, a waste liquid valve 243 for opening and closing the waste liquid pipe 242 is interposed. When the second nozzle pipe 232 is at the home position, the second nozzle pipe 232 is accommodated in the liquid storage groove 239. At this time, the second nozzle pipe 232 is inserted through the insertion holes 241 of both end walls 240.
　水供給ユニット２３０の水ノズル６１は、その吐出口５３を液溜め溝２３９に向けた状態で、待機ポッド２３７の上方に固定的に配置されている
　第２ノズル配管２３２がホームポジションに配置された状態で、廃液バルブ２４３が閉じられた状態で、水供給ユニット２３０の水ノズル６１からＤＩＷが吐出される。これにより、待機ポッド２３７の液溜め溝２３９にＤＩＷが溜められる。そして、液溜め溝２３９に溜められたＤＩＷによって、第２ノズル配管２３２（の水平部２３３）の周方向の全域が浸漬される。 The water nozzle 61 of the water supply unit 230 has a second nozzle pipe 232 fixedly disposed above the standby pod 237 with the discharge port 53 directed to the liquid storage groove 239. The second nozzle pipe 232 is disposed at the home position. In a state where the waste liquid valve 243 is closed, DIW is discharged from the water nozzle 61 of the water supply unit 230. As a result, DIW is stored in the liquid storage groove 239 of the standby pod 237. Then, the entire area in the circumferential direction of the second nozzle pipe 232 (the horizontal portion 233 thereof) is immersed by the DIW stored in the liquid storage groove 239.
　第２ノズル配管２３２がホームポジションにある期間（待機時）中は、水ノズル６１から吐出されるＤＩＷの吐出は続行される。このときにおける、水ノズル６１に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、水ノズル６１の吐出口５３から吐出されるＤＩＷの態様が、吐出口５３と液溜め溝２３９に溜められたＤＩＷとの双方に繋がる連続流状の態様をなしている。すなわち、吐出口５３から吐出されるＤＩＷが、吐出口５３と第２ノズル配管２３２の外周壁との間で液状に繋がっている。第１ノズル配管５１内では、ＤＩＷが液密状態にある。 During the period in which the second nozzle pipe 232 is in the home position (standby), the DIW discharged from the water nozzle 61 is continued. At this time, the supply flow rate of DIW to the water nozzle 61 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 53 of the water nozzle 61 is a continuous flow mode connected to both the discharge port 53 and the DIW stored in the liquid storage groove 239. That is, DIW discharged from the discharge port 53 is connected in a liquid state between the discharge port 53 and the outer peripheral wall of the second nozzle pipe 232. In the first nozzle pipe 51, DIW is in a liquid-tight state.
　また、第２ノズル配管２３２がホームポジションにある期間（待機時）中は、水ノズル６１（第１ノズル配管５１）の内部に、軟Ｘ線照射ユニット６２からの軟Ｘ線が照射される。第１ノズル配管５１内に存在しているＤＩＷに軟Ｘ線が照射される結果、ＤＩＷの照射部分５４（図５参照）において、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が形成される。このとき、ＤＩＷの照射部分５４と、第２ノズル配管２３２の外周壁に接液しているＤＩＷとが、ＤＩＷを介して繋がっている。 Further, during the period (standby) when the second nozzle pipe 232 is at the home position, the soft X-rays from the soft X-ray irradiation unit 62 are irradiated inside the water nozzle 61 (first nozzle pipe 51). As a result of irradiating the DIW existing in the first nozzle pipe 51 with soft X-rays, a large amount of electrons and a large amount of positive ions of water molecules are mixed in the irradiated portion 54 (see FIG. 5) of the DIW. A plasma state is formed. At this time, the DIW irradiation portion 54 and the DIW in contact with the outer peripheral wall of the second nozzle pipe 232 are connected via the DIW.
　ところで、第２ノズル配管２３２に対する処理液の供給停止中には、第２ノズル配管２３２の内部（とくに水平部２３３）に処理液が残留している。このとき、第２ノズル配管２３２の外周壁が正または負に帯電すると、誘導帯電により、第２ノズル配管２３２内の残留処理液までもが、正または負に帯電するおそれがある。このような帯電状態にある処理液が基板Ｗに供給されると、基板Ｗまでもが電荷を帯びてしまい、その電荷の放電が生じたときに、基板Ｗの上面に形成されるデバイスの破壊を生じるおそれがある。 Incidentally, while the supply of the processing liquid to the second nozzle pipe 232 is stopped, the processing liquid remains inside the second nozzle pipe 232 (particularly the horizontal portion 233). At this time, if the outer peripheral wall of the second nozzle pipe 232 is positively or negatively charged, the residual processing liquid in the second nozzle pipe 232 may be positively or negatively charged due to induction charging. When the processing liquid in such a charged state is supplied to the substrate W, even the substrate W is charged, and when the charge is discharged, the device formed on the upper surface of the substrate W is destroyed. May occur.
　第２ノズル配管２３２が正に帯電しているときには、ＤＩＷの照射部分５４（図５参照）と、正に帯電している第２ノズル配管２３２の外周壁との間の電位差で、ＤＩＷの照射部分５４（図５参照）からの電子が第２ノズル配管２３２の外周壁に向けて、連続流状のＤＩＷ、および液溜め溝２３９に溜められたＤＩＷを伝って移動する。これにより、正に帯電している第２ノズル配管２３２の外周壁が除電される。 When the second nozzle pipe 232 is positively charged, DIW irradiation is caused by a potential difference between the DIW irradiation portion 54 (see FIG. 5) and the outer peripheral wall of the positively charged second nozzle pipe 232. Electrons from the portion 54 (see FIG. 5) move toward the outer peripheral wall of the second nozzle pipe 232 through the continuous flow DIW and the DIW stored in the liquid storage groove 239. As a result, the outer peripheral wall of the second nozzle pipe 232 that is positively charged is removed.
　一方、第２ノズル配管２３２が負に帯電しているときには、第２ノズル配管２３２の外周壁からの電子が、ＤＩＷの照射部分５４（図５参照）の正イオンに向けて、連続流状のＤＩＷを伝って移動する。これにより、負に帯電している第２ノズル配管２３２が除電される。 On the other hand, when the second nozzle pipe 232 is negatively charged, electrons from the outer peripheral wall of the second nozzle pipe 232 are continuously flowed toward the positive ions in the DIW irradiation portion 54 (see FIG. 5). Move along the DIW. As a result, the negatively charged second nozzle pipe 232 is neutralized.
　図１６は、本発明の第８実施形態に係る基板処理装置２５１の構成を示す図である。 FIG. 16 is a diagram showing a configuration of a substrate processing apparatus 251 according to the eighth embodiment of the present invention.
　基板処理装置２５１が、第７実施形態に係る基板処理装置２３１（図１５（ａ），１５（ｂ）参照）と相違する点は、液溜め溝２３９に溜められたＤＩＷに第２ノズル配管２３２を浸漬するのではなく、水供給ユニット（処理液供給装置）２５０の水ノズル６１の吐出口５３からのＤＩＷを、第２ノズル配管２３２の外周壁に直接供給することにより、第２ノズル配管２３２を除電するようにした点である。水供給ユニット２５０は、次に述べる移動ユニット２５２の構成を除き、水供給ユニット１００（図１参照）と同等の構成を採用している。そのため、水供給ユニット１００の場合と同一の参照符号を付して説明を省略している。水供給ユニット２５０では、一体型ヘッド６に、当該一体型ヘッド６を水平方向に移動させるための移動ユニット２５２が結合されている。移動ユニット２５２はボールナットやモータを用いて構成されており、制御装置４０（図３参照）に制御対象として接続されている。 The substrate processing apparatus 251 is different from the substrate processing apparatus 231 according to the seventh embodiment (see FIGS. 15A and 15B) in that the second nozzle pipe 232 is connected to the DIW stored in the liquid storage groove 239. The DIW from the discharge port 53 of the water nozzle 61 of the water supply unit (processing liquid supply device) 250 is directly supplied to the outer peripheral wall of the second nozzle pipe 232, thereby immersing the second nozzle pipe 232. This is the point of eliminating static electricity. The water supply unit 250 employs a configuration equivalent to that of the water supply unit 100 (see FIG. 1) except for the configuration of the moving unit 252 described below. Therefore, the same reference numerals as those in the case of the water supply unit 100 are attached, and the description is omitted. In the water supply unit 250, a moving unit 252 for moving the integrated head 6 in the horizontal direction is coupled to the integrated head 6. The moving unit 252 is configured using a ball nut or a motor, and is connected to the control device 40 (see FIG. 3) as a control target.
　第２ノズル配管２３２がホームポジションにある期間（待機時）中は、制御装置４０は、水ノズル６１（第１ノズル配管５１）にＤＩＷ（水の一例）を供給するとともに、水ノズル６１（第１ノズル配管５１）の内部に軟Ｘ線照射ユニット６２からの軟Ｘ線を照射する。一体型ヘッド６の水ノズル６１から吐出されるＤＩＷは、第２ノズル配管２３２の外周壁に供給され、第２ノズル配管２３２の外周壁を伝って下方に流れ落ちる。 During a period in which the second nozzle pipe 232 is at the home position (standby), the control device 40 supplies DIW (an example of water) to the water nozzle 61 (first nozzle pipe 51) and at the same time the water nozzle 61 (first The soft X-rays from the soft X-ray irradiation unit 62 are irradiated inside the one nozzle pipe 51). DIW discharged from the water nozzle 61 of the integrated head 6 is supplied to the outer peripheral wall of the second nozzle pipe 232 and flows down along the outer peripheral wall of the second nozzle pipe 232.
　このときにおける、水ノズル６１に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、水ノズル６１の吐出口５３から吐出されるＤＩＷの態様が、吐出口５３と第２ノズル配管２３２の外周壁との双方に繋がる連続流状の態様をなしている。第１ノズル配管５１内では、ＤＩＷが液密状態にある。 At this time, the supply flow rate of DIW to the water nozzle 61 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 53 of the water nozzle 61 is a continuous flow mode connected to both the discharge port 53 and the outer peripheral wall of the second nozzle pipe 232. In the first nozzle pipe 51, DIW is in a liquid-tight state.
　また、第２ノズル配管２３２がホームポジションにある期間（待機時）中は、水ノズル６１（第１ノズル配管５１）の内部に、軟Ｘ線照射ユニット６２からの軟Ｘ線が照射される。第１ノズル配管５１内に存在しているＤＩＷに軟Ｘ線が照射される結果、ＤＩＷの照射部分５４（図５参照）において、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が形成される。このとき、ＤＩＷの照射部分５４と、第２ノズル配管２３２の外周壁に接液しているＤＩＷとが、ＤＩＷを介して繋がっている。 Further, during the period (standby) when the second nozzle pipe 232 is at the home position, the soft X-rays from the soft X-ray irradiation unit 62 are irradiated inside the water nozzle 61 (first nozzle pipe 51). As a result of irradiating the DIW existing in the first nozzle pipe 51 with soft X-rays, a large amount of electrons and a large amount of positive ions of water molecules are mixed in the irradiated portion 54 (see FIG. 5) of the DIW. A plasma state is formed. At this time, the DIW irradiation portion 54 and the DIW in contact with the outer peripheral wall of the second nozzle pipe 232 are connected via the DIW.
　第２ノズル配管２３２が正に帯電しているときには、ＤＩＷの照射部分５４（図５参照）と、正に帯電している第２ノズル配管２３２との間の電位差で、ＤＩＷの照射部分５４（図５参照）からの電子が、第２ノズル配管２３２におけるＤＩＷの接液位置に向けて、連続流状のＤＩＷを伝って移動する。これにより、第２ノズル配管２３２におけるＤＩＷの着液部位が除電される。 When the second nozzle pipe 232 is positively charged, the DIW irradiation part 54 (see FIG. 5) and the potential difference between the DIW irradiation part 54 (see FIG. 5) and the second nozzle pipe 232 positively charged. Electrons from (see FIG. 5) move along the continuous flow DIW toward the DIW wetted position in the second nozzle pipe 232. As a result, the DIW landing site in the second nozzle pipe 232 is neutralized.
　一方、第２ノズル配管２３２が負に帯電しているときには、第２ノズル配管２３２からの電子が、ＤＩＷの照射部分５４（図５参照）の正イオンに向けて、連続流状のＤＩＷを伝って移動する。これにより、第２ノズル配管２３２におけるＤＩＷの着液部位が除電される。 On the other hand, when the second nozzle pipe 232 is negatively charged, electrons from the second nozzle pipe 232 travel through the DIW in a continuous flow toward positive ions in the DIW irradiation portion 54 (see FIG. 5). Move. As a result, the DIW landing site in the second nozzle pipe 232 is neutralized.
　そして、制御装置４０は、移動ユニット２５２を制御して、第２ノズル配管２３２（水平部２３３）の外周壁におけるＤＩＷの着液部位を、第２ノズル配管２３２の長手方向に沿って一方向移動または往復移動させる。これにより、除電される第２ノズル配管２３２の位置を、第２ノズル配管２３２（水平部２３３）の長手方向に沿って移動させることができ、ゆえに、第２ノズル配管２３２（水平部２３３）の外周壁の略全域を良好に除電できる。 Then, the control device 40 controls the moving unit 252 to move the DIW liquid landing site on the outer peripheral wall of the second nozzle pipe 232 (horizontal portion 233) in one direction along the longitudinal direction of the second nozzle pipe 232. Or reciprocate. Accordingly, the position of the second nozzle pipe 232 to be neutralized can be moved along the longitudinal direction of the second nozzle pipe 232 (horizontal portion 233). Therefore, the second nozzle pipe 232 (horizontal portion 233) It is possible to remove static electricity in a substantially entire area of the outer peripheral wall.
　図１７（ａ），１７（ｂ）は、本発明の第９実施形態に係る基板処理装置２６１の構成を示す図である。 17 (a) and 17 (b) are diagrams showing the configuration of the substrate processing apparatus 261 according to the ninth embodiment of the present invention.
　基板処理装置２６１は、第１実施形態に係る水供給ユニット１００（図１参照）に代えて水供給ユニット（処理液供給装置）２６０を備える点で、第１実施形態に係る基板処理装置１（図１参照）と相違しており、その他の構成は、基板処理装置１と共通している。図１７（ａ），１７（ｂ）には、水供給ユニット２６０に関連する構成のみを記載し、その他の部分の図示は省略する。図１７（ａ）は、次に述べる第２ノズル配管２６２および第３ノズル配管２７２の縦断面図であり、図１７（ｂ）は、図１７（ａ）の切断面線Ｂ１－Ｂ１から見た断面図である。 The substrate processing apparatus 261 includes a water supply unit (processing liquid supply apparatus) 260 instead of the water supply unit 100 (see FIG. 1) according to the first embodiment, and the substrate processing apparatus 1 according to the first embodiment ( The other configuration is the same as that of the substrate processing apparatus 1. 17 (a) and 17 (b) show only the configuration related to the water supply unit 260, and the other parts are not shown. FIG. 17A is a longitudinal sectional view of a second nozzle pipe 262 and a third nozzle pipe 272 to be described next, and FIG. 17B is viewed from a cutting plane line B1-B1 in FIG. 17A. It is sectional drawing.
　水供給ユニット２６０は、第２ノズル配管２６２と、第３ノズル配管２７２とを備えている。第２ノズル配管２６２および第３ノズル配管２７２は、第３ノズル配管２７２内に第２ノズル配管２６２が挿通されることにより二重配管構造を形成している。 The water supply unit 260 includes a second nozzle pipe 262 and a third nozzle pipe 272. The second nozzle pipe 262 and the third nozzle pipe 272 form a double pipe structure by inserting the second nozzle pipe 262 into the third nozzle pipe 272.
　第２ノズル配管２６２は、水平方向に延びる円筒状の水平部２６３と、この水平部２６３の先端から垂下する円筒状の垂下部２６４とを一体的に備えている。第２ノズル配管２６２は、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料によって形成されている。 The second nozzle pipe 262 is integrally provided with a cylindrical horizontal portion 263 extending in the horizontal direction and a cylindrical hanging portion 264 that hangs down from the tip of the horizontal portion 263. The second nozzle pipe 262 is formed of a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
　第２ノズル配管２６２の内部には処理液流通路２６５が形成されている。処理液流通路２６５は、垂下部２６４の下端において、吐出口２６６として円形状に開口している。第２ノズル配管２６２には、処理液供給源からの処理液（薬液または水）が、処理液バルブ（図示しない）を介して供給されている。 A processing liquid flow passage 265 is formed inside the second nozzle pipe 262. The processing liquid flow passage 265 opens in a circular shape as the discharge port 266 at the lower end of the hanging part 264. A processing liquid (chemical solution or water) from a processing liquid supply source is supplied to the second nozzle pipe 262 via a processing liquid valve (not shown).
　水供給ユニット２６０は、第４実施形態に係る水供給ユニット２００（図１１参照）の構成の一部を含む。すなわち、水供給ユニット２６０は、水供給配管２０４と、軟Ｘ線照射ユニット２０３と、水バルブ２０５を含む。水供給配管２０４が第３ノズル配管２７２に対し、ＤＩＷ供給源からのＤＩＷ（水の一例）を供給する点を除き、軟Ｘ線照射ユニット２０３および水供給配管２０４は、第４実施形態で説明した通りの構成であるので、詳細な説明は省略する。 The water supply unit 260 includes a part of the configuration of the water supply unit 200 (see FIG. 11) according to the fourth embodiment. That is, the water supply unit 260 includes a water supply pipe 204, a soft X-ray irradiation unit 203, and a water valve 205. The soft X-ray irradiation unit 203 and the water supply pipe 204 are described in the fourth embodiment except that the water supply pipe 204 supplies DIW (an example of water) from the DIW supply source to the third nozzle pipe 272. Since it is the structure as it was, detailed description is abbreviate | omitted.
　第３ノズル配管２７２は、水平方向に延びる円筒状の水平部２７３と、この水平部２７３の先端から垂下する円筒状の垂下部２７４とを一体的に備えている。第３ノズル配管２７２は、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料によって形成されている。第３ノズル配管２７２の水平部２７３内を、第２ノズル配管２６２の水平部２６３が挿通し、第３ノズル配管２７２の垂下部２７４の管壁を貫通して、その下流端が第２ノズル配管２６２の垂下部２６４に接続されている。第３ノズル配管２７２の内壁と第２ノズル配管２６２の外壁との間の空間には、水流通路２７５が形成されている。水流通路２７５は、垂下部２７４の下端において、吐出口２７６として円環状に開口している。 The third nozzle pipe 272 is integrally provided with a cylindrical horizontal portion 273 extending in the horizontal direction and a cylindrical hanging portion 274 depending from the tip of the horizontal portion 273. The third nozzle pipe 272 is formed of a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). The horizontal portion 263 of the second nozzle pipe 262 passes through the horizontal portion 273 of the third nozzle pipe 272, passes through the wall of the drooping portion 274 of the third nozzle pipe 272, and the downstream end thereof is the second nozzle pipe. It is connected to the drooping portion 264 of 262. A water flow passage 275 is formed in a space between the inner wall of the third nozzle pipe 272 and the outer wall of the second nozzle pipe 262. The water flow passage 275 opens in an annular shape as a discharge port 276 at the lower end of the hanging portion 274.
　基板Ｗに対して処理液を用いた処理液処理を施す際には、前記の処理液バルブが開かれる。処理液バルブが開かれると、第２ノズル配管２６２の水平部２６３の上流端に、処理液が供給される。第２ノズル配管２６２に導入された処理液は、処理液流通路２６５を流通した後、吐出口２６６から吐出される。処理液の供給停止タイミングになると、前記の処理液バルブが閉じられるが、その後、第２ノズル配管２６２の内部（とくに水平部２６３）に処理液が残留する。 When performing the processing liquid processing using the processing liquid on the substrate W, the processing liquid valve is opened. When the processing liquid valve is opened, the processing liquid is supplied to the upstream end of the horizontal portion 263 of the second nozzle pipe 262. The processing liquid introduced into the second nozzle pipe 262 is discharged from the discharge port 266 after flowing through the processing liquid flow passage 265. When the supply stop timing of the processing liquid comes, the processing liquid valve is closed, but then the processing liquid remains inside the second nozzle pipe 262 (particularly the horizontal portion 263).
　基板Ｗに対してＤＩＷを供給する際には、水バルブ２０５が開かれる。第３ノズル配管２７２の水流通路２７５の上流端に、ＤＩＷが供給される。第３ノズル配管２７２に導入されたＤＩＷは、水流通路２７５を流通した後、吐出口２７６から吐出される。ＤＩＷの供給停止タイミングになると、水バルブ２０５が閉じられるが、その後も、第３ノズル配管２７２の内壁と第２ノズル配管２６２の外壁との間の空間にＤＩＷが残留する。 When supplying DIW to the substrate W, the water valve 205 is opened. DIW is supplied to the upstream end of the water flow passage 275 of the third nozzle pipe 272. DIW introduced into the third nozzle pipe 272 is discharged from the discharge port 276 after flowing through the water flow passage 275. When the DIW supply stop timing is reached, the water valve 205 is closed, but DIW remains in the space between the inner wall of the third nozzle pipe 272 and the outer wall of the second nozzle pipe 262 thereafter.
　ところで、第２ノズル配管２６２の外周壁が正または負に帯電すると、誘導帯電により、第２ノズル配管２６２内の残留処理液までもが、正または負に帯電するおそれがある。このような帯電状態にある処理液が基板Ｗに供給されると、基板Ｗまでもが電荷を帯びてしまい、その電荷の放電が生じたときに、基板Ｗの上面に形成されるデバイスの破壊を生じるおそれがある。 By the way, if the outer peripheral wall of the second nozzle pipe 262 is positively or negatively charged, the residual processing liquid in the second nozzle pipe 262 may be positively or negatively charged due to induction charging. When the processing liquid in such a charged state is supplied to the substrate W, even the substrate W is charged, and when the charge is discharged, the device formed on the upper surface of the substrate W is destroyed. May occur.
　このような第２ノズル配管２６２の外周壁の帯電メカニズムとしては、まず、第３ノズル配管２７２の外周壁が先に帯電し、次いで、第２ノズル配管２６２の外壁と第３ノズル配管２７２の内壁との間の残留ＤＩＷを介して第２ノズル配管２６２の外周壁が帯電することが考えられる。 As a charging mechanism of the outer peripheral wall of the second nozzle pipe 262, first, the outer peripheral wall of the third nozzle pipe 272 is charged first, and then the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272. It is conceivable that the outer peripheral wall of the second nozzle pipe 262 is charged through the residual DIW between the first nozzle pipe 262 and the second nozzle pipe 262.
　基板処理装置２６１では、第３ノズル配管２７２により基板ＷにＤＩＷを供給しないとき（つまり、リンス処理時以外）であっても、軟Ｘ線照射ユニット２０３による、水供給配管２０４の内部への軟Ｘ線の照射を続行している。 In the substrate processing apparatus 261, even when DIW is not supplied to the substrate W by the third nozzle pipe 272 (that is, other than during the rinsing process), the soft X-ray irradiation unit 203 softens the water supply pipe 204. X-ray irradiation continues.
　このとき、第２ノズル配管２６２の外壁と第３ノズル配管２７２の内壁との間に残留するＤＩＷと、水供給配管２０４内に存在しているＤＩＷとが液密状態で（連続流の形で）繋がっている。 At this time, DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272 and DIW existing in the water supply pipe 204 are in a liquid-tight state (in a continuous flow form). )It is connected.
　第３ノズル配管２７２が正に帯電しているときには、水供給配管２０４内におけるＤＩＷの照射部分と、正に帯電している第３ノズル配管２７２との間の電位差で、水供給配管２０４内におけるＤＩＷの照射部分からの電子が、水供給配管２０４内のＤＩＷおよび第２ノズル配管２６２の外壁と第３ノズル配管２７２の内壁との間に残留するＤＩＷを伝って、第３ノズル配管２７２に向けて移動する。これにより、正に帯電している第３ノズル配管２７２が除電される。 When the third nozzle pipe 272 is positively charged, the potential difference between the DIW irradiated portion in the water supply pipe 204 and the positively charged third nozzle pipe 272 causes a difference in the water supply pipe 204. Electrons from the irradiated portion of DIW travel through DIW in the water supply pipe 204 and DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272 toward the third nozzle pipe 272. Move. As a result, the positively charged third nozzle pipe 272 is neutralized.
　一方、第３ノズル配管２７２が負に帯電しているときには、第３ノズル配管２７２からの電子が、水供給配管２０４内におけるＤＩＷの照射部分の正イオンに向けて、水供給配管２０４内のＤＩＷおよび第２ノズル配管２６２の外壁と第３ノズル配管２７２の内壁との間に残留するＤＩＷを伝って移動する。これにより、第３ノズル配管２７２が除電される。 On the other hand, when the third nozzle pipe 272 is negatively charged, the electrons from the third nozzle pipe 272 are directed toward the positive ions at the DIW irradiated portion in the water supply pipe 204, and the DIW in the water supply pipe 204. The second nozzle pipe 262 moves along the DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272. As a result, the third nozzle pipe 272 is neutralized.
　すなわち、第３ノズル配管２７２の除電が達成されるので、第２ノズル配管２６２が帯電することがない。 That is, since neutralization of the third nozzle pipe 272 is achieved, the second nozzle pipe 262 is not charged.
　また、仮に、第２ノズル配管２６２が正に帯電しているときには、水供給配管２０４内におけるＤＩＷの照射部分からの電子が、水供給配管２０４内のＤＩＷおよび第２ノズル配管２６２の外壁と第３ノズル配管２７２の内壁との間に残留するＤＩＷを伝って、第２ノズル配管２６２に向けて移動する。仮に、第２ノズル配管２６２が負に帯電しているときには、第２ノズル配管２６２からの電子が、水供給配管２０４内におけるＤＩＷの照射部分の正イオンに向けて、水供給配管２０４内のＤＩＷおよび第２ノズル配管２６２の外壁と第３ノズル配管２７２の内壁との間に残留するＤＩＷを伝って移動する。つまり、仮に、第２ノズル配管２６２が帯電したとしても、このように、第２ノズル配管２６２の除電を達成できる。 In addition, if the second nozzle pipe 262 is positively charged, electrons from the DIW irradiated portion in the water supply pipe 204 are transferred to the DIW in the water supply pipe 204 and the outer wall of the second nozzle pipe 262. The residual DIW is transferred to the inner wall of the three-nozzle pipe 272 and moves toward the second nozzle pipe 262. If the second nozzle pipe 262 is negatively charged, the electrons from the second nozzle pipe 262 are directed toward the positive ions at the DIW irradiated portion in the water supply pipe 204, and the DIW in the water supply pipe 204. The second nozzle pipe 262 moves along the DIW remaining between the outer wall of the second nozzle pipe 262 and the inner wall of the third nozzle pipe 272. That is, even if the second nozzle pipe 262 is charged, the charge removal of the second nozzle pipe 262 can be achieved in this way.
　図１８は、本発明の第１０実施形態に係る基板処理装置３０１の構成を示す図である。 FIG. 18 is a diagram showing a configuration of a substrate processing apparatus 301 according to the tenth embodiment of the present invention.
　第１０実施形態において、第１実施形態と共通する部分には、図１～図６の場合と同一の参照符号を付し説明を省略する。基板処理装置３０１は、基板Ｗの下面に対してＤＩＷ（水の一例）を供給するための水供給ユニット（処理液供給装置）３００を備える点、および基板Ｗの上面に対し、水供給ユニット１００（図１参照）に代えて水ノズル３０２でＤＩＷ（水の一例）を供給する点の主に２点において、第１実施形態に係る基板処理装置１（図１参照）と相違している。 In the tenth embodiment, portions common to the first embodiment are denoted by the same reference numerals as in FIGS. 1 to 6, and description thereof is omitted. The substrate processing apparatus 301 includes a water supply unit (treatment liquid supply apparatus) 300 for supplying DIW (an example of water) to the lower surface of the substrate W, and the water supply unit 100 with respect to the upper surface of the substrate W. It differs from the substrate processing apparatus 1 (refer FIG. 1) which concerns on 1st Embodiment in the point which replaces (refer FIG. 1) and supplies DIW (an example of water) with the water nozzle 302 mainly.
　水ノズル３０２は、連続流の状態で液を吐出するストレートノズルによって構成されていて、その吐出口を、基板Ｗの上面中央部に向けた状態で、処理室３内に固定的に配置されている。水ノズル３０２には、ＤＩＷ供給源からＤＩＷが供給される水供給配管３０３が接続されている。水供給配管３０３には、水供給配管３０３を開閉するための水バルブ３０４が介装されている。 The water nozzle 302 is constituted by a straight nozzle that discharges liquid in a continuous flow state, and the water nozzle 302 is fixedly disposed in the processing chamber 3 with the discharge port directed toward the center of the upper surface of the substrate W. Yes. A water supply pipe 303 to which DIW is supplied from a DIW supply source is connected to the water nozzle 302. The water supply pipe 303 is provided with a water valve 304 for opening and closing the water supply pipe 303.
　基板処理装置３０１では、スピン軸９は中空軸とされている。スピン軸９の内部には、下側処理液供給管３０５が非接触状態で挿通されている。 In the substrate processing apparatus 301, the spin shaft 9 is a hollow shaft. A lower processing liquid supply pipe 305 is inserted into the spin shaft 9 in a non-contact state.
　水供給ユニット３００は、下側処理液供給管３０５と、下側処理液供給管３０５の上端に取り付けられた下面ノズル３０６と、下側処理液供給管３０５に対し、ＤＩＷ供給源からのＤＩＷを供給する水供給配管（処理液配管）３０７と、水供給配管３０７内に存在しているＤＩＷに軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）３０９とを含む。軟Ｘ線照射ユニット３０９は、水供給配管３０７に取り付けられている。下面ノズル３０６は、その吐出口３０６Ａ（図１９参照）が、挟持部材１１により支持された基板Ｗの下面中央部に近接するように配置されている。 The water supply unit 300 supplies DIW from the DIW supply source to the lower processing liquid supply pipe 305, the lower surface nozzle 306 attached to the upper end of the lower processing liquid supply pipe 305, and the lower processing liquid supply pipe 305. A water supply pipe (treatment liquid pipe) 307 to be supplied and a soft X-ray irradiation unit (X-ray irradiation means) 309 for irradiating the DIW existing in the water supply pipe 307 with soft X-rays are included. The soft X-ray irradiation unit 309 is attached to the water supply pipe 307. The lower surface nozzle 306 is disposed so that its discharge port 306A (see FIG. 19) is close to the center of the lower surface of the substrate W supported by the sandwiching member 11.
　下側処理液供給配管３０５に、水供給配管３０７が接続されている。これにより、下側処理液供給配管３０５から下面ノズル３０６にＤＩＷを供給して、下面ノズル３０６の吐出口３０６Ａ（図１９参照）から基板Ｗの下面中央部に向けてＤＩＷを吐出させることができる。 A water supply pipe 307 is connected to the lower processing liquid supply pipe 305. As a result, DIW can be supplied from the lower processing liquid supply pipe 305 to the lower surface nozzle 306 and discharged from the discharge port 306A (see FIG. 19) of the lower surface nozzle 306 toward the center of the lower surface of the substrate W. .
　水供給配管３０７は、丸管状（円筒状）をなしている。水供給配管３０７は、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。水供給配管３０７の途中部の管壁には、開口（図示しない）が形成されている。 The water supply pipe 307 has a round tubular shape (cylindrical shape). The water supply pipe 307 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer). . An opening (not shown) is formed in the tube wall in the middle of the water supply pipe 307.
　軟Ｘ線照射ユニット３０９は、第１実施形態に係る軟Ｘ線照射ユニット６２（図２参照）と同等の構成を採用している。軟Ｘ線照射ユニット３０９は、水供給配管３０７の開口を塞ぐように水供給配管３０７に取り付けられている。具体的には、軟Ｘ線照射ユニット３０９のカバーの開口（軟Ｘ線照射ユニット６２のカバー２６の第２開口２８（図２参照）に相当）が水供給配管３０７の前記の開口に一致し、かつ軟Ｘ線照射ユニット３０９のカバーの壁面（軟Ｘ線照射ユニット６２のカバー２６の横壁２６Ａ（図２参照）に相当）が水供給配管３０７の外周に密着している。軟Ｘ線照射ユニット３０９の高電圧ユニット（第１実施形態に係る軟Ｘ線照射ユニット６２の高電圧ユニット３１（図２参照）に相当）は、制御装置４０（図３参照）に接続されている。 The soft X-ray irradiation unit 309 employs the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment. The soft X-ray irradiation unit 309 is attached to the water supply pipe 307 so as to close the opening of the water supply pipe 307. Specifically, the opening of the cover of the soft X-ray irradiation unit 309 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) coincides with the opening of the water supply pipe 307. The wall surface of the cover of the soft X-ray irradiation unit 309 (corresponding to the lateral wall 26A (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is in close contact with the outer periphery of the water supply pipe 307. The high voltage unit of the soft X-ray irradiation unit 309 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
　水供給配管３０７には、水供給配管３０７を開閉するための水バルブ３０８が介装されている。水バルブ３０８は、制御装置４０（図３参照）に接続されている。 The water supply pipe 307 is provided with a water valve 308 for opening and closing the water supply pipe 307. The water valve 308 is connected to the control device 40 (see FIG. 3).
　基板処理装置３０１では、図４に示す処理例の場合と同様の処理が実施される。 In the substrate processing apparatus 301, the same processing as in the processing example shown in FIG. 4 is performed.
　リンス処理（図４のステップＳ４～Ｓ６）では、制御装置４０（図３参照）は、水バルブ３０４を開く。これにより、水ノズル３０２から、基板Ｗの上面中央部に向けてＤＩＷが吐出される。また、制御装置４０（図３参照）は、水バルブ３０８を開く。これにより、水供給配管３０７を流通するＤＩＷが下面ノズル３０６に供給される。下面ノズル３０６の吐出口３０６Ａから、基板Ｗの下面中央部に向けて上向きにＤＩＷが吐出される。 In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 304. Thereby, DIW is discharged from the water nozzle 302 toward the center of the upper surface of the substrate W. The control device 40 (see FIG. 3) opens the water valve 308. As a result, DIW flowing through the water supply pipe 307 is supplied to the lower surface nozzle 306. DIW is discharged upward from the discharge port 306A of the lower surface nozzle 306 toward the center of the lower surface of the substrate W.
　水バルブ３０８の開成後所定時間経過して軟Ｘ線照射タイミングになると、制御装置４０は、軟Ｘ線照射ユニット３０９の高電圧ユニットを制御して、軟Ｘ線照射ユニット３０９の軟Ｘ線発生器（第１実施形態に係る軟Ｘ線照射ユニット６２の軟Ｘ線発生器２５（図２参照）に相当）に軟Ｘ線を発生させて、この軟Ｘ線を、水供給配管３０７の内部に向けて照射させる。これにより、水供給配管３０７内を流通しているＤＩＷに、軟Ｘ線が照射される。 When the soft X-ray irradiation timing is reached after the opening of the water valve 308, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 309 to generate soft X-rays of the soft X-ray irradiation unit 309. A soft X-ray is generated in a vessel (corresponding to the soft X-ray generator 25 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment), and this soft X-ray is generated inside the water supply pipe 307. Irradiate toward Thereby, soft X-rays are irradiated to DIW which distribute | circulates the inside of the water supply piping 307. FIG.
　図１９は、基板処理装置３０１におけるリンス処理のＤＩＷの流れを示す図である。 FIG. 19 is a diagram showing a DIW flow of the rinsing process in the substrate processing apparatus 301.
　基板Ｗの上面中央部に供給されたＤＩＷは、基板Ｗの回転による遠心力を受けて、基板Ｗの上面上を、中央部から周縁部に向けて拡がる。これにより、基板Ｗの上面の全域にＤＩＷの液膜が形成される。ＤＩＷの液膜によって、基板Ｗの上面に付着している薬液が洗い流される。 The DIW supplied to the central portion of the upper surface of the substrate W receives a centrifugal force due to the rotation of the substrate W, and spreads on the upper surface of the substrate W from the central portion toward the peripheral portion. As a result, a DIW liquid film is formed over the entire upper surface of the substrate W. The chemical liquid adhering to the upper surface of the substrate W is washed away by the liquid film of DIW.
　一方、基板Ｗの下面中央部に供給されたＤＩＷは、基板Ｗの回転による遠心力を受けて、基板Ｗの下面を伝って回転半径外方側へと拡がり、基板Ｗの下面周縁部３２１に至る。そのため、基板Ｗの下面の全域にＤＩＷの液膜が形成される。このとき、下面周縁部３２１に達したＤＩＷは、基板Ｗの周端面３２２を回り込んで基板Ｗの上面周縁部３２３に至る。そして、基板Ｗの上面を伝ってきたＤＩＷと、基板Ｗの周端面３２２から回り込んだＤＩＷとが、図１９に示すように、基板Ｗの上面周縁部３２３において合流するようになる。そのため、基板Ｗの上面に形成されるＤＩＷの液膜と、基板Ｗの下面に形成されるＤＩＷの液膜とが互いに繋がった状態になる。 On the other hand, DIW supplied to the central portion of the lower surface of the substrate W receives a centrifugal force due to the rotation of the substrate W, propagates along the lower surface of the substrate W to the outer side of the rotation radius, and reaches the lower peripheral edge 321 of the substrate W It reaches. Therefore, a DIW liquid film is formed on the entire lower surface of the substrate W. At this time, DIW that has reached the lower surface peripheral portion 321 goes around the peripheral end surface 322 of the substrate W and reaches the upper surface peripheral portion 323 of the substrate W. Then, the DIW that has passed through the upper surface of the substrate W and the DIW that has come around from the peripheral end surface 322 of the substrate W come to merge at the upper peripheral edge 323 of the substrate W as shown in FIG. Therefore, the DIW liquid film formed on the upper surface of the substrate W and the DIW liquid film formed on the lower surface of the substrate W are connected to each other.
　リンス処理時における、下面ノズル３０６に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、下面ノズル３０６の吐出口３０６Ａから吐出されるＤＩＷの態様が、吐出口３０６Ａと基板Ｗの下面に形成されるＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。前述のように基板Ｗの上面に形成されるＤＩＷの液膜と、基板Ｗの下面に形成されるＤＩＷの液膜が互いに繋がっているので、吐出口３０６Ａから吐出されるＤＩＷが、基板Ｗの下面に形成されるＤＩＷの液膜だけでなく、基板Ｗの上面に形成されるＤＩＷの液膜とも液状に繋がっている。また、下面ノズル３０６のノズル配管内、下側処理液供給管３０５内、水供給配管３０７内で、ＤＩＷが液密状態にある。 The supply flow rate of DIW to the lower surface nozzle 306 during the rinsing process is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 306A of the lower surface nozzle 306 is a continuous flow mode connected to both the discharge port 306A and the liquid film of DIW formed on the lower surface of the substrate W. As described above, since the DIW liquid film formed on the upper surface of the substrate W and the DIW liquid film formed on the lower surface of the substrate W are connected to each other, the DIW discharged from the discharge port 306A is Not only the DIW liquid film formed on the lower surface but also the DIW liquid film formed on the upper surface of the substrate W are connected in liquid form. Further, DIW is in a liquid-tight state in the nozzle pipe of the lower surface nozzle 306, the lower processing liquid supply pipe 305, and the water supply pipe 307.
　リンス処理中に、水供給配管３０７内に存在しているＤＩＷに軟Ｘ線が照射されると、水供給配管３０７内におけるＤＩＷの照射部分（図５に示す、第１実施形態に係るＤＩＷの照射部分５４と同等）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、水供給配管３０７内におけるＤＩＷの照射部分に形成される。ＤＩＷの照射部分は、基板Ｗの下面に形成されたＤＩＷの液膜および基板Ｗの上面に形成されたＤＩＷの液膜と、それぞれ、ＤＩＷを介して繋がっている。 During the rinsing process, when DIX existing in the water supply pipe 307 is irradiated with soft X-rays, the DIW irradiated portion in the water supply pipe 307 (shown in FIG. 5 of the DIW according to the first embodiment) In the same manner as the irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water supply pipe 307. The DIW irradiated portion is connected to the DIW liquid film formed on the lower surface of the substrate W and the DIW liquid film formed on the upper surface of the substrate W via the DIW.
　基板Ｗの下面が正に帯電とすると、水供給配管３０７内におけるＤＩＷの照射部分と、正に帯電している基板Ｗとの間の電位差で、水供給配管３０７内におけるＤＩＷの照射部分からの電子が、基板Ｗの上面および下面のＤＩＷの液膜に向けて、下側処理液供給管３０５、水供給配管３０７および連続流状のＤＩＷを伝って移動する。これにより、基板Ｗの下面および上面に形成されているＤＩＷの液膜が、それぞれ多量の電子を有するようになる。 If the lower surface of the substrate W is positively charged, the potential difference between the DIW irradiated portion in the water supply pipe 307 and the positively charged substrate W is different from the DIW irradiated portion in the water supply pipe 307. Electrons move along the lower processing liquid supply pipe 305, the water supply pipe 307, and the continuous flow DIW toward the DIW liquid films on the upper surface and the lower surface of the substrate W. Thereby, the liquid films of DIW formed on the lower surface and the upper surface of the substrate W each have a large amount of electrons.
　以上により、基板Ｗの上下両面に同時リンス処理を施す場合において、回転状態の基板Ｗの上下面にＤＩＷが供給されても、ＤＩＷとの接触分離による基板Ｗの帯電を生じないから、リンス処理時における基板Ｗの帯電を防止できる。また、リンス処理前から基板Ｗが帯電していても、その基板Ｗに帯びた電荷を除去（すなわち、除電）できる。その結果、基板Ｗの帯電に起因するデバイス破壊を防止できる。 As described above, when simultaneous rinsing processing is performed on both the upper and lower surfaces of the substrate W, even if DIW is supplied to the upper and lower surfaces of the rotating substrate W, the substrate W is not charged by contact separation with the DIW. The charging of the substrate W at the time can be prevented. Further, even if the substrate W is charged before the rinsing process, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
　図２０は、本発明の第１１実施形態に係る基板処理装置３１１の構成を示す図である。 FIG. 20 is a diagram showing a configuration of a substrate processing apparatus 311 according to the eleventh embodiment of the present invention.
　基板処理装置３１１が、第１０実施形態に係る基板処理装置３０１と共通する部分には、図１８の場合と同一の参照符号を付し説明を省略する。基板処理装置３１１では、水供給ユニット３００（図１８参照）に代えて、水供給ユニット（処理液供給装置）３１０が設けられている。また、軟Ｘ線照射装置３１４が、処理室３内に配置されている。第１１実施形態では、これらの点が第１０実施形態と相違している。 In the substrate processing apparatus 311, parts common to the substrate processing apparatus 301 according to the tenth embodiment are denoted by the same reference numerals as those in FIG. In the substrate processing apparatus 311, a water supply unit (processing liquid supply apparatus) 310 is provided instead of the water supply unit 300 (see FIG. 18). A soft X-ray irradiation device 314 is disposed in the processing chamber 3. In the eleventh embodiment, these points are different from the tenth embodiment.
　水供給ユニット３１０は、下側処理液供給管３０５と、下面ノズル３０６と、水供給配管３０７と、水供給配管３０７の途中部から分岐する第２分岐配管（分岐配管）３１２と、第２分岐配管３１２内に存在しているＤＩＷ（水の一例）に軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）３１９とを含む。軟Ｘ線照射ユニット３１９は、第２分岐配管３１２に取り付けられている。 The water supply unit 310 includes a lower processing liquid supply pipe 305, a lower surface nozzle 306, a water supply pipe 307, a second branch pipe (branch pipe) 312 that branches from a middle portion of the water supply pipe 307, and a second branch. And a soft X-ray irradiation unit (X-ray irradiation means) 319 for irradiating DIW (an example of water) existing in the pipe 312 with soft X-rays. The soft X-ray irradiation unit 319 is attached to the second branch pipe 312.
　第２分岐配管３１２は、水供給配管３０７における水バルブ３０８よりも上流側の部分から分岐している。第２分岐配管３１２は、丸管状（円筒状）をなし、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。第２分岐配管３１２の途中部には、第２分岐配管３１２を開閉するための分岐バルブ３１８が介装されている。分岐バルブ３１８は、制御装置４０（図３参照）に接続されている。第２分岐配管３１２には、分岐バルブ３１８よりも上流側の所定部分の管壁に開口（図示しない）が形成されている。 The second branch pipe 312 branches from a portion upstream of the water valve 308 in the water supply pipe 307. The second branch pipe 312 has a round tubular shape (cylindrical shape), such as poly-vinyl-chloride, PTFE (polytetrafluoroethylene), PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer), etc. These resin materials are used. A branch valve 318 for opening and closing the second branch pipe 312 is interposed in the middle of the second branch pipe 312. The branch valve 318 is connected to the control device 40 (see FIG. 3). The second branch pipe 312 has an opening (not shown) in a predetermined portion of the pipe wall upstream of the branch valve 318.
　第２分岐配管３１２の下流端には、第２カップ用ノズル３１３が取り付けられている。第２カップ用ノズル３１３は、連続流の状態で液を吐出するストレートノズルによって構成されていて、その吐出口３１３Ａ（図２１参照。液受け用吐出口）を、カップ上部１９の内壁（たとえば傾斜部２１の下面）に向けた状態で、たとえばスピンチャック４の外壁に、固定的に配置されている。 A second cup nozzle 313 is attached to the downstream end of the second branch pipe 312. The second cup nozzle 313 is constituted by a straight nozzle that discharges liquid in a continuous flow state, and the discharge port 313A (see FIG. 21. liquid receiving discharge port) is connected to the inner wall (for example, inclined) of the cup upper portion 19. In a state facing the lower surface of the portion 21, for example, it is fixedly disposed on the outer wall of the spin chuck 4.
