WO2020004214A1 - 基板処理装置および基板処理方法 - Google Patents

基板処理装置および基板処理方法 Download PDF

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Publication number
WO2020004214A1
WO2020004214A1 PCT/JP2019/024478 JP2019024478W WO2020004214A1 WO 2020004214 A1 WO2020004214 A1 WO 2020004214A1 JP 2019024478 W JP2019024478 W JP 2019024478W WO 2020004214 A1 WO2020004214 A1 WO 2020004214A1
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Prior art keywords
substrate
solvent
auxiliary substance
drying auxiliary
mixed
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PCT/JP2019/024478
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English (en)
French (fr)
Japanese (ja)
Inventor
直澄 藤原
佑 山口
正幸 尾辻
加藤　雅彦
悠太 佐々木
弘明 ▲高▼橋
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
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Priority to CN201980036610.8A priority Critical patent/CN112219265A/zh
Priority to KR1020207037785A priority patent/KR102475175B1/ko
Publication of WO2020004214A1 publication Critical patent/WO2020004214A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • H01L21/67034—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for drying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
    • F26B5/06—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum the process involving freezing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/16—Drying solid materials or objects by processes not involving the application of heat by contact with sorbent bodies, e.g. absorbent mould; by admixture with sorbent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like
    • 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
    • H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
    • H01L21/67161—Apparatus for manufacturing or treating in a plurality of work-stations characterized by the layout of the process chambers
    • H01L21/67167—Apparatus for manufacturing or treating in a plurality of work-stations characterized by the layout of the process chambers surrounding a central transfer chamber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H01L21/67739—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations into and out of processing chamber
    • H01L21/67742—Mechanical parts of transfer devices
    • 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
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/687—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches
    • H01L21/68714—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support
    • H01L21/68764—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support characterised by a movable susceptor, stage or support, others than those only rotating on their own vertical axis, e.g. susceptors on a rotating caroussel

Definitions

  • the present invention relates to a substrate processing apparatus and a substrate processing method.
  • Substrates to be processed include semiconductor wafers, substrates for liquid crystal display devices, substrates for flat panel displays (FPDs) such as organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, Photomask substrates, ceramic substrates, solar cell substrates and the like are included.
  • FPDs flat panel displays
  • Photomask substrates ceramic substrates, solar cell substrates and the like are included.
  • an etching residue, a metal impurity, an organic contaminant, or the like, which is a reaction by-product, is attached to a surface (pattern forming surface) of a substrate on which a fine pattern having irregularities is formed through a dry etching process or the like.
  • a chemical treatment using a chemical such as an etching liquid or a cleaning liquid
  • a rinsing treatment for removing the chemical with a rinsing liquid is performed.
  • a typical rinse solution is deionized water or the like.
  • a drying process for drying the substrate by removing the rinsing liquid from the surface of the substrate is performed.
  • the aspect ratio of the convex portion of the pattern (the ratio of the height to the width of the convex portion) tends to increase. Therefore, at the time of the drying process, adjacent convex portions are attracted to each other by surface tension acting on the liquid surface of the rinse liquid (the interface between the rinse liquid and the gas thereon) that has entered the concave portions between the convex portions of the pattern. May be collapsed.
  • Patent Literature 1 discloses that after a rinsing liquid present on the surface of a substrate inside a chamber is replaced with a liquid of tertiary butanol as a sublimable substance, a tertiary butanol film-like solidified body is formed. It is disclosed that the surface of a substrate is dried by changing tertiary butanol contained in a solidified body from a solid phase to a gas phase without passing through a liquid phase.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2015-142069
  • the freezing point of tertiary butanol is slightly higher (about 25.7 ° C.) than room temperature (23 ° C. to 25 ° C., for example, about 23 ° C.) used for general substrate processing. Therefore, when a sublimable substance having a freezing point higher than room temperature, such as tertiary butanol, is used, it is necessary to apply heat to the sublimable substance in the pipe in order to prevent solidification in the pipe. Specifically, it is conceivable to provide a temperature control mechanism in the pipe. In this case, it is desirable to provide a temperature control mechanism in the entire area of the pipe through which the sublimable substance flows. Therefore, the cost may be significantly increased.
  • the sublimable substance solidifies in the pipe due to a stop of the temperature control mechanism due to a trouble of the apparatus, a long time is required for recovery. That is, when a sublimable substance having a freezing point above room temperature, such as tertiary butanol, is used as it is for drying the substrate, there is a concern that the sublimable substance solidifies in the piping.
  • one of the objects of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of suppressing or preventing the growth of cracks in a solidified film, thereby more effectively suppressing pattern collapse. is there.
  • Another object of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of satisfactorily processing the surface of a substrate while avoiding unintentional solidification of a drying auxiliary substance without a large increase in cost. is there.
  • the present invention provides a substrate holding unit for holding a substrate, a drying auxiliary substance, a first solvent, and the drying auxiliary substance and the first solvent on a surface of the substrate held by the substrate holding unit.
  • a mixed drying auxiliary substance supply unit for supplying a mixed drying auxiliary substance in which different chemicals are mixed with each other, and an evaporation unit for evaporating the first solvent from a surface of the substrate held by the substrate holding unit
  • a removing unit for removing the drying auxiliary substance from the surface of the substrate held by the substrate holding unit, and a control device for controlling the mixed drying auxiliary substance supply unit, the evaporation unit, and the removal unit.
  • the controller supplies the mixed and dried auxiliary substance to the surface of the substrate by the mixed and dried auxiliary substance supply unit.
  • a substrate processing apparatus that performs a film forming step and a removing step of removing the drying aid contained in the solidified film.
  • the mixed drying auxiliary substance in which the drying auxiliary substance, the first solvent, and the chemical are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may contain drugs as well as drying aids.
  • the growth can be inhibited by the chemical.
  • the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the freezing point drop occurs by mixing the drying aid with the first solvent and the drug.
  • the solidification point of the mixed drying auxiliary substance is lower than the solidification point of the drying auxiliary substance, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. This makes it possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying auxiliary material without increasing the cost.
  • the first drying auxiliary substance contains a sublimable substance having sublimability.
  • the mixed and dried auxiliary substance in which the sublimable substance, the first solvent, and the chemical are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may contain not only a sublimable substance but also a drug.
  • the growth can be inhibited by the chemical.
  • the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the drug contains a second solvent different from the first solvent.
