WO2004095550A1 - Dispositif d'elimination de matiere organique, procede d'elimination de matiere organique, buse de projection de jet d'eau a l'ozone, et dispositif d'elimination de matiere organique pour substrat de masquage - Google Patents

Dispositif d'elimination de matiere organique, procede d'elimination de matiere organique, buse de projection de jet d'eau a l'ozone, et dispositif d'elimination de matiere organique pour substrat de masquage Download PDF

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Publication number
WO2004095550A1
WO2004095550A1 PCT/JP2004/005681 JP2004005681W WO2004095550A1 WO 2004095550 A1 WO2004095550 A1 WO 2004095550A1 JP 2004005681 W JP2004005681 W JP 2004005681W WO 2004095550 A1 WO2004095550 A1 WO 2004095550A1
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WO
WIPO (PCT)
Prior art keywords
ozone water
substrate
nozzle
organic matter
organic
Prior art date
Application number
PCT/JP2004/005681
Other languages
English (en)
Japanese (ja)
Inventor
Kazutoshi Yamazaki
Yoshihiko Furuno
Yoji Fujimori
Original Assignee
Sekisui Chemical Co. Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003116217A external-priority patent/JP4351862B2/ja
Priority claimed from JP2003116216A external-priority patent/JP2006196477A/ja
Priority claimed from JP2003116218A external-priority patent/JP2006196479A/ja
Priority claimed from JP2003409375A external-priority patent/JP2006164996A/ja
Application filed by Sekisui Chemical Co. Ltd. filed Critical Sekisui Chemical Co. Ltd.
Publication of WO2004095550A1 publication Critical patent/WO2004095550A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/02—Cleaning by the force of jets or sprays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
    • B08B2203/005—Details of cleaning machines or methods involving the use or presence of liquid or steam the liquid being ozonated

Definitions

  • Organic substance removal device organic substance removal method, ozone water injection nozzle, and for mask substrate
  • the present invention can remove an organic substance, particularly a resist, from a substrate surface with high efficiency, an organic substance removal method, an ozone water injection nozzle, and a highly efficient removal of organic substances on a mask substrate surface. It relates to an organic matter removing device for a mask substrate. Background art
  • a process for removing organic substances attached to the substrate surface is essential.
  • a photolithography step is an essential step.
  • an organic resist is applied to the substrate, an image consisting of a resist pattern is formed by a normal photo process, and etching is performed using this as a mask.
  • a circuit is formed by removing the remaining resist, and in order to form the next circuit, the resist is applied again, and a cycle of image formation, etching and removal of the resist is repeated.
  • Ozone water obtained by dissolving ozone gas in water is due to the strong and oxidizing power of ozone. Disinfecting Deodorizing It has excellent effects on deodorizing and bleaching, etc. In addition, ozone gas self-decomposes into harmless oxygen (gas) over time and has no residual properties. Have been. In recent years, with increasing interest in the environment, an organic matter removal process using ozone water has attracted attention as an alternative to the above-described resist removal method.
  • Japanese Patent Application Laid-Open No. 6-120092 discloses that a circuit-free surface of a substrate is cleaned with a rotary brush together with ozone water supplied by a high-pressure jet nozzle. There is disclosed a resist removing apparatus for cleaning a circuit forming surface of a substrate with ozone water supplied by a high-pressure jet nozzle.
  • Japanese Patent Application Laid-Open No. 2001-351893 discloses that gas-mixed ozone water in which ozone gas is mixed in a bubble state is supplied to the center of a rotating substrate, and the substrate is centrifuged.
  • a method is disclosed in which gas-mixed ozone water flows from the center to the outer periphery of a substrate by force.
  • a resist removing apparatus or a resist removing method using ozone water disclosed in these documents no practical resist removing speed was obtained.
  • it is difficult to produce a large amount of high-concentration ozone water there has been a demand for efficient removal of the resist with a smaller amount of ozone water.
  • Japanese Patent No. 3016301 discloses a method in which an object to be cleaned is diagonally immersed in a liquid in which ozone is dissolved, and the object to be cleaned is irradiated with ultraviolet light.
  • JP-A-2001-79502 discloses that ozone water produced by dissolving ozone gas in pure water by pressurizing ozone gas is placed in a sealed cleaning chamber containing an object to be cleaned while maintaining the pressure. A method for guiding and cleaning an object to be cleaned is disclosed.
  • the object to be cleaned is irradiated with ultraviolet rays.
  • the cleaning performance of the object to be cleaned is improved by applying pressure or applying pressure.However, it is said that any of these methods can achieve a sufficient organic substance removal rate when trying to remove organic substances on the substrate surface. It is difficult to uniformly remove organic substances on the substrate surface. It was very difficult.
  • An object of the present invention is to provide an organic substance removing apparatus, an organic substance removing method, an ozone water jet nozzle, and an organic substance on a mask substrate surface, which can remove organic substances, particularly a resist, on a substrate surface with high efficiency in view of the above situation and problems. It is an object of the present invention to provide an organic matter removing device for a mask substrate, which can remove odors with high efficiency.
  • an organic substance removing apparatus for removing organic substances on a surface of the substrate by flowing ozone water along a processing surface of the substrate, wherein at least the organic substance removing apparatus has A reaction unit comprising: a fixing unit that fixes the substrate so that the processing surface is substantially parallel; and a conversion member that is provided at a position facing the processing surface of the fixed substrate and changes the direction of the flow of the ozone water. It is an organic substance removal device having.
  • the organic matter removing apparatus is preferably configured such that the direction of the flow of the ozone water converted by the conversion member is in a direction toward substantially the entire surface of the substrate, and it is preferable that the apparatus has a means for pressurizing the ozone water. .
  • a second aspect of the present invention is an organic substance removing apparatus for removing organic substances on a substrate surface using ozone water, wherein at least 450 cm / sec or more of ozone water is applied from a nozzle to a processing surface of the substrate.
  • This is an organic matter removing device having a means for jetting at a linear velocity.
  • the organic matter removing apparatus according to the second aspect of the present invention preferably has means for injecting ozone water from the nozzle to the processing surface of the substrate at a linear velocity of 200 cm / sec or less.
  • the inner diameter of the nozzle is 1.0 mm or less, and the distance between the arrival points of the ozone water injected through the nozzle is 3 to 10 mm It is preferable to reach almost the entire processing surface of the substrate as shown in FIG.
  • the organic substance removing method using the first or second organic substance removing apparatus of the present invention is also one of the present inventions.
  • An ozone water injection nozzle used when removing organic substances on the substrate surface using ozone water, wherein a plurality of projection holes are formed at positions corresponding to the entire surface of the processing surface of the substrate, The distance between the adjacent injection holes is 1 Omm or less, and when rotated in a direction perpendicular to the direction of the ozone water injection, the vertical holes are perpendicular to the direction of the ozone water injection.
  • the present invention also includes an ozone water injection nozzle that is arranged so that the trajectories of points corresponding to the center of the injection hole on an arbitrary plane do not overlap.
  • the ozone water injected from the water injection hole be a rod flow, and the water injection hole introduces ozone water into the inside from one end thereof.
  • a large-diameter ozone water supply unit and a relatively small-diameter ozone water injection unit that injects ozone water from one end communicate with each other. Is preferably from 0.5 to 0.5 ram.
  • an organic substance removing apparatus having at least the ozone water injection flap of the present invention and a rotating means for rotating the substrate is also one of the present invention.
  • An organic matter removing method for removing organic matter on a substrate surface using ozone water comprising: a nozzle having a plurality of injection holes formed at positions corresponding to substantially the entire surface of a processing surface of the substrate; An organic matter removing method of injecting ozone water onto substantially the entire surface of the processing surface of the substrate in a state where the ozone water is close to the substrate to such an extent that an ozone water layer is apparently formed between the substrate and the processing surface is also provided.
  • the distance between the nozzle and the substrate is preferably 3 mm or less, and it is preferable that the ozone water is injected through the nozzle while rotating the substrate.
  • An organic substance removing apparatus used when performing the organic substance removing method of the present invention comprising: a nozzle for injecting ozone water onto at least substantially the entire surface of the processing surface of the substrate; and a moving means for moving the nozzle
  • An organic matter removing apparatus having a rotating means for rotating the substrate is also one of the present invention.
  • An organic matter removing method in which ozone water is sprayed onto substantially the entire surface of the processing surface of the substrate while swinging in a direction parallel to the substrate is still another aspect of the present invention.
  • the nozzle is swung so as to orbit above the processing surface of the substrate, and it is preferable to inject ozone water from the nozzle while rotating the substrate. It is preferable to inject ozone water in a stick flow.
  • An organic substance removing apparatus used when performing the organic substance removing method of the present invention according to still another aspect comprising at least a nozzle for projecting ozone water onto substantially the entire surface of the processing surface of the substrate; and
  • An organic matter removing device having a rocking means for rocking is also one of the present inventions.
  • a third aspect of the present invention is a mask substrate organic substance removing apparatus for removing organic substances on a mask substrate surface using ozone water, wherein the organic substance removing apparatus is at least opposed to the upper surface of the mask substrate and between the upper surface of the mask substrate.
  • a mask substrate having a lid portion comprising an upper plate forming an ozone water flow channel, and a side plate facing a side surface of the mask substrate and forming an ozone water flow channel between the mask substrate and a side surface thereof.
  • an organic matter removing apparatus for a mask substrate wherein an ozone water supply unit for supplying ozone water to an ozone water flow channel is formed substantially at the center of the upper plate, and the upper surface of the upper substrate of the mask substrate is provided.
  • a plurality of conversion members for changing the direction of the flow of the ozone water flowing along the upper surface of the mask substrate are formed on the surface facing the mask substrate, and the direction of the flow of the ozone water converted by the conversion member is preferably formed.
  • the direction is directed toward substantially the entire surface of the mask substrate.
  • a plurality of nozzles for injecting ozone water onto the upper surface of the mask substrate are formed at positions corresponding to substantially the entire upper surface of the upper mask substrate. It is preferable that a lower plate facing the lower surface of the mask substrate and forming a channel for an ozone water flow be formed between the lower plate and the lower surface of the mask substrate, wherein the lower plate has ozone for discharging ozone water to the outside. It is preferable to provide a water discharge part, and it is preferable to have a means for pressurizing ozone water.
  • FIG. 1 is a cross-sectional view showing one embodiment of the reaction section of the organic substance removing device of the first invention.
  • FIG. 2 is a schematic view showing one embodiment of the first organic substance removing apparatus of the present invention.
  • 3A is a plan view schematically showing an example of a reaction section of the organic matter removing apparatus according to the first embodiment of the present invention
  • FIG. 3B is a cross-sectional view of the reaction section shown in FIG. (C) is a cross-sectional view taken along line AA of the reaction section shown in (a).
  • FIG. 4A is a plan view schematically showing an example of a holder to be fitted to the holder holding portion of the reaction section shown in FIG. 3, and FIG. 4B is a front view of the holder shown in FIG. It is.
  • FIG. 5 is a perspective view schematically showing another example of the reaction section in the organic matter removing device of the first invention.
  • FIG. 6 is a schematic diagram showing a state of organic matter removal in a conventional organic matter removal device.
  • FIG. 7 is a schematic view showing how organic substances on a substrate are removed by the organic substance removing apparatus of the second invention.
  • FIG. 8 is a schematic view showing another example of the manner in which the organic substance on the substrate is removed by the organic substance removing apparatus of the second invention.
  • FIGS. 9A and 9B are schematic diagrams illustrating an example of an embodiment of a reaction section in the organic substance removing apparatus according to the second invention.
  • FIG. 9B is a schematic view illustrating a reaction section in the organic substance removing apparatus according to the second invention. It is a schematic diagram which shows another example of this embodiment, and (c) is a schematic diagram which shows another example of embodiment of the reaction part in the organic substance removal apparatus of 2nd this invention.
  • FIG. 10 (a) is a plan view schematically showing an example of the ozone water injection nozzle of the present invention, and (b) is a cross-sectional view taken along line AA of the ozone water injection nozzle shown in (a). is there.
  • FIG. 11 is a plan view schematically showing a state in which the ozone water injection nozzle shown in FIG. 10 is rotated in a predetermined direction.
  • FIG. 12 is a plan view schematically showing another example of the ozone water injection nozzle of the present invention.
  • FIG. 13 is a half sectional view schematically showing an example of an embodiment of a reaction section in the organic matter removing device of the present invention.
  • FIG. 14 is a plan view schematically showing an example of a nozzle used in the organic matter removing / removing method of the present invention according to another embodiment.
  • FIG. 15 is a cross-sectional view showing an example of an embodiment of the reaction section in the organic matter removing apparatus according to another embodiment of the present invention.
  • FIG. 16 (a) is a plan view schematically showing an example of a state in which the nozzle is moved
  • (b) is a plan view schematically showing another example of a state in which the nozzle is swung.
  • FIG. 17 (a) is a plan view schematically showing one embodiment when removing organic substances on the substrate surface in the reaction section of the organic substance removing apparatus according to still another embodiment of the present invention
  • (b) is a plan view schematically showing an embodiment in which organic substances on the substrate surface are not removed in the reaction section.
  • FIG. 18 is a cross-sectional view schematically showing one example of the organic substance removing apparatus according to the third aspect of the present invention.
  • FIG. 19 (a) is a plan view schematically showing another example of the upper plate constituting the lid in the organic matter removing device of the third invention, and
  • FIG. 19 (b) is a sectional view thereof.
  • FIG. 20 is a plan view schematically showing another example of the side plate constituting the lid in the organic matter removing device of the third invention.
  • FIG. 21 is a schematic diagram showing an example of a conventional organic substance removing apparatus for a mask substrate that removes organic substances by flowing ozone water over the upper surface of a mask substrate.
  • FIG. 22 (a) is a cross-sectional view schematically showing a part of the conversion member in the reaction section according to Example 1, and (b) is a plan view thereof.
  • FIG. 23 is a three-dimensional diagram showing the thickness of the resist 20 seconds after the start of measurement in Example 1.
  • FIG. 24 is a three-dimensional diagram showing the thickness of the resist 20 seconds after the start of measurement in Example 2.
  • FIG. 25 is a cross-sectional view schematically illustrating the reaction section used in Comparative Example 1.