　軟Ｘ線照射ユニット３１９は、第１実施形態に係る軟Ｘ線照射ユニット６２（図２参照）と同等の構成を採用している。軟Ｘ線照射ユニット３１９は、第２分岐配管３１２の開口を塞ぐように第２分岐配管３１２に取り付けられている。具体的には、軟Ｘ線照射ユニット３１９のカバーの開口（軟Ｘ線照射ユニット６２のカバー２６の第２開口２８（図２参照）に相当）が第２分岐配管３１２の前記の開口に一致し、かつ軟Ｘ線照射ユニット３１９のカバーの壁面（軟Ｘ線照射ユニット６２のカバー２６の横壁２６Ａ（図２参照）に相当）が第２分岐配管３１２の外周に密着している。軟Ｘ線照射ユニット３１９の高電圧ユニット（第１実施形態に係る軟Ｘ線照射ユニット６２の高電圧ユニット３１（図２参照）に相当）は、制御装置４０（図３参照）に接続されている。 The soft X-ray irradiation unit 319 employs the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment. The soft X-ray irradiation unit 319 is attached to the second branch pipe 312 so as to close the opening of the second branch pipe 312. Specifically, the opening of the cover of the soft X-ray irradiation unit 319 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is equal to the opening of the second branch pipe 312. In addition, the wall surface of the cover of the soft X-ray irradiation unit 319 (corresponding to the lateral wall 26A (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is in close contact with the outer periphery of the second branch pipe 312. The high voltage unit of the soft X-ray irradiation unit 319 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
　分岐バルブ３１８が閉じられた状態で水バルブ３０８を開くと、水供給配管３０７から、下側処理液供給管３０５を介して下面ノズル３０６にＤＩＷが供給されて、下面ノズル３０６の吐出口３０６ＡからＤＩＷが吐出される。水バルブ３０８が閉じられた状態で分岐バルブ３１８を開くと、第２分岐配管３１２から第２カップ用ノズル３１３にＤＩＷが供給されて、第２カップ用ノズル３１３の吐出口３１３ＡからＤＩＷが吐出される。 When the water valve 308 is opened while the branch valve 318 is closed, DIW is supplied from the water supply pipe 307 to the lower surface nozzle 306 via the lower processing liquid supply pipe 305 and is discharged from the discharge port 306A of the lower surface nozzle 306. DIW is discharged. When the branch valve 318 is opened with the water valve 308 closed, DIW is supplied from the second branch pipe 312 to the second cup nozzle 313, and DIW is discharged from the discharge port 313A of the second cup nozzle 313. The
　軟Ｘ線照射装置３１４は、照射窓３１６を有する軟Ｘ線発生器３１５を内蔵している。照射窓３１６で発生する軟Ｘ線が、軟Ｘ線照射装置３１４の外部に射出（放射）されるようになっている。照射窓３１６からの軟Ｘ線の照射角（照射範囲）はたとえば130°であり、照射窓３１６から照射される軟Ｘ線は、その波長がたとえば0.13～0.41nmである。軟Ｘ線発生器３１５は、軟Ｘ線照射ユニット３０９に含まれる軟Ｘ線発生器２５（図２参照）と同等の構成を採用しており、照射窓３１６が照射窓３５（図２参照）に相当する。軟Ｘ線照射装置３１４は、照射窓３１６がカップ上部１９の傾斜部２１の上面に対向するように、カップ上部１９の上方に配置されている。 The soft X-ray irradiation device 314 includes a soft X-ray generator 315 having an irradiation window 316. Soft X-rays generated in the irradiation window 316 are emitted (radiated) outside the soft X-ray irradiation device 314. The irradiation angle (irradiation range) of soft X-rays from the irradiation window 316 is, for example, 130 °, and the soft X-rays irradiated from the irradiation window 316 have a wavelength of, for example, 0.13 to 0.41 nm. The soft X-ray generator 315 adopts the same configuration as the soft X-ray generator 25 (see FIG. 2) included in the soft X-ray irradiation unit 309, and the irradiation window 316 is the irradiation window 35 (see FIG. 2). It corresponds to. The soft X-ray irradiation device 314 is disposed above the cup upper portion 19 so that the irradiation window 316 faces the upper surface of the inclined portion 21 of the cup upper portion 19.
　基板処理装置３１１では、図４に示す処理例の場合と同様の処理が実施されるが、図４のステップＳ１の基板Ｗの搬入に先立って、カップ１７に対して除電が行われる。 In the substrate processing apparatus 311, the same processing as in the processing example shown in FIG. 4 is performed. However, before the substrate W is loaded in step S 1 of FIG.
　第１１実施形態は、カップ１７に対して除電を行う点で第６実施形態の場合と共通しているが、カップ上部１９へのＤＩＷの供給だけでなく、このＤＩＷの供給に並行して軟Ｘ線照射装置３１４から軟Ｘ線を照射してカップ１７を除電している点で第６実施形態の場合と相違している。 The eleventh embodiment is common to the sixth embodiment in that the cup 17 is subjected to charge removal. However, the eleventh embodiment is not limited to supplying DIW to the cup upper portion 19 but also softening in parallel with the supply of DIW. It differs from the case of 6th Embodiment by the point which soft X-rays are irradiated from the X-ray irradiation apparatus 314, and the cup 17 is neutralized.
　具体的には、制御装置４０は、軟Ｘ線照射ユニット３１９の高電圧ユニットを制御して、軟Ｘ線照射ユニット３１９の軟Ｘ線発生器（第１実施形態に係る軟Ｘ線照射ユニット６２の軟Ｘ線発生器２５（図２参照）に相当）に軟Ｘ線を発生させて、この軟Ｘ線を、第２分岐配管３１２の内部に向けて照射させる。また、制御装置４０は、水バルブ３０８を閉じながら分岐バルブ３１８を開く。これにより、第２分岐配管３１２を流通したＤＩＷが第２カップ用ノズル３１３の吐出口３１３Ａ（図２１参照）から吐出される。 Specifically, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 319, and the soft X-ray generator of the soft X-ray irradiation unit 319 (the soft X-ray irradiation unit 62 according to the first embodiment). The soft X-ray generator 25 (refer to FIG. 2) generates soft X-rays and irradiates the soft X-rays toward the inside of the second branch pipe 312. Further, the control device 40 opens the branch valve 318 while closing the water valve 308. Thereby, DIW which circulated through the 2nd branch piping 312 is discharged from discharge port 313A (refer to Drawing 21) of nozzle 313 for the 2nd cup.
　図２１は、図２０に示す水供給ユニット３１０がカップ上部１９の傾斜部２１にＤＩＷを供給している状態を示す図である。 FIG. 21 is a view showing a state where the water supply unit 310 shown in FIG. 20 supplies DIW to the inclined portion 21 of the cup upper portion 19.
　図２１に示すように、吐出口３１３Ａから吐出されたＤＩＷは、カップ上部１９の傾斜部２１の下面に供給され、傾斜部２１の下面を伝って下方に向けて流れる。そのため、傾斜部２１の下面には、ＤＩＷの液膜が形成される。 As shown in FIG. 21, DIW discharged from the discharge port 313A is supplied to the lower surface of the inclined portion 21 of the cup upper portion 19 and flows downward along the lower surface of the inclined portion 21. Therefore, a DIW liquid film is formed on the lower surface of the inclined portion 21.
　このとき、第２カップ用ノズル３１３に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、第２カップ用ノズル３１３の吐出口３１３Ａから吐出されるＤＩＷの態様が、吐出口３１３Ａと傾斜部２１の下面のＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。また、第２カップ用ノズル３１３のノズル配管内および第２分岐配管３１２内では、ＤＩＷが液密状態にある。 At this time, the supply flow rate of DIW to the second cup nozzle 313 is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the mode of DIW discharged from the discharge port 313A of the second cup nozzle 313 has a continuous flow mode connected to both the discharge port 313A and the DIW liquid film on the lower surface of the inclined portion 21. Further, DIW is in a liquid-tight state in the nozzle pipe of the second cup nozzle 313 and in the second branch pipe 312.
　カップ上部１９が正に帯電しているときには、第２分岐配管３１２内におけるＤＩＷの照射部分と、正に帯電しているカップ上部１９との間の電位差で、第２分岐配管３１２内におけるＤＩＷの照射部分からの電子が、傾斜部２１の下面のＤＩＷの液膜に向けて、連続流状のＤＩＷを伝って移動する。これにより、傾斜部２１の下面のＤＩＷの液膜が多量の電子を有するようになるので、正に帯電しているカップ上部１９のうち、ＤＩＷの液膜に接する部分が除電される。 When the cup upper portion 19 is positively charged, the potential difference between the DIW irradiated portion in the second branch pipe 312 and the positively charged cup upper portion 19 causes the DIW in the second branch pipe 312 to be positive. Electrons from the irradiated portion move along the continuous flow DIW toward the DIW liquid film on the lower surface of the inclined portion 21. As a result, the DIW liquid film on the lower surface of the inclined portion 21 has a large amount of electrons, so that a portion of the positively charged cup upper portion 19 that is in contact with the DIW liquid film is discharged.
　一方、カップ上部１９が負に帯電しているときには、カップ上部１９からの電子が、第２分岐配管３１２内におけるＤＩＷの照射部分の正イオンに向けて、連続流状の処理液を伝って移動する。そのため、負に帯電しているカップ上部１９のうち、ＤＩＷの液膜に接する部分が除電される。 On the other hand, when the cup upper portion 19 is negatively charged, the electrons from the cup upper portion 19 move along the continuous flow treatment liquid toward the positive ions in the DIW irradiated portion in the second branch pipe 312. To do. Therefore, the portion of the cup upper portion 19 that is negatively charged and in contact with the DIW liquid film is neutralized.
　また、制御装置４０は、軟Ｘ線照射装置３１４の高電圧ユニットを制御して、軟Ｘ線照射装置３１４の軟Ｘ線発生器３１５に軟Ｘ線を発生させて、この軟Ｘ線を、カップ上部１９の傾斜部２１の上面に照射させる。カップ上部１９の傾斜部２１は処理中に基板Ｗの周囲に配置される部材であるが、軟Ｘ線照射装置３１４からの軟Ｘ線の照射により、傾斜部２１の帯電防止および除電を達成できる。 In addition, the control device 40 controls the high voltage unit of the soft X-ray irradiation device 314 to generate soft X-rays in the soft X-ray generator 315 of the soft X-ray irradiation device 314, Irradiate the upper surface of the inclined portion 21 of the cup upper portion 19. The inclined portion 21 of the cup upper portion 19 is a member that is disposed around the substrate W during processing. However, by applying soft X-rays from the soft X-ray irradiation device 314, the inclined portion 21 can be prevented from being charged and discharged. .
　カップ上部１９に対する除電が行われた後、未処理の基板Ｗが処理室３に搬入され、スピンチャック４に受け渡される。 After the static electricity is removed from the cup upper part 19, the unprocessed substrate W is carried into the processing chamber 3 and delivered to the spin chuck 4.
　スピンチャック４に基板Ｗが保持された後、制御装置４０はスピンモータ８を制御して、スピンチャック４による基板Ｗの回転を開始させる（図４のステップＳ２）。基板Ｗの回転速度が所定の液処理速度（たとえば500rpm）まで上げられ、その後、その液処理速度に維持される。 After the substrate W is held on the spin chuck 4, the control device 40 controls the spin motor 8 to start the rotation of the substrate W by the spin chuck 4 (step S2 in FIG. 4). The rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
　リンス処理（図４のステップＳ４～Ｓ６）では、制御装置４０（図３参照）は、分岐バルブ３１８を閉じつつ水バルブ３０８を開く。また、水バルブ３０８の開成後所定時間経過して軟Ｘ線照射タイミングになると、制御装置４０は、軟Ｘ線照射ユニット３１９の高電圧ユニットを制御して、軟Ｘ線照射ユニット３１９の軟Ｘ線発生器に軟Ｘ線を発生させて、この軟Ｘ線を、第２分岐配管３１２の内部に向けて照射させる。これにより、下面ノズル３０６から、基板Ｗの下面中央部に向けてＤＩＷが吐出される。 In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 308 while closing the branch valve 318. In addition, when a predetermined time elapses after the opening of the water valve 308 and the soft X-ray irradiation timing is reached, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 319 so that the soft X-ray irradiation unit 319 has a soft X-ray irradiation timing. Soft X-rays are generated in the line generator, and the soft X-rays are irradiated toward the inside of the second branch pipe 312. Thus, DIW is discharged from the lower surface nozzle 306 toward the center of the lower surface of the substrate W.
　基板Ｗの下面中央部に供給されたＤＩＷは、第１０実施形態の場合と同様、基板Ｗの下面を伝って回転半径外方側へと拡がり、基板Ｗの周端面３２２（図１９参照）を回り込んで基板Ｗの上面周縁部に至る。そして、基板Ｗの上面を伝ってきたＤＩＷと、基板Ｗの周端面３２２から回り込んだＤＩＷとが、基板Ｗの上面周縁部において合流し、その結果、基板Ｗの上面全域に形成されるＤＩＷの液膜と、基板Ｗの下面全域に形成されるＤＩＷの液膜とが互いに繋がった状態になる。 The DIW supplied to the central portion of the lower surface of the substrate W spreads to the outer side of the rotation radius along the lower surface of the substrate W, as in the case of the tenth embodiment, and the peripheral end surface 322 (see FIG. 19) of the substrate W. It goes around and reaches the peripheral edge of the upper surface of the substrate W. Then, the DIW that has traveled along the upper surface of the substrate W and the DIW that has circulated from the peripheral end surface 322 of the substrate W merge at the peripheral edge of the upper surface of the substrate W, and as a result, the DIW formed over the entire upper surface of the substrate W. And the DIW liquid film formed over the entire lower surface of the substrate W are connected to each other.
　また下面ノズル３０６の吐出口３０６Ａから吐出されるＤＩＷの態様が、吐出口３０６Ａと基板Ｗの下面に形成されるＤＩＷの液膜との双方に繋がる連続流状の態様をなしている。基板Ｗの上面に形成されるＤＩＷの液膜と、基板Ｗの下面に形成されるＤＩＷの液膜が互いに繋がっているので、吐出口３０６Ａから吐出されるＤＩＷが、基板Ｗの下面に形成されるＤＩＷの液膜だけでなく、基板Ｗの上面に形成されるＤＩＷの液膜とも液状に繋がっている。また、下面ノズル３０６のノズル配管内、下側処理液供給管３０５内、水供給配管３０７内および第２分岐配管３１２内で、ＤＩＷが液密状態にある。 Further, the mode of DIW discharged from the discharge port 306A of the lower surface nozzle 306 is a continuous flow mode connected to both the discharge port 306A and the liquid film of DIW formed on the lower surface of the substrate W. Since the DIW liquid film formed on the upper surface of the substrate W and the DIW liquid film formed on the lower surface of the substrate W are connected to each other, the DIW discharged from the discharge port 306A is formed on the lower surface of the substrate W. In addition to the DIW liquid film, the DIW liquid film formed on the upper surface of the substrate W is connected in liquid form. Further, DIW is in a liquid-tight state in the nozzle pipe of the lower surface nozzle 306, the lower processing liquid supply pipe 305, the water supply pipe 307, and the second branch pipe 312.
　リンス処理中に、第２分岐配管３１２内に存在しているＤＩＷに軟Ｘ線が照射されると、第２分岐配管３１２内におけるＤＩＷの照射部分（図５に示す、第１実施形態に係るＤＩＷの照射部分５４と同等）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、第２分岐配管３１２内におけるＤＩＷの照射部分に形成される。ＤＩＷの照射部分は、基板Ｗの下面に形成されたＤＩＷの液膜および基板Ｗの上面に形成されたＤＩＷの液膜と、それぞれ、ＤＩＷを介して繋がっている。 When the DIW existing in the second branch pipe 312 is irradiated with soft X-rays during the rinsing process, the DIW irradiated portion in the second branch pipe 312 (according to the first embodiment shown in FIG. 5). In the DIW irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the second branch pipe 312. The DIW irradiated portion is connected to the DIW liquid film formed on the lower surface of the substrate W and the DIW liquid film formed on the upper surface of the substrate W via the DIW.
　基板Ｗが正に帯電すると、第２分岐配管３１２内におけるＤＩＷの照射部分と、正に帯電している基板Ｗとの間の電位差で、第２分岐配管３１２内におけるＤＩＷの照射部分からの電子が、基板Ｗの上面および下面のＤＩＷの液膜に向けて、下側処理液供給管３０５、水供給配管３０７、第２分岐配管３１２および連続流状のＤＩＷを伝って移動する。これにより、基板Ｗの上面および下面のＤＩＷの液膜が多量の電子を有するようになる。 When the substrate W is positively charged, electrons from the DIW irradiated portion in the second branch pipe 312 are caused by a potential difference between the DIW irradiated portion in the second branch pipe 312 and the positively charged substrate W. However, it moves along the lower processing liquid supply pipe 305, the water supply pipe 307, the second branch pipe 312 and the continuous flow DIW toward the DIW liquid films on the upper and lower surfaces of the substrate W. Thereby, the liquid film of DIW on the upper surface and the lower surface of the substrate W has a large amount of electrons.
　以上により、第１１実施形態においても、第１０実施形態で述べた作用効果と同等の作用効果に加えて、カップ上部１９の除電を良好に行えるという作用効果を奏することができる。 As described above, also in the eleventh embodiment, in addition to the operational effects equivalent to the operational effects described in the tenth embodiment, there can be exhibited the operational effect that the neutralization of the cup upper portion 19 can be performed satisfactorily.
　軟Ｘ線照射ユニット３１９の窓部材の外表面（窓部材７１の外表面７１Ｂ（図２参照）に相当）から親水性皮膜（親水性皮膜３８（図２参照）に相当）が剥がれると、当該窓部材に含まれるベリリウムが処理液（たとえば、ＤＩＷ等の水）に溶け出すおそれがある。このような場合であっても、軟Ｘ線照射ユニット３１９が第２分岐配管３１２に設けられているので、そのようなベリリウムを含むＤＩＷは、下面ノズル３０６ではなく第２カップ用ノズル３１３に供給される。これにより、ベリリウムを含むＤＩＷが基板Ｗに供給されるのを、確実に防止できる。 When the hydrophilic film (corresponding to the hydrophilic film 38 (see FIG. 2)) is peeled off from the outer surface of the window member of the soft X-ray irradiation unit 319 (corresponding to the outer surface 71B (see FIG. 2) of the window member 71), There is a possibility that beryllium contained in the window member is dissolved in the processing liquid (for example, water such as DIW). Even in such a case, since the soft X-ray irradiation unit 319 is provided in the second branch pipe 312, DIW containing such beryllium is supplied to the second cup nozzle 313 instead of the lower surface nozzle 306. Is done. Thereby, it is possible to reliably prevent the DIW containing beryllium from being supplied to the substrate W.
　なお、前述の説明では、軟Ｘ線照射装置３１４による軟Ｘ線の照射を、基板Ｗの搬入に先立って実行するものと説明したが、基板Ｗの搬入前だけでなく、スピンドライ（図４のステップＳ８）時にも軟Ｘ線照射装置３１４による軟Ｘ線の照射を行うようにしてもよい。この場合、基板Ｗの表面（上面）に軟Ｘ線を照射することが好ましく、これにより、処理液が振り切られた直後の基板Ｗの表面に軟Ｘ線が照射されるから、基板Ｗの帯電防止および除電を、より一層確実に達成できる。 In the above description, it has been described that the soft X-ray irradiation by the soft X-ray irradiation apparatus 314 is performed prior to the loading of the substrate W, but not only before the loading of the substrate W but also spin dry (FIG. 4). In step S8), soft X-ray irradiation by the soft X-ray irradiation apparatus 314 may be performed. In this case, it is preferable to irradiate the surface (upper surface) of the substrate W with soft X-rays. As a result, the surface of the substrate W immediately after the treatment liquid is shaken off is irradiated with soft X-rays. Prevention and static elimination can be achieved more reliably.
　なお、第１１実施形態の構成として、第１０実施形態の構成と比較して、第２カップ用ノズル３１３を含む構成の水供給ユニット３１０と軟Ｘ線照射装置３１４との２つを設けたが、第１０実施形態の構成に加え、水供給ユニット３１０および軟Ｘ線照射装置３１４の一方のみが設けられた構成であってもよい。 As the configuration of the eleventh embodiment, compared to the configuration of the tenth embodiment, two water supply units 310 and a soft X-ray irradiation device 314 having a configuration including the second cup nozzle 313 are provided. In addition to the configuration of the tenth embodiment, only one of the water supply unit 310 and the soft X-ray irradiation device 314 may be provided.
　図２２は、本発明の第１２実施形態に係る基板処理装置４０１の構成を示す図である。 FIG. 22 is a diagram showing a configuration of a substrate processing apparatus 401 according to the twelfth embodiment of the present invention.
　第１２実施形態において、第１０実施形態と共通する部分には、図１８および図１９の場合と同一の参照符号を付し説明を省略する。基板処理装置４０１は、スピンチャック４に代えてスピンチャック（基板保持回転手段）４０２を備える点、およびスピンチャック４０２を介して基板Ｗの下面にＤＩＷ（水の一例）を供給する点の主に２点において、第１０実施形態に係る基板処理装置３０１（図１８参照）と相違している。基板処理装置４０１は、水供給ユニット（処理液供給装置）４００を備えている。 In the twelfth embodiment, the same reference numerals as those in FIGS. 18 and 19 denote the same parts as in the tenth embodiment, and a description thereof will be omitted. The substrate processing apparatus 401 mainly includes a spin chuck (substrate holding and rotating means) 402 instead of the spin chuck 4 and supplies DIW (an example of water) to the lower surface of the substrate W via the spin chuck 402. Two points are different from the substrate processing apparatus 301 (see FIG. 18) according to the tenth embodiment. The substrate processing apparatus 401 includes a water supply unit (processing liquid supply apparatus) 400.
　スピンチャック４０２は、挟持式のものである。具体的には、スピンチャック４０２は、スピンモータ４０３と、このスピンモータ４０３の駆動軸と一体化されたスピン軸（支持部材）４０４と、スピン軸４０４の上端にほぼ水平に取り付けられた円板状のスピンベース（支持部材）４０５と、スピンベース４０５の周縁部の複数箇所にほぼ等間隔で設けられた複数個の挟持部材４０６とを備えている。 The spin chuck 402 is a sandwich type. Specifically, the spin chuck 402 includes a spin motor 403, a spin shaft (support member) 404 integrated with a drive shaft of the spin motor 403, and a disc attached substantially horizontally to the upper end of the spin shaft 404. A spin base (support member) 405 having a plurality of shapes, and a plurality of sandwiching members 406 provided at substantially equal intervals at a plurality of positions on the peripheral edge of the spin base 405 are provided.
　スピン軸４０４は、樹脂や鋼材等を用いて形成された内軸部４０７と、多孔質材料を用いて形成された外筒部４０８とを含み、内軸部４０７を外筒部４０８に挿通した状態で一体化している。すなわち、内軸部４０７の外周が外筒部４０８に密着状態で包囲されている。 The spin shaft 404 includes an inner shaft portion 407 formed using a resin, steel, or the like, and an outer cylinder portion 408 formed using a porous material, and the inner shaft portion 407 is inserted into the outer cylinder portion 408. It is integrated in the state. That is, the outer periphery of the inner shaft portion 407 is surrounded by the outer cylinder portion 408 in a close contact state.
　スピンベース４０５は、多孔質材料を用いて形成されている。スピンベース４０５の下面４０５Ｂには、外筒部４０８の上端面が密着状態で接続されている。 The spin base 405 is formed using a porous material. An upper end surface of the outer cylinder portion 408 is connected to the lower surface 405B of the spin base 405 in a close contact state.
　挟持部材４０６は鋼材等を用いて形成されている。複数の挟持部材４０６により基板Ｗを挟持した状態で、基板Ｗの下面の全域がスピンベース４０５の上面に接触するように、挟持部材４０６の諸元や、スピンベース４０５の高さ方向の厚みが、それぞれ設定されている。 The clamping member 406 is formed using a steel material or the like. In a state where the substrate W is sandwiched by the plurality of sandwiching members 406, the specifications of the sandwiching member 406 and the thickness in the height direction of the spin base 405 are such that the entire lower surface of the substrate W is in contact with the upper surface of the spin base 405. , Each is set.
　スピン軸４０４の外筒部４０８やスピンベース４０５の材質である多孔質材料は、たとえばＰＶＡ（polyvinyl alcohol）製のスポンジであり、多数の空孔を有している。多孔質材料の空孔は、ＤＩＷ（水の一例）が通過可能な大きさ（たとえば、０．０５～１００μmの径）を有している。そのため、多孔質材料の空孔を介してＤＩＷを通過させることが可能であり、ゆえに、外筒部４０８の内部やスピンベース４０５の内部を、ＤＩＷを移動させることが可能である。 The porous material that is the material of the outer cylindrical portion 408 of the spin shaft 404 and the spin base 405 is, for example, a sponge made of PVA (polyvinyl alcohol) and has a large number of pores. The pores of the porous material have a size (for example, a diameter of 0.05 to 100 μm) through which DIW (an example of water) can pass. Therefore, it is possible to pass the DIW through the pores of the porous material. Therefore, it is possible to move the DIW in the outer cylinder portion 408 or the spin base 405.
　なお、多孔質材料の原材料としては、ＰＶＡの他に、ウレタン樹脂、フッ素系樹脂(ＰＴＦＥ(poly tetra-fluoro ethylene))、ＰＥＥＫ(polyether-ether-ketone)、ＰＶＣ(poly-vinyl chloride)、およびＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)を例示できる。 In addition to PVA, as a raw material of the porous material, urethane resin, fluorine resin (PTFE (polytetrafluoroethylene)), PEEK (polyether-ether-ketone), PVC (polyvinyl chloride), and An example is PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
　水供給ユニット４００は、水ノズル４０９と、水ノズル４０９に対し、ＤＩＷ供給源からのＤＩＷ（水の一例）を供給する水供給配管（処理液配管）４１０と、水供給配管４１０内に存在しているＤＩＷに軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）４１２とを含む。軟Ｘ線照射ユニット４１２は、水供給配管４１０に取り付けられている。 The water supply unit 400 exists in the water nozzle 409, a water supply pipe (treatment liquid pipe) 410 that supplies DIW (an example of water) from a DIW supply source to the water nozzle 409, and the water supply pipe 410. And a soft X-ray irradiation unit (X-ray irradiation means) 412 for irradiating the DIW with soft X-rays. The soft X-ray irradiation unit 412 is attached to the water supply pipe 410.
　水ノズル４０９は、丸管状（円筒状）のノズル配管を有しており、水供給配管４１０の先端に取り付けられている。水ノズル４０９は、連続流の状態で液を吐出するストレートノズルによって構成されていて、その吐出口４０９Ａを、スピン軸４０４の外筒部４０８に向けた状態で、処理室３内に固定的に配置されている。 The water nozzle 409 has a round tubular (cylindrical) nozzle pipe and is attached to the tip of the water supply pipe 410. The water nozzle 409 is configured by a straight nozzle that discharges liquid in a continuous flow state, and the discharge port 409A is fixed in the processing chamber 3 with the discharge port 409A facing the outer cylindrical portion 408 of the spin shaft 404. Has been placed.
　水供給配管４１０は、丸管状（円筒状）をなしている。水供給配管４１０は、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。水供給配管４１０の途中部の管壁には、開口（図示しない）が形成されている。 The water supply pipe 410 has a round tubular shape (cylindrical shape). The water supply pipe 410 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). . An opening (not shown) is formed in the tube wall in the middle of the water supply pipe 410.
　軟Ｘ線照射ユニット４１２は、第１実施形態に係る軟Ｘ線照射ユニット６２（図２参照）と同等の構成を採用している。軟Ｘ線照射ユニット４１２は、水供給配管４１０の開口を塞ぐように水供給配管４１０に取り付けられている。具体的には、軟Ｘ線照射ユニット４１２のカバーの開口（軟Ｘ線照射ユニット６２のカバー２６の第２開口２８（図２参照）に相当）が水供給配管４１０の前記の開口に一致し、かつ軟Ｘ線照射ユニット４１２のカバーの壁面（軟Ｘ線照射ユニット６２のカバー２６の横壁２６Ａ（図２参照）に相当）が水供給配管４１０の外周に密着している。軟Ｘ線照射ユニット４１２の高電圧ユニット（第１実施形態に係る軟Ｘ線照射ユニット６２の高電圧ユニット３１（図２参照）に相当）は、制御装置４０（図３参照）に接続されている。 The soft X-ray irradiation unit 412 adopts the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment. The soft X-ray irradiation unit 412 is attached to the water supply pipe 410 so as to close the opening of the water supply pipe 410. Specifically, the opening of the cover of the soft X-ray irradiation unit 412 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) coincides with the opening of the water supply pipe 410. The wall surface of the cover of the soft X-ray irradiation unit 412 (corresponding to the lateral wall 26A (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is in close contact with the outer periphery of the water supply pipe 410. A high voltage unit of the soft X-ray irradiation unit 412 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes.
　水供給配管４１０には、水供給配管４１０を開閉するための水バルブ４１１が介装されている。水バルブ４１１は、制御装置４０（図３参照）に接続されている。水バルブ４１１が開かれると、水供給配管４１０から水ノズル４０９にＤＩＷが供給され、水バルブ４１１が閉じられると、水ノズル４０９へのＤＩＷの供給が停止される。 A water valve 411 for opening and closing the water supply pipe 410 is interposed in the water supply pipe 410. The water valve 411 is connected to the control device 40 (see FIG. 3). When the water valve 411 is opened, DIW is supplied from the water supply pipe 410 to the water nozzle 409, and when the water valve 411 is closed, the supply of DIW to the water nozzle 409 is stopped.
　図２３は、水供給ユニット４００が外筒部４０８にＤＩＷを供給している状態を示す図である。 FIG. 23 is a diagram illustrating a state in which the water supply unit 400 is supplying DIW to the outer cylinder portion 408.
　基板処理装置４０１では、図４に示す処理例の場合と同様の処理が実施される。 In the substrate processing apparatus 401, the same processing as in the processing example shown in FIG. 4 is performed.
　リンス処理（図４のステップＳ４～Ｓ６）では、制御装置４０（図３参照）は、水バルブ３０４を開く。これにより、水ノズル３０２の吐出口３０２Ａから、基板Ｗの上面中央部に向けてＤＩＷが吐出される。基板Ｗの上面中央部に供給されたＤＩＷは、基板Ｗの回転による遠心力を受けて、基板Ｗの上面上を、中央部から周縁部に向けて拡がる。これにより、基板Ｗの上面の全域にＤＩＷの液膜が形成される。ＤＩＷの液膜によって、基板Ｗの上面に付着している薬液が洗い流される。 In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 304. Accordingly, DIW is discharged from the discharge port 302A of the water nozzle 302 toward the center of the upper surface of the substrate W. The DIW supplied to the central portion of the upper surface of the substrate W receives a centrifugal force due to the rotation of the substrate W and spreads on the upper surface of the substrate W from the central portion toward the peripheral portion. As a result, a DIW liquid film is formed over the entire upper surface of the substrate W. The chemical liquid adhering to the upper surface of the substrate W is washed away by the liquid film of DIW.
　リンス処理（図４のステップＳ４～Ｓ６）では、制御装置４０（図３参照）は、水バルブ３０４の開成に併せて、水バルブ４１１を開く。これにより、水供給配管４１０を流通するＤＩＷが水ノズル４０９に供給される。水ノズル４０９の吐出口４０９Ａから、スピン軸４０４の外筒部４０８に向けて横向きにＤＩＷが吐出される。 In the rinsing process (steps S4 to S6 in FIG. 4), the control device 40 (see FIG. 3) opens the water valve 411 in conjunction with the opening of the water valve 304. As a result, DIW flowing through the water supply pipe 410 is supplied to the water nozzle 409. DIW is discharged laterally from the discharge port 409A of the water nozzle 409 toward the outer cylinder portion 408 of the spin shaft 404.
　外筒部４０８の外周面に供給されたＤＩＷは、外筒部４０８の内部に浸透し、外筒部４０８の内部を通って、スピンベース４０５の下面４０５Ｂに供給される。スピンベース４０５の下面４０５Ｂに供給されたＤＩＷは、スピンベース４０５の内部に浸透し、外筒部４０８の内部を通って、スピンベース４０５の上面４０５Ａに供給される。スピンベース４０５の内部に含浸されているＤＩＷが上面４０５Ａから染み出し、図２３に示すように、上面４０５ＡにＤＩＷの液膜が形成される。このＤＩＷの液膜が基板Ｗの下面に接液されることにより、基板Ｗの下面に付着している薬液がＤＩＷによって洗い流されていく。これにより、基板Ｗの下面の全域にリンス処理を施すことができる。 DIW supplied to the outer peripheral surface of the outer cylinder portion 408 penetrates into the outer cylinder portion 408, passes through the outer cylinder portion 408, and is supplied to the lower surface 405B of the spin base 405. The DIW supplied to the lower surface 405B of the spin base 405 penetrates into the spin base 405, passes through the outer cylindrical portion 408, and is supplied to the upper surface 405A of the spin base 405. The DIW impregnated in the spin base 405 oozes out from the upper surface 405A, and as shown in FIG. 23, a DIW liquid film is formed on the upper surface 405A. When the DIW liquid film is in contact with the lower surface of the substrate W, the chemical liquid adhering to the lower surface of the substrate W is washed away by the DIW. Thereby, the rinsing process can be performed on the entire lower surface of the substrate W.
　水ノズル４０９は、その吐出口４０９Ａが、外筒部４０８の外周面と微小な間隔Ｓ１を隔てて配置されている。また、リンス処理中における、水ノズル６１に対するＤＩＷの供給流量は、比較的大流量（たとえば０．５～２．０L/min）に設定されている。そのため、水ノズル４０９の吐出口４０９Ａから吐出されるＤＩＷの態様が、吐出口４０９Ａとスピン軸４０４の外筒部４０８の外周面との双方に繋がる連続流状をなしている。そのため、吐出口４０９Ａから吐出されるＤＩＷが、基板Ｗの下面に形成されるＤＩＷの液膜に液状に繋がっている。また、水ノズル４０９のノズル配管内および水供給配管４１０内で、ＤＩＷが液密状態にある。 The water nozzle 409 has a discharge port 409A disposed at a small distance S1 from the outer peripheral surface of the outer tube portion 408. Further, the DIW supply flow rate to the water nozzle 61 during the rinsing process is set to a relatively large flow rate (for example, 0.5 to 2.0 L / min). Therefore, the form of DIW discharged from the discharge port 409A of the water nozzle 409 forms a continuous flow that is connected to both the discharge port 409A and the outer peripheral surface of the outer cylindrical portion 408 of the spin shaft 404. Therefore, the DIW discharged from the discharge port 409A is connected in liquid form to the DIW liquid film formed on the lower surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 409 and the water supply pipe 410.
　水バルブ４１１の開成後所定時間経過して軟Ｘ線照射タイミングになると、制御装置４０は、軟Ｘ線照射ユニット４１２の高電圧ユニットを制御して、軟Ｘ線照射ユニット４１２の軟Ｘ線発生器（第１実施形態に係る軟Ｘ線照射ユニット６２の軟Ｘ線発生器２５（図２参照）に相当）に軟Ｘ線を発生させて、この軟Ｘ線を、水供給配管４１０の内部に向けて照射させる。これにより、水供給配管４１０内を流通しているＤＩＷに、軟Ｘ線が照射される。 When a predetermined time elapses after the water valve 411 is opened, the control device 40 controls the high voltage unit of the soft X-ray irradiation unit 412 to generate soft X-rays of the soft X-ray irradiation unit 412. A soft X-ray is generated in a vessel (corresponding to the soft X-ray generator 25 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment), and the soft X-ray is generated inside the water supply pipe 410. Irradiate toward Thereby, soft X-rays are irradiated to DIW circulating in the water supply pipe 410.
　リンス処理中に、水供給配管４１０内を流通しているＤＩＷに軟Ｘ線が照射されると、水供給配管４１０内におけるＤＩＷの照射部分（図５に示す、第１実施形態に係るＤＩＷの照射部分５４と同等）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、水供給配管４１０内におけるＤＩＷの照射部分に形成される。ＤＩＷの照射部分は、基板Ｗの下面に形成されたＤＩＷの液膜と、ＤＩＷを介して繋がっている。 During the rinsing process, if soft X-rays are irradiated to the DIW flowing through the water supply pipe 410, the DIW irradiated portion in the water supply pipe 410 (shown in FIG. 5 of the DIW according to the first embodiment) In the same manner as the irradiated portion 54), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water supply pipe 410. The DIW irradiated portion is connected to the DIW liquid film formed on the lower surface of the substrate W via the DIW.
　基板Ｗの下面が正に帯電しているとすると、水供給配管４１０内におけるＤＩＷの照射部分と、正に帯電している基板Ｗの下面との間の電位差で、水供給配管４１０内におけるＤＩＷの照射部分からの電子が、基板Ｗの下面に接液しているＤＩＷの液膜に向けて、連続流状のＤＩＷを伝って移動する。これにより、基板Ｗの下面に接液しているＤＩＷの液膜が多量の電子を有するようになる。 If the lower surface of the substrate W is positively charged, the DIW in the water supply pipe 410 is determined by the potential difference between the DIW irradiated portion in the water supply pipe 410 and the lower surface of the positively charged substrate W. Electrons from the irradiated portion move toward the DIW liquid film in contact with the lower surface of the substrate W along the continuous flow DIW. As a result, the liquid film of DIW in contact with the lower surface of the substrate W has a large amount of electrons.
　以上により、第１２実施形態においても、第１０実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, also in the twelfth embodiment, the same effects as the effects described in the tenth embodiment are achieved.
　以上、第１～第１２実施形態では、本発明を、円形の基板Ｗを処理するための枚葉型の基板処理装置１，２０１，２１１，２２１，２３１，２５１，２６１，３０１，３１１，４０１に適用する場合を例に挙げて説明したが、本発明は、角形（シート状）の基板を処理するための基板搬送型の基板処理装置に本発明を適用することもできる。 As described above, in the first to twelfth embodiments, the present invention is based on the single wafer processing apparatus 1,201, 211, 221, 231, 251, 261, 301, 311, 401 for processing the circular substrate W. However, the present invention can also be applied to a substrate transport type substrate processing apparatus for processing a square (sheet-like) substrate.
　図２４は、本発明の第１３実施形態に係る基板処理装置５０１の構成を示す図解的な斜視図である。基板処理装置５０１は、基板Ｗの一例としての角形の液晶表示装置用ガラス基板の表面（処理対象面）を、水等の処理液を用いて洗浄するために用いられる装置である。処理対象となる角形の基板Ｗの一辺の長さは、例えば数十ｃｍ～２ｍ程度の範囲であり、その板厚は０．５～１．２mm程度である。 FIG. 24 is an illustrative perspective view showing the configuration of the substrate processing apparatus 501 according to the thirteenth embodiment of the present invention. The substrate processing apparatus 501 is an apparatus used for cleaning the surface (surface to be processed) of a square glass substrate for a liquid crystal display device as an example of the substrate W using a processing liquid such as water. The length of one side of the square substrate W to be processed is, for example, in the range of several tens of cm to 2 m, and the plate thickness is in the range of about 0.5 to 1.2 mm.
　以下、次に述べる、基板Ｗの搬送方向に沿う水平方向をＸ方向とし、Ｘ方向に直交する水平方向をＹ方向とし、上下方向をＺ方向とする。 Hereinafter, the horizontal direction along the transport direction of the substrate W, which will be described below, is defined as the X direction, the horizontal direction orthogonal to the X direction is defined as the Y direction, and the vertical direction is defined as the Z direction.
　基板処理装置５０１は、基板ＷをＸ方向に沿って搬送するためのコロ搬送ユニット５０４（基板保持搬送手段）と、コロ搬送ユニット５０４によって搬送されている基板Ｗの表面に処理液としてのＤＩＷ（水の一例）を供給する水供給ユニット（処理液供給装置）５００と、コロ搬送ユニット５０４によって搬送されている基板Ｗの表面に不活性ガスの一例としての窒素ガスを吹き付けるガスナイフノズル５１９と、コロ搬送ユニット５０４によって搬送されている基板Ｗの表面に軟Ｘ線を照射する軟Ｘ線照射装置５１２とを含む。 The substrate processing apparatus 501 includes a roller transport unit 504 (substrate holding and transporting unit) for transporting the substrate W along the X direction, and DIW (treatment liquid) on the surface of the substrate W transported by the roller transport unit 504. A water supply unit (processing liquid supply device) 500 for supplying water (an example of water), a gas knife nozzle 519 for blowing nitrogen gas as an example of an inert gas onto the surface of the substrate W being transferred by the roller transfer unit 504, And a soft X-ray irradiation device 512 that irradiates the surface of the substrate W transported by the roller transport unit 504 with soft X-rays.
　基板処理装置５０１は、基板Ｗの表面にＤＩＷを供給して、基板Ｗの表面に洗浄処理を施すための洗浄処理室５０２と、基板Ｗの表面に付着したＤＩＷを液切りする液切り処理を施すための液切り室５０３とを含む。洗浄処理室５０２および液切り室５０３は、互いに隣接して配置されている。洗浄処理室５０２内には、コロ搬送ユニット５０４の上方に、供給ユニット５００が配置されている。液切り室５０３内には、コロ搬送ユニット５０４の上方に、ガスナイフノズル５１９および軟Ｘ線照射装置５１２が搬送方向にこの順で配置されている。 The substrate processing apparatus 501 supplies DIW to the surface of the substrate W and performs a cleaning process chamber 502 for cleaning the surface of the substrate W, and a liquid draining process for draining DIW adhering to the surface of the substrate W. A liquid draining chamber 503 for application. The cleaning processing chamber 502 and the liquid draining chamber 503 are disposed adjacent to each other. A supply unit 500 is disposed above the roller transport unit 504 in the cleaning processing chamber 502. In the liquid draining chamber 503, a gas knife nozzle 519 and a soft X-ray irradiation device 512 are arranged in this order in the transport direction above the roller transport unit 504.
　コロ搬送ユニット５０４は、洗浄処理室５０２の内部空間と、液切り室５０３の内部空間との間を跨るように、左右方向に延びた状態で配置されている。洗浄処理室５０２の上流側の側壁に形成された基板搬入口５２３から搬入された基板Ｗは、コロ搬送ユニット５０４により搬送させられ、洗浄処理室５０２と液切り室５０３とを仕切る仕切り壁５２１に形成された基板通過口５２２を介して、液切り室５０３に移される。そして、コロ搬送ユニット５０４により液切り室５０３内を搬送させられ、液切り室５０３の下流側の側壁に形成された基板搬出口５２４から搬出させられる。 The roller transport unit 504 is arranged in a state extending in the left-right direction so as to straddle between the internal space of the cleaning processing chamber 502 and the internal space of the liquid draining chamber 503. The substrate W carried in from the substrate carry-in port 523 formed on the upstream side wall of the cleaning processing chamber 502 is transported by the roller transport unit 504, and is supplied to the partition wall 521 that partitions the cleaning processing chamber 502 and the liquid draining chamber 503. It is transferred to the liquid draining chamber 503 through the formed substrate passage port 522. Then, the inside of the liquid draining chamber 503 is transported by the roller transport unit 504, and unloaded from the substrate unloading port 524 formed on the side wall on the downstream side of the liquid draining chamber 503.
　基板Ｗは、その表面を上方に向けてコロ搬送ユニット５０４上に載置される。基板ＷをＸ方向に沿って搬送することにより、基板Ｗの表面が、水供給位置Ｐ１および不活性ガス噴射位置Ｐ２によって順次走査される。これにより、基板Ｗの表面において、まずＤＩＷが供給され、その後所定の時間だけ遅れて窒素ガスが噴射される。 The substrate W is placed on the roller transport unit 504 with its surface facing upward. By transporting the substrate W along the X direction, the surface of the substrate W is sequentially scanned by the water supply position P1 and the inert gas injection position P2. Thus, DIW is first supplied on the surface of the substrate W, and then nitrogen gas is injected after a predetermined time delay.
　図２５は、コロ搬送ユニット５０４の構成を示す斜視図である。 FIG. 25 is a perspective view showing the configuration of the roller transport unit 504.
　コロ搬送ユニット５０４は、搬送コロ５０５が、Ｘ方向にほぼ等ピッチで並設されている。各搬送コロ５０５は、駆動ユニット（図示しない）の駆動により同一方向に同期回転されるようになっている。 In the roller conveyance unit 504, the conveyance rollers 505 are arranged in parallel at substantially equal pitches in the X direction. Each transport roller 505 is synchronously rotated in the same direction by driving of a drive unit (not shown).
　各搬送コロ５０５は、Ｘ方向に直交する面（Ｙ－Ｚ面）内で、水平面に対し傾斜したコロ軸５１５を備える。そのため、コロ搬送ユニット５０４により実現される搬送路は、水平面に対して全体的にＹ方向に傾斜している。基板Ｗは、傾斜姿勢を保ちながら搬送される。なお、基板Ｗの水平面に対する傾斜角度α（図２６参照）は、たとえば約５°に設定されている。 Each conveyance roller 505 includes a roller shaft 515 that is inclined with respect to a horizontal plane in a plane (YZ plane) orthogonal to the X direction. Therefore, the conveyance path realized by the roller conveyance unit 504 is entirely inclined in the Y direction with respect to the horizontal plane. The substrate W is transported while maintaining an inclined posture. The inclination angle α (see FIG. 26) of the substrate W with respect to the horizontal plane is set to about 5 °, for example.
　各搬送コロ５０５は、たとえば、コロ軸５１５の左右両側部にコロ軸５１５と同伴回転可能に外嵌された左右一対の側部ローラ５１６と、コロ軸５１５の中央部に設けられた中央ローラ５１７とを含む、いわゆる部分支持型搬送コロである。 Each conveying roller 505 includes, for example, a pair of left and right side rollers 516 that are fitted on the left and right sides of the roller shaft 515 so as to be able to rotate together with the roller shaft 515, and a center roller 517 provided at the center of the roller shaft 515. Is a so-called partially supported transport roller.
　個々の各側部ローラ５１６は、外方側部に、側部ローラ５１６と一体的に設けられた鍔部５１６Ａを有している。鍔部５１６Ａは、搬送される基板Ｗの横ずれを防止するとともに、下側の鍔部５１６Ａによって基板Ｗが傾斜面に沿って滑落するのを防止している。また、各ローラ５１６，５１７には、ゴム等からなるＯリング（図示しない）が外嵌されており、このＯリングの滑り止め作用により、基板Ｗの滑落をより確実に防止している。 Each individual side roller 516 has a flange 516A provided integrally with the side roller 516 on the outer side. The flange 516A prevents the substrate W to be transported from being laterally displaced, and prevents the substrate W from sliding along the inclined surface by the lower flange 516A. In addition, an O-ring (not shown) made of rubber or the like is externally fitted to each of the rollers 516 and 517, and the sliding of the O-ring prevents the substrate W from falling down more reliably.
　図２４に示すように、水供給ユニット５００は、洗浄処理室５０２内に配置された複数（図２４では、たとえば３つ）の水ノズル５３１と、個々の水ノズル５３１にＤＩＷを供給するための水供給配管（処理液配管）５３３と、個々の水供給配管５３３の上流端が接続される水集合配管５３２とを含む。複数の水ノズル５３１は、Ｘ方向に沿ってたとえば等間隔を隔てて配置されている。各水ノズル５３１は、その吐出口５３１Ａを、コロ搬送ユニット５０４によって搬送される基板Ｗの上部に対向する位置で下に向けた状態で、固定的に配置されている。水集合配管５３２は、ＤＩＷ供給源からのＤＩＷ（水の一例）を、複数の水供給配管５３３にＤＩＷを供給するための配管である。各水ノズル５３１の先端部には、円環状の電極５６が外嵌固定されており、かつ電極５６には、電源５７（図３参照）によって装置グラウンドに対する電圧が印加されるようになっている。 As shown in FIG. 24, the water supply unit 500 is for supplying DIW to a plurality (for example, three in FIG. 24) of water nozzles 531 disposed in the cleaning processing chamber 502 and to each of the water nozzles 531. A water supply pipe (treatment liquid pipe) 533 and a water collecting pipe 532 to which the upstream ends of the individual water supply pipes 533 are connected are included. The plurality of water nozzles 531 are arranged, for example, at equal intervals along the X direction. Each water nozzle 531 is fixedly arranged with its discharge port 531A facing downward at a position facing the upper portion of the substrate W transported by the roller transport unit 504. The water collecting pipe 532 is a pipe for supplying DIW (an example of water) from the DIW supply source to the plurality of water supply pipes 533. An annular electrode 56 is fitted and fixed to the tip of each water nozzle 531, and a voltage with respect to the apparatus ground is applied to the electrode 56 by a power source 57 (see FIG. 3). .
　図２４に示すように、水供給ユニット５００は、さらに、水集合配管５３２内に存在しているＤＩＷに軟Ｘ線を照射するための軟Ｘ線照射ユニット（Ｘ線照射手段）５３４を含む。軟Ｘ線照射ユニット５３４は、水集合配管５３２に取り付けられている。 As shown in FIG. 24, the water supply unit 500 further includes a soft X-ray irradiation unit (X-ray irradiation means) 534 for irradiating the DIW existing in the water collecting pipe 532 with soft X-rays. The soft X-ray irradiation unit 534 is attached to the water collecting pipe 532.