  • the mixed drying auxiliary substance in which the drying auxiliary substance, the first solvent, and the second solvent are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may include a second solvent as well as a drying aid.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the drying auxiliary substance and the vapor pressure of the second solvent.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the drying auxiliary substance and the vapor pressure of the second solvent. Therefore, the first solvent is preferentially evaporated from the mixed drying auxiliary substance present on the surface of the substrate, whereby a solidified film containing the drying auxiliary substance is formed.
  • the solidified film may include a second solvent as well as a drying aid. In this case, even if a crack due to a crystal defect occurs in the solidified film, the growth can be inhibited by the second solvent. Thereby, the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • control device solidifies the drying auxiliary substance contained in the mixed drying auxiliary substance while evaporating the first solvent from the mixed drying auxiliary substance in the solidified film forming step. Execute the process.
  • the mixed drying auxiliary substance is solidified while evaporating the first solvent from the mixed drying auxiliary substance supplied to the surface of the substrate. As the first solvent evaporates, a drying aid is deposited. Thereby, the solidification of the mixed drying auxiliary substance proceeds.
  • the solidified film formed in the solidified film forming step does not include the first solvent.
  • the vapor pressure of the second solvent is lower than the vapor pressure of the drying aid.
  • the vapor pressure of the drying auxiliary substance is higher than the vapor pressure of the second solvent. Therefore, the second solvent does not evaporate from the mixed drying auxiliary substance present on the surface of the substrate. Since the solidified film contains not only the drying aid but also the second solvent, even if cracks due to crystal defects occur in the solidified film, the growth can be inhibited by the second solvent. Thereby, the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the second solvent may be in a liquid state.
  • the liquid second solvent is contained in the solidified film. Therefore, after the drying aid is removed from the solidified film, the liquid second solvent remains.
  • control device after the removing step, the control device further executes a solvent evaporation step of evaporating the liquid second solvent from the surface of the substrate.
  • the liquid second solvent remains after removing the drying aid from the solidified film. This second solvent is removed by evaporation. Thus, all of the drying aid, the first solvent, and the second solvent can be removed from the surface of the substrate.
  • a pattern is formed on the surface of the substrate, and the thickness of the second solvent remaining after the removing step is smaller than the height of the pattern.
  • the thickness of the liquid second solvent remaining after the removal of the drying auxiliary substance is smaller than the height of the pattern. Therefore, the surface tension of the second solvent acting on the pattern is small. This makes it possible to remove the second solvent from the surface of the substrate while suppressing pattern collapse.
  • the mixed drying auxiliary substance contains the second solvent in a smaller ratio than both the drying auxiliary substance and the first solvent.
  • the content of the second solvent is smaller than both the content of the drying auxiliary substance and the content of the first solvent. Therefore, even when the second solvent is removed after the drying aid and the first solvent are removed from the surface of the substrate, the surface tension acting on the pattern can be reduced. Thereby, pattern collapse can be further suppressed.
  • the mixed drying auxiliary substance contains the drying auxiliary substance in a smaller proportion than the first solvent.
  • the content ratio of the drying auxiliary substance that is mainly included in the solidified film before the start of the solidified film forming step is reduced by the first solvent that can be removed by evaporation in the evaporation step. Less than the content ratio. Therefore, the thickness of the liquid film before the start of the solidified film forming step can be reduced.
  • the thinner the thickness of the solidified film the smaller the residue remaining on the surface of the substrate after the removing step.
  • the thickness of the solidified film can be adjusted to be small. Thereby, generation of residues after the removing step can be suppressed.
  • the drying auxiliary substance in the solidified film formed in the solidified film forming step, is contained more than the second solvent, and the second solvent is mixed with the solidified film. Exist in a dispersed state.
  • the second solvent exists in a dispersed state in the solidified film. Therefore, even if cracks due to crystal defects occur at various places in the solidified film, the growth can be inhibited by the second solvent. Thereby, the growth of cracks in the solidified film can be suppressed or prevented in the entire region of the solidified film. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the formation rate of the solidified film in the solidified film forming step is such that the solidified film is formed based on a liquid containing the drying auxiliary substance and the first solvent and not containing the chemical. Slower than the forming speed.
  • the mixed drying auxiliary substance including the drying auxiliary substance, the first solvent, and the second solvent is more liquid than the liquid including the drying auxiliary substance and the first solvent, and not including the second solvent.
  • the formation speed of the solidified film is low. That is, according to this configuration, the solidified film can be formed in a short time, so that the time required for forming the solidified film can be reduced.
  • the drying auxiliary substance has a freezing point equal to or higher than room temperature, and the freezing point of the mixed drying auxiliary substance is lower than the freezing point of the drying auxiliary substance.
  • room temperature refers to a temperature in a room where a substrate processing apparatus is installed. Generally, it is in the range of 23 ° C. to 25 ° C., for example about 23 ° C.
  • the drying auxiliary substance since the drying auxiliary substance has a freezing point higher than room temperature, a part or the whole of the auxiliary substance may be in a solid state at room temperature.
  • the freezing point of the mixed drying auxiliary substance is lower than the freezing point of the drying auxiliary substance due to the freezing point drop caused by mixing the first solvent and the drug with the drying auxiliary substance. Therefore, when the freezing point of the mixed drying auxiliary substance is lower than room temperature, the mixed drying auxiliary substance maintains a liquid state at room temperature. Further, even when the solidification point of the mixed drying auxiliary substance is higher than room temperature, the solidification point of the mixed drying auxiliary substance is low. Therefore, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. This makes it possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying auxiliary material without increasing the cost.
  • the drying auxiliary substance has a freezing point higher than room temperature, and the solidification point of the mixed drying auxiliary substance is lower than room temperature.
  • the mixed drying auxiliary substance since the solidification point of the mixed drying auxiliary substance is lower than room temperature, the mixed drying auxiliary substance maintains a liquid state at room temperature. Therefore, unintentional solidification of the drying aid can be reliably avoided.
  • the drying aid, the first solvent, and the drug are mutually soluble.
  • the sublimable substance, the first solvent, and the drug can be dissolved in each other. Therefore, in the mixing and drying auxiliary substance, the sublimable substance, the first solvent, and the drug can be uniformly mixed without bias.
  • the apparatus further includes a rotating unit for rotating the substrate held by the substrate holding unit around a rotation axis passing through a central portion of the substrate. Then, the control device rotates the substrate by the rotating unit in parallel with the solidified film forming step and / or prior to the solidified film forming step, and removes the mixed and dried auxiliary substance from the surface of the substrate. The portion is removed by centrifugal force to further execute a film thickness reducing step of reducing the film thickness of the liquid film of the mixed drying auxiliary substance formed on the surface.