  • FIG. 26 is a three-dimensional diagram showing the thickness of the resist 20 seconds after the start of measurement in Comparative Example 1.
  • FIG. 27 is a diagram in which the resist removal volume is plotted against the linear velocity in Example 3.
  • FIG. 28 is a diagram plotting the resist removal rate with respect to the linear velocity in Example 4.
  • FIG. 29 is a three-dimensional diagram showing the thickness of the resist 30 seconds after the start of ozone injection in Example 5.
  • FIG. 30 is a plan view schematically showing the ozone water injection nozzle used in Comparative Example 2.
  • FIG. 31 is a plan view schematically showing a state in which the ozone water injection nozzle shown in FIG. 30 is rotated in a direction perpendicular to the ozone water injection direction.
  • FIG. 32 is a three-dimensional diagram illustrating the state of the processing surface of the processing sample according to the eighth embodiment.
  • FIG. 33 is a three-dimensional view showing the state of the processed surface of the processed sample according to Comparative Example 3 after processing. Explanation of reference numerals
  • the present invention is disclosed below.
  • the organic substance to be treated in the present invention is not particularly limited, as long as it can be treated with ozone water. It is preferably used when performing treatment using sucrose. That is, the organic substance removing apparatus, the organic substance removing method, and the organic substance removing apparatus for a mask substrate of the present invention can be considered as a resist removing apparatus, a resist removing method, and a resist removing apparatus for a mask substrate, respectively.
  • An organic substance removing apparatus is an organic substance removing apparatus that removes organic substances on the substrate surface by flowing ozone water along a processing surface of the substrate.
  • a fixing unit that fixes the substrate so that the processing surface of the substrate is substantially parallel; and a conversion member that is provided at a position facing the processing surface of the fixed substrate and converts the flow direction of the ozone water. Reaction section.
  • the organic substance removing apparatus removes organic substances from the surface of the substrate by flowing ozone water along a processing surface (main surface) of the substrate.
  • the ozone water includes not only a solution obtained by dissolving ozone gas in an aqueous solution but also a solution obtained by dissolving ozone gas in water in which an organic acid such as acetic acid or a derivative thereof is dissolved.
  • the substrate is not particularly limited, and includes, for example, various silicon wafers used for semiconductor devices, glass substrates used for display panels, and other resin substrates.
  • the organic matter removing apparatus includes a fixing part for fixing the substrate so that a processing surface (main surface) of the substrate is substantially parallel to a direction of the ozone water flow (hereinafter, also referred to as an ozone water flow). And a reaction member that is provided at a position facing the processing surface of the fixed substrate and that converts the direction of the ozone water flow and a force.
  • FIG. 6 is a schematic diagram showing a state of organic matter removal in a conventional organic matter removal apparatus.
  • the substrate 12 is arranged upside down.
  • the saturated concentration of ozone water at room temperature is as low as about 60 ppm, and the ozone water concentration decreases immediately after reacting with organic matter.
  • ozone water flows into the pipe as a water flow parallel to the surface direction of the substrate, the ozone water near the substrate processing surface that hit the organic matter on the inflow side is consumed for the removal of organic matter and the ozone concentration decreases. Since the ozone water with reduced ozone concentration flows directly near the substrate's surface, the ozone water no longer has an ozone concentration enough to remove organic matter at the outflow side.
  • ozone water flowing relatively far away from the processing surface of the substrate may flow away without being provided with organic matter removal. 'it is considered as.
  • the direction of the ozone water flow is changed to a position opposed to the processing surface of the substrate fixed to the fixing section so as to be substantially parallel to the direction of the ozone water flow.
  • the organic matter is extremely highly efficient.
  • the shape of the conversion member is not particularly limited, and examples thereof include a rod shape having a round or polygonal cross section, a mesh member, and a corrugated plate.
  • the conversion member 3 shown in FIG. 1 has a structure in which the corrugated portion 3a having an oblique portion with respect to the direction of the ozone water flow is continuous in the direction of the ozone water flow.
  • FIG. 1 is a schematic view showing one embodiment of the reaction section of the organic matter removing apparatus according to the first invention.
  • the angle of the oblique portion of the corrugated portion 3a is not particularly limited, but if the angle is too small, the ozone water flow toward the processing surface of the substrate 1 will not be generated, and the above-mentioned effects may not be sufficiently obtained.
  • a preferable lower limit to the processing surface of the substrate 1 is 15 °
  • a preferable upper limit is 85 °
  • a more preferable lower limit is 30 °
  • a more preferable upper limit Is 80 °.
  • the conversion member may be integrated with a member constituting the flow path of the ozone water (for example, a container or a partition in which the substrate is accommodated) or may be separate.
  • the distance between the conversion member and the processing surface of the substrate is preferably 1.5 mm or less. If the thickness exceeds 1.5 mm, the effect of the turbulence of the ozone water flow generated by the above-mentioned conversion member is difficult to reach the processing surface of the substrate, and organic substances are removed. Speed may be insufficient. It is more preferably 0.5 mm or less, and further preferably 0.3 mm.
  • the distance between the conversion member and the processing surface of the substrate means the distance between the closest points between the conversion member and the processing surface of the substrate.
  • the material constituting the conversion member is not particularly limited as long as it has ozone resistance.
  • a material made of a fluorine-based resin is suitable.
  • the fluorine-based resin include tetrafluoroethylene copolymers such as polytetrafluoroethylene resin (PTFE), perfluoroalkoxy resin (PFA), and fluoroethylenepropylene resin (FEP); fluororubber, etc. Is mentioned.
  • the conversion member is disposed so as to face substantially the entire processing surface of the substrate, or has a size that faces substantially the entire processing surface of the substrate.
  • the ozone water flow toward the entire processing surface of the substrate can be more reliably generated, and the probability of the ozone water reaching the organic matter on the entire surface of the substrate increases with a high probability, and the organic matter can be more reliably removed. It is.
  • the substrate is fixed to the fixing part such that the processing surface is substantially parallel to the flow direction of the ozone water.
  • the means for fixing the substrate to the fixing part so that the processing surface is substantially parallel to the flow direction of the ozone water is not particularly limited.
  • the substrate is fixed to the fixing part by an adhesive means such as a double-sided tape.
  • Method a method of fitting a holder (fixed part) on which a substrate is placed, to a holder holding part; a vacuum chucking method in which a substrate is adsorbed to a fixed part by a vacuum pump.
  • FIG. 2 is a schematic view showing one embodiment of the first organic substance removing apparatus of the present invention.
  • the organic matter removing apparatus of the embodiment shown in FIG. 2 includes an ozone generator 4, an ozone gas detector 5, an ozone dissolving module 6, an ozone water concentration detector 7, a reaction unit 8, and a pump 9.
  • ozone gas is generated.
  • the ozone generator 4 is not particularly limited, and a known ozone generator can be used.
  • the concentration of ozone gas generated by the ozone generator 4 is measured and monitored by the ozone gas detector 5.
  • ozone The value of the ozone gas concentration measured by the gas detector 5 is fed back to the ozone generator 4, and the concentration of ozone gas generated by the ozone generator 4 is adjusted as needed.
  • the ozone gas generated by the ozone generator 4 is dissolved in water in the ozone dissolving module 6.
  • the ozone dissolving module 6 preferably contains a gas permeable membrane made of a non-porous membrane.
  • the non-porous membrane means a membrane that allows gas to permeate but does not allow liquid to permeate. If such an ozone dissolving module 6 is used, the ozone molecules permeate between the molecular chains of the resin constituting the gas permeable membrane and diffuse into the organic acid aqueous solution. There is no intrusion of bubbles that lower the water content. Furthermore, the ozone solution once used for removing organic substances can be circulated and used, so that an ozone solution having a high ozone concentration can be easily and efficiently obtained.
  • the ozone water generated in the ozone dissolving module 6 is discharged from the ozone water outlet 6a to the outward pipe 10 and sent to the ozone water concentration detector 7, where the dissolved ozone gas concentration of the ozone water is monitored and managed.
  • the obtained ozone water is sent from the ozone water inlet 8a to the inside of the reaction section 8 through the outward pipe 10, and is used in the reaction section 8 to remove organic substances on the substrate surface.
  • the reaction section 8 will be described later in detail.
  • the reaction section 8 may be provided with a means for irradiating ultraviolet rays.
  • ultraviolet rays When removing organic substances from the substrate surface, ultraviolet rays are irradiated, and ozone is decomposed to generate hydroxy radicals with higher oxidizing power.
  • the effect of removing organic substances can be enhanced. Therefore, a higher organic substance removing effect can be obtained by using the ozonated water and the ultraviolet irradiation together.
  • the means for irradiating the ultraviolet light is not particularly limited, and examples thereof include a UV lamp.
  • the wavelength of the irradiated ultraviolet light is preferably around 254 nm which is absorbed by ozone.
  • the generated ozone water is circulated for use. Is preferred. By circulating and using the ozone water, the required amount of ozone water can be saved, and a higher concentration of ozone water can be easily obtained.
  • the ozone water discharged from the water outlet 8 to the return pipe 11 may be sent to the ozone water inlet 6 of the ozone dissolving module 6 using the pump 9. It is preferable that substantially solid exfoliated organic matter contained in the ozone water discharged into the return pipe 11 without being dissolved therein is removed by filtration.
  • the organic matter removing device of the first aspect of the present invention has means for heating ozone water. Since the removal of organic substances is performed by a chemical reaction between organic substances and ozone, the rate of removing organic substances can be increased by applying a temperature.
  • the organic matter removing device of the first invention has a means for pressurizing the inside of the device.
  • Super-saturated ozone water can be generated by pressurizing the inside of the device with a known technique such as a pressure pump, and organic substances can be removed with higher efficiency by using such a high-concentration ozone water. Can be.
  • FIG. 3 (a) is a plan view schematically showing one embodiment of the reaction section in the organic substance removing apparatus of the first invention described with reference to FIG. 2, and FIG. 3 (b) is a plan view of FIG. It is a front view of a reaction part, (c) is a sectional view on the AA line of the reaction part shown in (a). In FIG. 3, the conversion member is omitted.
  • the reaction section 8 of the present embodiment includes a substantially disk-shaped main body section 30.
  • a holder holder 31 having a substantially rectangular concave shape in plan view near the center thereof, and a groove-shaped inflow-side storage part 33 and an outflow-side storage part 37 near the outer periphery thereof.
  • a plurality of parallel inflow grooves 3 are provided between the inflow-side storage part 33 and the holder holding part 31.
  • a plurality of parallel outflow grooves 36 are provided between the outflow side storage section 37 and the holder holding section 31.
  • one end of the main body 30 is exposed to the side near the inflow-side storage section 33 of the main body 30, and the other end is extended to a portion directly below the inflow-side storage section 33.
  • the extended inflow pipe 35 one end of which is exposed on the side surface of the main body 30 near the outflow / storage section 37, and the other end extends to a portion immediately below the outflow side storage section 37
  • An outlet pipe 39 is provided, and the vicinity of the other end of the inlet pipe 35 and the inflow-side storage section 33 are circulated through an inflow path 34 having a V-shaped cross section.
  • the vicinity of the other end of the outflow pipe 39 and the outflow-side storage section 37 are circulated through an outflow path 38 having a V-shaped cross section.
  • FIG. 4A is a plan view schematically showing one example of the holder
  • FIG. 4B is a front view of the holder shown in FIG.
  • the holder 40 in the first organic substance removing device of the present invention has a groove-shaped holding portion 41 on the upper surface of a substantially plate-shaped main body portion 42. It is approximately U-shaped in cross section.
  • the holder 140 is used for smoothly flowing ozone water from the inflow groove 32 of the reaction section 8 onto the organic matter on the substrate surface and flowing out the ozone water to the outflow groove 36.
  • the groove direction of the holding part 41 of the reaction part 8 is fitted to the holder holding part 31 of the reaction part 8 so that the groove directions of the inflow groove 32 and the outflow groove 36 of the reaction part 8 are in the same direction.
  • the conversion member includes a main body 3 at a position facing the processing surface of the substrate of the holder 40 fitted to the holder-holding section 31. 0, and a plurality of triangular ridges having a triangular cross section are formed on the lower surface (the surface facing the substrate) of the lid so that the ridges of the conversion member are orthogonal to the flow of the ozone water flow. Is performed.
  • the ozone water is stored in the inflow-side storage section 33 from the inflow pipe 35 through the inflow path 34, and after filling the inflow-side storage section 33, the inflow groove 3 2 Then, the liquid flows uniformly and in parallel between the processing surface of the substrate fixed on the holding portion 41 of the holder 40 fitted into the holder holding portion 31 and the conversion member. Then, after removing the organic substances on the surface of the substrate, the ozone flows out from the outflow groove 36. It is collected in the side reservoir 37 and discharged from the outflow pipe 39 through the outflow channel 38.
  • the inflow pipe 35 communicates with the ozone water inflow port 8a in FIG. 2, and the outflow pipe 39 communicates with the ozone water outflow port 8b.
  • the surface of the main body 30 of the reaction section 8 on which the holder holding section 31 is provided includes a holder holding section 31, an inflow groove 32, and an inflow side storage section. 3 3, an outflow groove 36 and an outflow-side storage section 37 can be attached with a lid that can be housed in the interior, and the above-mentioned removal of organic substances on the substrate surface is described above. Can be done inside the department.
  • the reaction section 8 becomes a closed reaction section, and the inside of the organic substance removal apparatus of the first invention can be pressurized and organic substances on the surface of the substrate can be removed using supersaturated ozone water. Speed can be improved.
  • the flow rate of the ozone water when removing the organic substance from the substrate surface is not particularly limited, and the size and temperature of the substrate, the distance between the conversion members and the pattern of the conversion member are not particularly limited.
  • a preferable lower limit in treating a 4-inch wafer is 0.5 LZ
  • a preferable upper limit is 1.2 LZ. If the flow rate of the ozone water is less than 0.5 minutes, organic substances cannot be efficiently removed, and it may take a long time to completely remove the organic substances on the substrate surface.
  • the material constituting the reaction section 8 is not particularly limited as long as it has ozone resistance.
  • a material made of the same fluorine-based resin as the above-mentioned conversion member is preferable.
  • the reaction section in the organic matter removing apparatus of the first invention is not limited to a substantially disk shape as in the reaction section 8 shown in FIG. 3, but may be any shape such as a plate shape. Further, by adjusting the depth of the holding portion 41 of the holder 40, the depth of the ozone water flowing on the processing surface of the substrate can be adjusted.