　水集合配管５３２は、丸管状（円筒状）をなし、たとえば塩ビ(poly-vinyl-chloride)を用いて形成されている。水集合配管５３２の途中部には、水集合配管５３２を開閉するための集合バルブ５３５が介装されている。水集合配管５３２には、集合よりも下流側の所定部分の管壁に開口（図示しない）が形成されている。 The water collecting pipe 532 has a round tubular shape (cylindrical shape), and is formed using, for example, polyvinyl-chloride. A collecting valve 535 for opening and closing the water collecting pipe 532 is interposed in the middle of the water collecting pipe 532. In the water collecting pipe 532, an opening (not shown) is formed in a predetermined portion of the pipe wall downstream of the collecting.
　図２４に示すように、軟Ｘ線照射ユニット５３４は、第１実施形態に係る軟Ｘ線照射ユニット６２（図２参照）と同等の構成を採用している。軟Ｘ線照射ユニット５３４は、水集合配管５３２の開口を塞ぐように水集合配管５３２に取り付けられている。具体的には、軟Ｘ線照射ユニット５３４のカバーの開口（軟Ｘ線照射ユニット６２のカバー２６の第２開口２８（図２参照）に相当）が水集合配管５３２の前記の開口に一致し、かつ軟Ｘ線照射ユニット５３４のカバーの壁面（軟Ｘ線照射ユニット６２のカバー２６の横壁２６Ａ（図２参照）に相当）が水集合配管５３２の外周に密着している。軟Ｘ線照射ユニット５３４の高電圧ユニット（第１実施形態に係る軟Ｘ線照射ユニット６２の高電圧ユニット３１（図２参照）に相当）は、制御装置４０（図３参照）に接続されている。集合バルブ５３５が開かれると、水集合配管５３２から個々の水供給配管５３３にＤＩＷが供給されて、各水ノズル５３１の吐出口５３１ＡからＤＩＷが吐出される。 As shown in FIG. 24, the soft X-ray irradiation unit 534 has the same configuration as the soft X-ray irradiation unit 62 (see FIG. 2) according to the first embodiment. The soft X-ray irradiation unit 534 is attached to the water collecting pipe 532 so as to close the opening of the water collecting pipe 532. Specifically, the opening of the cover of the soft X-ray irradiation unit 534 (corresponding to the second opening 28 (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) coincides with the opening of the water collecting pipe 532. The wall surface of the cover of the soft X-ray irradiation unit 534 (corresponding to the lateral wall 26A (see FIG. 2) of the cover 26 of the soft X-ray irradiation unit 62) is in close contact with the outer periphery of the water collecting pipe 532. The high voltage unit of the soft X-ray irradiation unit 534 (corresponding to the high voltage unit 31 (see FIG. 2) of the soft X-ray irradiation unit 62 according to the first embodiment) is connected to the control device 40 (see FIG. 3). Yes. When the collecting valve 535 is opened, DIW is supplied from the water collecting pipe 532 to each water supply pipe 533, and DIW is discharged from the discharge port 531A of each water nozzle 531.
　図２４に示すように、ガスナイフノズル５１９は、基板Ｗの上面に付着しているＤＩＷを吹き飛ばすために、コロ搬送ユニット５０４によって搬送される基板Ｗの上面に不活性ガスの一例としての窒素ガスを噴射するためのノズルである。不活性ガスの他の例として、ＣＤＡ（低湿度の清浄空気）を挙げることができる。ガスナイフノズル５１９は、Ｙ方向に長いスリット噴射口５１９Ａを先端に有し、コロ搬送ユニット５０４によって搬送される基板ＷのＹ方向全幅にわたる範囲に窒素ガスを供給できるものである。ガスナイフノズル５１９は、スリット噴射口５１９Ａが基板Ｗの上面に微小間隔を隔てて対向するように、液切り室５０３内に固定的に配置されている。 As shown in FIG. 24, the gas knife nozzle 519 has a nitrogen gas as an example of an inert gas on the upper surface of the substrate W transported by the roller transport unit 504 in order to blow off DIW adhering to the upper surface of the substrate W. It is a nozzle for injecting. Another example of the inert gas is CDA (clean air with low humidity). The gas knife nozzle 519 has a slit injection port 519 </ b> A that is long in the Y direction, and can supply nitrogen gas over the entire width in the Y direction of the substrate W transported by the roller transport unit 504. The gas knife nozzle 519 is fixedly disposed in the liquid draining chamber 503 so that the slit injection port 519A faces the upper surface of the substrate W with a minute gap.
　ガスナイフノズル５１９には、窒素ガス供給源からの窒素ガスが、不活性ガスバルブ５１１を介して供給されている。ガスナイフノズル５１９は、窒素ガスをＹ方向に沿う帯状に噴射する。 Nitrogen gas from a nitrogen gas supply source is supplied to the gas knife nozzle 519 via an inert gas valve 511. The gas knife nozzle 519 injects nitrogen gas in a strip shape along the Y direction.
　基板Ｗの上面に対する、ガスナイフノズル５１９のスリット噴射口５１９Ａからの不活性ガスの吹付け方向は、鉛直方向に対し、基板Ｗの搬送方向と逆方向（図２４に示す左側）に傾斜している。その傾斜角度θ（図２７参照）は、たとえば２０°～７０°の範囲内である。　 The blowing direction of the inert gas from the slit injection port 519A of the gas knife nozzle 519 with respect to the upper surface of the substrate W is inclined in the direction opposite to the transport direction of the substrate W (left side shown in FIG. 24) with respect to the vertical direction. Yes. The inclination angle θ (see FIG. 27) is in the range of 20 ° to 70 °, for example. *
　図２４に示すように、軟Ｘ線照射装置５１２は、照射窓５１４を有する軟Ｘ線発生器５１３を内蔵している。照射窓５１４で発生する軟Ｘ線が、軟Ｘ線照射装置５１２の外部に射出（放射）されるようになっている。照射窓５１４からの軟Ｘ線の照射角（照射範囲）はたとえば130°であり、照射窓５１４から照射される軟Ｘ線は、その波長がたとえば0.13～0.41nmである。軟Ｘ線発生器５１３は、軟Ｘ線照射ユニット５３４に含まれる軟Ｘ線発生器２５（図２参照）と同等の構成を採用しており、照射窓５１４が照射窓３５（図２参照）に相当する。軟Ｘ線照射装置５１２は、コロ搬送ユニット５０４によって搬送される基板Ｗの上方において、ガスナイフノズル５１９よりも下流側に配置されている。具体的には、軟Ｘ線照射装置５１２は、不活性ガス噴射位置Ｐ２に照射窓５１４が対向するように配置されている。 As shown in FIG. 24, the soft X-ray irradiation apparatus 512 has a built-in soft X-ray generator 513 having an irradiation window 514. Soft X-rays generated in the irradiation window 514 are emitted (radiated) outside the soft X-ray irradiation apparatus 512. The irradiation angle (irradiation range) of soft X-rays from the irradiation window 514 is, for example, 130 °, and the soft X-rays irradiated from the irradiation window 514 have a wavelength of, for example, 0.13 to 0.41 nm. The soft X-ray generator 513 has the same configuration as the soft X-ray generator 25 (see FIG. 2) included in the soft X-ray irradiation unit 534, and the irradiation window 514 is the irradiation window 35 (see FIG. 2). It corresponds to. The soft X-ray irradiation device 512 is disposed on the downstream side of the gas knife nozzle 519 above the substrate W transported by the roller transport unit 504. Specifically, the soft X-ray irradiation apparatus 512 is disposed so that the irradiation window 514 faces the inert gas injection position P2.
　図２６は、水供給ユニット５００が基板ＷにＤＩＷを供給している状態を示す断面図である。図２７は、軟Ｘ線照射装置５１２が、基板Ｗの上面に軟Ｘ線を照射している状態を示す断面図である。 FIG. 26 is a cross-sectional view showing a state where the water supply unit 500 supplies DIW to the substrate W. FIG. 27 is a cross-sectional view showing a state where the soft X-ray irradiation apparatus 512 irradiates the upper surface of the substrate W with soft X-rays.
　図２６および図２７に示すように、各吐出口５３１Ａから吐出されたＤＩＷは、基板Ｗの上面の水供給位置Ｐ１に供給され、基板Ｗの上面を傾斜面に沿って流れる。これにより、基板Ｗの上面にＤＩＷの液膜が形成される。また、各水ノズル５３１に対するＤＩＷの供給流量は、比較的大流量（ガラス基板の大きさや洗浄程度に応じて例えば１～数十L/min）に設定されている。そのため、各吐出口５３１Ａから吐出されるＤＩＷが、水ノズル５３１の吐出口５３１Ａと、基板Ｗの上面のＤＩＷの液膜との双方に繋がる連続流の態様をなしている。また、水ノズル５３１のノズル配管内、水集合配管５３２内および水供給配管５３３内では、ＤＩＷが液密状態にある。 As shown in FIGS. 26 and 27, DIW discharged from each discharge port 531A is supplied to the water supply position P1 on the upper surface of the substrate W, and flows along the inclined surface on the upper surface of the substrate W. As a result, a liquid film of DIW is formed on the upper surface of the substrate W. The DIW supply flow rate to each water nozzle 531 is set to a relatively large flow rate (for example, 1 to several tens L / min depending on the size of the glass substrate and the degree of cleaning). Therefore, the DIW discharged from each of the discharge ports 531A is in a continuous flow mode connected to both the discharge port 531A of the water nozzle 531 and the DIW liquid film on the upper surface of the substrate W. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 531, the water collecting pipe 532, and the water supply pipe 533.
　一連の処理中は、水集合配管５３２の内部に、軟Ｘ線照射ユニット５３４からの軟Ｘ線が照射される。水集合配管５３２内に存在しているＤＩＷに軟Ｘ線が照射されると、水集合配管５３２内におけるＤＩＷの照射部分（図５に示す、第１実施形態に係るＤＩＷの照射部分５４と同等）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、水集合配管５３２内におけるＤＩＷの照射部分に形成される。ＤＩＷの照射部分は、基板Ｗの上面に形成されたＤＩＷの液膜と、ＤＩＷを介して繋がっている。 During the series of processing, soft X-rays from the soft X-ray irradiation unit 534 are irradiated into the water collecting pipe 532. When soft X-rays are irradiated to the DIW existing in the water collecting pipe 532, the DIW irradiated portion in the water collecting pipe 532 (equivalent to the DIW irradiated portion 54 according to the first embodiment shown in FIG. 5). ), Electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the DIW irradiated portion in the water collecting pipe 532. The DIW irradiated portion is connected to the DIW liquid film formed on the upper surface of the substrate W via the DIW.
　基板Ｗが正に帯電すると水集合配管５３２内におけるＤＩＷの照射部分と、正に帯電している基板Ｗとの間の電位差で、水集合配管５３２内におけるＤＩＷの照射部分からの電子が、基板Ｗの上面のＤＩＷの液膜に向けて、連続流状のＤＩＷを伝って移動する。これにより、基板Ｗの上面のＤＩＷの液膜が多量の電子を有するようになる。 When the substrate W is positively charged, the electrons from the DIW irradiated portion in the water collecting pipe 532 are converted into a substrate by the potential difference between the DIW irradiated portion in the water collecting pipe 532 and the positively charged substrate W. It moves along the continuous flow of DIW toward the liquid film of DIW on the upper surface of W. Thus, the DIW liquid film on the upper surface of the substrate W has a large amount of electrons.
　これにより、ＤＩＷを用いた処理によって、基板Ｗの帯電を防止できる。また、洗浄処理前から基板Ｗが帯電していても、その基板Ｗに帯びた電荷を除去（すなわち、除電）できる。その結果、基板Ｗの帯電に起因するデバイス破壊を防止できる。 Thereby, charging of the substrate W can be prevented by the processing using DIW. Further, even if the substrate W is charged before the cleaning process, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
　また、不活性ガス噴射位置Ｐ２では、ガスナイフノズル５１９のスリット噴射口５１９Ａからの窒素ガスが、基板Ｗの上面に形成されるＤＩＷの液膜（ＤＩＷの連続流を介して吐出口５３１Ａと繋がっている液膜）に吹き付けられる。また、不活性ガス噴射位置Ｐ２において、基板Ｗの上面には、軟Ｘ線照射装置５１２の軟Ｘ線発生器５１３で発生された軟Ｘ線が照射される。 Further, at the inert gas injection position P2, the nitrogen gas from the slit injection port 519A of the gas knife nozzle 519 is connected to the discharge port 531A via a DIW liquid film (DIW continuous flow) formed on the upper surface of the substrate W. Sprayed on the liquid film). At the inert gas injection position P2, the upper surface of the substrate W is irradiated with soft X-rays generated by the soft X-ray generator 513 of the soft X-ray irradiation apparatus 512.
　窒素ガスの吹付けにより、基板Ｗの上面からＤＩＷが吹き飛ばされ、基板Ｗの上面に付着したＤＩＷが除去される。そして、不活性ガス噴射位置Ｐ２において、軟Ｘ線が照射される。基板Ｗの上面におけるＤＩＷが切れた（吹き飛ばされた）直後の部分に軟Ｘ線が照射されるので、基板Ｗの帯電防止および除電を、より一層確実に達成できる。 By blowing nitrogen gas, DIW is blown off from the upper surface of the substrate W, and DIW adhering to the upper surface of the substrate W is removed. Then, soft X-rays are irradiated at the inert gas injection position P2. Since soft X-rays are applied to the portion of the upper surface of the substrate W immediately after DIW is cut (blowed off), it is possible to more reliably achieve antistatic and static elimination of the substrate W.
　第１３実施形態において、洗浄処理室５０２内で水（たとえばＤＩＷ）を用いて基板Ｗを処理する場合を例に挙げて説明したが、洗浄処理室５０２内で薬液および水を用いた処理を用いて基板Ｗを処理することもできる。この場合、図２４に二点鎖線で示すように、水供給ユニット５００よりも上流側に、薬液ノズル５０６が配置される。薬液ノズル５０６には、薬液バルブ５０８を介して薬液供給源からの薬液が供給されるようになっている。つまり、水供給位置Ｐ１よりも上流側に、薬液供給位置Ｐ０が設定される。 In the thirteenth embodiment, the case where the substrate W is processed using water (for example, DIW) in the cleaning processing chamber 502 has been described as an example. However, processing using a chemical solution and water is used in the cleaning processing chamber 502. Thus, the substrate W can be processed. In this case, as shown by a two-dot chain line in FIG. 24, the chemical liquid nozzle 506 is arranged on the upstream side of the water supply unit 500. A chemical solution from a chemical solution supply source is supplied to the chemical solution nozzle 506 via a chemical solution valve 508. That is, the chemical solution supply position P0 is set upstream of the water supply position P1.
　第１３実施形態において、基板Ｗを傾斜姿勢で搬送するコロ搬送ユニット５０４を例に挙げて説明したが、コロ搬送ユニット５０４は、基板Ｗを水平姿勢に保ちつつ搬送するものであってもよい。 In the thirteenth embodiment, the roller transport unit 504 that transports the substrate W in an inclined posture has been described as an example, but the roller transport unit 504 may transport the substrate W while maintaining the horizontal posture.
　また、第１３実施形態の基板処理装置５０１は、基板Ｗの上面（上側の主面）を洗浄するものを例に挙げて説明したが、基板の両面に洗浄処理を施すタイプの基板処理装置にも本願発明を適用できる。この場合、洗浄処理室５０２および液切り室５０３において、コロ搬送ユニット５０４の下方側にも、水供給ユニット５００およびガスナイフノズル５１９をそれぞれ配置し、水供給位置Ｐ１において、下方側の水供給ユニット５００によって基板Ｗの下面にＤＩＷを供給するとともに、不活性ガス噴射位置Ｐ２において、下方側のガスナイフノズル５１９によって、基板Ｗの下面に窒素ガスを噴射する。 The substrate processing apparatus 501 according to the thirteenth embodiment has been described by taking as an example an apparatus that cleans the upper surface (upper main surface) of the substrate W. However, the substrate processing apparatus 501 is a type of substrate processing apparatus that performs a cleaning process on both surfaces of the substrate. Also, the present invention can be applied. In this case, in the cleaning processing chamber 502 and the liquid draining chamber 503, the water supply unit 500 and the gas knife nozzle 519 are also arranged below the roller transport unit 504, respectively, and the water supply unit on the lower side at the water supply position P1. DIW is supplied to the lower surface of the substrate W by 500, and nitrogen gas is injected to the lower surface of the substrate W by the lower gas knife nozzle 519 at the inert gas injection position P2.
　第１～第１３実施形態では、処理対象物が基板Ｗとする基板処理装置１，２０１，２１１，２２１，２３１，２５１，２６１，３０１，３１１，４０１，５０１に搭載される処理液供給ユニット１００，２００，２２０，２３０，２５０，２６０，３００，３１０，４００，５００を例に挙げて説明したが、本発明は、基板Ｗ以外を処理対象物とする処理ユニットにも適用できる。以下、処理対象物を基板収容器（収容器）６０２とし、処理対象物を洗浄液（処理液）を用いて洗浄するための収容器洗浄装置６０１を例に挙げて説明する。 In the first to thirteenth embodiments, the processing liquid supply unit 100 mounted on the substrate processing apparatuses 1, 201, 211, 2221, 231, 251, 261, 301, 311, 401, 501 whose processing object is the substrate W. , 200, 220, 230, 250, 260, 300, 310, 400, 500 have been described as examples, but the present invention can also be applied to processing units other than the substrate W as processing objects. Hereinafter, the processing object is a substrate container (container) 602, and a container cleaning device 601 for cleaning the processing object using a cleaning liquid (processing liquid) will be described as an example.
　図２８は、本発明の第１４実施形態に係る物品洗浄装置６０１の構成を示す図である。図２９は、基板収容器６０２の構成を示す斜視図である。 FIG. 28 is a diagram showing a configuration of an article cleaning apparatus 601 according to the fourteenth embodiment of the present invention. FIG. 29 is a perspective view showing the configuration of the substrate container 602.
　図２９に示すように、基板収容器６０２は、基板Ｗを密閉した状態で収容する容器である。基板収容器６０２の一例として、ＦＯＳＢ（Front Opening Shipping Box）を挙げることができる。ＦＯＳＢは、専ら、半導体ウエハメーカから半導体装置メーカに、基板Ｗを納入するために用いられる。ＦＯＳＢは、未処理の複数枚の基板Ｗを収容し、これらの基板Ｗの清浄度を維持しつつ、基板Ｗへの損傷を防止する。 As shown in FIG. 29, the substrate container 602 is a container that accommodates the substrate W in a sealed state. An example of the substrate container 602 is FOSB (Front Opening Shipping Box). The FOSB is exclusively used to deliver the substrate W from the semiconductor wafer manufacturer to the semiconductor device manufacturer. The FOSB accommodates a plurality of unprocessed substrates W and prevents damage to the substrates W while maintaining the cleanliness of these substrates W.
　図２８に示すように、物品洗浄装置６０１は、基板収容器６０２の収容器本体６０３を載置するための載置台６０７と、基板収容器６０２に対して洗浄液の一例としてのＤＩＷを供給する水供給ユニット（処理液供給装置）６００を備えている。水供給ユニット６００は、第１実施形態に係る水供給ユニット１００（図１参照）と同等の構成を採用している。そのため、図２８には同一の参照符号を付し、説明を省略する。水供給ユニット６００の水ノズル６１は、載置台６０７に載置された収容器本体６０３の上方で、その吐出口５３を下方に向けて配置されている。 As shown in FIG. 28, the article cleaning apparatus 601 includes a mounting table 607 for mounting the container main body 603 of the substrate container 602, and water for supplying DIW as an example of a cleaning liquid to the substrate container 602. A supply unit (processing liquid supply device) 600 is provided. The water supply unit 600 employs the same configuration as the water supply unit 100 (see FIG. 1) according to the first embodiment. Therefore, the same reference numerals are given to FIG. 28 and the description is omitted. The water nozzle 61 of the water supply unit 600 is disposed above the container main body 603 mounted on the mounting table 607 with its discharge port 53 facing downward.
　基板収容器６０２は、側方に開口６０３Ａを有する有底箱状の収容器本体６０３と、収容器本体６０３の開口６０３Ａを開閉するための蓋６０４（図２８では、蓋６０４の閉状態を示している）と、収容器本体６０３の内壁に取り付けられた多段の収容器支持棚６０６と、蓋６０４に取り付けられた多段の蓋支持棚６０５とを含む。開口６０３Ａを介して収容器本体６０３の内部に対し、基板Ｗの出し入れが行われる。収容器本体６０３および蓋６０４は、それぞれ、たとえば塩ビ(poly-vinyl-chloride)等の樹脂材料を用いて形成されている。収容器本体６０３は、略立方形状の外郭形状を有し、図２８に示すように、開口側が底部側に比べてやや大径を有していてもよい。この場合、収容器本体６０３の上面は傾斜面を有している。 The substrate container 602 includes a bottomed box-shaped container body 603 having an opening 603A on the side, and a lid 604 for opening and closing the opening 603A of the container body 603 (FIG. 28 shows a closed state of the lid 604). A multi-stage container support shelf 606 attached to the inner wall of the container body 603, and a multi-stage lid support shelf 605 attached to the lid 604. The substrate W is put in and out of the container main body 603 through the opening 603A. The container body 603 and the lid 604 are each formed using a resin material such as polyvinyl-chloride. The container main body 603 has a substantially cubic outer shape, and as shown in FIG. 28, the opening side may have a slightly larger diameter than the bottom side. In this case, the upper surface of the container body 603 has an inclined surface.
　洗浄処理では、水供給ユニット６００から基板収容器６０２の収容器本体６０３の外壁に対してＤＩＷが供給される。具体的には、水バルブ１４が開かれ、水供給配管１３を流通するＤＩＷが水ノズル６１に供給される。これにより、水ノズル６１の吐出口５３から、収容器本体６０３の外壁の上面に向けて下向きにＤＩＷが吐出される。また、制御装置４０は、軟Ｘ線発生器２５（図２参照）に軟Ｘ線を発生させて、この軟Ｘ線を、水ノズル６１の第１ノズル配管５１の内部に向けて照射させる。これにより、第１ノズル配管５１内を流通しているＤＩＷに、軟Ｘ線が照射される。 In the cleaning process, DIW is supplied from the water supply unit 600 to the outer wall of the container body 603 of the substrate container 602. Specifically, the water valve 14 is opened, and DIW flowing through the water supply pipe 13 is supplied to the water nozzle 61. Accordingly, DIW is discharged downward from the discharge port 53 of the water nozzle 61 toward the upper surface of the outer wall of the container body 603. In addition, the control device 40 generates soft X-rays in the soft X-ray generator 25 (see FIG. 2) and irradiates the soft X-rays toward the inside of the first nozzle pipe 51 of the water nozzle 61. Thereby, soft X-rays are irradiated to DIW which distribute | circulates the inside of the 1st nozzle piping 51. FIG.
　収容器本体６０３の外壁の上方の側面に供給されたＤＩＷは、傾斜面からなる当該上方の側面および底面を伝って流下する。これにより、収容器本体６０３の外壁にＤＩＷの液膜が形成される。この液膜によって、収容器本体６０３の外壁に付着している汚れやゴミなどが洗い流される。 The DIW supplied to the upper side surface of the outer wall of the container main body 603 flows down along the upper side surface and the bottom surface formed of inclined surfaces. As a result, a DIW liquid film is formed on the outer wall of the container body 603. By this liquid film, dirt or dust adhering to the outer wall of the container body 603 is washed away.
　洗浄処理中に、第１ノズル配管５１内に存在しているＤＩＷに軟Ｘ線が照射されると、第１ノズル配管５１内におけるＤＩＷの照射部分５４（図５参照）において、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、ＤＩＷの照射部分５４に形成される。 During the cleaning process, when DIW existing in the first nozzle pipe 51 is irradiated with soft X-rays, excitation of water molecules occurs in the DIW irradiation portion 54 (see FIG. 5) in the first nozzle pipe 51. As a result, electrons are emitted from the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 54 of DIW.
　洗浄処理中における、水ノズル６１に対するＤＩＷの供給流量は、比較的大流量（基板収容器６０２の大きさ等に応じてたとえば１～１０L/min）に設定されている。そのため、水ノズル６１の吐出口５３から吐出されるＤＩＷの態様が、吐出口５３と収容器本体６０３の外壁との双方に繋がる連続流状の態様をなしている。そのため、収容器本体６０３の外壁にＤＩＷの液膜が形成される。この液膜によって、収容器本体６０３の外壁に形成された液膜６３とＤＩＷの照射部分５４とが、ＤＩＷを介して繋がっている。また、水ノズル６１のノズル配管内では、ＤＩＷが液密状態にある。 During the cleaning process, the DIW supply flow rate to the water nozzle 61 is set to a relatively large flow rate (for example, 1 to 10 L / min depending on the size of the substrate container 602). Therefore, the mode of DIW discharged from the discharge port 53 of the water nozzle 61 is a continuous flow mode connected to both the discharge port 53 and the outer wall of the container body 603. Therefore, a DIW liquid film is formed on the outer wall of the container body 603. By this liquid film, the liquid film 63 formed on the outer wall of the container body 603 and the DIW irradiation portion 54 are connected via the DIW. Further, DIW is in a liquid-tight state in the nozzle pipe of the water nozzle 61.
　収容器本体６０３の外壁が正に帯電しているとすると、ＤＩＷの照射部分５４と、正に帯電している収容器本体６０３の外壁との間の電位差で、ＤＩＷの照射部分５４からの電子が、収容器本体６０３の外壁に接液しているＤＩＷの液膜に向けて、連続流状のＤＩＷを伝って移動する。これにより、収容器本体６０３の外壁に接液しているＤＩＷの液膜が多量の電子を有するようになる。
このとき、ＤＩＷの液膜６３とＤＩＷの照射部分５４とが、ＤＩＷを介して繋がっている。 Assuming that the outer wall of the container main body 603 is positively charged, the potential difference between the DIW irradiation portion 54 and the outer wall of the container main body 603 that is positively charged causes an electron from the DIW irradiation portion 54. However, it moves along the continuous flow DIW toward the DIW liquid film in contact with the outer wall of the container body 603. As a result, the DIW liquid film in contact with the outer wall of the container body 603 has a large amount of electrons.
At this time, the DIW liquid film 63 and the DIW irradiated portion 54 are connected via the DIW.
　以上により、第１４実施形態によれば、洗浄処理時における収容器本体６０３の帯電を防止できる。また、洗浄処理前から収容器本体６０３が帯電していても、その収容器本体６０３に帯びた電荷を除去（すなわち、除電）できる。 As described above, according to the fourteenth embodiment, charging of the container body 603 during the cleaning process can be prevented. Moreover, even if the container main body 603 is charged before the cleaning process, the charge on the container main body 603 can be removed (that is, static elimination).
　なお、第１４実施形態では、収容器本体６０３を洗浄する場合を例に挙げて説明したが、蓋６０４や、支持棚６０５，６０６を洗浄する場合にも、同様に洗浄方法を採用することにより、蓋６０４や支持棚６０５，６０６の除電を図りつつ、蓋６０４や支持棚６０５，６０６に洗浄処理を施すことができる。 In the fourteenth embodiment, the case where the container main body 603 is cleaned has been described as an example. However, when the lid 604 and the support shelves 605 and 606 are cleaned, the cleaning method is similarly adopted. The lid 604 and the support shelves 605 and 606 can be subjected to a cleaning process while removing electricity from the lid 604 and the support shelves 605 and 606.
　また、基板収容器６０２として、ＦＯＳＢを例に挙げて説明したが、専ら、半導体ウエハメーカの工場内で基板Ｗを搬送するために用いられ、基板Ｗを密閉した状態で収容するＦＯＵＰ（Front Opening Unified Pod）を挙げることもできる。その他、基板収容器６０２として、ＦＯＵＰ（Front Opening Unified Pod）や、ＳＭＩＦ（Standard Mechanical Interface）ポッド、ＯＣ（Open Cassette）等の他の形態の基板収容器を例示することもできる。 Further, although the FOSB has been described as an example of the substrate container 602, the FOUP (Front-Opening-Unified) is used exclusively for transporting the substrate W in the factory of the semiconductor wafer manufacturer and stores the substrate W in a sealed state. Pod). In addition, as the substrate container 602, other types of substrate containers such as FOUP (Front Opening Unified Unified Pod), SMIF (Standard Mechanical Interface) pod, OC (Open Cassette) can be exemplified.
　また、収容器は、基板Ｗを収容するものに限られず、収容器として、ＣＤ、ＤＶＤ、ブルーディスク等の円盤状のメディアを収容するメディア収容器や、レンズ、ミラー、回折格子等の光学部品を収容する部品収容器を、処理対象物とすることができる。 The container is not limited to the one that accommodates the substrate W. As the container, a medium container that accommodates a disk-shaped medium such as a CD, a DVD, or a blue disk, or an optical component such as a lens, a mirror, or a diffraction grating. The component container which accommodates can be made into a process target object.
　次に、軟Ｘ線照射ユニットを内蔵する水供給ユニットからのＤＩＷ（水の一例）の供給によって、シリコンウエハ、ガラス基板、収容器等の処理対象物を除電できることを確認するための除電試験を行った。この除電試験の内容および結果について、以下説明する。 Next, a static elimination test is performed to confirm that the processing object such as a silicon wafer, a glass substrate, and a container can be eliminated by supplying DIW (an example of water) from a water supply unit containing a soft X-ray irradiation unit. went. The contents and results of this static elimination test will be described below.
　図３０は、除電試験に用いられる試験装置６５１を説明するための図である。 FIG. 30 is a diagram for explaining a test apparatus 651 used in the static elimination test.
　試験装置６５１は、樹脂製の有底状の容器６５２と、容器６５２内で、帯電体Ｅを保持する帯電体保持台６５３と、帯電体保持台６５３に保持されている帯電体Ｅに対して、処理液を供給するための水供給ユニット６５４と、帯電体保持台６５３に保持されている帯電体Ｅを帯電させつつ、当該帯電体Ｅの帯電量を計測するための帯電プレートモニタ６５５と、帯電プレートモニタ６５５にて計測された帯電量を記録するためのレコーダ６５６とを含む。帯電プレートモニタ６５５は、帯電体Ｅと導通する金属プレート６７１を有している。帯電プレートモニタ６５５の一例として米国イオンシステムズ社製CPM210を例示でき、また、レコーダ６５６の一例として日置電機株式会社製HIOKI8841を例示できる。 The test apparatus 651 includes a resin-made bottomed container 652, a charged body holding base 653 that holds the charged body E in the container 652, and the charged body E that is held by the charged body holding base 653. A water supply unit 654 for supplying the treatment liquid, a charging plate monitor 655 for measuring the charge amount of the charging body E while charging the charging body E held on the charging body holding base 653, And a recorder 656 for recording the charge amount measured by the charge plate monitor 655. The charging plate monitor 655 has a metal plate 671 that is electrically connected to the charged body E. An example of the charging plate monitor 655 is CPM210 manufactured by Ion Systems, Inc., and an example of the recorder 656 is HIOKI8841 manufactured by Hioki Electric Co., Ltd.
　水供給ユニット６５４は、水ノズル６６１と、水ノズル６６１内を流通するＤＩＷ（水の一例）に軟Ｘ線を照射するための軟Ｘ線照射ユニット６６２と、水ノズル６６１に対し、ＤＩＷタンク６７０からのＤＩＷを供給する水供給配管６６３とを含む。軟Ｘ線照射ユニット６６２は、水供給配管６６３に取り付けられている。水供給配管６６３には、水供給配管６６３の開閉および開度を調節するためのバルブ６６４が介装されている。 The water supply unit 654 includes a water nozzle 661, a soft X-ray irradiation unit 662 for irradiating the DIW (an example of water) flowing through the water nozzle 661 with soft X-rays, and a DIW tank 670 for the water nozzle 661. And a water supply pipe 663 for supplying DIW. The soft X-ray irradiation unit 662 is attached to the water supply pipe 663. The water supply pipe 663 is provided with a valve 664 for adjusting the opening / closing and opening of the water supply pipe 663.
　水ノズル６６１は、電離チャンバ６６５と、電離チャンバ６６５内にＤＩＷを流入させるための入口６６６Ａを有する流入口部６６６と、電離チャンバ６６５内を流通したＤＩＷの出口６６７Ａを有する流出口部６６７とを有する。電離チャンバ６６５は矩形扁平状に形成されており、電離チャンバ６６５の内部空間は、流通方向の長さ約100mm×流通方向の幅約5mm×流通方向の奥行約60mm の矩形空間に設定されている。 The water nozzle 661 includes an ionization chamber 665, an inlet portion 666 having an inlet 666A for allowing DIW to flow into the ionization chamber 665, and an outlet portion 667 having an outlet 667A of DIW flowing through the ionization chamber 665. Have. The ionization chamber 665 is formed in a rectangular flat shape, and the internal space of the ionization chamber 665 is set to a rectangular space having a length of about 100 mm in the flow direction, a width of about 5 mm in the flow direction, and a depth of about 60 mm in the flow direction. .
　軟Ｘ線照射ユニット６６２は、第１実施形態に係る軟Ｘ線照射ユニット６２と同等の構成を採用している。軟Ｘ線照射ユニット６６２は、第１実施形態に係る軟Ｘ線発生器２５（図２参照）に相当する軟Ｘ線発生器を有している。この軟Ｘ線発生器として軟Ｘ線イオナイザー（L9490。浜松ホトニクス（株）製）を例示できる。軟Ｘ線照射ユニット６６２において、第２開口２８（図２参照）に相当する丸型開口の直径はたとえば17mmである。 The soft X-ray irradiation unit 662 adopts the same configuration as the soft X-ray irradiation unit 62 according to the first embodiment. The soft X-ray irradiation unit 662 has a soft X-ray generator corresponding to the soft X-ray generator 25 (see FIG. 2) according to the first embodiment. An example of the soft X-ray generator is a soft X-ray ionizer (L9490, manufactured by Hamamatsu Photonics). In the soft X-ray irradiation unit 662, the diameter of the round opening corresponding to the second opening 28 (see FIG. 2) is, for example, 17 mm.
　この除電試験では、計測対象の帯電体Ｅとして、角形の金属板（130mm×93 mm×厚み1mm）が用いられる。基板保持台６５３は、帯電体Ｅを、水平面に対し所定角度傾斜する傾斜姿勢に保持する。帯電体Ｅが基板保持台６５３によって保持された状態では、基板保持台６５３に含まれるＰＴＦＥ（poly tetra-fluoro ethylene）製のブロック６６８により、帯電体Ｅが容器６５２と絶縁されている。帯電体Ｅの上端部と、出口６６７Ａとの間の間隔は、たとえば55mmである。 In this static elimination test, a rectangular metal plate (130 mm × 93 mm × thickness 1 mm) is used as the charged body E to be measured. The substrate holding table 653 holds the charged body E in an inclined posture inclined at a predetermined angle with respect to the horizontal plane. In a state where the charged body E is held by the substrate holding table 653, the charged body E is insulated from the container 652 by a block 668 made of PTFE (polytetrafluoroethylene) contained in the substrate holding table 653. The distance between the upper end of the charged body E and the outlet 667A is, for example, 55 mm.
　この試験装置６５１において、以下の手順で実験を行う。
第１工程：バルブ６６４を調節して、水ノズル６６１の出口６６７ＡからＤＩＷ（この場合、導電率：1μS/cm以下）を、液滴状（非連続流状）で滴下させる。液滴状とは、液滴と次の液滴とが繋がらない状態をいう。
第２工程：帯電プレートモニタ６５５の金属プレート６７１を介して帯電体Ｅを帯電させ、軟Ｘ線照射ユニット６６２の軟Ｘ線発生器をオン／オフさせて、そのときに帯電体Ｅの電位が+/-4.5kV →+/-3.5kVまで減衰する時間（除電時間）を、帯電プレートモニタ６５５と、レコーダ６５６とを用いて計測した。
第３工程：次いで、バルブ６６４を調節して、水ノズル６６１の出口６６７ＡからＤＩＷを一定流量（0.77L/minまたは0.08L/min）で連続流状（液柱状に流れている状態）で流下させる。このとき、水ノズル６６１の高さを可変とし、水ノズル６６１の出口６６７Ａから帯電体Ｅの上端までの距離が、55mm、1000mmおよび3000mmである場合をそれぞれ計測した。距離が1000mmおよび3000mmの場合は、コイル状に巻回されたφ6×4mmの塩化ビニールチューブを水ノズル６６１の先端に取り付けた。
第４工程：帯電プレートモニタ６５５の金属プレート６７１を介して容器６５２内の帯電体Ｅを帯電させ、軟Ｘ線発生器をオン／オフさせて、そのときに帯電体Ｅの電位がが+/-1kV →+/-0.1kVまで減衰する時間（除電時間）を、帯電プレートモニタ６５５と、レコーダ６５６とを用いて計測した。この実験結果を、表１～表３に示す。 In this test apparatus 651, an experiment is performed according to the following procedure.
First step: Adjusting the valve 664, DIW (conductivity: 1 μS / cm or less in this case) is dropped in the form of droplets (discontinuous flow) from the outlet 667A of the water nozzle 661. A droplet form means a state where a droplet is not connected to the next droplet.
Second step: The charged body E is charged via the metal plate 671 of the charging plate monitor 655, and the soft X-ray generator of the soft X-ray irradiation unit 662 is turned on / off. The time (static elimination time) of decay from +/− 4.5 kV to +/− 3.5 kV was measured using a charged plate monitor 655 and a recorder 656.
Third step: Next, by adjusting the valve 664, the DIW flows down from the outlet 667A of the water nozzle 661 in a continuous flow state (a state of flowing in a liquid column) at a constant flow rate (0.77 L / min or 0.08 L / min). Let At this time, the height of the water nozzle 661 was variable, and the distances from the outlet 667A of the water nozzle 661 to the upper end of the charged body E were 55 mm, 1000 mm, and 3000 mm, respectively. When the distance was 1000 mm and 3000 mm, a φ6 × 4 mm vinyl chloride tube wound in a coil shape was attached to the tip of the water nozzle 661.
Fourth step: The charged body E in the container 652 is charged via the metal plate 671 of the charged plate monitor 655, and the soft X-ray generator is turned on / off. The time (static elimination time) of decay from -1 kV to +/- 0.1 kV was measured using a charged plate monitor 655 and a recorder 656. The experimental results are shown in Tables 1 to 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　ＤＩＷを液滴状に滴下した場合の実験結果を表１に示す。表１に示すように、軟Ｘ線発生器のオン／オフに拘らず、帯電体Ｅの電位が+/-4.5kV → +/-3.0kVまで減衰する時間（除電時間）がほぼ一定であった。表１に示す実験結果から、ＤＩＷを液滴状に滴下した場合は、帯電体Ｅがほとんど除電されていないことがわかる。 Table 1 shows the experimental results when DIW was dropped into droplets. As shown in Table 1, the time (static elimination time) during which the potential of the charged body E decays from +/− 4.5 kV to +/− 3.0 kV is almost constant regardless of whether the soft X-ray generator is on or off. It was. From the experimental results shown in Table 1, it can be seen that when DIW is dropped into droplets, the charged body E is hardly neutralized.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　ＤＩＷを連続流状に流下させた場合の実験結果を表２に示す。表２に示すように、ＤＩＷの流量が0.774L/minのときおよび0.08L/minのときの双方において、軟Ｘ線発生器のオンにより帯電体Ｅの電位が+/-1kV → +/-0.1kVまで減衰する時間（除電時間）が短くなった。この場合の除電時間は1秒間強である。表２に示す実験結果から、ＤＩＷを連続流状に流下させた場合には、除電性能が向上することがわかる。 Table 2 shows the experimental results when DIW was allowed to flow down continuously. As shown in Table 2, when the DIW flow rate is 0.774 L / min and 0.08 L / min, the potential of the charged body E is +/- 1 kV → +/− when the soft X-ray generator is turned on. Time to decay to 0.1kV (static elimination time) has been shortened. The static elimination time in this case is just over 1 second. From the experimental results shown in Table 2, it can be seen that when DIW is allowed to flow down in a continuous flow, the charge removal performance is improved.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　ＤＩＷを連続流状に流下させさせながら、水ノズル６６１の出口から帯電体Ｅまでの距離を変化させた場合の実験結果を表３に示す。表３に示すように、水ノズル６６１の出口から帯電体Ｅまでの距離が長くなるに従って、帯電体Ｅの電位が+/-1kV → +/-0.1kVまで減衰する時間（除電時間）が僅かに長くなるが、この距離が3000mmの場合であっても1～2秒間で除電できる。このことから、水ノズル６６１の出口から帯電体Ｅまでの距離は、除電性能に大きな影響を及ぼさないことがわかる。 Table 3 shows the experimental results when the distance from the outlet of the water nozzle 661 to the charged body E is changed while allowing DIW to flow down in a continuous flow. As shown in Table 3, as the distance from the outlet of the water nozzle 661 to the charged body E becomes longer, the time required for the potential of the charged body E to decay from +/- 1 kV to +/− 0.1 kV (static elimination time) is small. However, even if this distance is 3000 mm, the charge can be removed in 1 to 2 seconds. From this, it can be seen that the distance from the outlet of the water nozzle 661 to the charged body E does not significantly affect the charge removal performance.
　これらの実験結果から、軟Ｘ線照射ユニットを内蔵する水供給ユニットからのＤＩＷの供給によって処理対象物を除電する除電原理は以下のように推定される。すなわち、軟Ｘ線照射により励起された水分子から電子が放出され、この照射部分は、軟Ｘ線により励起された水分子の正イオンと電子が混在したプラズマ状態になっている。 From these experimental results, the principle of static elimination that neutralizes the processing object by supplying DIW from the water supply unit incorporating the soft X-ray irradiation unit is estimated as follows. That is, electrons are emitted from water molecules excited by soft X-ray irradiation, and this irradiated portion is in a plasma state in which positive ions and electrons of water molecules excited by soft X-rays are mixed.
　処理対象物が正に帯電しているときは、ＤＩＷの照射部分と帯電している処理対象物との間の電位差で、ＤＩＷの照射部分の電子が正に帯電している処理対象物に向かって移動し、正に帯電している処理対象物は除電される。また、処理対象物が負に帯電しているときは、帯電している処理対象物からＤＩＷの照射部分の正イオンに向かって電子が移動し、負に帯電している処理対象物は除電される。 When the object to be treated is positively charged, the potential difference between the DIW irradiated part and the charged object to be processed is directed toward the object to be charged which is positively charged with electrons in the DIW irradiated part. The object to be processed which is moved and positively charged is neutralized. In addition, when the object to be processed is negatively charged, electrons move from the charged object to be processed toward positive ions in the irradiated part of the DIW, and the object to be negatively charged is neutralized. The
　図３１は、本発明の第１５実施形態に係る基板処理装置７０１の構成を示す図である。 FIG. 31 is a diagram showing a configuration of a substrate processing apparatus 701 according to the fifteenth embodiment of the present invention.
　基板処理装置７０１は、基板Ｗの一例としての円形の半導体ウエハ（シリコンウエハ）の表面（処理対象面）に処理液（薬液および水）による処理を施すために用いられる枚葉式の装置である。この実施形態では、薬液処理後に行われる基板Ｗのリンスのために水が用いられる。処理対象の基板Ｗの表面には、たとえば酸化膜等が形成されている。 The substrate processing apparatus 701 is a single-wafer type apparatus used for processing a surface (processing target surface) of a circular semiconductor wafer (silicon wafer) as an example of the substrate W with a processing liquid (chemical solution and water). . In this embodiment, water is used for rinsing the substrate W performed after the chemical treatment. For example, an oxide film or the like is formed on the surface of the substrate W to be processed.
　基板処理装置７０１は、隔壁７０２により区画された処理室７０３内に、基板Ｗを水平姿勢に保持して回転させるスピンチャック（基板保持手段）７０４と、スピンチャック７０４に保持されている基板Ｗの表面（上面）に水の一例としてのＤＩＷ（脱イオン水。純水）を吐出するための水ノズル（水供給手段）７０５と、スピンチャック７０４に保持されている基板Ｗの表面に軟Ｘ線を照射するための軟Ｘ線照射ヘッド（Ｘ線照射手段）７０６と、スピンチャック７０４に保持されている基板Ｗの表面に薬液を吐出するための薬液ノズル７とを備えている。 A substrate processing apparatus 701 includes a spin chuck (substrate holding means) 704 that rotates a substrate W held in a horizontal posture in a processing chamber 703 partitioned by a partition wall 702, and a substrate W held by the spin chuck 704. Soft X-rays are applied to the surface of a substrate W held by a spin nozzle 704 and a water nozzle (water supply means) 705 for discharging DIW (deionized water, pure water) as an example of water onto the surface (upper surface). Are provided with a soft X-ray irradiation head (X-ray irradiation means) 706 and a chemical nozzle 7 for discharging a chemical onto the surface of the substrate W held by the spin chuck 704.
　スピンチャック７０４として、たとえば挟持式のものが採用されている。具体的には、スピンチャック７０４は、スピンモータ７０８と、このスピンモータ７０８の駆動軸と一体化されたスピン軸７０９と、スピン軸７０９の上端にほぼ水平に取り付けられた円板状のスピンベース７１０と、スピンベース７１０の周縁部の複数箇所にほぼ等間隔で設けられた複数個の挟持部材７１１とを備えている。これにより、スピンチャック７０４は、複数個の挟持部材７１１によって基板Ｗを挟持した状態で、スピンモータ７０８の回転駆動力によってスピンベース７１０を回転させることにより、その基板Ｗを、ほぼ水平な姿勢を保った状態で、スピンベース７１０とともに回転軸線Ｃまわりに回転させることができる。 As the spin chuck 704, for example, a sandwich type is adopted. Specifically, the spin chuck 704 includes a spin motor 708, a spin shaft 709 integrated with a drive shaft of the spin motor 708, and a disk-shaped spin base attached substantially horizontally to the upper end of the spin shaft 709. 710 and a plurality of clamping members 711 provided at a plurality of positions on the peripheral edge of the spin base 710 at substantially equal intervals. As a result, the spin chuck 704 rotates the spin base 710 by the rotational driving force of the spin motor 708 in a state where the substrate W is sandwiched by the plurality of sandwiching members 711, so that the substrate W is placed in a substantially horizontal posture. In this state, it can be rotated around the rotation axis C together with the spin base 710.
　なお、スピンチャック７０４としては、挟持式のものに限らず、たとえば基板Ｗの裏面を真空吸着することにより、基板Ｗを水平な姿勢で保持し、さらにその状態で鉛直な回転軸線Ｃまわりに回転することにより、その保持した基板Ｗを回転させることができる真空吸着式のもの（バキュームチャック）が採用されてもよい。 Note that the spin chuck 704 is not limited to a sandwich type, and for example, the back surface of the substrate W is vacuum-sucked to hold the substrate W in a horizontal posture and further rotate around the vertical rotation axis C in that state. By doing so, a vacuum chucking type (vacuum chuck) capable of rotating the held substrate W may be employed.
　水ノズル７０５は、たとえば、連続流の状態でＤＩＷを吐出するストレートノズルであり、スピンチャック７０４の上方で、その吐出口を基板Ｗの回転中心付近に向けて固定的に配置されている。水ノズル７０５には、ＤＩＷ供給源からのＤＩＷが供給される水供給管７１３が接続されている。水供給管７１３の途中部には、水ノズル７０５からのＤＩＷの供給／供給停止を切り換えるための水バルブ（水供給手段）７１４が介装されている。 The water nozzle 705 is, for example, a straight nozzle that discharges DIW in a continuous flow state, and is fixedly disposed above the spin chuck 704 so that the discharge port faces the vicinity of the rotation center of the substrate W. A water supply pipe 713 to which DIW from a DIW supply source is supplied is connected to the water nozzle 705. A water valve (water supply means) 714 for switching supply / stop of supply of DIW from the water nozzle 705 is interposed in the middle of the water supply pipe 713.
