WO2023047724A1 - Substrate processing method, substrate processing apparatus, and processing liquid - Google Patents

Substrate processing method, substrate processing apparatus, and processing liquid Download PDF

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Publication number
WO2023047724A1
WO2023047724A1 PCT/JP2022/024527 JP2022024527W WO2023047724A1 WO 2023047724 A1 WO2023047724 A1 WO 2023047724A1 JP 2022024527 W JP2022024527 W JP 2022024527W WO 2023047724 A1 WO2023047724 A1 WO 2023047724A1
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Prior art keywords
substrate
liquid
processing
supply
solvent
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PCT/JP2022/024527
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French (fr)
Japanese (ja)
Inventor
洋祐 塙
悠太 佐々木
省吾 國枝
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
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Publication of WO2023047724A1 publication Critical patent/WO2023047724A1/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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid.
  • Substrates include, for example, semiconductor wafers, liquid crystal display substrates, organic EL (Electroluminescence) substrates, FPD (Flat Panel Display) substrates, optical display substrates, magnetic disk substrates, optical disk substrates, magneto-optical disk substrates, They are substrates for photomasks and substrates for solar cells.
  • Patent Document 1 discloses a substrate processing method for drying a substrate.
  • the substrate processing method of Patent Document 1 includes a processing liquid supply step, a solidified film forming step, and a sublimation step.
  • the process liquid supply step the process liquid is supplied to the substrate.
  • the processing liquid contains a solvent and a sublimable substance.
  • the sublimable substance is cyclohexanone oxime.
  • the solvent evaporates and a solidified film is formed on the substrate.
  • the solidified film contains cyclohexanone oxime.
  • the sublimation process the solidified film is sublimated.
  • the solidified film changes to gas without going through liquid. According to the substrate processing method of Patent Document 1, the substrate can be dried appropriately.
  • the pattern formed on the substrate may collapse.
  • the conventional substrate processing method may not be able to sufficiently suppress the collapse of the pattern.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid capable of properly drying a substrate.
  • the present invention has the following configuration. That is, the present invention provides a substrate processing method for processing a substrate on which a pattern is formed, comprising: a processing liquid supply step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate; and a sublimation step of sublimating the solidified film, wherein the sublimable substance is 4-nitrotoluene.
  • a substrate processing method for processing a substrate on which a pattern is formed, comprising: a processing liquid supply step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate; and a sublimation step of sublimating the solidified film, wherein the sublimable substance is 4-nitrotoluene.
  • the substrate processing method is for processing a patterned substrate.
  • the substrate processing method includes a processing liquid supply step, a solidified film forming step, and a sublimation step.
  • the processing liquid is supplied to the substrate.
  • the treatment liquid contains a sublimable substance and a solvent.
  • the solvent evaporates from the processing liquid on the substrate.
  • a solidified film is formed on the substrate.
  • the solidified film contains a sublimable substance.
  • the solidified film is sublimated. Sublimation of the solidified film dries the substrate.
  • the sublimable substance is 4-nitrotoluene. That is, the treatment liquid contains 4-nitrotoluene and a solvent. Therefore, the solidified film contains 4-nitrotoluene.
  • the substrate is thus properly dried. Specifically, the substrate is dried while the pattern formed on the substrate is favorably protected.
  • the substrate is properly dried.
  • the solvent is preferably isopropyl alcohol.
  • Isopropyl alcohol preferably dissolves 4-nitrotoluene. Furthermore, isopropyl alcohol evaporates more easily than 4-nitrotoluene. The substrate is thus dried better.
  • the present invention is a substrate processing apparatus comprising: a substrate holding section for holding a substrate; and a processing liquid supply section for supplying a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding section. , the substrate processing apparatus, wherein the sublimable substance is 4-nitrotoluene.
  • the substrate processing apparatus includes a substrate holding section and a processing liquid supply section.
  • the substrate holding part holds the substrate.
  • the processing liquid supply section supplies the processing liquid to the substrate held by the substrate holding section.
  • the treatment liquid contains a sublimable substance and a solvent.
  • the sublimable substance is 4-nitrotoluene. Therefore, when the processing liquid is supplied to the substrate, the solvent preferably evaporates from the processing liquid on the substrate. Therefore, the solidified film is preferably formed on the substrate.
  • the solidified film contains 4-nitrotoluene. Therefore, the solidified film is appropriately sublimated. Sublimation of the solidified film properly dries the substrate. As described above, according to the present substrate processing apparatus, the substrate is properly dried.
  • the solvent is preferably isopropyl alcohol.
  • Isopropyl alcohol preferably dissolves 4-nitrotoluene. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. The substrate is thus dried better.
  • the present invention provides a processing liquid used for drying a substrate on which a pattern is formed, wherein the processing liquid contains a sublimation substance and a solvent, and the sublimation substance is 4-nitrotoluene. is.
  • the processing liquid is used for drying the patterned substrate.
  • the treatment liquid is specifically a drying auxiliary liquid.
  • the treatment liquid contains a sublimable substance and a solvent.
  • the sublimable substance is 4-nitrotoluene. Therefore, the processing liquid is useful for drying the substrate. Specifically, by using the treatment liquid, the substrate is dried while the pattern formed on the substrate is favorably protected. As described above, the substrate is properly dried using the treatment liquid.
  • the solvent is preferably isopropyl alcohol.
  • Isopropyl alcohol preferably dissolves 4-nitrotoluene. Furthermore, isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the processing liquid is more useful for drying the substrate. With the processing liquid the substrate is dried better.
  • the substrate is properly dried.
  • FIG. 10 is a diagram schematically showing the substrate in the treatment liquid supply step;
  • FIG. 4 is a diagram schematically showing a substrate in a solidified film forming step;
  • FIG. 4 is a diagram schematically showing a substrate in a solidified film forming step;
  • It is a figure which shows typically the board
  • It is a figure which shows typically the board
  • the substrate W is, for example, a semiconductor wafer, a liquid crystal display substrate, an organic EL (Electroluminescence) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, or a magneto-optical disk substrate. , photomask substrates, and solar cell substrates.
  • the substrate W has a thin flat plate shape.
  • the substrate W has a substantially circular shape in plan view.
  • FIG. 1 is a diagram schematically showing part of the substrate W.
  • the substrate W has a pattern P.
  • a pattern P is formed on the surface of the substrate W. As shown in FIG.
  • the pattern P has, for example, an uneven shape.
  • the pattern P has a convex portion W1 and a concave portion A, for example.
  • the protrusion W1 is part of the substrate W. As shown in FIG.
  • the protrusion W1 is a structure.
  • the protrusion W1 is composed of, for example, at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN) and a polysilicon film.
  • the protrusion W1 protrudes upward from the surface of the substrate W, for example.
  • the concave portion A is laterally adjacent to the convex portion W1.
  • the recess A is a space.
  • the recess A is, for example, open upward.
  • the protrusion W1 corresponds to a wall that partitions the recess A. As shown in FIG.
  • Processing liquid (Drying Auxiliary Liquid)>
  • processing liquid has a function of assisting the substrate W to be dried.
  • the processing liquid can be rephrased as a drying auxiliary liquid.
  • the treatment liquid contains a sublimable substance.
  • a sublimable substance has a sublimation property. "Sublimation” is the property of an element, compound or mixture to undergo a phase transition from solid to gas or from gas to solid without going through a liquid.
  • Sublimable substances include 4-nitrotoluene.
  • Sublimable substances include, for example, only 4-nitrotoluene.
  • 4-Nitrotoluene is represented by the following chemical formula (1).
  • the treatment liquid contains a solvent.
  • the solvent dissolves the sublimable substance.
  • the sublimable substance in the treatment liquid is dissolved in the solvent. That is, the treatment liquid contains a solvent and a sublimable substance dissolved in the solvent.
  • the sublimable substance corresponds to the solute of the treatment liquid.
  • the solvent has a relatively high vapor pressure at room temperature.
  • the vapor pressure of the solvent at normal temperature is preferably higher than the vapor pressure of the sublimable substance at normal temperature.
  • room temperature includes room temperature.
  • Normal temperature is, for example, a temperature within the range of 5° C. or higher and 35° C. or lower. Normal temperature is, for example, a temperature within the range of 10° C. or higher and 30° C. or lower. Normal temperature is, for example, a temperature within the range of 20° C. or higher and 25° C. or lower.
  • the volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid.
  • the volume ratio RV of the treatment liquid is preferably 1 [Vol %] or more and 20 [Vol %] or less.
  • the volume ratio RV of the treatment liquid is the ratio of the volume of the sublimable substance contained in the treatment liquid to the volume of the solvent contained in the treatment liquid.
  • the solvent is, for example, an organic solvent.
  • Solvents are, for example, alcohols.
  • the solvent includes, for example, isopropyl alcohol (IPA).
  • Solvents include, for example, isopropyl alcohol (IPA) only.
  • the vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of 4-nitrotoluene at room temperature.
  • the treatment liquid for example, consists only of a sublimable substance and a solvent.
  • the treatment liquid consists of, for example, 4-nitrotoluene and isopropyl alcohol.
  • FIG. 2 is a plan view showing the inside of the substrate processing apparatus 1 of the embodiment.
  • the substrate processing apparatus 1 processes a substrate W. As shown in FIG.
  • the processing in the substrate processing apparatus 1 includes drying processing.
  • the substrate processing apparatus 1 includes an indexer section 3 and a processing block 7.
  • a processing block 7 is connected to the indexer section 3 .
  • the indexer unit 3 supplies substrates W to the processing block 7 .
  • the processing block 7 performs processing on the substrate W.
  • FIG. The indexer section 3 retrieves the substrates W from the processing block 7 .
  • the direction in which the indexer unit 3 and the processing blocks 7 are arranged is called the "front-back direction X".
  • the front-rear direction X is horizontal.
  • the direction from the processing block 7 to the indexer unit 3 is called “forward”.
  • the direction opposite to forward is called “backward”.
  • a horizontal direction orthogonal to the front-rear direction X is called a “width direction Y”.
  • One direction of the "width direction Y" is appropriately called “right side”.
  • the direction opposite to right is called “left”.
  • a direction perpendicular to the horizontal direction is called a “vertical direction Z”.
  • front, rear, right, left, top, and bottom are indicated as appropriate for reference.
  • the indexer section 3 includes a plurality of (for example, four) carrier placement sections 4 .
  • Each carrier mounting portion 4 mounts one carrier C thereon.
  • a carrier C accommodates a plurality of substrates W.
  • Carrier C is, for example, FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), or OC (Open Cassette).
  • the indexer section 3 has a transport mechanism 5 .
  • the transport mechanism 5 is arranged behind the carrier placement section 4 .
  • the transport mechanism 5 transports the substrate W. As shown in FIG.
  • the transport mechanism 5 can access the carrier C placed on the carrier placement section 4 .
  • the transport mechanism 5 includes a hand 5a and a hand driving section 5b.
  • the hand 5a supports the substrate W.
  • the hand driving section 5b is connected to the hand 5a.
  • the hand driving section 5b moves the hand 5a.
  • the hand drive unit 5b moves the hand 5a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example.
  • the hand drive unit 5b rotates the hand 5a in a horizontal plane, for example.
  • the processing block 7 has a transport mechanism 8 .
  • the transport mechanism 8 transports the substrate W. As shown in FIG.
  • the transport mechanism 8 and the transport mechanism 5 can transfer substrates W to each other.
  • the transport mechanism 8 includes a hand 8a and a hand driving section 8b.
  • the hand 8a supports the substrate W.
  • the hand driving section 8b is connected to the hand 8a.
  • the hand driving section 8b moves the hand 8a.
  • the hand drive unit 8b moves the hand 8a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example.
  • the hand driving section 8b rotates the hand 8a in a horizontal plane, for example.
  • the processing block 7 includes a plurality of processing units 11.
  • the processing unit 11 is arranged on the side of the transport mechanism 8 .
  • Each processing unit 11 processes the substrate W.
  • the processing unit 11 includes a substrate holding section 13 .
  • the substrate holding part 13 holds the substrate W. As shown in FIG.
  • the transport mechanism 8 can access each processing unit 11 .
  • the transport mechanism 8 can transfer the substrate W to the substrate holder 13 .
  • the transport mechanism 8 can take the substrate W from the substrate holder 13 .
  • FIG. 3 is a control block diagram of the substrate processing apparatus 1.
  • the substrate processing apparatus 1 includes a control section 10 .
  • the controller 10 can communicate with the transport mechanisms 5 and 8 and the processing unit 11 .
  • the controller 10 controls the transport mechanisms 5 and 8 and the processing unit 11 .
  • the control unit 10 is realized by a central processing unit (CPU) that executes various processes, a RAM (Random-Access Memory) that serves as a work area for arithmetic processing, a storage medium such as a fixed disk, and the like.
  • the control unit 10 has various types of information stored in advance in a storage medium.
  • Information held by the control unit 10 is, for example, transport condition information for controlling the transport mechanisms 5 and 8 .
  • the information held by the control unit 10 is, for example, processing condition information for controlling the processing unit 11 . Processing condition information is also called a processing recipe.
  • the indexer section 3 supplies substrates W to the processing block 7 .
  • the transport mechanism 5 transfers the substrate W from the carrier C to the transport mechanism 8 of the processing block 7 .
  • the transport mechanism 8 distributes the substrates W to the processing units 11 . Specifically, the transport mechanism 8 transports the substrate W from the transport mechanism 5 to the substrate holder 13 of each processing unit 11 .
  • the processing unit 11 processes the substrate W held by the substrate holding section 13 .
  • the processing unit 11 performs a drying process on the substrate W, for example.
  • the transport mechanism 8 recovers the substrate W from each processing unit 11 . Specifically, the transport mechanism 8 receives the substrate W from each substrate holder 13 . Then, the transport mechanism 8 transfers the substrate W to the transport mechanism 5 .
  • the indexer section 3 recovers the substrates W from the processing block 7 .
  • the transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C. As shown in FIG.
  • FIG. 4 is a diagram showing the configuration of the processing unit 11. As shown in FIG. Each processing unit 11 has the same structure. The processing unit 11 is classified as a single wafer type. That is, each processing unit 11 processes only one substrate W at a time.
  • the processing unit 11 has a housing 12 .
  • the housing 12 has a substantially box shape.
  • the substrate W is processed inside the enclosure 12 .
  • the inside of the housing 12 is kept at room temperature.
  • the temperature of the gas inside the housing 12 is kept at room temperature. Therefore, the substrate W is processed under a room temperature environment.
  • the inside of the housing 12 is kept at normal pressure.
  • the gas pressure inside the housing 12 is kept at normal pressure. Therefore, the substrate W is processed under an environment of normal pressure.
  • normal pressure includes standard atmospheric pressure (1 atm, 101325 Pa). Normal pressure is, for example, an atmospheric pressure in the range of 0.7 atmospheres or more and 1.3 atmospheres or less. Pressure values are given herein in absolute pressure relative to absolute vacuum.
  • the substrate holding part 13 described above is installed inside the housing 12 .
  • the substrate holding part 13 holds one substrate W. As shown in FIG.
  • the substrate holding part 13 holds the substrate W in a substantially horizontal posture.
  • the substrate holding part 13 is positioned below the substrate W held by the substrate holding part 13 .
  • the substrate holding part 13 contacts at least one of the bottom surface of the substrate W and the peripheral edge of the substrate W. As shown in FIG.
  • the bottom surface of the substrate W is also called the backside of the substrate W. As shown in FIG.
  • the substrate holding part 13 does not contact the upper surface of the substrate W. As shown in FIG.
  • the processing unit 11 includes a rotation drive section 14 . At least part of the rotation drive unit 14 is installed inside the housing 12 .
  • the rotation driving section 14 is connected to the substrate holding section 13 .
  • the rotation driving section 14 rotates the substrate holding section 13 .
  • the substrate W held by the substrate holding portion 13 rotates together with the substrate holding portion 13 .
  • the substrate W held by the substrate holding part 13 rotates around the rotation axis B. As shown in FIG.
  • the rotation axis B extends in the vertical direction Z through the center of the substrate W, for example.
  • the processing unit 11 includes a supply section 15 .
  • the supply unit 15 supplies liquid or gas to the substrate W held by the substrate holding unit 13 .
  • the supply unit 15 supplies liquid or gas to the upper surface of the substrate W held by the substrate holding unit 13 .
  • the supply unit 15 includes a first supply unit 15a, a second supply unit 15b, a third supply unit 15c, a fourth supply unit 15d, and a fifth supply unit 15e.
  • the first supply unit 15a supplies the processing liquid.
  • the second supply unit 15b supplies the chemical solution.
  • the third supply part 15c supplies the rinse liquid.
  • the fourth supply part 15d supplies the replacement liquid.
  • the fifth supply unit 15e supplies dry gas.
  • the first supply section 15a is an example of a processing liquid supply section in the present invention.
  • the inside of the housing 12 is at normal temperature and normal pressure. Therefore, the treatment liquid is used under normal temperature environment.
  • the processing liquid is used under normal pressure environment.
  • the chemical liquid supplied by the second supply unit 15b is, for example, an etchant.
  • the etchant contains, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).
  • the rinse liquid supplied by the third supply unit 15c is, for example, deionized water (DIW).
  • DIW deionized water
  • the replacement liquid supplied by the fourth supply unit 15d is, for example, an organic solvent.
  • the replacement liquid is, for example, isopropyl alcohol (IPA).
  • the dry gas supplied by the fifth supply unit 15e is, for example, at least one of air and inert gas.
  • Air is, for example, compressed air.
  • An inert gas is, for example, nitrogen gas.
  • the dry gas has a dew point below ambient temperature.
  • the first supply unit 15a includes a nozzle 16a.
  • the second-fifth feeders 15b-15e are provided with nozzles 16b-16e, respectively.
  • Nozzles 16 a - 16 e are each located inside housing 12 .
  • the nozzle 16a ejects the processing liquid.
  • the nozzle 16b ejects the chemical liquid.
  • the nozzle 16c ejects the rinse liquid.
  • the nozzle 16d ejects the replacement liquid.
  • the nozzle 16e ejects dry gas.
  • the first supply unit 15a includes a pipe 17a and a valve 18a.
  • the pipe 17a is connected to the nozzle 16a.
  • the valve 18a is provided on the pipe 17a.
  • the second through fifth feeds 15b-15e are provided with pipes 17b-17e and valves 18b-18e, respectively.
  • Pipes 17b-17e are connected to nozzles 16b-16e, respectively.
  • Valves 18b-18e are provided on lines 17b-17e, respectively. Valves 18b-18e control the discharge of chemical liquid, rinse liquid, replacement liquid and dry gas, respectively.
  • At least part of the pipe 17 a may be provided outside the housing 12 .
  • Lines 17b-17e may also be arranged similarly to line 17a.
  • the valve 18 a may be provided outside the housing 12 .
  • Valves 18b-18e may also be arranged similarly to valve 18a.
  • the substrate processing apparatus 1 includes a first supply source 19a.
  • the first supply source 19a is connected to the first supply section 15a.
  • the first supply source 19a communicates with the first supply section 15a.
  • the first supply source 19a is connected to, for example, a pipe 17a.
  • the first supply source 19a sends the treatment liquid to the first supply section 15a.
  • the second supply unit 15b is connected to the second supply source 19b.
  • the second supply part 15b communicates with the second supply source 19b.
  • the second supply source 19b is connected to, for example, a pipe 17b.
  • the second supply source 19b sends the chemical solution to the second supply section 15b.
  • the third-fifth supplies 15c-15e are connected to the third-fifth supply sources 19c-19e, respectively.
  • the third-fifth supply parts 15c-15e respectively communicate with the third-fifth supply sources 19c-19e.
  • the third-fifth sources 19c-19e are connected, for example, to pipes 17c-17e, respectively.
  • the third supply source 19c sends the rinse liquid to the third supply section 15c.
  • the fourth supply source 19d sends the replacement liquid to the fourth supply section 15d.
  • the fifth supply source 19e delivers dry gas to the fifth supply section 15e.
  • the first supply source 19 a is provided outside the housing 12 .
  • the second through fifth sources 19b-19e are provided outside the enclosure 12, respectively.
  • the first supply source 19a may supply the processing liquid to a plurality of processing units 11. Alternatively, the first supply source 19 a may supply the processing liquid to only one processing unit 11 . The same is true for the second to fifth supply sources 19b-19e.
  • the second supply source 19b may be an element of the substrate processing apparatus 1.
  • the second supply source 19b may be a chemical bath included in the substrate processing apparatus 1.
  • the second supply source 19b may not be a component of the substrate processing apparatus 1.
  • the second supply source 19b may be utility equipment installed outside the substrate processing apparatus 1 .