  • the structure of the reaction section in the organic matter removing apparatus of the first invention is provided on the surface thereof.
  • the substrate having the equipment can be held and fixed to the fixing portion, and the conversion member described above can be disposed at a position facing the processing surface of the substrate, and between the processing surface of the substrate and the conversion member.
  • the structure is not particularly limited to the structure shown in FIG. 3 as long as the structure allows ozone water to flow therethrough.
  • FIG. 5 is a partial cross-sectional perspective view schematically showing another example of the reaction section in the organic matter removing device of the first invention.
  • the reaction part 50 shown in FIG. 5 has a fixed part 54 composed of a disk-shaped support base and a vacuum chuck for fixing the substrate 52, and a cylindrical ozone water supply pipe 55 inserted into the center thereof.
  • the doughnut-shaped conversion member 53 is configured to face the same.
  • the surface of the conversion member 53 on the side of the fixing portion 54 has a waveform portion 53 having substantially the same shape as the waveform portion shown in FIG. a is formed concentrically.
  • the substrate 52 is held and fixed on the surface of the fixed portion 54 on the side of the conversion member 53, and the conversion member 53 is provided between the processing surface of the substrate 52 and the corrugated portion 53a.
  • the gap is fixed at a predetermined distance.
  • the ozone water is supplied from the ozone water supply pipe 55 to the vicinity of the center of the substrate 52 between the conversion member 53 and the processing surface of the substrate 52. Flows to spread toward the outer edge of 2. At that time, the ozone water flow is turbulent due to the corrugated portion 53a of the conversion member 53, so that even in the vicinity of the outer edge portion of the plate 52, high-concentration ozone water always hits. Organic substances on the substrate surface can be removed uniformly and with high efficiency.
  • the size of the reaction section 50 can be made substantially the same as the size of the substrate, even when removing organic substances on the surface of a large-diameter substrate, the size of the organic substance removing device is increased. And organic substances on the surface of a large-diameter substrate can be efficiently and uniformly removed.
  • reaction section with the above structure is usually used as an open type reaction section.
  • reaction section having the above structure may be installed in a closed vessel to form a closed reaction section.
  • the organic substance removing apparatus is an organic substance removing apparatus that removes organic substances on the surface of a substrate using ozone water, wherein at least 450 cm / ozone water is applied from a nozzle to a processing surface of the substrate. It has a means to fire at a linear velocity of more than sec.
  • a second organic substance removing apparatus removes organic substances on the substrate surface using ozone water.
  • the present inventors have conducted intensive studies and found that the organic matter on the substrate reached when the ozone water reached a point on the processing surface of the substrate at a linear velocity of more than 450 cm / sec. In this regard, it has been found that organic matter can be removed with the highest efficiency and extremely high efficiency.
  • ozone water When removing organic substances using ozone water, it is necessary to oxidize and decompose organic substances to a molecular weight that can be dissolved in water by the ozone component in the ozone water.
  • the saturated concentration of ozone water at room temperature is about 60 ppm, and it cannot be sufficiently high for organic matter.
  • ozone water was supplied to a certain point, and ozone water was supplied to the entire surface by centrifugal force by spin, etc., but in this method, the ozone water becomes laminar and flows on the surface of the substrate. Is thought to flow.
  • the ozone component is consumed by the reaction with the organic matter at the moment of first contact with the organic matter, resulting in a laminar flow of the low-concentration ozone water. Therefore, when viewed from a microscopic point of view, only a low concentration of ozone water is present near the substrate surface, and it is considered that the organic matter removing effect was poor.
  • the organic matter removing apparatus removes, as soon as possible, organic matter decomposed to a molecular weight level that can be removed by an ozonized water stream having a certain linear velocity or more, and removes the organic matter that has not been decomposed. Since new high-concentration ozone water can always be reached, it is considered that organic matter can be removed with extremely high efficiency. This is different from washing by the physical effect of a mere water stream, and the oxidative decomposition reaction of organic matter by ozone and the decomposed organic matter by a high linear velocity ozone water stream. This is the first effect that can be obtained by the two functions of removal of odor.
  • the organic matter is not removed in a water stream that does not contain ozone, and even if high-concentration organic water is used, the organic matter can be efficiently removed if it is not injected at a sufficient linear velocity. Cannot be achieved.
  • FIG. 7 is a schematic view showing how organic substances on a substrate are removed by the organic substance removing apparatus of the second invention.
  • the organic matter removing apparatus according to the second aspect of the present invention, when the ozone water reaches, for example, a vertical direction with respect to the processing surface of the substrate 15, the organic matter 16 on the surface of the substrate 15 becomes ozone water. It is removed in an inverted conical shape centered on the arrival point. This is considered to be because the organic matter decomposed to a molecular weight level that can be removed by an ozone water stream having a certain linear velocity or higher is removed as soon as possible, and fresh ozone water always reaches organic substances that have not been decomposed. .
  • the linear velocity of the ozone water flow is equal to or greater than 450 cm / sec. If it is less than 460 cmZsec, organic substances cannot be efficiently removed. It is preferably at least 500 c / sec, more preferably at least 800 c mZ sec.
  • the upper limit of the linear velocity of the ozone water flow is not particularly limited, but is preferably 400 cm / sec or less.
  • the reaction rate between ozone and organic matter has a large effect, rather than physical removal by a simple water flow. If it exceeds 400 cm / sec, the rate of reaction between ozone and organic matter will no longer increase the organic matter removal rate even if the linear velocity is increased, and the efficiency of organic matter removal relative to the amount of ozone water used will decrease. Sometimes. Also, with the current technology, it is difficult to construct a system exceeding 400 cm / sec, and when the amount of ozone water used increases, it becomes difficult to maintain a high concentration of ozone water. It is more preferably at most 200 cm / sec, and even more preferably at most 1500 cm / sec.
  • the nozzle is a rod-shaped nozzle.
  • organic substances can be removed with higher efficiency.
  • the rod-shaped nozzle refers to ozone water injected from the nozzle. This means a nozzle that can reach the processing surface of the substrate as a rod flow with a diameter substantially the same as the nozzle inside diameter without spreading much beyond the inside diameter of the nozzle.
  • the injection angle of the rod-shaped nozzle that is, the spread angle of the ozone water injected from the nozzle is preferably 10 ° or less, more preferably 5 ° or less.
  • Such a rod-like nozzle can be obtained by drilling a tubular member using a drill, a laser, or the like, or by using a hollow fiber as a nozzle.
  • the ozone water flow injected from the nozzle is supplied as a substantially continuous flow.
  • the nozzle preferably has a nozzle inner diameter of 1.0 mm or less. If it exceeds 1.0 mm, a large amount of ozone water is required for the ozone water injected from the nozzle to obtain a constant linear velocity, and the efficiency of removing organic substances may decrease with respect to the amount of ozone water used. .
  • the ozone water injected from the nozzle reaches almost the entire processing surface of the substrate so that the distance between the arrival points is 3 to 10 mm.
  • FIG. 7 is a schematic view showing another example of a state in which organic substances on a substrate are removed by the organic substance removing apparatus of the second invention.
  • the distance between the arrival points of the ozone water that is ejected from the nozzles and reaches the processing surface of the substrate is 3 to 10 mm. If it is less than 3 mm, the amount of ozone water used will increase and interference between ozone water flows will occur. For example, the ozone water repelled on the treated surface may lower the linear velocity of the next ozone water, which may lower the organic matter removal efficiency.If it exceeds 10 mm, uniform organic matter removal will occur. May not be possible.
  • the method of causing the ozone water flow to reach a substantially entire surface of the processing surface of the substrate as a continuous line arranged at regular intervals is not particularly limited.
  • a sufficient number of nozzles may be provided for substantially the entire processing surface of the substrate.
  • organic substances can be removed efficiently and uniformly.
  • the organic substance removing apparatus of the second aspect of the present invention differs from the reaction section of the organic substance removing apparatus of the first aspect of the present invention described with reference to FIG. Similar embodiments are mentioned.
  • the reaction section of the organic substance removing apparatus includes means for injecting ozone water from at least a substrate fixing section for fixing the substrate and a nozzle to substantially the entire processing surface of the substrate (hereinafter also referred to as an injection section). ).
  • the means for fixing the substrate to the substrate fixing portion is not particularly limited, and includes, for example, a method of fixing with a bonding means such as a double-sided tape; a method of fitting a holder on which the substrate is mounted to the holder holding portion; Vacuum chucking method in which the substrate is adsorbed to the substrate fixing portion is exemplified.
  • FIG. 9 (a) is a schematic diagram showing an example of an embodiment of the reaction section in the organic substance removing apparatus of the second invention
  • FIG. 9 (b) is a schematic view of the reaction section in the organic substance removing apparatus of the second invention. It is a schematic diagram which shows another example of embodiment
  • (c) is a schematic diagram which shows another example of embodiment of the reaction part in the organic substance removal apparatus of 2nd this invention.
  • the reaction part in the organic matter removing apparatus of the second invention is the same as that shown in FIGS. 9 (a) to 9 (c).
  • This form may be used, or another form may be used.
  • the substrate 23 is fixed to the upper surface of the substrate fixing portion 21, and the nozzle is positioned above the substrate 23 regardless of the form of the reaction portion. Are located.
  • the nozzle 22 shown in FIG. 9 (a) has a large number of nozzles 22 at the tip end 20b of the injection part 20 composed of a cylindrical main body part 20a connected to the outward pipe and a hemispherical tip part 20b.
  • the nozzle 22 is formed at a position where the ozone water can be jetted onto substantially the entire processing surface of the substrate 23.
  • the ozone water sent from the outward pipe to the reaction section reaches the tip section 20b from the main body section 20a of the injection section 20, and is sprayed from the nozzle 22 onto substantially the entire processing surface of the substrate 23. Is done.
  • the nozzle 26 shown in FIG. 9 (b) is formed on the end face of an injection part 24 composed of a cylindrical main body part 25 connected to the outward pipe, and this injection part 24 Toward 23, they are arranged in a line above the substrate 23. Further, the substrate fixing part 21 or the jetting part 24 can be moved so as to rotate back and forth, right and left, or rotate. By moving them, the ozone water sent from the outgoing pipe to the reaction part is removed from the main body. It is jetted from the nozzle 26 to almost the entire processing surface of the substrate 23 through the part 25.
  • the nozzles 29 shown in FIG. 9 (c) are provided in a row at a predetermined interval on the side surface of the injection section 27 composed of a tubular main body 28 connected to the outward pipe.
  • a plurality of substrates are arranged in parallel above the substrate 23.
  • the substrate fixing part 21 or the jetting part 27 can be moved so as to rotate back and forth, right and left, or rotate. By moving these, the ozone water sent from the outgoing pipe to the reaction part is removed from the main body. It is jetted from the nozzle 29 to almost the entire processing surface of the substrate 23 through the part 28.
  • the material of the injection section in which the nozzle is formed is not particularly limited as long as it has ozone resistance and can withstand a certain level of water pressure.
  • a fluorine-based resin is suitable.
  • the fluorine-based resin include tetrafluoroethylene copolymers such as polytetrafluoroethylene resin (PTFE), perfluoroalkoxy resin (PFA), and fluorinated ethylene propylene resin (FEP); Fluorinated rubber, etc.
  • the reaction section in the organic substance removing device of the second present invention may have means for irradiating ultraviolet rays, similarly to the reaction section of the organic substance removing apparatus of the first present invention.
  • the generated ozone water is circulated and used, as in the organic matter removing apparatus according to the first aspect of the present invention, and that the apparatus has means for heating the ozone water. It is preferable to have a means for pressurizing the inside of the apparatus.
  • the organic substance formed on the substrate surface can be removed efficiently and uniformly.
  • An organic matter removing method using the first or second organic matter removing apparatus of the present invention is also one of the present inventions.
  • An ozone water injection nozzle used for removing organic substances on the substrate surface using ozone water, wherein a plurality of injection holes are formed at positions corresponding to the entire surface of the processing surface of the substrate.
  • the injection hole has a distance between adjacent injection holes of 1 Omm or less, and, when rotated in a direction perpendicular to the above-described ozone water injection direction, an arbitrary one perpendicular to the above-described ozone water injection direction.
  • An ozone water injection nozzle which is arranged so that the trajectories drawn by points corresponding to the centers of the injection holes on a plane do not overlap with each other, is also one of the present invention. It is used when removing organic substances from the substrate surface by using it.
  • a plurality of injection holes are formed at positions corresponding to the entire surface of the processing surface of the substrate, and the distance between adjacent injection holes is 10 mm or less.
  • any plane perpendicular to the above-mentioned ozone water jetting direction hereinafter, also referred to as any plane
  • the trajectories drawn by the points corresponding to the center of the above-mentioned apertures are arranged so that they do not overlap.
  • ozone water When ozone water is sprayed onto the processing surface of the substrate rotated in a predetermined direction using such an ozone water injection nozzle of the present invention, the ozone water is concentrically formed on the processing surface of the substrate with tight spaces. Will be supplied, + New high-concentration ozone water can always be supplied over the entire surface of the treated surface. Especially when used in the second organic substance removing apparatus of the present invention, organic substances can be removed uniformly and with extremely high efficiency. .
  • FIG. 10 (a) is a plan view schematically showing an example of the ozone water injection nozzle of the present invention, and (b) is a cross-sectional view of the ozone water injection nozzle taken along line A—A shown in (a). is there.
  • FIG. 11 is a plan view schematically showing a state where the ozone water injection nozzle shown in FIG. 10 is rotated in a predetermined direction.
  • the ozone water injection nozzle 60 of the present invention has a flange on the outer edge and an inner part of a nozzle body 65 having a step in the thickness direction.
  • the ozone water injection part 62 having a relatively small diameter and the ozone water supply part 63 having a relatively large diameter communicate with a plurality of injection holes 61 so as to penetrate the nozzle body 65. Is formed.
  • the ozone water is introduced from the end of the ozone water supply unit 63 exposed on the upper surface of the nozzle body 65, and the ozone water is injected into the lower surface of the nozzle body 65 (injection surface).
  • the end of the ozone water injection section 62 exposed at 6 4) is sprayed.
  • the injection direction of the ozone water is a direction perpendicular to the injection surface 64.