　薬液ノズル７０７は、たとえば、連続流の状態で薬液を吐出するストレートノズルであり、スピンチャック７０４の上方で、その吐出口を基板Ｗの回転中心付近に向けて固定的に配置されている。薬液ノズル７０７には、薬液供給源からの薬液が供給される薬液供給管７１５が接続されている。薬液供給管７１５の途中部には、薬液ノズル７０７からの薬液の供給／供給停止を切り換えるための薬液バルブ７１６が介装されている。 The chemical nozzle 707 is, for example, a straight nozzle that discharges the chemical in a continuous flow state, and is fixedly disposed above the spin chuck 704 with its discharge port directed toward the vicinity of the rotation center of the substrate W. A chemical solution supply pipe 715 to which a chemical solution from a chemical solution supply source is supplied is connected to the chemical solution nozzle 707. A chemical solution valve 716 for switching supply / stop of supply of the chemical solution from the chemical solution nozzle 707 is interposed in the middle of the chemical solution supply pipe 715.
　また、薬液ノズル７０７は、スピンチャック７０４に対して固定的に配置されている必要はなく、たとえば、スピンチャック７０４上方において水平面内で揺動可能なアームに取り付けられて、このアームの揺動により基板Ｗの表面における薬液の着液位置がスキャンされる、いわゆるスキャンノズルの形態が採用されてもよい。 The chemical nozzle 707 does not need to be fixedly arranged with respect to the spin chuck 704. For example, the chemical nozzle 707 is attached to an arm that can be swung in a horizontal plane above the spin chuck 704, and the arm is swung. A so-called scan nozzle form in which the position of the chemical solution on the surface of the substrate W is scanned may be employed.
　スピンチャック７０４の側方には、鉛直方向に延びる支持軸７１７が配置されている。支持軸７１７の上端部には、水平方向に延びるアーム７１８が結合されており、アーム７１８の先端に軟Ｘ線照射ヘッド７０６が取り付けられている。また、支持軸７１７には、支持軸７１７を軸まわりに回動させるための揺動駆動機構（移動手段）７１９と、支持軸７１７をその軸方向に沿って上下動させるための昇降駆動機構（移動手段）７２０とが結合されている。 A support shaft 717 extending in the vertical direction is disposed on the side of the spin chuck 704. An arm 718 extending in the horizontal direction is coupled to the upper end of the support shaft 717, and a soft X-ray irradiation head 706 is attached to the tip of the arm 718. The support shaft 717 includes a swing drive mechanism (moving means) 719 for rotating the support shaft 717 around the axis, and a lift drive mechanism (for moving the support shaft 717 up and down along the axial direction). Moving means) 720.
　揺動駆動機構７１９から支持軸７１７に駆動力を入力して、支持軸７１７を所定の角度範囲内で回動させることにより、スピンチャック７０４に保持された基板Ｗの上方で、アーム７１８を、支持軸７１７を支点として揺動させる。アーム７１８の揺動により、軟Ｘ線照射ヘッド７０６を、基板Ｗの回転軸線Ｃ上を含む位置（基板Ｗの回転中心に対向する位置）と、スピンチャック７０４の側方に設定されたホームポジションとの間で移動させることができる。また、昇降駆動機構７２０から支持軸７１７に駆動力を入力して、支持軸７１７を昇降させることにより、軟Ｘ線照射ヘッド７０６を、スピンチャック７０４に保持された基板Ｗの表面に近接する近接位置（図３１に二点鎖線で示す位置）と、その基板Ｗの上方に退避する退避位置（図３１に実線で示す位置）との間で昇降させる。この実施形態では、近接位置は、スピンチャック７０４に保持された基板Ｗの表面と軟Ｘ線照射ヘッド７０６の下面（下壁７２６Ａの下面）との間隔が1～30mmの範囲の所定間隔（たとえば10mm程度）になる位置に設定されている。 By inputting a driving force from the swing drive mechanism 719 to the support shaft 717 and rotating the support shaft 717 within a predetermined angular range, the arm 718 is moved above the substrate W held by the spin chuck 704. The support shaft 717 is swung as a fulcrum. By swinging the arm 718, the soft X-ray irradiation head 706 is moved to a position including the rotation axis C of the substrate W (a position facing the rotation center of the substrate W) and a home position set to the side of the spin chuck 704. Can be moved between. Further, the soft X-ray irradiation head 706 is brought close to the surface of the substrate W held by the spin chuck 704 by inputting a driving force to the support shaft 717 from the lifting drive mechanism 720 and moving the support shaft 717 up and down. It is moved up and down between a position (a position indicated by a two-dot chain line in FIG. 31) and a retreat position (a position indicated by a solid line in FIG. 31) for retreating above the substrate W. In this embodiment, the proximity position is a predetermined distance (for example, the distance between the surface of the substrate W held by the spin chuck 704 and the lower surface of the soft X-ray irradiation head 706 (the lower surface of the lower wall 726A) is 1 to 30 mm (for example, It is set to a position that will be about 10mm).
　隔壁７０２の側壁（複数の側壁のうちの１つ）には、処理室７０３内に対し基板Ｗを搬出入するための開口７２１が形成されている。基板Ｗの搬出入の際には、処理室７０３外で開口７２１に対向する搬送ロボット（図示しない）が、開口７２１を通して処理室７０３内にハンドをアクセスさせる。これにより、スピンチャック７０４上に未処理の基板Ｗを載置したり、スピンチャック７０４上から処理済の基板Ｗを取り除いたりすることができる。開口７２１はシャッタ７２２によって開閉される。シャッタ７２２は、当該シャッタ７２２に結合されたシャッタ昇降機構（図示しない）によって、開口７２１を覆う閉位置（図３１に実線で示す）と、開口７２１を開放する開位置（図３１に二点鎖線で示す）との間で昇降される。 An opening 721 for carrying the substrate W in and out of the processing chamber 703 is formed on the side wall (one of the plurality of side walls) of the partition wall 702. When the substrate W is carried in / out, a transfer robot (not shown) facing the opening 721 outside the processing chamber 703 accesses the hand into the processing chamber 703 through the opening 721. As a result, the unprocessed substrate W can be placed on the spin chuck 704, or the processed substrate W can be removed from the spin chuck 704. The opening 721 is opened and closed by a shutter 722. The shutter 722 has a closed position (shown by a solid line in FIG. 31) covering the opening 721 and an open position (open by a two-dot chain line in FIG. 31) covering the opening 721 by a shutter lifting mechanism (not shown) coupled to the shutter 722. As shown).
　図３２は、軟Ｘ線照射ヘッド７０６の図解的な断面図である。 FIG. 32 is a schematic cross-sectional view of the soft X-ray irradiation head 706.
　軟Ｘ線照射ヘッド７０６は、Ｘ線発生器７２５と、Ｘ線発生器７２５の周囲を取り囲むように覆うたとえば塩ビ（ＰＶＣ）製のカバー７２６と、カバー７２６の内部に気体を供給するための気体ノズル（気体供給手段）７２７とを備えている。カバー７２６は、Ｘ線発生器７２５の周囲を、Ｘ線発生器７２５と間隔を空けて取り囲む縦長の矩形箱状のものであり、水平板状の下壁７２６Ａにおいて、Ｘ線発生器７２５の次に述べる照射窓７３５に対向する部分にたとえば円形の開口７２８を形成している。 The soft X-ray irradiation head 706 includes an X-ray generator 725, a cover 726 made of, for example, polyvinyl chloride (PVC) covering the periphery of the X-ray generator 725, and a gas for supplying gas to the inside of the cover 726. And a nozzle (gas supply means) 727. The cover 726 is in the shape of a vertically long rectangular box that surrounds the X-ray generator 725 with a space from the X-ray generator 725. The cover 726 has a horizontal plate-like lower wall 726A next to the X-ray generator 725. For example, a circular opening 728 is formed in a portion facing the irradiation window 735 described above.
　Ｘ線発生器７２５は、基板Ｗ上のＤＩＷを電離させるために用いられる軟Ｘ線を射出（放射）する。Ｘ線発生器７２５は、ケース体７２９と、Ｘ線を発生させるための上下に長いＸ線管７３０と、Ｘ線管７３０に高電圧を供給する高電圧ユニット７３１とを備えている。ケース体７２９は、その内部に、Ｘ線管７３０および高電圧ユニット７３１を収容する縦長の矩形筒状のものであり、導電性および熱伝導性を有する材料（たとえばアルミニウム等の金属材料）を用いて形成されている。 The X-ray generator 725 emits (radiates) soft X-rays used to ionize DIW on the substrate W. The X-ray generator 725 includes a case body 729, a vertically long X-ray tube 730 for generating X-rays, and a high voltage unit 731 that supplies a high voltage to the X-ray tube 730. The case body 729 is a vertically long rectangular tube that accommodates the X-ray tube 730 and the high voltage unit 731 and is made of a material having conductivity and thermal conductivity (for example, a metal material such as aluminum). Is formed.
　高電圧ユニット７３１は、たとえば-9.5kVという高電位の駆動電圧をＸ線管７３０に入力する。高電圧ユニット７３１には、カバー７２６に形成された貫通孔７４２を通してカバー７２６外に引き出されたる給電線７４３を介して電源（図示しない）からの電圧が供給されている。 The high voltage unit 731 inputs, for example, a high potential drive voltage of −9.5 kV to the X-ray tube 730. The high voltage unit 731 is supplied with a voltage from a power source (not shown) through a feed line 743 drawn out of the cover 726 through a through hole 742 formed in the cover 726.
　Ｘ線管７３０は、ガラス製または金属製の円筒形状の真空管からなり、管方向が鉛直となるように配置されている。Ｘ線管７３０の下端部（開口端部）は開いて円形の開口７４１を形成している。Ｘ線管７３０の上端部は閉じており、ステム７３２となっている。Ｘ線管７３０内には、陰極であるフィラメント７３３と、陽極であるターゲット７３６とが対向するように配置されている。Ｘ線管７３０は、フィラメント７３３およびフォーカス７３４を収容している。具体的には、ステム７３２に、カソードとしてのフィラメント７３３が配置されている。フィラメント７３３は、高電圧ユニット７３１と電気的に接続されている。フィラメント７３３は円筒状のフォーカス７３４によって取り囲まれている。 The X-ray tube 730 is made of a glass or metal cylindrical vacuum tube, and is arranged so that the tube direction is vertical. A lower end portion (opening end portion) of the X-ray tube 730 is opened to form a circular opening 741. The upper end portion of the X-ray tube 730 is closed and serves as a stem 732. In the X-ray tube 730, a filament 733 serving as a cathode and a target 736 serving as an anode are disposed so as to face each other. The X-ray tube 730 contains a filament 733 and a focus 734. Specifically, a filament 733 as a cathode is disposed on the stem 732. The filament 733 is electrically connected to the high voltage unit 731. The filament 733 is surrounded by a cylindrical focus 734.
　Ｘ線管７３０の開口端部は、鉛直姿勢をなす板状の照射窓７３５によって閉塞されている。照射窓７３５はたとえば円板状をなし、銀ロウ付けによってＸ線管７３０の開口端部の壁面に固定されている。照射窓７３５の材料として、透過力の弱い軟Ｘ線が透過しやすい原子量の小さい物質が使用され、本実施形態ではベリリウム（Ｂｅ）が採用されている。照射窓７３５の厚みは、たとえば0.3mm程度に設定されている。 The open end of the X-ray tube 730 is closed by a plate-shaped irradiation window 735 that has a vertical posture. The irradiation window 735 has a disk shape, for example, and is fixed to the wall surface of the open end of the X-ray tube 730 by silver brazing. As the material of the irradiation window 735, a substance having a small atomic weight that is easy to transmit soft X-rays having a low transmission power is used, and beryllium (Be) is employed in this embodiment. The thickness of the irradiation window 735 is set to about 0.3 mm, for example.
　照射窓７３５の内面７３５Ａには、金属製のターゲット７３６が蒸着によって形成されている。ターゲット７３６には、タングステン（Ｗ）やタンタル（Ｔａ）等の原子量の大きく融点の高い金属が用いられる。 A metal target 736 is formed on the inner surface 735A of the irradiation window 735 by vapor deposition. For the target 736, a metal having a high atomic weight and a high melting point such as tungsten (W) or tantalum (Ta) is used.
　高電圧ユニット７３１からの駆動電圧が陰極であるフィラメント７３３に印加されることにより、フィラメント７３３が電子を放出する。フィラメント７３３から放出された電子は、フォーカス７３４で収束されて電子ビームとなり、ターゲット７３６に衝突することによって軟Ｘ線が発生する。発生した軟Ｘ線は照射窓７３５から下方に向けて射出（放射）される。照射窓７３５からの軟Ｘ線の照射角（照射範囲）は、図３７に示すように広角（たとえば130°）である。照射窓７３５から軟Ｘ線照射ヘッド７０６外に照射される軟Ｘ線は、その波長がたとえば0.13～0.41nmである。 When the drive voltage from the high voltage unit 731 is applied to the filament 733 that is a cathode, the filament 733 emits electrons. The electrons emitted from the filament 733 are converged at the focus 734 to become an electron beam, and soft X-rays are generated by colliding with the target 736. The generated soft X-rays are emitted (radiated) downward from the irradiation window 735. The irradiation angle (irradiation range) of soft X-rays from the irradiation window 735 is a wide angle (for example, 130 °) as shown in FIG. The wavelength of soft X-rays irradiated from the irradiation window 735 to the outside of the soft X-ray irradiation head 706 is, for example, 0.13 to 0.41 nm.
　照射窓７３５は、軟Ｘ線を発生する発生源である。そのため、外表面７３５Ｂへの水滴の付着等により、当該照射窓７３５が曇っていると、照射窓７３５からの軟Ｘ線の照射を阻害するおそれがあり、好ましくない。 The irradiation window 735 is a generation source that generates soft X-rays. Therefore, if the irradiation window 735 is clouded due to adhesion of water droplets or the like to the outer surface 735B, there is a possibility that the irradiation of soft X-rays from the irradiation window 735 may be hindered.
　照射窓７３５の外表面７３５Ｂの全域は、撥水性を有するポリイミド樹脂皮膜７３８によって被覆されている。照射窓７３５の外表面７３５Ｂを皮膜７３８で覆ったのは、耐酸性の劣るベリリウム製の照射窓７３５を、水等の処理液に含まれる酸から守るためのものである。ポリイミド樹脂皮膜７３８は、ポリアミック酸タイプのポリイミド樹脂を有している。ポリイミド樹脂皮膜７３８の膜厚は、50μm以下であり、とくに10μm程度であることが好ましい。皮膜７３８が撥水性を有しているので、照射窓７３５の外表面７３５Ｂから水分を排除することができる。これにより、照射窓７３５が曇るのを抑制または防止することができる。また、ポリイミド樹脂皮膜７３８は化学安定性が高いので、照射窓７３５の外表面７３５Ｂを長期にわたって保護し続けることができる。 The entire outer surface 735B of the irradiation window 735 is covered with a polyimide resin film 738 having water repellency. The reason why the outer surface 735B of the irradiation window 735 is covered with the film 738 is to protect the irradiation window 735 made of beryllium having poor acid resistance from an acid contained in a treatment liquid such as water. The polyimide resin film 738 has a polyamic acid type polyimide resin. The film thickness of the polyimide resin film 738 is 50 μm or less, and preferably about 10 μm. Since the film 738 has water repellency, moisture can be excluded from the outer surface 735B of the irradiation window 735. Thereby, it can suppress or prevent that the irradiation window 735 fogs. In addition, since the polyimide resin film 738 has high chemical stability, the outer surface 735B of the irradiation window 735 can be protected for a long period of time.
　ところで、Ｘ線発生器７２５の周囲をカバー７２６で覆っているのは、Ｘ線発生器７２５を水分から守るためである。前述のようにＸ線発生器７２５が高電圧ユニット７３１を備えているので、Ｘ線発生器７２５の周囲の雰囲気が多くの水分を含んでいると、軟Ｘ線の発生の際に、高電圧がリークするおそれがある。したがって、Ｘ線発生器７２５に水分が侵入するのを抑制するために、Ｘ線発生器７２５の周囲をカバー７２６で覆っている。 Incidentally, the reason why the X-ray generator 725 is covered with the cover 726 is to protect the X-ray generator 725 from moisture. Since the X-ray generator 725 includes the high voltage unit 731 as described above, if the atmosphere around the X-ray generator 725 contains a large amount of moisture, a high voltage is generated when soft X-rays are generated. May leak. Therefore, the X-ray generator 725 is covered with a cover 726 in order to prevent moisture from entering the X-ray generator 725.
　気体ノズル７２７の吐出口は、カバー７２６の上壁に開口している。気体ノズル７２７には気体バルブ（気体供給手段）７３７を介して気体供給源（図示しない）からの気体が供給されている。また、気体ノズル７２７には、常温（たとえば２５℃）よりも高温（たとえば６０℃）の気体が供給されており、そのため、気体ノズル７２７は高温（たとえば６０℃）の気体を吐出する。気体ノズル７２７が吐出する気体として、ＣＤＡ（低湿度の清浄空気）や窒素ガス等の不活性ガスを例示することができる。気体ノズル７２７から吐出された気体は、カバー７２６の内部に供給される。 The discharge port of the gas nozzle 727 opens on the upper wall of the cover 726. Gas from a gas supply source (not shown) is supplied to the gas nozzle 727 via a gas valve (gas supply means) 737. Further, the gas nozzle 727 is supplied with a gas having a temperature higher than room temperature (for example, 25 ° C.) (for example, 60 ° C.). Therefore, the gas nozzle 727 discharges a gas having a high temperature (for example, 60 ° C.). Examples of the gas discharged from the gas nozzle 727 include CDA (clean air with low humidity) and inert gas such as nitrogen gas. The gas discharged from the gas nozzle 727 is supplied into the cover 726.
　前述のように、カバー７２６の下壁７２６Ａには、照射窓７３５からの軟Ｘ線を透過させるための開口７２８が形成されている。そのため、カバー７２６の内部に気体が供給されるのと相俟って、すなわちカバー７２６とＸ線発生器７２５の外壁との間の空間に、開口７２８に向かう気流が形成される。そのため、カバー７２６外の雰囲気が、開口７２８を介してカバー７２６内に進入するのを抑制または防止することができ、Ｘ線発生器７２５の周囲の雰囲気に水分が進入するのをより一層抑制することができる。 As described above, the lower wall 726A of the cover 726 is formed with an opening 728 for transmitting soft X-rays from the irradiation window 735. Therefore, in combination with the supply of gas into the cover 726, that is, in the space between the cover 726 and the outer wall of the X-ray generator 725, an air flow toward the opening 728 is formed. Therefore, the atmosphere outside the cover 726 can be suppressed or prevented from entering the cover 726 through the opening 728, and moisture can be further prevented from entering the atmosphere around the X-ray generator 725. be able to.
　また、前述のように、照射窓７３５の外表面７３５Ｂには撥水性の皮膜７３８が形成されている。そのため、照射窓７３５前面に水分が膜状に析出するのではなく微細な水滴となる。照射窓７３５の外表面７３５Ｂに付着するその水滴が、高い接触角で外表面７３５Ｂに接しているので、当該水滴は、外表面７３５Ｂを移動し易い状態であるといえる。カバー７２６内に供給される気体は、Ｘ線発生器７２５とカバー７２６との間の空間７３９を通って照射窓７３５の外表面に達する。照射窓７３５の外表面７３５Ｂに付着している水滴は、空間７３９に形成された気流を受けて移動する。これにより、照射窓７３５の外表面７３５Ｂから良好に水滴を排除することができ、照射窓７３５が曇るのを確実に防止することができる。さらに、カバー７２６内に供給される気体が高温であるために、照射窓７３５の外表面７３５Ｂに付着する水滴を蒸発により除去することもでき、これにより、照射窓７３５が曇るのを、より一層確実に防止することができる。 Further, as described above, the water repellent coating 738 is formed on the outer surface 735B of the irradiation window 735. Therefore, moisture is not deposited in the form of a film on the front surface of the irradiation window 735, but becomes fine water droplets. Since the water droplets adhering to the outer surface 735B of the irradiation window 735 are in contact with the outer surface 735B at a high contact angle, it can be said that the water droplets easily move on the outer surface 735B. The gas supplied into the cover 726 reaches the outer surface of the irradiation window 735 through the space 739 between the X-ray generator 725 and the cover 726. The water droplets adhering to the outer surface 735B of the irradiation window 735 move in response to the airflow formed in the space 739. Thereby, water droplets can be favorably eliminated from the outer surface 735B of the irradiation window 735, and the irradiation window 735 can be reliably prevented from being fogged. Further, since the gas supplied into the cover 726 is at a high temperature, water droplets adhering to the outer surface 735B of the irradiation window 735 can be removed by evaporation, so that the irradiation window 735 can be further clouded. It can be surely prevented.
　カバー７２６の下壁７２６Ａには、開口７２８の周囲付近に、シート状のヒータ（発熱部材）７４４が配置されている。ヒータ７４４は、抵抗体をシートにプリントすることにより形成されている。ヒータ７４４への通電によりヒータ７４４が昇温し、その周囲の部材が温められて、照射窓７３５も温められる。そのため、照射窓７３５の外表面７３５Ｂに付着する水滴を蒸発により除去することもでき、これにより、照射窓７３５が曇るのを、さらに一層確実に防止することができる。 A sheet-like heater (heating member) 744 is disposed in the vicinity of the periphery of the opening 728 on the lower wall 726A of the cover 726. The heater 744 is formed by printing a resistor on a sheet. The heater 744 is heated by energization of the heater 744, the surrounding members are warmed, and the irradiation window 735 is also warmed. Therefore, water droplets adhering to the outer surface 735B of the irradiation window 735 can also be removed by evaporation, and thereby the irradiation window 735 can be more reliably prevented from being fogged.
　図３３は、軟Ｘ線照射ヘッド７０６の配置位置を示す平面図である。 FIG. 33 is a plan view showing an arrangement position of the soft X-ray irradiation head 706.
　揺動駆動機構７１９が制御されることにより、スピンチャック７０４に保持された基板Ｗの表面上を、軟Ｘ線照射ヘッド７０６が、基板Ｗの回転方向と交差する円弧状の軌跡を描くように移動可能に設けられている。軟Ｘ線照射ヘッド７０６により、基板Ｗの表面に軟Ｘ線を照射する場合、軟Ｘ線照射ヘッド７０６は近接位置に配置される。そして、軟Ｘ線の照射中は、その近接位置に配置されたままである。図３３に実線で示す軟Ｘ線照射ヘッド７０６の配置位置はセンター近接位置であり、基板Ｗの表面の回転中心（回転軸線Ｃ上）を、軟Ｘ線照射ヘッド７０６の照射窓７３５からの照射領域に含む近接位置である。図３３に二点鎖線で示す軟Ｘ線照射ヘッド７０６の配置位置はエッジ近接位置であり、基板Ｗの表面の周縁を、軟Ｘ線照射ヘッド７０６の照射窓７３５からの照射領域に含む近接位置である。 By controlling the swing drive mechanism 719, the soft X-ray irradiation head 706 draws an arc-shaped locus intersecting the rotation direction of the substrate W on the surface of the substrate W held by the spin chuck 704. It is provided to be movable. When the soft X-ray irradiation head 706 irradiates the surface of the substrate W with soft X-rays, the soft X-ray irradiation head 706 is disposed at a close position. And, during irradiation with soft X-rays, it remains arranged in the proximity position. The arrangement position of the soft X-ray irradiation head 706 shown by a solid line in FIG. 33 is a center proximity position, and the rotation center (on the rotation axis C) of the surface of the substrate W is irradiated from the irradiation window 735 of the soft X-ray irradiation head 706. It is a proximity position included in the region. The arrangement position of the soft X-ray irradiation head 706 indicated by a two-dot chain line in FIG. 33 is the edge proximity position, and the proximity position including the peripheral edge of the surface of the substrate W in the irradiation area from the irradiation window 735 of the soft X-ray irradiation head 706. It is.
　図３４は、基板処理装置７０１の電気的構成を示すブロック図である。基板処理装置７０１は、さらに、マイクロコンピュータを含む構成の制御装置（制御手段）７４０を備えている。制御装置７４０には、スピンモータ７０８、高電圧ユニット７３１、揺動駆動機構７１９、昇降駆動機構７２０、薬液バルブ７１６、水バルブ７１４、気体バルブ７３７、ヒータ７４４等が制御対象として接続されている。 FIG. 34 is a block diagram showing an electrical configuration of the substrate processing apparatus 701. The substrate processing apparatus 701 further includes a control device (control means) 740 having a configuration including a microcomputer. A spin motor 708, a high voltage unit 731, a swing drive mechanism 719, a lift drive mechanism 720, a chemical solution valve 716, a water valve 714, a gas valve 737, a heater 744, and the like are connected to the control device 740 as control targets.
　なお、照射窓７３５を曇りがない状態に保つため、基板処理装置７０１に電源が投入されている間、気体バルブ７３７は常に開放されているとともに、ヒータ７４４は駆動されている。ヒータ７４４は加熱されて、たとえば100℃程度まで昇温している。 In order to keep the irradiation window 735 free from fogging, the gas valve 737 is always opened and the heater 744 is driven while the substrate processing apparatus 701 is powered on. The heater 744 is heated and raised to about 100 ° C., for example.
　図３５は、基板処理装置７０１において実行される基板Ｗの処理例を示す工程図である。この処理例では、薬液処理の実行後、リンス処理が実行される。このリンス処理において、基板Ｗの表面に、軟Ｘ線照射ヘッド７０６からの軟Ｘ線が照射される。図３１、図３３、図３４および図３５を参照して、基板処理装置７０１における基板Ｗの処理について説明する。 FIG. 35 is a process diagram showing a processing example of the substrate W executed in the substrate processing apparatus 701. In this process example, the rinse process is performed after the chemical process. In this rinsing process, the surface of the substrate W is irradiated with soft X-rays from the soft X-ray irradiation head 706. With reference to FIG. 31, FIG. 33, FIG. 34, and FIG. 35, the processing of the substrate W in the substrate processing apparatus 701 will be described.
　基板Ｗの処理に際して、シャッタ７２２が閉状態から開状態にされる。これにより、開口７２１が開放される。その後、搬送ロボット（図示しない）によって、未処理の基板Ｗが開口７２１を通って処理室７０３内に搬入されて（ステップＳ７０１）、その表面を上方に向けた状態でスピンチャック７０４に受け渡される。このとき、基板Ｗの搬入の妨げにならないように、軟Ｘ線照射ヘッド７０６はホームポジションに配置されている。搬送ロボットのハンドが処理室７０３外に退避した後、シャッタ７２２が閉状態にされる。 When processing the substrate W, the shutter 722 is changed from the closed state to the open state. Thereby, the opening 721 is opened. Thereafter, an unprocessed substrate W is carried into the processing chamber 703 through the opening 721 by a transfer robot (not shown) (step S701), and delivered to the spin chuck 704 with the surface thereof facing upward. . At this time, the soft X-ray irradiation head 706 is disposed at the home position so as not to hinder the loading of the substrate W. After the hand of the transfer robot has retreated from the processing chamber 703, the shutter 722 is closed.
　スピンチャック７０４に基板Ｗが保持された後、制御装置７４０はスピンモータ７０８を制御して、スピンチャック７０４による基板Ｗの回転を開始させる（ステップＳ７０２）。基板Ｗの回転速度が所定の液処理速度（たとえば500ｒｐｍ）まで上げられ、その後、その液処理速度に維持される。 After the substrate W is held on the spin chuck 704, the control device 740 controls the spin motor 708 to start the rotation of the substrate W by the spin chuck 704 (step S702). The rotation speed of the substrate W is increased to a predetermined liquid processing speed (for example, 500 rpm), and then maintained at the liquid processing speed.
　基板Ｗの回転速度が液処理速度に達すると、制御装置７４０は薬液バルブ７１６を開いて、薬液ノズル７０７から基板Ｗの表面の回転中心に向けて薬液を吐出する（Ｓ７０３：薬液供給）。基板Ｗの表面に供給された薬液は、基板Ｗの回転による遠心力を受けて、基板Ｗの周縁に向けて流れる（基板Ｗの全域へと拡がる）。これにより、基板Ｗの表面の全域に薬液による処理が施される。 When the rotation speed of the substrate W reaches the liquid processing speed, the controller 740 opens the chemical liquid valve 716 and discharges the chemical liquid from the chemical liquid nozzle 707 toward the rotation center of the surface of the substrate W (S703: supply of chemical liquid). The chemical solution supplied to the surface of the substrate W receives a centrifugal force due to the rotation of the substrate W and flows toward the periphery of the substrate W (spreads over the entire area of the substrate W). As a result, the entire surface of the substrate W is treated with the chemical solution.
　薬液の供給開始から所定の薬液処理時間が経過すると、制御装置７４０は薬液バルブ７１６が閉じ、薬液ノズル７０７からの薬液の供給を停止する。 When a predetermined chemical solution processing time has elapsed from the start of supply of the chemical solution, the control device 740 closes the chemical solution valve 716 and stops the supply of the chemical solution from the chemical solution nozzle 707.
　また、制御装置７４０は水バルブ７１４を開いて、回転状態にある基板Ｗの表面の回転中心に向けて水ノズル７０５からＤＩＷを吐出する（ステップＳ７０４）。また、制御装置７４０は揺動駆動機構７１９を制御して、軟Ｘ線照射ヘッド７０６を、スピンチャック７０４の側方に設定されたホームポジションから、スピンチャック７０４の上方に移動させ、その後昇降駆動機構７２０を制御して、軟Ｘ線照射ヘッド７０６を、基板Ｗの表面に近接する近接位置に配置する。そして、制御装置７４０は高電圧ユニット７３１を制御して、軟Ｘ線照射ヘッド７０６のＸ線発生器７２５に軟Ｘ線を発生させて、照射窓７３５から下方に向けて照射させる（ステップＳ７０４）。 Further, the control device 740 opens the water valve 714 and discharges DIW from the water nozzle 705 toward the rotation center of the surface of the substrate W in a rotating state (step S704). Further, the control device 740 controls the swing drive mechanism 719 to move the soft X-ray irradiation head 706 from the home position set on the side of the spin chuck 704 to above the spin chuck 704 and then drive it up and down. By controlling the mechanism 720, the soft X-ray irradiation head 706 is disposed at a close position close to the surface of the substrate W. Then, the control device 740 controls the high voltage unit 731 to generate soft X-rays in the X-ray generator 725 of the soft X-ray irradiation head 706 and irradiate downward from the irradiation window 735 (step S704). .
　基板Ｗの表面に供給されたＤＩＷは、基板Ｗの回転による遠心力によって、基板Ｗの周縁に向けて流れる（基板Ｗの全域へと拡がる）。これにより、基板Ｗの表面に付着している薬液がＤＩＷによって洗い流される（リンス処理）。 The DIW supplied to the surface of the substrate W flows toward the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W (spreads over the entire area of the substrate W). Thereby, the chemical solution adhering to the surface of the substrate W is washed away by DIW (rinsing process).
　図３６は、リンス処理を説明するための図解的な図である。 FIG. 36 is an illustrative view for explaining the rinsing process.
　図３５および図３６に示すように、基板ＷへのＤＩＷの供給に並行して、軟Ｘ線照射ヘッド７０６による軟Ｘ線の照射が継続実行される。また、軟Ｘ線照射ヘッド７０６が、センター近接位置とエッジ近接位置との間で往復移動される。換言すると、軟Ｘ線照射ヘッド７０６からの軟Ｘ線が導かれる基板Ｗの表面の照射位置は、基板Ｗの回転中心から基板Ｗの周縁部に至る範囲内を、基板Ｗの回転方向と交差する円弧状の軌跡を描きつつ往復移動する。これにより、基板Ｗの表面の全域にわたって軟Ｘ線を照射することができる。 35 and 36, the soft X-ray irradiation by the soft X-ray irradiation head 706 is continuously executed in parallel with the supply of DIW to the substrate W. The soft X-ray irradiation head 706 is reciprocated between the center proximity position and the edge proximity position. In other words, the irradiation position on the surface of the substrate W to which the soft X-rays from the soft X-ray irradiation head 706 are guided crosses the rotation direction of the substrate W within a range from the rotation center of the substrate W to the peripheral edge of the substrate W. It moves back and forth while drawing an arcuate trajectory. As a result, soft X-rays can be irradiated over the entire surface of the substrate W.
　図３７は、リンス処理における基板Ｗの表面近傍の状態を示す図解的な図である。 FIG. 37 is an illustrative view showing a state in the vicinity of the surface of the substrate W in the rinsing process.
　リンス処理中は、前述のように、基板Ｗの表面にＤＩＷが供給されつつ、その基板Ｗの表面に軟Ｘ線が照射される。このとき、基板Ｗの表面を周縁に向けて流れるＤＩＷに、軟Ｘ線が照射される。具体的には、基板Ｗの表面を流れるＤＩＷによって、基板Ｗに表面に、当該表面に接液するＤＩＷの液膜が形成されるが、この液膜の表面部分（図３７に網掛け示す部分）に軟Ｘ線が照射される。軟Ｘ線の照射により、ＤＩＷの液膜のうち軟Ｘ線が照射される部分では、水分子の励起により当該水分子から電子が放出される結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が形成される。そして、回転状態の基板ＷへのＤＩＷの供給により、ＤＩＷとの接触分離により基板Ｗに正電荷が生じた場合であっても、軟Ｘ線の照射によりＤＩＷ中に発生した電子が、基板Ｗに発生した負電荷に引っ張られて移動し、当該電荷を打ち消すように作用する。これにより基板Ｗの帯電を抑制することができる。 During the rinse process, as described above, the surface of the substrate W is irradiated with soft X-rays while DIW is supplied to the surface of the substrate W. At this time, the soft X-rays are applied to the DIW flowing toward the periphery of the surface of the substrate W. Specifically, DIW flowing on the surface of the substrate W forms a liquid film of DIW in contact with the surface on the surface of the substrate W. The surface portion of this liquid film (the portion shaded in FIG. 37) ) Is irradiated with soft X-rays. In the portion of the DIW liquid film that is irradiated with soft X-rays by soft X-ray irradiation, electrons are emitted from the water molecules by excitation of water molecules, resulting in a large amount of electrons and a large amount of positive water molecules. A plasma state in which ions are mixed is formed. Even if positive charge is generated in the substrate W due to contact separation with DIW due to the supply of DIW to the rotating substrate W, electrons generated in the DIW due to soft X-ray irradiation are transferred to the substrate W. It moves by being pulled by the negative charge generated in the device and acts to cancel the charge. Thereby, charging of the substrate W can be suppressed.
　図３１、図３４および図３５に示すようにＤＩＷの供給開始から所定のリンス時間が経過すると、制御装置７４０は水バルブ７１４を閉じてＤＩＷを供給停止する（ステップＳ７０５）。これにより、リンス処理が終了する。 As shown in FIG. 31, FIG. 34 and FIG. 35, when a predetermined rinse time has elapsed from the start of DIW supply, the control device 740 closes the water valve 714 and stops supplying DIW (step S705). Thereby, the rinsing process ends.
　ＤＩＷの供給停止から所定の時間が経過した後、制御装置７４０は高電圧ユニット７３１を制御して、軟Ｘ線照射ヘッド７０６の照射窓７３５からの軟Ｘ線の照射を停止させる（ステップＳ７０６）。また、制御装置７４０は、揺動駆動機構７１９および昇降駆動機構７２０を制御して、軟Ｘ線照射ヘッド７０６をホームポジションに戻す。なお、軟Ｘ線照射ヘッド７０６による基板Ｗの表面へのＸ線の照射は、次に述べるスピンドライの開始の直前まで実行される。 After a predetermined time has elapsed since the DIW supply was stopped, the control device 740 controls the high voltage unit 731 to stop the soft X-ray irradiation from the irradiation window 735 of the soft X-ray irradiation head 706 (step S706). . In addition, the control device 740 controls the swing drive mechanism 719 and the lift drive mechanism 720 to return the soft X-ray irradiation head 706 to the home position. It should be noted that the X-ray irradiation on the surface of the substrate W by the soft X-ray irradiation head 706 is executed until immediately before the start of the spin dry described below.
　所定のスピンドライ開始タイミングになると、制御装置７４０はスピンモータ７０８を制御して、基板Ｗの回転速度をスピンドライ回転速度（たとえば2500ｒｐｍ）に上昇する。これにより、リンス処理後の基板Ｗの表面に付着しているＤＩＷが遠心力で振り切られて乾燥される（Ｓ７０７：スピンドライ）。 At a predetermined spin dry start timing, the control device 740 controls the spin motor 708 to increase the rotation speed of the substrate W to a spin dry rotation speed (for example, 2500 rpm). Thereby, DIW adhering to the surface of the substrate W after the rinsing process is shaken off by the centrifugal force and dried (S707: spin dry).
　スピンドライが所定の乾燥時間にわたって行われると、スピンチャック７０４の回転が停止される。その後、シャッタ７２２が閉状態から開状態にされ、開口７２１が開放される。そして、処理済の基板Ｗが開口７２１を通して搬送ロボット（図示しない）によって搬出される（ステップＳ７０８）。 When the spin drying is performed for a predetermined drying time, the rotation of the spin chuck 704 is stopped. Thereafter, the shutter 722 is changed from the closed state to the open state, and the opening 721 is opened. Then, the processed substrate W is unloaded by the transfer robot (not shown) through the opening 721 (step S708).
　以上により、この実施形態によれば、基板Ｗの表面に形成されるＤＩＷの液膜に軟Ｘ線Ｘ線が照射される。ＤＩＷの液膜のうち軟Ｘ線が照射される部分では、水分子の励起により当該水分子から電子が放出される結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が形成される。これにより、ＤＩＷとの接触分離により基板Ｗに正電荷が生じた場合であっても、軟Ｘ線の照射によりＤＩＷ中に発生した電子が、ＤＩＷの液膜を介して、基板Ｗに発生した負電荷に引っ張られて移動し、当該電荷を打ち消すように作用する。これにより基板Ｗの帯電を抑制することができる。また、リンス処理前から基板Ｗが帯電していても、基板Ｗの表面に接液するＤＩＷの液膜によって、その帯電した基板Ｗを除電することができる。その結果、基板Ｗの帯電に起因するデバイス破壊を防止することができる。 As described above, according to this embodiment, the liquid film of DIW formed on the surface of the substrate W is irradiated with soft X-ray X-rays. In the DIW liquid film irradiated with soft X-rays, electrons are emitted from the water molecules by excitation of the water molecules, resulting in a plasma state in which a large amount of electrons and a large amount of positive ions of the water molecules coexist. Is formed. Thereby, even when a positive charge is generated on the substrate W due to contact separation with DIW, electrons generated in DIW by soft X-ray irradiation are generated on the substrate W through the liquid film of DIW. It moves by being pulled by a negative charge and acts to cancel the charge. Thereby, charging of the substrate W can be suppressed. Further, even if the substrate W is charged before the rinsing process, the charged substrate W can be neutralized by the DIW liquid film in contact with the surface of the substrate W. As a result, device destruction due to charging of the substrate W can be prevented.
 
　次に、Ｘ線照射ヘッドからの軟Ｘ線の照射によって、シリコンウエハやガラス基板等の基板を除電できることを確認するために、除電試験および電離試験という２つの試験を行った。この試験の内容および結果について以下説明する。
Next, in order to confirm that a substrate such as a silicon wafer or a glass substrate can be neutralized by soft X-ray irradiation from the X-ray irradiation head, two tests, a static elimination test and an ionization test, were performed. The contents and results of this test will be described below.
　図３８は、これらの試験に用いられる試験装置９０２を説明するための断面図である。 FIG. 38 is a cross-sectional view for explaining a test apparatus 902 used for these tests.
　試験装置９０２は、ＤＩＷを貯留しておくための矩形箱状の水槽９０３と、水槽９０３に上方から取り付けられ、水槽９０３に溜められたＤＩＷに対して軟Ｘ線を照射するためのＸ線照射ヘッド９０４とを備えている。 The test apparatus 902 has a rectangular box-shaped water tank 903 for storing DIW and an X-ray irradiation for irradiating soft X-rays to the DIW attached to the water tank 903 from above and stored in the water tank 903. A head 904.
　水槽９０３は、幅100mm、奥行き100mm、高さ100 mmに形成されている。水槽９０３の底壁、４つの側壁および天壁は、それぞれ厚さ5mmの塩ビ板によって構成されている。Ｘ線照射ヘッド９０４は、図３２等に示すＸ線発生器７２５と同等の構成を有する軟Ｘ線イオナイザー（浜松ホトニクス（株）製）であり、照射窓７３５を下方に向けて配置されている。水槽９０３の上壁には開口９０５が形成されており、この開口９０５を介して、照射窓７３５を含む軟Ｘ線照射ヘッド９０４の下端部が水槽内に入り込んでいる。軟Ｘ線照射ヘッド９０４を水槽９０３に装着した状態で、軟Ｘ線照射ヘッド９０４は、照射窓の下面が、水槽９０３の上壁の下面よりも5mm下方に位置している。水槽９０３の上壁における開口９０５の側端辺と、軟Ｘ線照射ヘッド９０４の下端部との間の隙間にはシリコンゴム製のパッキン９０６が嵌め込まれており、これにより、軟Ｘ線照射ヘッド９０４が水槽９０３の上壁に固定されている。 The water tank 903 has a width of 100 mm, a depth of 100 mm, and a height of 100 mm. The bottom wall, the four side walls, and the top wall of the water tank 903 are each made of a PVC plate having a thickness of 5 mm. The X-ray irradiation head 904 is a soft X-ray ionizer (manufactured by Hamamatsu Photonics) having a configuration equivalent to that of the X-ray generator 725 shown in FIG. 32 and the like, and is arranged with the irradiation window 735 facing downward. . An opening 905 is formed in the upper wall of the water tank 903, and the lower end portion of the soft X-ray irradiation head 904 including the irradiation window 735 enters the water tank through the opening 905. With the soft X-ray irradiation head 904 mounted on the water tank 903, the lower surface of the irradiation window of the soft X-ray irradiation head 904 is located 5 mm below the lower surface of the upper wall of the water tank 903. A silicon rubber packing 906 is fitted in a gap between the side edge of the opening 905 on the upper wall of the water tank 903 and the lower end of the soft X-ray irradiation head 904, and thereby the soft X-ray irradiation head 904 is fixed to the upper wall of the water tank 903.
　この試験では、シリコンウエハやガラス基板等の基板に代えて、ステンレス製の方形（80cm×80cm）のメッシュ９１１，９１２（格子状を有し全体として板状をなす）が、計測対象として用いられる。水槽９０３には、２枚のメッシュ９１１，９１２が、上下に間隔を空けつつそれぞれ水平姿勢で取り付けられる。上メッシュ９１１と、軟Ｘ線照射ヘッド９０４の照射窓７３５の外表面７３５Ｂとの間隔はたとえば10mmである。下メッシュ９１２と、軟Ｘ線照射ヘッド９０４の照射窓７３５の外表面７３５Ｂとの間隔はたとえば25mmである。 In this test, a stainless steel square (80 cm × 80 cm) mesh 911, 912 (having a lattice shape and forming a plate shape as a whole) is used as a measurement object in place of a substrate such as a silicon wafer or a glass substrate. . Two meshes 911 and 912 are attached to the water tank 903 in a horizontal posture with a space in the vertical direction. The distance between the upper mesh 911 and the outer surface 735B of the irradiation window 735 of the soft X-ray irradiation head 904 is, for example, 10 mm. The distance between the lower mesh 912 and the outer surface 735B of the irradiation window 735 of the soft X-ray irradiation head 904 is, for example, 25 mm.
　水槽９０３の側壁には、排水用ニップル９０７と、注水用ニップル９０８とが取り付けられている。各ニップル９０７，９０８は、水槽９０３の側壁の内外をそれぞれ貫通している。排水用ニップル９０７は、水槽９０３の上壁の下面から20mmの位置（すなわち、上メッシュ９１１の5mm下方で下メッシュ９１２の10mm上方の位置）に配置されている。注水用ニップル９０８は、下メッシュ９１２に対し、大きく間隔の空いた下方に配置されている。注水用ニップル９０８には注水用ホース（図示しない）が接続されており、排水用ニップル９０７には排水用ホース（図示しない）が接続されている。注水用ホースを介して水槽９０３に水が供給されるとともに、排水用ニップル９０７および排水用ホースを介して排出されるようになっている。 A drain nipple 907 and a water injection nipple 908 are attached to the side wall of the water tank 903. The nipples 907 and 908 respectively penetrate the inside and outside of the side wall of the water tank 903. The drain nipple 907 is disposed at a position 20 mm from the lower surface of the upper wall of the water tank 903 (that is, a position 5 mm below the upper mesh 911 and 10 mm above the lower mesh 912). The water injection nipple 908 is disposed below the lower mesh 912 with a large gap. A water injection hose (not shown) is connected to the water injection nipple 908, and a water discharge hose (not shown) is connected to the water discharge nipple 907. Water is supplied to the water tank 903 via the water injection hose and discharged through the drainage nipple 907 and the drainage hose.
　下メッシュ９１２は、帯電プレートモニタＣＰＭ（米国イオンシステムズ社製　CPM210）の金属プレート（図示しない）と高電圧ケーブルで接続されている。 The lower mesh 912 is connected to a metal plate (not shown) of a charged plate monitor CPM (CPM210, manufactured by Ion Systems Inc., USA) with a high voltage cable.
　そして、注水用ホースを介して水槽９０３に水が供給される。このとき、水槽９０３への給水が続けられても、水槽９０３に溜められたＤＩＷの水位が排水用ニップル９０７の高さよりも上位に達することはない。排水用ニップル９０７の高さまで水槽９０３にＤＩＷが溜められた状態では、排水用ニップル９０７よりも下方にある下メッシュ９１２はＤＩＷ中に浸漬され、その一方で、排水用ニップル９０７よりも上方にある上メッシュ９１１はＤＩＷには浸漬されない。
（１）除電試験
　水槽９０３への水の供給と並行して、帯電プレートモニタＣＰＭにより、液中の下メッシュ９１２を+/-1kVまたは+/-5kVに帯電させた。そして、軟Ｘ線照射ヘッド９０４をオンさせて水槽９０３に溜められたＤＩＷに軟Ｘ線を照射し、その照射開始から、下メッシュ９１２の電位が+/-100kVになるまでの時間（除電時間）を計測した。 Then, water is supplied to the water tank 903 through the water injection hose. At this time, even if water supply to the water tank 903 is continued, the DIW water level stored in the water tank 903 does not reach a higher level than the height of the drain nipple 907. In a state where DIW is accumulated in the water tank 903 up to the height of the drain nipple 907, the lower mesh 912 below the drain nipple 907 is immersed in the DIW, while it is above the drain nipple 907. The upper mesh 911 is not immersed in DIW.
(1) Static elimination test In parallel with the supply of water to the water tank 903, the lower mesh 912 in the liquid was charged to +/- 1 kV or +/- 5 kV by the charging plate monitor CPM. Then, the soft X-ray irradiation head 904 is turned on to irradiate DIW stored in the water tank 903 with soft X-rays, and the time from the start of irradiation until the potential of the lower mesh 912 becomes +/- 100 kV (static elimination time) ) Was measured.