  • each of the third-fifth sources 19c-19e may be elements of the substrate processing apparatus 1.
  • the third-fifth sources 19c-19e, respectively, may not be elements of the substrate processing apparatus 1.
  • the processing unit 11 may further include a cup (not shown).
  • the cup is installed inside the housing 12 .
  • the cup is arranged around the substrate holder 13 .
  • the cup receives the liquid scattered from the substrate W held by the substrate holding part 13 .
  • the control section 10 controls the rotation driving section 14 .
  • the control section 10 controls the supply section 15 .
  • the controller 10 controls the valves 18a-18e.
  • first supply source 19a ⁇ 5. Configuration of first supply source 19a> Please refer to FIG.
  • the first supply source 19a also produces a processing liquid.
  • the first supply source 19a is divided into a generating unit 21 and a pumping unit 31 .
  • the generation unit 21 generates a treatment liquid.
  • the pumping unit 31 sends the treatment liquid to the first supply section 15a.
  • the generation unit 21 includes a tank 22 and supply units 23a and 23b.
  • the supply unit 23 a supplies the sublimable substance to the tank 22 .
  • the supply unit 23b supplies the solvent to the tank 22. As shown in FIG.
  • the sublimable substance and solvent are mixed in vessel 22 .
  • the sublimable substance and solvent become the treatment liquid g in the tank 22 .
  • the tank 22 is installed under a normal temperature environment.
  • the bath 22 is installed under a normal pressure environment. Therefore, the processing liquid g is generated under a normal temperature environment.
  • the treatment liquid g is generated under normal pressure environment.
  • the generation unit 21 stores the treatment liquid g. Specifically, the treatment liquid g is stored in the tank 22 .
  • the treatment liquid g is stored under normal temperature environment.
  • the treatment liquid g is stored under a normal pressure environment.
  • the supply unit 23a includes, for example, a pipe 24a and a valve 25a.
  • the pipe 24 a is connected to the tank 22 .
  • the pipe 24 a communicates with the tank 22 .
  • the valve 25a is provided on the pipe 24a.
  • the supply portion 23a supplies the sublimable substance to the bath 22 when the valve 25a is opened. When the valve 25a is closed, the supply portion 23a does not supply the sublimable substance to the tank 22.
  • the supply section 23b comprises a pipe 24b and a valve 25b.
  • the pipe 24 b is connected to the tank 22 .
  • the pipe 24 b communicates with the bath 22 .
  • the valve 25b is provided on the pipe 24b. Valve 25b controls the supply of solvent to bath 22 .
  • the amount of sublimable substance in the bath 22 is controlled by the valve 25a.
  • the amount of solvent in bath 22 is controlled by valve 25b. Therefore, the volume ratio RV of the processing liquid g in the tank 22 is controlled by valves 25a and 25b.
  • Each of the valves 25a, 25b may include, for example, a flow control valve.
  • Valves 25a, 25b may each include, for example, a flow control valve and an on-off valve.
  • the supply unit 23a is connected to the supply source 26a.
  • the supply part 23a communicates with the supply source 26a.
  • source 26a is connected to pipe 24a.
  • the supply source 26a sends the sublimable substance to the supply section 23a.
  • supply 23b is connected to supply 26b.
  • the supply part 23b communicates with the supply source 26b.
  • source 26b is connected to pipe 24b.
  • Source 26b delivers solvent to supply 23b.
  • the pumping unit 31 includes a pipe 32 and a joint 33.
  • a pipe 32 is connected to the tank 22 .
  • the pipe 32 communicates with the bath 22 .
  • the joint 33 is connected to the pipe 32 .
  • the joint 33 is further connected to the pipe 17a.
  • the pipe 32 is connected to the pipe 17 a by a joint 33 .
  • the pipe 32 communicates with the pipe 17 a through a joint 33 . Therefore, the tank 22 is connected to the first supply section 15a via a pipe 32 and a joint 33. As shown in FIG.
  • the tank 22 communicates with the first supply section 15 a via a pipe 32 and a joint 33 .
  • a tank 22 is connected to the nozzle 16a.
  • the tank 22 communicates with the nozzle 16a.
  • the pumping unit 31 further includes a pump 34 and a filter 35.
  • a pump 34 is provided in the pipe 32 . When the pump 34 operates, the pump 34 sends the treatment liquid g from the bath 22 to the first supply section 15a. When the pump 34 operates, the pump 34 pumps the processing liquid g from the tank 22 to the first supply section 15a. When the pump 34 stops operating, the pump 34 does not send the treatment liquid g from the tank 22 to the first supply section 15a. When the pump 34 stops operating, the pump 34 does not force-feed the treatment liquid g from the tank 22 to the first supply section 15a.
  • a filter 35 is provided in the pipe 32 . The processing liquid g passes through the filter 35 . The filter 35 filters the processing liquid g. The filter 35 removes foreign matter from the processing liquid g.
  • the control unit 10 can communicate with the first supply source 19a.
  • the control unit 10 controls the first supply source 19a.
  • the control section 10 controls the generation unit 21 .
  • the control unit 10 controls the supply units 23a and 23b.
  • the control unit 10 controls the valves 25a and 25b.
  • the control section 10 controls the pumping unit 31 .
  • the controller 10 controls the pump 34 .
  • the control unit 10 has treatment liquid condition information for controlling the first supply source 19a.
  • the treatment liquid condition information includes, for example, a target value regarding the volume ratio RV of the treatment liquid g.
  • the processing liquid condition information is pre-stored in the storage medium of the control unit 10 .
  • FIG. 5 is a flow chart showing the procedure of the substrate processing method of the embodiment.
  • the substrate processing method includes step S1 and steps S11-S18.
  • Step S1 is performed by the first source 19a.
  • Steps S 11 -S 18 are substantially performed by processing unit 11 .
  • Step S1 is executed in parallel with steps S11-S18.
  • the first supply source 19 a and the processing unit 11 operate under the control of the control section 10 .
  • Step S1 Treatment Liquid Generation Step
  • the treatment liquid g is generated.
  • the generation unit 21 generates the treatment liquid g.
  • the supply unit 23 a supplies the sublimable substance to the tank 22 .
  • the supply unit 23b supplies the solvent to the tank 22.
  • a treatment liquid g is produced in the tank 22 .
  • the treatment liquid g is stored in the bath 22 .
  • the control unit 10 controls the valves 25a and 25b. Thereby, the control unit 10 adjusts the volume ratio RV of the treatment liquid g in the tank 22 to the target value defined by the treatment liquid condition information.
  • Step S11 Rotation Start Step
  • the substrate holder 13 holds the substrate W. As shown in FIG. The substrate W is held in a substantially horizontal posture.
  • the rotation driving section 14 rotates the substrate holding section 13 . As a result, the substrate W held by the substrate holding part 13 starts rotating.
  • steps S12-S17 which will be described later, the substrate W continues to rotate, for example.
  • Step S12 Chemical Solution Supplying Process Chemical solution is supplied to the substrate W in the chemical solution supplying process.
  • the second supply unit 15b supplies the chemical solution to the substrate W held by the substrate holding unit 13. Specifically, valve 18b opens. The nozzle 16b ejects the chemical liquid. A chemical solution is supplied to the upper surface of the substrate W. As shown in FIG. The chemical etches the substrate W, for example. For example, the chemical removes the native oxide film from the substrate W. FIG.
  • the second supply unit 15b stops supplying the chemical solution to the substrate W. Specifically, the valve 18b is closed. The nozzle 16b stops discharging the chemical liquid.
  • Step S13 Rinse liquid supply step In the rinse liquid supply step, the substrate W is supplied with the rinse liquid.
  • the third supply unit 15c supplies the rinse liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18c is opened. The nozzle 16c ejects the rinse liquid. A rinse liquid is supplied to the upper surface of the substrate W. As shown in FIG. For example, the rinse liquid cleans the substrate W. FIG. For example, the rinse removes chemicals from the substrate W. FIG.
  • the third supply unit 15c stops supplying the rinse liquid to the substrate W. Specifically, the valve 18c is closed. The nozzle 16c stops discharging the rinse liquid.
  • Step S14 Substitute liquid supply step A substitute liquid is supplied to the substrate W in the substitute liquid supply step.
  • the fourth supply unit 15d supplies the replacement liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18d is opened. The nozzle 16d ejects the replacement liquid. A replacement liquid is supplied to the upper surface of the substrate W. As shown in FIG. The replacement liquid removes the rinse liquid from the substrate W. FIG. The rinsing liquid on the substrate W is replaced with the replacement liquid.
  • the fourth supply unit 15d stops supplying the replacement liquid to the substrate W. Specifically, the valve 18d is closed. The nozzle 16d stops discharging the replacement liquid.
  • Step S15 Processing Liquid Supplying Process
  • the processing liquid g is supplied to the substrate W. As shown in FIG.
  • the pumping unit 31 supplies the treatment liquid g to the first supply section 15a.
  • the first supply unit 15 a supplies the processing liquid g to the substrate W held by the substrate holding unit 13 .
  • the pump 34 sends the treatment liquid g from the tank 22 to the first supply section 15a.
  • the pump 34 pumps the treatment liquid g from the tank 22 to the first supply section 15a.
  • Valve 18a opens.
  • the nozzle 16a ejects the treatment liquid g.
  • the processing liquid g is supplied to the upper surface of the substrate W. As shown in FIG.
  • the processing liquid g removes the replacement liquid from the substrate W.
  • FIG. The replacement liquid on the substrate W is replaced with the processing liquid g.
  • the pumping unit 31 stops supplying the treatment liquid g to the first supply unit 15a.
  • the first supply unit 15a stops supplying the processing liquid g to the substrate W.
  • the pump 34 is stopped.
  • Valve 18a is closed.
  • the nozzle 16a stops ejecting the treatment liquid g.
  • FIG. 6 is a diagram schematically showing the substrate W in the process of supplying the processing liquid.
  • the pattern P is positioned on the upper surface of the substrate W when the substrate W is held by the substrate holding unit 13 .
  • the pattern P faces upward.
  • the processing liquid g on the substrate W forms a liquid film G.
  • a liquid film G is located on the substrate W. As shown in FIG. The liquid film G is in contact with the substrate W. As shown in FIG. A liquid film G covers the substrate W. FIG. The liquid film G covers the upper surface of the substrate W. As shown in FIG.
  • the entire pattern P is immersed in the liquid film G. All of the protrusions W1 are immersed in the liquid film G.
  • the recess A is filled with the liquid film G. All of the recesses A are filled with the liquid film G only.
  • the liquid film G has an upper surface G1.
  • the upper surface G1 is positioned higher than the entire pattern P. As shown in FIG. The upper surface G1 does not intersect the pattern P.
  • the upper surface G1 is positioned higher than all of the protrusions W1.
  • the upper surface G1 does not intersect with the protrusion W1.
  • the replacement liquid has already been removed from the substrate W by the processing liquid g. Therefore, the replacement liquid does not exist on the substrate W.
  • FIG. The replacement liquid does not remain in the recess A.
  • the gas J exists above the liquid film G.
  • the pattern P does not come into contact with the gas J.
  • the pattern P is not exposed to the gas J.
  • the convex portion W1 does not come into contact with the gas J.
  • the convex portion W1 is not exposed to the gas J.
  • the gas J is in contact with the liquid film G.
  • the gas J is in contact with the upper surface G1.
  • the upper surface G1 corresponds to the gas-liquid interface between the liquid film G and the gas J.
  • FIG. Therefore, the pattern P does not intersect the gas-liquid interface between the liquid film G and the gas J.
  • the convex portion W1 does not intersect the gas-liquid interface between the liquid film G and the gas J.
  • the height position of the upper surface G1 may be further adjusted.
  • the height position of the upper surface G1 may be adjusted while the nozzle 16a supplies the processing liquid g to the substrate W.
  • FIG. the height position of the upper surface G1 may be adjusted after the nozzle 16a stops supplying the treatment liquid g.
  • the height position of the upper surface G1 may be adjusted.
  • the rotation time of the substrate W the height position of the upper surface G1 may be adjusted.
  • adjusting the height position of the upper surface G1 corresponds to adjusting the thickness H of the liquid film G.
  • the thickness H of the liquid film G is, for example, the distance in the vertical direction Z between the lower end W1a of the protrusion W1 and the upper surface G1.
  • Step S16 Solidified Film Forming Step
  • the solvent evaporates from the processing liquid g on the substrate W.
  • FIG. A solidified film is formed on the substrate W in the solidified film forming step.
  • the solidified film contains a sublimable substance.
  • FIG. 7 is a diagram schematically showing the substrate W in the solidified film forming step.
  • solvents have relatively high vapor pressures. At normal temperature, the solvent has a higher vapor pressure than the sublimable substance. Therefore, the solvent smoothly evaporates from the processing liquid g on the substrate W.
  • FIG. The solvent smoothly changes from liquid to gas.
  • the solvent leaves from the processing liquid g on the substrate W when the solvent evaporates from the processing liquid g on the substrate W.
  • the amount of solvent contained in the liquid film G decreases.
  • the volume ratio RV of the liquid film G increases.
  • the sublimable substance in the liquid film G begins to precipitate on the substrate W. That is, the sublimable substance changes from the solute of the treatment liquid g to a solid-phase sublimable substance.
  • a solid-phase sublimable substance forms a solidified film K.
  • FIG. The solidified film K does not contain solvent.
  • the solidified film K is solid.
  • a solidified film K is formed on the substrate W. As shown in FIG.
  • the liquid film G gradually decreases due to the evaporation of the solvent and the precipitation of sublimable substances.
  • the liquid film G gradually transforms into a solidified film K by the deposition of the sublimable substance.
  • the solidified film K gradually increases due to the deposition of the sublimable substance.
  • the upper part of the liquid film G turns into a solidified film K.
  • the solidified film K is positioned above the liquid film G. As shown in FIG.
  • the solidified film K covers the upper surface G1 of the liquid film G. As shown in FIG.
  • the solidified film K covers the entire upper surface G1
  • the solidified film K separates the liquid film G from the gas J.
  • the liquid film G is in contact with the solidified film K.
  • the gas J is in contact with the solidified film K.
  • the liquid film G does not come into contact with the gas J.
  • the upper surface G1 does not come into contact with the gas J.
  • the gas-liquid interface between the liquid film G and the gas J disappears.
  • the pattern P does not cross the gas-liquid interface.
  • the liquid film G exerts no significant force on the pattern P.
  • the convex portion W1 does not cross the gas-liquid interface.
  • the liquid film G does not exert a significant force on the protrusion W1.
  • the height position of the upper surface G1 gradually decreases.
  • the thickness H of the liquid film G gradually decreases.
  • the liquid film G is reduced without exerting a significant force on the convex portion W1.
  • the solvent leaves the substrate W without the solvent exerting any significant force on the protrusions W1.
  • FIG. 8 is a diagram schematically showing the substrate W in the solidified film forming step.
  • FIG. 8 for example, schematically shows the substrate W at the end of the solidified film forming process. Only the solidified film K exists on the substrate W.
  • FIG. The entire liquid film G disappears from the substrate W at the end of the solidified film forming process.
  • the liquid film G does not remain in the recess A. All of the solvent disappears from the substrate W.
  • the solvent does not remain in the recesses A either.
  • the recess A is filled with the solidified film K. All of the recesses A are filled with the solidified film K only.
  • the pattern P is in contact with the solidified film K. As shown in FIG.
  • the solidified film K supports the pattern P.
  • the solidified film K protects the pattern P. For example, the solidified film K prevents the pattern P from collapsing.
  • the convex portion W1 is in contact with the solidified film K. As shown in FIG.
  • the solidified film K supports the protrusion W1.
  • the solidified film K protects the protrusion W1. For example, the solidified film K prevents the protrusion W1 from collapsing.
  • Step S17 Sublimation Process In the sublimation process, the solidified film K is sublimated.
  • the fifth supply unit 15e supplies dry gas to the substrate W held by the substrate holding unit 13. Specifically, valve 18e is opened. The nozzle 16e ejects dry gas. The nozzle 16e blows off the dry gas onto the substrate W. As shown in FIG. A drying gas is supplied to the top surface of the substrate W. As shown in FIG. A dry gas is supplied to the solidified film K. As shown in FIG. The solidified film K is exposed to dry gas. Thereby, the solidified film K is sublimated. The solidified film K changes to gas without passing through liquid. The solidified film K is removed from the substrate W by the sublimation of the solidified film K. As shown in FIG.
  • the fifth supply unit 15e stops supplying the dry gas to the solidified film K. Specifically, valve 18e is closed. The nozzle 16e stops blowing dry gas.
  • FIG. 9 is a diagram schematically showing the substrate W in the sublimation process. As the solidified film K sublimates, the solidified film K gradually decreases. As the solidified film K sublimates, the solidified film K gradually becomes thinner.
  • the pattern P begins to be exposed to the gas J.
  • the protrusion W1 begins to be exposed to the gas J.
  • the solidified film K When the solidified film K sublimates, the solidified film K does not change into a liquid. Therefore, no liquid exists on the substrate W in the sublimation process. No liquid exists in the recess A in the sublimation process. A gas-liquid interface does not occur near the pattern P in the sublimation process.
  • the pattern P does not cross the gas-liquid interface.
  • the solidified film K does not exert a significant force on the pattern P.
  • the solidified film K leaves the substrate W without the solidified film K exerting any significant force on the pattern P.
  • the convex portion W1 does not cross the gas-liquid interface.
  • the solidified film K does not exert a significant force on the protrusion W1.
  • the solidified film K leaves the substrate W without the solidified film K exerting a significant force on the protrusions W1.
  • FIG. 10 is a diagram schematically showing the substrate W in the sublimation process.
  • FIG. 10 schematically shows the substrate W, for example, at the end of the sublimation process. All of the solidified film K disappears from the substrate W at the end of the sublimation process. No liquid is present on the substrate W. All of the pattern P is exposed to the gas J. All of the protrusions W1 are exposed to the gas J. All of the recesses A are filled with gas J only. The substrate W is dried.
  • the processes in the above-described treatment liquid supply process, solidified film formation process, and sublimation process are examples of the drying process.
  • the treatments in the treatment liquid supply step, the solidified film formation step, and the sublimation step described above correspond to examples of using the treatment liquid g.
  • the treatment liquid g is used under normal temperature environment.
  • the treatment liquid g is used under normal pressure environment.
  • Step S ⁇ b>18 Rotation Stopping Step
  • the rotation driving section 14 stops the rotation of the substrate holding section 13 .
  • the substrate W held by the substrate holding part 13 stops rotating.
  • the substrate W is stationary.
  • the processing unit 11 finishes processing the substrate W.
  • the substrate W undergoes a series of processes including a chemical liquid supply process, a rinse liquid supply process, a replacement liquid supply process, a treatment liquid supply process, a solidified film formation process, and a sublimation process.
  • the chemical solution used in the chemical solution supply step is hydrofluoric acid.
  • Hydrofluoric acid is a mixture of hydrogen fluoride and water.
  • the rinse liquid used in the rinse liquid supply process is deionized water (DIW).
  • the replacement liquid used in the replacement liquid supply process is isopropyl alcohol.
  • the processing liquid g used in the processing liquid supply process consists of a sublimable substance and a solvent.
  • the sublimable substance is 4-nitrotoluene.
  • the solvent is isopropyl alcohol (IPA).
  • the volume ratio RV of the treatment liquid g is 2.5 [Vol %].
  • the substrate W is rotated at a rotation speed of 1500 rpm.
  • dry gas is supplied to the substrate W while rotating the substrate W at a rotation speed of 1500 rpm.
  • the sublimable substance is cyclohexanone oxime.
  • Other conditions are the same in the comparative example as in the experimental example.
  • the average collapse rate Fa is the average value of a plurality of local collapse rates Fi.
  • Each local collapse rate Fi is a collapse rate in a local area Pi.
  • i is any natural number from 1 to N.
  • N is the number of local areas Pi.
  • Each local area Pi is a minute region of the substrate W. As shown in FIG.
  • Each local area Pi is magnified 50,000 times, for example, by a scanning electron microscope.
  • the observer observes the pattern P (convex portion W1) in each local area Pi.
  • the observer evaluates the convex portion W1 in each local area Pi one by one.
  • the observer judges the convex portion W1 in each local area Pi one by one. Specifically, the observer determines whether or not each convex portion W1 has collapsed.
  • the observer counts the number Ei of evaluated protrusions W1 in each local area Pi.
  • the observer counts the number Ei of the determined convex portions W1 in each local area Pi.
  • the observer counts the number ei of collapsed protrusions W1 in each local area Pi.
  • the number ei is less than or equal to the number Ei.