  • the injection hole 61 is formed at a position corresponding to the entire processing surface of the substrate. This is for uniformly spraying ozonized water on the entire surface of the processing surface of the substrate.
  • injecting ozone water uniformly to the entire surface of the processing surface of the substrate means that the ozone water jetted through the ozone water injection nozzle of the present invention treats the substrate.
  • reaching the surface it means reaching the entire surface of the processing surface of the substrate at substantially equal intervals. Therefore, as shown in FIG. 10, the injection holes 61 are formed so as to be distributed at substantially equal intervals on the injection surface 64.
  • the distance between the adjacent injection holes of the injection holes 61 is 10 mm or less. If it exceeds 10 mm, ozone water cannot be sprayed uniformly on the processing surface of the substrate rotated in a predetermined direction, and uniform organic substances cannot be removed.
  • the distance between adjacent injection holes is 3 mm It is preferable that it is above. If it is less than 3 mm, the amount of ozone water used will increase, and the ozone water sprayed from adjacent holes will be integrated before reaching the processing surface of the substrate rotated in a predetermined direction. However, it may not be possible to supply ozone water uniformly over the entire surface of the processing surface of the substrate, and the organic matter removal efficiency may be worsened.
  • the injection hole 61 is positioned at the center of the water injection hole 61 on the above-mentioned arbitrary plane.
  • the trajectories 6 6 drawn by the corresponding points do not overlap and are arranged so as to form concentric circles with tight intervals. That is, the injection holes 61 are arranged at positions where the distances from the center of the injection surface 64 of the ozone water injection nozzle 60 are different from each other.
  • the ozone water jetted from the ozone water jet nozzle of the present invention usually reaches a processing surface of a substrate rotated in a predetermined direction as a rod-shaped ozone water flow having a predetermined linear velocity.
  • the rod-shaped ozon water flow on the processing surface of the substrate rotated in the direction described above draws a locus similar to the locus drawn on the arbitrary plane. That is, since the point of reaching the processing surface of the substrate rotated in the above-described predetermined direction of the ozone water injected from the ozone water injection nozzle of the present invention does not overlap on the processing surface of the substrate, the interval between the injection holes is reduced.
  • the ozone water can be sprayed on the entire surface of the processing surface of the substrate without bringing the substrate into close proximity. Therefore, according to the ozone water injection nozzle of the present invention, organic substances on the entire surface of the processing surface can be efficiently and uniformly removed. It is preferable that the ozone water injected from the injection holes formed in the ozone water injection nozzle of the present invention be a stick flow. This is because organic substances can be removed with higher efficiency. That is, the ozone water injection nozzle of the present invention is preferably the rod-flow nozzle described in the second organic substance removing apparatus of the present invention.
  • the linear velocity of ozone water injected from the ozone water injection nozzle of the present invention is preferably at least 460 cm / sec.
  • the organic matter is most efficiently removed, and organic matter can be removed with extremely high efficiency. This is because, when the organic substances are removed from the substrate surface, the organic substances can be removed extremely uniformly and efficiently. That is, the ozone water injection nozzle of the present invention can be particularly suitably used in the organic matter removing device of the second present invention.
  • the injection hole formed in the ozone water injection nozzle of the present invention has a relatively large diameter, such as an injection hole 61 shown in FIG. 10, for introducing ozone water into the inside from one end thereof. It is preferable that the water supply section and the ozone water injection section having a relatively small diameter for injecting ozone water from one end thereof communicate with each other. This is for the following reasons.
  • the nozzle body is not easily broken or deformed by the pressure of the ozone water. To achieve this, it is necessary to increase the thickness of the nozzle body to maintain high mechanical strength. However, when the thickness of the nozzle body is increased, it is necessary to drill the holes or to form them using a high-power laser. However, when a drill hole is formed by drilling, the injected ozone water becomes a rod flow. A small-diameter spray hole cannot be formed with high precision. This causes a problem of high prices.
  • a bottomed hole is formed in advance at the position corresponding to the injection hole of the nozzle body by drilling from the opposite side of the projection surface, and laser processing is performed on the bottom of this bottomed hole to eject it.
  • the structure of the injection hole is made similar to the structure of the injection hole 61 shown in FIG. 10, so that the ozone water injected onto the injection surface at low cost becomes a stick flow.
  • Small injection holes can be formed with high precision.
  • the injection hole with such a structure has a large diameter on the side to which ozone water is supplied, the injection hole to ozone water injection holes is also reduced. It will be excellent.
  • the diameter of the end of the injection hole on the side where the ozone water is injected be 0.05 to 0.5 mm. If it is less than 0.05 mm, clogging of the injection hole is likely to occur, and if it exceeds 0.5 mm, a large amount of ozone water is required to obtain a constant flow rate of ozone water injected from the injection hole. Water is required, and the efficiency of organic matter removal with respect to the amount of ozone water used may decrease.
  • the material constituting the nozzle body is not particularly limited as long as it has ozone resistance, and for example, a material made of a fluorine-based resin is suitable.
  • fluorine-based resin examples include tetrafluoroethylene copolymers such as polytetrafluoroethylene resin (PTFE), perfluoroalkoxy resin (PFA), and fluorinated ethylene propylene resin (FEP). Fluorinated rubber and the like.
  • PTFE polytetrafluoroethylene resin
  • PFA perfluoroalkoxy resin
  • FEP fluorinated ethylene propylene resin
  • the nozzle main body has a size facing substantially the entire processing surface of the substrate to be processed. This is because the ozone water sprayed from the ozone water spray nozzle of the present invention can be uniformly sprayed on the entire surface of the substrate rotated in a predetermined direction.
  • FIG. 12 is a plan view schematically showing another example of the ozone water injection nozzle of the present invention.
  • the distance between adjacent injection holes 68 is shorter than that of the ozone water injection nozzle 60 shown in FIG. 6 8 are formed.
  • the locus drawn by the center of the injection hole 68 on the above-mentioned arbitrary plane is more spaced than the locus 66 shown in FIG. Concentric circles. Therefore, by removing organic substances from the substrate surface using the ozone water injection nozzle 67, the ozone water can be injected more uniformly on the entire processing surface of the substrate rotated in a predetermined direction. Organic substances on the substrate surface can be uniformly and efficiently removed.
  • the structure of the ozone water spray nozzle of the present invention is limited to a structure having a nozzle body having a plurality of water spray holes formed therein, such as the ozone water spray nozzle 60 shown in FIG.
  • a structure in which a plurality of injection holes are provided on the side surface of a tubular member and a plurality of nozzles are arranged in parallel, or a structure in which a plurality of hollow fibers are used as nozzles and bundled are used. Is also good.
  • the end on the side where the ozone water is jetted need not necessarily be on the same plane.
  • the ozone water injection nozzle of the present invention has a structure having a nozzle body having a plurality of injection holes formed in a part thereof, like the ozone water injection nozzle 60 shown in FIG. 10,
  • the nozzle main body has a flange provided on the outer edge as in the case of the nozzle main body 65 shown in FIG. 10, and a step is formed in the thickness direction.
  • the present invention is not limited to this.
  • a simple disk shape or a polygonal prism shape in a plan view may be used.
  • the ends of the plurality of injection holes on the side where ozone water is injected oppose above the processing surface of the substrate.
  • an ozone water injection nozzle having a nozzle body portion having a plurality of water injection holes formed therein such as an ozone water injection nozzle 60 shown in FIG.
  • a brief description will be given of a method of manufacturing the injection nozzle.
  • a nozzle body is manufactured by compression molding, extrusion molding, melt molding, or the like using the raw material resin constituting the nozzle body described above.
  • the nozzle body is manufactured at once by the above-described molding method.
  • two columnar members having different diameters may be respectively manufactured, and then these members may be integrally manufactured.
  • the ozone water injection nozzle of the present invention can be manufactured by forming a blind hole at a predetermined position of the manufactured nozzle body.
  • the method for forming the above-mentioned injection hole is not particularly limited.
  • a force that can be formed by any processing method such as drilling, laser processing, etc. Since small injection holes can be formed with high precision, they are preferably formed by laser processing.
  • a bottomed hole may be formed in advance, and laser processing may be performed on the bottom of the bottomed hole to form an ejection hole.
  • a plurality of injection holes are formed at positions corresponding to the entire surface of the processing surface of the substrate, and the distance between adjacent injection holes is 10 mm or less.
  • At least one of the present inventions is an organic matter removing apparatus having the ozone water injection nozzle of the present invention and a rotating means for rotating the substrate.
  • the organic substance removing apparatus using the ozone water injection nozzle of the present invention (hereinafter, also referred to as the nozzle organic substance removing apparatus of the present invention) has a reaction section for removing organic substances on the substrate surface, which is the first organic substance removing apparatus described with reference to FIG.
  • a similar embodiment can be mentioned except that it is different from the reaction section in the organic matter removing device of the present invention.
  • the reaction section of the apparatus for removing organic matter for a nozzle according to the present invention is configured to include at least the ozone water spray nozzle of the present invention and rotating means for rotating the substrate.
  • FIG. 13 is a half sectional view schematically showing one example of an embodiment of a reaction section in the organic matter removing device for a nozzle of the present invention.
  • the ozone water injection nozzle 60 is used by being attached to the ozone water injection device 70 in the reaction section.
  • the ozone water injector 70 is mainly an inverted bottomed cylindrical shape having a joint 75 provided with an ozone water supply pipe 74 near the center of the upper surface thereof, and a bottomed cylindrical shape.
  • a nut 72 having an opening on the bottom surface into which an ozone water injection nozzle can be fitted is formed, and the housing 71 and the nut 72 can be fitted or screwed together. ing.
  • the ozone water injection nozzle 60 is fitted into an opening formed on the bottom surface of the nut 72, and is attached while a flange provided on the outer edge thereof is supported by the bottom surface of the nut 72.
  • An O-ring 73 is embedded in a portion of the lower surface of the side wall of the housing 71 that is in contact with the ozone water injection nozzle 60, and is formed by the housing 71 and the ozone water injection nozzle 60. The tightness of the space is ensured.
  • the ozone water injector 70 provided with the ozone water injection nozzle 60 as described above is disposed above the reaction section so as to face the substrate fixed to the substrate fixing section. The jet surface and the substrate surface are fixed so that they are parallel. Have been.
  • the material forming the housing 71, the nut 72, and the joint 75 forming the ozone water injector 70 is not particularly limited, but it is preferable that the material has ozone resistance. And those made of a fluororesin constituting the above. Further, as the O-ring 73, for example, a known O-ring made of a rubber material such as nitrile rubber, fluorine rubber, or silicone rubber may be used. Of these, fluorine rubber and silicone rubber, which have excellent ozone resistance, are preferred.
  • the means for fixing the substrate to the substrate fixing portion is not particularly limited, and includes, for example, a method of fixing with a bonding means such as a double-sided tape; a method of fitting a holder on which the substrate is mounted to the holder holding portion; Vacuum chucking method in which the substrate is adsorbed to the substrate fixing portion is exemplified.
  • the reaction section further has a rotating means for rotating the substrate.
  • the rotating means is not particularly limited, and includes, for example, a known device such as a motor.
  • the method of rotating the substrate using the rotating means is not particularly limited.
  • a method of transmitting the rotational motion generated in step (1) to the substrate fixing part and rotating the substrate by rotating the substrate fixing part is exemplified.
  • the substrate fixing portion may function as a rotating means, and rotate the entire substrate fixing portion or only the portion fixing the substrate.
  • the direction of rotation of the substrate rotated by the rotating means is a direction perpendicular to the direction of the ozone water sprayed from the ozone water spray nozzle of the present invention. This is because the ozone water is uniformly sprayed on the entire processing surface of the substrate.
  • the ozone water sent from the outgoing pipe to the reaction part 70 passes through the ozone water supply pipe 74 in the joint 75 connected to the ozone water inflow port and the housing 71. It is supplied into the space formed by the ozone water injection nozzle 60, and is uniformly injected from the injection surface to the processing surface of the substrate rotated by the rotating means through the injection hole of the ozone water injection nozzle 60.
  • the reaction section in the organic substance removing apparatus for a nozzle of the present invention may be provided with means for irradiating ultraviolet rays, similarly to the reaction section of the organic substance removing apparatus of the first present invention.
  • the generated ozone water is circulated and used, similarly to the organic matter removing device according to the first aspect of the present invention, and that a means for heating the ozone water is provided. It is preferable to have a means for pressurizing the inside of the apparatus.
  • the organic matter removing device for a nozzle of the present invention uses the above-described ozone water spray nozzle of the present invention, when removing the organic matter on the substrate surface, the substrate rotated in a direction perpendicular to the ozone water spraying direction is used. Ozone water can be sprayed uniformly on the entire surface of the treated surface, and the organic substances on the substrate surface can be uniformly and highly efficiently removed.
  • the present invention provides The organic matter removing device for a nozzle is in a preferred form of the organic matter removing device of the second present invention described above. '
  • An organic matter removing method for removing organic matter on a substrate surface using ozone water comprising: a nozzle having a plurality of injection holes formed at positions corresponding to substantially the entire surface of a processing surface of the substrate; An organic substance removal method of injecting ozone water onto substantially the entire surface of the processing surface of the substrate in a state where the ozone water is close to the substrate to such an extent that an ozone water layer is apparently formed between the substrate and the processing surface is also provided.
  • This is one of the present invention according to another embodiment.
  • organic substance removing method according to another aspect of the present invention organic substances on a substrate surface are removed using ozone water.
  • a nozzle having a plurality of injection holes formed at a position corresponding to substantially the entire processing surface of the substrate is provided between the nozzle and the processing surface of the substrate. Then, the ozone water is sprayed on substantially the entire processing surface of the substrate in a state where the ozone water is close to the substrate so that an ozone water layer is apparently formed.
  • injecting ozone water to substantially the entire surface of the substrate means that the ozone water injected from the injection hole of the nozzle reaches the processing surface of the substrate. Means to reach almost the entire surface of the processing surface of the substrate at substantially equal intervals . That is, in the organic matter removing method of the present invention, for example, a nozzle as shown in FIG. 14 is used as a nozzle for injecting ozone water.
  • FIG. 14 is a plan view schematically showing an example of a nozzle used in the organic matter removing method of the present invention according to another embodiment.