　その結果、+/-1kVに帯電させた場合の除電時間は１秒間以内であり、+/-5kVに帯電させた場合の除電時間は2秒程度であった。 As a result, the charge removal time when charged to +/- 1 kV was within 1 second, and the charge removal time when charged to +/- 5 kV was about 2 seconds.
　この除電試験により、ＤＩＷへの軟Ｘ線の照射により、ＤＩＷ中の帯電体（下メッシュ９１２）を良好に除電できることがわかる。
（２）電離試験
　上および下メッシュ９１１，９１２間に、超絶縁抵抗計（横河ヒューレット・パッカード（株）製　Model　4329A）を接続し、軟Ｘ線照射の有無による２枚のメッシュ９１１，９１２間の電気抵抗の変化を計測した。 This static elimination test shows that the charged body (lower mesh 912) in the DIW can be satisfactorily eliminated by irradiating the DIW with soft X-rays.
(2) Ionization test A superinsulation resistance meter (Model 4329A manufactured by Yokogawa Hewlett-Packard Co., Ltd.) was connected between the upper and lower meshes 911, 912, and two meshes 911, 912 depending on the presence or absence of soft X-ray irradiation. The change in electrical resistance was measured.
　先ず、排水用ニップル９０７の高さまで水槽９０３にＤＩＷを溜める。そして、軟Ｘ線照射ヘッド９０４をオフのまま、下メッシュ９１２に10Vの電圧を印加して、2枚のメッシュ９１１，９１２間の電気抵抗を計測した。次いで、下メッシュ９１２に10Vの電圧を印加したまま、軟Ｘ線照射ヘッド９０４をオンさせて水槽９０３に溜められたＤＩＷに軟Ｘ線を照射した状態で、２枚のメッシュ９１１，９１２間の電気抵抗を計測した。 First, DIW is accumulated in the water tank 903 up to the height of the nipple 907 for drainage. Then, with the soft X-ray irradiation head 904 turned off, a voltage of 10 V was applied to the lower mesh 912, and the electrical resistance between the two meshes 911 and 912 was measured. Next, while applying a voltage of 10 V to the lower mesh 912, the soft X-ray irradiation head 904 is turned on, and the DIW stored in the water tank 903 is irradiated with soft X-rays, and between the two meshes 911, 912 The electrical resistance was measured.
　その結果、軟Ｘ線照射時の電気抵抗は、軟Ｘ線照前の１×１０１１（Ω）から１×１０９（Ω）に低下した。 As a result, the electrical resistance during soft X-ray irradiation decreased from 1 × 10 11 (Ω) before soft X-ray irradiation to 1 × 10 9 (Ω).
　この電離試験により、ＤＩＷへの軟Ｘ線の照射により、ＤＩＷを電離させることができることがわかる。 This ionization test shows that DIW can be ionized by irradiating DIW with soft X-rays.
　以上により、ＤＩＷへの軟Ｘ線の照射により、ＤＩＷを電離させることができ、このＤ
ＩＷの電離に起因して、ＤＩＷに接液する帯電体を良好に除電できることがわかる。 As described above, DIW can be ionized by irradiating DIW with soft X-rays.
It can be seen that due to the ionization of the IW, the charged body in contact with the DIW can be well discharged.
　図３９は、本発明の第１６実施形態に係る基板処理装置８２０の構成を模式的に示す図である。基板処理装置８２０が、第１５実施形態に係る基板処理装置７０１と共通する部分には、図３１～図３７と同一の参照符号を付し説明を省略する。基板処理装置８２０が基板処理装置７０１と相違する主たる点は、固定的な水ノズル７０５に代えて、スキャンノズルの形態が採用された水ノズル（水供給手段）８２１を設けた点である。 FIG. 39 is a diagram schematically showing the configuration of the substrate processing apparatus 820 according to the sixteenth embodiment of the present invention. Parts common to the substrate processing apparatus 820 according to the fifteenth embodiment are denoted by the same reference numerals as in FIGS. 31 to 37, and description thereof is omitted. The main difference between the substrate processing apparatus 820 and the substrate processing apparatus 701 is that a water nozzle (water supply means) 821 adopting a scan nozzle form is provided in place of the fixed water nozzle 705.
　水ノズル８２１は、たとえば、連続流の状態でＤＩＷを吐出するストレートノズルである。水ノズル８２１は、その吐出口を下方に向けた状態で、ほぼ水平に延びる水アーム８２３の先端に取り付けられている。水ノズル８２１には水供給管７１３が接続されている。水アーム８２３は、鉛直方向に延びる所定の揺動軸線まわりに旋回可能に設けられている。水アーム８２３には、水アーム８２３を所定角度範囲内で揺動させるための水アーム揺動駆動機構８２２が結合されている。水アーム８２３の揺動により、水ノズル８２１は、基板Ｗの回転軸線Ｃ上の位置（基板Ｗの回転中心に対向する位置）と、スピンチャック７０４の側方に設定されたホームポジションとの間で移動される。 The water nozzle 821 is, for example, a straight nozzle that discharges DIW in a continuous flow state. The water nozzle 821 is attached to the tip of a water arm 823 that extends substantially horizontally with its discharge port facing downward. A water supply pipe 713 is connected to the water nozzle 821. The water arm 823 is provided so as to be able to turn around a predetermined swing axis extending in the vertical direction. The water arm 823 is coupled to a water arm swing drive mechanism 822 for swinging the water arm 823 within a predetermined angle range. By swinging the water arm 823, the water nozzle 821 is positioned between the position on the rotation axis C of the substrate W (position facing the rotation center of the substrate W) and the home position set to the side of the spin chuck 704. It is moved with.
　リンス処理時には、水アーム揺動駆動機構８２２が制御されて、水ノズル８２１が、基板Ｗの回転中心上と周縁部上との間で往復移動させられる。これによって、水ノズル８２１からのＤＩＷが導かれる基板Ｗの表面上の供給位置は、基板Ｗの回転中心から基板Ｗの周縁部に至る範囲内を、基板Ｗの回転方向と交差する円弧状の軌跡を描きつつ往復移動する。このとき、水ノズル８２１と軟Ｘ線照射ヘッド７０６とが干渉しないように、水ノズル８２１および軟Ｘ線照射ヘッド７０６の揺動位置がそれぞれ制御されている。 During the rinsing process, the water arm swing driving mechanism 822 is controlled, and the water nozzle 821 is reciprocated between the rotation center of the substrate W and the peripheral edge. As a result, the supply position on the surface of the substrate W to which DIW from the water nozzle 821 is guided is an arc shape that intersects the rotation direction of the substrate W within a range from the rotation center of the substrate W to the peripheral edge of the substrate W. Move back and forth while drawing a trajectory. At this time, the swing positions of the water nozzle 821 and the soft X-ray irradiation head 706 are controlled so that the water nozzle 821 and the soft X-ray irradiation head 706 do not interfere with each other.
　図４０は、本発明の第１７実施形態に係る基板処理装置８３０の構成を模式的に示す図である。基板処理装置８３０が、第１５実施形態に係る基板処理装置７０１と共通する部分には、図３１～図３７と同一の参照符号を付し説明を省略する。基板処理装置８３０が基板処理装置７０１と相違する主たる点は、水ノズルと軟Ｘ線照射ヘッドとを一体的に有する一体型ヘッド８３１を備えた点である。一体型ヘッド８３１は、第２実施形態の水ノズル８２１と同等の構成を有する水ノズル（水供給手段）８３３と、第１実施形態の軟Ｘ線照射ヘッド７０６と同等の構成を有する軟Ｘ線照射ユニット（Ｘ線照射手段）８３４と、水ノズル８３３と軟Ｘ線照射ユニット８３４とを保持するホルダ８３５とを備えている。一体型ヘッド８３１は、ほぼ水平に延びるアーム８３２の先端に取り付けられている。アーム８３２は、鉛直方向に延びる所定の揺動軸線まわりに旋回可能に設けられている。アーム８３２の揺動により、一体型ヘッド８３１は、基板Ｗの回転軸線Ｃ上の位置（基板Ｗの回転中心に対向する位置）と、スピンチャック７０４の側方に設定されたホームポジションとの間で移動される。リンス処理時には、一体型ヘッド８３１が、基板Ｗの回転中心上と周縁部上との間で往復移動させられる。これによって、水ノズル８３３からのＤＩＷが導かれる基板Ｗの表面上の供給位置、および軟Ｘ線照射ユニット８３４からの軟Ｘ線が導かれる基板Ｗの表面の照射位置が、基板Ｗの回転中心から基板Ｗの周縁部に至る範囲内を、基板Ｗの回転方向と交差する円弧状の軌跡を描きつつ往復移動する。 FIG. 40 is a diagram schematically showing the configuration of the substrate processing apparatus 830 according to the seventeenth embodiment of the present invention. Portions common to the substrate processing apparatus 701 according to the fifteenth embodiment are denoted by the same reference numerals as in FIGS. 31 to 37, and description thereof is omitted. The main difference between the substrate processing apparatus 830 and the substrate processing apparatus 701 is that an integrated head 831 having a water nozzle and a soft X-ray irradiation head is provided. The integrated head 831 includes a water nozzle (water supply means) 833 having a configuration equivalent to that of the water nozzle 821 of the second embodiment and a soft X-ray having a configuration equivalent to that of the soft X-ray irradiation head 706 of the first embodiment. An irradiation unit (X-ray irradiation means) 834 and a holder 835 for holding a water nozzle 833 and a soft X-ray irradiation unit 834 are provided. The integrated head 831 is attached to the tip of an arm 832 that extends substantially horizontally. The arm 832 is provided so as to be able to turn around a predetermined swing axis extending in the vertical direction. By swinging the arm 832, the integrated head 831 moves between a position on the rotation axis C of the substrate W (a position facing the rotation center of the substrate W) and a home position set to the side of the spin chuck 704. It is moved with. During the rinsing process, the integrated head 831 is reciprocated between the rotation center of the substrate W and the peripheral edge. As a result, the supply position on the surface of the substrate W to which DIW from the water nozzle 833 is guided and the irradiation position on the surface of the substrate W to which soft X-rays from the soft X-ray irradiation unit 834 are guided are the rotation center of the substrate W. And reciprocating in a range extending from the peripheral edge of the substrate W to an arc-shaped locus intersecting the rotation direction of the substrate W.
　図４１は、本発明の第１８実施形態に係る基板処理装置８４０の構成を模式的に示す図である。基板処理装置８４０は、第１実施形態の軟Ｘ線照射ヘッド７０６に代えて、軟Ｘ線照射ヘッド（Ｘ線照射手段）８４１を備えている。軟Ｘ線照射ヘッド８４１が軟Ｘ線照射ヘッド７０６と相違する主たる点は、カバー７２６の側壁下縁から、水平方向に沿って外方に向けて張り出す（カバー７２６から側方に向けて突出する）遮蔽板部（遮蔽部材）８４２を備えた点である。遮蔽板部８４２は四角環板状をなし、その下面がカバー７２６の下壁７２６Ａと連続する水平面を有している。リンス処理時において、遮蔽板部８４２は、スピンチャック７０４に保持されている基板Ｗの表面に対向して配置される。遮蔽板部８４２によって、照射窓７３５から照射された軟Ｘ線が、基板Ｗと遮蔽板部８４２との間の空間内に留めて置かれる。したがって、照射窓７３５から照射された軟Ｘ線が基板Ｗの周囲に散乱するのを抑制または防止することができ、これにより、基板処理装置８４０の安全性を高めることができる。 FIG. 41 is a diagram schematically showing the configuration of the substrate processing apparatus 840 according to the eighteenth embodiment of the present invention. The substrate processing apparatus 840 includes a soft X-ray irradiation head (X-ray irradiation means) 841 instead of the soft X-ray irradiation head 706 of the first embodiment. The main difference between the soft X-ray irradiation head 841 and the soft X-ray irradiation head 706 is that it projects outward from the lower edge of the side wall of the cover 726 in the horizontal direction (projects from the cover 726 to the side). This is a point provided with a shielding plate portion (shielding member) 842. The shielding plate portion 842 has a square ring plate shape, and the lower surface thereof has a horizontal plane continuous with the lower wall 726A of the cover 726. During the rinsing process, the shielding plate portion 842 is disposed to face the surface of the substrate W held by the spin chuck 704. Soft X-rays emitted from the irradiation window 735 are placed in the space between the substrate W and the shielding plate 842 by the shielding plate 842. Therefore, it is possible to suppress or prevent the soft X-rays irradiated from the irradiation window 735 from being scattered around the substrate W, and thus the safety of the substrate processing apparatus 840 can be improved.
　図４４は、本発明の第１９実施形態に係る処理液処理装置が適用された基板処理装置１００１の構成を示す図である。 FIG. 44 is a diagram showing a configuration of a substrate processing apparatus 1001 to which the processing liquid processing apparatus according to the nineteenth embodiment of the present invention is applied.
　基板処理装置１００１は、たとえば、複数枚の基板Ｗに対し、一括して処理液処理（洗浄処理）を施すバッチ式の基板処理装置である。基板処理装置１００１は、処理液を貯留する処理槽１００２と、処理槽１００２に処理液を供給する処理液ノズル１００３と、処理槽１００２に貯留されている処理液に基板Ｗを浸漬させるリフター１００４と、処理槽１００２に貯留されている処理液を循環させる循環機構１００５と、基板処理装置１００１に備えられた各機器やバルブを制御する制御装置１００６とを含む。 The substrate processing apparatus 1001 is, for example, a batch type substrate processing apparatus that collectively performs processing liquid processing (cleaning processing) on a plurality of substrates W. The substrate processing apparatus 1001 includes a processing tank 1002 for storing a processing liquid, a processing liquid nozzle 1003 for supplying the processing liquid to the processing tank 1002, and a lifter 1004 for immersing the substrate W in the processing liquid stored in the processing tank 1002. A circulation mechanism 1005 that circulates the treatment liquid stored in the treatment tank 1002 and a control device 1006 that controls each device and valve provided in the substrate treatment apparatus 1001 are included.
　処理槽１００２は、上向きに開いた上部開口を有する内槽１００７および外槽１００８を含む二重槽構造を有している。内槽１００７は、処理液を貯留し、複数枚の基板Ｗを収容可能に構成されている。外槽１００８は、内槽１００７の上部開口の外側面に設けられており、その上縁の高さが内槽１００７の上縁の高さよりも高く設定されている。 The treatment tank 1002 has a double tank structure including an inner tank 1007 and an outer tank 1008 having an upper opening opened upward. The inner tank 1007 is configured to store the processing liquid and accommodate a plurality of substrates W. The outer tub 1008 is provided on the outer surface of the upper opening of the inner tub 1007, and the height of its upper edge is set higher than the height of the upper edge of the inner tub 1007.
　内槽１００７の底壁には排液バルブ１０２０が介装されている。排液バルブ１０２０は、ピストン（図示しない）が進退移動を行うことによって内槽１００７の底壁の一部を開閉するいわゆるピストンバルブによって構成されている。ピストン（図示しない）の後退により、内槽１００７の底面の一部が離脱して内槽１００７の底面に排液口が形成され、これにより、処理液が急速に排液されるようになっている。すなわち、処理槽１００２はＱＤＲ（クイック・ダンプ・リンス）機能を備えている。内槽１００７の底部から排出された処理液は、廃液装置へと送られ、処理されるようになっている。 A drain valve 1020 is interposed on the bottom wall of the inner tank 1007. The drainage valve 1020 is a so-called piston valve that opens and closes a part of the bottom wall of the inner tank 1007 by moving a piston (not shown) forward and backward. Due to the retreat of the piston (not shown), a part of the bottom surface of the inner tank 1007 is detached and a drain port is formed on the bottom surface of the inner tank 1007, whereby the processing liquid is quickly drained. Yes. That is, the processing tank 1002 has a QDR (Quick Dump Rinse) function. The processing liquid discharged from the bottom of the inner tank 1007 is sent to a waste liquid device for processing.
　処理液ノズル１００３は、処理液バルブ１００９が介装された処理液配管１０１０に接続されている。処理液ノズル１００３は、多数の微細な吐出口（図示しない）を有し、たとえば液を液滴の態様で吐出するシャワーノズルによって構成されている。制御装置１００６が処理液バルブ１００９を開くと、処理液ノズル１００３からシャワー状に吐出された処理液が、内槽１００７内に供給される。そして、内槽１００７の上縁から処理液が溢れると、溢れた処理液は、外槽１００８によって受け止められ、回収される。 The processing liquid nozzle 1003 is connected to a processing liquid pipe 1010 in which a processing liquid valve 1009 is interposed. The processing liquid nozzle 1003 has a large number of fine discharge ports (not shown), and is constituted by, for example, a shower nozzle that discharges liquid in the form of droplets. When the control device 1006 opens the processing liquid valve 1009, the processing liquid discharged from the processing liquid nozzle 1003 in a shower shape is supplied into the inner tank 1007. When the processing liquid overflows from the upper edge of the inner tank 1007, the overflowing processing liquid is received by the outer tank 1008 and collected.
　処理液として、水や希釈薬液が採用される。水としては、ＤＩＷ（脱イオン水）、炭酸水、電解イオン水、水素水、オゾン水および希釈濃度（たとえば、１０ｐｐｍ～１００ｐｐｍ程度）の塩酸水のいずれかを採用することもできる。希釈薬液としては、所定濃度に希釈されたフッ酸、BHF（Bufferd HF）、ＡＰＭ（ammonia-hydrogen peroxide mixture：アンモニア過酸化水素水混合液）、ＴＭＡＨ（水酸化テトラメチルアンモニウム水溶液）、アンモニア水、ＨＰＭ（hydrochloric acid/hydrogen peroxide mixture：塩酸過酸化水素水混合液）等を用いることができる。この実施形態（第１９実施形態）だけでなく、第１９～第２７実施形態において同様である。 水 Water or diluted chemical is used as the treatment liquid. As the water, any of DIW (deionized water), carbonated water, electrolytic ionic water, hydrogen water, ozone water, and dilute concentration (for example, about 10 ppm to 100 ppm) hydrochloric acid water can be employed. Diluent solutions include hydrofluoric acid diluted to a predetermined concentration, BHF (BufferdＰＭHF), APM (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide aqueous solution), aqueous ammonia, HPM (hydrochloric acid / hydrogen / peroxide mixture) can be used. The same applies to not only this embodiment (19th embodiment) but also the 19th to 27th embodiments.
　リフター１００４によって保持されている基板Ｗは、内槽１００７に貯留されている処理液に浸漬される。 The substrate W held by the lifter 1004 is immersed in the processing liquid stored in the inner tank 1007.
　リフター１００４は、水平に延びる複数の保持棒１０１１を含む。複数枚の基板Ｗは、紙面の奥手前方向に複数枚の基板Ｗを整列した状態で、複数の保持棒１０１１によって各基板Ｗの下縁が当接されて起立姿勢（鉛直姿勢）で保持される。 The lifter 1004 includes a plurality of holding bars 1011 extending horizontally. The plurality of substrates W are held in an upright position (vertical posture) with the lower edges of the substrates W being brought into contact with each other by the plurality of holding rods 1011 in a state where the plurality of substrates W are aligned in the frontward direction of the drawing. The
　リフター１００４は、昇降機構１０２２を含む。昇降機構１０２２は、リフター１００４に保持されている基板Ｗが内槽１００７内に位置する処理位置（図４４に示す位置）と、リフター１００４に保持されている基板Ｗが内槽１００７の上方に位置する退避位置（図示しない）との間でリフター１００４を昇降させる。したがって、昇降機構１０２２によってリフター１００４が処理位置に移動させられることにより、リフター１００４に保持されている複数枚の基板Ｗが処理液に浸漬される。これにより、基板Ｗに対する処理液を用いた処理が施される。 Lifter 1004 includes an elevating mechanism 1022. The lifting mechanism 1022 includes a processing position where the substrate W held by the lifter 1004 is positioned in the inner tank 1007 (position shown in FIG. 44), and the substrate W held by the lifter 1004 is positioned above the inner tank 1007. The lifter 1004 is moved up and down between the retracted position (not shown). Accordingly, when the lifter 1004 is moved to the processing position by the lifting mechanism 1022, a plurality of substrates W held by the lifter 1004 are immersed in the processing liquid. Thereby, the process using the process liquid with respect to the board | substrate W is performed.
　循環機構１００５は、処理槽１００２から排出された処理液を再び処理槽１００２に導く循環配管１０１２と、循環配管１０１２の下流側の端部にそれぞれ接続された複数の循環ノズル１０１３と、循環配管１０１２から循環ノズル１０１３に処理液を送る循環ポンプ１０１４とを含む。循環配管１０１２は、上流側の端部が外槽１００８の底部に接続された帰還配管（オーバーフロー配管）１０１９と、帰還配管１０１９の下流側の端部から複数に分岐する分岐配管（処理液供給配管）１０１６とを含む。各分岐配管１０１６の先端に、循環ノズル１０１３が取り付けられている。各循環ノズル１０１３は、一または複数の吐出口を有し、内槽１００７内に向けて処理液を吐出する。帰還配管１０１９には、上流側から順に、循環ポンプ１０１４、フィルタ１０１５、循環バルブ１０２１が介装されている。フィルタ１０１５は、循環配管１０１２を流れる処理液をろ過するフィルタ１０１５であり、循環バルブ１０２１は帰還配管１０１９を開閉するためのバルブである。 The circulation mechanism 1005 includes a circulation pipe 1012 that guides the treatment liquid discharged from the treatment tank 1002 to the treatment tank 1002 again, a plurality of circulation nozzles 1013 connected to the downstream end of the circulation pipe 1012, and the circulation pipe 1012. And a circulation pump 1014 for sending the processing liquid to the circulation nozzle 1013. The circulation pipe 1012 includes a return pipe (overflow pipe) 1019 having an upstream end connected to the bottom of the outer tank 1008, and a branch pipe (treatment liquid supply pipe) branched into a plurality from the downstream end of the return pipe 1019. ) 1016. A circulation nozzle 1013 is attached to the tip of each branch pipe 1016. Each circulation nozzle 1013 has one or a plurality of discharge ports, and discharges the processing liquid into the inner tank 1007. In the return pipe 1019, a circulation pump 1014, a filter 1015, and a circulation valve 1021 are interposed in this order from the upstream side. The filter 1015 is a filter 1015 for filtering the processing liquid flowing through the circulation pipe 1012, and the circulation valve 1021 is a valve for opening and closing the return pipe 1019.
　複数の分岐配管１０１６のうちの少なくとも１つ（この実施形態では１つ）には、軟Ｘ線照射ユニット（Ｘ線照射手段）１０１７が取り付けられている。軟Ｘ線照射ユニット１０１７は、分岐配管１０１６内に存在している処理液に軟Ｘ線を照射するためのユニットである。 A soft X-ray irradiation unit (X-ray irradiation means) 1017 is attached to at least one of the plurality of branch pipes 1016 (one in this embodiment). The soft X-ray irradiation unit 1017 is a unit for irradiating the processing liquid existing in the branch pipe 1016 with soft X-rays.
　図４５Ａは、分岐配管１０１６および軟Ｘ線照射ユニット１０１７の構成をそれぞれ示す図解的な断面図である。 FIG. 45A is a schematic cross-sectional view showing the configuration of the branch pipe 1016 and the soft X-ray irradiation unit 1017, respectively.
　分岐配管１０１６は、たとえば塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。分岐配管１０１６には、途中部の管壁に、たとえば円形の第１開口１０５２が形成されている。分岐配管１０１６には、第１開口１０５２を塞ぐように軟Ｘ線照射ユニット１０１７が取り付けられている。 The branch pipe 1016 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). . In the branch pipe 1016, for example, a circular first opening 1052 is formed in the middle pipe wall. A soft X-ray irradiation unit 1017 is attached to the branch pipe 1016 so as to close the first opening 1052.
　軟Ｘ線照射ユニット１０１７は、軟Ｘ線発生器（Ｘ線発生器）１０２５と、軟Ｘ線発生器１０２５の周囲を取り囲むように覆うたとえば塩ビ(poly-vinyl-chloride)製のカバー１０２６と、カバー１０２６の内部に気体を供給するための気体ノズル（気体供給手段）１０２７とを備え、横向きに軟Ｘ線を照射する。カバー１０２６は、軟Ｘ線発生器１０２５の周囲を、軟Ｘ線発生器１０２５と間隔を空けて取り囲む横長の矩形箱状のものであり、鉛直板状の横壁１０２６Ａにおいて、軟Ｘ線発生器１０２５の次に述べる照射窓１０３５に対向する部分に、第１開口１０５２と同径を有するたとえば円形の第２開口１０２８を形成している。軟Ｘ線照射ユニット１０１７は、カバー１０２６の第２開口１０２８が、分岐配管１０１６の第１開口１０５２に一致し、かつ横壁１０２６Ａが分岐配管１０１６の外周に密着するように、分岐配管１０１６に取り付けられる。 The soft X-ray irradiation unit 1017 includes a soft X-ray generator (X-ray generator) 1025, a cover 1026 made of, for example, polyvinyl-chloride covering the periphery of the soft X-ray generator 1025, A gas nozzle (gas supply means) 1027 for supplying a gas to the inside of the cover 1026 is provided, and soft X-rays are irradiated sideways. The cover 1026 is in the shape of a horizontally long rectangular box surrounding the soft X-ray generator 1025 with a space from the soft X-ray generator 1025, and the soft X-ray generator 1025 is formed on the vertical plate-shaped horizontal wall 1026A. For example, a circular second opening 1028 having the same diameter as the first opening 1052 is formed in a portion facing the irradiation window 1035 described next. The soft X-ray irradiation unit 1017 is attached to the branch pipe 1016 so that the second opening 1028 of the cover 1026 coincides with the first opening 1052 of the branch pipe 1016 and the lateral wall 1026A is in close contact with the outer periphery of the branch pipe 1016. .
　第２開口１０２８は、円板状の窓部材１０７１によって閉塞されている。窓部材１０７１は、カバー１０２６の内側から第２開口１０２８を閉塞する。窓部材１０７１により、第２開口１０２８だけでなく、第１開口１０５２も閉塞される。窓部材１０７１の材料として、透過力の弱い軟Ｘ線が透過し易いように原子量の小さい物質が使用され、たとえばベリリウム（Ｂｅ）が採用されている。窓部材１０７１の厚みは、たとえば0.3mm程度に設定されている。 The second opening 1028 is closed by a disk-shaped window member 1071. The window member 1071 closes the second opening 1028 from the inside of the cover 1026. The window member 1071 closes not only the second opening 1028 but also the first opening 1052. As the material of the window member 1071, a substance having a small atomic weight is used so that soft X-rays having a low penetrating power are easily transmitted. For example, beryllium (Be) is adopted. The thickness of the window member 1071 is set to about 0.3 mm, for example.
　軟Ｘ線発生器１０２５は、分岐配管１０１６を通る処理液を電離させるために用いられる軟Ｘ線を射出（放射）する。軟Ｘ線発生器１０２５は、ケース体１０２９と、軟Ｘ線を発生させるための左右に長い軟Ｘ線管１０３０と、軟Ｘ線管１０３０に高電圧を供給する高電圧ユニット１０３１とを備えている。ケース体１０２９は、その内部に、軟Ｘ線管１０３０および高電圧ユニット１０３１を収容する横長の矩形筒状のものであり、導電性および熱伝導性を有する材料（たとえばアルミニウム等の金属材料）を用いて形成されている。 Soft X-ray generator 1025 emits (radiates) soft X-rays used to ionize the processing liquid passing through the branch pipe 1016. The soft X-ray generator 1025 includes a case body 1029, a soft X-ray tube 1030 that is long to generate soft X-rays, and a high voltage unit 1031 that supplies a high voltage to the soft X-ray tube 1030. Yes. The case body 1029 is a horizontally long rectangular tube housing the soft X-ray tube 1030 and the high voltage unit 1031 therein, and is made of a material having conductivity and heat conductivity (for example, a metal material such as aluminum). It is formed using.
　高電圧ユニット１０３１は、たとえば－９．５ｋＶという高電位の駆動電圧を軟Ｘ線管１０３０に入力する。高電圧ユニット１０３１には、カバー１０２６に形成された貫通孔１０４２を通してカバー１０２６外に引き出された給電線１０４３を介して電源（図示しない）からの電圧が供給されている。 The high voltage unit 1031 inputs a driving voltage having a high potential of −9.5 kV, for example, to the soft X-ray tube 1030. The high voltage unit 1031 is supplied with a voltage from a power source (not shown) through a feed line 1043 drawn out of the cover 1026 through a through hole 1042 formed in the cover 1026.
　軟Ｘ線管１０３０は、ガラス製または金属製の円筒形状の真空管からなり、管方向が水平となるように配置されている。軟Ｘ線管１０３０の一端部（開口端部。図４５Ａに示す左端部）は円形開口１０４１を形成している。軟Ｘ線管１０３０の他端部（図４５Ａに示す右端部）は閉じており、ステム１０３２となっている。軟Ｘ線管１０３０内には、陰極であるフィラメント１０３３と、陽極であるターゲット１０３６とが対向するように配置されている。軟Ｘ線管１０３０は、フィラメント１０３３およびフォーカス１０３４を収容している。具体的には、ステム１０３２に、カソードとしてのフィラメント１０３３が配置されている。フィラメント１０３３は、高電圧ユニット１０３１と電気的に接続されている。フィラメント１０３３は円筒状のフォーカス１０３４によって取り囲まれている。 The soft X-ray tube 1030 is made of a glass or metal cylindrical vacuum tube, and is arranged so that the tube direction is horizontal. One end (opening end, left end shown in FIG. 45A) of the soft X-ray tube 1030 forms a circular opening 1041. The other end of the soft X-ray tube 1030 (the right end shown in FIG. 45A) is closed and serves as a stem 1032. In the soft X-ray tube 1030, a filament 1033 serving as a cathode and a target 1036 serving as an anode are disposed so as to face each other. The soft X-ray tube 1030 contains a filament 1033 and a focus 1034. Specifically, a filament 1033 as a cathode is disposed on the stem 1032. The filament 1033 is electrically connected to the high voltage unit 1031. Filament 1033 is surrounded by a cylindrical focus 1034.
　軟Ｘ線管１０３０の開口端部は、鉛直姿勢をなす板状の照射窓１０３５によって閉塞されている。照射窓１０３５はたとえば円板状をなし、銀ロウ付けによって軟Ｘ線管１０３０の開口端部の壁面に固定されている。照射窓１０３５の材料として、透過力の弱い軟Ｘ線が透過し易いように原子量の小さい物質が使用され、たとえばベリリウム（Ｂｅ）が採用されている。照射窓１０３５の厚みは、たとえば0.3mm程度に設定されている。照射窓１０３５は、窓部材１０７１の内面１０７１Ａに対向して、当該窓部材１０７１と微小の間隔を空けて配置されている。 The open end of the soft X-ray tube 1030 is closed by a plate-shaped irradiation window 1035 having a vertical posture. The irradiation window 1035 has a disk shape, for example, and is fixed to the wall surface of the open end of the soft X-ray tube 1030 by silver brazing. As a material of the irradiation window 1035, a substance having a small atomic weight is used so that soft X-rays having a low transmission power can be easily transmitted. For example, beryllium (Be) is adopted. The thickness of the irradiation window 1035 is set to about 0.3 mm, for example. The irradiation window 1035 faces the inner surface 1071A of the window member 1071 and is arranged with a small gap from the window member 1071.
　照射窓１０３５の内面１０３５Ａには、金属製のターゲット１０３６が蒸着によって形成されている。ターゲット１０３６には、タングステン（Ｗ）やタンタル（Ｔａ）等の原子量の大きく融点の高い金属が用いられる。 A metal target 1036 is formed on the inner surface 1035A of the irradiation window 1035 by vapor deposition. For the target 1036, a metal having a high atomic weight and a high melting point such as tungsten (W) or tantalum (Ta) is used.
　高電圧ユニット１０３１からの駆動電圧が陰極であるフィラメント１０３３に印加されることにより、フィラメント１０３３が電子を放出する。フィラメント１０３３から放出された電子は、フォーカス１０３４で収束されて電子ビームとなり、ターゲット１０３６に衝突することによって軟Ｘ線が発生する。発生した軟Ｘ線は照射窓１０３５から横方向（図４５Ａに示す左方）に向けて射出（放射）され、窓部材１０７１および第１開口１０５２を通して分岐配管１０１６の内部を照射する。照射窓１０３５からの軟Ｘ線の照射角（照射範囲）は、図４６に示すように広角（たとえば130°）である。照射窓１０３５から分岐配管１０１６の内部に照射される軟Ｘ線は、その波長がたとえば0.13～0.4nmである。 When the driving voltage from the high voltage unit 1031 is applied to the filament 1033 which is a cathode, the filament 1033 emits electrons. The electrons emitted from the filament 1033 are converged at the focus 1034 to become an electron beam, and soft X-rays are generated by colliding with the target 1036. The generated soft X-rays are emitted (radiated) from the irradiation window 1035 in the lateral direction (leftward in FIG. 45A), and irradiate the inside of the branch pipe 1016 through the window member 1071 and the first opening 1052. The irradiation angle (irradiation range) of soft X-rays from the irradiation window 1035 is a wide angle (for example, 130 °) as shown in FIG. The wavelength of the soft X-ray irradiated from the irradiation window 1035 to the inside of the branch pipe 1016 is, for example, 0.13 to 0.4 nm.
　窓部材１０７１の外表面（閉塞窓における処理液が流通する側の壁面）１０７１Ｂの全域は、親水性皮膜（皮膜）１０３８によって被覆されている。親水性皮膜１０３８は、たとえばポリイミド樹脂皮膜である。窓部材１０７１の外表面１０７１Ｂを親水性皮膜１０３８で覆ったのは、耐酸性の劣るベリリウム製の窓部材１０７１を、水等の処理液に含まれる酸から守るためのものである。親水性皮膜１０３８の膜厚は、50μm以下であり、とくに10μm程度であることが好ましい。親水性皮膜１０３８が親水性を有しているので、皮膜１０３８と処理液との間に気泡が混入するのを、抑制または防止することができる。これにより、照射窓１０３５からの軟Ｘ線を、分岐配管１０１６を流通している処理液に対して良好に照射できる。 The entire outer surface of the window member 1071 (wall surface on the side where the treatment liquid flows in the closed window) 1071B is covered with a hydrophilic film (film) 1038. The hydrophilic film 1038 is, for example, a polyimide resin film. The reason why the outer surface 1071B of the window member 1071 is covered with the hydrophilic film 1038 is to protect the beryllium-made window member 1071 having poor acid resistance from acid contained in the treatment liquid such as water. The film thickness of the hydrophilic film 1038 is 50 μm or less, and preferably about 10 μm. Since the hydrophilic film 1038 has hydrophilicity, it is possible to suppress or prevent air bubbles from being mixed between the film 1038 and the treatment liquid. Thereby, the soft X-rays from the irradiation window 1035 can be satisfactorily irradiated to the processing liquid flowing through the branch pipe 1016.
　気体ノズル１０２７の吐出口は、カバー１０２６の上壁に開口している。気体ノズル１０２７には気体バルブ（気体供給手段）１０３７を介して気体供給源（図示しない）からの気体が供給されている。気体ノズル１０２７が吐出する気体として、ＣＤＡ（低湿度の清浄空気）や窒素ガスの不活性ガスを例示できる。気体ノズル１０２７から吐出された気体は、カバー１０２６の内部に供給される。軟Ｘ線発生器１０２５の駆動により当該軟Ｘ線発生器１０２５が発熱するおそれがあるが、カバー１０２６の内部に気体を供給することにより、軟Ｘ線発生器１０２５を冷却し、軟Ｘ線発生器１０２５の周囲雰囲気の昇温を抑制できる。 The discharge port of the gas nozzle 1027 opens in the upper wall of the cover 1026. Gas from a gas supply source (not shown) is supplied to the gas nozzle 1027 via a gas valve (gas supply means) 1037. Examples of the gas discharged from the gas nozzle 1027 include CDA (clean air with low humidity) and an inert gas such as nitrogen gas. The gas discharged from the gas nozzle 1027 is supplied into the cover 1026. Although the soft X-ray generator 1025 may be heated by driving the soft X-ray generator 1025, supplying the gas into the cover 1026 cools the soft X-ray generator 1025 and generates soft X-rays. The temperature increase in the ambient atmosphere of the vessel 1025 can be suppressed.
　図４４に示すように、制御装置１００６はマイクロコンピュータを含む構成を有し、予め定められたプログラムに従って、昇降機構１０２２および循環ポンプ１０１４等の動作を制御する。さらに、制御装置１００６は、処理液バルブ１００９、排液バルブ１０２０等の開閉動作を制御する。 As shown in FIG. 44, the control device 1006 has a configuration including a microcomputer, and controls operations of the elevating mechanism 1022 and the circulation pump 1014 according to a predetermined program. Further, the control device 1006 controls opening / closing operations of the processing liquid valve 1009, the drain valve 1020, and the like.
　図４５Ｂは、基板処理装置１００１において実行される基板処理の処理例を示す工程図である。図４４、図４５Ａおよび図４５Ｂを参照しながら、基板処理の処理例について説明する。 FIG. 45B is a process diagram illustrating a processing example of substrate processing executed in the substrate processing apparatus 1001. An example of substrate processing will be described with reference to FIGS. 44, 45A, and 45B.
　処理槽１００２にて基板Ｗの処理を行っていないときであっても、循環機構１００５において、処理液の循環が継続して行われている。すなわち、処理液の交換や装置メンテナンス等の特定の状況を除き、処理槽１００２内には常時処理液が貯留されており、処理液は処理槽１００２内で滞留せずに循環配管１０１２を通って循環している。このような循環の際には、循環バルブ１０２１が開放されている。その結果、外槽１００８から流出した処理液が循環配管１０１２を通って、循環ノズル１０１３から内槽１００７の内部に供給される。内槽１００７の内部が処理液で満たされている状態にて循環ノズル１０１３からさらに処理液が供給されることにより、余った処理液が内槽１００７の上端部からオーバーフローして外槽１００８に流れ込む。そして、外槽１００８から流出した処理液が循環配管１０１２を通って循環ノズル１０１３から内槽１００７の内部に供給される。 Even when the substrate W is not processed in the processing tank 1002, the circulation of the processing liquid is continuously performed in the circulation mechanism 1005. That is, except for specific situations such as replacement of processing liquid and apparatus maintenance, the processing liquid is always stored in the processing tank 1002, and the processing liquid does not stay in the processing tank 1002 and passes through the circulation pipe 1012. It is circulating. During such circulation, the circulation valve 1021 is opened. As a result, the processing liquid flowing out from the outer tank 1008 passes through the circulation pipe 1012 and is supplied from the circulation nozzle 1013 to the inside of the inner tank 1007. When the processing liquid is further supplied from the circulation nozzle 1013 while the inside of the inner tank 1007 is filled with the processing liquid, the surplus processing liquid overflows from the upper end of the inner tank 1007 and flows into the outer tank 1008. . Then, the processing liquid that has flowed out of the outer tank 1008 passes through the circulation pipe 1012 and is supplied from the circulation nozzle 1013 to the inside of the inner tank 1007.
　基板浸漬処理の開始に伴って、循環バルブ１０２１が閉じられかつ循環ポンプ１０１４の駆動が停止させられるとともに、排液バルブ１０２０が開かれて、内槽１００７に貯留されていた処理液が急速に排液される（ステップＳ１００１）。 With the start of the substrate immersion process, the circulation valve 1021 is closed and the circulation pump 1014 is stopped, and the drain valve 1020 is opened, so that the treatment liquid stored in the inner tank 1007 is rapidly drained. Liquid is applied (step S1001).
　内槽１００７から処理液を排液して、内槽１００７内が空になった後、制御装置１００６は、リフター１００４を制御して、受渡位置にて受け取った複数枚の基板Ｗを内槽１００７の内部の処理位置にまで降下させる。これにより、基板Ｗが処理槽１００２内に投入される（ステップＳ１００２）。基板Ｗは、空となっている内槽１００７の内部に保持される。 After the processing liquid is drained from the inner tank 1007 and the inner tank 1007 is emptied, the control device 1006 controls the lifter 1004 to receive the plurality of substrates W received at the delivery position into the inner tank 1007. To the processing position inside. As a result, the substrate W is put into the processing bath 1002 (step S1002). The substrate W is held inside an empty inner tank 1007.
　未処理の基板Ｗが空の処理槽１００２に投入されて処理位置に保持された後、制御装置１００６は、処理液バルブ１００９を開放して、処理液ノズル１００３から処理液をシャワー状に吐出する（ステップＳ１００３）。このとき、排液バルブ１０２０は開かれたままであり、排液口（図示しない）が開放されているため、汚染物質を含んだ処理液は溜められない。 After the unprocessed substrate W is put into the empty processing tank 1002 and held at the processing position, the control device 1006 opens the processing liquid valve 1009 and discharges the processing liquid from the processing liquid nozzle 1003 in a shower shape. (Step S1003). At this time, the drainage valve 1020 remains open and the drainage port (not shown) is opened, so that the treatment liquid containing the contaminant cannot be stored.
　その後、予め定めるシャワー洗浄時間が過ぎると、制御装置１００６は、排液バルブ１０２０を閉じる。このとき、処理液ノズル１００３からの処理液の吐出は継続されているので、内槽１００７に処理液が溜められる。これにより、基板Ｗが処理液に浸漬される基板浸漬処理が実行される。 Thereafter, when a predetermined shower cleaning time has passed, the control device 1006 closes the drain valve 1020. At this time, since the discharge of the processing liquid from the processing liquid nozzle 1003 is continued, the processing liquid is stored in the inner tank 1007. Thereby, the board | substrate immersion process in which the board | substrate W is immersed in a process liquid is performed.
　内槽１００７に処理液が満タンに溜められると、制御装置１００６は処理液バルブ１００９を閉じて、処理液ノズル１００３からの処理液の吐出を停止する。また、制御装置１００６は、循環ポンプ１０１４の駆動を開始させるとともに、循環バルブ１０２１を開く。これにより、処理液は処理槽１００２内で滞留せずに循環配管１０１２を通って循環する（ステップＳ１００４）。具体的には、外槽１００８から流出した処理液が循環配管１０１２を通って循環ノズル１０１３から内槽１００７の内部に供給される。内槽１００７の内部が処理液で満たされている状態にて循環ノズル１０１３からさらに処理液が供給されることにより、余った処理液が内槽１００７の上端部からオーバーフローして外槽１００８に流れ込む。そして、外槽１００８から流出した処理液が循環配管１０１２を通って循環ノズル１０１３から内槽１００７の内部に供給される。循環する処理液がフィルタ１０１５を通過するときにパーティクル等の汚染物質は除去される。このため、循環ノズル１０１３からは汚染物質が取り除かれた清浄な処理液が内槽１００７内に向けて吐出される。この状態で、循環ノズル１０１３のノズル配管内および分岐配管１０１６内では、処理液が液密状態にある。 When the processing liquid is fully stored in the inner tank 1007, the control device 1006 closes the processing liquid valve 1009 and stops the discharge of the processing liquid from the processing liquid nozzle 1003. The control device 1006 starts driving the circulation pump 1014 and opens the circulation valve 1021. As a result, the treatment liquid does not stay in the treatment tank 1002 and circulates through the circulation pipe 1012 (step S1004). Specifically, the processing liquid flowing out from the outer tank 1008 is supplied to the inside of the inner tank 1007 from the circulation nozzle 1013 through the circulation pipe 1012. When the processing liquid is further supplied from the circulation nozzle 1013 while the inside of the inner tank 1007 is filled with the processing liquid, the surplus processing liquid overflows from the upper end of the inner tank 1007 and flows into the outer tank 1008. . Then, the processing liquid that has flowed out of the outer tank 1008 passes through the circulation pipe 1012 and is supplied from the circulation nozzle 1013 to the inside of the inner tank 1007. Contaminants such as particles are removed when the circulating processing liquid passes through the filter 1015. For this reason, a clean processing liquid from which contaminants have been removed is discharged from the circulation nozzle 1013 toward the inner tank 1007. In this state, the processing liquid is in a liquid-tight state in the nozzle pipe and the branch pipe 1016 of the circulation nozzle 1013.
　また、制御装置１００６は、高電圧ユニット１０３１（図４５Ａ参照）を制御して、軟Ｘ線照射ユニット１０１７の軟Ｘ線発生器１０２５（図４５Ａ参照）に軟Ｘ線を発生させて、この軟Ｘ線を、照射窓１０３５（図４５Ａ参照）から窓部材１０７１を介して、分岐配管１０１６の内部に向けて照射させる（ステップＳ１００５）。これにより、分岐配管１０１６内を流通している処理液に、軟Ｘ線が照射される。 In addition, the control device 1006 controls the high voltage unit 1031 (see FIG. 45A) to generate soft X-rays in the soft X-ray generator 1025 (see FIG. 45A) of the soft X-ray irradiation unit 1017. X-rays are irradiated from the irradiation window 1035 (see FIG. 45A) through the window member 1071 toward the inside of the branch pipe 1016 (step S1005). Thereby, soft X-rays are irradiated to the processing liquid flowing through the branch pipe 1016.
　図４６は、図４４に示す分岐配管１０１６内への軟Ｘ線の照射状態を示す図解図である。 FIG. 46 is an illustrative view showing a state of irradiation of soft X-rays into the branch pipe 1016 shown in FIG.
　基板浸漬処理に並行して、分岐配管１０１６内を流通している処理液に軟Ｘ線が照射される。分岐配管１０１６内の処理液のうち軟Ｘ線が照射される部分（分岐配管１０１６内の第１開口１０５２に対向する部分。図４６に示す網掛け部分（以下、「処理液の照射部分１０５４」という。））では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、処理液の照射部分１０５４に形成される。 In parallel with the substrate immersion process, the processing liquid flowing through the branch pipe 1016 is irradiated with soft X-rays. Of the processing liquid in the branch pipe 1016, the part irradiated with soft X-rays (the part facing the first opening 1052 in the branch pipe 1016. The shaded part shown in FIG. 46 (hereinafter referred to as “processing liquid irradiation part 1054”). In ())), electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion 1054 of the processing liquid.
　この場合、前述のように循環ノズル１０１３のノズル配管内および分岐配管１０１６内で処理液が液密状態であるので、内槽１００７に貯留されている処理液に浸漬されている基板Ｗと処理液の照射部分１０５４とが、内槽１００７に貯留されている処理液および分岐配管１０１６内の処理液を介して繋がっている。このとき、基板Ｗが正に帯電すると、処理液の照射部分１０５４と、正に帯電している基板Ｗとの間の電位差で、処理液の照射部分１０５４からの電子が基板Ｗに向けて、内槽１００７に貯留されている処理液および分岐配管１０１６内の処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, since the processing liquid is liquid-tight in the nozzle pipe and the branch pipe 1016 of the circulation nozzle 1013 as described above, the substrate W and the processing liquid immersed in the processing liquid stored in the inner tank 1007 are used. The irradiation portion 1054 is connected to the processing liquid stored in the inner tank 1007 and the processing liquid in the branch pipe 1016. At this time, when the substrate W is positively charged, electrons from the irradiation portion 1054 of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion 1054 of the processing liquid and the positively charged substrate W. It moves through the processing liquid stored in the inner tank 1007 and the processing liquid in the branch pipe 1016. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　また、処理液への浸漬の前から基板Ｗが正に帯電している場合にも、同様の原理により、内槽１００７内の処理液や分岐配管１０１６内の処理液を介して当該基板Ｗを除電できる。 In addition, even when the substrate W is positively charged before being immersed in the processing liquid, the substrate W is transferred via the processing liquid in the inner tank 1007 or the processing liquid in the branch pipe 1016 according to the same principle. Static neutralization is possible.