  • the local collapse rate Fi is the ratio of the number ei to the number Ei.
  • the average collapse rate Fa is a value obtained by dividing the sum of the local collapse rates Fi in each local area Pi by the number N of local areas Pi.
  • the average collapse rate Fa was 2.70%. In the comparative example, the average collapse rate Fa was 4.45%. The average collapse rate Fa in the experimental example was lower than the average collapse rate Fa in the comparative example. In the experimental example, the pattern P on the substrate W is less likely to collapse than in the comparative example.
  • the pattern P formed on the substrate W was protected more appropriately than in the comparative example. That is, in the experimental example, the substrate W was dried more appropriately than in the comparative example.
  • a substrate processing method is for processing a substrate W on which a pattern P is formed.
  • the substrate processing method includes a processing liquid supply step, a solidified film forming step, and a sublimation step.
  • the processing liquid g is supplied to the substrate W in the processing liquid supply step.
  • the treatment liquid g contains a sublimable substance and a solvent.
  • the solvent evaporates from the processing liquid g on the substrate W in the solidified film forming step.
  • a solidified film K is formed on the substrate W in the solidified film forming step.
  • the solidified film K contains a sublimable substance. In the sublimation process, the solidified film K is sublimated.
  • the substrate W is dried by sublimation of the solidified film.
  • the sublimable substance is 4-nitrotoluene. That is, the treatment liquid g contains 4-nitrotoluene and a solvent. Therefore, the solidified film K contains 4-nitrotoluene.
  • the substrate W is thus properly dried. Specifically, the substrate W is dried while the pattern P formed on the substrate W is suitably protected.
  • the solvent is isopropyl alcohol.
  • Isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, it is easy to use the treatment liquid g containing 4-nitrotoluene as a sublimable substance.
  • the processing liquid g containing 4-nitrotoluene is appropriately supplied to the substrate W. As shown in FIG.
  • Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, isopropyl alcohol is preferably evaporated from the processing liquid g on the substrate W in the solidified film forming step. Therefore, the solidified film K is preferably formed on the substrate W in the solidified film forming step. The substrate W is thus dried better.
  • the substrate processing method includes a processing liquid generation step.
  • the treatment liquid generating step the treatment liquid g is generated. Therefore, the processing liquid g is preferably prepared.
  • isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, in the treatment liquid generating step, the treatment liquid g containing 4-nitrotoluene is preferably generated.
  • isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, the treatment liquid g containing 4-nitrotoluene is preferably stored.
  • the substrate processing apparatus 1 includes a substrate holding section 13 and a first supply section 15a.
  • the substrate holding part 13 holds the substrate W.
  • the processing liquid supply part 15 a supplies the processing liquid g to the substrate W held by the substrate holding part 13 .
  • the treatment liquid g contains a sublimable substance and a solvent.
  • the sublimable substance is 4-nitrotoluene. Therefore, when the processing liquid g is supplied to the substrate W, the solvent is preferably evaporated from the processing liquid g on the substrate W.
  • FIG. Therefore, the solidified film K is preferably formed on the substrate W.
  • the solidified film K contains 4-nitrotoluene. Therefore, the solidified film K is appropriately sublimated. Sublimation of the solidified film K properly dries the substrate W. As described above, according to the substrate processing apparatus 1, the substrate W is properly dried.
  • the solvent is isopropyl alcohol.
  • isopropyl alcohol preferably dissolves 4-nitrotoluene.
  • Isopropyl alcohol evaporates more easily than 4-nitrotoluene. The substrate W is thus dried better.
  • the processing liquid g is used for drying the substrate W on which the pattern P is formed.
  • the treatment liquid g is specifically a drying auxiliary liquid.
  • the treatment liquid g contains a sublimable substance and a solvent.
  • the sublimable substance is 4-nitrotoluene. Therefore, the processing liquid g is useful for drying the substrate W.
  • FIG. Specifically, by using the treatment liquid g, the substrate W is dried while the pattern P formed on the substrate W is suitably protected. As described above, the substrate W is properly dried using the treatment liquid g.
  • the solvent is isopropyl alcohol.
  • isopropyl alcohol preferably dissolves 4-nitrotoluene. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the processing liquid g is more useful for drying the substrate W. FIG. Using the treatment liquid g, the substrate W is more properly dried.
  • isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, the treatment liquid g containing 4-nitrotoluene can be easily handled. For example, it is easy to prepare a treatment liquid g containing 4-nitrotoluene. For example, it is easy to generate a treatment liquid g containing 4-nitrotoluene. For example, it is easy to store the treatment liquid g containing 4-nitrotoluene. For example, it is easy to use a treatment liquid g containing 4-nitrotoluene.
  • the processing liquid g is generated before the processing liquid g is supplied to the first supply section 15a.
  • the first source 19a produced processing liquid in vessel 22 .
  • the treatment liquid g may be generated when the treatment liquid g is supplied to the first supply section 15a.
  • the first supply source 19a may generate the treatment liquid g in a channel that supplies the treatment liquid g to the first supply section 15a.
  • FIG. 11 is a diagram showing the configuration of the processing unit 11 and the first supply source 19a of the modified embodiment.
  • detailed description is abbreviate
  • the first supply source 19a includes a first tank 41 and a second tank 42.
  • the first tank 41 stores a sublimable substance.
  • the first tank 41 may store the solvent together with the sublimable substance.
  • the second tank 42 stores the solvent.
  • the second tank 42 stores only the solvent.
  • the first supply source 19 a includes a mixing section 44 .
  • the mixing section 44 is connected to the first tank 41 and the second tank 42 .
  • the mixing section 44 communicates with the first tank 41 and the second tank 42 .
  • the mixing section 44 generates the treatment liquid g.
  • the mixing section 44 is connected to the first supply section 15a.
  • the mixing section 44 communicates with the first supply section 15a.
  • the mixing section 44 supplies the treatment liquid g to the first supply section 15a.
  • the mixing section 44 includes pipes 45 a and 45 b and a joint 46 .
  • the pipe 45 a is connected to the first tank 41 .
  • the pipe 45 a communicates with the first tank 41 .
  • the pipe 45 b is connected to the second tank 42 .
  • the pipe 45b communicates with the second tank 42 .
  • the joint 46 is connected to the pipes 45a and 45b.
  • the joint 46 communicates with the pipes 45a and 45b.
  • the joint 46 is further connected to the pipe 17a.
  • the joint 46 also communicates with the pipe 17a.
  • the pipes 45a and 45b are connected to the pipe 17a via a joint 46. As shown in FIG.
  • the pipes 45 a and 45 b communicate with the pipe 17 a via a joint 46 .
  • the mixing section 44 includes pumps 47a and 47b. Pumps 47a and 47b are provided in pipes 45a and 45b, respectively.
  • the pump 47a sends the sublimable substance from the first tank 41 to the joint 46 through the pipe 45a.
  • Pump 47b sends the solvent from second tank 42 to joint 46 through pipe 45b.
  • the mixing section 44 includes filters 48a and 48b. Filters 48a and 48b are provided in pipes 45a and 45b, respectively. Sublimable substances pass through the filter 48a. The filter 48a filters sublimable substances. Solvent passes through filter 48b. Filter 48b filters the solvent.
  • the mixing section 44 includes valves 49a and 49b.
  • Valves 49a and 49b are provided in pipes 45a and 45b, respectively.
  • the valve 49a adjusts the flow rate of the sublimable substance flowing through the pipe 45a.
  • the valve 49b adjusts the flow rate of solvent flowing through the pipe 45b.
  • Valves 49a, 49b may each include, for example, a flow control valve.
  • Valves 49a, 49b may each include, for example, a flow control valve and an on-off valve.
  • the first supply source 19a In the process liquid supply step, the first supply source 19a generates the process liquid g and sends the process liquid g to the first supply section 15a. Specifically, the valves 49a, 49b are opened. A pump 47 a sends the sublimable substance from the first tank 41 to the joint 46 . The pump 47 a pumps the sublimable substance from the first tank 41 to the joint 46 . A pump 47 b sends solvent from the second tank 42 to the joint 46 . A pump 47 b pumps the solvent from the second tank 42 to the joint 46 . The sublimable substance and solvent are mixed at joint 46 . The sublimable substance and the solvent become the treatment liquid g at the joint 46 . Further, the processing liquid g flows from the joint 46 to the first supply section 15a. The nozzle 16a ejects the treatment liquid g.
  • the volume ratio RV of the processing liquid is controlled with high accuracy. The substrate W is thus more properly dried.
  • the first supply source 19a does not include the tank 22. Therefore, the structure of the first supply source 19a is preferably simplified.
  • the first supply source 19a is preferably miniaturized.
  • the substrate processing method of the embodiment includes a chemical liquid supply process, a rinse liquid supply process, and a replacement liquid supply process.
  • a chemical liquid supply process at least one of the chemical liquid supply process, the rinse liquid supply process, and the replacement liquid supply process may be omitted.
  • the chemical liquid supply process, the rinse liquid supply process, and the replacement liquid supply process may all be omitted.
  • the liquid for example, replacement liquid
  • the process liquid g was supplied to the substrate W in an undried state.
  • the liquid (for example, replacement liquid) does not have to be present on the substrate W when performing the process liquid supply step.
  • the process liquid g may be supplied to the substrate W in a dry state.
  • the processing liquid g removes the substitution liquid from the substrate W.
  • the processing liquid g may wash the substrate W in the processing liquid supply step.
  • the processing liquid g may remove foreign matter adhering to the substrate W.
  • the processing liquid g may dissolve foreign substances adhering to the substrate W.
  • FIG. Foreign matter is, for example, resist residue.
  • Dry gas was not supplied to the substrate W in the solidified film forming process of the embodiment.
  • a dry gas may be supplied to the substrate W in the solidified film forming step.
  • Dry gas may be supplied to the processing liquid g on the substrate W in the solidified film forming step.
  • the processing liquid g on the substrate W is exposed to the dry gas in the solidified film forming step. Therefore, the solvent is efficiently evaporated from the processing liquid g on the substrate W in the solidified film forming step.
  • the solidified film K is efficiently formed on the substrate W in the solidified film forming step.
  • the pattern P on the substrate W may be formed on the substrate W before the processing unit 11 processes the substrate W, for example.
  • the pattern P may be formed on the substrate W when the processing unit 11 processes the substrate W.
  • FIG. The pattern P may be formed on the substrate W, for example, in the chemical supply step (step S12).

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Abstract

The present invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid. This substrate processing method comprises a processing liquid supply step, a solidified film formation step and a sublimation step. In the processing liquid supply step, a processing liquid is supplied to a substrate. The processing liquid contains a sublimable substance and a solvent. In the solidified film formation step, the solvent is evaporated from the processing liquid on the substrate. In the solidified film formation step, a solidified film is formed on the substrate. The solidified film contains the sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by means of the sublimation of the solidified film. Meanwhile, the sublimable substance is 4-nitrotoluene.

Description

基板処理方法と基板処理装置と処理液SUBSTRATE PROCESSING METHOD, SUBSTRATE PROCESSING APPARATUS, AND PROCESSING LIQUID
　本発明は、基板処理方法と基板処理装置と処理液に関する。基板は、例えば、半導体ウエハ、液晶ディスプレイ用基板、有機ＥＬ(Electroluminescence)用基板、ＦＰＤ(Flat Panel Display)用基板、光ディスプレイ用基板、磁気ディスク用基板、光ディスク用基板、光磁気ディスク用基板、フォトマスク用基板、太陽電池用基板である。 The present invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid. Substrates include, for example, semiconductor wafers, liquid crystal display substrates, organic EL (Electroluminescence) substrates, FPD (Flat Panel Display) substrates, optical display substrates, magnetic disk substrates, optical disk substrates, magneto-optical disk substrates, They are substrates for photomasks and substrates for solar cells.
　特許文献１は、基板を乾燥する基板処理方法を開示する。具体的には、特許文献１の基板処理方法は、処理液供給工程と、固化膜形成工程と、昇華工程を備える。処理液供給工程では、処理液は基板に供給される。処理液は、溶媒と昇華性物質を含む。昇華性物質は、シクロヘキサノンオキシムである。固化膜形成工程では、溶媒は蒸発し、固化膜が基板上に形成される。固化膜は、シクロヘキサノンオキシムを含む。昇華工程では、固化膜は昇華する。固化膜は、液体を経ずに、気体に変化する。特許文献１の基板処理方法によれば、基板を適切に乾燥できる。 Patent Document 1 discloses a substrate processing method for drying a substrate. Specifically, the substrate processing method of Patent Document 1 includes a processing liquid supply step, a solidified film forming step, and a sublimation step. In the process liquid supply step, the process liquid is supplied to the substrate. The processing liquid contains a solvent and a sublimable substance. The sublimable substance is cyclohexanone oxime. In the solidified film forming step, the solvent evaporates and a solidified film is formed on the substrate. The solidified film contains cyclohexanone oxime. In the sublimation process, the solidified film is sublimated. The solidified film changes to gas without going through liquid. According to the substrate processing method of Patent Document 1, the substrate can be dried appropriately.
特開２０２１－９９８８公報Japanese Patent Application Laid-Open No. 2021-9988
　従来の基板処理方法であっても、基板を適切に乾燥できない場合があった。例えば、従来の基板処理方法であっても、基板に形成されるパターンが倒壊する場合があった。例えば、パターンが微細であるとき、従来の基板処理方法はパターンの倒壊を十分に抑制できない場合があった。 Even with the conventional substrate processing method, there were cases where the substrate could not be properly dried. For example, even with the conventional substrate processing method, the pattern formed on the substrate may collapse. For example, when the pattern is fine, the conventional substrate processing method may not be able to sufficiently suppress the collapse of the pattern.
　本発明は、このような事情に鑑みてなされたものであって、基板を適切に乾燥できる基板処理方法と基板処理装置と処理液を提供することを目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid capable of properly drying a substrate.
　本発明は、このような目的を達成するために、次のような構成をとる。すなわち、本発明は、パターンが形成された基板を処理する基板処理方法であって、昇華性物質と溶媒を含む処理液を基板に供給する処理液供給工程と、基板上の前記処理液から前記溶媒を蒸発させて、前記昇華性物質を含む固化膜を基板上に形成する固化膜形成工程と、前記固化膜を昇華させる昇華工程と、を備え、前記昇華性物質は、４－ニトロトルエンである基板処理方法である。 In order to achieve this purpose, the present invention has the following configuration. That is, the present invention provides a substrate processing method for processing a substrate on which a pattern is formed, comprising: a processing liquid supply step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate; and a sublimation step of sublimating the solidified film, wherein the sublimable substance is 4-nitrotoluene. A substrate processing method.
　基板処理方法は、パターンが形成された基板を処理するためのものである。基板処理方法は、処理液供給工程と固化膜形成工程と昇華工程を備える。処理液供給工程では、処理液が基板に供給される。処理液は、昇華性物質と溶媒を含む。固化膜形成工程では、溶媒は基板上の処理液から蒸発する。固化膜形成工程では、固化膜が基板上に形成される。固化膜は、昇華性物質を含む。昇華工程では、固化膜は昇華する。固化膜の昇華により、基板は乾燥される。ここで、昇華性物質は、４－ニトロトルエンである。すなわち、処理液は、４－ニトロトルエンと溶媒を含む。このため、固化膜は４－ニトロトルエンを含む。よって、基板は適切に乾燥される。具体的には、基板に形成されるパターンは好適に保護されつつ、基板は乾燥される。 The substrate processing method is for processing a patterned substrate. The substrate processing method includes a processing liquid supply step, a solidified film forming step, and a sublimation step. In the processing liquid supply step, the processing liquid is supplied to the substrate. The treatment liquid contains a sublimable substance and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. In the sublimation process, the solidified film is sublimated. Sublimation of the solidified film dries the substrate. Here, the sublimable substance is 4-nitrotoluene. That is, the treatment liquid contains 4-nitrotoluene and a solvent. Therefore, the solidified film contains 4-nitrotoluene. The substrate is thus properly dried. Specifically, the substrate is dried while the pattern formed on the substrate is favorably protected.
　以上の通り、本基板処理方法によれば、基板は適切に乾燥される。 As described above, according to this substrate processing method, the substrate is properly dried.
　上述の基板処理方法において、前記溶媒は、イソプロピルアルコールであることが好ましい。イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。さらに、イソプロピルアルコールは、４－ニトロトルエンよりも容易に蒸発する。したがって、基板は、一層適切に乾燥される。 In the substrate processing method described above, the solvent is preferably isopropyl alcohol. Isopropyl alcohol preferably dissolves 4-nitrotoluene. Furthermore, isopropyl alcohol evaporates more easily than 4-nitrotoluene. The substrate is thus dried better.
　本発明は、基板処理装置であって、基板を保持する基板保持部と、前記基板保持部によって保持される基板に昇華性物質と溶媒を含む処理液を供給する処理液供給部と、を備え、前記昇華性物質は、４－ニトロトルエンである基板処理装置である。 The present invention is a substrate processing apparatus comprising: a substrate holding section for holding a substrate; and a processing liquid supply section for supplying a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding section. , the substrate processing apparatus, wherein the sublimable substance is 4-nitrotoluene.
　基板処理装置は、基板保持部と処理液供給部を備える。基板保持部は、基板を保持する。処理液供給部は、基板保持部によって保持される基板に処理液を供給する。処理液は、昇華性物質と溶媒を含む。昇華性物質は、４－ニトロトルエンである。このため、処理液が基板に供給されたとき、溶媒は基板上の処理液から好適に蒸発する。よって、固化膜は基板上に好適に形成される。固化膜は、４－ニトロトルエンを含む。よって、固化膜は、適切に昇華する。固化膜の昇華により、基板は適切に乾燥される。以上の通り、本基板処理装置によれば、基板は適切に乾燥される。 The substrate processing apparatus includes a substrate holding section and a processing liquid supply section. The substrate holding part holds the substrate. The processing liquid supply section supplies the processing liquid to the substrate held by the substrate holding section. The treatment liquid contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, when the processing liquid is supplied to the substrate, the solvent preferably evaporates from the processing liquid on the substrate. Therefore, the solidified film is preferably formed on the substrate. The solidified film contains 4-nitrotoluene. Therefore, the solidified film is appropriately sublimated. Sublimation of the solidified film properly dries the substrate. As described above, according to the present substrate processing apparatus, the substrate is properly dried.
　上述の基板処理装置において、前記溶媒は、イソプロピルアルコールであることが好ましい。イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。イソプロピルアルコールは、４－ニトロトルエンよりも容易に蒸発する。したがって、基板は、一層適切に乾燥される。 In the substrate processing apparatus described above, the solvent is preferably isopropyl alcohol. Isopropyl alcohol preferably dissolves 4-nitrotoluene. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. The substrate is thus dried better.
　本発明は、パターンが形成された基板の乾燥に用いられる処理液であって、前記処理液は、昇華性物質と、溶媒と、を含み、前記昇華性物質は、４－ニトロトルエンである処理液である。 The present invention provides a processing liquid used for drying a substrate on which a pattern is formed, wherein the processing liquid contains a sublimation substance and a solvent, and the sublimation substance is 4-nitrotoluene. is.
　処理液は、パターンが形成された基板の乾燥に用いられる。処理液は、具体的には、乾燥補助液である。処理液は、昇華性物質と溶媒を含む。昇華性物質は、４－ニトロトルエンである。このため、処理液は、基板を乾燥させるために、有用である。具体的には、処理液を用いることによって、基板に形成されるパターンは好適に保護されつつ、基板は乾燥される。以上の通り、処理液を用いて、基板は適切に乾燥される。 The processing liquid is used for drying the patterned substrate. The treatment liquid is specifically a drying auxiliary liquid. The treatment liquid contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, the processing liquid is useful for drying the substrate. Specifically, by using the treatment liquid, the substrate is dried while the pattern formed on the substrate is favorably protected. As described above, the substrate is properly dried using the treatment liquid.
　上述の処理液において、前記溶媒は、イソプロピルアルコールであることが好ましい。イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。さらに、イソプロピルアルコールは、４－ニトロトルエンよりも容易に蒸発する。このため、処理液は、基板を乾燥させるために、一層有用である。処理液を用いて、基板は一層適切に乾燥される。 In the treatment liquid described above, the solvent is preferably isopropyl alcohol. Isopropyl alcohol preferably dissolves 4-nitrotoluene. Furthermore, isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the processing liquid is more useful for drying the substrate. With the processing liquid the substrate is dried better.
　本発明の基板処理方法と基板処理装置と処理液によれば、基板は適切に乾燥される。 According to the substrate processing method, substrate processing apparatus, and processing liquid of the present invention, the substrate is properly dried.