  • the thickness reducing step is performed in parallel with the solidified film forming step and / or prior to the solidified film forming step. Therefore, the thickness of the liquid film before the start of the solidified film forming step can be reduced.
  • the thinner the thickness of the solidified film the smaller the residue remaining on the surface of the substrate after the removing step.
  • the thickness of the solidified film can be adjusted to be small. Thereby, generation of residues after the removing step can be suppressed.
  • the apparatus further includes a processing liquid supply unit for supplying a processing liquid to the surface of the substrate held by the substrate holding unit. Then, the control device may further execute a step of supplying a processing liquid to the surface of the substrate by the processing liquid supply unit prior to the mixing and drying auxiliary substance supplying step. Further, the control device may execute a step of supplying the mixed drying auxiliary substance to a surface of the substrate to which the processing liquid is attached in the mixed drying auxiliary substance supplying step.
  • the evaporating unit includes a heating unit for heating the substrate held by the substrate holding unit, and a cooling unit for cooling the substrate held by the substrate holding unit.
  • a gas blowing unit for blowing gas onto the substrate held by the substrate holding unit, a pressure reducing unit for reducing the space around the substrate held by the substrate holding unit, and a gas holding unit held by the substrate holding unit
  • a rotation unit for rotating the substrate around a rotation axis passing through a central portion of the substrate.
  • the control device in the solidified film forming step, a step of heating the mixed and dried auxiliary substance by the heating unit, a step of cooling the mixed and dried auxiliary substance by the cooling unit, and A step of blowing a gas to the mixed drying auxiliary substance, a depressurizing step of depressurizing a space around the mixed drying auxiliary substance by the decompression unit, and a high-speed rotation step of rotating the mixed drying auxiliary substance around the rotation axis at a high speed. And at least one of the following.
  • a sublimation step of sublimating the solidified film from a solid to a gas, and decomposition of the solidified film converts the solidified film into a gas without passing through a liquid state.
  • At least one of a decomposition step of changing the solidified film and a reaction step of changing the solidified film into a gas without undergoing a liquid state by the reaction of the solidified film is performed.
  • the sublimation step is a gas blowing step of blowing gas to the solidified film, a heating step of heating the solidified film, a depressurizing step of reducing a space around the solidified film, and a light irradiating light to the solidified film.
  • the method may include at least one of an irradiation step and an ultrasonic vibration applying step of applying ultrasonic vibration to the solidified film.
  • the substrate processing apparatus includes: a first chamber; a second chamber different from the first chamber; and a second chamber between the first chamber and the second chamber.
  • the present invention provides a mixing / drying aid for supplying, to a surface of a substrate, a mixing / drying aid in which a drying aid, a first solvent, and a drying agent and a drug different from the first solvent are mixed with each other.
  • a substance supplying step by evaporating the first solvent from the mixed drying auxiliary substance present on the surface of the substrate and solidifying the drying auxiliary substance contained in the mixed drying auxiliary substance, the drying auxiliary substance and
  • a substrate processing method comprising: a solidified film forming step of forming a solidified film containing the chemical; and a removing step of removing the drying auxiliary substance contained in the solidified film.
  • the mixed drying auxiliary substance in which the drying auxiliary substance, the first solvent, and the chemical are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may contain drugs as well as drying aids.
  • the growth can be inhibited by the chemical.
  • the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the freezing point drop occurs by mixing the drying aid with the first solvent and the drug.
  • the solidification point of the mixed drying auxiliary substance is lower than the solidification point of the drying auxiliary substance, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. This makes it possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying auxiliary material without increasing the cost.
  • the drying auxiliary substance includes a sublimable substance having sublimability.
  • the mixed and dried auxiliary substance in which the sublimable substance, the first solvent, and the chemical are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may contain not only a sublimable substance but also a drug.
  • the growth can be inhibited by the chemical.
  • the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the drug contains a second solvent different from the first solvent.
  • the mixed drying auxiliary substance in which the drying auxiliary substance, the first solvent, and the second solvent are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may include a second solvent as well as a drying aid.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the drying auxiliary substance and the vapor pressure of the second solvent.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the drying auxiliary substance and the vapor pressure of the second solvent. Therefore, the first solvent is preferentially evaporated from the mixed drying auxiliary substance present on the surface of the substrate, whereby a solidified film containing the drying auxiliary substance is formed.
  • the solidified film may include a second solvent as well as a drying aid. In this case, even if a crack due to a crystal defect occurs in the solidified film, the growth can be inhibited by the second solvent. Thereby, the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the solidified film forming step includes a step of solidifying the drying auxiliary substance contained in the mixed drying auxiliary substance while evaporating the first solvent from the mixed drying auxiliary substance.
  • the mixed drying auxiliary substance is solidified while evaporating the first solvent from the mixed drying auxiliary substance supplied to the surface of the substrate. As the first solvent evaporates, a drying aid is deposited. Thereby, the solidification of the mixed drying auxiliary substance proceeds.
  • the solidified film formed in the solidified film forming step does not include the first solvent.
  • the vapor pressure of the second solvent is lower than the vapor pressure of the drying aid.
  • the vapor pressure of the drying auxiliary substance is higher than the vapor pressure of the second solvent. Therefore, the second solvent does not evaporate from the mixed drying auxiliary substance present on the surface of the substrate. Since the solidified film contains not only the drying aid but also the second solvent, even if cracks due to crystal defects occur in the solidified film, the growth can be inhibited by the second solvent. Thereby, the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • FIG. 1 is a schematic view of a substrate processing apparatus according to an embodiment of the present invention as viewed from above.
  • FIG. 2 is an illustrative sectional view for explaining a configuration example of a processing unit provided in the substrate processing apparatus.
  • FIG. 3 is a diagram showing the relationship between the concentration of the first solvent contained in the mixed sublimation agent and the freezing point of the mixed sublimation agent.
  • FIG. 4 is a block diagram for explaining an electrical configuration of a main part of the substrate processing apparatus.
  • FIG. 5 is an enlarged sectional view showing the surface of a substrate to be processed by the substrate processing apparatus.
  • FIG. 6 is a flowchart for explaining the contents of a substrate processing example executed in the processing unit.
  • FIGS. 1 is a schematic view of a substrate processing apparatus according to an embodiment of the present invention as viewed from above.
  • FIG. 2 is an illustrative sectional view for explaining a configuration example of a processing unit provided in the substrate processing apparatus.