　図４５Ｂに示すように、浸漬処理の開始から予め定める浸漬処理時間が経過すると、制御装置１００６は、軟Ｘ線照射ユニット１０１７からの軟Ｘ線の照射を停止させる（ステップＳ１００６）。 As shown in FIG. 45B, when a predetermined immersion treatment time has elapsed from the start of the immersion treatment, the control device 1006 stops the soft X-ray irradiation from the soft X-ray irradiation unit 1017 (step S1006).
　その後、処理済みの基板Ｗが内槽１００７から搬出される（ステップＳ１００７）。基板Ｗの搬出は、複数の基板Ｗを一括保持するリフター１００４が内槽１００７の内部の処理位置から上方の受渡位置にまで上昇されることによって行われる。受渡位置に上昇した複数の基板Ｗからなるロットは次工程の処理槽へと搬送される。 Thereafter, the processed substrate W is unloaded from the inner tank 1007 (step S1007). The unloading of the substrates W is performed by lifting the lifter 1004 that collectively holds the plurality of substrates W from the processing position inside the inner tank 1007 to the upper delivery position. A lot consisting of a plurality of substrates W raised to the delivery position is transferred to the processing tank of the next process.
　そして、引き続いて処理を行う後続の基板Ｗが存在している場合、ステップＳ１００１に戻って前述の一連の処理が繰り返し実行される。 If there is a subsequent substrate W to be processed subsequently, the process returns to step S1001 and the above-described series of processing is repeatedly executed.
　以上により、第１９実施形態によれば、処理液の浸漬処理時における基板Ｗの帯電を防止できる。また、浸漬処理前から基板Ｗが帯電していても、その基板Ｗに帯びた電荷を除去（すなわち、除電）できる。その結果、基板Ｗの帯電に起因するデバイス破壊を防止できる。 As described above, according to the nineteenth embodiment, the substrate W can be prevented from being charged during the immersion treatment of the treatment liquid. Further, even if the substrate W is charged before the immersion treatment, the charge on the substrate W can be removed (that is, static elimination). As a result, device destruction due to charging of the substrate W can be prevented.
　図４７は、本発明の第２０実施形態に係る処理液処理装置が適用された基板処理装置１２０１の構成を示す図である。 FIG. 47 is a diagram showing a configuration of a substrate processing apparatus 1201 to which the processing liquid processing apparatus according to the twentieth embodiment of the present invention is applied.
　第２０実施形態において、第１９実施形態と共通する部分には、図４４～図４６の場合と同一の参照符号を付し説明を省略する。第２０実施形態に係る基板処理装置１２０１が、第１９実施形態に係る基板処理装置１００１と相違する点は、軟Ｘ線照射ユニット（Ｘ線照射手段）１２１７が、帰還配管１０１９における循環ポンプ１０１４よりも上流側に介装されている点である。軟Ｘ線照射ユニット１２１７は、帰還配管１０１９に取り付けられている。 In the twentieth embodiment, portions common to the nineteenth embodiment are denoted by the same reference numerals as in FIGS. 44 to 46, and description thereof is omitted. The substrate processing apparatus 1201 according to the twentieth embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that the soft X-ray irradiation unit (X-ray irradiation means) 1217 is more than the circulation pump 1014 in the return pipe 1019. Is also located upstream. The soft X-ray irradiation unit 1217 is attached to the return pipe 1019.
　帰還配管１０１９は、丸管状（円筒状）をなしており、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。帰還配管１０１９の途中部には、循環ポンプ１０１４よりも上流側の管壁に、開口（図示しない）が形成されている。 The return pipe 1019 has a round tubular shape (cylindrical shape), such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer), etc. These resin materials are used. In the middle of the return pipe 1019, an opening (not shown) is formed in the pipe wall upstream of the circulation pump 1014.
　軟Ｘ線照射ユニット１２１７は、第１９実施形態に係る軟Ｘ線照射ユニット１０１７（図４５Ａ参照）と同等の構成を採用している。軟Ｘ線照射ユニット１２１７は、帰還配管１０１９の開口を塞ぐように帰還配管１０１９に取り付けられている。具体的には、軟Ｘ線照射ユニット１２１７のカバーの開口（軟Ｘ線照射ユニット１０１７のカバー１０２６の第２開口１０２８（図４５Ａ参照）に相当する開口）が帰還配管１０１９の前記の開口に一致し、かつ軟Ｘ線照射ユニット１２１７のカバーの壁面（軟Ｘ線照射ユニット１０１７のカバー１０２６の横壁１０２６Ａ（図４５Ａ参照）に相当）が帰還配管１０１９の外周に密着している。軟Ｘ線照射ユニット１２１７の高電圧ユニット（第１９実施形態に係る軟Ｘ線照射ユニット１０１７の高電圧ユニット１０３１（図４５Ａ参照）に相当）は、制御装置１００６に接続されている。 The soft X-ray irradiation unit 1217 adopts the same configuration as the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment. The soft X-ray irradiation unit 1217 is attached to the return pipe 1019 so as to close the opening of the return pipe 1019. Specifically, the opening of the cover of the soft X-ray irradiation unit 1217 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) matches the opening of the return pipe 1019. In addition, the wall surface of the cover of the soft X-ray irradiation unit 1217 (corresponding to the lateral wall 1026A of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) is in close contact with the outer periphery of the return pipe 1019. A high voltage unit of the soft X-ray irradiation unit 1217 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
　基板処理装置１２０１では、図４５Ｂに示す処理例の場合と同様の処理が実施される。基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）では、処理液は処理槽１００２内で滞留せずに循環配管１０１２を通って循環している。内槽１００７の内部が処理液で満たされている状態で循環ノズル１０１３からさらに処理液が供給されることにより、余った処理液が内槽１００７の上端部からオーバーフローして（溢れて）外槽１００８に流れ込む。 In the substrate processing apparatus 1201, the same processing as in the processing example shown in FIG. 45B is performed. In the substrate immersion process (steps S1004 to S1006 in FIG. 45B), the processing liquid does not stay in the processing tank 1002 and circulates through the circulation pipe 1012. When the processing liquid is further supplied from the circulation nozzle 1013 while the inside of the inner tank 1007 is filled with the processing liquid, the excess processing liquid overflows (overflows) from the upper end of the inner tank 1007. Flows into 1008.
　図４８は、処理液が内槽１００７の上端部からオーバーフローしている状態を示す模式的な断面図である。 FIG. 48 is a schematic cross-sectional view showing a state where the processing liquid has overflowed from the upper end of the inner tank 1007.
　外槽１００８は、内槽１００７の外周を取り囲む円環板状の底壁１０８１と、底壁１０８１の外周縁から鉛直上方に向けて立ち上がる立上壁１０８２とを有している。底壁１０８１の周方向のたとえば一箇所には、底壁１０８１を厚み方向に貫通する貫通孔より構成されるオーバーフロー口１０８３が形成されている。オーバーフロー口１０８３に、帰還配管１０１９の上流側端部が接続されている。 The outer tank 1008 has an annular plate-shaped bottom wall 1081 that surrounds the outer periphery of the inner tank 1007, and a rising wall 1082 that rises vertically upward from the outer peripheral edge of the bottom wall 1081. An overflow port 1083 formed of a through-hole penetrating the bottom wall 1081 in the thickness direction is formed at, for example, one place in the circumferential direction of the bottom wall 1081. The upstream end of the return pipe 1019 is connected to the overflow port 1083.
　基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）において、循環ノズル１０１３からの処理液の供給が断続的に続行されるから、帰還配管１０１９内が処理液で液密状態にされる。また、図４８に示すように、処理液の液塊１０８０が内槽１００７の上端部を乗り越える状態が常時続くから、内槽１００７に貯留されている処理液と外槽１００８に貯留されている処理液とが、このような処理液の液塊１０８０によって常時繋がっている。 In the substrate immersion process (steps S1004 to S1006 in FIG. 45B), the supply of the processing liquid from the circulation nozzle 1013 is intermittently continued, so that the inside of the return pipe 1019 is made liquid-tight with the processing liquid. Further, as shown in FIG. 48, the state where the liquid mass 1080 of the processing liquid gets over the upper end of the inner tank 1007 always continues, so that the processing liquid stored in the inner tank 1007 and the processing stored in the outer tank 1008 are performed. The liquid is always connected by such a liquid mass 1080 of the processing liquid.
　基板浸漬処理に並行して、帰還配管１０１９内を流通している処理液に、軟Ｘ線照射ユニット１２１７から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。 In parallel with the substrate immersion process, the soft X-ray is irradiated from the soft X-ray irradiation unit 1217 to the processing liquid circulating in the return pipe 1019 (step S1005 in FIG. 45B).
　帰還配管１０１９内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、処理液の照射部分に形成される。 Of the treatment liquid in the return pipe 1019, the portion irradiated with soft X-rays (treatment liquid irradiation portion. The portion equivalent to the treatment liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is a water molecule. Electrons are emitted from the water molecules by excitation of. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
　この場合、前述のように帰還配管１０１９内で処理液が液密状態であり、かつ内槽１００７に貯留されている処理液と外槽１００８に貯留されている処理液とが処理液の液塊１０８０によって常時繋がっているので、内槽１００７に貯留されている処理液に浸漬されている基板Ｗと処理液の照射部分とが、内槽１００７に貯留されている処理液、外槽１００８に貯留されている処理液、および帰還配管１０１９内の処理液を介して繋がっている。このとき、基板Ｗが正に帯電すると、処理液の照射部分と、正に帯電している基板Ｗとの間の電位差で、処理液の照射部分からの電子が基板Ｗに向けて、内槽１００７に貯留されている処理液および帰還配管１０１９内の処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, as described above, the processing liquid is liquid-tight in the return pipe 1019, and the processing liquid stored in the inner tank 1007 and the processing liquid stored in the outer tank 1008 are a liquid mass of the processing liquid. Since it is always connected by 1080, the substrate W immersed in the processing liquid stored in the inner tank 1007 and the irradiated portion of the processing liquid are stored in the processing liquid stored in the inner tank 1007 and the outer tank 1008. And the processing liquid in the return pipe 1019. At this time, if the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W, and the inner tank It moves through the processing liquid stored in 1007 and the processing liquid in the return pipe 1019. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　以上により、第２０実施形態においても、第１９実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, also in the twentieth embodiment, the same operational effects as the operational effects described in the nineteenth embodiment are exhibited.
　図４９は、本発明の第２１実施形態に係る処理液処理装置が適用された基板処理装置１３０１の構成を示す図である。 FIG. 49 is a diagram showing a configuration of a substrate processing apparatus 1301 to which the processing liquid processing apparatus according to the twenty-first embodiment of the present invention is applied.
　第２１実施形態において、第１９実施形態と共通する部分には、図４４～図４６の場合と同一の参照符号を付し説明を省略する。第２１実施形態に係る基板処理装置１３０１が、第１９実施形態に係る基板処理装置１００１と相違する点は、内槽１００７に代えて、略箱状の第１膨出部分１３１８を有する内槽１３０７を備えた点、および軟Ｘ線照射ユニット（Ｘ線照射手段）１３１７が第１膨出部分１３１８の壁に取り付けられている点である。 In the twenty-first embodiment, parts common to the nineteenth embodiment are denoted by the same reference numerals as in FIGS. 44 to 46, and description thereof is omitted. The substrate processing apparatus 1301 according to the twenty-first embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that an inner tank 1307 having a substantially box-shaped first bulging portion 1318 instead of the inner tank 1007. And a soft X-ray irradiation unit (X-ray irradiation means) 1317 is attached to the wall of the first bulging portion 1318.
　第１膨出部分１３１８は、内槽１３０７の円筒状の周壁１３０７Ａから、水平に沿って外方に向けて膨出しており、内槽１３０７の周壁１３０７Ａと一体的に形成されている。第１膨出部分１３１８の上壁または下壁（図４９では上面）には、開口１３２１が形成されている。 The first bulging portion 1318 bulges outward from the cylindrical peripheral wall 1307A of the inner tank 1307 along the horizontal direction, and is formed integrally with the peripheral wall 1307A of the inner tank 1307. An opening 1321 is formed in the upper wall or lower wall (upper surface in FIG. 49) of the first bulging portion 1318.
　軟Ｘ線照射ユニット１３１７は、第１９実施形態に係る軟Ｘ線照射ユニット１０１７（図４５Ａ参照）と同等の構成を採用している。軟Ｘ線照射ユニット１３１７は、第１膨出部分１３１８の開口１３２１を塞ぐように取り付けられている。具体的には、軟Ｘ線照射ユニット１３１７のカバーの開口（軟Ｘ線照射ユニット１０１７のカバー１０２６の第２開口１０２８（図４５Ａ参照）に相当する開口）が第１膨出部分１３１８の開口１３２１に一致し、かつ軟Ｘ線照射ユニット１３１７のカバーの壁面（軟Ｘ線照射ユニット１０１７のカバー１０２６の横壁１０２６Ａ（図４５Ａ参照）に相当）が第１膨出部分１３１８の上壁に密着している。軟Ｘ線照射ユニット１３１７の高電圧ユニット（第１９実施形態に係る軟Ｘ線照射ユニット１０１７の高電圧ユニット１０３１（図４５Ａ参照）に相当）は、制御装置１００６に接続されている。 The soft X-ray irradiation unit 1317 employs a configuration equivalent to that of the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment. The soft X-ray irradiation unit 1317 is attached so as to close the opening 1321 of the first bulging portion 1318. Specifically, the opening of the cover of the soft X-ray irradiation unit 1317 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) is the opening 1321 of the first bulging portion 1318. And the wall surface of the cover of the soft X-ray irradiation unit 1317 (corresponding to the side wall 1026A (see FIG. 45A) of the cover 1026 of the soft X-ray irradiation unit 1017) is in close contact with the upper wall of the first bulging portion 1318. Yes. A high voltage unit of the soft X-ray irradiation unit 1317 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
　基板処理装置１３０１では、図４５Ｂに示す処理例の場合と同様の処理が実施される。基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）では、内槽１３０７内に処理液が溜められ、これにより、第１膨出部分１３１８内が処理液により液密状態になる。 In the substrate processing apparatus 1301, the same processing as in the processing example shown in FIG. 45B is performed. In the substrate immersion process (steps S1004 to S1006 in FIG. 45B), the processing liquid is stored in the inner tank 1307, and thereby the inside of the first bulging portion 1318 becomes liquid-tight with the processing liquid.
　基板浸漬処理に並行して、第１膨出部分１３１８内の処理液に、軟Ｘ線照射ユニット１３１７から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。 In parallel with the substrate immersion process, the soft X-ray is irradiated from the soft X-ray irradiation unit 1317 to the processing liquid in the first bulging portion 1318 (step S1005 in FIG. 45B).
　第１膨出部分１３１８内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、処理液の照射部分に形成される。 Of the processing liquid in the first bulging portion 1318, the portion irradiated with soft X-rays (the processing liquid irradiation portion; a portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46). Electrons are emitted from the water molecules by excitation of the water molecules. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
　この場合、内槽１３０７に貯留されている処理液に浸漬されている基板Ｗと処理液の照射部分とが、内槽１３０７に貯留されている処理液を介して繋がっている。このとき、基板Ｗが正に帯電すると、処理液の照射部分と、正に帯電している基板Ｗとの間の電位差で、処理液の照射部分からの電子が基板Ｗに向けて、内槽１３０７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, the substrate W immersed in the processing liquid stored in the inner tank 1307 and the irradiated portion of the processing liquid are connected via the processing liquid stored in the inner tank 1307. At this time, if the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W, and the inner tank It moves through the processing liquid stored in 1307. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　以上により、第２１実施形態においても、第１９実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, also in the twenty-first embodiment, the same function and effect as those described in the nineteenth embodiment are achieved.
　図５０は、本発明の第２２実施形態に係る処理液処理装置が適用された基板処理装置１４０１の構成を示す図である。 FIG. 50 is a diagram showing a configuration of a substrate processing apparatus 1401 to which the processing liquid processing apparatus according to the twenty-second embodiment of the present invention is applied.
　第２２実施形態において、第１９実施形態と共通する部分には、図４４～図４６の場合と同一の参照符号を付し説明を省略する。第２２実施形態に係る基板処理装置１４０１が、第１９実施形態に係る基板処理装置１００１と相違する点は、内槽１００７に代えて、底部に略箱状の第２膨出部分１４１８を有する内槽１４０７を備えた点、および第２膨出部分１４１８に接続された配管１４２３に、軟Ｘ線照射ユニット（Ｘ線照射手段）１４１７が取り付けられている点である。 In the twenty-second embodiment, the same reference numerals as those in FIGS. 44 to 46 denote the same parts as in the nineteenth embodiment, and a description thereof will be omitted. The substrate processing apparatus 1401 according to the twenty-second embodiment differs from the substrate processing apparatus 1001 according to the nineteenth embodiment in that it has a substantially box-shaped second bulging portion 1418 at the bottom instead of the inner tank 1007. A point provided with a tank 1407 and a point where a soft X-ray irradiation unit (X-ray irradiation means) 1417 is attached to a pipe 1423 connected to the second bulging portion 1418.
　なお、図５０では、基板処理装置１４０１は、循環機構１００５（図４４参照）と同等の構成の循環機構を備えているが、その図示を省略している。 In FIG. 50, the substrate processing apparatus 1401 includes a circulation mechanism having the same configuration as the circulation mechanism 1005 (see FIG. 44), but the illustration thereof is omitted.
　第２膨出部分１４１８は、内槽１４０７の底壁１４０７Ａから、水平に沿って外方に向けて膨出しており、内槽１４０７の底壁１４０７Ａと一体的に形成されている。第２膨出部分１４１８の下壁の所定位置には、排液バルブ１４２０が介装されている。排液バルブ１４２０は排液バルブ１０２０（図４４参照）と同等の構成を有する。すなわち、第２膨出部分１４１８はＱＤＲ（クイック・ダンプ・リンス）設置用の部分である。内槽１４０７の底部から排出された処理液は、廃液装置または回収装置へと送られ、処理されるようになっている。 The second bulging portion 1418 bulges outward from the bottom wall 1407A of the inner tank 1407 along the horizontal, and is formed integrally with the bottom wall 1407A of the inner tank 1407. A drainage valve 1420 is interposed at a predetermined position on the lower wall of the second bulging portion 1418. The drainage valve 1420 has the same configuration as the drainage valve 1020 (see FIG. 44). That is, the second bulging portion 1418 is a portion for installing a QDR (Quick Dump Rinse). The processing liquid discharged from the bottom of the inner tank 1407 is sent to a waste liquid device or a recovery device to be processed.
　第２膨出部分１４１８のたとえば上壁には、配管１４２３の一端が接続されている。配管１４２３の内部は、第２膨出部分１４１８の内部と連通している。第２膨出部分１４１８における配管１４２３の接続位置は、第２膨出部分１４１８における排液バルブ１４２０の配設位置と平面視において異なる位置であることが望ましい。 One end of a pipe 1423 is connected to the upper wall of the second bulging portion 1418, for example. The inside of the pipe 1423 communicates with the inside of the second bulging portion 1418. The connection position of the pipe 1423 in the second bulging portion 1418 is desirably a position different from the arrangement position of the drainage valve 1420 in the second bulging portion 1418 in plan view.
　配管１４２３は、丸管状（円筒状）をなしており、塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。配管１４２３の途中部には、開口１４２１が形成されている。 The pipe 1423 has a round tubular shape (cylindrical shape), such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer). It is formed using a resin material. An opening 1421 is formed in the middle of the pipe 1423.
　軟Ｘ線照射ユニット１４１７は、第１９実施形態に係る軟Ｘ線照射ユニット１０１７（図４５Ａ参照）と同等の構成を採用している。軟Ｘ線照射ユニット１４１７は、配管１４２３の開口１４２１を塞ぐように配管１４２３に取り付けられている。具体的には、軟Ｘ線照射ユニット１４１７のカバーの開口（軟Ｘ線照射ユニット１０１７のカバー１０２６の第２開口１０２８（図４５Ａ参照）に相当する開口）が配管１４２３の開口１４２１に一致し、かつ軟Ｘ線照射ユニット１４１７のカバーの壁面（軟Ｘ線照射ユニット１０１７のカバー１０２６の横壁１０２６Ａ（図４５Ａ参照）に相当）が配管１４２３の外周に密着している。軟Ｘ線照射ユニット１４１７の高電圧ユニット（第１９実施形態に係る軟Ｘ線照射ユニット１０１７の高電圧ユニット１０３１（図４５Ａ参照）に相当）は、制御装置１００６に接続されている。 The soft X-ray irradiation unit 1417 employs a configuration equivalent to that of the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment. The soft X-ray irradiation unit 1417 is attached to the pipe 1423 so as to close the opening 1421 of the pipe 1423. Specifically, the opening of the cover of the soft X-ray irradiation unit 1417 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) matches the opening 1421 of the pipe 1423, The wall surface of the cover of the soft X-ray irradiation unit 1417 (corresponding to the lateral wall 1026A of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) is in close contact with the outer periphery of the pipe 1423. The high voltage unit of the soft X-ray irradiation unit 1417 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
　基板処理装置１４０１では、図４５Ｂに示す処理例の場合と同様の処理が実施される。基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）では、内槽１４０７内に処理液が溜められ、これにより、第２膨出部分１４１８内や配管１４２３内も、処理液により液密状態になる。 In the substrate processing apparatus 1401, the same processing as in the processing example shown in FIG. 45B is performed. In the substrate immersion process (steps S1004 to S1006 in FIG. 45B), the processing liquid is stored in the inner tank 1407, and the second bulging portion 1418 and the pipe 1423 are also made liquid-tight by the processing liquid.
　基板浸漬処理に並行して、配管１４２３内を流通している処理液に、軟Ｘ線照射ユニット１４１７から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。 In parallel with the substrate immersion process, the soft X-ray is irradiated from the soft X-ray irradiation unit 1417 to the processing liquid circulating in the pipe 1423 (step S1005 in FIG. 45B).
　配管１４２３内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、処理液の照射部分に形成される。 Of the treatment liquid in the pipe 1423, the portion irradiated with soft X-rays (treatment liquid irradiation portion. The portion equivalent to the treatment liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) contains water molecules. Electrons are emitted from the water molecules by excitation. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
　この場合、前述のように配管１４２３内で処理液が液密状態であり、また第２膨出部分１４１８内も処理液により液密とされているので、内槽１４０７に貯留されている処理液に浸漬されている基板Ｗと処理液の照射部分とが、内槽１４０７（第２膨出部分１４１８を含む）に貯留されている処理液および配管１４２３内の処理液を介して繋がっている。このとき、基板Ｗが正に帯電すると、処理液の照射部分と、正に帯電している基板Ｗとの間の電位差で、処理液の照射部分からの電子が基板Ｗに向けて、配管１４２３内の処理液および内槽１４０７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, as described above, the processing liquid is in a liquid-tight state in the pipe 1423 and the second bulging portion 1418 is also liquid-tight with the processing liquid, so that the processing liquid stored in the inner tank 1407 is stored. The substrate W immersed in the substrate and the irradiated portion of the processing liquid are connected via the processing liquid stored in the inner tank 1407 (including the second bulging portion 1418) and the processing liquid in the pipe 1423. At this time, when the substrate W is positively charged, the electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W, and the pipe 1423. It moves through the inner processing liquid and the processing liquid stored in the inner tank 1407. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　以上により、第２２実施形態においても、第１９実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, in the twenty-second embodiment, the same function and effect as those described in the nineteenth embodiment are achieved.
　図５１は、本発明の第２３実施形態に係る処理液処理装置が適用された基板処理装置１５０１の構成を示す図である。 FIG. 51 is a diagram showing a configuration of a substrate processing apparatus 1501 to which the processing liquid processing apparatus according to the twenty-third embodiment of the present invention is applied.
　第２３実施形態において、第１９実施形態と共通する部分には、図４４～図４６の場合と同一の参照符号を付し説明を省略する。第２３実施形態に係る基板処理装置１５０１が、第１９実施形態に係る基板処理装置１００１と相違する点は、循環機構１００５（図４４参照）を設けずに、外槽１００８から流出した処理液がドレイン配管１５１９を通って廃液または回収される点、および処理液ノズル１００３（図４４参照）に代えて、処理液ノズル１５６１を設けた点である。処理液ノズル１５６１には、処理液ノズル１５６１内を流通する処理液に軟Ｘ線を照射するための軟Ｘ線照射ユニット１５６２が取り付けられている。処理液ノズル１５６１は、たとえば、連続流の状態で液を吐出するストレートノズルであり、その吐出口１５５３を内槽１００７の内部に向けた状態で配置されている。処理液ノズル１５６１には、処理液供給源からの処理液が供給される処理液配管１５１３が接続されている。処理液配管１５１３の途中部には、処理液ノズル１５６１からの処理液の供給／供給停止を切り換えるための処理液バルブ１５１４が介装されている。 In the twenty-third embodiment, the same reference numerals as those in FIGS. 44 to 46 denote the same parts as in the nineteenth embodiment, and a description thereof will be omitted. The substrate processing apparatus 1501 according to the twenty-third embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that the processing liquid flowing out from the outer tank 1008 is not provided with the circulation mechanism 1005 (see FIG. 44). In other words, waste liquid is collected or collected through the drain pipe 1519, and a treatment liquid nozzle 1561 is provided instead of the treatment liquid nozzle 1003 (see FIG. 44). A soft X-ray irradiation unit 1562 for irradiating the processing liquid flowing through the processing liquid nozzle 1561 with soft X-rays is attached to the processing liquid nozzle 1561. The treatment liquid nozzle 1561 is, for example, a straight nozzle that discharges liquid in a continuous flow state, and is disposed with the discharge port 1553 facing the inside of the inner tank 1007. A processing liquid pipe 1513 to which a processing liquid from a processing liquid supply source is supplied is connected to the processing liquid nozzle 1561. A processing liquid valve 1514 for switching supply / stop of processing liquid from the processing liquid nozzle 1561 is interposed in the middle of the processing liquid pipe 1513.
　処理液ノズル１５６１は、鉛直方向に延びる丸管状（円筒状）のノズル配管１５５１を有している。ノズル配管１５５１は、たとえば塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。ノズル配管１５５１の先端部（下端部）には、丸型の吐出口１５５３が開口している。ノズル配管１５５１には、途中部の管壁に、たとえば円形の開口１５５２が形成されている。 The treatment liquid nozzle 1561 has a round tubular (cylindrical) nozzle pipe 1551 extending in the vertical direction. The nozzle pipe 1551 is formed using a resin material such as polyvinyl-chloride, PTFE (poly-tetra-fluoro-ethylene), or PFA (perfluoro-alkyl vinyl-ether-tetrafluoro-ethlene-copolymer). . A round discharge port 1553 is opened at the front end (lower end) of the nozzle pipe 1551. In the nozzle pipe 1551, for example, a circular opening 1552 is formed in the middle pipe wall.
　軟Ｘ線照射ユニット１５６２は、第１９実施形態に係る軟Ｘ線照射ユニット１０１７（図４５Ａ参照）と同等の構成を採用している。軟Ｘ線照射ユニット１５６２は、ノズル配管１５５１の開口１５５２を塞ぐようにノズル配管１５５１に取り付けられている。具体的には、軟Ｘ線照射ユニット１５６２のカバーの開口（軟Ｘ線照射ユニット１０１７のカバー１０２６の第２開口１０２８（図４５Ａ参照）に相当する開口）が開口１５５２に一致し、かつ軟Ｘ線照射ユニット１５６２のカバーの壁面（軟Ｘ線照射ユニット１０１７のカバー１０２６の横壁１０２６Ａ（図４５Ａ参照）に相当）がノズル配管１５５１の外周に密着している。軟Ｘ線照射ユニット１５６２の高電圧ユニット（第１９実施形態に係る軟Ｘ線照射ユニット１０１７の高電圧ユニット１０３１（図４５Ａ参照）に相当）は、制御装置１００６に接続されている。 The soft X-ray irradiation unit 1562 adopts the same configuration as the soft X-ray irradiation unit 1017 (see FIG. 45A) according to the nineteenth embodiment. The soft X-ray irradiation unit 1562 is attached to the nozzle pipe 1551 so as to close the opening 1552 of the nozzle pipe 1551. Specifically, the opening of the cover of the soft X-ray irradiation unit 1562 (the opening corresponding to the second opening 1028 of the cover 1026 of the soft X-ray irradiation unit 1017 (see FIG. 45A)) coincides with the opening 1552 and the soft X-ray irradiation unit 1562 The wall surface of the cover of the X-ray irradiation unit 1562 (corresponding to the lateral wall 1026A (see FIG. 45A) of the cover 1026 of the soft X-ray irradiation unit 1017) is in close contact with the outer periphery of the nozzle pipe 1551. The high voltage unit of the soft X-ray irradiation unit 1562 (corresponding to the high voltage unit 1031 (see FIG. 45A) of the soft X-ray irradiation unit 1017 according to the nineteenth embodiment) is connected to the control device 1006.
　基板処理装置１５０１では、処理槽１５０２に処理液が溜められた後、リフター１００４により基板Ｗが一括して処理槽１５０２内に投入される。その後、基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）が実行される。但し、基板処理装置１５０１には循環機構１００５（図４４参照）が設けられていないので、基板浸漬処理では、処理槽１５０２に貯留されている処理液は循環されない。その代わりに、基板浸漬処理中において、処理液ノズル１５６１からの処理液の供給が断続的に続行される。基板浸漬処理では、処理液ノズル１５６１の吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしており、また、処理液ノズル１５６１のノズル配管１５５１内では、処理液が液密状態にある。 In the substrate processing apparatus 1501, after the processing liquid is stored in the processing tank 1502, the substrates W are collectively put into the processing tank 1502 by the lifter 1004. Thereafter, substrate immersion processing (steps S1004 to S1006 in FIG. 45B) is performed. However, since the substrate processing apparatus 1501 is not provided with the circulation mechanism 1005 (see FIG. 44), the processing liquid stored in the processing tank 1502 is not circulated in the substrate immersion processing. Instead, the supply of the processing liquid from the processing liquid nozzle 1561 is continued intermittently during the substrate immersion process. In the substrate immersion process, the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007. In addition, in the nozzle pipe 1551 of the processing liquid nozzle 1561, the processing liquid is in a liquid-tight state.
　基板浸漬処理に並行して、ノズル配管１５５１内を流通している処理液に、軟Ｘ線照射ユニット１５６２から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。 In parallel with the substrate immersion process, the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B).
　ノズル配管１５５１内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、処理液の照射部分に形成される。 In a portion irradiated with soft X-rays in the processing liquid in the nozzle pipe 1551 (irradiated portion of the processing liquid. A portion equivalent to the irradiated portion 1054 of the processing liquid according to the nineteenth embodiment shown in FIG. 46), water molecules Electrons are emitted from the water molecules by excitation of. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
　この場合、前述のように、ノズル配管１５５１内で処理液が液密状態であり、かつ吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしているので、内槽１００７に貯留されている処理液に浸漬されている基板Ｗと処理液の照射部分とが、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して繋がっている。このとき、基板Ｗが正に帯電すると、処理液の照射部分と、正に帯電している基板Ｗとの間の電位差で、処理液の照射部分からの電子が基板Ｗに向けて、ノズル配管１５５１内の処理液、前記の連続流状の処理液および内槽１００７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, as described above, the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007. Therefore, the substrate W immersed in the processing liquid stored in the inner tank 1007 and the irradiated portion of the processing liquid are stored in the inner tank 1007. Are connected through the processing liquid in the continuous flow state and the processing liquid in the nozzle pipe 1551. At this time, if the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W. It moves through the processing liquid in 1551, the above-described continuous flow processing liquid, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　以上により、第２３実施形態においても、第１９実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, in the twenty-third embodiment, the same function and effect as those described in the nineteenth embodiment are achieved.
　なお、第２３実施形態では、ノズル配管１５５１内を流通している処理液に軟Ｘ線照射ユニット１５６２から軟Ｘ線を照射する場合を例に挙げて説明したが、ノズル配管１５５１内に内部が連通する配管に軟Ｘ線照射ユニット１５６２を設け、当該配管内を流通している処理液に軟Ｘ線照射ユニット１５６２からの軟Ｘ線を照射させるようにしてもよい。 In the 23rd embodiment, the case where soft X-rays are irradiated from the soft X-ray irradiation unit 1562 to the processing liquid flowing in the nozzle pipe 1551 has been described as an example. A soft X-ray irradiation unit 1562 may be provided in a pipe that communicates, and the processing liquid flowing through the pipe may be irradiated with soft X-rays from the soft X-ray irradiation unit 1562.
　図５２は、本発明の第２４実施形態に係る処理液処理装置が適用された基板処理装置１６０１の構成を示す図である。 FIG. 52 is a diagram showing a configuration of a substrate processing apparatus 1601 to which the processing liquid processing apparatus according to the twenty-fourth embodiment of the present invention is applied.
　第２４実施形態において、第１９実施形態と共通する部分には、図４４～図４６の場合と同一の参照符号を付し説明を省略する。第２４実施形態に係る基板処理装置１６０１が、第１９実施形態に係る基板処理装置１００１と相違する点は、循環機構１００５（図４４参照）を設けずに、外槽１００８から流出した処理液がドレイン配管１５１９を通って廃液または回収される点、および外槽１００８に向けて処理液を吐出する処理液ノズル１５６１を設けた点である。 In the twenty-fourth embodiment, portions common to the nineteenth embodiment are denoted by the same reference numerals as in FIGS. 44 to 46, and description thereof is omitted. The substrate processing apparatus 1601 according to the twenty-fourth embodiment is different from the substrate processing apparatus 1001 according to the nineteenth embodiment in that the processing liquid flowing out from the outer tank 1008 is not provided with the circulation mechanism 1005 (see FIG. 44). This is a point where waste liquid is collected or collected through the drain pipe 1519 and a processing liquid nozzle 1561 for discharging the processing liquid toward the outer tank 1008 is provided.
　処理液ノズル１５６１は、たとえば、連続流の状態で液を吐出するストレートノズルであり、その吐出口１５５３を外槽１００８の内部に向けた状態で配置されている。処理液ノズル１５６１には、処理液ノズル１５６１内を流通する処理液に軟Ｘ線を照射するための軟Ｘ線照射ユニット１５６２が取り付けられている。処理液ノズル１５６１および軟Ｘ線照射ユニット１５６２に関する一連の構成は第２３実施形態の場合と同一であるので、第２３実施形態の場合と同一参照符号を付して説明を省略する。 The treatment liquid nozzle 1561 is, for example, a straight nozzle that discharges liquid in a continuous flow state, and is disposed with its discharge port 1553 facing the inside of the outer tank 1008. A soft X-ray irradiation unit 1562 for irradiating the processing liquid flowing through the processing liquid nozzle 1561 with soft X-rays is attached to the processing liquid nozzle 1561. Since a series of configurations related to the treatment liquid nozzle 1561 and the soft X-ray irradiation unit 1562 are the same as those in the twenty-third embodiment, the same reference numerals as those in the twenty-third embodiment are attached and description thereof is omitted.
　基板処理装置１６０１では、図４５Ｂに示す処理例の場合と同様の処理が実施される。但し、基板処理装置１６０１には循環機構１００５（図４４参照）が設けられていないので、基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）中に、処理槽１５０２に貯留されている処理液が循環されない。その代わりに、基板浸漬処理中において、処理液ノズル１００３からの処理液の供給が断続的に続行される。内槽１００７の内部が処理液で満たされている状態で処理液ノズル１００３からさらに処理液が供給されることにより、余った処理液が内槽１００７の上端部からオーバーフローして（溢れて）外槽１００８に流れ込む。このとき、処理液の液塊（図４８の処理液の液塊１０８０と同様の液塊）が内槽１００７の上端部を乗り越える状態が常時続くから、内槽１００７に貯留されている処理液と外槽１００８に貯留されている処理液とが、処理液の液塊によって常時繋がっている。 In the substrate processing apparatus 1601, the same processing as in the processing example shown in FIG. 45B is performed. However, since the substrate processing apparatus 1601 is not provided with the circulation mechanism 1005 (see FIG. 44), the processing liquid stored in the processing tank 1502 is circulated during the substrate immersion processing (steps S1004 to S1006 in FIG. 45B). Not. Instead, the supply of the processing liquid from the processing liquid nozzle 1003 is intermittently continued during the substrate immersion process. When the processing liquid is further supplied from the processing liquid nozzle 1003 while the inside of the inner tank 1007 is filled with the processing liquid, the surplus processing liquid overflows (overflows) from the upper end of the inner tank 1007. It flows into the tank 1008. At this time, a state in which the liquid volume of the processing liquid (liquid volume similar to the liquid volume 1080 of the processing liquid in FIG. 48) rides over the upper end portion of the inner tank 1007 always continues, so that the processing liquid stored in the inner tank 1007 The processing liquid stored in the outer tank 1008 is always connected by a liquid mass of the processing liquid.
　基板浸漬処理に並行して、処理液バルブ１５１４が開かれて、処理液ノズル１５６１の吐出口１５５３から処理液が外槽１００８の内部に向けて吐出される。処理液ノズル１５６１の吐出口１５５３から吐出される処理液の態様は、吐出口１５５３と外槽１００８に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしている。このとき、処理液ノズル１５６１のノズル配管１５５１内では、処理液が液密状態にある。 In parallel with the substrate immersion process, the processing liquid valve 1514 is opened, and the processing liquid is discharged from the discharge port 1553 of the processing liquid nozzle 1561 toward the inside of the outer tank 1008. The mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 has a continuous flow mode connected to both the discharge port 1553 and the liquid level of the processing liquid stored in the outer tank 1008. At this time, the processing liquid is in a liquid-tight state in the nozzle pipe 1551 of the processing liquid nozzle 1561.
　また、基板浸漬処理に並行して、ノズル配管１５５１内を流通している処理液に、軟Ｘ線照射ユニット１５６２から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。 In parallel with the substrate immersion process, the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B).
　ノズル配管１５５１内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）では、水分子の励起により当該水分子から電子が放出される。その結果、多量の電子と、水分子の多量の正イオンとが混在するプラズマ状態が、処理液の照射部分に形成される。 In a portion irradiated with soft X-rays in the processing liquid in the nozzle pipe 1551 (irradiated portion of the processing liquid. A portion equivalent to the irradiated portion 1054 of the processing liquid according to the nineteenth embodiment shown in FIG. 46), water molecules Electrons are emitted from the water molecules by excitation of. As a result, a plasma state in which a large amount of electrons and a large amount of positive ions of water molecules are mixed is formed in the irradiated portion of the treatment liquid.
　この場合、ノズル配管１５５１内で処理液が液密状態であり、吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と外槽１００８に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしており、かつ内槽１００７に貯留されている処理液と外槽１００８に貯留されている処理液とが処理液の液塊によって常時繋がっているので、内槽１００７に貯留されている処理液に浸漬されている基板Ｗと処理液の照射部分とが、内槽１００７に貯留されている処理液、外槽１００８に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して繋がっている。このとき、基板Ｗが正に帯電すると、処理液の照射部分と、正に帯電している基板Ｗとの間の電位差で、処理液の照射部分からの電子が基板Ｗに向けて、ノズル配管１５５１内の処理液、前記の連続流状の処理液、外槽１００８に貯留されている処理液および内槽１００７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the mode of the processing liquid discharged from the discharge port 1553 is both the discharge port 1553 and the liquid level of the processing liquid stored in the outer tank 1008. Since the processing liquid stored in the inner tank 1007 and the processing liquid stored in the outer tank 1008 are always connected by the liquid mass of the processing liquid, the inner tank The substrate W immersed in the processing liquid stored in 1007 and the irradiated portion of the processing liquid are the processing liquid stored in the inner tank 1007, the processing liquid stored in the outer tank 1008, and the continuous flow Are connected to each other via a treatment liquid in the nozzle pipe 1551. At this time, if the substrate W is positively charged, electrons from the irradiation portion of the processing liquid are directed toward the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W. It moves through the processing liquid in 1551, the above-described continuous flow processing liquid, the processing liquid stored in the outer tank 1008, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　以上により、第２４実施形態においても、第１９実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, also in the twenty-fourth embodiment, the same effects as those described in the nineteenth embodiment are achieved.
　また、軟Ｘ線照射ユニット１５６２の窓部材の外表面（窓部材１０７１の外表面７１Ｂ（図４５Ａ参照）に相当）から親水性皮膜（親水性皮膜１０３８（図４５参照）に相当）が剥がれると、当該窓部材に含まれるベリリウムが処理液に溶け出すおそれがある。このような場合であっても、ベリリウムを含む処理液がドレイン配管１５１９を介して排液されるので、これにより、ベリリウムを含む処理液が基板Ｗに供給されるのを確実に回避することができる。 Further, when the hydrophilic film (corresponding to the hydrophilic film 1038 (refer to FIG. 45)) is peeled off from the outer surface of the window member of the soft X-ray irradiation unit 1562 (corresponding to the outer surface 71B (refer to FIG. 45A) of the window member 1071). The beryllium contained in the window member may be dissolved in the treatment liquid. Even in such a case, since the processing liquid containing beryllium is drained through the drain pipe 1519, this reliably prevents the processing liquid containing beryllium from being supplied to the substrate W. it can.
　図５３は、本発明の第２５実施形態に係る処理液処理装置が適用された基板処理装置１７０１の構成を示す図である。 FIG. 53 is a diagram showing a configuration of a substrate processing apparatus 1701 to which the processing liquid processing apparatus according to the twenty-fifth embodiment of the present invention is applied.
　第２５実施形態において、第２３実施形態と共通する部分には、図５１の場合と同一の参照符号を付し説明を省略する。第２５実施形態に係る基板処理装置１７０１が、第２３実施形態に係る基板処理装置１５０１と相違する点は、複数枚の基板Ｗを一括して保持するカセット１７０２ごと複数枚の基板Ｗを処理槽１５０２内に浸漬させた点である。図５３では図示していないが、基板処理装置１７０１には、第２３実施形態のリフター１００４や昇降機構１０２２などの構成が設けられている。このリフター１００４によって、複数枚の基板Ｗが一括して保持されたカセット１７０２が保持され、昇降される。 In the twenty-fifth embodiment, parts common to the twenty-third embodiment are denoted by the same reference numerals as in FIG. 51, and description thereof is omitted. The substrate processing apparatus 1701 according to the twenty-fifth embodiment is different from the substrate processing apparatus 1501 according to the twenty-third embodiment in that a plurality of substrates W are handled together with a cassette 1702 that holds a plurality of substrates W collectively. This is a point immersed in 1502. Although not shown in FIG. 53, the substrate processing apparatus 1701 is provided with configurations such as a lifter 1004 and an elevating mechanism 1022 of the twenty-third embodiment. The lifter 1004 holds and raises the cassette 1702 in which a plurality of substrates W are held together.
　カセット１７０２は、たとえば塩ビ(poly-vinyl-chloride)や、ＰＴＦＥ（poly tetra-fluoro ethylene）、ＰＦＡ(perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer)などの樹脂材料を用いて形成されている。 The cassette 1702 is formed using a resin material such as polyvinyl-chloride, PTFE (polytetrafluoroethylene), or PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer).
　基板処理装置１７０１では、処理槽１５０２に処理液が溜められた後、複数枚の基板Ｗおよびカセット１７０２が処理槽１５０２内に投入される。その後、基板浸漬処理（図４５ＢのステップＳ１００４～Ｓ１００６）が実行される。 In the substrate processing apparatus 1701, after the processing liquid is stored in the processing tank 1502, a plurality of substrates W and cassettes 1702 are put into the processing tank 1502. Thereafter, substrate immersion processing (steps S1004 to S1006 in FIG. 45B) is performed.
　基板浸漬処理中には、第２３実施形態の場合と同様、処理液ノズル１５６１からの処理液の供給が断続的に続行される。基板浸漬処理では、処理液ノズル１５６１の吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしており、また、処理液ノズル１５６１のノズル配管１５５１内では、処理液が液密状態にある。 During the substrate immersion process, the supply of the processing liquid from the processing liquid nozzle 1561 is continued intermittently as in the case of the twenty-third embodiment. In the substrate immersion process, the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007. In addition, in the nozzle pipe 1551 of the processing liquid nozzle 1561, the processing liquid is in a liquid-tight state.
　また、基板浸漬処理に並行して、ノズル配管１５５１内を流通している処理液に、軟Ｘ線照射ユニット１５６２から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。ノズル配管１５５１内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）に、前述のプラズマ状態が、処理液の照射部分に形成される。 In parallel with the substrate immersion process, the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B). Of the processing liquid in the nozzle pipe 1551, the portion irradiated with soft X-rays (the processing liquid irradiation portion. The portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is described above. A plasma state is formed in the irradiated portion of the processing liquid.
　この場合、前述のように、ノズル配管１５５１内で処理液が液密状態であり、かつ吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしているので、内槽１００７に貯留されている処理液に浸漬されている基板Ｗやカセット１７０２と、処理液の照射部分とが、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して繋がっている。このとき、基板Ｗやカセット１７０２が正に帯電すると、処理液の照射部分と、正に帯電している基板Ｗやカセット１７０２との間の電位差で、処理液の照射部分からの電子が基板Ｗやカセット１７０２に向けて、ノズル配管１５５１内の処理液、前記の連続流状の処理液および内槽１００７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板Ｗが除電される。 In this case, as described above, the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007. The substrate W immersed in the processing liquid stored in the inner tank 1007 and the cassette 1702 and the irradiation portion of the processing liquid are included in the inner surface 1007. The processing liquid stored in the tank 1007, the continuous flow processing liquid, and the processing liquid in the nozzle pipe 1551 are connected. At this time, if the substrate W or the cassette 1702 is positively charged, electrons from the irradiated portion of the processing liquid are transferred to the substrate W due to a potential difference between the irradiation portion of the processing liquid and the positively charged substrate W or cassette 1702. And moving toward the cassette 1702 through the processing liquid in the nozzle pipe 1551, the above-described continuous flow processing liquid, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate W is neutralized.
　また、カセット１７０２の材質によっては、カセット１７０２が負に帯電することも考えられるが、この場合、カセット１７０２からの電子が、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して、処理液の照射部分の正イオンに向けて移動する。これにより、カセット１７０２から電子が除去される結果、負に帯電しているカセット１７０２が除電される。 Further, depending on the material of the cassette 1702, the cassette 1702 may be negatively charged. In this case, electrons from the cassette 1702 are treated with the treatment liquid stored in the inner tank 1007, and the continuous flow treatment described above. It moves toward the positive ions at the irradiated portion of the processing liquid via the processing liquid in the nozzle pipe 1551. As a result, electrons are removed from the cassette 1702, and as a result, the negatively charged cassette 1702 is discharged.
　以上により、第２５実施形態においても、第１９実施形態で述べた作用効果と同等の作用効果を奏する。 As described above, also in the twenty-fifth embodiment, the same function and effect as those described in the nineteenth embodiment are achieved.
　また、処理液の浸漬処理時におけるカセット１７０２の帯電をも防止できる。また、浸漬処理前からカセット１７０２が帯電していても、その基板Ｗに帯びた電荷を除去（すなわち、除電）できる。 Also, charging of the cassette 1702 during the immersion treatment of the treatment liquid can be prevented. Further, even if the cassette 1702 is charged before the immersion treatment, the charge on the substrate W can be removed (that is, static elimination).