基板の一部を模式的に示す図である。It is a figure which shows a part of board|substrate typically. 実施形態の基板処理装置の内部を示す平面図である。It is a top view which shows the inside of the substrate processing apparatus of embodiment. 基板処理装置の制御ブロック図である。It is a control block diagram of a substrate processing apparatus. 処理ユニットおよび第１供給源の構成を示す図である。It is a figure which shows the structure of a processing unit and a 1st supply source. 実施形態の基板処理方法の手順を示すフローチャートである。It is a flow chart which shows the procedure of the substrate processing method of an embodiment. 処理液供給工程における基板を模式的に示す図である。FIG. 10 is a diagram schematically showing the substrate in the treatment liquid supply step; 固化膜形成工程における基板を模式的に示す図である。FIG. 4 is a diagram schematically showing a substrate in a solidified film forming step; 固化膜形成工程における基板を模式的に示す図である。FIG. 4 is a diagram schematically showing a substrate in a solidified film forming step; 昇華工程における基板を模式的に示す図である。It is a figure which shows typically the board|substrate in a sublimation process. 昇華工程における基板を模式的に示す図である。It is a figure which shows typically the board|substrate in a sublimation process. 変形実施形態の処理ユニットおよび第１供給源の構成を示す図である。It is a figure which shows the structure of the processing unit of deformation|transformation embodiment, and a 1st supply source.
　以下、図面を参照して、本発明の基板処理方法と基板処理装置と処理液を説明する。 The substrate processing method, substrate processing apparatus, and processing solution of the present invention will be described below with reference to the drawings.
　＜１．基板＞
　基板Ｗは、例えば、半導体ウエハ、液晶ディスプレイ用基板、有機ＥＬ(Electroluminescence)用基板、ＦＰＤ(Flat Panel Display)用基板、光ディスプレイ用基板、磁気ディスク用基板、光ディスク用基板、光磁気ディスク用基板、フォトマスク用基板、太陽電池用基板である。基板Ｗは、薄い平板形状を有する。基板Ｗは、平面視で略円形状を有する。 <1. Substrate>
The substrate W is, for example, a semiconductor wafer, a liquid crystal display substrate, an organic EL (Electroluminescence) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, or a magneto-optical disk substrate. , photomask substrates, and solar cell substrates. The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in plan view.
　図１は、基板Ｗの一部を模式的に示す図である。基板Ｗは、パターンＰを有する。パターンＰは、基板Ｗの表面に形成される。 FIG. 1 is a diagram schematically showing part of the substrate W. FIG. The substrate W has a pattern P. A pattern P is formed on the surface of the substrate W. As shown in FIG.
　パターンＰは、例えば、凹凸形状を有する。パターンＰは、例えば、凸部Ｗ１と凹部Ａを有する。凸部Ｗ１は、基板Ｗの一部である。凸部Ｗ１は、構造体である。凸部Ｗ１は、例えば、シリコン酸化膜（ＳｉＯ２）、シリコン窒化膜（ＳｉＮ）およびポリシリコン膜の少なくともいずれかで構成される。凸部Ｗ１は、例えば、基板Ｗの表面から上方に隆起する。凹部Ａは、凸部Ｗ１の側方に隣接する。凹部Ａは、空間である。凹部Ａは、例えば、上方に開放されている。凸部Ｗ１は、凹部Ａを区画する壁に相当する。 The pattern P has, for example, an uneven shape. The pattern P has a convex portion W1 and a concave portion A, for example. The protrusion W1 is part of the substrate W. As shown in FIG. The protrusion W1 is a structure. The protrusion W1 is composed of, for example, at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN) and a polysilicon film. The protrusion W1 protrudes upward from the surface of the substrate W, for example. The concave portion A is laterally adjacent to the convex portion W1. The recess A is a space. The recess A is, for example, open upward. The protrusion W1 corresponds to a wall that partitions the recess A. As shown in FIG.
　＜２．処理液（乾燥補助液）＞
　本明細書では、基板Ｗの乾燥に用いられる処理液を、単に、「処理液」と呼ぶ。処理液は、基板Ｗを乾燥させることを補助する機能を有する。処理液は、乾燥補助液と言い換えることができる。 <2. Processing Liquid (Drying Auxiliary Liquid)>
In this specification, the processing liquid used for drying the substrate W is simply referred to as "processing liquid". The processing liquid has a function of assisting the substrate W to be dried. The processing liquid can be rephrased as a drying auxiliary liquid.
　処理液は、昇華性物質を含む。昇華性物質は、昇華性を有する。「昇華性」とは、単体、化合物若しくは混合物が、液体を経ずに、固体から気体、又は気体から固体へと相転移する特性である。 The treatment liquid contains a sublimable substance. A sublimable substance has a sublimation property. "Sublimation" is the property of an element, compound or mixture to undergo a phase transition from solid to gas or from gas to solid without going through a liquid.
　昇華性物質は、４－ニトロトルエンを含む。昇華性物質は、例えば、４－ニトロトルエンのみを含む。４－ニトロトルエンは、以下の化学式（１）で表される。 Sublimable substances include 4-nitrotoluene. Sublimable substances include, for example, only 4-nitrotoluene. 4-Nitrotoluene is represented by the following chemical formula (1).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　処理液は、溶媒を含む。溶媒は、昇華性物質を溶解する。処理液中の昇華性物質は、溶媒に溶解されている。すなわち、処理液は、溶媒と、溶媒に溶解された昇華性物質を含む。昇華性物質は、処理液の溶質に相当する。 The treatment liquid contains a solvent. The solvent dissolves the sublimable substance. The sublimable substance in the treatment liquid is dissolved in the solvent. That is, the treatment liquid contains a solvent and a sublimable substance dissolved in the solvent. The sublimable substance corresponds to the solute of the treatment liquid.
　溶媒は、常温において比較的に高い蒸気圧を有する。例えば、常温における溶媒の蒸気圧は、常温における昇華性物質の蒸気圧よりも高いことが好ましい。 The solvent has a relatively high vapor pressure at room temperature. For example, the vapor pressure of the solvent at normal temperature is preferably higher than the vapor pressure of the sublimable substance at normal temperature.
　ここで、常温は、室温を含む。常温は、例えば、５℃以上で３５℃以下の範囲内の温度である。常温は、例えば、１０℃以上で３０℃以下の範囲内の温度である。常温は、例えば、２０℃以上で２５℃以下の範囲内の温度である。 Here, room temperature includes room temperature. Normal temperature is, for example, a temperature within the range of 5° C. or higher and 35° C. or lower. Normal temperature is, for example, a temperature within the range of 10° C. or higher and 30° C. or lower. Normal temperature is, for example, a temperature within the range of 20° C. or higher and 25° C. or lower.
　処理液に含まれる昇華性物質の体積は、処理液に含まれる溶媒の体積よりも小さい。例えば、処理液の体積比ＲＶは、１［Ｖｏｌ％］以上、かつ、２０［Ｖｏｌ％］以下であることが好ましい。ここで、処理液の体積比ＲＶは、処理液に含まれる溶媒の体積に対する処理液に含まれる昇華性物質の体積の割合である。言い換えれば、処理液の体積比ＲＶは、次式によって、規定される。
　　ＲＶ＝（処理液に含まれる昇華性物質の体積）／（処理液に含まれる溶媒の体積）＊１００　　［Ｖｏｌ％］ The volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. For example, the volume ratio RV of the treatment liquid is preferably 1 [Vol %] or more and 20 [Vol %] or less. Here, the volume ratio RV of the treatment liquid is the ratio of the volume of the sublimable substance contained in the treatment liquid to the volume of the solvent contained in the treatment liquid. In other words, the volume ratio RV of the treatment liquid is defined by the following equation.
RV = (volume of sublimable substance contained in treatment liquid)/(volume of solvent contained in treatment liquid) * 100 [Vol%]
　溶媒は、例えば、有機溶剤である。溶媒は、例えば、アルコールである。 The solvent is, for example, an organic solvent. Solvents are, for example, alcohols.
　溶媒は、例えば、イソプロピルアルコール（ＩＰＡ）を含む。溶媒は、例えば、イソプロピルアルコール（ＩＰＡ）のみを含む。イソプロピルアルコールの常温における蒸気圧は、４－ニトロトルエンの常温における蒸気圧よりも高い。 The solvent includes, for example, isopropyl alcohol (IPA). Solvents include, for example, isopropyl alcohol (IPA) only. The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of 4-nitrotoluene at room temperature.
　処理液は、例えば、昇華性物質と溶媒のみからなる。 The treatment liquid, for example, consists only of a sublimable substance and a solvent.
　処理液は、例えば、４－ニトロトルエンとイソプロピルアルコールのみからなる。 The treatment liquid consists of, for example, 4-nitrotoluene and isopropyl alcohol.
　＜３．基板処理装置の概要＞
　図２は、実施形態の基板処理装置１の内部を示す平面図である。基板処理装置１は、基板Ｗに処理を行う。基板処理装置１における処理は、乾燥処理を含む。 <3. Overview of Substrate Processing Apparatus>
FIG. 2 is a plan view showing the inside of the substrate processing apparatus 1 of the embodiment. The substrate processing apparatus 1 processes a substrate W. As shown in FIG. The processing in the substrate processing apparatus 1 includes drying processing.
　基板処理装置１は、インデクサ部３と処理ブロック７を備える。処理ブロック７はインデクサ部３に接続される。インデクサ部３は、処理ブロック７に基板Ｗを供給する。処理ブロック７は、基板Ｗに処理を行う。インデクサ部３は、処理ブロック７から基板Ｗを回収する。 The substrate processing apparatus 1 includes an indexer section 3 and a processing block 7. A processing block 7 is connected to the indexer section 3 . The indexer unit 3 supplies substrates W to the processing block 7 . The processing block 7 performs processing on the substrate W. FIG. The indexer section 3 retrieves the substrates W from the processing block 7 .
　本明細書では、便宜上、インデクサ部３と処理ブロック７が並ぶ方向を、「前後方向Ｘ」と呼ぶ。前後方向Ｘは水平である。前後方向Ｘのうち、処理ブロック７からインデクサ部３に向かう方向を「前方」と呼ぶ。前方と反対の方向を「後方」と呼ぶ。前後方向Ｘと直交する水平方向を、「幅方向Ｙ」と呼ぶ。「幅方向Ｙ」の一方向を適宜に「右方」と呼ぶ。右方とは反対の方向を「左方」と呼ぶ。水平方向に対して垂直な方向を「鉛直方向Ｚ」と呼ぶ。各図では、参考として、前、後、右、左、上、下を適宜に示す。 In this specification, for the sake of convenience, the direction in which the indexer unit 3 and the processing blocks 7 are arranged is called the "front-back direction X". The front-rear direction X is horizontal. Of the front-back direction X, the direction from the processing block 7 to the indexer unit 3 is called "forward". The direction opposite to forward is called "backward". A horizontal direction orthogonal to the front-rear direction X is called a “width direction Y”. One direction of the "width direction Y" is appropriately called "right side". The direction opposite to right is called "left". A direction perpendicular to the horizontal direction is called a “vertical direction Z”. In each figure, front, rear, right, left, top, and bottom are indicated as appropriate for reference.
　インデクサ部３は、複数（例えば、４つ）のキャリア載置部４を備える。各キャリア載置部４はそれぞれ、１つのキャリアＣを載置する。キャリアＣは、複数枚の基板Ｗを収容する。キャリアＣは、例えば、ＦＯＵＰ（Front Opening Unified Pod）、ＳＭＩＦ（Standard Mechanical Interface）、または、ＯＣ（Open Cassette）である。 The indexer section 3 includes a plurality of (for example, four) carrier placement sections 4 . Each carrier mounting portion 4 mounts one carrier C thereon. A carrier C accommodates a plurality of substrates W. As shown in FIG. Carrier C is, for example, FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), or OC (Open Cassette).
　インデクサ部３は、搬送機構５を備える。搬送機構５は、キャリア載置部４の後方に配置される。搬送機構５は、基板Ｗを搬送する。搬送機構５は、キャリア載置部４に載置されるキャリアＣにアクセス可能である。搬送機構５はハンド５ａとハンド駆動部５ｂを備える。ハンド５ａは、基板Ｗを支持する。ハンド駆動部５ｂは、ハンド５ａに連結される。ハンド駆動部５ｂは、ハンド５ａを移動させる。ハンド駆動部５ｂは、例えば、前後方向Ｘ、幅方向Ｙおよび鉛直方向Ｚにハンド５ａを移動させる。ハンド駆動部５ｂは、例えば、水平面内においてハンド５ａを回転させる。 The indexer section 3 has a transport mechanism 5 . The transport mechanism 5 is arranged behind the carrier placement section 4 . The transport mechanism 5 transports the substrate W. As shown in FIG. The transport mechanism 5 can access the carrier C placed on the carrier placement section 4 . The transport mechanism 5 includes a hand 5a and a hand driving section 5b. The hand 5a supports the substrate W. The hand driving section 5b is connected to the hand 5a. The hand driving section 5b moves the hand 5a. The hand drive unit 5b moves the hand 5a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example. The hand drive unit 5b rotates the hand 5a in a horizontal plane, for example.
　処理ブロック７は、搬送機構８を備える。搬送機構８は、基板Ｗを搬送する。搬送機構８と搬送機構５は、相互に、基板Ｗを受け渡し可能である。搬送機構８は、ハンド８ａとハンド駆動部８ｂを備える。ハンド８ａは、基板Ｗを支持する。ハンド駆動部８ｂは、ハンド８ａに連結される。ハンド駆動部８ｂは、ハンド８ａを移動させる。ハンド駆動部８ｂは、例えば、前後方向Ｘ、幅方向Ｙおよび鉛直方向Ｚにハンド８ａを移動させる。ハンド駆動部８ｂは、例えば、水平面内においてハンド８ａを回転させる。 The processing block 7 has a transport mechanism 8 . The transport mechanism 8 transports the substrate W. As shown in FIG. The transport mechanism 8 and the transport mechanism 5 can transfer substrates W to each other. The transport mechanism 8 includes a hand 8a and a hand driving section 8b. The hand 8a supports the substrate W. The hand driving section 8b is connected to the hand 8a. The hand driving section 8b moves the hand 8a. The hand drive unit 8b moves the hand 8a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example. The hand driving section 8b rotates the hand 8a in a horizontal plane, for example.
　処理ブロック７は、複数の処理ユニット１１を備える。処理ユニット１１は、搬送機構８の側方に配置される。各処理ユニット１１は、基板Ｗに処理を行う。 The processing block 7 includes a plurality of processing units 11. The processing unit 11 is arranged on the side of the transport mechanism 8 . Each processing unit 11 processes the substrate W. FIG.
　処理ユニット１１は、基板保持部１３を備える。基板保持部１３は、基板Ｗを保持する。 The processing unit 11 includes a substrate holding section 13 . The substrate holding part 13 holds the substrate W. As shown in FIG.
　搬送機構８は、各処理ユニット１１にアクセス可能である。搬送機構８は、基板保持部１３に基板Ｗを渡すことができる。搬送機構８は、基板保持部１３から基板Ｗを取ることができる。 The transport mechanism 8 can access each processing unit 11 . The transport mechanism 8 can transfer the substrate W to the substrate holder 13 . The transport mechanism 8 can take the substrate W from the substrate holder 13 .
　図３は、基板処理装置１の制御ブロック図である。基板処理装置１は、制御部１０を備える。制御部１０は、搬送機構５、８および処理ユニット１１と通信可能である。制御部１０は、搬送機構５、８と処理ユニット１１を制御する。 FIG. 3 is a control block diagram of the substrate processing apparatus 1. FIG. The substrate processing apparatus 1 includes a control section 10 . The controller 10 can communicate with the transport mechanisms 5 and 8 and the processing unit 11 . The controller 10 controls the transport mechanisms 5 and 8 and the processing unit 11 .
　制御部１０は、各種処理を実行する中央演算処理装置（ＣＰＵ）、演算処理の作業領域となるＲＡＭ（Random-Access Memory）、固定ディスク等の記憶媒体等によって実現されている。制御部１０は、記憶媒体に予め格納される各種の情報を有する。制御部１０が有する情報は、例えば、搬送機構５、８を制御するための搬送条件情報である。制御部１０が有する情報は、例えば、処理ユニット１１を制御するための処理条件情報である。処理条件情報は、処理レシピとも呼ばれる。 The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a RAM (Random-Access Memory) that serves as a work area for arithmetic processing, a storage medium such as a fixed disk, and the like. The control unit 10 has various types of information stored in advance in a storage medium. Information held by the control unit 10 is, for example, transport condition information for controlling the transport mechanisms 5 and 8 . The information held by the control unit 10 is, for example, processing condition information for controlling the processing unit 11 . Processing condition information is also called a processing recipe.
　基板処理装置１の動作例を簡単に説明する。 An operation example of the substrate processing apparatus 1 will be briefly described.
　インデクサ部３は、処理ブロック７に基板Ｗを供給する。具体的には、搬送機構５は、キャリアＣから処理ブロック７の搬送機構８に基板Ｗを渡す。 The indexer section 3 supplies substrates W to the processing block 7 . Specifically, the transport mechanism 5 transfers the substrate W from the carrier C to the transport mechanism 8 of the processing block 7 .
　搬送機構８は、処理ユニット１１に基板Ｗを分配する。具体的には、搬送機構８は、搬送機構５から、各処理ユニット１１の基板保持部１３に基板Ｗを搬送する。 The transport mechanism 8 distributes the substrates W to the processing units 11 . Specifically, the transport mechanism 8 transports the substrate W from the transport mechanism 5 to the substrate holder 13 of each processing unit 11 .
　処理ユニット１１は、基板保持部１３によって保持された基板Ｗを処理する。処理ユニット１１は、例えば、基板Ｗに乾燥処理を行う。 The processing unit 11 processes the substrate W held by the substrate holding section 13 . The processing unit 11 performs a drying process on the substrate W, for example.
　処理ユニット１１が基板Ｗを処理した後、搬送機構８は、各処理ユニット１１から基板Ｗを回収する。具体的には、搬送機構８は、各基板保持部１３から基板Ｗを受ける。そして、搬送機構８は、搬送機構５に基板Ｗを渡す。 After the processing unit 11 processes the substrate W, the transport mechanism 8 recovers the substrate W from each processing unit 11 . Specifically, the transport mechanism 8 receives the substrate W from each substrate holder 13 . Then, the transport mechanism 8 transfers the substrate W to the transport mechanism 5 .
　インデクサ部３は、処理ブロック７から基板Ｗを回収する。具体的には、搬送機構５は、搬送機構８からキャリアＣに基板Ｗを搬送する。 The indexer section 3 recovers the substrates W from the processing block 7 . Specifically, the transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C. As shown in FIG.
　＜４．処理ユニット１１の構成＞
　図４は、処理ユニット１１の構成を示す図である。各処理ユニット１１は、同一の構造を有する。処理ユニット１１は、枚葉式に分類される。すなわち、各処理ユニット１１は、一度に１枚の基板Ｗのみを処理する。 <4. Configuration of Processing Unit 11>
FIG. 4 is a diagram showing the configuration of the processing unit 11. As shown in FIG. Each processing unit 11 has the same structure. The processing unit 11 is classified as a single wafer type. That is, each processing unit 11 processes only one substrate W at a time.
　処理ユニット１１は、筐体１２を備える。筐体１２は、略箱形状を有する。基板Ｗは、筐体１２の内部において、処理される。 The processing unit 11 has a housing 12 . The housing 12 has a substantially box shape. The substrate W is processed inside the enclosure 12 .
　筐体１２の内部は、常温に保たれる。筐体１２の内部における気体の温度は、常温に保たれる。このため、基板Ｗは、常温の環境の下で、処理される。 The inside of the housing 12 is kept at room temperature. The temperature of the gas inside the housing 12 is kept at room temperature. Therefore, the substrate W is processed under a room temperature environment.
　筐体１２の内部は、常圧に保たれる。筐体１２の内部における気体の圧力は、常圧に保たれる。このため、基板Ｗは、常圧の環境の下で、処理される。 The inside of the housing 12 is kept at normal pressure. The gas pressure inside the housing 12 is kept at normal pressure. Therefore, the substrate W is processed under an environment of normal pressure.
　ここで、常圧は、標準大気圧（１気圧、１０１３２５Ｐａ）を含む。常圧は、例えば、０．７気圧以上で、１．３気圧以下の範囲内の気圧である。本明細書では、圧力の値は、絶対真空を基準とした絶対圧力で、示される。 Here, normal pressure includes standard atmospheric pressure (1 atm, 101325 Pa). Normal pressure is, for example, an atmospheric pressure in the range of 0.7 atmospheres or more and 1.3 atmospheres or less. Pressure values are given herein in absolute pressure relative to absolute vacuum.