  • FIG. 3 is a diagram
  • FIGS. 7A to 7C are schematic diagrams showing the state of the periphery of the substrate when the substrate processing example is being executed.
  • 7D to 7F are schematic views showing the next step after FIG. 7C.
  • 8A and 8B are enlarged views showing a state near the surface of the substrate in the substrate processing example.
  • 8C to 8E are schematic views showing the next step after FIG. 8B.
  • 9A and 9B are schematic diagrams showing a first modification.
  • FIG. 10 is a schematic diagram showing a second modification.
  • FIG. 11 is a schematic diagram showing a third modification.
  • FIG. 12 is a schematic diagram showing a fourth modification.
  • FIG. 13 is a schematic diagram showing a fifth modification.
  • FIG. 1 is a schematic view of a substrate processing apparatus according to an embodiment of the present invention as viewed from above.
  • the substrate processing apparatus 1 is a single wafer processing apparatus that processes a substrate W such as a silicon wafer one by one.
  • the substrate W is a disk-shaped substrate.
  • a plurality of processing units 2 for processing a substrate W with a processing liquid including a chemical solution and a rinsing liquid, and a substrate container for storing a plurality of substrates W to be processed by the processing unit 2 are mounted.
  • the substrate processing apparatus 1 includes a load port LP, an indexer robot IR and a substrate transfer robot CR for transferring a substrate W between the load port LP and the processing unit 2, and a control device 3 for controlling the substrate processing apparatus 1.
  • the indexer robot IR transports the substrate W between the substrate container and the substrate transport robot CR.
  • the substrate transfer robot CR transfers the substrate W between the indexer robot IR and the processing unit 2.
  • the plurality of processing units 2 have, for example, a similar configuration.
  • the substrate processing apparatus 1 is installed under normal pressure and room temperature (for example, about 23 ° C.) environment.
  • FIG. 2 is an illustrative cross-sectional view for explaining a configuration example of the processing unit 2.
  • the processing unit 2 includes a box-shaped chamber 4 and a spin chuck that holds one substrate W in a horizontal position in the chamber 4 and rotates the substrate W about a vertical rotation axis A1 passing through the center of the substrate W.
  • a rinsing liquid supply unit (processing liquid supply unit) 7 for supplying a rinsing liquid (processing liquid) to the upper surface of the substrate W held by the spin chuck 5, and an upper surface of the substrate W held by the spin chuck 5
  • Supply unit (processing liquid supply unit) 8 for supplying a solvent (processing liquid) to the substrate, and a mixing and supplying unit for supplying a mixed sublimation agent (mixing and drying auxiliary substance) to the upper surface of the substrate W held by the spin chuck 5
  • An agent supply unit (mixing / drying auxiliary substance supply unit) 9 a blocking member 10 that faces the upper surface of the substrate W held by the spin chuck 5 and blocks the space above the substrate W from the surrounding atmosphere;
  • a lower surface nozzle 11 for discharging the processing liquid toward the center of the lower surface of the substrate W (the rear surface Wb of the substrate W (see FIG. 7A and the like)) held by the chuck 5, and a cylindrical shape surrounding the side of the spin chuck 5 And
  • the chamber 4 includes a box-shaped partition 13 that accommodates the spin chuck 5 and the nozzle, and an FFU (fan filter filter) as a blowing unit that sends clean air (air filtered by a filter) into the partition 13 from above the partition 13.
  • Unit 14 an exhaust duct 15 for exhausting gas in the chamber 4 from below the partition 13, and an exhaust device 99 connected to the other end of the exhaust duct 15.
  • the FFU 14 is arranged above the partition 13 and is attached to the ceiling of the partition 13.
  • the FFU 14 sends clean air downward from the ceiling of the partition 13 into the chamber 4.
  • the exhaust device 99 sucks the inside of the processing cup 12 via the exhaust duct 15 connected to the bottom of the processing cup 12.
  • the FFU 15 and the exhaust device 99 form a downflow (downflow) in the chamber 4.
  • the processing of the substrate W is performed in a state where a downflow is formed in the chamber 4.
  • the spin chuck 5 As the spin chuck 5, a clamping chuck that holds the substrate W horizontally while sandwiching the substrate W in the horizontal direction is employed.
  • the spin chuck 5 includes a spin motor (rotation unit) 16, a spin shaft 17 integrated with a drive shaft of the spin motor 16, and a disk mounted substantially horizontally on an upper end of the spin shaft 17. And a spin base 18 in the shape of a circle.
  • the spin base 18 includes a horizontal circular upper surface 18a having an outer diameter larger than the outer diameter of the substrate W.
  • a plurality (three or more, for example, six) of holding members 19 are arranged on a peripheral portion thereof.
  • the plurality of sandwiching members 19 are arranged at, for example, equal intervals on a circumference corresponding to the outer peripheral shape of the substrate W at a peripheral portion of the upper surface 18a.
  • the blocking member 10 includes a blocking plate 20 and an upper surface nozzle 21 that vertically passes through a central portion of the blocking plate 20.
  • a blocking plate rotating unit 26 having a configuration including an electric motor and the like is connected to the blocking plate 20.
  • the blocking plate rotation unit 26 rotates the blocking plate 20 around a rotation axis (not shown) coaxial with the rotation axis A1.
  • the blocking plate 20 has a circular substrate facing surface 20a on the lower surface thereof facing the entire upper surface of the substrate W. At the center of the substrate facing surface 20a, a cylindrical through-hole 20b vertically penetrating the blocking plate 20 is formed. The upper surface nozzle 21 is inserted through the through hole 20b. A cylindrical portion projecting downward over the entire area may be formed on the outer peripheral edge of the substrate facing surface 20a.
  • the upper surface nozzle 21 is attached to the blocking plate 20 so as to be able to move up and down integrally.
  • the upper surface nozzle 21 has, at the lower end thereof, an ejection port 21 a facing the center of the upper surface of the substrate W held by the spin chuck 5.
  • a blocking member elevating unit 22 (see FIG. 4) having a configuration including an electric motor, a ball screw, and the like is connected to the blocking member 10.
  • the blocking member elevating unit 22 vertically moves the blocking plate 20 and the upper surface nozzle 21 up and down.
  • the blocking member elevating unit 22 sets the blocking plate 20 at a blocking position (the position shown in FIGS. 7C to 7E) where the substrate facing surface 20a is close to the upper surface of the substrate W held by the spin chuck 5, and is larger than the blocking position. It is moved up and down between the retracted positions (positions shown in FIG. 2) retracted upward.