  • the nozzle 80 used in the organic matter removing method includes a disc-shaped main body 83 inside the ejection face 82 from the ejection face 82 opposite to the ejection face 8.
  • a plurality of through holes 81 penetrating to 2 are formed.
  • the injection hole 81 is formed at a position corresponding to substantially the entire surface of the processing surface of the substrate, and is exposed on the side opposite to the injection surface 82 of the injection hole 81.
  • the ozone water flowed in from the end of the substrate can be sprayed from the end exposed to the injection surface 82 of the injection hole 81 almost uniformly to almost the entire processing surface of the substrate.
  • the nozzle used in the organic matter removing method according to another aspect of the present invention is disposed above the processing surface of the substrate such that the ejection surface faces the processing surface of the substrate.
  • the structure of the nozzle according to the present invention is not limited to the structure shown in FIG.
  • the injection surface of the main body may be formed with injection holes arranged in a radial, concentric or lattice shape, etc. Further, if the main body is also plate-shaped, it is particularly limited to a disk shape. It will not be done.
  • the nozzle is preferably the above-described ozone water injection nozzle of the present invention. This is because, by using the ozone water injection nozzle of the present invention, the ozone water can uniformly reach the entire surface of the substrate, so that organic substances on the substrate surface can be uniformly and extremely efficiently removed.
  • the material of the nozzle used in the organic matter removing method of the present invention according to another embodiment is not particularly limited as long as it has ozone resistance and can withstand a certain water pressure.
  • a fluorine resin is preferable. is there.
  • the fluorine-based resin include polytetrafluoroethylene resin (PTFE), perfluoroalkoxy resin (PFA), and fluorinated ethylene propylene resin (FEP). Coalescence; fluorine-based rubber and the like.
  • the size of the nozzle is not particularly limited, but it is preferable that at least the ejection surface has the same size as the treatment surface of the substrate in order to eject ozone water onto substantially the entire surface of the treatment surface of the substrate.
  • ozone water is sprayed onto substantially the entire surface of the processing surface of the substrate in the conventional manner.
  • the organic substances on the substrate surface can be more efficiently and uniformly removed than the organic substance removing method using ozone water. This is thought to be due to the following reasons. That is, in the conventional organic matter removal method using ozone water, for example, ozone water is supplied to a negative point on the processing surface of the substrate, and centrifugal force generated by rotating the substrate is applied to other portions of the processing surface of the substrate.
  • Ozone water was supplied by flowing ozone water by force or the like, but it is considered that the ozone water flow flowing through the processing surface of this substrate is laminar.
  • the saturated concentration of ozone water at room temperature is as low as about 60 ppm, and the ozone water concentration decreases immediately after reacting with organic matter. Therefore, in the ozone water flow that flows near the treatment surface where the ozone water is not directly supplied, the ozone component is consumed by the reaction with the organic matter at the moment when the ozone water comes into contact with the organic matter for the first time. It becomes. Therefore, from a microscopic point of view, only low-concentration ozone water is present in the vicinity of the treated surface where ozone water is not directly supplied, and it is considered that the organic matter removal effect was poor.
  • the nozzle is brought into close proximity to the substrate to such an extent that an ozone water layer is apparently formed between the nozzle and the processing surface of the substrate. Then, ozone water is sprayed on substantially the entire processing surface of the substrate. In order to bring the processing surface of the substrate and the ejection surface of the nozzle sufficiently close to each other, these gaps are filled with ozone water, and the ozone in the ozone water is brought into the atmosphere by being pressurized. It is hard to escape and can be processed with high concentration.
  • the ozone water is vigorously supplied so that the gap between the processing surface of the substrate and the ejection surface of the nozzle is filled with the ozone water, so that the ozone water is agitated and the high-concentration ozone water always comes into contact with organic substances on the substrate. Will be done.
  • the apparent ozone water layer formed between the processing surface of the substrate and the nozzle is referred to as a “pseudo ozone water layer”.
  • the pseudo ozone water jetted from the nozzle is jetted into the pseudo ozone water layer, and the ozone water is jetted into the pseudo ozone water layer. Convection will occur. As a result, the pseudo ozone water layer formed on the entire surface of the processing surface of the substrate is agitated, and a high concentration of ozone water always hits the processing surface of the substrate. It is considered that organic matter can be removed.
  • the ozone water jetted from the nozzle does not directly reach the processing surface of the substrate, but the convection of ozone water generated in the pseudo ozone water layer by the ozone water jetted from the nozzle does not occur. Will be reached. Since the contact area between the convection of the ozone water and the processing surface of the substrate is larger than the contact area between the ozone water injected from the nozzle and the processing surface of the substrate, the ozone water is removed by the convection of the ozone water. Since the area of the organic substance on the substrate surface is larger than the area of the organic substance removed by the ozone water jetted from the nozzle, it is considered that the organic substance on the substrate surface can be removed efficiently and uniformly. Can be
  • the ozone water does not directly collide with the processing surface of the substrate, even if the substrate is thin and brittle, the impact received by the substrate is reduced, and the substrate is not damaged.
  • the apparatus can be made compact because ozone water does not splash during removal of organic substances on the substrate surface.
  • the pseudo ozone water layer is pressurized.
  • the ozone water having an ozone concentration of supersaturated is removed.
  • the super-saturated state of the ozone concentration in the pseudo ozone water layer can be maintained, and the organic matter on the substrate surface can be Removal can be performed.
  • the distance between the nozzle and the processing surface of the substrate is appropriately adjusted according to the size of the nozzle to be used and the like, but is preferably 1 to 3 mm. If it exceeds 3 mm, a large amount of ozone water is required to form a pseudo ozone water layer between the nozzle and the processing surface of the substrate, and the efficiency of removing organic substances with respect to the amount of ozone water used may decrease. . If it is less than 1 mm, the nozzle may come into contact with the substrate.
  • the ozone water is injected while rotating the substrate. This is because organic substances on the substrate surface can be more uniformly and efficiently removed.
  • the method for rotating the substrate is not particularly limited.
  • the substrate is fixed on a rotary table connected to rotating means such as a motor and the substrate is rotated by driving the rotating means. Method and the like.
  • the rotation speed is not too fast.
  • the rotation speed is preferably about 250 rpm.
  • a plurality of injection holes are formed at positions corresponding to substantially the entire surface of the processing surface of the substrate.
  • the apparatus can be made compact because ozone water is not scattered during removal of organic substances on the substrate surface.
  • the pseudo ozone water layer is pressurized. As a result, it is possible to maintain the supersaturated state of the ozone concentration in the pseudo ozone water layer, As a result, organic substances on the substrate surface can be removed.
  • An organic matter removing device used when performing the organic matter removing method of the present invention according to another aspect is also one of the present inventions according to another aspect.
  • An organic substance removing apparatus is an organic substance removing apparatus used when performing the organic substance removing method according to another aspect of the present invention, wherein at least substantially the entire processing surface of the substrate is provided.
  • An organic matter removing apparatus is the same as the organic matter removing apparatus of the first aspect of the present invention described with reference to FIG. Embodiments are given.
  • the reaction unit of the organic matter removing apparatus includes at least a nozzle for injecting ozone water onto substantially the entire surface of the processing surface of the substrate, a moving unit for moving the nozzle, and rotating the substrate. And rotating means.
  • FIG. 15 is a cross-sectional view showing an example of an embodiment of a reaction section in an organic matter removing apparatus according to another aspect of the present invention.
  • the substrate 87 is fixed on the upper surface of the fixing portion 88, and the horns 85 are arranged above the substrate 87.
  • the fixing portion 88 is a member for holding and fixing the substrate 87 on its upper surface, and the material thereof is not particularly limited, but is preferably one having ozone resistance.
  • the same fluorine-based resin as the constituent material may be used.
  • the means for fixing the substrate 87 to the fixing portion 88 is not particularly limited.
  • the fixed portion 88 is connected to a rotating means (not shown) via a rotating shaft 89 near the center of the lower surface thereof, and the rotating motion generated by driving the rotating means causes the rotating motion via the rotating shaft 89. By being transmitted, it is possible to rotate in the outer circumferential direction.
  • the fixing portion 88 itself also functions as a rotating means, and the entire fixing portion 88 or the substrate Only the part holding the 8 7 may rotate.
  • the rotating means is not particularly limited, and includes, for example, a known device such as a motor.
  • the nozzle 85 is connected to a moving means (not shown) and can be freely moved in the vertical and / or horizontal directions. When removing organic substances on the surface of the substrate 87, the nozzle 85 is used. 5, as shown in FIG. 15, the ejection surface faces the processing surface of the substrate 87, and is arranged at a position where the distance to the substrate 87 is sufficiently close.
  • the moving means is not particularly limited, and includes, for example, a known device such as a mechanical arm.
  • the ozone water sent from the outgoing pipe to the reaction section is arranged by the above-mentioned moving means from the ozone water inflow port so that the ejection surface is at a predetermined position facing the processing surface of the substrate 87.
  • the nozzles 85 are supplied to the ejection holes of the nozzles 85, and are held and fixed on the fixing portion 88 from the ejection surface through the ejection holes, and are ejected onto substantially the entire processing surface of the substrate 87 rotated by the rotating means. You.
  • the pseudo ozone water layer 86 described in the sixth organic substance removing method of the present invention is formed between the nozzle 85 and the processing surface of the substrate 87.
  • the reaction section in the organic substance removing apparatus may be provided with means for irradiating ultraviolet rays, similarly to the reaction section of the organic substance removing apparatus according to the first aspect of the present invention.
  • the generated ozone water is circulated and used similarly to the organic matter removing apparatus according to the first aspect of the present invention. It is preferable to have a means for pressurizing the inside of the apparatus.
  • the distance between the nozzle and the substrate can be freely set by the moving means, so that the above-described organic substance removing method according to another aspect of the present invention can be suitably realized. can do.
  • An organic matter removing method for removing organic matter on a substrate surface using ozone water comprising: a nozzle having a plurality of injection holes formed at positions corresponding to substantially the entire surface of the processing surface of the substrate;
  • An organic matter removing method of injecting ozone water onto substantially the entire surface of the processing surface of the substrate while rotating in a direction parallel to the processing surface of the substrate is also described in another aspect of the present invention.
  • organic matter on a substrate surface is removed using ozone water.
  • a nozzle having a plurality of injection holes formed at positions corresponding to the entire surface of the processing surface of the substrate is arranged in a direction parallel to the processing surface of the substrate. While oscillating, ozone water is sprayed on substantially the entire processing surface of the substrate.
  • injecting ozone water to substantially the entire surface of the processing surface of the substrate refers to the case of the organic substance removing method of the present invention according to the above-described another aspect.
  • the nozzle used in the organic matter removing method of the present invention according to still another embodiment is the same as the nozzle 8 shown in FIG. The same as 0 is mentioned.
  • the nose is preferably the above-described ozone water injection nose of the present invention. By using the ozone water spray nozzle of the present invention.
  • the nozzle When removing organic matter from the substrate surface using such a nozzle, the nozzle is placed above the processing surface of the substrate such that the ends of the plurality of injection holes on the side where the ozone water is injected face the processing surface of the substrate.
  • the ozone water is sprayed from the nozzle onto substantially the entire surface of the processing surface of the substrate.
  • the organic substance on the substrate surface is removed using the above nozzle, the organic substance can be efficiently and uniformly removed as compared with the conventional method for removing the organic substance on the substrate surface using ozone water.
  • the nozzle is further swung in a direction parallel to the processing surface of the substrate, and the ozone water is jetted onto substantially the entire surface of the processing surface of the substrate. .
  • the nozzle is connected to the substrate While oscillating in the direction parallel to the processing surface of ', the ozone water is projected onto substantially the entire surface of the processing surface of the substrate, so that the arrival point of the ozone water on the processing surface of the substrate is complicated. Will overlap.
  • the ozonized water can reach the entire surface of the processing surface of the substrate uniformly and directly, and organic substances on the substrate surface can be removed very efficiently and uniformly.
  • FIG. 16 (a) is a plan view schematically showing an example of the manner in which the nozzle is swung, and (b) is a plan view schematically showing another example of the manner in which the nozzle is swung. It is. .
  • a nozzle 80 for injecting ozone water onto substantially the entire surface of the processing surface of the substrate is connected to one end of a support rod 92 via a fixed shaft 91.
  • the other end of the supporting rod 92 is connected to a swinging means (not shown).
  • the nozzle 80 is disposed above the processing surface of the substrate and in a position parallel to the processing surface.
  • a support rod 92 is provided. Oscillating water can be sprayed onto substantially the entire surface of the processing surface of the substrate while swinging in a direction parallel to the processing surface of the substrate via the fixed shaft 91.
  • the swing means is not particularly limited as long as it can swing the nozzle 80 in a direction parallel to the processing surface of the substrate via the support rod 92 and the fixed shaft 91.
  • a known driving device may be used.
  • the direction in which the nozzle is swung is not particularly limited. For example, as shown by an arrow in FIG. It is preferable to oscillate so as to orbit above the processing surface of the substrate. By injecting the ozone water while oscillating the nozzle in this way, the ozone water reaches the processing surface of the substrate while oscillating so as to circulate, and can be removed by the ozone water injected from the injection hole 1 The area of the organic matter increases, and the lens can be uniformly removed with higher efficiency.
  • the organic matter removing method of the present invention it is preferable to inject ozone water from a nozzle while rotating the substrate. Swing and base of the above nozzle Combined with the rotation of the plate, even if the above-mentioned nozzle swing is a simpler motion such as reciprocating a part of an arc as shown in Fig. 16 (b), The ozone water arrives at the treated surface in a complicated swinging manner, and organic substances on the substrate surface can be removed very efficiently and uniformly. Further, the organic substance removing apparatus of the present invention used when performing the organic substance removing method of the present invention according to still another embodiment described later can be easily made compact.
  • the method for rotating the substrate is not particularly limited.
  • a method for rotating the substrate by fixing the substrate on a rotating table connected to rotating means such as a motor and driving the rotating means And the like.
  • the direction in which the substrate is rotated is the same as the direction in which the ozone water is ejected from the nozzle in order to ensure that the ozone water uniformly and uniformly reaches a substantially entire surface of the processing surface of the substrate. It is preferable to rotate in a vertical direction.
  • the magnitude of the nozzle swing It is preferable that the end of the ozone water jetting side of the water injection hole does not come off much from above the processing surface of the substrate.