　上述した基板保持部１３は、筐体１２の内部に設置される。基板保持部１３は、１枚の基板Ｗを保持する。基板保持部１３は、基板Ｗを略水平姿勢で保持する。 The substrate holding part 13 described above is installed inside the housing 12 . The substrate holding part 13 holds one substrate W. As shown in FIG. The substrate holding part 13 holds the substrate W in a substantially horizontal posture.
　基板保持部１３は、基板保持部１３が保持する基板Ｗの下方に位置する。基板保持部１３は、基板Ｗの下面および基板Ｗの周縁部の少なくともいずれかと接触する。基板Ｗの下面は、基板Ｗのバックサイドとも呼ばれる。基板保持部１３は、基板Ｗの上面と接触しない。 The substrate holding part 13 is positioned below the substrate W held by the substrate holding part 13 . The substrate holding part 13 contacts at least one of the bottom surface of the substrate W and the peripheral edge of the substrate W. As shown in FIG. The bottom surface of the substrate W is also called the backside of the substrate W. As shown in FIG. The substrate holding part 13 does not contact the upper surface of the substrate W. As shown in FIG.
　処理ユニット１１は、回転駆動部１４を備える。回転駆動部１４の少なくとも一部は、筐体１２の内部に設置される。回転駆動部１４は、基板保持部１３に連結される。回転駆動部１４は、基板保持部１３を回転させる。基板保持部１３によって保持される基板Ｗは、基板保持部１３と一体に回転する。基板保持部１３によって保持される基板Ｗは、回転軸線Ｂ回りに回転する。回転軸線Ｂは、例えば、基板Ｗの中心を通り、鉛直方向Ｚに延びる。 The processing unit 11 includes a rotation drive section 14 . At least part of the rotation drive unit 14 is installed inside the housing 12 . The rotation driving section 14 is connected to the substrate holding section 13 . The rotation driving section 14 rotates the substrate holding section 13 . The substrate W held by the substrate holding portion 13 rotates together with the substrate holding portion 13 . The substrate W held by the substrate holding part 13 rotates around the rotation axis B. As shown in FIG. The rotation axis B extends in the vertical direction Z through the center of the substrate W, for example.
　処理ユニット１１は、供給部１５を備える。供給部１５は、基板保持部１３によって保持される基板Ｗに、液体または気体を供給する。具体的には、供給部１５は、基板保持部１３によって保持される基板Ｗの上面に、液体または気体を供給する。 The processing unit 11 includes a supply section 15 . The supply unit 15 supplies liquid or gas to the substrate W held by the substrate holding unit 13 . Specifically, the supply unit 15 supplies liquid or gas to the upper surface of the substrate W held by the substrate holding unit 13 .
　供給部１５は、第１供給部１５ａと第２供給部１５ｂと第３供給部１５ｃと第４供給部１５ｄと第５供給部１５ｅを備える。第１供給部１５ａは、処理液を供給する。第２供給部１５ｂは、薬液を供給する。第３供給部１５ｃは、リンス液を供給する。第４供給部１５ｄは、置換液を供給する。第５供給部１５ｅは、乾燥ガスを供給する。 The supply unit 15 includes a first supply unit 15a, a second supply unit 15b, a third supply unit 15c, a fourth supply unit 15d, and a fifth supply unit 15e. The first supply unit 15a supplies the processing liquid. The second supply unit 15b supplies the chemical solution. The third supply part 15c supplies the rinse liquid. The fourth supply part 15d supplies the replacement liquid. The fifth supply unit 15e supplies dry gas.
　第１供給部１５ａは、本発明における処理液供給部の例である。 The first supply section 15a is an example of a processing liquid supply section in the present invention.
　上述の通り、筐体１２の内部は、常温および常圧である。このため、処理液は、常温の環境の下で、使用される。処理液は、常圧の環境の下で、使用される。 As described above, the inside of the housing 12 is at normal temperature and normal pressure. Therefore, the treatment liquid is used under normal temperature environment. The processing liquid is used under normal pressure environment.
　第２供給部１５ｂによって供給される薬液は、例えば、エッチング液である。エッチング液は、例えば、フッ化水素酸（ＨＦ）およびバッファードフッ酸（ＢＨＦ）の少なくともいずれかを含む。 The chemical liquid supplied by the second supply unit 15b is, for example, an etchant. The etchant contains, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).
　第３供給部１５ｃによって供給されるリンス液は、例えば、脱イオン水（ＤＩＷ）である。 The rinse liquid supplied by the third supply unit 15c is, for example, deionized water (DIW).
　第４供給部１５ｄによって供給される置換液は、例えば、有機溶剤である。置換液は、例えば、イソプロピルアルコール（ＩＰＡ）である。 The replacement liquid supplied by the fourth supply unit 15d is, for example, an organic solvent. The replacement liquid is, for example, isopropyl alcohol (IPA).
　第５供給部１５ｅによって供給される乾燥ガスは、例えば、エアおよび不活性ガスの少なくともいずれかである。エアは、例えば、圧縮エアである。不活性ガスは、例えば、窒素ガスである。乾燥ガスは、常温よりも低い露点を有することが好ましい。 The dry gas supplied by the fifth supply unit 15e is, for example, at least one of air and inert gas. Air is, for example, compressed air. An inert gas is, for example, nitrogen gas. Preferably, the dry gas has a dew point below ambient temperature.
　第１供給部１５ａは、ノズル１６ａを備える。同様に、第２－第５供給部１５ｂ－１５ｅはそれぞれ、ノズル１６ｂ－１６ｅを備える。ノズル１６ａ－１６ｅはそれぞれ、筐体１２の内部に設置される。ノズル１６ａは、処理液を吐出する。ノズル１６ｂは、薬液を吐出する。ノズル１６ｃは、リンス液を吐出する。ノズル１６ｄは、置換液を吐出する。ノズル１６ｅは、乾燥ガスを吐出する。 The first supply unit 15a includes a nozzle 16a. Similarly, the second-fifth feeders 15b-15e are provided with nozzles 16b-16e, respectively. Nozzles 16 a - 16 e are each located inside housing 12 . The nozzle 16a ejects the processing liquid. The nozzle 16b ejects the chemical liquid. The nozzle 16c ejects the rinse liquid. The nozzle 16d ejects the replacement liquid. The nozzle 16e ejects dry gas.
　第１供給部１５ａは、配管１７ａと弁１８ａを備える。配管１７ａは、ノズル１６ａに接続される。弁１８ａは、配管１７ａに設けられる。弁１８ａが開くとき、ノズル１６ａは処理液を吐出する。弁１８ａが閉じるとき、ノズル１６ａは処理液を吐出しない。同様に、第２－第５供給部１５ｂ－１５ｅはそれぞれ、配管１７ｂ－１７ｅと弁１８ｂ－１８ｅを備える。配管１７ｂ－１７ｅはそれぞれ、ノズル１６ｂ－１６ｅに接続される。弁１８ｂ－１８ｅはそれぞれ、配管１７ｂ－１７ｅに設けられる。弁１８ｂ－１８ｅはそれぞれ、薬液、リンス液、置換液および乾燥ガスの吐出を制御する。 The first supply unit 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is opened, the nozzle 16a ejects processing liquid. When valve 18a is closed, nozzle 16a does not eject processing liquid. Similarly, the second through fifth feeds 15b-15e are provided with pipes 17b-17e and valves 18b-18e, respectively. Pipes 17b-17e are connected to nozzles 16b-16e, respectively. Valves 18b-18e are provided on lines 17b-17e, respectively. Valves 18b-18e control the discharge of chemical liquid, rinse liquid, replacement liquid and dry gas, respectively.
　配管１７ａの少なくとも一部は、筐体１２の外部に設けられてもよい。配管１７ｂ－１７ｅも、配管１７ａと同様に配置されてもよい。弁１８ａは、筐体１２の外部に設けられてもよい。弁１８ｂ－１８ｅも、弁１８ａと同様に配置されてもよい。 At least part of the pipe 17 a may be provided outside the housing 12 . Lines 17b-17e may also be arranged similarly to line 17a. The valve 18 a may be provided outside the housing 12 . Valves 18b-18e may also be arranged similarly to valve 18a.
　基板処理装置１は、第１供給源１９ａを備える。第１供給源１９ａは、第１供給部１５ａに接続される。第１供給源１９ａは、第１供給部１５ａに連通する。第１供給源１９ａは、例えば、配管１７ａに接続される。第１供給源１９ａは、第１供給部１５ａに処理液を送る。 The substrate processing apparatus 1 includes a first supply source 19a. The first supply source 19a is connected to the first supply section 15a. The first supply source 19a communicates with the first supply section 15a. The first supply source 19a is connected to, for example, a pipe 17a. The first supply source 19a sends the treatment liquid to the first supply section 15a.
　第２供給部１５ｂは、第２供給源１９ｂに接続される。第２供給部１５ｂは、第２供給源１９ｂに連通する。第２供給源１９ｂは、例えば、配管１７ｂに接続される。第２供給源１９ｂは、第２供給部１５ｂに薬液を送る。同様に、第３－第５供給部１５ｃ－１５ｅはそれぞれ、第３－第５供給源１９ｃ－１９ｅに接続される。第３－第５供給部１５ｃ－１５ｅはそれぞれ、第３－第５供給源１９ｃ－１９ｅに連通する。第３－第５供給源１９ｃ－１９ｅはそれぞれ、例えば、配管１７ｃ－１７ｅに接続される。第３供給源１９ｃは、第３供給部１５ｃにリンス液を送る。第４供給源１９ｄは、第４供給部１５ｄに置換液を送る。第５供給源１９ｅは、第５供給部１５ｅに乾燥ガスを送る。 The second supply unit 15b is connected to the second supply source 19b. The second supply part 15b communicates with the second supply source 19b. The second supply source 19b is connected to, for example, a pipe 17b. The second supply source 19b sends the chemical solution to the second supply section 15b. Similarly, the third-fifth supplies 15c-15e are connected to the third-fifth supply sources 19c-19e, respectively. The third-fifth supply parts 15c-15e respectively communicate with the third-fifth supply sources 19c-19e. The third-fifth sources 19c-19e are connected, for example, to pipes 17c-17e, respectively. The third supply source 19c sends the rinse liquid to the third supply section 15c. The fourth supply source 19d sends the replacement liquid to the fourth supply section 15d. The fifth supply source 19e delivers dry gas to the fifth supply section 15e.
　第１供給源１９ａは、筐体１２の外部に設けられる。同様に、第２－第５供給源１９ｂ－１９ｅはそれぞれ、筐体１２の外部に設けられる。 The first supply source 19 a is provided outside the housing 12 . Similarly, the second through fifth sources 19b-19e are provided outside the enclosure 12, respectively.
　第１供給源１９ａは、複数の処理ユニット１１に対して、処理液を供給してもよい。あるいは、第１供給源１９ａは、１つの処理ユニット１１のみに、処理液を供給してもよい。第２－第５供給源１９ｂ－１９ｅについても、同様である。 The first supply source 19a may supply the processing liquid to a plurality of processing units 11. Alternatively, the first supply source 19 a may supply the processing liquid to only one processing unit 11 . The same is true for the second to fifth supply sources 19b-19e.
　第２供給源１９ｂは、基板処理装置１の要素であってもよい。例えば、第２供給源１９ｂは、基板処理装置１が備える薬液槽であってもよい。あるいは、第２供給源１９ｂは、基板処理装置１の要素でなくてもよい。例えば、第２供給源１９ｂは、基板処理装置１の外部に設置されるユーティリティ設備であってもよい。同様に、第３－第５供給源１９ｃ－１９ｅはそれぞれ、基板処理装置１の要素であってもよい。あるいは、第３－第５供給源１９ｃ－１９ｅはそれぞれ、基板処理装置１の要素でなくてもよい。 The second supply source 19b may be an element of the substrate processing apparatus 1. For example, the second supply source 19b may be a chemical bath included in the substrate processing apparatus 1. FIG. Alternatively, the second supply source 19b may not be a component of the substrate processing apparatus 1. FIG. For example, the second supply source 19b may be utility equipment installed outside the substrate processing apparatus 1 . Similarly, each of the third-fifth sources 19c-19e may be elements of the substrate processing apparatus 1. FIG. Alternatively, the third-fifth sources 19c-19e, respectively, may not be elements of the substrate processing apparatus 1. FIG.
　処理ユニット１１は、さらに、不図示のカップを備えてもよい。カップは、筐体１２の内部に設置される。カップは、基板保持部１３の周囲に配置される。カップは、基板保持部１３に保持される基板Ｗから飛散した液体を受け止める。 The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12 . The cup is arranged around the substrate holder 13 . The cup receives the liquid scattered from the substrate W held by the substrate holding part 13 .
　図３を参照する。制御部１０は、回転駆動部１４を制御する。制御部１０は、供給部１５を制御する。制御部１０は、弁１８ａ－１８ｅを制御する。 See Figure 3. The control section 10 controls the rotation driving section 14 . The control section 10 controls the supply section 15 . The controller 10 controls the valves 18a-18e.
　＜５．第１供給源１９ａの構成＞
　図４を、参照する。第１供給源１９ａは、さらに、処理液を生成する。 <5. Configuration of first supply source 19a>
Please refer to FIG. The first supply source 19a also produces a processing liquid.
　第１供給源１９ａの構成例を例示する。第１供給源１９ａは、生成ユニット２１と圧送ユニット３１に区分される。生成ユニット２１は、処理液を生成する。圧送ユニット３１は、処理液を第１供給部１５ａに送る。 A configuration example of the first supply source 19a is illustrated. The first supply source 19 a is divided into a generating unit 21 and a pumping unit 31 . The generation unit 21 generates a treatment liquid. The pumping unit 31 sends the treatment liquid to the first supply section 15a.
　生成ユニット２１は、槽２２と供給部２３ａ、２３ｂを備える。供給部２３ａは、昇華性物質を槽２２に供給する。供給部２３ｂは、溶媒を槽２２に供給する。昇華性物質と溶媒は、槽２２において、混合される。昇華性物質と溶媒は、槽２２において、処理液ｇになる。 The generation unit 21 includes a tank 22 and supply units 23a and 23b. The supply unit 23 a supplies the sublimable substance to the tank 22 . The supply unit 23b supplies the solvent to the tank 22. As shown in FIG. The sublimable substance and solvent are mixed in vessel 22 . The sublimable substance and solvent become the treatment liquid g in the tank 22 .
　槽２２は、常温の環境の下に、設置される。槽２２は、常圧の環境の下に、設置される。このため、処理液ｇは、常温の環境の下で、生成される。処理液ｇは、常圧の環境の下で、生成される。 The tank 22 is installed under a normal temperature environment. The bath 22 is installed under a normal pressure environment. Therefore, the processing liquid g is generated under a normal temperature environment. The treatment liquid g is generated under normal pressure environment.
　さらに、生成ユニット２１は、処理液ｇを保管する。具体的には、処理液ｇは、槽２２において、保管される。処理液ｇは、常温の環境の下で、保管される。処理液ｇは、常圧の環境の下で、保管される。 Further, the generation unit 21 stores the treatment liquid g. Specifically, the treatment liquid g is stored in the tank 22 . The treatment liquid g is stored under normal temperature environment. The treatment liquid g is stored under a normal pressure environment.
　供給部２３ａは、例えば、配管２４ａと弁２５ａを備える。配管２４ａは、槽２２に接続される。配管２４ａは、槽２２に連通する。弁２５ａは、配管２４ａに設けられる。弁２５ａが開くとき、供給部２３ａは槽２２に昇華性物質を供給する。弁２５ａが閉じるとき、供給部２３ａは槽２２に昇華性物質を供給しない。同様に、供給部２３ｂは、配管２４ｂと弁２５ｂを備える。配管２４ｂは、槽２２に接続される。配管２４ｂは、槽２２に連通する。弁２５ｂは、配管２４ｂに設けられる。弁２５ｂは、槽２２に対する溶媒の供給を制御する。 The supply unit 23a includes, for example, a pipe 24a and a valve 25a. The pipe 24 a is connected to the tank 22 . The pipe 24 a communicates with the tank 22 . The valve 25a is provided on the pipe 24a. The supply portion 23a supplies the sublimable substance to the bath 22 when the valve 25a is opened. When the valve 25a is closed, the supply portion 23a does not supply the sublimable substance to the tank 22. Similarly, the supply section 23b comprises a pipe 24b and a valve 25b. The pipe 24 b is connected to the tank 22 . The pipe 24 b communicates with the bath 22 . The valve 25b is provided on the pipe 24b. Valve 25b controls the supply of solvent to bath 22 .
　さらに、槽２２における昇華性物質の量は、弁２５ａによって制御される。槽２２における溶媒の量は、弁２５ｂによって制御される。よって、槽２２内の処理液ｇの体積比ＲＶは、弁２５ａ、２５ｂによって制御される。 Furthermore, the amount of sublimable substance in the bath 22 is controlled by the valve 25a. The amount of solvent in bath 22 is controlled by valve 25b. Therefore, the volume ratio RV of the processing liquid g in the tank 22 is controlled by valves 25a and 25b.
　弁２５ａ、２５ｂはそれぞれ、例えば、流量調節弁を含んでもよい。弁２５ａ、２５ｂはそれぞれ、例えば、流量調節弁と開閉弁を含んでもよい。 Each of the valves 25a, 25b may include, for example, a flow control valve. Valves 25a, 25b may each include, for example, a flow control valve and an on-off valve.
　供給部２３ａは、供給源２６ａに接続される。供給部２３ａは、供給源２６ａに連通する。例えば、供給源２６ａは、配管２４ａに接続される。供給源２６ａは、供給部２３ａに昇華性物質を送る。同様に、供給部２３ｂは、供給源２６ｂに接続される。供給部２３ｂは、供給源２６ｂに連通する。例えば、供給源２６ｂは、配管２４ｂに接続される。供給源２６ｂは、供給部２３ｂに溶媒を送る。 The supply unit 23a is connected to the supply source 26a. The supply part 23a communicates with the supply source 26a. For example, source 26a is connected to pipe 24a. The supply source 26a sends the sublimable substance to the supply section 23a. Similarly, supply 23b is connected to supply 26b. The supply part 23b communicates with the supply source 26b. For example, source 26b is connected to pipe 24b. Source 26b delivers solvent to supply 23b.
　圧送ユニット３１は、配管３２と継ぎ手３３を備える。配管３２は、槽２２に接続される。配管３２は、槽２２に連通する。継ぎ手３３は、配管３２に接続される。継ぎ手３３は、さらに、配管１７ａに接続される。配管３２は、継ぎ手３３によって、配管１７ａと接続される。配管３２は、継ぎ手３３によって、配管１７ａに連通する。このため、槽２２は、配管３２および継ぎ手３３を介して、第１供給部１５ａに接続される。槽２２は、配管３２および継ぎ手３３を介して、第１供給部１５ａに連通する。槽２２は、ノズル１６ａに接続される。槽２２は、ノズル１６ａに連通する。 The pumping unit 31 includes a pipe 32 and a joint 33. A pipe 32 is connected to the tank 22 . The pipe 32 communicates with the bath 22 . The joint 33 is connected to the pipe 32 . The joint 33 is further connected to the pipe 17a. The pipe 32 is connected to the pipe 17 a by a joint 33 . The pipe 32 communicates with the pipe 17 a through a joint 33 . Therefore, the tank 22 is connected to the first supply section 15a via a pipe 32 and a joint 33. As shown in FIG. The tank 22 communicates with the first supply section 15 a via a pipe 32 and a joint 33 . A tank 22 is connected to the nozzle 16a. The tank 22 communicates with the nozzle 16a.
　圧送ユニット３１は、さらに、ポンプ３４とフィルタ３５を備える。ポンプ３４は、配管３２に設けられる。ポンプ３４が運転するとき、ポンプ３４は槽２２から第１供給部１５ａに処理液ｇを送る。ポンプ３４が運転するとき、ポンプ３４は槽２２から第１供給部１５ａに処理液ｇを圧送する。ポンプ３４が運転を停止するとき、ポンプ３４は槽２２から第１供給部１５ａに処理液ｇを送らない。ポンプ３４が運転を停止するとき、ポンプ３４は槽２２から第１供給部１５ａに処理液ｇを圧送しない。フィルタ３５は、配管３２に設けられる。処理液ｇは、フィルタ３５を通過する。フィルタ３５は、処理液ｇを濾過する。フィルタ３５は、処理液ｇから異物を除去する。 The pumping unit 31 further includes a pump 34 and a filter 35. A pump 34 is provided in the pipe 32 . When the pump 34 operates, the pump 34 sends the treatment liquid g from the bath 22 to the first supply section 15a. When the pump 34 operates, the pump 34 pumps the processing liquid g from the tank 22 to the first supply section 15a. When the pump 34 stops operating, the pump 34 does not send the treatment liquid g from the tank 22 to the first supply section 15a. When the pump 34 stops operating, the pump 34 does not force-feed the treatment liquid g from the tank 22 to the first supply section 15a. A filter 35 is provided in the pipe 32 . The processing liquid g passes through the filter 35 . The filter 35 filters the processing liquid g. The filter 35 removes foreign matter from the processing liquid g.