  • the blocking member elevating unit 22 can hold the blocking plate 20 at both the blocking position and the retracted position.
  • the blocking position is a position where the substrate facing surface 20a forms a blocking space 30 (see FIGS. 7C to 7E and the like) between the substrate facing surface 20a and the surface Wa of the substrate W.
  • the shielding space 30 is not completely isolated from the surrounding space, no gas flows into the shielding space 30 from the surrounding space. That is, the cutoff space 30 is substantially cut off from the surrounding space.
  • a gas pipe 24 is connected to the upper surface nozzle 21.
  • the gas pipe 24 is provided with a gas valve 25 for opening and closing the gas pipe 24.
  • the gas applied to the gas pipe 24 is a dehumidified gas, particularly an inert gas.
  • the inert gas includes, for example, nitrogen gas and argon gas.
  • an inert gas is supplied to the upper surface nozzle 21.
  • the inert gas is discharged downward from the discharge port 21a, and the discharged inert gas is sprayed on the surface Wa of the substrate W.
  • the inert gas may be an active gas such as air.
  • a gas blowing unit is constituted by the upper surface nozzle 21, the gas pipe 24, and the gas valve 25, respectively.
  • the chemical solution supply unit 6 includes a chemical solution nozzle 31, a nozzle arm 32 having the chemical solution nozzle 31 attached to the tip, and a nozzle moving unit 33 that moves the chemical solution nozzle 31 by moving the nozzle arm 32 (see FIG. 4). And
  • the nozzle moving unit 33 horizontally moves the chemical solution nozzle 31 by horizontally moving the nozzle arm 32 around the swing axis.
  • the nozzle moving unit 33 has a configuration including a motor and the like.
  • the nozzle moving unit 33 moves the chemical liquid nozzle 31 between the processing position where the chemical liquid discharged from the chemical liquid nozzle 31 lands on the surface Wa of the substrate W and the retracted position set around the spin chuck 5 in plan view. Is moved horizontally.
  • the processing position is a position at which the chemical discharged from the chemical nozzle 31 is supplied to the front surface Wa of the substrate W.
  • the nozzle moving unit 33 includes a central position where the chemical liquid discharged from the chemical liquid nozzle 31 lands on the central portion of the surface Wa of the substrate W, and a peripheral part of the surface Wa of the substrate Wa where the chemical liquid discharged from the chemical liquid nozzle 31 is formed.
  • the chemical liquid nozzle 31 is moved horizontally between the peripheral position where the liquid is brought into contact with the liquid.
  • the center position and the peripheral position are both processing positions.
  • the chemical supply unit 6 includes a chemical pipe 34 for guiding the chemical to the chemical nozzle 31, and a chemical valve 35 for opening and closing the chemical pipe 34.
  • a chemical valve 35 for opening and closing the chemical pipe 34.
  • the chemical supplied to the chemical pipe 34 includes a cleaning liquid and an etching liquid.
  • the chemicals include sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, aqueous ammonia, aqueous hydrogen peroxide, organic acids (eg, citric acid, oxalic acid, etc.), and organic alkalis (eg, TMAH: tetramethylammonium hydro Liquid containing at least one of an oxide, a surfactant, and a corrosion inhibitor.
  • the rinsing liquid supply unit 7 includes a rinsing liquid nozzle 36.
  • the rinsing liquid nozzle 36 is, for example, a straight nozzle that discharges the liquid in a continuous flow state, and is fixedly disposed above the spin chuck 5 with its discharge port facing the center of the upper surface of the substrate W.
  • a rinse liquid pipe 37 to which a rinse liquid is supplied from a rinse liquid supply source is connected to the rinse liquid nozzle 36.
  • a rinsing liquid valve 38 for switching supply / stop of the rinsing liquid from the rinsing liquid nozzle 36 is provided at an intermediate portion of the rinsing liquid pipe 37.
  • the rinsing liquid valve 38 When the rinsing liquid valve 38 is opened, the rinsing liquid supplied from the rinsing liquid pipe 37 to the rinsing liquid nozzle 36 is discharged from a discharge port set at the lower end of the rinsing liquid nozzle 36. When the rinsing liquid valve 38 is closed, the supply of the rinsing liquid from the rinsing liquid nozzle 36 to the rinsing liquid nozzle 36 is stopped.
  • the rinsing liquid is water.
  • the water is, for example, deionized water (DIW), but is not limited to DIW, and may be carbonated water, electrolytic ionized water, hydrogen water, ozone water, ammonia water, and hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm). You may.
  • DIW deionized water
  • the water may be carbonated water, electrolytic ionized water, hydrogen water, ozone water, ammonia water, and hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm). You may.
  • the rinsing liquid supply unit 7 may include a rinsing liquid nozzle moving device that moves the rinsing liquid nozzle 36 to scan the rinsing liquid landing position on the upper surface of the substrate W within the surface of the substrate W. .
  • the rinsing liquid supply unit 7 may include the upper surface nozzle 21 as a rinsing liquid nozzle. That is, the rinsing liquid from the rinsing liquid pipe 37 may be supplied to the upper surface nozzle 21.
  • the solvent supply unit 8 includes a solvent nozzle 41, a nozzle arm 42 having the solvent nozzle 41 attached to a tip end thereof, and a nozzle movement for moving the solvent nozzle 41 by moving the nozzle arm 42.
  • Unit 43 (see FIG. 4).
  • the nozzle moving unit 43 horizontally moves the solvent nozzle 41 by horizontally moving the nozzle arm 42 around the swing axis.
  • the nozzle moving unit 43 has a configuration including a motor and the like.
  • the nozzle moving unit 43 moves the solvent nozzle 41 between the processing position where the solvent discharged from the solvent nozzle 41 lands on the surface Wa of the substrate W and the retreat position set around the spin chuck 5 in plan view. Is moved horizontally.
  • the processing position is a position where the solvent discharged from the solvent nozzle 41 is supplied to the front surface Wa of the substrate W.
  • the solvent supply unit 8 includes a solvent pipe 44 for guiding the solvent to the solvent nozzle 41, and a solvent valve 45 for opening and closing the solvent pipe 44.
  • the solvent valve 45 When the solvent valve 45 is opened, the solvent from the solvent supply source is supplied from the solvent pipe 44 to the solvent nozzle 41. Thus, the solvent is discharged from the solvent nozzle 41.