  • the processing of the ozone water substrate reaching a position off the processing surface of the substrate Preferably, the distance to the surface is about 10 mm or less.
  • the rotation speed of the oscillating nozzle is not particularly limited, but is preferably 1 to 100 rpm, and 100 to 3 rpm. More preferably, it is 0 rpm. If it is less than l rpm, organic substances may not be uniformly removed. If it exceeds 100 rpm, the amount of ozone water that is lost due to centrifugal force increases.
  • the organic matter removing method of the present invention it is preferable that the ozone water is ejected in a stick flow. This is because organic substances can be removed with higher efficiency. Further, in the organic matter removing method of the present invention according to still another aspect, it is preferable that the linear velocity of the ozone water ejected from the nozzle is 460 to 40 cm / sec. If it is less than 400 cm / sec, it may not be possible to efficiently remove organic substances on the substrate.If it exceeds 400 cm / sec, the linear velocity can no longer be increased due to the reaction rate between ozone and organic substances. However, the organic matter removal rate does not increase, and the efficiency of organic matter removal relative to the amount of ozone water used may decrease.
  • the organic substance removing method of the present invention is a preferable aspect of the organic substance removing method using the above-described organic substance removing apparatus of the second present invention.
  • the nozzle when removing organic substances on the substrate surface, the nozzle having a plurality of injection holes formed at positions corresponding to substantially the entire surface of the processing surface of the substrate, While oscillating in a direction parallel to the processing surface of the substrate, ozone water is sprayed on substantially the entire processing surface of the substrate.
  • ozone water By injecting ozone water onto substantially the entire surface of the processing surface of the substrate in this manner, the ozone water injected from the nozzle can directly reach substantially the entire surface of the processing surface of the substrate uniformly and directly. Organic matter can be removed very efficiently and uniformly.
  • An organic matter removing device used when performing the organic matter removing method of the present invention according to still another embodiment is also one of the present invention according to still another embodiment.
  • An organic substance removing apparatus is an organic substance removing apparatus used when performing the organic substance removing method according to still another aspect of the present invention, wherein at least substantially the entire processing surface of the substrate is treated.
  • An organic matter removing device having a nozzle for injecting ozone water and a rocking means for rocking the nozzle.
  • An organic matter removing apparatus of the present invention according to still another aspect is the same as the organic substance removing apparatus of the first embodiment of the present invention described with reference to FIG. Embodiments are given.
  • the reaction section of the organic matter removing apparatus includes at least a nozzle for projecting ozone water onto substantially the entire surface of the substrate, and a rocking means for rocking the nozzle. 'Have.
  • FIG. 17 (a) is a plan view schematically showing one embodiment when removing organic substances on the substrate surface in the reaction section of the organic substance removing apparatus according to another embodiment of the present invention.
  • 3) is a plan view schematically showing an embodiment in which organic substances on the substrate surface are not removed in the reaction section.
  • the nozzle 80 is supported at one end of a support rod 92 via a fixed shaft 91.
  • the other end of 2 is connected to swing means 93.
  • the substrate 94 is connected to rotating means (not shown), and is disposed at a predetermined position below the nose / slip 80.
  • a nozzle supported on a support rod 92 via a fixed shaft 91 is used.
  • the organic substance on the surface of the substrate 94 is removed by the method described in the organic substance removing method of the present invention according to still another embodiment. That is, by driving the driving means 93, the nozzle 80 is swung in a direction parallel to the processing surface of the substrate 94 via the support rod 92 and the fixed shaft 91, and the substrate 94 is swung. Ozone water is sprayed on almost the entire surface of the substrate to remove organic substances on the surface of the substrate 94. Further, as shown in FIG. 17 (b), when the removal of the organic substances from the surface of the substrate 94 is completed, the nozzle 80 is moved to another position from above the substrate 94.
  • the moving means and the rocking means 93 for moving the nozzle 80 to a position above the substrate 94 or another position may be separate devices, respectively, but the organic substance of the present invention according to still another aspect In order to make the removing device compact, these means are preferably one device.
  • the oscillating means 93 serves to oscillate the nozzle 80 above the surface of the substrate 94 in order to spray ozone water uniformly over substantially the entire surface of the substrate 94.
  • the nozzle 80 may be arranged above the processing surface of the substrate 94 or may be arranged at another place. As shown in FIG.
  • the apparatus further includes a rotation unit for rotating the substrate. That is, in the reaction section 90, it is preferable that the substrate 94 be connected to the rotating means and disposed at a predetermined position below the nozzle 80 in a rotatable state.
  • the recommendation of the nozzle 80 is, for example, as shown in FIG. 6
  • the movement is simpler, such as reciprocating a part of the arc as shown in (b)
  • the ozone water arrives at the processing surface of the substrate 94 while moving in a complicated manner. This is because organic substances on the surface of the substrate 94 can be extremely efficiently and uniformly removed.
  • the rotation means is not particularly limited, and includes, for example, a known device such as a motor.
  • the substrate 94 is preferably held and fixed on a rotatable substrate fixing portion such as a turntable.
  • the means for fixing the substrate 94 to the substrate fixing portion is not particularly limited, and includes, for example, a method of fixing the substrate 94 with an adhesive means such as a double-sided tape; a method of fitting a holder on which the substrate is mounted to the holder holding portion; A vacuum chucking method in which a substrate is adsorbed to a fixing means by a vacuum pump is used.
  • the method for rotating the substrate using the rotating means is not particularly limited.
  • the upper rotating means and the substrate fixing portion are connected by a rotating shaft or the like, and the rotating means is driven via the rotating shaft.
  • a method of transmitting the rotational motion generated by the rotation to the substrate fixing portion and rotating the substrate is exemplified.
  • the substrate fixing portion itself may function as a rotating means, and the entire substrate fixing portion or only the portion holding and fixing the substrate may rotate.
  • the ozone water sent from the outgoing pipe to the reaction section 90 is disposed above the processing surface of the substrate 94 from the ozone water inflow port, and oscillates above the substrate 94.
  • the liquid is supplied to the nozzle 80 of the nozzle 80 that has been moved, and is uniformly injected from the end of the injection hole onto substantially the entire processing surface of the substrate 94 rotated by the rotating means.
  • the reaction section in the organic matter removing apparatus of the present invention according to still another aspect is the above-mentioned first book.
  • means for irradiating ultraviolet rays may be added.
  • the organic matter removing apparatus of the present invention similarly to the organic matter removing apparatus of the first present invention, it is preferable to circulate and use the generated ozone water. It is preferable to have a means for pressurizing the inside of the apparatus.
  • the nozzle is swung in a predetermined direction above the processing surface of the substrate, and the ozone water is applied to substantially the entire surface of the processing surface of the substrate rotated by the rotating means. Can be injected. Therefore, according to the organic substance removing apparatus of the present invention according to another aspect, the organic substance removing method of the present invention according to another aspect can be suitably realized.
  • a third aspect of the present invention is a mask substrate organic substance removing apparatus for removing organic substances on the surface of a mask substrate using ozone water, wherein at least the organic substance removing apparatus faces the upper surface of the mask substrate and is located between the upper surface of the mask substrate.
  • a mask substrate comprising a lid comprising an upper plate forming a channel for the ozone water flow, and a side plate facing the side surface of the mask substrate and forming a channel for the ozone water flow between the side surface of the mask substrate. It is an organic matter removal device.
  • the third organic substance removing apparatus for a mask substrate of the present invention (hereinafter, also simply referred to as an organic substance removing apparatus) is configured such that ozone water is caused to flow along the upper surface (main surface) and the side surface of the mask substrate so that the upper surface and the side surface of the mask substrate are removed. This removes the organic matter formed on the substrate.
  • An organic substance removing device includes: an upper plate facing at least an upper surface of a mask substrate, forming an ozone water flow passage between the upper surface of the mask substrate, and a side surface of the mask substrate; And a side plate that forms an ozone water flow channel between the mask substrate and a side surface of the mask substrate.
  • FIG. 21 is a schematic diagram showing an example of a conventional organic substance removing apparatus for a mask substrate that removes organic substances by flowing ozone water over the upper surface of a mask substrate.
  • the lid is provided so as to form a predetermined gap with respect to the upper surface and the side surface of the mask substrate and cover them.
  • the gap formed between the lid and the surface of the mask substrate serves as a channel for the ozone water flow, and the ozone water supplied to the channel is subjected to a high pressure so that the ozone water flows along the upper and lower surfaces of the mask substrate. Therefore, organic substances formed on the upper surface and side surfaces of the mask substrate can be uniformly and efficiently removed.
  • FIG. 18 is a cross-sectional view schematically showing one example of the organic matter removing apparatus of the third present invention.
  • the third organic matter removing apparatus 100 of the present invention mainly comprises: A box-shaped lid 101 that can cover the upper surface and side surfaces of the mask substrate 110; and a lower plate 1 that is disposed below the mask substrate 110 and faces the lower surface of the mask substrate 110.
  • the mask substrate 110 having the organic substance 111 formed on the surface thereof is installed in a space formed by the inner surface of the lid 101 and the upper surface of the lower plate 106. ing.
  • the lid 101 faces the upper surface of the mask substrate 110, and the upper plate 1 in which an ozone water supply unit 104 for supplying ozone water to the upper surface of the mask substrate 110 is formed at a substantially central portion thereof. And a side plate 103 facing a side surface of the mask substrate 110.
  • the upper plate constituting the upper part has a surface facing the upper surface of the mask substrate, and a channel for an ozone water flow is formed between the upper plate and the upper surface of the mask substrate. is set up.
  • the upper plate is not particularly limited as long as it has a shape having a surface facing the upper surface of the mask substrate.
  • the distance between the upper plate and the upper surface of the mask substrate is preferably 1.5 mm or less. If the thickness exceeds 1.5 mm, the pressure applied to the ozone water supplied to the flow path of the ozone water flow becomes insufficient, and the flow speed of the ozone water flowing along the upper surface of the mask substrate is not sufficiently increased, so that the mask In some cases, organic substances on the substrate surface cannot be sufficiently removed. It is more preferably not more than 0.5 mm, and further preferably not more than 0.3 mm.
  • the material constituting the upper plate is not particularly limited as long as it has ozone resistance, and includes, for example, metals such as SUS, and fluorine-based resins. Is preferred.
  • fluorine-based resin include polyfluoroethylene resin; polytetrafluoroethylene resin (PTFE), perfluoroalkoxy resin (PFA), and fluorotetraethylene propylene resin (FEP).
  • Polymer fluorine-based rubber and the like.
  • a plurality of conversion members for changing the direction of the flow of the ozone water flowing along the upper surface of the mask substrate are formed on the surface of the upper plate facing the upper surface of the mask substrate.
  • the formation of the conversion member causes turbulence in the ozone water flow flowing on the surface of the mask substrate due to the stirring effect of the conversion member. This is because high-concentration ozone water is always applied to the upper surface of the substrate, and organic substances formed on the upper surface of the mask substrate can be removed more uniformly and with higher efficiency.
  • the present inventors further investigated an organic substance removing apparatus that removes organic substances by flowing ozone water on the upper surface of a conventional mask substrate.
  • the organic substance removing apparatus shown in FIG. 21 the organic substance removing apparatus shown in FIG. In the case of 42, the portion supplied with the ozone water stream 144 was relatively removed, whereas the outflow portion of the ozone water stream 144 was almost completely removed even though the ozone water concentration was still high enough. Found that it was not removed.
  • the saturated concentration of ozone water at room temperature is as low as about 60 ppm and reacts with organic substances. Then the ozone water concentration immediately drops.
  • ozone water is supplied to a certain point on the mask substrate and centrifugal force caused by spin causes ozone water to flow as a parallel stream to the top surface of the mask substrate, the mask substrate that hits organic matter near the supplied location
  • the ozone water near the upper surface is consumed by the ozone to remove organic substances, and the ozone concentration is reduced.
  • the ozone water having the reduced ozone concentration flows directly near the upper surface of the mask substrate. However, it is thought that ozone water no longer has an ozone concentration sufficient to remove organic matter.
  • ozone water flowing relatively far from the upper surface of the mask substrate is considered to flow away without being provided with organic matter removal.
  • the organic substance removing device by using an upper surface provided with a conversion member for changing the direction of the ozone water flow at a position facing the upper surface of the mask substrate, the device can be provided near the ozone water flow supply point. Even when ozone is consumed, turbulence occurs in the ozone water flow due to the agitating effect of the conversion member, so that high-concentration ozone water always hits the entire upper surface of the mask substrate, thereby uniformly and efficiently removing organic substances. .
  • the conversion material in the organic substance removing apparatus according to the third aspect of the present invention is not particularly limited as long as it can produce the above-described effect on the ozone water flow flowing on the upper surface of the mask substrate.
  • the shape is the same as that of the conversion member described with reference to FIG.
  • the material forming the conversion member is not particularly limited as long as it has ozone resistance, and examples thereof include the same materials as those of the upper plate.
  • the conversion member is disposed so as to face substantially the entire upper surface of the mask substrate, or has a size that is substantially opposite to the entire upper surface of the mask substrate.
  • the ozone water flow toward the entire upper surface of the mask substrate can be more reliably generated, and the probability of the ozone water reaching the organic substances on the entire surface of the mask substrate increases with a high probability, and the organic substances can be more reliably removed. Because you can.
  • the distance between the conversion member and the upper surface of the mask substrate is preferably 1.5 mm or less. If the thickness exceeds 1.5 mm, the effect of the turbulent flow of the ozone water flow generated by the above-mentioned conversion member may not reach the upper surface of the mask substrate, and the organic matter removal rate may be insufficient. It is more preferably 0.5 mm or less, and further preferably 0.3 min or less.
  • the distance between the conversion member and the upper surface of the mask substrate means a distance between points where the conversion member and the upper surface of the mask substrate are closest.
  • the ozone water flow is provided substantially at the center of the upper plate in the channel of the ozone water flow between the upper plate and the upper surface of the mask substrate. It is preferable that an ozone water supply unit for supplying water is formed. Since the ozone water supplied to the flow path of the ozone water flow flows from the center of the mask substrate toward the outer periphery thereof, organic substances formed on the upper surface of the mask substrate can be uniformly removed.