　第１９～第２５実施形態では、処理対象物を基板Ｗとする基板処理装置１００１，１２０１，１３０１，１４０１，１５０１，１６０１に本発明を適用した場合について説明したが、本発明は、基板Ｗ以外を処理対象物とする処理液処理装置（物品洗浄装置）にも適用できる。 In the nineteenth to twenty-fifth embodiments, the case where the present invention is applied to the substrate processing apparatuses 1001, 1201, 1301, 1401, 1501, 1601 in which the processing object is the substrate W has been described. The present invention can also be applied to a processing liquid processing apparatus (article cleaning apparatus) that treats as a processing object.
　図５４は、本発明の第２６実施形態に係る処理液処理装置が適用された物品洗浄装置１８０１の構成を示す図である。 FIG. 54 is a diagram showing a configuration of an article cleaning apparatus 1801 to which the processing liquid processing apparatus according to the twenty-sixth embodiment of the present invention is applied.
　物品洗浄装置１８０１は、たとえばレンズＬなどの光学部品を処理対象物とし、光学部品を、処理液（洗浄液）を用いて洗浄するための装置である。物品洗浄装置１８０１は、処理槽１５０２にレンズＬを浸漬させることにより、当該レンズＬを洗浄する。複数個のレンズＬがカセット１８０２に一括して収容された状態で、処理槽１５０２内に浸漬される。物品洗浄装置１８０１には、処理槽１５０２に貯留されている処理液に超音波振動を発生させる超音波発生装置（図示しない）が設けられている。 The article cleaning apparatus 1801 is an apparatus for cleaning an optical component using a processing liquid (cleaning liquid), for example, using an optical component such as a lens L as a processing target. The article cleaning apparatus 1801 cleans the lens L by immersing the lens L in the treatment tank 1502. A plurality of lenses L are immersed in the processing tank 1502 in a state where they are collectively accommodated in the cassette 1802. The article cleaning apparatus 1801 is provided with an ultrasonic generator (not shown) that generates ultrasonic vibrations in the processing liquid stored in the processing tank 1502.
　超音波発生装置（図示しない）を設ける点を除いて、物品洗浄装置１８０１の概略構成は、第２５実施形態に係る基板処理装置１７０１の構成と同等であるので、第２６実施形態において、第２５実施形態と共通する部分には、図５３の場合と同一の参照符号を付し説明を省略する。 The general configuration of the article cleaning apparatus 1801 is the same as that of the substrate processing apparatus 1701 according to the 25th embodiment except that an ultrasonic generator (not shown) is provided. Portions common to the embodiment are denoted by the same reference numerals as in FIG. 53, and description thereof is omitted.
　物品洗浄装置１８０１では、レンズＬおよびカセット１８０２が処理槽１５０２内に投入された後、処理槽１５０２に処理液が溜められる。これにより、レンズＬおよびカセット１８０２が処理液に浸漬され、このような浸漬処理が予め定める期間の間続行されることによりレンズＬが洗浄される。 In the article cleaning apparatus 1801, after the lens L and the cassette 1802 are put into the processing tank 1502, the processing liquid is stored in the processing tank 1502. Accordingly, the lens L and the cassette 1802 are immersed in the processing liquid, and the lens L is cleaned by continuing such immersion processing for a predetermined period.
　浸漬処理中には、第２３実施形態の場合と同様、処理液ノズル１５６１からの処理液の供給が断続的に続行される。浸漬処理では、処理液ノズル１５６１の吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしており、また、処理液ノズル１５６１のノズル配管１５５１内では、処理液が液密状態にある。 During the immersion treatment, the supply of the processing liquid from the processing liquid nozzle 1561 is continued intermittently as in the case of the twenty-third embodiment. In the dipping process, the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007. In addition, the processing liquid is in a liquid-tight state in the nozzle pipe 1551 of the processing liquid nozzle 1561.
　また、浸漬処理に並行して、ノズル配管１５５１内を流通している処理液に、軟Ｘ線照射ユニット１５６２から軟Ｘ線が照射される（図４５ＢのステップＳ１００５）。ノズル配管１５５１内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）に、前述のプラズマ状態が、処理液の照射部分に形成される。 In parallel with the immersion treatment, the soft X-ray is irradiated from the soft X-ray irradiation unit 1562 to the processing liquid circulating in the nozzle pipe 1551 (step S1005 in FIG. 45B). Of the processing liquid in the nozzle pipe 1551, the portion irradiated with soft X-rays (the processing liquid irradiation portion. The portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is described above. A plasma state is formed in the irradiated portion of the processing liquid.
　この場合、前述のように、ノズル配管１５５１内で処理液が液密状態であり、かつ吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしているので、内槽１００７に貯留されている処理液に浸漬されているレンズＬやカセット１８０２と、処理液の照射部分とが、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して繋がっている。このとき、レンズＬやカセット１８０２が正に帯電すると、処理液の照射部分と、正に帯電しているレンズＬやカセット１８０２との間の電位差で、処理液の照射部分からの電子がレンズＬやカセット１８０２に向けて、ノズル配管１５５１内の処理液、前記の連続流状の処理液および内槽１００７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電しているレンズＬが除電される。 In this case, as described above, the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007. In this way, the lens L and the cassette 1802 immersed in the processing liquid stored in the inner tank 1007 and the irradiation portion of the processing liquid are included. The processing liquid stored in the tank 1007, the continuous flow processing liquid, and the processing liquid in the nozzle pipe 1551 are connected. At this time, if the lens L or the cassette 1802 is positively charged, the electrons from the irradiation portion of the processing liquid are converted into the lens L by the potential difference between the irradiation portion of the processing liquid and the positively charged lens L or the cassette 1802. And move toward the cassette 1802 through the processing liquid in the nozzle pipe 1551, the above-described continuous flow processing liquid, and the processing liquid stored in the inner tank 1007. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged lens L is neutralized.
　また、カセット１８０２の材質によっては、カセット１８０２が負に帯電することも考えられるが、この場合、カセット１８０２からの電子が、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して、処理液の照射部分の正イオンに向けて移動する。これにより、カセット１８０２から電子が除去される結果、負に帯電しているカセット１８０２が除電される。 In addition, depending on the material of the cassette 1802, the cassette 1802 may be negatively charged. In this case, electrons from the cassette 1802 are treated with the treatment liquid stored in the inner tank 1007 and the continuous flow treatment. It moves toward the positive ions at the irradiated portion of the processing liquid via the processing liquid in the nozzle pipe 1551. As a result, electrons are removed from the cassette 1802, and as a result, the negatively charged cassette 1802 is discharged.
　以上により、第２６実施形態によれば、処理液の浸漬処理時におけるレンズＬの帯電を防止できる。また、浸漬処理前からレンズＬが帯電していても、そのレンズＬに帯びた電荷を除去（すなわち、除電）できる。 As described above, according to the twenty-sixth embodiment, the lens L can be prevented from being charged during the immersion treatment of the treatment liquid. Further, even if the lens L is charged before the immersion treatment, the charge on the lens L can be removed (that is, static elimination).
　なお、前述の説明では複数個のレンズＬがカセット１８０２に収容された状態で処理液に浸漬されるとして説明したが、レンズＬが直接（カセット１８０２に収容されずに）処理液に浸漬されるようになっていてもよい。 In the above description, it has been described that a plurality of lenses L are immersed in the processing liquid while being accommodated in the cassette 1802. However, the lens L is directly immersed in the processing liquid (not accommodated in the cassette 1802). It may be like this.
　また、光学部品としてレンズＬ（図５４参照）を例に挙げて説明したが、ミラー、回折格子等の光学部品を収容する部品収容器を処理対象とすることができる。光学部品以外の部品を洗浄対象（処理対象）とすることもできる。 Further, although the lens L (see FIG. 54) has been described as an example of the optical component, a component container that accommodates an optical component such as a mirror or a diffraction grating can be processed. Parts other than the optical parts can also be set as objects to be cleaned (processing objects).
　また、第２６実施形態に係る物品洗浄装置１８０１において、第１９～第２２および第２４実施形態の場合と同様の構成が採用されていてもよい。この場合、第１９～第２２および第２４実施形態で説明したものと同様の処理が施される。すなわち、処理槽１５０２に貯留されている処理液に光学部品（レンズＬ）等の部品が浸漬され、それと並行して、当該処理槽１５０２に貯留された処理液、または内部が処理槽１５０２内に連通する配管１０１６，１０１９，１４２３内に存在する処理液に、軟Ｘ線ユニット１０１７，１２１７，１３１７，１４１７からの軟Ｘ線が照射される。 Further, in the article cleaning apparatus 1801 according to the 26th embodiment, the same configuration as that of the 19th to 22nd and 24th embodiments may be adopted. In this case, processing similar to that described in the nineteenth to twenty-second and twenty-fourth embodiments is performed. That is, parts such as an optical component (lens L) are immersed in the processing liquid stored in the processing tank 1502, and in parallel therewith, the processing liquid stored in the processing tank 1502 or the inside is stored in the processing tank 1502. Soft X-rays from the soft X-ray units 1017, 1217, 1317, and 1417 are irradiated to the processing liquid existing in the pipes 1016, 1019, and 1423 that communicate with each other.
　図５５は、本発明の第２７実施形態に係る処理液処理装置が適用された物品洗浄装置１９０１の構成を示す図である。 FIG. 55 is a diagram showing a configuration of an article cleaning apparatus 1901 to which the processing liquid processing apparatus according to the twenty-seventh embodiment of the present invention is applied.
　物品洗浄装置１９０１は、たとえば基板収容器（収容器）１６０２を処理対象物とし、基板収容器１６０２を、処理液（洗浄液）を用いて洗浄するための装置である。物品洗浄装置１９０１は、処理槽１５０２に基板収容器１６０２を浸漬させることにより、当該基板収容器１６０２を洗浄する。 The article cleaning apparatus 1901 is an apparatus for cleaning the substrate container 1602 using a processing liquid (cleaning liquid), for example, using the substrate container (container) 1602 as an object to be processed. The article cleaning apparatus 1901 cleans the substrate container 1602 by immersing the substrate container 1602 in the treatment tank 1502.
　図５６は、基板収容器１６０２の構成を示す斜視図である。 FIG. 56 is a perspective view showing the configuration of the substrate container 1602.
　図５６に示すように、基板収容器１６０２は、基板Ｗを密閉した状態で収容する容器である。基板収容器１６０２の一例として、ＦＯＳＢ（Front Opening Shipping Box）を挙げることができる。ＦＯＳＢは、専ら、半導体ウエハメーカから半導体装置メーカに、基板Ｗを納入するために用いられる。ＦＯＳＢは、未処理の複数枚の基板Ｗを収容し、これらの基板Ｗの清浄度を維持しつつ、基板Ｗへの損傷を防止する。 As shown in FIG. 56, the substrate container 1602 is a container that accommodates the substrate W in a sealed state. An example of the substrate container 1602 is FOSB (Front Opening Shipping Shipping Box). The FOSB is exclusively used to deliver the substrate W from the semiconductor wafer manufacturer to the semiconductor device manufacturer. The FOSB accommodates a plurality of unprocessed substrates W and prevents damage to the substrates W while maintaining the cleanliness of these substrates W.
　基板収容器１６０２は、側方に開口１６０３Ａを有する有底箱状の収容器本体１６０３と、収容器本体１６０３の開口１６０３Ａを開閉するための蓋１６０４と、収容器本体１６０３の内壁に取り付けられた多段の収容器支持棚１６０６と、蓋１６０４に取り付けられた多段の蓋支持棚１６０５とを含む。開口１６０３Ａを介して収容器本体１６０３の内部に対し、基板Ｗの出し入れが行われる。収容器本体１６０３および蓋１６０４は、それぞれ、たとえば塩ビ(poly-vinyl-chloride)等の樹脂材料を用いて形成されている。 The substrate container 1602 is attached to a bottomed box-shaped container body 1603 having an opening 1603A on the side, a lid 1604 for opening and closing the opening 1603A of the container body 1603, and an inner wall of the container body 1603. A multi-stage container support shelf 1606 and a multi-stage lid support shelf 1605 attached to the lid 1604 are included. The substrate W is taken in and out of the container main body 1603 through the opening 1603A. Container body 1603 and lid 1604 are each formed using a resin material such as polyvinyl-chloride.
　図５５に示すように物品洗浄装置１９０１の概略構成は、第２５実施形態に係る基板処理装置１７０１の構成と同等であるので、第２７実施形態において、第２５実施形態と共通する部分には、図５３の場合と同一の参照符号を付し説明を省略する。 As shown in FIG. 55, the schematic configuration of the article cleaning apparatus 1901 is the same as the configuration of the substrate processing apparatus 1701 according to the 25th embodiment. Therefore, in the 27th embodiment, the parts common to the 25th embodiment include The same reference numerals as those in FIG.
　基板処理装置１９０１では、基板収容器１６０２（収容器本体１６０３）が処理槽１５０２内に投入された後、処理槽１５０２に処理液が溜められる。これにより、基板収容器１６０２が処理液に浸漬され、このような浸漬処理が予め定める期間の間続行されることにより基板収容器１６０２が洗浄される。 In the substrate processing apparatus 1901, after the substrate container 1602 (container body 1603) is put into the processing tank 1502, the processing liquid is stored in the processing tank 1502. Accordingly, the substrate container 1602 is immersed in the processing liquid, and the substrate container 1602 is cleaned by continuing such immersion processing for a predetermined period.
　浸漬処理中には、第２５実施形態の場合と同様、処理液ノズル１５６１からの処理液の供給が断続的に続行される。浸漬処理では、処理液ノズル１５６１の吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしており、また、処理液ノズル１５６１のノズル配管１５５１内では、処理液が液密状態にある。 During the immersion treatment, the supply of the treatment liquid from the treatment liquid nozzle 1561 is continued intermittently as in the case of the twenty-fifth embodiment. In the dipping process, the mode of the processing liquid discharged from the discharge port 1553 of the processing liquid nozzle 1561 is a continuous flow mode that leads to both the discharge port 1553 and the liquid level of the processing liquid stored in the inner tank 1007. In addition, the processing liquid is in a liquid-tight state in the nozzle pipe 1551 of the processing liquid nozzle 1561.
　また、浸漬処理に並行して、ノズル配管１５５１内を流通している処理液に、軟Ｘ線照射ユニット１５６２から軟Ｘ線が照射される（図４５ＢのステップＳ５）。ノズル配管１５５１内の処理液のうち軟Ｘ線が照射される部分（処理液の照射部分。図４６に示す、第１９実施形態に係る処理液の照射部分１０５４と同等の部分）に、前述のプラズマ状態が、処理液の照射部分に形成される。 In parallel with the immersion treatment, soft X-rays are irradiated from the soft X-ray irradiation unit 1562 to the processing liquid flowing in the nozzle pipe 1551 (step S5 in FIG. 45B). Of the processing liquid in the nozzle pipe 1551, the portion irradiated with soft X-rays (the processing liquid irradiation portion. The portion equivalent to the processing liquid irradiation portion 1054 according to the nineteenth embodiment shown in FIG. 46) is described above. A plasma state is formed in the irradiated portion of the processing liquid.
　この場合、前述のように、ノズル配管１５５１内で処理液が液密状態であり、かつ吐出口１５５３から吐出される処理液の態様が、吐出口１５５３と内槽１００７に貯留されている処理液の液面との双方に繋がる連続流状の態様をなしているので、内槽１００７に貯留されている処理液に浸漬されている基板収容器１６０２と、処理液の照射部分とが、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して繋がっている。このとき、基板収容器１６０２が正に帯電すると、処理液の照射部分と、正に帯電している基板収容器１６０２との間の電位差で、処理液の照射部分からの電子が基板収容器１６０２に向けて、ノズル配管１５５１内の処理液、前記の連続流状の処理液および内槽１００７に貯留されている処理液を介して移動する。これにより、基板Ｗに多量の電子が供給される結果、正に帯電している基板収容器１６０２（収容器本体１６０３）が除電される。 In this case, as described above, the processing liquid is in a liquid-tight state in the nozzle pipe 1551, and the processing liquid discharged from the discharge port 1553 is the processing liquid stored in the discharge port 1553 and the inner tank 1007. The substrate container 1602 immersed in the processing liquid stored in the inner tank 1007 and the irradiated portion of the processing liquid are in the inner tank. The processing liquid stored in 1007, the above-described continuous flow processing liquid, and the processing liquid in the nozzle pipe 1551 are connected. At this time, if the substrate container 1602 is positively charged, electrons from the irradiated part of the processing liquid are transferred to the substrate container 1602 due to a potential difference between the irradiation part of the processing liquid and the positively charged substrate container 1602. Toward, the processing liquid in the nozzle pipe 1551, the processing liquid in the continuous flow state, and the processing liquid stored in the inner tank 1007 are moved. Thereby, as a result of supplying a large amount of electrons to the substrate W, the positively charged substrate container 1602 (container body 1603) is neutralized.
　また、基板収容器１６０２の材質によっては、基板収容器１６０２が負に帯電することも考えられるが、この場合、基板収容器１６０２からの電子が、内槽１００７に貯留されている処理液、前記の連続流状の処理液およびノズル配管１５５１内の処理液を介して、処理液の照射部分の正イオンに向けて移動する。これにより、基板収容器１６０２から電子が除去される結果、負に帯電している基板収容器１６０２が除電される。 Further, depending on the material of the substrate container 1602, the substrate container 1602 may be negatively charged. In this case, electrons from the substrate container 1602 are stored in the inner tank 1007, It moves toward the positive ions at the irradiated portion of the processing liquid through the continuous flow processing liquid and the processing liquid in the nozzle pipe 1551. As a result, the electrons are removed from the substrate container 1602, and as a result, the negatively charged substrate container 1602 is neutralized.
　以上により、第２７実施形態によれば、処理液の浸漬処理時における基板収容器１６０２の帯電を防止できる。また、浸漬処理前から基板収容器１６０２が帯電していても、その基板収容器１６０２に帯びた電荷を除去（すなわち、除電）できる。 As described above, according to the twenty-seventh embodiment, the substrate container 1602 can be prevented from being charged during the immersion treatment of the processing liquid. Further, even if the substrate container 1602 is charged before the immersion treatment, the charge on the substrate container 1602 can be removed (that is, static elimination).
　なお、図５５では、基板収容器１６０２のうち収容器本体１６０３を洗浄する場合を例に挙げて説明したが、蓋１６０４や、支持棚１６０５，１６０６を洗浄する場合にも、同様に洗浄方法を採用することにより、蓋１６０４や支持棚１６０５，１６０６の除電を図りつつ、蓋１６０４や支持棚１６０５，１６０６に洗浄処理を施すことができる。 In FIG. 55, the case where the container body 1603 of the substrate container 1602 is cleaned has been described as an example, but the cleaning method is similarly applied to the case where the lid 1604 and the support shelves 1605 and 1606 are cleaned. By adopting, the lid 1604 and the support shelves 1605 and 1606 can be subjected to a cleaning process while removing electricity from the lid 1604 and the support shelves 1605 and 1606.
　また、基板収容器１６０２として、ＦＯＳＢを例に挙げて説明したが、専ら、半導体ウエハメーカの工場内で基板Ｗを搬送するために用いられ、基板Ｗを密閉した状態で収容するＦＯＵＰ（Front Opening Unified Pod）を挙げることもできる。その他、基板収容器１６０２として、ＳＭＩＦ（Standard Mechanical Interface）ポッドや、ＯＣ（Open Cassette）等の他の形態の基板収容器を例示することもできる。 Further, although the FOSB has been described as an example of the substrate container 1602, the FOUP (Front-Opening-Unified) is used exclusively for transporting the substrate W in the factory of the semiconductor wafer manufacturer and stores the substrate W in a sealed state. Pod). In addition, examples of the substrate container 1602 include other types of substrate containers such as a SMIF (Standard Mechanical Interface) pod and OC (Open Cassette).
　また、収容器は、基板Ｗを収容するものに限られず、ＣＤ、ＤＶＤ、ブルーディスク等の円盤状のメディアを収容するメディア収容器や、レンズＬ（図５４参照）、ミラー、回折格子等の光学部品を収容する部品収容器を処理対象とすることができる。 The container is not limited to the one that accommodates the substrate W, but a medium container that accommodates a disk-shaped medium such as a CD, a DVD, or a blue disk, a lens L (see FIG. 54), a mirror, a diffraction grating, or the like. A component container that accommodates an optical component can be a processing target.
　また、第２７実施形態に係る物品洗浄装置１９０１において、第１９～第２２および第２４実施形態の場合と同様の構成が採用されていてもよい。この場合、第１９～第２２および第２４実施形態で説明したものと同様の処理が施される。すなわち、処理槽１００２に貯留されている処理液に基板収容器１６０２等の収容器が浸漬され、それと並行して、当該処理槽１００２に貯留された処理液、または内部が処理槽１００２内に連通する配管１０１６，１０１９，１４２３内に存在する処理液に、軟Ｘ線ユニット１０１７，１２１７，１３１７，１４１７からの軟Ｘ線が照射される。 Further, in the article cleaning apparatus 1901 according to the 27th embodiment, the same configuration as in the 19th to 22nd and 24th embodiments may be adopted. In this case, processing similar to that described in the nineteenth to twenty-second and twenty-fourth embodiments is performed. That is, a container such as the substrate container 1602 is immersed in the processing liquid stored in the processing tank 1002, and the processing liquid stored in the processing tank 1002 or the inside communicates with the inside of the processing tank 1002 in parallel therewith. The soft X-rays from the soft X-ray units 1017, 1217, 1317, and 1417 are irradiated to the processing liquid existing in the pipes 1016, 1019, and 1423.
　以上、この発明の実施形態について説明したが、この発明は他の形態で実施することもできる。 As mentioned above, although embodiment of this invention was described, this invention can also be implemented with another form.
　第１～第８、第１３および第１４実施形態において、水ノズル６１，２０２，２１２，５３１のノズル配管の先端部にそれぞれ電極５６（図１、図８、図１０（ａ）、図１１、図１２、図１４、図１５（ａ）、図１６、図２４および図２８参照）が設けられているとして説明したが、この電極５６をノズル配管に設けない構成であってもよい。この場合、電源５７（図３参照）も省略される。 In the first to eighth, thirteenth and fourteenth embodiments, electrodes 56 (FIGS. 1, 8, 10 (a), 11, 12, 14, 15 (a), FIG. 16, FIG. 24, and FIG. 28) are described as being provided, but a configuration in which the electrode 56 is not provided in the nozzle pipe may be employed. In this case, the power source 57 (see FIG. 3) is also omitted.
　逆に、第１２実施形態の水ノズル４０９の先端部や第６および第１１実施形態のカップ用ノズル２２４，３１３の先端部に電極５６を設け、電極５６に、電源５７（図３参照）によって装置グラウンドに対する電圧が印加されるようになってもよい。 Conversely, an electrode 56 is provided at the tip of the water nozzle 409 of the twelfth embodiment and the tips of the cup nozzles 224 and 313 of the sixth and eleventh embodiments, and the electrode 56 is powered by a power source 57 (see FIG. 3). A voltage with respect to the device ground may be applied.
　また、図４、図１８、図２２、図２４、図１４、図２０に二点鎖線で示すように、第４、第１０、第１２および第１３実施形態の水供給配管２０４，３０７，４１０，５３３や第６および第１１実施形態の分岐配管２２２，３１２に、液検出センサ（処理液検出手段）１０１が配置されていてもよい。液検出センサ１０１は、水供給配管２０４，３０７，４１０，５３３や分岐配管２２２，３１２内の所定の水検出位置１０２でのＤＩＷの存否を検出するためのセンサである。この場合、水検出位置１０２は、水供給配管２０４，３０７，４１０，５３３や分岐配管２２２，３１２に形成される開口（軟Ｘ線が照射される開口）と同じ位置あるいは近い位置に設定されている。また、この場合には、図７の処理と同等の処理を実行することもできる。 Moreover, as shown by a two-dot chain line in FIGS. 4, 18, 22, 24, 14, and 20, the water supply pipes 204, 307, and 410 of the fourth, tenth, twelfth, and thirteenth embodiments are used. , 533 and the branch pipes 222 and 312 of the sixth and eleventh embodiments may be provided with a liquid detection sensor (treatment liquid detection means) 101. The liquid detection sensor 101 is a sensor for detecting the presence or absence of DIW at a predetermined water detection position 102 in the water supply pipes 204, 307, 410, 533 and the branch pipes 222, 312. In this case, the water detection position 102 is set at the same position as or close to the opening (opening to which soft X-rays are irradiated) formed in the water supply pipes 204, 307, 410, 533 and the branch pipes 222, 312. Yes. In this case, a process equivalent to the process of FIG. 7 can also be executed.
　また、第４、第５、第１２および第１３実施形態において、水ノズル２０２，２１２，４０９，５３１の吐出口２０２Ａ，２１６，４０９Ａ，５３１Ａならびに第６および第１１実施形態のカップ用ノズル２２４，３１３の吐出口２２４Ａ，３１３Ａに、第３実施形態に係る繊維状物質をそれぞれ設けることもできる。 Further, in the fourth, fifth, twelfth and thirteenth embodiments, the discharge ports 202A, 216, 409A and 531A of the water nozzles 202, 212, 409 and 531 and the cup nozzle 224 of the sixth and eleventh embodiments are used. The fibrous substances according to the third embodiment can be provided in the discharge ports 224A and 313A of 313, respectively.
　また、第６および第１１実施形態では、分岐配管２２２，３１２の先端に設けられたノズル２２４，３１３からのＤＩＷを用いてカップ１７の除電を行うとしたが、このようなノズル２２４，３１３からのＤＩＷを用いて、第２ノズル配管２３２（図１５（ａ），１５（ｂ）参照）の除電を行うようにしてもよい。 In the sixth and eleventh embodiments, the cup 17 is neutralized using DIW from the nozzles 224 and 313 provided at the ends of the branch pipes 222 and 312. The DIW of the second nozzle pipe 232 (see FIGS. 15A and 15B) may be used for static elimination.
　また、第６および第１１実施形態において、分岐配管２２２，３１２に軟Ｘ線照射ユニット２２３，３１９を配置するとして説明したが、軟Ｘ線照射ユニット２２３，３１９が水供給配管２０４，３０７にそれぞれ配置されていてもよい。 In the sixth and eleventh embodiments, the soft X-ray irradiation units 223 and 319 are disposed in the branch pipes 222 and 312. However, the soft X-ray irradiation units 223 and 319 are provided in the water supply pipes 204 and 307, respectively. It may be arranged.
　また、第７、第８および第１４実施形態に係る水供給ユニット２３０，２５０，６００　　　では、第１実施形態に係る水供給ユニット１００と同等の構成を採用するとして説明したが、第４実施形態に係る水供給ユニット２００（図１参照）、第５実施形態に係る水供給ユニット２２０と同等の構成を採用することもできる。 Further, the water supply units 230, 250, and 600 according to the seventh, eighth, and fourteenth embodiments have been described as adopting the same configuration as the water supply unit 100 according to the first embodiment, but the fourth embodiment. The structure equivalent to the water supply unit 200 (refer FIG. 1) which concerns on, and the water supply unit 220 which concerns on 5th Embodiment is also employable.
　また、第１０～第１２実施形態において、水ノズル３０２から基板Ｗの上面に水を供給するとして説明したが、水ノズル３０２に代えて、第１～第３実施形態に係る水供給ユニット１００（図１参照）や、第４実施形態に係る水供給ユニット２００（図１１参照）、第５実施形態に係る水供給ユニット２２０を採用することもできる。 In the tenth to twelfth embodiments, it has been described that water is supplied from the water nozzle 302 to the upper surface of the substrate W. Instead of the water nozzle 302, the water supply unit 100 according to the first to third embodiments ( 1), a water supply unit 200 according to the fourth embodiment (see FIG. 11), and a water supply unit 220 according to the fifth embodiment may be employed.
　また、第１０～第１２実施形態において、基板Ｗに両面リンスを施す場合を例に挙げて説明したが、第１０～第１２実施形態において、基板Ｗの下面のみをリンス処理するようにしてもよい。この場合、図１８、図２０および図２２に示す構成から、水ノズル３０２、水供給配管３０３および水バルブ３０４をそれぞれ取り除いた構成を採用することが可能である。 In the tenth to twelfth embodiments, the case where the substrate W is rinsed on both sides has been described as an example. However, in the tenth to twelfth embodiments, only the lower surface of the substrate W may be rinsed. Good. In this case, it is possible to employ a configuration in which the water nozzle 302, the water supply pipe 303, and the water valve 304 are removed from the configurations shown in FIGS. 18, 20, and 22, respectively.
　また、第１１実施形態に係る軟Ｘ線照射装置３１４を、第１～第１０および第１２実施形態において、処理室３内に配置することもできる。この場合、軟Ｘ線照射装置３１４からの軟Ｘ線がカップ上部１９に照射されるようになっていてもよい。 Further, the soft X-ray irradiation apparatus 314 according to the eleventh embodiment can be arranged in the processing chamber 3 in the first to tenth and twelfth embodiments. In this case, soft X-rays from the soft X-ray irradiation device 314 may be irradiated to the cup upper portion 19.
　また、第１～第１２および第１４実施形態において、１つのノズル６１，２０２，２１２，３０６，４０９から処理対象物（基板Ｗや基板収容器６０２、第２ノズル配管２３２）に、ＤＩＷ（水の一例）を供給する場合を例に挙げて説明したが、複数のノズルからＤＩＷを供給するようにしてもよい。この場合、第１３実施形態の水供給ユニット５００のように、ノズル６１，２０２，２１２，３０６，４０９にＤＩＷを供給するための複数の水供給配管の上流端が水集合配管に接続されており、かつ当該水集合配管内に存在しているＤＩＷに、軟Ｘ線照射ユニットからの軟Ｘ線が照射されるようになっていることが好ましい。 Further, in the first to twelfth and fourteenth embodiments, DIW (water) is supplied from one nozzle 61, 202, 212, 306, 409 to a processing object (substrate W, substrate container 602, second nozzle pipe 232). In the above example, the DIW is supplied from a plurality of nozzles. In this case, like the water supply unit 500 of the thirteenth embodiment, the upstream ends of a plurality of water supply pipes for supplying DIW to the nozzles 61, 202, 212, 306, 409 are connected to the water collecting pipe. In addition, it is preferable that the DIW existing in the water collecting pipe is irradiated with soft X-rays from the soft X-ray irradiation unit.
　また、第１～第１４実施形態では、たとえば、窓部材７１の外表面７１Ｂを覆う親水性皮膜３８として、親水性を有するＤＬＣ（Diamond Like Carbon）皮膜や、親水性を有するフッ素樹脂皮膜、炭化水素樹脂皮膜などを用いることができる。 In the first to fourteenth embodiments, for example, as the hydrophilic film 38 covering the outer surface 71B of the window member 71, a hydrophilic DLC (Diamond Like Carbon) film, a hydrophilic fluororesin film, carbonized A hydrogen resin film or the like can be used.
　また、窓部材７１を、ポリイミド樹脂を用いて形成することもできる。この場合、窓部材７１に軟Ｘ線を透過させることができる。また、ポリイミド樹脂は化学安定性に優れているので、窓部材７１を長期にわたって使用し続けることができる。この場合、外表面７１Ｂを親水性皮膜３８で覆う必要はない。 Also, the window member 71 can be formed using polyimide resin. In this case, soft X-rays can be transmitted through the window member 71. Moreover, since the polyimide resin is excellent in chemical stability, the window member 71 can be continuously used for a long time. In this case, it is not necessary to cover the outer surface 71B with the hydrophilic film 38.
　前述の第１～第１４実施形態では、軟Ｘ線が照射され、かつ吐出口から吐出される水の一例としてＤＩＷを挙げたが、ＤＩＷに限らず、炭酸水、電解イオン水、水素溶存水、オゾン溶存水および希釈濃度（たとえば、１０ｐｐｍ～１００ｐｐｍ程度）の塩酸水のいずれか水として採用することもできる。 In the first to fourteenth embodiments described above, DIW has been exemplified as an example of water that is irradiated with soft X-rays and discharged from the discharge port. However, the present invention is not limited to DIW, but carbonated water, electrolytic ionic water, hydrogen-dissolved water. In addition, ozone-dissolved water and dilute concentration (for example, about 10 ppm to 100 ppm) hydrochloric acid water can also be employed.
　また、第１～第１４実施形態において、軟Ｘ線が照射され、かつ吐出口から吐出される処理液として、薬液（希釈薬液）を採用することもできる。この場合、薬液としては、所定濃度に希釈されたフッ酸、BHF（Bufferd HF）、ＡＰＭ（ammonia-hydrogen peroxide mixture：アンモニア過酸化水素水混合液）、ＴＭＡＨ（水酸化テトラメチルアンモニウム水溶液）、アンモニア水、ＨＰＭ（hydrochloric acid/hydrogen peroxide mixture：塩酸過酸化水素水混合液）等を用いることができる。 Further, in the first to fourteenth embodiments, a chemical solution (diluted chemical solution) can be adopted as a processing solution irradiated with soft X-rays and discharged from the discharge port. In this case, as a chemical solution, hydrofluoric acid diluted to a predetermined concentration, BHF (Bufferd HF), APM (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide aqueous solution), ammonia Water, HPM (hydrochloric acid / hydrogen-peroxide mixture), etc. can be used.
　さらには、第１～第１４実施形態において、処理液を供給しつつ、基板Ｗの表面や周縁部をブラシやスクラバで洗浄する処理において、処理液の供給と並行して、第１配管内を流通する処理液に軟Ｘ線を照射することもできる。 Furthermore, in the first to fourteenth embodiments, in the process of cleaning the surface and peripheral portion of the substrate W with a brush or a scrubber while supplying the processing liquid, the inside of the first pipe is performed in parallel with the supply of the processing liquid. It is also possible to irradiate soft X-rays to the processing solution that is distributed.
　また、第１５～第１８実施形態において、照射窓７３５の外表面７３５Ｂに形成され、当該外表面７３５Ｂを覆う撥水性皮膜として、他の皮膜を用いることができる。 Further, in the fifteenth to eighteenth embodiments, other films can be used as the water-repellent film formed on the outer surface 735B of the irradiation window 735 and covering the outer surface 735B.
　この撥水性皮膜として、図４２に示すように、撥水性を有するＤＬＣ（Diamond Like Carbon）皮膜８５１（ダイヤモンドライクカーボンの皮膜）を採用することができる。ＤＬＣ皮膜８５１は、微小の水素原子を含有している（原子数の比で、Ｃ：Ｈ＝９９：１～９６：４）。ＤＬＣ皮膜８５１の膜厚は、10μm以下であり、とくに1～2μm程度であることが好ましい。 42. As this water-repellent film, as shown in FIG. 42, a water-repellent DLC (Diamond-Like Carbon) film 851 (diamond-like carbon film) can be employed. The DLC film 851 contains minute hydrogen atoms (at the ratio of the number of atoms, C: H = 99: 1 to 96: 4). The film thickness of the DLC film 851 is 10 μm or less, and preferably about 1 to 2 μm.
　第１５～第１８実施形態において、イオン注入法等により、照射窓７３５の外表面７３５Ｂにケイ素（Ｓｉ）イオンが注入され、次いで、スパッタリング法等により、照射窓７３５の外表面７３５Ｂに炭素（Ｃ）イオンが注入される。これにより、照射窓７３５の外表面７３５Ｂが改質される。その後、プラズマＣＶＤ法等により、照射窓７３５の外表面７３５ＢにＤＬＣの堆積膜が形成され、これにより、ＤＬＣ皮膜８５１が形成される。ケイ素（Ｓｉ）イオンの注入、炭素（Ｃ）イオンの注入、およびＤＬＣの堆積は、室温～150℃の低温環境下で行われる。 In the fifteenth to eighteenth embodiments, silicon (Si) ions are implanted into the outer surface 735B of the irradiation window 735 by ion implantation or the like, and then carbon (C) is implanted into the outer surface 735B of the irradiation window 735 by sputtering or the like. ) Ions are implanted. Thereby, the outer surface 735B of the irradiation window 735 is modified. Thereafter, a deposited film of DLC is formed on the outer surface 735B of the irradiation window 735 by plasma CVD or the like, whereby a DLC film 851 is formed. Silicon (Si) ion implantation, carbon (C) ion implantation, and DLC deposition are performed in a low temperature environment of room temperature to 150 ° C.
　このような方法（プラズマイオンアシスト方式）により形成したＤＬＣ皮膜８５１は、撥水性を有している。照射窓７３５の外表面７３５Ｂに撥水性のＤＬＣ皮膜８５１が形成されていると、照射窓７３５の外表面７３５Ｂに水滴が付着するのを防止することができる。その結果、照射窓７３５が曇るのを抑制または防止することができる。 DLC film 851 formed by such a method (plasma ion assist method) has water repellency. When the water-repellent DLC film 851 is formed on the outer surface 735B of the irradiation window 735, water droplets can be prevented from adhering to the outer surface 735B of the irradiation window 735. As a result, clouding of the irradiation window 735 can be suppressed or prevented.
 また、ＤＬＣ皮膜８５１は、高温環境下でも高い密着性を有している。そのため、剥がれたＤＬＣが照射窓７３５を汚染するのを確実に防止することができる。 In addition, the DLC film 851 has high adhesion even under a high temperature environment. Therefore, it is possible to reliably prevent the peeled DLC from contaminating the irradiation window 735.
　さらに、ＤＬＣの堆積を低温環境下で行うために、堆積後の降下温度が少なく、ＤＬＣ皮膜８５１中に応力が残留し難い。これにより、割れにくい（耐久性の高い）皮膜を形成することができる。 Furthermore, since the DLC is deposited in a low temperature environment, the temperature drop after the deposition is small, and the stress hardly remains in the DLC film 851. Thereby, it is possible to form a film that is difficult to break (high durability).
　また、第１５～第１８実施形態において、撥水性皮膜として、図４３に示すように、撥水性を有するアモルファスフッ素樹脂皮膜８６１を採用することができる。アモルファスフッ素樹脂皮膜８６１は、たとえばサイトップ樹脂（商品名）からなるアモルファスフッ素によって形成されている。アモルファスフッ素樹脂皮膜８６１の膜厚は、50μm以下であり、とくに5～10μm程度であることが好ましい。照射窓７３５の外表面７３５Ｂに撥水性のアモルファスフッ素樹脂皮膜８６１が形成されていると、照射窓７３５の外表面７３５Ｂに水滴が付着するのを防止することができる。その結果、照射窓７３５が曇るのを抑制または防止することができる。 Further, in the fifteenth to eighteenth embodiments, as shown in FIG. 43, an amorphous fluororesin film 861 having water repellency can be adopted as the water repellent film. The amorphous fluororesin film 861 is made of amorphous fluorine made of, for example, Cytop resin (trade name). The film thickness of the amorphous fluororesin film 861 is 50 μm or less, and preferably about 5 to 10 μm. When the water repellent amorphous fluororesin film 861 is formed on the outer surface 735B of the irradiation window 735, it is possible to prevent water droplets from adhering to the outer surface 735B of the irradiation window 735. As a result, clouding of the irradiation window 735 can be suppressed or prevented.
　なお、第１５～第１８実施形態において、皮膜としてＤＬＣ、アモルファスフッ素樹脂の実施形態について説明したが、本皮膜としては、軟Ｘ線が透過し易く、百数十℃程度の耐熱性を有し、ベリリウムとの密着性に優れ、耐水性を有し、薬品や薬品蒸気に対する耐腐食性を有し、純水中への溶出イオンが少なく、剥がれたりクラックが入りにくい材料の皮膜であれば他の材料であっても、適用することができる。 In the fifteenth to eighteenth embodiments, embodiments of DLC and amorphous fluororesin were described as the coating. However, the present coating is easy to transmit soft X-rays and has heat resistance of about several hundred degrees Celsius. , Any film that has excellent adhesion to beryllium, water resistance, corrosion resistance to chemicals and chemical vapors, low elution ions in pure water, and does not easily peel or crack. Even if it is the material of, it is applicable.
　また、第１８実施形態において、遮蔽部材を軟Ｘ線照射ヘッド８４１と一体に設けた構成について説明したが、遮蔽部材は照射ヘッド８４１と個別に設けられていてもよい。この場合、スピンチャック７０４上方において水平面内で揺動可能なアームに取り付けられて、このアームの揺動によりスピンチャック７０４上を移動可能に設けられていてもよい。 In the eighteenth embodiment, the configuration in which the shielding member is provided integrally with the soft X-ray irradiation head 841 has been described. However, the shielding member may be provided separately from the irradiation head 841. In this case, it may be attached to an arm that can be swung in a horizontal plane above the spin chuck 704 so as to be movable on the spin chuck 704 by the swing of this arm.
　また、第１８実施形態において、前述の各実施形態において、シャッタ７２１が開状態になったときには、軟Ｘ線照射ヘッド７０６，８４１やＸ線照射ユニット８３４からのＸ線の照射が停止されるようになっていてもよい。 In the eighteenth embodiment, when the shutter 721 is opened in each of the foregoing embodiments, the X-ray irradiation from the soft X-ray irradiation heads 706 and 841 and the X-ray irradiation unit 834 is stopped. It may be.
　また、第１５～第１８実施形態において、気体ノズル７２７は、常温よりも高温の気体を吐出するとして説明したが、気体ノズル７２７から常温の気体が吐出されてもよい。 Further, in the fifteenth to eighteenth embodiments, the gas nozzle 727 has been described as ejecting a gas having a temperature higher than normal temperature, but normal temperature gas may be ejected from the gas nozzle 727.
　また、第１５～第１８実施形態では、発熱部材としてのシート状のヒータ７４４を配置する構成を採用したが、他の熱源を発熱部材として設ける構成であってもよい。また、カバー７２６の下壁７２６Ａのような開口７２８の周囲に限られず、照射窓７３５に設けられていてもよい。また、カバー７２６の下壁７２６Ａと照射窓７３５との双方に設けられる構成であってもよい。また、ヒータ７４４等の加熱部材を照射窓７３５の周囲に設けない構成であってもよい。 In the fifteenth to eighteenth embodiments, the configuration in which the sheet-like heater 744 as the heat generating member is arranged is adopted, but another heat source may be provided as the heat generating member. In addition, the irradiation window 735 may be provided without being limited to the periphery of the opening 728 such as the lower wall 726 </ b> A of the cover 726. Moreover, the structure provided in both the lower wall 726A of the cover 726 and the irradiation window 735 may be sufficient. Further, a configuration in which a heating member such as the heater 744 is not provided around the irradiation window 735 may be employed.
　また、第１５～第１８実施形態では、移動型の軟Ｘ線照射ヘッド７０６，８４１や、同じく移動型のＸ線照射ユニット８３４を、Ｘ線照射手段として設ける構成を例示したが、固定式のＸ線照射手段を、スピンチャック７０４に保持された基板Ｗに対して上方に固定的に対向配置させてもよい。この場合、固定式のＸ線照射手段から照射された軟Ｘ線が、当該基板Ｗの全域に照射されるようになっている必要がある。 In the fifteenth to eighteenth embodiments, the movable soft X-ray irradiation heads 706 and 841 and the movable X-ray irradiation unit 834 are provided as X-ray irradiation means. The X-ray irradiation means may be disposed so as to be fixedly opposed to the substrate W held by the spin chuck 704. In this case, it is necessary that the soft X-rays irradiated from the fixed X-ray irradiation unit are irradiated to the entire area of the substrate W.
　また、第１５～第１８実施形態では、軟Ｘ線の照射と並行して基板Ｗに供給される水の一例としてＤＩＷを挙げたが、ＤＩＷに限らず、炭酸水、電解イオン水、水素溶存水、オゾン溶存水および希釈濃度（たとえば、１０ｐｐｍ～１００ｐｐｍ程度）の塩酸水のいずれか水として採用することもできる。 In the fifteenth to eighteenth embodiments, DIW is given as an example of water supplied to the substrate W in parallel with the soft X-ray irradiation. However, the water is not limited to DIW, but carbonated water, electrolytic ionic water, hydrogen dissolved. Any of water, ozone-dissolved water and hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm) can also be employed.
　また、第１５～第１８実施形態では、リンス処理のための水の供給と並行して、基板Ｗの表面に軟Ｘ線を照射する場合を例にとって説明したが、薬液（希釈薬液）の供給と並行して軟Ｘ線の照射を実行することもできる。この場合、この場合、薬液としては、所定濃度に希釈されたフッ酸、BHF（Bufferd HF）、ＡＰＭ（ammonia-hydrogen peroxide mixture：アンモニア過酸化水素水混合液）、ＴＭＡＨ（水酸化テトラメチルアンモニウム水溶液）、アンモニア水、ＨＰＭ（hydrochloric acid/hydrogen peroxide mixture：塩酸過酸化水素水混合液）等を用いることができる。　さらには、第１～第１４実施形態において、処理液を供給しつつ、基板Ｗの表面や周縁部をブラシやスクラバで洗浄する処理において、処理液の供給と並行して、第１配管内を流通する処理液に軟Ｘ線を照射することもできる。 In the fifteenth to eighteenth embodiments, the case where soft X-rays are applied to the surface of the substrate W in parallel with the supply of water for the rinsing process has been described as an example. However, the supply of a chemical solution (diluted chemical solution) In parallel, soft X-ray irradiation can be performed. In this case, in this case, as the chemical solution, hydrofluoric acid diluted to a predetermined concentration, BHF (BufferdＡHF), APM (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide aqueous solution) ), Ammonia water, HPM (hydrochloric acid / hydrogen peroxide mixture). Furthermore, in the first to fourteenth embodiments, in the process of cleaning the surface and peripheral portion of the substrate W with a brush or a scrubber while supplying the processing liquid, the inside of the first pipe is performed in parallel with the supply of the processing liquid. It is also possible to irradiate soft X-rays to the processing solution that is distributed.
　また、第１５～第１８実施形態において、水を供給しつつ、基板Ｗの表面や周縁部をブラシやスクラバで洗浄する処理において、水の供給と並行して、基板Ｗの表面に軟Ｘ線を照射することもできる。 In the fifteenth to eighteenth embodiments, in the process of cleaning the surface and peripheral edge of the substrate W with a brush or a scrubber while supplying water, the soft X-rays are applied to the surface of the substrate W in parallel with the supply of water. Can also be irradiated.
　また、第１５～第１８実施形態では、表面に酸化膜が形成された基板Ｗに対する処理を行う場合を例に挙げたが、表面に銅膜やＴｉ（チタン）膜等の金属膜（配線膜）が形成された基板Ｗに対する処理を行うものであってもよい。 In the fifteenth to eighteenth embodiments, the case where the processing is performed on the substrate W on which the oxide film is formed is taken as an example. ) May be performed on the substrate W on which is formed.
　第１９～第２５実施形態において、基板浸漬処理の後に処理槽１００２内の全ての処理液を排出し、処理液ノズル１００３から基板Ｗに処理後のシャワーリンスを行うようにしてもよい。この場合、浸漬処理後もなお基板Ｗに付着したままとなっている汚染物質を洗い流すことができ、基板Ｗに再付着することが防止される。 In the nineteenth to twenty-fifth embodiments, all the processing liquid in the processing tank 1002 may be discharged after the substrate immersion processing, and the post-processing shower rinsing may be performed from the processing liquid nozzle 1003 to the substrate W. In this case, the contaminants that remain attached to the substrate W even after the immersion treatment can be washed away, and are prevented from reattaching to the substrate W.
　また、第１９～第２３実施形態において、図４４、図４７および図４９に破線で示すように、循環機構１００５の循環配管１０１２（帰還配管１０１９）の途中部に、循環配管１０１２を流れる処理液を加熱するためのヒータ２５が介装されていてもよい。 Further, in the nineteenth to twenty-third embodiments, as shown by broken lines in FIGS. 44, 47 and 49, the processing liquid flowing through the circulation pipe 1012 in the middle of the circulation pipe 1012 (return pipe 1019) of the circulation mechanism 1005. The heater 25 for heating may be interposed.