  • the solvent supplied to the solvent pipe 44 has solubility (miscibility) with respect to the mixed sublimation agent supplied by the mixed sublimation agent supply unit 9. That is, the solvent has solubility (miscibility) with the sublimable substance contained in the mixed sublimation agent, the first solvent, and the second solvent.
  • the solvent is used as a pre-supply liquid to be supplied to the surface Wa prior to the supply of the mixed sublimation agent to the surface Wa of the substrate W.
  • the solvent is supplied to the surface Wa prior to the supply of the mixed sublimation agent to the surface Wa of the substrate W. Therefore, it is desirable that the solvent further has solubility (miscibility) with respect to the rinsing liquid (water).
  • a specific example of the solvent supplied to the solvent pipe 44 is an organic solvent represented by, for example, IPA (isopropyl alcohol).
  • organic solvents other than IPA include, for example, methanol, ethanol, acetone, EG (ethylene glycol), HFE (hydrofluoroether), n-butanol, t-butanol, isobutyl alcohol and 2-butanol.
  • the organic solvent is not limited to the case where the organic solvent is composed of only a single component, and may be a liquid mixed with another component. Also, other solvents can be used.
  • the mixed sublimation supply unit 9 performs mixed sublimation by moving the mixed sublimation nozzle 46, the nozzle arm 47 having the mixed sublimation nozzle 46 attached to the tip, and the nozzle arm 47.
  • a nozzle moving unit 48 (see FIG. 4) for moving the agent nozzle 46.
  • the nozzle moving unit 48 horizontally moves the mixed sublimation agent nozzle 46 by horizontally moving the nozzle arm 47 around the swing axis.
  • the nozzle moving unit 48 has a configuration including a motor and the like. The nozzle moving unit 48 moves between the processing position where the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 lands on the surface Wa of the substrate W, and the retracted position set around the spin chuck 5 in plan view.
  • the mixed sublimation agent nozzle 46 is moved horizontally.
  • the processing position is the position where the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 is supplied to the surface Wa of the substrate W.
  • the nozzle moving unit 48 controls the center position where the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 lands on the center of the upper surface of the substrate W, and the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46
  • the mixed sublimation agent nozzle 46 is moved horizontally between a peripheral position where the liquid lands on the peripheral portion of the upper surface.
  • the center position and the peripheral position are both processing positions.
  • the mixed sublimation supply unit 9 includes a mixed sublimation pipe 49 that guides the mixed sublimation agent to the mixing sublimation nozzle 46, and a mixed sublimation valve 50 that opens and closes the mixed sublimation pipe 49. .
  • the mixed sublimation valve 50 When the mixed sublimation valve 50 is opened, the mixed sublimation from the mixed sublimation supply source is supplied to the mixed sublimation nozzle 46 from the mixed sublimation piping 49. Thereby, the mixed sublimation agent is discharged from the mixed sublimation agent nozzle 46.
  • the mixed sublimation agent (mixing / drying auxiliary substance) supplied to the mixed sublimation pipe 49 includes a sublimable substance having sublimability, a first solvent, and a second solvent (drug) different from the first solvent.
  • a sublimable substance having sublimability a first solvent, and a second solvent (drug) different from the first solvent.
  • the sublimable substance, the first solvent, and the second solvent are mutually soluble.
  • the sublimable substance, the first solvent, and the second solvent are in an aspect in which they are mutually dissolved. Therefore, in the mixed sublimation agent, the sublimable substance, the first solvent, and the second solvent are uniformly mixed without bias.
  • the sublimable substance and the first solvent are preferably soluble in each other, but the second solvent is soluble in at least one of the sublimable substance and the first solvent. Good.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the sublimable substance and the vapor pressure of the second solvent. Further, the vapor pressure of the second solvent is lower than the vapor pressure of the sublimable substance.
  • a combination of 1,3,5-trioxane, IPA and PGMEA can be exemplified.
  • the vapor pressures of 1,3,5-trioxane, IPA and PGMEA are, for example, 2.3 kPa, 4.3 kPa and 0.5 kPa, respectively.
  • the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 contains only a small content of the second solvent as compared with the sublimable substance and the first solvent.
  • the second solvent (content ratio) contained in the mixed sublimation agent is, for example, in the range of several percent by weight to several percent by weight. In this embodiment, for example, it is 0.1% (% by weight).
  • the mixing ratio (content ratio) of the sublimable substance and the first solvent in the mixed sublimation agent discharged from the mixed sublimation nozzle 46 is such that the content ratio of the first solvent is higher than that of the sublimable substance. More than the content ratio.
  • the second solvent is contained in a smaller proportion than the sublimable substance and the first solvent.
  • the mixing ratio (content ratio) of the sublimable substance, the first solvent, and the second solvent contained in the mixed sublimation agent is, for example, 10: 89.9: 0.1 in weight ratio.
  • FIG. 3 is a diagram showing the relationship between the concentration of the first solvent contained in the mixed sublimation agent (the mixing ratio of the first solvent to the mixed sublimation agent) and the freezing point of the mixed sublimation agent.
  • Freezing point T F0 at normal pressure of sublimable substances (1,3,5 trioxane) is 64 ° C..
  • the freezing point T FM of the mixed sublimation agent is lower than the freezing point T F0 of the sublimable substance due to the freezing point drop due to the mixing of the sublimable substance and the first solvent.
  • the freezing point TFM of the mixed sublimation agent depends on the content of the first solvent contained in the mixed sublimation agent. As shown in FIG. 3, the content of the first solvent is increased, the freezing point T FM mixtures sublimation agent falls below room temperature.
  • the content ratio of the first solvent in this embodiment is about 90%.
  • the second solvent also slightly contributes to the lowering of the freezing point of the mixed sublimation agent. However, since the mixing ratio of the second solvent in the mixed subliming agent is very small, the effect on the lowering of the freezing point of the mixed subliming agent is affected. Is almost negligible.
  • a chemical solution supply device is provided integrally with the substrate processing apparatus or separately from the substrate processing apparatus.
  • This chemical solution supply device is also installed in an environment of room temperature and normal pressure.
  • the chemical liquid supply device is provided with a storage tank for storing the mixed sublimation agent.
  • the mixed sublimation agent In a room temperature environment, the mixed sublimation agent is in a liquid state. Therefore, a heating device or the like for keeping the sublimable substance in a liquid state is unnecessary. Even when such a heating device is provided, it is not necessary to constantly heat the mixed sublimation agent. Therefore, the required amount of heat can be reduced, and as a result, the cost can be reduced.
  • the lower surface nozzle 11 has a single discharge port 11 a facing the center of the lower surface of the substrate W held by the spin chuck 5.