  • the ozone water supply section is not particularly limited, and examples thereof include a tubular member formed so as to penetrate substantially the center of the upper plate, as in the ozone water supply section 104 shown in FIG.
  • the upper plate constituting the lid portion is substantially similar to the upper plate 122 shown in FIGS. It is preferable that a plurality of nozzles 124 for projecting ozone water be formed on the upper surface of the mask substrate at positions corresponding to the entire surface. In this case, the ozone water can uniformly reach almost the entire upper surface of the mask substrate, and organic substances formed on the upper surface of the mask substrate can be uniformly and efficiently removed.
  • FIG. 19 (a) is a plan view schematically showing another example of the upper plate constituting the sunflower part in the organic matter removing apparatus of the third invention, and (b) is a sectional view thereof. is there.
  • the linear velocity of the ozone water jetted from each nozzle ⁇ / onto the upper surface of the mask substrate is 460 to 400 cm / sec. . If it is less than 460 cm / sec, organic matter can be removed efficiently. If it exceeds 400 cm / sec, the rate of reaction between ozone and organic matter will not increase the organic matter removal rate even if the linear velocity is increased anymore. Efficiency may instead decrease.
  • the nozzles are preferably the ozone water injection nozzles of the present invention described above, and the upper surface of the mask substrate It is preferable to remove the organic substance formed in the above-mentioned manner by the same method as the organic substance removing method of the present invention according to another embodiment described above or the still another embodiment of the present invention. This is because organic substances on the upper surface of the mask substrate can be removed extremely uniformly and efficiently.
  • the side plate constituting the lid portion has a surface facing the side surface of the mask substrate, and is installed such that an ozone water flow channel is formed between the side plate and the side surface of the mask substrate. Have been.
  • the side plate has a surface facing a side surface of the mask substrate.
  • the shape of the side plate is not particularly limited as long as the surface facing the side surface of the mask substrate faces the entire side surface of the mask substrate.
  • the side surface of the mask substrate has a shape in which the corners are chamfered like the mask substrate 110 shown in FIG. 18, the upper surface side of the mask substrate is chamfered like the side plate 103.
  • the side surface of the mask substrate is a uniform plane
  • the surface of the side plate opposing the side surface of the mask substrate is a uniform plane.
  • a chamfered portion is also formed at a corner on the lower surface side, but such a portion is a part of the lower surface.
  • the shape of the side plate 103 of the lid portion 101 is changed to a shape having a surface facing a chamfered portion formed at a corner on the lower surface side. Then, a mask substrate 110 is set inside the lid 101 in which the upper plate 102 and the side plate 103 are integrated. It is impossible to place them.
  • the material forming the side plate is not particularly limited as long as it has ozone resistance, and examples thereof include the same materials as those of the upper plate.
  • the distance between the side plate and the side surface of the mask substrate is preferably 1.5 mm or less. If the thickness exceeds 1.omm, ozone water may not be able to flow along the side surface of the mask substrate, and sufficient pressure may not be applied to the ozone water flowing on the side surface of the mask substrate, resulting in a flow rate of the ozone water. In some cases, the organic matter on the side surface of the mask substrate cannot be sufficiently removed. It is more preferably at most 0.5 mm, even more preferably at most 0.2 mm, most preferably at most 0.1 mm.
  • the side plate constituting the lid may be integral with the upper plate as shown in FIG. 18, or the upper plate and the side plate may be separate bodies. It is good. Further, when the upper plate and the side plate are separate bodies, the side plate may be separable for each surface facing the side surface of the mask substrate as shown in FIG.
  • FIG. 20 is a plan view schematically showing another example of the side plate forming the hood in the third organic substance removing device according to the present invention.
  • the side plates 133 are substantially flat, and the bottom surface (the surface of the smallest area) of one side plate 133 projects from the side surface (the surface of the largest area) of the other side plate 133.
  • a total of four are arranged so as to fit each other, and the mask substrate is housed in the internal space formed by the four side plates 13 3 .
  • the side plates 13 3 are preferably movable in the directions indicated by arrows in FIG. 20. .
  • the size of the space formed by the side plates 13 3 can be arbitrarily changed, and the distance between the mask substrate and the side plates 1 3 3 falls within a predetermined range according to the variation in the size of each mask substrate. This is because fine adjustment can be performed as follows.
  • the outer shape of the lid portion including the upper plate and the side plate is not particularly limited as long as the inner surface faces the upper surface and the side surface of the mask substrate, and is, for example, square or circular. Shape.
  • the size of such a lid is not particularly limited, and when a mask substrate is installed inside, the distance between the upper surface of the mask substrate and the surface of the upper plate of the lid facing the upper surface, In addition, the distance between the side surface of the mask substrate and the surface of the side plate of the sand section facing the side surface is appropriately adjusted to a size within a predetermined range.
  • the organic substance removing apparatus of the third invention include a lower surface facing the lower surface of the mask substrate and forming a channel for an ozone water flow between the lower surface of the mask substrate and the lower surface of the mask substrate.
  • An organic substance may be formed on the lower surface of the mask substrate. When the lower plate is formed, the organic substance formed on the lower surface of the mask substrate can be removed.
  • the shape of the lower plate is not particularly limited as long as the surface facing the lower surface of the mask substrate faces the entire lower surface of the mask substrate.
  • the mask substrate is chamfered like the lower plate 106.
  • the surface of the lower plate facing the lower surface of the mask substrate is a uniform plane.
  • an ozone water discharge section for discharging ozone water to the outside is formed in such a lower plate.
  • the material constituting the lower plate is not particularly limited as long as it has ozone resistance, and examples thereof include the same materials as those for the upper plate.
  • the size of the lower plate is preferably the same as the size of the lid. This is because when the lower plate is attached to the above-mentioned section, a gap is formed at the boundary between them, and ozone water is prevented from leaking.
  • the mask substrate having the organic substance formed on the surface is disposed such that its upper surface and side surfaces are at least opposed to the upper plate and the side plate of the lid.
  • the method for installing the mask substrate at the position is not particularly limited.
  • a method of fixing the mask substrate to the fixing portion by means of an adhesive means such as a double-sided tape; The jacking method and the like can be mentioned.
  • a method of mounting and fixing on a columnar support member provided on the lower plate may be used.
  • the organic matter removing device of the third aspect of the present invention has means for heating ozone water.
  • Organic matter removal is achieved by the chemical reaction between organic matter and ozone By increasing the temperature, temperature, etc., the organic matter removal rate can be increased.
  • the organic matter removing device of the third aspect of the present invention has means for pressurizing the inside of the device. By pressurizing the inside of the apparatus, supersaturated ozone water can be generated, and by using such high concentration ozone water, organic substances can be removed with higher efficiency.
  • the ozone water supplied to the flow path (gap) of the ozone water flow between the ozone water and the upper surface of the mask substrate flows through the water channel, and the end of the upper surface of the mask substrate
  • the ozone water that has arrived at the section changes its flow direction and flows through the ozone water flow channel (gap) formed between the side plate and the side surface of the mask substrate. That is, according to the organic substance removing apparatus of the third aspect of the present invention, ozone water to which a high pressure is applied can flow reliably along the organic substance formed on the upper surface and the side surface of the mask substrate. Organic matter can be removed efficiently and uniformly.
  • the aspect of the organic substance removal including the organic substance removal apparatus of the third invention is different from the reaction section in the organic substance removal apparatus of the first invention described with reference to FIG. 2 in the reaction section for removing organic substances on the substrate surface.
  • an embodiment similar to the first embodiment of the organic matter removing apparatus of the present invention is given.
  • the organic substance removing apparatus is provided inside the reaction section, and removes organic substances on the surface of the mask substrate in the reaction section. That is, in the reaction section, the ozone water supply section formed on the upper plate constituting the lid of the organic matter removal device is connected to the ozone water inlet, and the ozone water introduced from the ozone water inlet is After flowing through the organic substance removing apparatus of the third aspect of the present invention in the manner described above to remove organic substances on the surface of the mask substrate, the organic substance is discharged from the ozone water discharge port of the reaction section.
  • the reaction section in the organic substance removing apparatus according to the third aspect of the present invention may be provided with means for irradiating ultraviolet rays, similarly to the reaction section in the organic substance removing apparatus according to the first aspect of the present invention.
  • the organic substance removing apparatus of the third aspect of the present invention When removing organic substances on the surface of the mask substrate by the organic substance removing apparatus of the third aspect of the present invention, by irradiating ultraviolet rays, the decomposition rate of ozone is accelerated, and accordingly, the organic substances are removed. Removal effect can be improved. Therefore, by using the ozone water and the ultraviolet irradiation together, a higher organic substance removing effect can be obtained.
  • high-concentration ozone water to which high pressure is applied can flow along the upper surface and the side surface of the mask substrate, so that organic substances formed on the surface of the mask substrate can be efficiently removed. Can be removed.
  • the organic matter removing apparatus in a reaction section for removing organic matter on the substrate surface, faces a processing surface of the substrate fixed to the fixing section so as to be substantially parallel to the direction of the ozone water flow.
  • a conversion member for changing the direction of the ozone water flow is provided at a position where the ozone water flow flows. Therefore, even if ozone is consumed on the inflow side of the ozone water flow, a turbulent flow occurs in the ozone water flow due to the stirring effect of the conversion member and the flow is always high. Since the ozone water of the concentration hits the entire processing surface of the substrate, organic substances can be uniformly and efficiently removed. In particular, when a conversion member having a shape that generates a turbulent flow is selected so that the direction of the ozone water flow converted by the conversion member is substantially in the direction of the processing surface of the substrate, the organic matter is extremely highly efficient. Can be removed.
  • the organic matter removing apparatus injects ozone water through a nozzle such that the ozone water reaches a point on the processing surface of the substrate at a linear velocity of 450 c / sec or more. Therefore, the organic matter decomposed to a molecular weight level that can be removed by the ozone water stream with a linear velocity of 450 cm / sec or more is removed as soon as possible, and the organic matter that has not been decomposed is always a new high-concentration ozone. Since it can reach hydraulic power, organic matter can be removed with extremely high efficiency.
  • the organic substance removing method of the present invention using the first or second organic substance removing apparatus of the present invention can remove organic substances formed on the substrate surface with high efficiency and uniformly.
  • a plurality of injection holes are formed at positions corresponding to the entire surface of the processing surface of the substrate on which the organic substance is formed, and the injection holes are formed between adjacent injection holes.
  • the entire surface of the substrate rotated in the direction perpendicular to the ozone water spray direction Ozone water can be sprayed uniformly, and when organic substances are removed from the substrate surface using the ozone water injection nozzle of the present invention, organic substances can be uniformly and extremely efficiently removed.
  • At least the organic matter removing device for a nozzle according to the present invention which has the ozone water spray nozzle of the present invention and a rotating means for rotating the substrate, is capable of removing the organic matter from the surface of the substrate in a direction in which the ozone water is sprayed.
  • Ozone water can be uniformly sprayed on the entire surface of the processing surface of the substrate rotated in the vertical direction, and the organic substances on the substrate surface can be uniformly and highly efficiently removed.
  • an organic matter removing method comprising: providing a nozzle having a plurality of injection holes formed at positions corresponding to substantially the entire surface of a processing surface of a substrate; Ozone water is sprayed onto almost the entire surface of the processing surface of the substrate in a state where it is close to the substrate so that an ozone water layer is apparently formed in between.
  • Organic substances can be removed very efficiently and uniformly. Further, even when the substrate is thin and brittle, the substrate is not damaged by the ozone water flow jetted from the nozzle. Furthermore, the apparatus can be made compact because ozone water does not scatter during removal of organic substances on the substrate surface.
  • the pseudo ozone water layer is pressurized. As a result, a supersaturated state of the ozone concentration of the pseudo ozone water layer can be maintained, and organic substances on the substrate surface can be removed by the high concentration ozone water.
  • a nozzle for injecting ozone water onto substantially the entire surface of the processing surface of the substrate a moving unit for moving the nozzle, and a rotating unit for rotating the substrate according to another aspect of the present invention. Since the distance between the nozzle and the substrate can be freely set by the moving means, the organic matter removing method of the present invention according to another aspect can be suitably realized.
  • an organic matter removing method comprising: disposing a nozzle having a plurality of injection holes formed at positions corresponding to the entire surface of the processing surface of the substrate in a direction parallel to the processing surface of the substrate. While moving, ozone water is applied to almost the entire processing surface of the substrate. Since the jetting is performed, the arrival points of the ozone water are complicatedly overlapped on the processing surface of the substrate, and the ozone water can directly reach almost the entire surface of the processing surface of the substrate uniformly. Organic substances on the surface can be removed very efficiently and uniformly.
  • At least the organic matter removing apparatus of the present invention according to still another aspect, further including a nozzle for injecting ozone water onto substantially the entire surface of the processing surface of the substrate, and a rocking means for rotating the nozzle.
  • the organic matter removing method of the present invention according to another aspect can be suitably realized.
  • An organic substance removing device includes: an upper plate facing at least an upper surface of a mask substrate, forming an ozone water flow passage between the upper surface of the mask substrate, and a side surface of the mask substrate; Since a lid portion comprising a side plate forming an ozone water flow channel between the mask substrate and the side surface of the mask substrate is provided, the ozone water supplied to the water channel is subjected to a high V and a pressure so that the ozone water is supplied to the mask substrate. Since it flows at a high flow velocity along the top and side surfaces of the mask substrate, organic substances formed on the top and side surfaces of the mask substrate can be removed uniformly and with high efficiency.
  • FIG. 22 (a) is a cross-sectional view schematically showing a negative part of the conversion member in the reaction part according to Example 1
  • FIG. 22 (b) is a plan view thereof.
  • a reaction section having the configuration shown in FIGS. 2 to 4 was manufactured using this conversion member.
  • the distance between the conversion member and the wafer was 0.3 mm.
  • a resist solution (FHi3950, manufactured by Fuji Film Arch Co., Ltd.) is applied in advance to the wafer, and the wafer is coated with a spin coater (1H-DX2, manufactured by Mikasa). After processing at 0 rpm for 30 seconds, it was further dried at 105 ° C for 20 minutes, coated with a resist having a thickness of about 1.0 im, and pressed to a size of 30 mm ⁇ 3.0 mm. Was used.