　図３を参照する。制御部１０は、第１供給源１９ａと通信可能である。制御部１０は、第１供給源１９ａを制御する。制御部１０は、生成ユニット２１を制御する。制御部１０は、供給部２３ａ、２３ｂを制御する。制御部１０は、弁２５ａ、２５ｂを制御する。制御部１０は、圧送ユニット３１を制御する。制御部１０は、ポンプ３４を制御する。 See Figure 3. The control unit 10 can communicate with the first supply source 19a. The control unit 10 controls the first supply source 19a. The control section 10 controls the generation unit 21 . The control unit 10 controls the supply units 23a and 23b. The control unit 10 controls the valves 25a and 25b. The control section 10 controls the pumping unit 31 . The controller 10 controls the pump 34 .
　制御部１０は、第１供給源１９ａを制御するための処理液条件情報を有する。処理液条件情報は、例えば、処理液ｇの体積比ＲＶに関する目標値を含む。処理液条件情報は、制御部１０の記憶媒体に予め記憶されている。 The control unit 10 has treatment liquid condition information for controlling the first supply source 19a. The treatment liquid condition information includes, for example, a target value regarding the volume ratio RV of the treatment liquid g. The processing liquid condition information is pre-stored in the storage medium of the control unit 10 .
　＜６．第１供給源１９ａおよび処理ユニット１１の動作例＞
　図５は、実施形態の基板処理方法の手順を示すフローチャートである。基板処理方法は、ステップＳ１とステップＳ１１－Ｓ１８を備える。ステップＳ１は、第１供給源１９ａによって実行される。ステップＳ１１－Ｓ１８は、実質的に処理ユニット１１によって実行される。ステップＳ１は、ステップＳ１１－Ｓ１８と並行して実行される。第１供給源１９ａおよび処理ユニット１１は、制御部１０の制御にしたがって、動作する。 <6. Example of Operation of First Supply Source 19a and Processing Unit 11>
FIG. 5 is a flow chart showing the procedure of the substrate processing method of the embodiment. The substrate processing method includes step S1 and steps S11-S18. Step S1 is performed by the first source 19a. Steps S 11 -S 18 are substantially performed by processing unit 11 . Step S1 is executed in parallel with steps S11-S18. The first supply source 19 a and the processing unit 11 operate under the control of the control section 10 .
　適宜に図４を参照して、各ステップＳ１、Ｓ１１－Ｓ１８を説明する。 Each step S1, S11-S18 will be described with reference to FIG. 4 as appropriate.
　ステップＳ１：処理液生成工程
　処理液生成工程では、処理液ｇが生成される。 Step S1: Treatment Liquid Generation Step In the treatment liquid generation step, the treatment liquid g is generated.
　生成ユニット２１は、処理液ｇを生成する。具体的には、供給部２３ａは、昇華性物質を槽２２に供給する。供給部２３ｂは、溶媒を槽２２に供給する。処理液ｇは、槽２２において生成される。処理液ｇは、槽２２に貯留される。 The generation unit 21 generates the treatment liquid g. Specifically, the supply unit 23 a supplies the sublimable substance to the tank 22 . The supply unit 23b supplies the solvent to the tank 22. As shown in FIG. A treatment liquid g is produced in the tank 22 . The treatment liquid g is stored in the bath 22 .
　制御部１０は、弁２５ａ、２５ｂを制御する。これにより、制御部１０は、槽２２内における処理液ｇの体積比ＲＶを、処理液条件情報に規定される目標値に調整する。 The control unit 10 controls the valves 25a and 25b. Thereby, the control unit 10 adjusts the volume ratio RV of the treatment liquid g in the tank 22 to the target value defined by the treatment liquid condition information.
　ステップＳ１１：回転開始工程
　基板保持部１３は、基板Ｗを保持する。基板Ｗは、略水平姿勢で保持される。回転駆動部１４は、基板保持部１３を回転させる。これにより、基板保持部１３に保持される基板Ｗは、回転を開始する。 Step S11: Rotation Start Step The substrate holder 13 holds the substrate W. As shown in FIG. The substrate W is held in a substantially horizontal posture. The rotation driving section 14 rotates the substrate holding section 13 . As a result, the substrate W held by the substrate holding part 13 starts rotating.
　後述のステップＳ１２－Ｓ１７では、基板Ｗは、例えば、回転し続ける。 In steps S12-S17, which will be described later, the substrate W continues to rotate, for example.
　ステップＳ１２：薬液供給工程
　薬液供給工程では、薬液が基板Ｗに供給される。 Step S12: Chemical Solution Supplying Process Chemical solution is supplied to the substrate W in the chemical solution supplying process.
　第２供給部１５ｂは、基板保持部１３によって保持される基板Ｗに薬液を供給する。具体的には、弁１８ｂは開く。ノズル１６ｂは薬液を吐出する。薬液は、基板Ｗの上面に供給される。例えば、薬液は、基板Ｗをエッチングする。例えば、薬液は、基板Ｗから自然酸化膜を除去する。 The second supply unit 15b supplies the chemical solution to the substrate W held by the substrate holding unit 13. Specifically, valve 18b opens. The nozzle 16b ejects the chemical liquid. A chemical solution is supplied to the upper surface of the substrate W. As shown in FIG. The chemical etches the substrate W, for example. For example, the chemical removes the native oxide film from the substrate W. FIG.
　その後、第２供給部１５ｂは、基板Ｗに対する薬液の供給を停止する。具体的には、弁１８ｂは閉じる。ノズル１６ｂは、薬液の吐出を停止する。 After that, the second supply unit 15b stops supplying the chemical solution to the substrate W. Specifically, the valve 18b is closed. The nozzle 16b stops discharging the chemical liquid.
　ステップＳ１３：リンス液供給工程
　リンス液供給工程では、リンス液が基板Ｗに供給される。 Step S13: Rinse liquid supply step In the rinse liquid supply step, the substrate W is supplied with the rinse liquid.
　第３供給部１５ｃは、基板保持部１３によって保持される基板Ｗにリンス液を供給する。具体的には、弁１８ｃは開く。ノズル１６ｃは、リンス液を吐出する。リンス液は、基板Ｗの上面に供給される。例えば、リンス液は、基板Ｗを洗浄する。例えば、リンス液は、基板Ｗから薬液を除去する。 The third supply unit 15c supplies the rinse liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18c is opened. The nozzle 16c ejects the rinse liquid. A rinse liquid is supplied to the upper surface of the substrate W. As shown in FIG. For example, the rinse liquid cleans the substrate W. FIG. For example, the rinse removes chemicals from the substrate W. FIG.
　その後、第３供給部１５ｃは、基板Ｗに対するリンス液の供給を停止する。具体的には、弁１８ｃは閉じる。ノズル１６ｃは、リンス液の吐出を停止する。 After that, the third supply unit 15c stops supplying the rinse liquid to the substrate W. Specifically, the valve 18c is closed. The nozzle 16c stops discharging the rinse liquid.
　ステップＳ１４：置換液供給工程
　置換液供給工程では、置換液が基板Ｗに供給される。 Step S14: Substitute liquid supply step A substitute liquid is supplied to the substrate W in the substitute liquid supply step.
　第４供給部１５ｄは、基板保持部１３によって保持される基板Ｗに置換液を供給する。具体的には、弁１８ｄは開く。ノズル１６ｄは、置換液を吐出する。置換液は、基板Ｗの上面に供給される。置換液は、基板Ｗからリンス液を除去する。基板Ｗ上のリンス液は置換液に置き換えられる。 The fourth supply unit 15d supplies the replacement liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18d is opened. The nozzle 16d ejects the replacement liquid. A replacement liquid is supplied to the upper surface of the substrate W. As shown in FIG. The replacement liquid removes the rinse liquid from the substrate W. FIG. The rinsing liquid on the substrate W is replaced with the replacement liquid.
　その後、第４供給部１５ｄは、基板Ｗに対する置換液の供給を停止する。具体的には、弁１８ｄは閉じる。ノズル１６ｄは、置換液の吐出を停止する。 After that, the fourth supply unit 15d stops supplying the replacement liquid to the substrate W. Specifically, the valve 18d is closed. The nozzle 16d stops discharging the replacement liquid.
　ステップＳ１５：処理液供給工程
　処理液供給工程では、処理液ｇが基板Ｗに供給される。 Step S15: Processing Liquid Supplying Process In the processing liquid supplying process, the processing liquid g is supplied to the substrate W. As shown in FIG.
　圧送ユニット３１は、処理液ｇを第１供給部１５ａに供給する。第１供給部１５ａは、基板保持部１３によって保持される基板Ｗに処理液ｇを供給する。具体的には、ポンプ３４は、槽２２から第１供給部１５ａに、処理液ｇを送る。ポンプ３４は、槽２２から第１供給部１５ａに、処理液ｇを圧送する。弁１８ａは開く。ノズル１６ａは、処理液ｇを吐出する。処理液ｇは、基板Ｗの上面に供給される。処理液ｇは、基板Ｗから置換液を除去する。基板Ｗ上の置換液は、処理液ｇに置き換えられる。 The pumping unit 31 supplies the treatment liquid g to the first supply section 15a. The first supply unit 15 a supplies the processing liquid g to the substrate W held by the substrate holding unit 13 . Specifically, the pump 34 sends the treatment liquid g from the tank 22 to the first supply section 15a. The pump 34 pumps the treatment liquid g from the tank 22 to the first supply section 15a. Valve 18a opens. The nozzle 16a ejects the treatment liquid g. The processing liquid g is supplied to the upper surface of the substrate W. As shown in FIG. The processing liquid g removes the replacement liquid from the substrate W. FIG. The replacement liquid on the substrate W is replaced with the processing liquid g.
　その後、圧送ユニット３１は、第１供給部１５ａに対する処理液ｇの供給を停止する。第１供給部１５ａは、基板Ｗに対する処理液ｇの供給を停止する。具体的には、ポンプ３４は停止する。弁１８ａは閉じる。ノズル１６ａは、処理液ｇの吐出を停止する。 After that, the pumping unit 31 stops supplying the treatment liquid g to the first supply unit 15a. The first supply unit 15a stops supplying the processing liquid g to the substrate W. As shown in FIG. Specifically, the pump 34 is stopped. Valve 18a is closed. The nozzle 16a stops ejecting the treatment liquid g.
　図６は、処理液供給工程における基板Ｗを模式的に示す図である。基板Ｗが基板保持部１３に保持されるとき、パターンＰは基板Ｗの上面に位置する。基板Ｗが基板保持部１３に保持されるとき、パターンＰは上方を向く。 FIG. 6 is a diagram schematically showing the substrate W in the process of supplying the processing liquid. The pattern P is positioned on the upper surface of the substrate W when the substrate W is held by the substrate holding unit 13 . When the substrate W is held by the substrate holding portion 13, the pattern P faces upward.
　基板Ｗ上の処理液ｇは、液膜Ｇを形成する。液膜Ｇは、基板Ｗ上に位置する。液膜Ｇは、基板Ｗと接する。液膜Ｇは、基板Ｗを覆う。液膜Ｇは、基板Ｗの上面を覆う。 The processing liquid g on the substrate W forms a liquid film G. A liquid film G is located on the substrate W. As shown in FIG. The liquid film G is in contact with the substrate W. As shown in FIG. A liquid film G covers the substrate W. FIG. The liquid film G covers the upper surface of the substrate W. As shown in FIG.
　パターンＰの全部は、液膜Ｇに浸漬される。凸部Ｗ１の全部は、液膜Ｇに浸漬される。凹部Ａは、液膜Ｇで満たされる。凹部Ａの全部は、液膜Ｇのみで満たされる。 The entire pattern P is immersed in the liquid film G. All of the protrusions W1 are immersed in the liquid film G. The recess A is filled with the liquid film G. All of the recesses A are filled with the liquid film G only.
　液膜Ｇは、上面Ｇ１を有する。上面Ｇ１は、パターンＰの全部よりも高い位置に位置する。上面Ｇ１は、パターンＰと交わらない。上面Ｇ１は、凸部Ｗ１の全部よりも高い位置に位置する。上面Ｇ１は、凸部Ｗ１と交わらない。 The liquid film G has an upper surface G1. The upper surface G1 is positioned higher than the entire pattern P. As shown in FIG. The upper surface G1 does not intersect the pattern P. The upper surface G1 is positioned higher than all of the protrusions W1. The upper surface G1 does not intersect with the protrusion W1.
　なお、置換液は、既に、処理液ｇによって、基板Ｗから除去された。このため、置換液は、基板Ｗ上に存在しない。置換液は、凹部Ａに残らない。 Note that the replacement liquid has already been removed from the substrate W by the processing liquid g. Therefore, the replacement liquid does not exist on the substrate W. FIG. The replacement liquid does not remain in the recess A.
　気体Ｊは、液膜Ｇの上方に存在する。パターンＰは、気体Ｊと接しない。パターンＰは、気体Ｊに露出しない。凸部Ｗ１は、気体Ｊと接しない。凸部Ｗ１は、気体Ｊに露出しない。 The gas J exists above the liquid film G. The pattern P does not come into contact with the gas J. The pattern P is not exposed to the gas J. The convex portion W1 does not come into contact with the gas J. The convex portion W1 is not exposed to the gas J.
　気体Ｊは、液膜Ｇと接する。気体Ｊは、上面Ｇ１と接する。上面Ｇ１は、液膜Ｇと気体Ｊの間の気液界面に相当する。したがって、パターンＰは、液膜Ｇと気体Ｊの間の気液界面と交わらない。凸部Ｗ１は、液膜Ｇと気体Ｊの間の気液界面と交わらない。 The gas J is in contact with the liquid film G. The gas J is in contact with the upper surface G1. The upper surface G1 corresponds to the gas-liquid interface between the liquid film G and the gas J. FIG. Therefore, the pattern P does not intersect the gas-liquid interface between the liquid film G and the gas J. The convex portion W1 does not intersect the gas-liquid interface between the liquid film G and the gas J.
　処理液供給工程では、さらに、上面Ｇ１の高さ位置を調整してもよい。例えば、ノズル１６ａが処理液ｇを基板Ｗに供給しながら、上面Ｇ１の高さ位置を調整してもよい。例えば、ノズル１６ａが処理液ｇの供給を停止した後に、上面Ｇ１の高さ位置を調整してもよい。例えば、基板Ｗの回転速度を調節することによって、上面Ｇ１の高さ位置を調整してもよい。例えば、基板Ｗの回転時間を調節することによって、上面Ｇ１の高さ位置を調整してもよい。 In the processing liquid supply process, the height position of the upper surface G1 may be further adjusted. For example, the height position of the upper surface G1 may be adjusted while the nozzle 16a supplies the processing liquid g to the substrate W. FIG. For example, the height position of the upper surface G1 may be adjusted after the nozzle 16a stops supplying the treatment liquid g. For example, by adjusting the rotation speed of the substrate W, the height position of the upper surface G1 may be adjusted. For example, by adjusting the rotation time of the substrate W, the height position of the upper surface G1 may be adjusted.
　ここで、上面Ｇ１の高さ位置を調整することは、液膜Ｇの厚みＨを調整することに相当する。液膜Ｇの厚みＨは、例えば、凸部Ｗ１の下端Ｗ１ａと上面Ｇ１との間の鉛直方向Ｚにおける距離である。 Here, adjusting the height position of the upper surface G1 corresponds to adjusting the thickness H of the liquid film G. The thickness H of the liquid film G is, for example, the distance in the vertical direction Z between the lower end W1a of the protrusion W1 and the upper surface G1.
　ステップＳ１６：固化膜形成工程
　固化膜形成工程では、溶媒は基板Ｗ上の処理液ｇから蒸発する。固化膜形成工程では、固化膜が基板Ｗ上に形成される。固化膜は昇華性物質を含む。 Step S16: Solidified Film Forming Step In the solidified film forming step, the solvent evaporates from the processing liquid g on the substrate W. FIG. A solidified film is formed on the substrate W in the solidified film forming step. The solidified film contains a sublimable substance.
　図７は、固化膜形成工程における基板Ｗを模式的に示す図である。上述の通り、溶媒は、比較的に高い蒸気圧を有する。常温において、溶媒は、昇華性物質よりも高い蒸気圧を有する。このため、溶媒は、円滑に、基板Ｗ上の処理液ｇから蒸発する。溶媒は、円滑に、液体から気体に変化する。 FIG. 7 is a diagram schematically showing the substrate W in the solidified film forming step. As mentioned above, solvents have relatively high vapor pressures. At normal temperature, the solvent has a higher vapor pressure than the sublimable substance. Therefore, the solvent smoothly evaporates from the processing liquid g on the substrate W. FIG. The solvent smoothly changes from liquid to gas.
　溶媒が基板Ｗ上の処理液ｇから蒸発するとき、溶媒は基板Ｗ上の処理液ｇから去る。溶媒が基板Ｗ上の処理液ｇから蒸発するにしたがって、液膜Ｇに含まれる溶媒の量は減少する。液膜Ｇに含まれる溶媒の量が減少するにしたがって、液膜Ｇの体積比ＲＶは上昇する。 The solvent leaves from the processing liquid g on the substrate W when the solvent evaporates from the processing liquid g on the substrate W. As the solvent evaporates from the processing liquid g on the substrate W, the amount of solvent contained in the liquid film G decreases. As the amount of solvent contained in the liquid film G decreases, the volume ratio RV of the liquid film G increases.
　やがて、液膜Ｇ中の昇華性物質は基板Ｗ上において析出し始める。すなわち、昇華性物質は、処理液ｇの溶質から、固相の昇華性物質に変わる。固相の昇華性物質は、固化膜Ｋを形成する。固化膜Ｋは、溶媒を含まない。固化膜Ｋは、固体である。固化膜Ｋは、基板Ｗ上に形成される。 Eventually, the sublimable substance in the liquid film G begins to precipitate on the substrate W. That is, the sublimable substance changes from the solute of the treatment liquid g to a solid-phase sublimable substance. A solid-phase sublimable substance forms a solidified film K. FIG. The solidified film K does not contain solvent. The solidified film K is solid. A solidified film K is formed on the substrate W. As shown in FIG.
　溶媒の蒸発および昇華性物質の析出によって、液膜Ｇは徐々に減少する。昇華性物質の析出によって、液膜Ｇは徐々に固化膜Ｋに変わる。昇華性物質の析出によって、固化膜Ｋは徐々に増大する。 The liquid film G gradually decreases due to the evaporation of the solvent and the precipitation of sublimable substances. The liquid film G gradually transforms into a solidified film K by the deposition of the sublimable substance. The solidified film K gradually increases due to the deposition of the sublimable substance.
　まず、液膜Ｇの上部が、固化膜Ｋに変わる。固化膜Ｋは、液膜Ｇの上方に位置する。固化膜Ｋは、液膜Ｇの上面Ｇ１を覆う。 First, the upper part of the liquid film G turns into a solidified film K. The solidified film K is positioned above the liquid film G. As shown in FIG. The solidified film K covers the upper surface G1 of the liquid film G. As shown in FIG.
　固化膜Ｋが上面Ｇ１の全部を覆ったとき、固化膜Ｋは液膜Ｇを気体Ｊから隔てる。液膜Ｇは固化膜Ｋと接する。気体Ｊは固化膜Ｋと接する。液膜Ｇは、気体Ｊと接しない。上面Ｇ１は、気体Ｊと接しない。液膜Ｇと気体Ｊの間の気液界面は、消失する。 When the solidified film K covers the entire upper surface G1, the solidified film K separates the liquid film G from the gas J. The liquid film G is in contact with the solidified film K. The gas J is in contact with the solidified film K. The liquid film G does not come into contact with the gas J. The upper surface G1 does not come into contact with the gas J. The gas-liquid interface between the liquid film G and the gas J disappears.
　このため、パターンＰは、気液界面と交わらない。液膜Ｇは、パターンＰに有意な力を作用しない。凸部Ｗ１は、気液界面と交わらない。液膜Ｇは、凸部Ｗ１に有意な力を作用しない。 Therefore, the pattern P does not cross the gas-liquid interface. The liquid film G exerts no significant force on the pattern P. The convex portion W1 does not cross the gas-liquid interface. The liquid film G does not exert a significant force on the protrusion W1.