  • the discharge port 11a discharges the liquid vertically upward.
  • the discharged liquid is incident almost perpendicularly on the center of the lower surface of the substrate W held by the spin chuck 5.
  • a lower surface supply pipe 51 is connected to the lower surface nozzle 11.
  • the lower surface supply pipe 51 is inserted into the inside of the spin shaft 17 composed of a vertically arranged hollow shaft.
  • a cooling fluid pipe 52 is connected to the lower surface supply pipe 51.
  • the cooling fluid pipe 52 is provided with a cooling fluid valve 56 for opening and closing the cooling fluid pipe 52.
  • the cooling fluid may be a cooling liquid or a cooling gas.
  • the cooling liquid may be room temperature water.
  • the cooling fluid has a lower temperature than the freezing point T FM mixtures sublimation agent.
  • a cooling unit includes the lower surface nozzle 11, the cooling fluid pipe 52, and the cooling fluid valve 56.
  • the processing cup 12 is disposed outside (in a direction away from the rotation axis A1) the substrate W held by the spin chuck 5.
  • the processing cup 12 surrounds the spin base 18.
  • a liquid such as a processing liquid, a rinsing liquid, a solvent, and a mixed sublimation agent is supplied to the substrate W while the spin chuck 5 is rotating the substrate W
  • the liquid supplied to the substrate W is placed around the substrate W. Be shaken off.
  • the upper end 12 a of the processing cup 12 is arranged above the spin base 18. Therefore, the liquid discharged around the substrate W is received by the processing cup 12. Then, the liquid received by the processing cup 12 is sent to a not-shown recovery device or waste liquid device.
  • FIG. 4 is a block diagram for explaining an electrical configuration of a main part of the substrate processing apparatus 1.
  • the control device 3 is configured using, for example, a microcomputer.
  • the control device 3 has an arithmetic unit such as a CPU, a fixed memory device, a storage unit such as a hard disk drive, and an input / output unit.
  • the storage unit stores a program executed by the arithmetic unit.
  • the control device 3 is connected with the spin motor 16, the blocking member elevating unit 22, the blocking plate rotating unit 26, the nozzle moving units 33, 43, and 48 as control objects.
  • the control device 3 controls the operations of the spin motor 16, the blocking member elevating unit 22, the blocking plate rotating unit 26, the nozzle moving units 33, 43, and 48 according to a predetermined program.
  • the control device 3 opens and closes the gas valve 25, the chemical liquid valve 35, the rinsing liquid valve 38, the solvent valve 45, the mixed sublimation valve 50, the cooling fluid valve 56, and the like according to a predetermined program.
  • FIG. 5 is an enlarged cross-sectional view showing the surface Wa of the substrate W to be processed by the substrate processing apparatus 1.
  • the substrate W to be processed is, for example, a silicon wafer, and a pattern 100 is formed on a surface Wa, which is a pattern forming surface thereof.
  • the pattern 100 is, for example, a fine pattern.
  • the structures 101 having a convex shape may be arranged in a matrix.
  • the line width W1 of the structure 101 is set to, for example, about 3 nm to 45 nm
  • the gap W2 of the pattern 100 is set to, for example, about 10 nm to several ⁇ m.
  • the height T of the pattern 100 is, for example, about 0.2 ⁇ m to 1.0 ⁇ m. Further, pattern 100 may have, for example, an aspect ratio (ratio of height T to line width W1) of, for example, about 5 to 500 (typically about 5 to 50).
  • the pattern 100 may be a pattern in which linear patterns formed by fine trenches are repeatedly arranged.
  • the pattern 100 may be formed by providing a plurality of fine holes (voids or pores) in a thin film.
  • Pattern 100 includes, for example, an insulating film. Further, the pattern 100 may include a conductive film. More specifically, the pattern 100 is formed by a laminated film in which a plurality of films are laminated, and may further include an insulating film and a conductive film. The pattern 100 may be a pattern composed of a single-layer film.
  • the insulating film may be a silicon oxide film (SiO 2 film) or a silicon nitride film (SiN film).
  • the conductor film may be an amorphous silicon film into which impurities for lowering resistance are introduced, or a metal film (for example, a TiN film).
  • the pattern 100 may be a hydrophilic film.
  • the hydrophilic film include a TEOS film (a type of silicon oxide film).
  • FIG. 6 is a flowchart for explaining an example of substrate processing by the processing unit 2.
  • 7A to 7F are schematic diagrams showing the state of the periphery of the substrate W when this substrate processing example is being executed.
  • FIGS. 8A to 8E are enlarged views showing the state near the surface Wa of the substrate W when the substrate processing example is executed.
  • the control device 3 controls the substrate transport robot CR holding the substrate W in a state where all the nozzles and the like are retracted from above the spin chuck 5 and the blocking member 10 is disposed at the retracted position (see FIG. 1). Is made to enter the inside of the chamber 4. As a result, the substrate W is transferred to the spin chuck 5 with its surface Wa facing upward, and is held by the spin chuck 5.
  • the control device 3 controls the spin motor 16 to increase the rotation speed of the spin base 18 to a predetermined liquid processing speed (for example, approximately 500 rpm within a range of approximately 10 to 1500 rpm). ) To maintain the liquid processing speed.
  • a predetermined liquid processing speed for example, approximately 500 rpm within a range of approximately 10 to 1500 rpm.
  • Step S2 in FIG. 6 the control device 3 starts executing the chemical liquid process. Specifically, the control device 3 controls the nozzle moving unit 33 to move the chemical liquid nozzle 31 from the retracted position to the processing position. The control device 3 opens the chemical liquid valve 35. As a result, the chemical is supplied to the chemical nozzle 31 through the chemical pipe 34, and the chemical discharged from the discharge port of the chemical nozzle 31 lands on the surface Wa of the substrate W.
  • the control device 3 controls the nozzle moving unit 23 to move the chemical solution nozzle 31 to a peripheral position facing the peripheral portion of the front surface Wa of the substrate W and to a central portion of the upper surface of the substrate W. May be moved between a center position and a center position facing the center position. In this case, the liquid landing position on the upper surface of the substrate W can be scanned over the entire surface Wa of the substrate W. Thus, the entire surface Wa of the substrate W can be uniformly processed.
  • the control device 3 closes the chemical valve 35 and stops the discharge of the chemical from the chemical nozzle 31.
  • the chemical solution step (S2) ends. Further, the control device 3 returns the chemical liquid nozzle 31 to the retracted position.