  • Figure 23 shows a three-dimensional diagram showing the resist thickness 20 seconds after the start of measurement based on data obtained using a film thickness meter (manufactured by Otsuka Electronics Co., Ltd., FE-30000 type). Was.
  • the arrow shown in FIG. 23 indicates the direction of the ozone water flow.
  • Example 2 Same as Example 1 except that the flow rate of the ozone water was set to 1.9 L / min.
  • FIG. 25 is a cross-sectional view schematically showing a reaction section according to Comparative Example 1, wherein 150 indicates a reaction section, 15 1 indicates a wafer, and 15 2 indicates a resist. I have.
  • Comparative Example 1 1.0 50 0.10 From Table 1, it was found that Examples 1 and 2 were able to obtain a higher resist removal rate than Comparative Example 1 in terms of strength.
  • a 0.5 mm hole was made in a fluororesin tube using a carbon dioxide laser, and the tip was stopped with a tubing stop to produce a nozzle.
  • the diameter of the water stream arriving at a point 30 cm away from the nozzle was measured to be about 0.5 mm. This proved that this nozzle was a rod-flow nozzle.
  • a nozzle was placed at a distance of 10 mm from the processing surface of the processed sample (wafer) prepared in the same manner as in Example 1 using ozone water at a temperature of 22 ° C and an ozone concentration of 55 ppm from this nozzle, Ozone water was continuously injected so that the linear velocities upon reaching from 480, 800, 1190 and 1460 cm / sec.
  • FIG. 27 is a plot of resist removal volume versus linear velocity. (Example 4)
  • Ozone water was continuously jetted at 1 190 and 1460 cm / sec.
  • the volume of the removed resist was calculated in the same manner as in Example 3.
  • FIG. 28 is a diagram in which the resist removal volume is plotted against the linear velocity.
  • This nozzle was placed at a position facing the processing surface of the processing sample (wafer) prepared in Example 1, and ozone water at a temperature of 22 ° C and an ozone concentration of 55 ppm was applied to the processing surface. Ozone water was continuously injected so that the linear velocity upon reaching from the vertical direction was 1500 cm / sec.
  • the resist thickness was measured using a film thickness meter (Otsuka Electronics Co., Ltd., type £ -3000), and the resist removal rate was calculated. From the obtained data, a three-dimensional diagram showing the thickness of the substrate 30 seconds after the start of the irradiation of the ozone water was prepared. This three-dimensional diagram is shown in FIG. 29. From FIG. 29, it was found that the resist was almost uniformly removed over almost the entire processing surface of the substrate. (Example 6)
  • a cylindrical member made of perfluoroalkoxy resin with a diameter of 106.9 mm, an inner diameter of 100 mm and a thickness of 10 mm (1) is integrated with a cylindrical member (2) of a diameter of 10 Omm and a thickness of 1 Omm (2)
  • the nozzle body was fabricated (see Figs. 10 (a) and (b)).
  • the diameter of the nozzle body was approximately evenly distributed over the entire surface of the nozzle body except for the center of the injection surface from the (1) side.
  • the created ozone water supply section is shown in Fig. 10 (a) with the distance between the centers of vertically adjacent ozone water supply sections. 1 Omm, the distance between one row formed by the ozone water supply section and the other adjacent row is 10 mm, and the ozone water supply section adjacent in the horizontal direction rises by 2 mm to the right. .
  • a 0.5 mm diameter ozone water injection part was formed at the center of the bottom surface of the ozone water supply part using a CO 2 laser, and an injection hole composed of the ozone water supply part and the ozone water injection part was produced.
  • An ozone water injection nozzle was manufactured.
  • the ozone water injection nozzle according to Example 6 was rotated in a direction perpendicular to the ozone water injection direction, and the locus of the center of the injection hole drawn on an arbitrary plane perpendicular to the ozone water injection direction was examined. However, the trajectories drawn by the centers of all the injection holes did not overlap (see Fig. 11).
  • the ozone water injection nozzle according to Example 6 was attached to the ozone water injection device having the structure shown in Fig. 13, and the ozone water at a temperature of 22 ° C and an ozone concentration of 55 ppm was rotated at a flow rate of 300 cm / sec.
  • the treated sample rotated at several 100 rpm (min " 1 ) was continuously ejected from the perpendicular direction to the treated surface for 3 minutes.
  • a resist solution (FHi 3950, manufactured by Fuji Film Arch Co., Ltd.) was applied to a 4 inch (101.6 mm) diameter wafer in advance, and a spin coater (Mikasa, 1H— DX2) for 30 seconds at 3000 rpm (min- 1 ), and then dried at 105 ° C for 20 minutes, and coated with a resist having a thickness of about 1.
  • An ozonized water injection nozzle was manufactured in the same manner as in Example 6, except that the center-to-center distance between adjacent holes was shortened (see FIG. 12).
  • the distance between the centers of the vertically adjacent ozone water supply units in Fig. 12 is 5 mm, and the distance between one row formed by the ozone water supply unit and another adjacent line is Was set to 5 mm, and the horizontally adjacent poison water supply section was set to rise to the right by 2 mm.
  • the ozone water injection nozzle according to the prepared example ⁇ ⁇ was rotated in the direction perpendicular to the ozone water injection direction, and the locus of the center of the injection hole drawn on an arbitrary plane perpendicular to the ozone water injection direction was examined. However, the trajectories drawn by the centers of the misaligned injection holes did not overlap. Further, when the water flow injected from the injection holes was examined in the same manner as in Example 6, it was found to be a stick flow.
  • drill holes were drilled at intervals of 10 mm to form ⁇ .5 holes in vertical and horizontal grids including the center of the injection surface 164.
  • the ozone water injection nozzle 160 was produced in the same manner as in Example 6.
  • the ozone water injection nozzle 160 according to Comparative Example 2 was rotated in a direction perpendicular to the ozone water injection direction, and the locus drawn by the center of the injection hole on an arbitrary plane perpendicular to the ozone water injection direction was drawn. Upon examination, as shown in FIG. 31, the trajectories 166 drawn by the centers of many injection holes 161 overlapped.
  • the fabricated nozzle was connected to a mechanical arm, and a reaction section having the structure shown in Fig. 15 was constructed.
  • the distance between the nozzle and the treated surface of the treated sample was 2 mm.
  • the pressure inside the system of the ozone water production equipment was set to 0.28 MPa, and the ozone water at a temperature of 22 ° C and an ozone concentration of 90 ppm was rotated by a motor at a rotation speed of 10 rpm. And sprayed continuously from the vertical direction for 60 seconds.
  • a resist solution (rich FHI3950) (manufactured by Shishi Film Arch Co., Ltd.), and treated with a spin coater (Mikasa, 1H-DX2 type) at 300 rpm (min- ⁇ , 30 seconds). Further, the resist was dried at 105 ° C. for 20 minutes and coated with a resist having a thickness of about 1.0.
  • Observation between the nozzle and the treated surface of the treated sample while injecting the ozone water confirmed that a pseudo ozone water layer was formed.
  • the thickness of the resist on the treated surface of the treated sample before and after treatment was measured using a film thickness meter (manufactured by Otsuka Electronics Co., Ltd., FE-300 type), and the resist removal rate and resist thickness were measured. Standard deviation was calculated.
  • FIG. 32 shows a three-dimensional diagram showing the processing surface of the processed sample after processing from the obtained data.
  • the resist was removed in the same manner as in Example 8, except that the distance between the nozzle and the treated surface of the treated sample was 1 Omm.
  • FIG. 33 shows a three-dimensional diagram showing the processing surface of the processed sample after processing from the obtained data.
  • Example 8 can obtain a higher resist removal rate than Comparative Example 3.
  • Example 8 the resist on the entire processed surface of the processed sample was extremely uniformly removed, whereas in Comparative Example 3, the resist removal state on the processed surface of the processed sample was slightly different depending on the location. As a result, the resist removal efficiency of the treated surface was inferior to that of Example 8.
  • a 0.5 mm diameter drilling hole is formed at intervals of 1 Omm on a disc-shaped main body made of perfluoroalkoxy resin with a diameter of 10 Omm and a thickness of 1 Omm.
  • the nozzle was fabricated so as to be distributed approximately evenly over the entire surface of the nozzle (see Fig. 14).
  • the diameter of water reaching the point 30 cm away from the injection hole was measured for the water flow injected from the injection hole of the nozzle. However, it was about 0.5 mm. From this, it was found that the water flow injected from the injection hole was a rod flow.
  • the fabricated nozzle was connected via a fixed shaft to the other end of a support rod, one end of which was connected to a motor functioning as a driving means, to constitute a reaction section having the structure shown in Fig. 17 did.
  • the nozzle is held and fixed on a rotary table connected to a motor as a rotating means, and a direction parallel to the processing surface above the processing surface of the processing sample rotated at a rotation speed lrpm (min 1 ).
  • a rotation speed lrpm (min 1 )
  • a resist solution (FHI 3950, manufactured by Fuji Film Arch Co., Ltd.) was applied to a wafer with a diameter of 10 Omm in advance, and the spin coater (Mikasa, 1H-DX2 type) was used at 3000 rpm. (min — 1 ), treated for 30 seconds, dried at 105 ° C. for 20 minutes, and coated with a resist having a thickness of about 1.0;
  • the resist was removed from the treated sample in the same manner as in Example 9, except that the nose was not rocked.
  • Chromium was sputtered uniformly on the surface of quartz glass with a smooth surface, and a low-reflection oxide film was formed uniformly on the chromium.
  • a resist solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., THMR IP 3100) was applied to the obtained quartz glass oxide film, and the spin coater (manufactured by Mikasa Co., Ltd., Model 111-102) was applied at 2000 rpm. After processing for 30 seconds, the product dried at 105 ° C for 20 minutes was further cut into a size of 10 mm x 1 Omm, exposed using an I-line stepper, developed with an alkaline system, and the outer periphery was chamfered. A processed sample of the shape was prepared.
  • the resist was formed on the top and side surfaces of this processed sample, and the thickness of the resist was 0.5 / m.
  • the upper surface of the prepared processed sample was made of perfluoroalkoxy resin.
  • a lid comprising an upper plate and a side plate having a surface facing the side surface and a side plate, and a lower plate having a surface facing the lower surface of the processed sample were produced (see FIG. 18).
  • a tubular ozone water supply part capable of supplying ozone water to the center of the upper surface of the processing sample is formed on the upper plate of the produced lid part, and an ozone water supply part is provided on the surface facing the upper surface of the processing sample.
  • conversion members arranged concentrically at 1.5 mm intervals were formed (see Fig. 1). The angle of the oblique portion of the conversion member was 45 ° and the height was 1.7 mm.
  • the treatment sample was set in the internal space formed by the produced lower plate and lid, and a resist removing device was produced.
  • the distance between the upper surface of the processed sample and the conversion member formed on the upper plate of the lid was 0.3 mm, and the distance between the side surface of the processed sample and the side plate of the lid was 0.1 mm.
  • the prepared resist removal apparatus was attached to a reaction section for resist removal similar to that of the embodiment shown in FIG. 2, and an ozone water having a concentration of 21 ° C. and a concentration of 50 ppm was applied to the reaction section between the conversion member and the substrate.
  • the flow rate was 1.0 L / min for 80 seconds.
  • a resist removing apparatus was manufactured in the same manner as in Example 10, except that a plate-like member having an ozone water supply section formed in the center was used instead of the lid section consisting of the upper plate and the side plates.
  • an organic substance removing apparatus an organic substance removing method, an ozone water jet nozzle, and an organic substance removing apparatus for a mask substrate, which can remove organic substances, particularly a resist, on a substrate surface with high efficiency.

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Abstract

La présente invention concerne un dispositif d'élimination de matière organique, un procédé d'élimination de matière organique et une buse de projection de jet d'eau à l'ozone qui permettent une élimination d'efficacité élevée de la matière organique présente à la surface d'un substrat. L'invention a également pour objet un dispositif d'élimination de matière organique pour substrat de masquage, qui permet une élimination d'efficacité élevée de la matière organique présente à la surface d'un substrat de masquage. Le dispositif d'élimination de matière organique élimine les matières organiques présentes à la surface d'un substrat, en faisant s'écouler de l'eau à l'ozone sur la surface du substrat à traiter, et comprend au moins une unité réactionnelle qui est composée d'une unité de fixation qui sert à fixer le substrat de sorte que sa surface à traiter se trouve généralement parallèle à la direction du flux d'eau à l'ozone, et d'un élément de changement de direction disposé à l'opposé de la surface du substrat fixé, qui sert à modifier la direction du flux d'eau à l'ozone.
PCT/JP2004/005681 2003-04-21 2004-04-21 Dispositif d'elimination de matiere organique, procede d'elimination de matiere organique, buse de projection de jet d'eau a l'ozone, et dispositif d'elimination de matiere organique pour substrat de masquage WO2004095550A1 (fr)

Applications Claiming Priority (8)

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JP2003116217A JP4351862B2 (ja) 2003-04-21 2003-04-21 レジスト除去方法及びレジスト除去装置
JP2003-116218 2003-04-21
JP2003116216A JP2006196477A (ja) 2003-04-21 2003-04-21 オゾン水噴射ノズル及びレジスト除去装置
JP2003-116216 2003-04-21
JP2003116218A JP2006196479A (ja) 2003-04-21 2003-04-21 レジスト除去方法及びレジスト除去装置
JP2003-116217 2003-04-21
JP2003-409375 2003-12-08
JP2003409375A JP2006164996A (ja) 2003-12-08 2003-12-08 マスク基板用レジスト除去装置

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US10960094B1 (en) 2020-06-16 2021-03-30 Innovative Technologies Disinfection system

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JP2000150349A (ja) * 1998-11-13 2000-05-30 Mitsubishi Electric Corp フォトレジスト膜除去方法および装置
JP2001269631A (ja) * 2000-03-27 2001-10-02 Dainippon Screen Mfg Co Ltd 基板洗浄装置
JP2001326210A (ja) * 2000-05-18 2001-11-22 Dainippon Screen Mfg Co Ltd 基板処理装置
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CN101373341B (zh) * 2007-08-24 2013-11-20 北京京东方光电科技有限公司 去除边缘光刻胶装置
US10960094B1 (en) 2020-06-16 2021-03-30 Innovative Technologies Disinfection system
US11938238B2 (en) 2020-06-16 2024-03-26 Innovative Technologies Disinfection system

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