　固化膜Ｋが増大するにしたがって、上面Ｇ１の高さ位置は徐々に低くなる。固化膜Ｋが増大するにしたがって、液膜Ｇの厚みＨは徐々に小さくなる。液膜Ｇが凸部Ｗ１に有意な力を作用することなく、液膜Ｇは減少する。溶媒が凸部Ｗ１に有意な力を作用することなく、溶媒は基板Ｗから去る。 As the solidified film K increases, the height position of the upper surface G1 gradually decreases. As the solidified film K increases, the thickness H of the liquid film G gradually decreases. The liquid film G is reduced without exerting a significant force on the convex portion W1. The solvent leaves the substrate W without the solvent exerting any significant force on the protrusions W1.
　図８は、固化膜形成工程における基板Ｗを模式的に示す図である。図８は、例えば、固化膜形成工程の終了時における基板Ｗを模式的に示す。固化膜Ｋのみが基板Ｗ上に存在する。固化膜形成工程の終了時、液膜Ｇの全部は基板Ｗ上から消失する。液膜Ｇは凹部Ａに残らない。溶媒の全部は基板Ｗ上から消失する。溶媒も凹部Ａに残らない。 FIG. 8 is a diagram schematically showing the substrate W in the solidified film forming step. FIG. 8, for example, schematically shows the substrate W at the end of the solidified film forming process. Only the solidified film K exists on the substrate W. FIG. The entire liquid film G disappears from the substrate W at the end of the solidified film forming process. The liquid film G does not remain in the recess A. All of the solvent disappears from the substrate W. The solvent does not remain in the recesses A either.
　凹部Ａは、固化膜Ｋで満たされる。凹部Ａの全部は、固化膜Ｋのみで満たされる。パターンＰは、固化膜Ｋと接する。固化膜Ｋは、パターンＰを支持する。固化膜Ｋは、パターンＰを保護する。例えば、パターンＰが倒壊することを、固化膜Ｋは防止する。凸部Ｗ１は、固化膜Ｋと接する。固化膜Ｋは、凸部Ｗ１を支持する。固化膜Ｋは、凸部Ｗ１を保護する。例えば、凸部Ｗ１が倒壊することを、固化膜Ｋは防止する。 The recess A is filled with the solidified film K. All of the recesses A are filled with the solidified film K only. The pattern P is in contact with the solidified film K. As shown in FIG. The solidified film K supports the pattern P. The solidified film K protects the pattern P. For example, the solidified film K prevents the pattern P from collapsing. The convex portion W1 is in contact with the solidified film K. As shown in FIG. The solidified film K supports the protrusion W1. The solidified film K protects the protrusion W1. For example, the solidified film K prevents the protrusion W1 from collapsing.
　ステップＳ１７：昇華工程
　昇華工程では、固化膜Ｋは昇華する。 Step S17: Sublimation Process In the sublimation process, the solidified film K is sublimated.
　第５供給部１５ｅは、基板保持部１３によって保持される基板Ｗに乾燥ガスを供給する。具体的には、弁１８ｅは開く。ノズル１６ｅは、乾燥ガスを吐出する。ノズル１６ｅは、基板Ｗに乾燥ガスを吹き出す。乾燥ガスは、基板Ｗの上面に供給される。乾燥ガスは、固化膜Ｋに供給される。固化膜Ｋは、乾燥ガスに晒される。これにより、固化膜Ｋは昇華する。固化膜Ｋは、液体を経ずに、気体に変化する。固化膜Ｋの昇華によって、固化膜Ｋは基板Ｗから除去される。 The fifth supply unit 15e supplies dry gas to the substrate W held by the substrate holding unit 13. Specifically, valve 18e is opened. The nozzle 16e ejects dry gas. The nozzle 16e blows off the dry gas onto the substrate W. As shown in FIG. A drying gas is supplied to the top surface of the substrate W. As shown in FIG. A dry gas is supplied to the solidified film K. As shown in FIG. The solidified film K is exposed to dry gas. Thereby, the solidified film K is sublimated. The solidified film K changes to gas without passing through liquid. The solidified film K is removed from the substrate W by the sublimation of the solidified film K. As shown in FIG.
　その後、第５供給部１５ｅは、固化膜Ｋに対する乾燥ガスの供給を停止する。具体的には、弁１８ｅは閉じる。ノズル１６ｅは、乾燥ガスの吹き出しを停止する。 After that, the fifth supply unit 15e stops supplying the dry gas to the solidified film K. Specifically, valve 18e is closed. The nozzle 16e stops blowing dry gas.
　図９は、昇華工程における基板Ｗを模式的に示す図である。固化膜Ｋが昇華するに従って、固化膜Ｋは徐々に減少する。固化膜Ｋが昇華するに従って、固化膜Ｋは徐々に薄くなる。 FIG. 9 is a diagram schematically showing the substrate W in the sublimation process. As the solidified film K sublimates, the solidified film K gradually decreases. As the solidified film K sublimates, the solidified film K gradually becomes thinner.
　パターンＰは、気体Ｊに露出し始める。凸部Ｗ１は、気体Ｊに露出し始める。 The pattern P begins to be exposed to the gas J. The protrusion W1 begins to be exposed to the gas J.
　固化膜Ｋが昇華するとき、固化膜Ｋは液体に変化しない。このため、昇華工程では、液体は、基板Ｗ上に存在しない。昇華工程では、液体は、凹部Ａに存在しない。昇華工程では、気液界面は、パターンＰの近傍に発生しない。 When the solidified film K sublimates, the solidified film K does not change into a liquid. Therefore, no liquid exists on the substrate W in the sublimation process. No liquid exists in the recess A in the sublimation process. A gas-liquid interface does not occur near the pattern P in the sublimation process.
　よって、パターンＰは、気液界面と交わらない。固化膜Ｋは、パターンＰに有意な力を作用しない。固化膜ＫがパターンＰに有意な力を作用することなく、固化膜Ｋは基板Ｗから去る。凸部Ｗ１は、気液界面と交わらない。固化膜Ｋは、凸部Ｗ１に有意な力を作用しない。固化膜Ｋが凸部Ｗ１に有意な力を作用することなく、固化膜Ｋは基板Ｗから去る。 Therefore, the pattern P does not cross the gas-liquid interface. The solidified film K does not exert a significant force on the pattern P. The solidified film K leaves the substrate W without the solidified film K exerting any significant force on the pattern P. FIG. The convex portion W1 does not cross the gas-liquid interface. The solidified film K does not exert a significant force on the protrusion W1. The solidified film K leaves the substrate W without the solidified film K exerting a significant force on the protrusions W1.
　図１０は、昇華工程における基板Ｗを模式的に示す図である。図１０は、例えば、昇華工程の終了時における基板Ｗを模式的に示す。昇華工程の終了時、固化膜Ｋの全部は、基板Ｗ上から消失する。液体は、基板Ｗ上に存在しない。パターンＰの全部は、気体Ｊに露出する。凸部Ｗ１の全部は、気体Ｊに露出する。凹部Ａの全部は、気体Ｊのみで満たされる。基板Ｗは、乾燥される。 FIG. 10 is a diagram schematically showing the substrate W in the sublimation process. FIG. 10 schematically shows the substrate W, for example, at the end of the sublimation process. All of the solidified film K disappears from the substrate W at the end of the sublimation process. No liquid is present on the substrate W. All of the pattern P is exposed to the gas J. All of the protrusions W1 are exposed to the gas J. All of the recesses A are filled with gas J only. The substrate W is dried.
　上述した処理液供給工程、固化膜形成工程および昇華工程における処理は、乾燥処理の例である。上述した処理液供給工程、固化膜形成工程および昇華工程における処理は、処理液ｇの使用例に相当する。処理液ｇは、常温の環境の下で、使用される。処理液ｇは、常圧の環境の下で、使用される。 The processes in the above-described treatment liquid supply process, solidified film formation process, and sublimation process are examples of the drying process. The treatments in the treatment liquid supply step, the solidified film formation step, and the sublimation step described above correspond to examples of using the treatment liquid g. The treatment liquid g is used under normal temperature environment. The treatment liquid g is used under normal pressure environment.
　ステップＳ１８：回転停止工程
　回転駆動部１４は、基板保持部１３の回転を停止する。基板保持部１３に保持される基板Ｗは、回転を停止する。基板Ｗは、静止する。処理ユニット１１は、基板Ｗに対する処理を終了する。 Step S<b>18 : Rotation Stopping Step The rotation driving section 14 stops the rotation of the substrate holding section 13 . The substrate W held by the substrate holding part 13 stops rotating. The substrate W is stationary. The processing unit 11 finishes processing the substrate W. FIG.
　＜７．処理液ｇの技術的意義＞
　実験例と比較例によって、処理液ｇの技術的意義を説明する。 <7. Technical significance of treatment liquid g>
The technical significance of the treatment liquid g will be explained through experimental examples and comparative examples.
　実験例の条件を説明する。実験例では、薬液供給工程とリンス液供給工程と置換液供給工程と処理液供給工程と固化膜形成工程と昇華工程を含む一連の処理を、基板Ｗは受ける。 Explain the conditions of the experimental example. In the experimental example, the substrate W undergoes a series of processes including a chemical liquid supply process, a rinse liquid supply process, a replacement liquid supply process, a treatment liquid supply process, a solidified film formation process, and a sublimation process.
　薬液供給工程で使用される薬液は、フッ化水素酸である。フッ化水素酸は、フッ化水素と水の混合液である。フッ化水素と水の体積比は、以下の通りである。
　　フッ化水素：水＝１：１０（体積比） The chemical solution used in the chemical solution supply step is hydrofluoric acid. Hydrofluoric acid is a mixture of hydrogen fluoride and water. The volume ratio of hydrogen fluoride and water is as follows.
Hydrogen fluoride: water = 1:10 (volume ratio)
　リンス液供給工程で使用されるリンス液は、脱イオン水（ＤＩＷ）である。 The rinse liquid used in the rinse liquid supply process is deionized water (DIW).
　置換液供給工程で使用される置換液は、イソプロピルアルコールである。 The replacement liquid used in the replacement liquid supply process is isopropyl alcohol.
　処理液供給工程で使用される処理液ｇは、昇華性物質と溶媒からなる。昇華性物質は、４－ニトロトルエンである。溶媒は、イソプロピルアルコール（ＩＰＡ）である。処理液ｇの体積比ＲＶは、２．５［Ｖｏｌ％］である。 The processing liquid g used in the processing liquid supply process consists of a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. The solvent is isopropyl alcohol (IPA). The volume ratio RV of the treatment liquid g is 2.5 [Vol %].
　固化膜形成工程では、１５００ｒｐｍの回転速度で、基板Ｗを回転する。 In the solidified film forming process, the substrate W is rotated at a rotation speed of 1500 rpm.
　昇華工程では、１５００ｒｐｍの回転速度で、基板Ｗを回転しつつ、乾燥ガスを基板Ｗに供給する。 In the sublimation process, dry gas is supplied to the substrate W while rotating the substrate W at a rotation speed of 1500 rpm.
　比較例の条件を説明する。比較例と実験例の違いは、昇華性物質のみである。比較例では、昇華性物質は、シクロヘキサノンオキシムである。これ以外の条件については、比較例は実験例と同じである。 Explain the conditions of the comparative example. The only difference between the comparative example and the experimental example is the sublimable substance. In a comparative example, the sublimable substance is cyclohexanone oxime. Other conditions are the same in the comparative example as in the experimental example.
　実験例および比較例で処理された各基板Ｗは、平均倒壊率Ｆａによって、評価された。平均倒壊率Ｆａは、複数の局所倒壊率Ｆｉの平均値である。 Each substrate W processed in the experimental example and comparative example was evaluated by the average collapse rate Fa. The average collapse rate Fa is the average value of a plurality of local collapse rates Fi.
　各局所倒壊率Ｆｉは、局所エリアＰｉにおける倒壊率である。ここで、ｉは、１からＮまでの任意の自然数である。Ｎは、局所エリアＰｉの数である。各局所エリアＰｉは、基板Ｗの微小領域である。各局所エリアＰｉは、例えば、走査型電子顕微鏡によって５０，０００倍に拡大される。観察者は、各局所エリアＰｉにおけるパターンＰ（凸部Ｗ１）を観察する。観察者は、各局所エリアＰｉにおける凸部Ｗ１を１つずつ評価する。観察者は、各局所エリアＰｉにおける凸部Ｗ１を１つずつ判定する。具体的には、観察者は、凸部Ｗ１が倒壊したか否かを、各凸部Ｗ１について、判定する。観察者は、各局所エリアＰｉにおいて、評価した凸部Ｗ１の数Ｅｉを計数する。観察者は、各局所エリアＰｉにおいて、判定した凸部Ｗ１の数Ｅｉを計数する。観察者は、各局所エリアＰｉにおいて、倒壊した凸部Ｗ１の数ｅｉを計数する。数ｅｉは、数Ｅｉ以下である。局所倒壊率Ｆｉは、数Ｅｉに対する数ｅｉの割合である。局所倒壊率Ｆｉは、例えば、次式によって、規定される。
　　Ｆｉ＝ｅｉ／Ｅｉ＊１００　（％） Each local collapse rate Fi is a collapse rate in a local area Pi. Here, i is any natural number from 1 to N. N is the number of local areas Pi. Each local area Pi is a minute region of the substrate W. As shown in FIG. Each local area Pi is magnified 50,000 times, for example, by a scanning electron microscope. The observer observes the pattern P (convex portion W1) in each local area Pi. The observer evaluates the convex portion W1 in each local area Pi one by one. The observer judges the convex portion W1 in each local area Pi one by one. Specifically, the observer determines whether or not each convex portion W1 has collapsed. The observer counts the number Ei of evaluated protrusions W1 in each local area Pi. The observer counts the number Ei of the determined convex portions W1 in each local area Pi. The observer counts the number ei of collapsed protrusions W1 in each local area Pi. The number ei is less than or equal to the number Ei. The local collapse rate Fi is the ratio of the number ei to the number Ei. The local collapse rate Fi is defined, for example, by the following equation.
Fi=ei/Ei*100 (%)
　平均倒壊率Ｆａは、各局所エリアＰｉにおける局所倒壊率Ｆｉの和を、局所エリアＰｉの数Ｎで除した値である。 The average collapse rate Fa is a value obtained by dividing the sum of the local collapse rates Fi in each local area Pi by the number N of local areas Pi.
　実験例では、平均倒壊率Ｆａは２．７０％であった。比較例では、平均倒壊率Ｆａは４．４５％であった。実験例における平均倒壊率Ｆａは、比較例における平均倒壊率Ｆａよりも低かった。実験例では、基板ＷのパターンＰは、比較例よりも倒壊し難い。 In the experimental example, the average collapse rate Fa was 2.70%. In the comparative example, the average collapse rate Fa was 4.45%. The average collapse rate Fa in the experimental example was lower than the average collapse rate Fa in the comparative example. In the experimental example, the pattern P on the substrate W is less likely to collapse than in the comparative example.
　したがって、実験例では、基板Ｗに形成されたパターンＰは、比較例よりも適切に、保護された。すなわち、実験例では、比較例よりも適切に、基板Ｗは乾燥された。 Therefore, in the experimental example, the pattern P formed on the substrate W was protected more appropriately than in the comparative example. That is, in the experimental example, the substrate W was dried more appropriately than in the comparative example.
　＜８．実施形態の効果＞
　実施形態の基板処理方法は、パターンＰが形成された基板Ｗを処理するためのものである。基板処理方法は、処理液供給工程と固化膜形成工程と昇華工程を備える。処理液供給工程では、処理液ｇが基板Ｗに供給される。処理液ｇは、昇華性物質と溶媒を含む。固化膜形成工程では、溶媒は基板Ｗ上の処理液ｇから蒸発する。固化膜形成工程では、固化膜Ｋが基板Ｗ上に形成される。固化膜Ｋは、昇華性物質を含む。昇華工程では、固化膜Ｋは昇華する。固化膜の昇華により、基板Ｗは乾燥される。ここで、昇華性物質は、４－ニトロトルエンである。すなわち、処理液ｇは、４－ニトロトルエンと溶媒を含む。このため、固化膜Ｋは４－ニトロトルエンを含む。よって、基板Ｗは適切に乾燥される。具体的には、基板Ｗに形成されるパターンＰは好適に保護されつつ、基板Ｗは乾燥される。 <8. Effect of Embodiment>
A substrate processing method according to an embodiment is for processing a substrate W on which a pattern P is formed. The substrate processing method includes a processing liquid supply step, a solidified film forming step, and a sublimation step. The processing liquid g is supplied to the substrate W in the processing liquid supply step. The treatment liquid g contains a sublimable substance and a solvent. The solvent evaporates from the processing liquid g on the substrate W in the solidified film forming step. A solidified film K is formed on the substrate W in the solidified film forming step. The solidified film K contains a sublimable substance. In the sublimation process, the solidified film K is sublimated. The substrate W is dried by sublimation of the solidified film. Here, the sublimable substance is 4-nitrotoluene. That is, the treatment liquid g contains 4-nitrotoluene and a solvent. Therefore, the solidified film K contains 4-nitrotoluene. The substrate W is thus properly dried. Specifically, the substrate W is dried while the pattern P formed on the substrate W is suitably protected.
　溶媒は、イソプロピルアルコールである。イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。このため、４－ニトロトルエンを昇華性物質として含む処理液ｇを使用することは、容易である。例えば、処理液供給工程では、４－ニトロトルエンを含む処理液ｇは、基板Ｗに適切に供給される。 The solvent is isopropyl alcohol. Isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, it is easy to use the treatment liquid g containing 4-nitrotoluene as a sublimable substance. For example, in the processing liquid supply step, the processing liquid g containing 4-nitrotoluene is appropriately supplied to the substrate W. As shown in FIG.
　イソプロピルアルコールは、４－ニトロトルエンよりも容易に蒸発する。このため、固化膜形成工程では、イソプロピルアルコールは、基板Ｗ上の処理液ｇから好適に蒸発する。よって、固化膜形成工程では、固化膜Ｋは、基板Ｗ上に、好適に形成される。したがって、基板Ｗは、一層適切に乾燥される。 Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, isopropyl alcohol is preferably evaporated from the processing liquid g on the substrate W in the solidified film forming step. Therefore, the solidified film K is preferably formed on the substrate W in the solidified film forming step. The substrate W is thus dried better.
　基板処理方法は、処理液生成工程を備える。処理液生成工程では、処理液ｇが生成される。よって、処理液ｇは好適に準備される。 The substrate processing method includes a processing liquid generation step. In the treatment liquid generating step, the treatment liquid g is generated. Therefore, the processing liquid g is preferably prepared.
　上述の通り、イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。このため、処理液生成工程では、４－ニトロトルエンを含む処理液ｇは、好適に生成される。 As mentioned above, isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, in the treatment liquid generating step, the treatment liquid g containing 4-nitrotoluene is preferably generated.
　上述の通り、イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。このため、４－ニトロトルエンを含む処理液ｇは、好適に保管される。 As mentioned above, isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, the treatment liquid g containing 4-nitrotoluene is preferably stored.
　基板処理装置１は、基板保持部１３と第１供給部１５ａを備える。基板保持部１３は、基板Ｗを保持する。処理液供給部１５ａは、基板保持部１３によって保持される基板Ｗに処理液ｇを供給する。処理液ｇは、昇華性物質と溶媒を含む。昇華性物質は、４－ニトロトルエンである。このため、処理液ｇが基板Ｗに供給されたとき、溶媒は基板Ｗ上の処理液ｇから好適に蒸発する。よって、固化膜Ｋは基板Ｗ上に好適に形成される。固化膜Ｋは、４－ニトロトルエンを含む。このため、固化膜Ｋは、適切に昇華する。固化膜Ｋの昇華により、基板Ｗは適切に乾燥される。以上の通り、基板処理装置１によれば、基板Ｗは適切に乾燥される。 The substrate processing apparatus 1 includes a substrate holding section 13 and a first supply section 15a. The substrate holding part 13 holds the substrate W. As shown in FIG. The processing liquid supply part 15 a supplies the processing liquid g to the substrate W held by the substrate holding part 13 . The treatment liquid g contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, when the processing liquid g is supplied to the substrate W, the solvent is preferably evaporated from the processing liquid g on the substrate W. FIG. Therefore, the solidified film K is preferably formed on the substrate W. As shown in FIG. The solidified film K contains 4-nitrotoluene. Therefore, the solidified film K is appropriately sublimated. Sublimation of the solidified film K properly dries the substrate W. As described above, according to the substrate processing apparatus 1, the substrate W is properly dried.