　また、第２０～第２３実施形態において、循環機構１００５（図４４参照）を設けない構成とすることもできる。この場合、処理槽１００２，１５０２に貯留されている処理液は循環されず、外槽１００８に回収された処理液は、廃液または回収される。 In the twentieth to twenty-third embodiments, the circulation mechanism 1005 (see FIG. 44) may be omitted. In this case, the processing liquid stored in the processing tanks 1002 and 1502 is not circulated, and the processing liquid recovered in the outer tank 1008 is waste liquid or recovered.
　また、第２４～第２７実施形態において、循環機構１００５（図４４参照）を設けた構成とすることもできる。この場合、処理槽１５０２に貯留されている処理液が循環され、外槽１００８に回収された処理液は、再び処理槽１５０２内へと供給される。 Also, in the twenty-fourth to twenty-seventh embodiments, a configuration in which a circulation mechanism 1005 (see FIG. 44) is provided may be employed. In this case, the processing liquid stored in the processing tank 1502 is circulated, and the processing liquid recovered in the outer tank 1008 is supplied again into the processing tank 1502.
　また、第２６および第２７実施形態では、浸漬処理に並行して、処理液に浸漬されている処理対象物をブラシで擦って洗浄する処理を並行して実行することもできる。 In the twenty-sixth and twenty-seventh embodiments, in parallel with the dipping process, the process of rubbing and cleaning the processing object immersed in the processing liquid with a brush can be executed in parallel.
　また、第１９および第２１～第２７実施形態において、外槽１００８は必須のものではない。とくに、処理槽１００２，１５０２に貯留されている処理液を循環させない場合には、外槽１００８の構成を省くこともできる。 In the nineteenth and twenty-first to twenty-seventh embodiments, the outer tub 1008 is not essential. In particular, when the processing liquid stored in the processing tanks 1002 and 1502 is not circulated, the configuration of the outer tank 1008 can be omitted.
　また、第１９～第２７実施形態では、たとえば、窓部材１０７１の外表面７１Ｂを覆う親水性皮膜１０３８として、親水性を有するＤＬＣ（Diamond Like Carbon）皮膜や、親水性を有するフッ素樹脂皮膜、炭化水素樹脂皮膜などを用いることができる。 In the nineteenth to twenty-seventh embodiments, for example, as the hydrophilic film 1038 covering the outer surface 71B of the window member 1071, a hydrophilic DLC (Diamond Like Carbon) film, a hydrophilic fluororesin film, or carbonized A hydrogen resin film or the like can be used.
　また、窓部材１０７１を、ポリイミド樹脂を用いて形成することもできる。この場合、窓部材１０７１に軟Ｘ線を透過させることができる。また、ポリイミド樹脂は化学安定性に優れているので、窓部材１０７１を長期にわたって使用し続けることができる。この場合、外表面７１Ｂを親水性皮膜１０３８で覆う必要はない。 The window member 1071 can also be formed using a polyimide resin. In this case, soft X-rays can be transmitted through the window member 1071. In addition, since the polyimide resin is excellent in chemical stability, the window member 1071 can be used for a long time. In this case, it is not necessary to cover the outer surface 71B with the hydrophilic film 1038.
　また、第２３～第２７実施形態において、軟Ｘ線照射ユニット１５６２による軟Ｘ線の照射に併せて、電源１５５７から電極１５５６に対し電圧を印加するようにしてもよい。この場合、たとえば電極１５５６は正電荷に帯電されることが好ましい。この場合、電極１５５６の正電荷によって、軟Ｘ線の照射により処理液の照射部分中に発生した電子は、電極１５５６側に引っ張られ、電極１５５６のあるノズル配管１５５１の先端部まで移動するようになる。すなわち、多量の電子を、処理液ノズル１５６１の吐出口１５５３に向けて引っ張ることができる。これにより、基板Ｗ側への電子の移動を促進させることができる。 In the twenty-third to twenty-seventh embodiments, a voltage may be applied from the power source 1557 to the electrode 1556 in conjunction with the soft X-ray irradiation by the soft X-ray irradiation unit 1562. In this case, for example, the electrode 1556 is preferably charged to a positive charge. In this case, the electrons generated in the irradiated portion of the treatment liquid by the soft X-ray irradiation due to the positive charge of the electrode 1556 are pulled toward the electrode 1556 and moved to the tip of the nozzle pipe 1551 where the electrode 1556 is provided. Become. That is, a large amount of electrons can be pulled toward the discharge port 1553 of the processing liquid nozzle 1561. Thereby, the movement of the electrons to the substrate W side can be promoted.
　また、第１～第２７実施形態においては、Ｘ線のなかでも比較的波長が長い「軟Ｘ線」を照射するものをＸ線照射手段として用いたが、これに限らず、比較的波長が短い「硬Ｘ線」（０．００１nm～０．１nm）を用いることもできる。この場合、装置のオペレータ等の人体に対する安全のため、例えば装置のオペレータ側の面を相当の厚みを有する鉛板で覆うなど、Ｘ線の装置外への漏洩を遮蔽する遮蔽構造を設けるか、あるいはＸ線照射時におけるオペレータの装置周辺への立ち入りを禁止するなどの対応をとることが望ましい。なお、各実施形態にある軟Ｘ線を照射するものを用いれば、硬Ｘ線を照射するものとくらべ、装置が小型で安価ですみ、また人体等に対する遮蔽も比較的容易である。 In the first to twenty-seventh embodiments, X-rays that emit “soft X-rays” having a relatively long wavelength are used as the X-ray irradiating means. Short “hard X-rays” (0.001 nm to 0.1 nm) can also be used. In this case, for safety to the human body such as the operator of the apparatus, for example, a surface of the apparatus operator side is covered with a lead plate having a considerable thickness, for example, a shielding structure for shielding leakage of X-rays to the outside of the apparatus is provided, Alternatively, it is desirable to take measures such as prohibiting an operator from entering the periphery of the apparatus during X-ray irradiation. In addition, if what irradiates soft X-ray in each embodiment is used, compared with what irradiates hard X-ray | X_line, an apparatus is small and cheap, and shielding with respect to a human body etc. is comparatively easy.
　なお、基板Ｗとして、半導体ウエハや液晶表示装置用ガラス基板を例に挙げて説明したが、基板Ｗにはその他に、プラズマディスプレイ用基板、ＦＥＤ(Field Emission Display)用基板、OLED（有機エレクトロルミネッセンス）用基板、光ディスク用基板、磁気ディスク用基板、光磁気ディスク用基板、フォトマスク用基板、セラミック基板、太陽電池用基板などの基板が含まれる。また、基板の材質としては、シリコンやガラスの他、ＳｉＣ、石英、サファイヤ、プラスチック、セラミック等を例示することができる。 The substrate W has been described by taking a semiconductor wafer or a glass substrate for a liquid crystal display device as an example. However, the substrate W can also be a plasma display substrate, a FED (Field Emission Display) substrate, an OLED (organic electroluminescence). ) Substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates, and the like. Moreover, as a material of a board | substrate, SiC, quartz, sapphire, a plastic, a ceramic, etc. other than silicon and glass can be illustrated.
　本発明の実施形態について詳細に説明してきたが、これらは本発明の技術的内容を明らかにするために用いられた具体例に過ぎず、本発明はこれらの具体例に限定して解釈されるべきではなく、本発明の範囲は添付の請求の範囲によってのみ限定される。
この出願は、２０１２年９月２７日に日本国特許庁に提出された特願２０１２－２１５２９３号、２０１２年９月２７日に日本国特許庁に提出された特願２０１２－２１５２９４号、２０１３年９月１９日に日本国特許庁に提出された特願２０１３－１９４２９３号および２０１３年９月１９日に日本国特許庁に提出された特願２０１３－１９４２９４号に対応しており、この出願の全開示はここに引用により組み込まれるものとする。 Although the embodiments of the present invention have been described in detail, these are merely specific examples used to clarify the technical contents of the present invention, and the present invention is construed to be limited to these specific examples. Rather, the scope of the present invention is limited only by the accompanying claims.
This application includes Japanese Patent Application No. 2012-215293 filed with the Japan Patent Office on September 27, 2012, Japanese Patent Application No. 2012-215294 filed with the Japan Patent Office on September 27, 2012, 2013 It corresponds to Japanese Patent Application No. 2013-194293 filed with the Japan Patent Office on September 19, and Japanese Patent Application No. 2013-194294 filed with the Japan Patent Office on September 19, 2013. The entire disclosure is hereby incorporated by reference.
　　１　　　基板処理装置
　　４　　　スピンチャック（基板保持回転手段）
　　６　　　一体型ヘッド
　　６Ａ　　一体型ヘッド
　　６Ｂ　　一体型ヘッド
　１７　　　カップ（液受け部材）
　２５　　　軟Ｘ線発生器（Ｘ線発生器）
　２６　　　カバー
　２７　　　気体ノズル（気体供給手段）
　３５　　　照射窓
　３７　　　気体バルブ（気体供給手段）
　３８　　　親水性皮膜（皮膜）
　４０　　　制御装置（Ｘ線照射制御手段）
　５１　　　第１ノズル配管（処理液配管）
　５１Ａ　　第１ノズル配管（処理液配管）
　５２　　　第１開口（開口、Ｘ線の照射位置）
　５２Ａ　　第３開口（開口、Ｘ線の照射位置）
　５３　　　吐出口
　５６　　　電極
　５７　　　電源
　６１　　　水ノズル（処理液ノズル）
　６２　　　軟Ｘ線照射ユニット（Ｘ線照射手段）
　６５　　　繊維束（繊維状物質）
　７１　　　窓部材
　７１Ｂ　　外表面（閉塞窓における処理液が流通する側の壁面）
１００　　　水供給ユニット（処理液供給装置）
１０１　　　液検出センサ（処理液検出手段）
２００　　　水供給ユニット（処理液供給装置）
２０１　　　基板処理装置
２０２Ａ　　吐出口
２０３　　　軟Ｘ線照射ユニット（Ｘ線照射手段）
２０４　　　水供給配管（処理液配管）
２１１　　　基板処理装置
２１６　　　吐出口
２２０　　　水供給ユニット（処理液供給装置）
２２１　　　基板処理装置
２２２　　　第１分岐配管（分岐配管）
２２４Ａ　　吐出口（液受け用吐出口）
２３０　　　水供給ユニット（処理液供給装置）
２３１　　　基板処理装置
２３２　　　第２ノズル配管（第２配管）
２５０　　　水供給ユニット（処理液供給装置）
２５１　　　基板処理装置
２６０　　　水供給ユニット（処理液供給装置）
２６１　　　基板処理装置
２６２　　　第２ノズル配管（第２配管）
２７６　　　吐出口
３００　　　水供給ユニット（処理液供給装置）
３０１　　　基板処理装置
３０６Ａ　　吐出口
３０７　　　水供給配管（処理液配管）
３０９　　　軟Ｘ線照射ユニット（Ｘ線照射手段）
３１０　　　水供給ユニット（処理液供給装置）
３１１　　　基板処理装置
３１２　　　第２分岐配管（分岐配管）
３１３Ａ　　吐出口（液受け用吐出口）
４００　　　水供給ユニット（処理液供給装置）
４０１　　　基板処理装置
４０２　　　スピンチャック（基板保持回転手段）
４０４　　　スピン軸（支持部材）
４０５　　　スピンベース（支持部材）
４０９Ａ　　吐出口
４１０　　　水供給配管（処理液配管）
４１２　　　軟Ｘ線照射ユニット（Ｘ線照射手段）
５００　　　水供給ユニット（処理液供給装置）
５０１　　　基板処理装置
５０４　　　コロ搬送ユニット（基板保持搬送手段）
５３１Ａ　　吐出口
５３３　　　水供給配管（処理液配管）
５３４　　　軟Ｘ線照射ユニット（Ｘ線照射手段）
６００　　　水供給ユニット（処理液供給装置）
６０２　　　基板収容器（収容器）
７０１　　　基板処理装置
７０４　　　スピンチャック（基板保持手段）
７０５　　　水ノズル（水供給手段）
７０６　　　軟Ｘ線照射ヘッド（Ｘ線照射手段）
７１４　　　水バルブ（水供給手段）
７１９　　　揺動駆動機構（移動手段）
７２０　　　昇降駆動機構（移動手段）
７２５　　　Ｘ線発生器
７２６　　　カバー
７２７　　　気体ノズル（気体供給手段）
７２８　　　開口
７３５　　　照射窓
７３７　　　気体バルブ（気体供給手段）
７３８　　　ポリイミド樹脂皮膜
７４０　　　制御装置（制御手段）
７４４　　　ヒータ（発熱部材）
８２０　　　基板処理装置
８２１　　　水ノズル（水供給手段）
８３０　　　基板処理装置
８３３　　　水ノズル（水供給手段）
８３４　　　軟Ｘ線照射ユニット（Ｘ線照射手段）
８４０　　　基板処理装置
８４１　　　軟Ｘ線照射ヘッド（Ｘ線照射手段）
８４２　　　遮蔽部材（遮蔽板部）
８５１　　　ＤＬＣ皮膜（ダイヤモンドライクカーボンの皮膜）
８６１　　　アモルファスフッ素樹脂皮膜
１００１　　基板処理装置（処理液処理装置）
１００２　　処理槽
１００７　　内槽
１００８　　外槽
１０１６　　分岐配管（処理液供給配管）
１０１７　　軟Ｘ線照射ユニット（Ｘ線照射手段）
１０１９　　帰還配管（オーバーフロー配管）
１０２５　　軟Ｘ線発生器（Ｘ線発生器）
１０２６　　カバー
１０２７　　気体ノズル（気体供給手段）
１０３５　　照射窓
１０３７　　気体バルブ（気体供給手段）
１０３８　　親水性皮膜（皮膜）
１０５２　　開口
１０７１　　窓部材
１０７１Ｂ　外表面（壁面）
１２０１　　基板処理装置（処理液処理装置）
１２１７　　軟Ｘ線照射ユニット（Ｘ線照射手段）
１３０１　　基板処理装置（処理液処理装置）
１３０７　　内槽
１３１７　　軟Ｘ線照射ユニット（Ｘ線照射手段）
１３２１　　開口
１４０１　　基板処理装置（処理液処理装置）
１４０７　　内槽
１４１７　　軟Ｘ線照射ユニット（Ｘ線照射手段）
１４２１　　開口
１４２３　　配管
１６０２　　基板収容器（処理対象物）
　　　Ｃ　　　回転軸線
　　　Ｌ　　　レンズ
　　　Ｗ　　　基板（処理対象物） 1 substrate processing equipment 4 spin chuck (substrate holding and rotating means)
6 Integrated Head 6A Integrated Head 6B Integrated Head 17 Cup (Liquid Receiving Member)
25 Soft X-ray generator (X-ray generator)
26 Cover 27 Gas nozzle (gas supply means)
35 Irradiation window 37 Gas valve (gas supply means)
38 Hydrophilic film (film)
40 Control device (X-ray irradiation control means)
51 1st nozzle piping (treatment liquid piping)
51A 1st nozzle piping (treatment liquid piping)
52 1st opening (opening, X-ray irradiation position)
52A 3rd opening (opening, X-ray irradiation position)
53 Discharge port 56 Electrode 57 Power supply 61 Water nozzle (treatment liquid nozzle)
62 Soft X-ray irradiation unit (X-ray irradiation means)
65 Fiber bundle (fibrous material)
71 Window member 71B outer surface (wall surface on the side where the processing liquid flows in the closed window)
100 Water supply unit (treatment liquid supply device)
101 Liquid detection sensor (treatment liquid detection means)
200 Water supply unit (treatment liquid supply device)
201 Substrate processing apparatus 202A Discharge port 203 Soft X-ray irradiation unit (X-ray irradiation means)
204 Water supply piping (treatment liquid piping)
211 Substrate processing apparatus 216 Discharge port 220 Water supply unit (processing liquid supply apparatus)
221 Substrate processing apparatus 222 First branch pipe (branch pipe)
224A Discharge port (Discharge port for receiving liquid)
230 Water supply unit (treatment liquid supply device)
231 Substrate processing apparatus 232 Second nozzle pipe (second pipe)
250 Water supply unit (treatment liquid supply device)
251 Substrate processing apparatus 260 Water supply unit (processing liquid supply apparatus)
261 Substrate processing apparatus 262 Second nozzle pipe (second pipe)
276 Discharge port 300 Water supply unit (treatment liquid supply device)
301 Substrate processing apparatus 306A Discharge port 307 Water supply piping (processing liquid piping)
309 Soft X-ray irradiation unit (X-ray irradiation means)
310 Water supply unit (treatment liquid supply device)
311 Substrate processing apparatus 312 Second branch pipe (branch pipe)
313A Discharge port (Discharge port for receiving liquid)
400 Water supply unit (treatment liquid supply device)
401 substrate processing apparatus 402 spin chuck (substrate holding and rotating means)
404 Spin axis (support member)
405 Spin base (support member)
409A Discharge port 410 Water supply pipe (treatment liquid pipe)
412 Soft X-ray irradiation unit (X-ray irradiation means)
500 Water supply unit (treatment liquid supply device)
501 Substrate processing apparatus 504 roller transport unit (substrate holding transport means)
531A Discharge port 533 Water supply pipe (treatment liquid pipe)
534 Soft X-ray irradiation unit (X-ray irradiation means)
600 Water supply unit (treatment liquid supply device)
602 Substrate container (container)
701 Substrate processing apparatus 704 Spin chuck (substrate holding means)
705 Water nozzle (water supply means)
706 Soft X-ray irradiation head (X-ray irradiation means)
714 Water valve (water supply means)
719 Oscillation drive mechanism (moving means)
720 Lifting drive mechanism (moving means)
725 X-ray generator 726 Cover 727 Gas nozzle (gas supply means)
728 Opening 735 Irradiation window 737 Gas valve (gas supply means)
738 Polyimide resin film 740 Control device (control means)
744 Heater (heat generating member)
820 Substrate processing apparatus 821 Water nozzle (water supply means)
830 Substrate processing apparatus 833 Water nozzle (water supply means)
834 Soft X-ray irradiation unit (X-ray irradiation means)
840 Substrate processing apparatus 841 Soft X-ray irradiation head (X-ray irradiation means)
842 Shielding member (shielding plate part)
851 DLC film (diamond-like carbon film)
861 Amorphous fluororesin film 1001 Substrate processing apparatus (processing liquid processing apparatus)
1002 Processing tank 1007 Inner tank 1008 Outer tank 1016 Branch piping (processing liquid supply piping)
1017 Soft X-ray irradiation unit (X-ray irradiation means)
1019 Return piping (overflow piping)
1025 Soft X-ray generator (X-ray generator)
1026 cover 1027 gas nozzle (gas supply means)
1035 Irradiation window 1037 Gas valve (gas supply means)
1038 Hydrophilic film (film)
1052 Opening 1071 Window member 1071B Outer surface (wall surface)
1201 Substrate processing apparatus (processing liquid processing apparatus)
1217 Soft X-ray irradiation unit (X-ray irradiation means)
1301 Substrate processing apparatus (processing liquid processing apparatus)
1307 Inner tank 1317 Soft X-ray irradiation unit (X-ray irradiation means)
1321 Opening 1401 Substrate processing apparatus (processing liquid processing apparatus)
1407 Inner tank 1417 Soft X-ray irradiation unit (X-ray irradiation means)
1421 Opening 1423 Piping 1602 Substrate container (object to be processed)
C Rotation axis L Lens W Substrate (object to be processed)

Claims (55)

  1. 　吐出口から処理液を吐出して、この処理液を処理対象物に供給するための処理液供給装置であって、
    　処理液が内部を流通可能な第１配管であって、当該内部が前記吐出口に連通する第１配管と、
    　前記第１配管内に存在する処理液に、Ｘ線を照射するＸ線照射手段とを含む、処理液供給装置。     A processing liquid supply device for discharging a processing liquid from a discharge port and supplying the processing liquid to a processing object,
    A first pipe through which the processing liquid can flow, and the inside communicates with the discharge port;
    A processing liquid supply apparatus, comprising: an X-ray irradiation means for irradiating the processing liquid existing in the first pipe with X-rays.
  2. 　前記第１配管は、その管壁に開口を有し、
    　前記開口は、Ｘ線が透過可能な材料を用いて形成された窓部材にて閉塞されており、
    　前記Ｘ線照射手段は、前記第１配管内に存在している処理液に、前記窓部材を介してＸ線を照射する、請求項１に記載の処理液供給装置。     The first pipe has an opening in the pipe wall;
    The opening is closed by a window member formed using a material capable of transmitting X-rays,
    The processing liquid supply apparatus according to claim 1, wherein the X-ray irradiation unit irradiates the processing liquid present in the first pipe with X-rays through the window member.
  3. 　前記窓部材は、ベリリウムまたはポリイミド樹脂を用いて形成されている、請求項２記載の処理液供給装置。 The processing liquid supply apparatus according to claim 2, wherein the window member is formed using beryllium or polyimide resin.
  4. 　前記窓部材における処理液が存在する側の壁面は、皮膜によりコーティングされている、請求項２または３に記載の処理液供給装置。 The processing liquid supply apparatus according to claim 2 or 3, wherein a wall surface of the window member on the side where the processing liquid exists is coated with a film.
  5. 　前記皮膜は、ポリイミド樹脂、ダイヤモンドライクカーボン、フッ素樹脂および炭化水素樹脂のうちの１つ以上の材質を含む皮膜である、請求項４に記載の処理液供給装置。 The treatment liquid supply apparatus according to claim 4, wherein the film is a film containing one or more materials of polyimide resin, diamond-like carbon, fluorine resin, and hydrocarbon resin.
  6. 　前記Ｘ線照射手段は、前記窓部材に対向して配置される照射窓を有し、Ｘ線を発生するとともに、発生したＸ線を前記照射窓から照射するＸ線発生器を含む、請求項２～５のいずれか一項に記載の処理液供給装置。 The X-ray irradiation means includes an X-ray generator that has an irradiation window disposed to face the window member, generates X-rays, and irradiates the generated X-rays from the irradiation window. The processing liquid supply apparatus according to any one of 2 to 5.
  7. 　前記Ｘ線照射手段は、
    　前記Ｘ線発生器の周囲を、当該Ｘ線発生器と間隔を空けて取り囲むカバーと、
    　前記カバーの内部に気体を供給する気体供給手段とをさらに含む、請求項６に記載の処理液供給装置。     The X-ray irradiation means includes
    A cover surrounding the X-ray generator with a space from the X-ray generator;
    The processing liquid supply apparatus according to claim 6, further comprising a gas supply unit configured to supply a gas to the inside of the cover.
  8. 　前記第１配管は、前記吐出口に向けて処理液が内部を流通する処理液配管を含み、
    　前記Ｘ線照射手段は、前記第１配管内を流通している処理液に前記Ｘ線を照射する、請求項１～７のいずれか一項に記載の処理液供給装置。     The first pipe includes a processing liquid pipe through which a processing liquid flows toward the discharge port,
    The processing liquid supply apparatus according to any one of claims 1 to 7, wherein the X-ray irradiation unit irradiates the processing liquid flowing in the first pipe with the X-ray.
  9. 　前記処理液供給装置は、前記吐出口に向けて処理液が内部を流通する処理液配管をさらに含み、
    　前記第１配管は、前記処理液配管から分岐する分岐配管を含む、請求項１～７のいずれか一項に記載の処理液供給装置。     The processing liquid supply device further includes a processing liquid pipe through which the processing liquid flows toward the discharge port,
    The processing liquid supply apparatus according to any one of claims 1 to 7, wherein the first pipe includes a branch pipe branched from the processing liquid pipe.
  10. 　前記吐出口に配置され、当該吐出口から吐出される処理液が伝って流れる繊維状物質をさらに含む、請求項１～９のいずれか一項に記載の処理液供給装置。 The processing liquid supply apparatus according to any one of claims 1 to 9, further comprising a fibrous substance that is disposed at the discharge port and flows through the processing liquid discharged from the discharge port.
  11. 　前記第１配管における前記Ｘ線の照射位置よりも、処理液流通方向の下流側に配置された電極と、
    　前記電極に対して電圧を印加する電源とをさらに含む、請求項１～１０のいずれか一項に記載の処理液供給装置。     An electrode disposed downstream of the X-ray irradiation position in the first pipe in the treatment liquid flow direction;
    The processing liquid supply apparatus according to any one of claims 1 to 10, further comprising a power source that applies a voltage to the electrodes.
  12. 　前記電極は、前記第１配管の先端部に配置されている、請求項１１に記載の処理液供給装置。 The treatment liquid supply apparatus according to claim 11, wherein the electrode is disposed at a tip portion of the first pipe.
  13. 　前記第１配管において、前記Ｘ線の前記照射位置における処理液の有無を検出するための処理液検出手段と、
    　前記照射位置に処理液が存在するときには、前記Ｘ線照射手段によるＸ線の照射を実行するとともに、前記照射位置に処理液が存在しないときには、前記Ｘ線照射手段によるＸ線の照射を行わないＸ線照射制御手段とをさらに含む、請求項１～１２のいずれか一項に記載の処理液供給装置。     Treatment liquid detection means for detecting the presence or absence of treatment liquid at the irradiation position of the X-ray in the first pipe;
    When the treatment liquid is present at the irradiation position, X-ray irradiation is performed by the X-ray irradiation means, and when the treatment liquid is not present at the irradiation position, X-ray irradiation is not performed by the X-ray irradiation means. The processing liquid supply apparatus according to any one of claims 1 to 12, further comprising X-ray irradiation control means.
  14. 　基板を保持する基板保持手段と、
    　請求項１～１３のいずれか一項に記載の処理液供給装置とを含み、
    　前記吐出口から吐出された処理液を前記基板の主面に供給する、基板処理装置。     Substrate holding means for holding the substrate;
    A treatment liquid supply apparatus according to any one of claims 1 to 13,
    A substrate processing apparatus for supplying a processing liquid discharged from the discharge port to a main surface of the substrate.
  15. 　前記基板保持手段は、基板を水平姿勢に保持しつつ、鉛直な所定の回転軸線周りに回転させる基板保持回転手段を含み、
    　前記基板処理装置は、前記基板保持回転手段の周囲を包囲する筒状の液受け部材をさらに含み、
    　前記処理液供給装置は、前記吐出口に向けて処理液が内部を流通する処理液配管をさらに含み、
    　前記処理液供給装置の前記第１配管は、前記処理液配管から分岐する分岐配管を含み、
    　前記分岐配管は、前記液受け部材に向けて処理液を吐出するための液受け用吐出口を有する、請求項１４に記載の基板処理装置。     The substrate holding means includes a substrate holding and rotating means for rotating around a predetermined vertical rotation axis while holding the substrate in a horizontal posture,
    The substrate processing apparatus further includes a cylindrical liquid receiving member that surrounds the periphery of the substrate holding and rotating means,
    The processing liquid supply device further includes a processing liquid pipe through which the processing liquid flows toward the discharge port,
    The first pipe of the processing liquid supply device includes a branch pipe branched from the processing liquid pipe,
    The substrate processing apparatus according to claim 14, wherein the branch pipe has a liquid receiving discharge port for discharging a processing liquid toward the liquid receiving member.
  16. 　前記基板保持手段は、基板を水平姿勢に保持しつつ、鉛直な所定の回転軸線周りに回転させる基板保持回転手段を含み、
    　前記基板保持回転手段は、前記基板の下面の少なくとも一部と接触して、当該基板を水平姿勢に支持する支持部材を有し、
    　前記支持部材は多孔質材料を用いて形成されており、
    　前記吐出口から吐出された処理液が前記支持部材に供給される、請求項１４または１５に記載の基板処理装置。     The substrate holding means includes a substrate holding and rotating means for rotating around a predetermined vertical rotation axis while holding the substrate in a horizontal posture,
    The substrate holding and rotating means has a support member that contacts at least a part of the lower surface of the substrate and supports the substrate in a horizontal posture.
    The support member is formed using a porous material,
    The substrate processing apparatus according to claim 14, wherein the processing liquid discharged from the discharge port is supplied to the support member.
  17. 　前記基板保持手段は、前記基板を保持しながら、当該基板を所定の搬送方向に向けて搬送する基板保持搬送手段を含む、請求項１４に記載の基板処理装置。 15. The substrate processing apparatus according to claim 14, wherein the substrate holding unit includes a substrate holding and conveying unit that conveys the substrate in a predetermined conveyance direction while holding the substrate.
  18. 　前記基板保持搬送手段は、前記基板を、前記搬送方向に沿い、かつ水平面に対し傾斜する姿勢に保持しつつ搬送する、請求項１７に記載の基板処理装置。 18. The substrate processing apparatus according to claim 17, wherein the substrate holding / conveying means conveys the substrate while holding the substrate in a posture that is inclined with respect to a horizontal plane along the conveyance direction.
  19. 　処理液供給装置の吐出口から処理液を吐出させ、この処理液を処理対象物に供給する処理液供給方法であって、
    　前記吐出口を、前記処理対象物に対向して配置する対向配置工程と、
    　前記吐出口に連通する第１配管の内部に存在する処理液にＸ線を照射する第１Ｘ線照射工程と、
    　前記第１Ｘ線照射工程と並行して、前記吐出口から処理液を吐出させる処理液吐出工程とを含み、
    　前記処理液吐出工程では、前記吐出口と前記処理対象物との間で処理液が液状に繋がっている、処理液供給方法。     A processing liquid supply method for discharging a processing liquid from a discharge port of a processing liquid supply apparatus and supplying the processing liquid to a processing object,
    An opposing arrangement step of arranging the discharge port opposite to the processing object;
    A first X-ray irradiation step of irradiating X-rays to the processing liquid existing inside the first pipe communicating with the discharge port;
    In parallel with the first X-ray irradiation step, a treatment liquid discharge step of discharging a treatment liquid from the discharge port,
    In the processing liquid discharge step, a processing liquid supply method in which the processing liquid is connected in a liquid state between the discharge port and the processing object.
  20. 　前記処理液吐出工程では、前記吐出口から吐出される処理液が、当該吐出口と前記処理対象物との双方に繋がる連続流状をなしている、請求項１９に記載の処理液供給方法。 20. The processing liquid supply method according to claim 19, wherein in the processing liquid discharge step, the processing liquid discharged from the discharge port has a continuous flow shape connected to both the discharge port and the processing object.
  21. 　前記処理対象物は、内部を液が流通する第２配管である、請求項１９または２０に記載の処理液供給方法。 21. The processing liquid supply method according to claim 19 or 20, wherein the processing object is a second pipe through which the liquid flows.
  22. 　前記処理対象物は、物品を収容するための収容器である、請求項１９または２０に記載の処理液供給方法。 21. The processing liquid supply method according to claim 19 or 20, wherein the processing object is a container for storing an article.
  23. 　処理液供給装置の吐出口から吐出される処理液を用いて基板を処理する基板処理方法であって、
    　前記吐出口を、基板保持手段に保持されている基板の主面に対向して配置する対向配置工程と、
    　前記吐出口に連通する第１配管の内部に存在する処理液にＸ線を照射する第１Ｘ線照射工程と、
    　前記第１Ｘ線照射工程と並行して、前記吐出口から処理液を吐出させる処理液吐出工程とを含み、
    　前記処理液吐出工程では、前記吐出口と前記基板の主面との間で処理液が液状に繋がっている、基板処理方法。     A substrate processing method for processing a substrate using a processing liquid discharged from a discharge port of a processing liquid supply apparatus,
    An opposing arrangement step of arranging the discharge port so as to face the main surface of the substrate held by the substrate holding means;
    A first X-ray irradiation step of irradiating X-rays to the processing liquid existing inside the first pipe communicating with the discharge port;
    In parallel with the first X-ray irradiation step, a treatment liquid discharge step of discharging a treatment liquid from the discharge port,
    In the processing liquid discharge step, the processing liquid is connected in a liquid state between the discharge port and the main surface of the substrate.
  24. 　前記処理液吐出工程では、前記吐出口から吐出される処理液が、当該吐出口と前記基板の主面との双方に繋がる連続流状をなしている、請求項２３に記載の基板処理方法。 24. The substrate processing method according to claim 23, wherein in the processing liquid discharge step, the processing liquid discharged from the discharge port has a continuous flow shape connected to both the discharge port and the main surface of the substrate.
  25. 　前記基板は、前記基板保持手段によって水平姿勢に保持されており、
    　前記対向配置工程は、前記吐出口を、前記基板保持手段に保持されている基板の上面に対向するように配置する工程を含む、請求項２３または２４に記載の基板処理方法。     The substrate is held in a horizontal posture by the substrate holding means,
    25. The substrate processing method according to claim 23, wherein the facing arrangement step includes a step of arranging the discharge port so as to face an upper surface of the substrate held by the substrate holding unit.
  26. 　前記基板は、前記基板保持手段によって水平姿勢に保持されており、
    　前記対向配置工程は、前記吐出口を、前記基板保持手段に保持されている基板の下面に対向するように配置する工程を含み、
    　前記基板処理方法は、
    　前記処理液吐出工程に並行して実行され、前記基板を、鉛直な所定の回転軸線まわりに回転させる基板回転工程と、
    　前記処理液吐出工程および前記基板回転工程に並行して、前記基板の上面に処理液を供給する上面処理液供給工程とをさらに含む、請求項２３または２４に記載の基板処理方法。     The substrate is held in a horizontal posture by the substrate holding means,
    The facing arrangement step includes a step of arranging the discharge port so as to face the lower surface of the substrate held by the substrate holding means,
    The substrate processing method includes:
    A substrate rotation step that is performed in parallel with the processing liquid discharge step, and rotates the substrate around a predetermined vertical rotation axis;
    25. The substrate processing method according to claim 23, further comprising an upper surface processing liquid supply step for supplying a processing liquid to the upper surface of the substrate in parallel with the processing liquid discharge step and the substrate rotation step.
  27. 　前記処理液吐出工程の終了後に実行される液切り処理または乾燥処理に並行して実行され、前記基板の主面にＸ線を照射する第２Ｘ線照射工程をさらに含む、請求項２３～２６のいずれか一項に記載の基板処理方法。 27. The second X-ray irradiation step of performing X-ray irradiation on the main surface of the substrate, which is performed in parallel with a liquid draining process or a drying process performed after the processing liquid discharge process is completed. The substrate processing method as described in any one of Claims.
  28. 　基板を保持する基板保持手段と、
    　前記基板保持手段に保持されている基板の表面にＸ線を照射するＸ線照射手段と、
    　前記基板保持手段に保持されている基板の表面に処理液を供給する処理液供給手段と、
    　基板の表面に対する処理液の供給とＸ線の照射とが並行して行われるように、前記Ｘ線
    照射手段および前記処理液供給手段を制御する制御手段とを含む、基板処理装置。     Substrate holding means for holding the substrate;
    X-ray irradiation means for irradiating the surface of the substrate held by the substrate holding means with X-rays;
    Treatment liquid supply means for supplying a treatment liquid to the surface of the substrate held by the substrate holding means;
    A substrate processing apparatus comprising: the X-ray irradiating means and a control means for controlling the processing liquid supplying means so that the supply of the processing liquid to the surface of the substrate and the X-ray irradiation are performed in parallel.
  29. 　前記Ｘ線照射手段は、照射窓を有し、Ｘ線を発生させるとともに、発生したＸ線を前記
    照射窓から照射するＸ線発生器を備えている、請求項２８に記載の基板処理装置。     29. The substrate processing apparatus according to claim 28, wherein the X-ray irradiation unit includes an X-ray generator that includes an irradiation window, generates X-rays, and irradiates the generated X-rays from the irradiation window.
  30. 　前記Ｘ線発生器の周囲を、間隔を空けて取り囲むカバーをさらに含み、
    　前記カバーには、前記照射窓に対向する部分に開口が形成されている、請求項２９に記載の基板処理装置。     A cover surrounding the X-ray generator around the X-ray generator at an interval;
    30. The substrate processing apparatus according to claim 29, wherein the cover is formed with an opening at a portion facing the irradiation window.
  31. 　前記カバーの内部に気体を供給する気体供給手段をさらに含む、請求項３０に記載の基板
    処理装置。     31. The substrate processing apparatus according to claim 30, further comprising gas supply means for supplying a gas into the cover.
  32. 　前記気体供給手段は、常温よりも高温の気体を供給する、請求項３１に記載の基板処理装置。 32. The substrate processing apparatus according to claim 31, wherein the gas supply means supplies a gas having a temperature higher than room temperature.
  33. 　前記照射窓の外表面は、皮膜によりコーティングされている、請求項２９～３２のいずれか一項に記載の基板処理装置。 The substrate processing apparatus according to any one of claims 29 to 32, wherein an outer surface of the irradiation window is coated with a film.
  34. 　前記皮膜は、ポリイミド樹脂の皮膜である、請求項３３に記載の基板処理装置。 The substrate processing apparatus according to claim 33, wherein the coating is a polyimide resin coating.
  35. 　前記皮膜は、ダイヤモンドライクカーボンの皮膜である、請求項３３に記載の基板処理装置。 The substrate processing apparatus according to claim 33, wherein the coating is a diamond-like carbon coating.
  36. 　前記皮膜は、アモルファスフッ素樹脂の皮膜である、請求項３３に記載の基板処理装置。 The substrate processing apparatus according to claim 33, wherein the film is an amorphous fluororesin film.
  37. 　前記カバーにおける前記開口の周囲および前記照射窓の少なくとも一方に、発熱部材が
    配設されている、請求項３０～３６のいずれか一項に記載の基板処理装置。     The substrate processing apparatus according to any one of claims 30 to 36, wherein a heat generating member is disposed around the opening of the cover and at least one of the irradiation window.
  38. 　前記基板保持手段に保持される基板の表面に対向配置され、当該基板の表面上の空間を
    その周囲から遮蔽するための遮蔽部材をさらに含み、
    　前記遮蔽部材は、前記照射窓から照射されたＸ線を当該基板の表面上の空間に留めてお
    くためのものである、請求項２９～３７のいずれか一項に記載の基板処理装置。     A shielding member that is disposed opposite to the surface of the substrate held by the substrate holding means and shields a space on the surface of the substrate from its surroundings;
    The substrate processing apparatus according to any one of claims 29 to 37, wherein the shielding member is for keeping X-rays irradiated from the irradiation window in a space on the surface of the substrate.
  39. 　前記遮蔽部材は、前記カバーと一体移動可能に設けられている、請求項３８に記載の基板処理装置。 The substrate processing apparatus according to claim 38, wherein the shielding member is provided so as to be movable together with the cover.
  40. 　前記Ｘ線照射手段を、前記基板保持手段によって保持された基板の表面に沿って移動さ
    せる移動手段をさらに含む、請求項２８～３９のいずれか一項に記載の基板処理装置。     The substrate processing apparatus according to any one of claims 28 to 39, further comprising moving means for moving the X-ray irradiation means along the surface of the substrate held by the substrate holding means.
  41. 　前記処理液は水である、請求項２８～４０のいずれか一項に記載の基板処理装置。 The substrate processing apparatus according to any one of claims 28 to 40, wherein the processing liquid is water.
  42. 　基板保持手段に保持された基板の表面に処理液を供給する処理液供給工程と、
    　前記処理液供給工程と並行して、前記基板保持手段に保持された基板の表面にＸ線を照
    射するＸ線照射工程とを含む、基板処理方法。     A treatment liquid supply step of supplying a treatment liquid to the surface of the substrate held by the substrate holding means;
    A substrate processing method including an X-ray irradiation step of irradiating the surface of the substrate held by the substrate holding unit with X-rays in parallel with the processing liquid supply step.
  43. 　処理液中に処理対象物を浸漬して処理を行う処理液処理装置であって、
    　処理液を貯留し、その処理液中に処理対象物を浸漬させる処理槽と、
    　前記処理槽に貯留された処理液、または処理液が内部を流通可能な配管であって、当該内部が前記処理槽内に連通する配管内に存在する処理液に、Ｘ線を照射するＸ線照射手段とを含む、処理液処理装置。     A treatment liquid treatment apparatus for performing treatment by immersing a treatment object in a treatment liquid,
    A treatment tank for storing the treatment liquid and immersing the treatment object in the treatment liquid;
    X-rays that irradiate the processing liquid stored in the processing tank or the processing liquid existing inside the pipe that allows the processing liquid to flow through the processing tank and that communicates with the processing tank. A treatment liquid treatment apparatus including irradiation means.
  44. 　前記配管の管壁または前記処理槽の壁は、開口を有し、
    　前記開口は、Ｘ線が透過可能な材料を用いて形成された窓部材にて閉塞されており、
    　前記Ｘ線照射手段は、前記窓部材を介してＸ線を照射する、請求項４３に記載の処理液処理装置。     The pipe wall of the pipe or the wall of the treatment tank has an opening,
    The opening is closed by a window member formed using a material capable of transmitting X-rays,
    44. The processing liquid processing apparatus according to claim 43, wherein the X-ray irradiation means irradiates X-rays through the window member.
  45. 　前記窓部材は、ベリリウムまたはポリイミド樹脂を用いて形成されている、請求項４４記載の処理液処理装置。 45. The processing solution processing apparatus according to claim 44, wherein the window member is formed using beryllium or polyimide resin.
  46. 　前記窓部材における処理液が存在する側の壁面は、皮膜によりコーティングされている、請求項４４または４５に記載の処理液処理装置。 The processing liquid processing apparatus according to claim 44 or 45, wherein a wall surface of the window member on the side where the processing liquid exists is coated with a film.
  47. 　前記皮膜は、ポリイミド樹脂、ダイヤモンドライクカーボン、フッ素樹脂および炭化水素樹脂のうちの１つ以上の材質を含む皮膜である、請求項４６に記載の処理液処理装置。 The processing solution treatment apparatus according to claim 46, wherein the coating is a coating containing one or more materials of polyimide resin, diamond-like carbon, fluorine resin, and hydrocarbon resin.
  48. 　前記Ｘ線照射手段は、前記窓部材に対向して配置される照射窓を有し、Ｘ線を発生するとともに、発生したＸ線を前記照射窓から照射するＸ線発生器を含む、請求項４４～４７のいずれか一項に記載の処理液処理装置。 The X-ray irradiation means includes an X-ray generator that has an irradiation window disposed to face the window member, generates X-rays, and irradiates the generated X-rays from the irradiation window. The processing liquid processing apparatus according to any one of 44 to 47.
  49. 　前記Ｘ線照射手段は、
    　前記Ｘ線発生器の周囲を、当該Ｘ線発生器と間隔を空けて取り囲むカバーと、
    　前記カバーの内部に気体を供給する気体供給手段とをさらに含む、請求項４８に記載の処理液処理装置。     The X-ray irradiation means includes
    A cover surrounding the X-ray generator with a space from the X-ray generator;
    49. The processing liquid processing apparatus according to claim 48, further comprising gas supply means for supplying a gas into the cover.
  50. 　前記配管は、前記処理槽内と連通し、前記処理槽内に処理液を供給するための処理液供給配管を含み、
    　前記Ｘ線照射手段は、前記処理液供給配管を流通している処理液に前記Ｘ線を照射する、請求項４３～４９のいずれか一項に記載の処理液処理装置。     The pipe communicates with the inside of the processing tank, and includes a processing liquid supply pipe for supplying a processing liquid into the processing tank,
    The processing liquid processing apparatus according to any one of claims 43 to 49, wherein the X-ray irradiation unit irradiates the processing liquid flowing through the processing liquid supply pipe with the X-ray.
  51. 　前記処理槽は、処理液を貯留し、その処理液中に処理対象物を浸漬させる内槽と、 前記内槽から溢れる処理液を回収する外槽とを含み、
    　前記配管は、前記外槽に回収された処理液が流通するオーバーフロー配管を含み、
    　前記Ｘ線照射手段は、前記オーバーフロー配管内を流通している処理液に前記Ｘ線を照射する、請求項４３～４９のいずれか一項に記載の処理液処理装置。     The processing tank includes an inner tank that stores the processing liquid and immerses the processing object in the processing liquid, and an outer tank that recovers the processing liquid overflowing from the inner tank,
    The pipe includes an overflow pipe through which the processing liquid collected in the outer tank flows.
    The processing liquid processing apparatus according to any one of claims 43 to 49, wherein the X-ray irradiation unit irradiates the processing liquid flowing in the overflow pipe with the X-ray.
  52. 　前記処理槽は、処理液を貯留し、その処理液中に処理対象物を浸漬させる内槽と、 前記内槽から溢れる処理液を回収する外槽とを含み、
    　前記Ｘ線照射手段は、前記内槽に貯留されている処理液に前記Ｘ線を照射する、請求項４３～４９のいずれか一項に記載の処理液処理装置。     The processing tank includes an inner tank that stores the processing liquid and immerses the processing object in the processing liquid, and an outer tank that recovers the processing liquid overflowing from the inner tank,
    The processing liquid processing apparatus according to any one of claims 43 to 49, wherein the X-ray irradiation unit irradiates the processing liquid stored in the inner tank with the X-rays.
  53. 　前記処理槽は、処理液を貯留し、その処理液中に処理対象物を浸漬させる内槽と、 前記内槽から溢れる処理液を回収する外槽とを含み、
    　前記配管は、前記内槽内に内部が連通する配管を含む、請求項４３～４９のいずれか一項に記載の処理液処理装置。     The processing tank includes an inner tank that stores the processing liquid and immerses the processing object in the processing liquid, and an outer tank that recovers the processing liquid overflowing from the inner tank,
    The processing liquid processing apparatus according to any one of claims 43 to 49, wherein the pipe includes a pipe that communicates with the inside of the inner tank.
  54. 　処理槽に貯留された処理液中に処理対象物を浸漬させる処理対象物浸漬工程と、
    　前記処理対象物浸漬工程に並行して、前記処理槽に貯留された処理液、または処理液が内部を流通可能な配管であって、当該内部が前記処理槽内に連通する配管内に存在する処理液に、Ｘ線を照射するＸ線照射工程とを含む、処理液処理方法。     A treatment object immersion step of immersing the treatment object in the treatment liquid stored in the treatment tank;
    In parallel with the treatment object immersion step, the treatment liquid stored in the treatment tank, or a pipe through which the treatment liquid can flow, is present in the pipe communicating with the treatment tank. A treatment liquid treatment method comprising: an X-ray irradiation step of irradiating the treatment liquid with X-rays.
  55. 　処理槽に貯留された処理液中に処理対象物を浸漬させる処理対象物浸漬工程と、
    　前記処理対象物浸漬工程に並行して、前記処理槽内に向けて吐出口から処理液を吐出させる処理液吐出工程と、
    　前記処理液吐出工程に並行して、前記吐出口に連通する配管の内部に存在する処理液にＸ線を照射するＸ線照射工程とを含み、
    　前記処理液吐出工程では、前記吐出口と前記処理槽に溜められている処理液の液面との間で処理液が液状に繋がっている、処理液処理方法。     A treatment object immersion step of immersing the treatment object in the treatment liquid stored in the treatment tank;
    In parallel with the treatment object immersion step, a treatment liquid discharge step for discharging treatment liquid from a discharge port toward the treatment tank,
    In parallel with the processing liquid discharge step, an X-ray irradiation step of irradiating the processing liquid existing inside the pipe communicating with the discharge port with X-rays,
    In the processing liquid discharge step, the processing liquid processing method, wherein the processing liquid is connected in a liquid state between the discharge port and the liquid level of the processing liquid stored in the processing tank.
PCT/JP2013/076006 2012-09-27 2013-09-26 Processing fluid supply device, substrate processing device, processing fluid supply method, substrate processing method, processing fluid processing device, and processing fluid processing method WO2014050941A1 (en)

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