　溶媒は、イソプロピルアルコールである。上述の通り、イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。イソプロピルアルコールは、４－ニトロトルエンよりも容易に蒸発する。したがって、基板Ｗは、一層適切に乾燥される。 The solvent is isopropyl alcohol. As mentioned above, isopropyl alcohol preferably dissolves 4-nitrotoluene. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. The substrate W is thus dried better.
　処理液ｇは、パターンＰが形成された基板Ｗの乾燥に用いられる。処理液ｇは、具体的には、乾燥補助液である。処理液ｇは、昇華性物質と溶媒を含む。昇華性物質は、４－ニトロトルエンである。このため、処理液ｇは、基板Ｗを乾燥させるために、有用である。具体的には、処理液ｇを用いることによって、基板Ｗに形成されるパターンＰは好適に保護されつつ、基板Ｗは乾燥される。以上の通り、処理液ｇを用いて、基板Ｗは適切に乾燥される。 The processing liquid g is used for drying the substrate W on which the pattern P is formed. The treatment liquid g is specifically a drying auxiliary liquid. The treatment liquid g contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, the processing liquid g is useful for drying the substrate W. FIG. Specifically, by using the treatment liquid g, the substrate W is dried while the pattern P formed on the substrate W is suitably protected. As described above, the substrate W is properly dried using the treatment liquid g.
　溶媒は、イソプロピルアルコールである。上述の通り、イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。イソプロピルアルコールは、４－ニトロトルエンよりも容易に蒸発する。このため、処理液ｇは、基板Ｗを乾燥させるために、一層有用である。処理液ｇを用いて、基板Ｗは一層適切に乾燥される。 The solvent is isopropyl alcohol. As mentioned above, isopropyl alcohol preferably dissolves 4-nitrotoluene. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the processing liquid g is more useful for drying the substrate W. FIG. Using the treatment liquid g, the substrate W is more properly dried.
　上述の通り、イソプロピルアルコールは、４－ニトロトルエンを好適に溶解する。よって、４－ニトロトルエンを含む処理液ｇの取り扱いは、容易である。例えば、４－ニトロトルエンを含む処理液ｇを準備することは、容易である。例えば、４－ニトロトルエンを含む処理液ｇを生成することは、容易である。例えば、４－ニトロトルエンを含む処理液ｇを保管することは、容易である。例えば、４－ニトロトルエンを含む処理液ｇを使用することは、容易である。 As mentioned above, isopropyl alcohol preferably dissolves 4-nitrotoluene. Therefore, the treatment liquid g containing 4-nitrotoluene can be easily handled. For example, it is easy to prepare a treatment liquid g containing 4-nitrotoluene. For example, it is easy to generate a treatment liquid g containing 4-nitrotoluene. For example, it is easy to store the treatment liquid g containing 4-nitrotoluene. For example, it is easy to use a treatment liquid g containing 4-nitrotoluene.
　＜９．変形実施形態＞
　本発明は、実施形態に限られることはなく、下記のように変形実施することができる。 <9. Modified embodiment>
The present invention is not limited to the embodiments, and can be modified as follows.
　（１）実施形態では、処理液ｇが第１供給部１５ａに供給される前に、処理液ｇは生成された。実施形態では、第１供給源１９ａは、槽２２において、処理液を生成した。但し、これに限られない。例えば、処理液ｇが第１供給部１５ａに供給されるときに、処理液ｇは生成されてもよい。例えば、第１供給源１９ａは、処理液ｇを第１供給部１５ａに供給する流路で、処理液ｇを生成してもよい。 (1) In the embodiment, the processing liquid g is generated before the processing liquid g is supplied to the first supply section 15a. In an embodiment, the first source 19a produced processing liquid in vessel 22 . However, it is not limited to this. For example, the treatment liquid g may be generated when the treatment liquid g is supplied to the first supply section 15a. For example, the first supply source 19a may generate the treatment liquid g in a channel that supplies the treatment liquid g to the first supply section 15a.
　図１１は、変形実施形態の処理ユニット１１および第１供給源１９ａの構成を示す図である。なお、実施形態と同じ構成については同符号を付すことで詳細な説明を省略する。 FIG. 11 is a diagram showing the configuration of the processing unit 11 and the first supply source 19a of the modified embodiment. In addition, detailed description is abbreviate|omitted by attaching|subjecting the same code|symbol about the same structure as embodiment.
　第１供給源１９ａは、第１槽４１と第２槽４２を備える。第１槽４１は、昇華性物質を貯留する。例えば、第１槽４１は、昇華性物質とともに溶媒を貯留してもよい。第２槽４２は、溶媒を貯留する。例えば、第２槽４２は、溶媒のみを貯留する。 The first supply source 19a includes a first tank 41 and a second tank 42. The first tank 41 stores a sublimable substance. For example, the first tank 41 may store the solvent together with the sublimable substance. The second tank 42 stores the solvent. For example, the second tank 42 stores only the solvent.
　第１供給源１９ａは、混合部４４を備える。混合部４４は、第１槽４１と第２槽４２に接続される。混合部４４は、第１槽４１と第２槽４２に連通する。混合部４４は、処理液ｇを生成する。 The first supply source 19 a includes a mixing section 44 . The mixing section 44 is connected to the first tank 41 and the second tank 42 . The mixing section 44 communicates with the first tank 41 and the second tank 42 . The mixing section 44 generates the treatment liquid g.
　混合部４４は、第１供給部１５ａに接続される。混合部４４は、第１供給部１５ａに連通する。混合部４４は、処理液ｇを第１供給部１５ａに供給する。 The mixing section 44 is connected to the first supply section 15a. The mixing section 44 communicates with the first supply section 15a. The mixing section 44 supplies the treatment liquid g to the first supply section 15a.
　具体的には、混合部４４は、配管４５ａ、４５ｂと継ぎ手４６を備える。配管４５ａは、第１槽４１に接続される。配管４５ａは、第１槽４１に連通する。配管４５ｂは、第２槽４２に接続される。配管４５ｂは、第２槽４２に連通する。継ぎ手４６は、配管４５ａ、４５ｂに接続される。継ぎ手４６は、配管４５ａ、４５ｂに連通する。継ぎ手４６は、さらに、配管１７ａに接続される。継ぎ手４６は、さらに、配管１７ａに連通する。配管４５ａ、４５ｂは、継ぎ手４６を介して、配管１７ａに接続される。配管４５ａ、４５ｂは、継ぎ手４６を介して、配管１７ａに連通する。 Specifically, the mixing section 44 includes pipes 45 a and 45 b and a joint 46 . The pipe 45 a is connected to the first tank 41 . The pipe 45 a communicates with the first tank 41 . The pipe 45 b is connected to the second tank 42 . The pipe 45b communicates with the second tank 42 . The joint 46 is connected to the pipes 45a and 45b. The joint 46 communicates with the pipes 45a and 45b. The joint 46 is further connected to the pipe 17a. The joint 46 also communicates with the pipe 17a. The pipes 45a and 45b are connected to the pipe 17a via a joint 46. As shown in FIG. The pipes 45 a and 45 b communicate with the pipe 17 a via a joint 46 .
　混合部４４は、ポンプ４７ａ、４７ｂを備える。ポンプ４７ａ、４７ｂはそれぞれ、配管４５ａ、４５ｂに設けられる。ポンプ４７ａは、配管４５ａを通じて、第１槽４１から継ぎ手４６に昇華性物質を送る。ポンプ４７ｂは、配管４５ｂを通じて、第２槽４２から継ぎ手４６に溶媒を送る。 The mixing section 44 includes pumps 47a and 47b. Pumps 47a and 47b are provided in pipes 45a and 45b, respectively. The pump 47a sends the sublimable substance from the first tank 41 to the joint 46 through the pipe 45a. Pump 47b sends the solvent from second tank 42 to joint 46 through pipe 45b.
　混合部４４は、フィルタ４８ａ、４８ｂを備える。フィルタ４８ａ、４８ｂはそれぞれ、配管４５ａ、４５ｂに設けられる。昇華性物質は、フィルタ４８ａを通過する。フィルタ４８ａは、昇華性物質を濾過する。溶媒は、フィルタ４８ｂを通過する。フィルタ４８ｂは、溶媒を濾過する。 The mixing section 44 includes filters 48a and 48b. Filters 48a and 48b are provided in pipes 45a and 45b, respectively. Sublimable substances pass through the filter 48a. The filter 48a filters sublimable substances. Solvent passes through filter 48b. Filter 48b filters the solvent.
　混合部４４は、弁４９ａ、４９ｂを備える。弁４９ａ、４９ｂはそれぞれ、配管４５ａ、４５ｂに設けられる。弁４９ａは、配管４５ａを流れる昇華性物質の流量を調整する。弁４９ｂは、配管４５ｂを流れる溶媒の流量を調整する。弁４９ａ、４９ｂはそれぞれ、例えば、流量調節弁を含んでもよい。弁４９ａ、４９ｂはそれぞれ、例えば、流量調節弁と開閉弁を含んでもよい。 The mixing section 44 includes valves 49a and 49b. Valves 49a and 49b are provided in pipes 45a and 45b, respectively. The valve 49a adjusts the flow rate of the sublimable substance flowing through the pipe 45a. The valve 49b adjusts the flow rate of solvent flowing through the pipe 45b. Valves 49a, 49b may each include, for example, a flow control valve. Valves 49a, 49b may each include, for example, a flow control valve and an on-off valve.
　変形実施形態における第１供給源１９ａの動作例を説明する。処理液供給工程では、第１供給源１９ａは、処理液ｇを生成し、処理液ｇを第１供給部１５ａに送る。具体的には、弁４９ａ、４９ｂは、開く。ポンプ４７ａは、第１槽４１から継ぎ手４６に昇華性物質を送る。ポンプ４７ａは、第１槽４１から継ぎ手４６に昇華性物質を圧送する。ポンプ４７ｂは、第２槽４２から継ぎ手４６に溶媒を送る。ポンプ４７ｂは、第２槽４２から継ぎ手４６に溶媒を圧送する。昇華性物質と溶媒は、継ぎ手４６において、混合される。昇華性物質と溶媒は、継ぎ手４６において、処理液ｇになる。さらに、処理液ｇは、継ぎ手４６から第１供給部１５ａに流れる。ノズル１６ａは、処理液ｇを吐出する。 An operation example of the first supply source 19a in the modified embodiment will be described. In the process liquid supply step, the first supply source 19a generates the process liquid g and sends the process liquid g to the first supply section 15a. Specifically, the valves 49a, 49b are opened. A pump 47 a sends the sublimable substance from the first tank 41 to the joint 46 . The pump 47 a pumps the sublimable substance from the first tank 41 to the joint 46 . A pump 47 b sends solvent from the second tank 42 to the joint 46 . A pump 47 b pumps the solvent from the second tank 42 to the joint 46 . The sublimable substance and solvent are mixed at joint 46 . The sublimable substance and the solvent become the treatment liquid g at the joint 46 . Further, the processing liquid g flows from the joint 46 to the first supply section 15a. The nozzle 16a ejects the treatment liquid g.
　本変形実施形態によれば、処理液ｇが第１供給部１５ａに供給される前に、処理液ｇを保管することを要しない。このため、処理液の体積比ＲＶは、精度良く管理される。よって、基板Ｗは一層適切に乾燥される。 According to this modified embodiment, it is not necessary to store the processing liquid g before it is supplied to the first supply section 15a. Therefore, the volume ratio RV of the processing liquid is controlled with high accuracy. The substrate W is thus more properly dried.
　さらに、第１供給源１９ａは槽２２を備えない。よって、第１供給源１９ａの構造は好適に簡素化される。第１供給源１９ａは好適に小型化される。 Furthermore, the first supply source 19a does not include the tank 22. Therefore, the structure of the first supply source 19a is preferably simplified. The first supply source 19a is preferably miniaturized.
　（２）実施形態の基板処理方法は、薬液供給工程、リンス液供給工程および置換液供給工程を備えた。但し、これに限られない。例えば、薬液供給工程、リンス液供給工程および置換液供給工程の少なくともいずれかを省略してもよい。例えば、薬液供給工程、リンス液供給工程および置換液供給工程の全部を省略してもよい。 (2) The substrate processing method of the embodiment includes a chemical liquid supply process, a rinse liquid supply process, and a replacement liquid supply process. However, it is not limited to this. For example, at least one of the chemical liquid supply process, the rinse liquid supply process, and the replacement liquid supply process may be omitted. For example, the chemical liquid supply process, the rinse liquid supply process, and the replacement liquid supply process may all be omitted.
　（３）実施形態では、処理液供給工程を実行するとき、液体（例えば、置換液）が、基板Ｗ上に存在した。すなわち、処理液供給工程では、乾燥していない状態の基板Ｗに、処理液ｇが供給された。但し、これに限られない。例えば、処理液供給工程を実行するとき、液体（例えば、置換液）は、基板Ｗ上に存在しなくてもよい。例えば、処理液供給工程では、乾燥した状態の基板Ｗに処理液ｇが供給されてもよい。 (3) In the embodiment, the liquid (for example, replacement liquid) was present on the substrate W when the processing liquid supply step was performed. That is, in the process liquid supply step, the process liquid g was supplied to the substrate W in an undried state. However, it is not limited to this. For example, the liquid (for example, replacement liquid) does not have to be present on the substrate W when performing the process liquid supply step. For example, in the process liquid supply step, the process liquid g may be supplied to the substrate W in a dry state.
　（４）実施形態の処理液供給工程では、処理液ｇは、基板Ｗから置換液を除去した。但し、これに限られない。例えば、処理液供給工程では、処理液ｇは、基板Ｗを洗浄してもよい。例えば、処理液供給工程では、処理液ｇは、基板Ｗに付着する異物を除去してもよい。例えば、処理液供給工程では、処理液ｇは、基板Ｗに付着する異物を溶解してもよい。異物は、例えば、レジスト残渣である。 (4) In the processing liquid supply process of the embodiment, the processing liquid g removes the substitution liquid from the substrate W. However, it is not limited to this. For example, the processing liquid g may wash the substrate W in the processing liquid supply step. For example, in the processing liquid supply step, the processing liquid g may remove foreign matter adhering to the substrate W. FIG. For example, in the processing liquid supply step, the processing liquid g may dissolve foreign substances adhering to the substrate W. FIG. Foreign matter is, for example, resist residue.
　（５）実施形態の固化膜形成工程では、乾燥ガスは基板Ｗに供給されなかった。但し、これに限られない。固化膜形成工程では、乾燥ガスが基板Ｗに供給されてもよい。固化膜形成工程では、乾燥ガスが基板Ｗ上の処理液ｇに供給されてもよい。本変形実施形態によれば、固化膜形成工程において、基板Ｗ上の処理液ｇは、乾燥ガスに晒される。このため、固化膜形成工程では、溶媒は、基板Ｗ上の処理液ｇから、効率良く蒸発する。固化膜形成工程では、固化膜Ｋは、基板Ｗ上に効率良く形成される。 (5) Dry gas was not supplied to the substrate W in the solidified film forming process of the embodiment. However, it is not limited to this. A dry gas may be supplied to the substrate W in the solidified film forming step. Dry gas may be supplied to the processing liquid g on the substrate W in the solidified film forming step. According to this modified embodiment, the processing liquid g on the substrate W is exposed to the dry gas in the solidified film forming step. Therefore, the solvent is efficiently evaporated from the processing liquid g on the substrate W in the solidified film forming step. The solidified film K is efficiently formed on the substrate W in the solidified film forming step.
　（６）実施形態において、例えば、処理ユニット１１が基板Ｗを処理する前に、基板Ｗ上のパターンＰは基板Ｗに形成されてもよい。あるいは、処理ユニット１１が基板Ｗを処理するときに、パターンＰは基板Ｗに形成されてもよい。パターンＰは、例えば、薬液供給工程（ステップＳ１２）において、基板Ｗに形成されてもよい。 (6) In the embodiment, the pattern P on the substrate W may be formed on the substrate W before the processing unit 11 processes the substrate W, for example. Alternatively, the pattern P may be formed on the substrate W when the processing unit 11 processes the substrate W. FIG. The pattern P may be formed on the substrate W, for example, in the chemical supply step (step S12).
　（７）実施形態および上記（１）から（６）で説明した各変形実施形態については、さらに各構成を他の変形実施形態の構成に置換または組み合わせるなどして適宜に変更してもよい。 (7) The embodiment and each modified embodiment described in (1) to (6) above may be modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment.
　１　　…　基板処理装置
　１０　…　制御部
　１１　…　処理ユニット
　１３　…　基板保持部
　１５　…　供給部
　１５ａ　…　第１供給部（処理液供給部）
　１９ａ　…　第１供給源
　ｇ　　…　処理液
　Ｇ　…　処理液の液膜
　Ｇ１　…　液膜の上面
　Ｈ　　…　液膜の厚み
　Ｋ　…　固化膜
　Ｗ　…　基板
　Ｐ　…　パターン
　Ｗ１　…　凸部
　Ａ　…　凹部 DESCRIPTION OF SYMBOLS 1... Substrate processing apparatus 10... Control part 11... Processing unit 13... Substrate holding part 15... Supply part 15a... First supply part (processing liquid supply part)
19a ... First supply source g ... Treatment liquid G ... Liquid film of treatment liquid G1 ... Upper surface of liquid film H ... Thickness of liquid film K ... Solidified film W ... Substrate P ... Pattern W1 ... Convex portion A ... Concave portion

Claims (6)

  1. 　パターンが形成された基板を処理する基板処理方法であって、
    　昇華性物質と溶媒を含む処理液を基板に供給する処理液供給工程と、
    　基板上の前記処理液から前記溶媒を蒸発させて、前記昇華性物質を含む固化膜を基板上に形成する固化膜形成工程と、
    　前記固化膜を昇華させる昇華工程と、
    　を備え、
    　前記昇華性物質は、４－ニトロトルエンである
    　基板処理方法。     A substrate processing method for processing a substrate on which a pattern is formed, comprising:
    a processing liquid supplying step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate;
    a solidified film forming step of forming a solidified film containing the sublimable substance on the substrate by evaporating the solvent from the treatment liquid on the substrate;
    a sublimation step of sublimating the solidified film;
    with
    The substrate processing method, wherein the sublimable substance is 4-nitrotoluene.
  2. 　請求項１に記載の基板処理方法において、
    　前記溶媒は、イソプロピルアルコールである
    　基板処理方法。     In the substrate processing method according to claim 1,
    The substrate processing method, wherein the solvent is isopropyl alcohol.
  3. 　基板処理装置であって、
    　基板を保持する基板保持部と、
    　前記基板保持部によって保持される基板に昇華性物質と溶媒を含む処理液を供給する処理液供給部と、
    　を備え、
    　前記昇華性物質は、４－ニトロトルエンである
    　基板処理装置。     A substrate processing apparatus,
    a substrate holder that holds the substrate;
    a processing liquid supply unit that supplies a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding unit;
    with
    The substrate processing apparatus, wherein the sublimable substance is 4-nitrotoluene.
  4. 　請求項３に記載の基板処理装置において、
    　前記溶媒は、イソプロピルアルコールである
    　基板処理装置。     In the substrate processing apparatus according to claim 3,
    The substrate processing apparatus, wherein the solvent is isopropyl alcohol.
  5. 　パターンが形成された基板の乾燥に用いられる処理液であって、
    　前記処理液は、
    　　昇華性物質と、
    　　溶媒と、
    　を含み、
    　前記昇華性物質は、４－ニトロトルエンである
    　処理液。     A treatment liquid used for drying a patterned substrate,
    The treatment liquid is
    a sublimable substance;
    a solvent;
    including
    The sublimable substance is 4-nitrotoluene. The treatment liquid.
  6. 　請求項５に記載の処理液において、
    　前記溶媒は、イソプロピルアルコールである
    　処理液。     In the treatment liquid according to claim 5,
    The solvent is isopropyl alcohol. The treatment liquid.
PCT/JP2022/024527 2021-09-24 2022-06-20 Substrate processing method, substrate processing apparatus, and processing liquid WO2023047724A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017025210A (en) * 2015-07-23 2017-02-02 セントラル硝子株式会社 Solvent composition
JP2021009988A (en) * 2019-06-28 2021-01-28 株式会社Ｓｃｒｅｅｎホールディングス Substrate processing method and substrate processing apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017025210A (en) * 2015-07-23 2017-02-02 セントラル硝子株式会社 Solvent composition
JP2021009988A (en) * 2019-06-28 2021-01-28 株式会社Ｓｃｒｅｅｎホールディングス Substrate processing method and substrate processing apparatus

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