  • control device 3 executes a rinsing step (Step S3 in FIG. 6) in which the chemical solution on the substrate W is replaced with a rinsing liquid and the surface Wa of the substrate W is washed away.
  • control device 3 opens rinse liquid valve 38.
  • the rinsing liquid is discharged from the rinsing liquid nozzle 36 toward the center of the rotating surface Wa.
  • the rinsing liquid supplied to the front surface Wa of the substrate W receives the centrifugal force due to the rotation of the substrate W, moves to the peripheral edge of the substrate W, and is discharged from the peripheral edge of the substrate W to the side of the substrate W. Thereby, the chemical liquid adhering on the substrate W is washed away by the rinse liquid.
  • the control device 3 closes the rinsing liquid valve 38.
  • the rinsing liquid supply step (S3) ends.
  • the replacement step (S4) is a step of replacing the rinsing liquid on the substrate W with a solvent having an affinity for both the rinsing liquid (water) and the mixed sublimant (in this example, an organic solvent such as IPA).
  • a solvent having an affinity for both the rinsing liquid (water) and the mixed sublimant in this example, an organic solvent such as IPA.
  • the control device 3 controls the nozzle moving unit 43 to move the solvent nozzle 41 upward from the retracted position on the side of the spin chuck 5 to the center of the surface Wa of the substrate W. Then, the control device 3 opens the solvent valve 45 and discharges the liquid solvent from the solvent nozzle 41 toward the center of the upper surface (front surface Wa) of the substrate W.
  • the organic solvent supplied to the surface Wa of the substrate W receives the centrifugal force due to the rotation of the substrate W and spreads over the entire surface Wa. As a result, the rinsing liquid adhering to the surface Wa of the entire surface Wa of the substrate W is replaced by the organic solvent.
  • the organic solvent moving on the surface Wa of the substrate W is discharged from the peripheral edge of the substrate W to the side of the substrate W.
  • the replacement step (S4) may be performed while rotating the substrate W at the liquid processing speed. Further, the replacement step (S4) may be performed while rotating the substrate W at a liquid filling speed lower than the liquid processing speed or while stopping the substrate W.
  • the control device 3 closes the solvent valve 45 and stops the discharge of the solvent from the solvent nozzle 41.
  • the replacement step (S4) ends. Further, the control device 3 returns the solvent nozzle 41 to the retracted position.
  • control device 3 executes a mixed sublimation agent supply step (step S5 in FIG. 6).
  • the control device 3 controls the nozzle moving unit 48 to move the mixed sublimation nozzle 46 upward from the retracted position on the side of the spin chuck 5 to the center of the surface Wa of the substrate W. . Then, the control device 3 opens the mixed sublimation agent valve 50 and discharges the mixed sublimation agent from the mixed sublimation nozzle 46 toward the center of the upper surface (front surface Wa) of the substrate W, as shown in FIG. 7A.
  • the mixed sublimation agent supplied to the mixed sublimation agent nozzle 46 has a first solvent and a second solvent that have a freezing point T FM (see FIG. 3) below room temperature under atmospheric pressure. (In particular, the content of the first solvent) is determined. Therefore, the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 maintains a liquid state.
  • the mixed sublimation agent supply step (S5) may be performed while rotating the substrate W at the liquid processing speed.
  • the substrate W is subjected to a liquid filling speed lower than the liquid processing speed (the centrifugal force acting on the mixed sublimation liquid film 71 on the upper surface of the substrate W causes the mixed sublimation agent and the substrate While rotating at a speed that is smaller than the surface tension acting between the upper surface of W and the above-mentioned centrifugal force and the above-mentioned surface tension are substantially opposed to each other (for example, 5 rpm), or when the substrate W is stopped, It may be performed while doing.
  • the controller 3 closes the mixed sublimation valve 50.
  • the supply of the mixed sublimation agent to the surface Wa of the substrate W is stopped. Further, the control device 3 returns the mixed sublimation agent nozzle 46 to the retracted position.
  • step S6 in FIG. 6 a film thickness reducing step for reducing the film thickness of the mixed sublimant liquid film 71 is performed.
  • the control device 3 controls the spin motor 16 to rotate the spin base 18 at a predetermined speed without supplying the mixed sublimation agent to the surface Wa of the substrate W.
  • a large centrifugal force is applied to the surface Wa of the substrate, the mixed sublimation agent contained in the liquid film 71 is eliminated from the surface Wa of the substrate W, and the film thickness of the liquid film 71 decreases.
  • a thin film 72 of the mixed sublimation agent is formed on the surface Wa of the substrate W.
  • the thickness W12 of the thin film 72 is thinner, that is, lower than the thickness W11 of the liquid film.
  • the thickness W12 of the thin film 72 is on the order of several hundred nanometers to several micrometers.
  • the upper surface of the thin film 72 is located above the upper end of each pattern 100 (see FIG. 5) formed on the front surface Wa.
  • the thickness W12 of the thin film 72 is adjusted by adjusting the rotation speed of the substrate W.
  • control device 3 ends the film thickness reducing step (S6), and then executes a solidified film forming step (step S7 in FIG. 6).
  • the solidified film forming step (S7) is a step of solidifying a sublimable substance contained in the mixed sublimation agent while evaporating the first solvent from the mixed subliming agent.
  • the solidified film forming step (S7) includes a gas blowing step of blowing an inert gas as a gas onto the surface Wa of the substrate W, a cooling step of cooling the surface Wa of the substrate W, and a predetermined step.
  • the control device 3 controls the blocking member elevating unit 27 prior to the start of the solidified film forming step (S7), and lowers the blocking member 10 and arranges it in the blocking position as shown in FIG. 7C.
  • the control device 3 opens the gas valve 25.
  • the dehumidified inert gas is discharged from the discharge port 21a of the upper surface nozzle 21 toward the center of the front surface Wa of the substrate W in the rotating state.
  • the inert gas from the upper nozzle 21 is sprayed on the surface Wa of the substrate W.
  • the inert gas blown from the shielding space 30 to the surface Wa of the substrate W moves toward the outer peripheral portion of the substrate W in the shielding space 30.
  • the control device 3 opens the cooling fluid valve 56 while closing the heating fluid valve 57. Thereby, a cooling fluid is supplied from the lower surface nozzle 11 to the lower surface (back surface Wb) of the substrate W.
  • the cooling fluid supplied to the back surface Wb of the substrate W spreads toward the outer peripheral portion of the substrate W under the centrifugal force caused by the rotation of the substrate W.
  • the cooling fluid is supplied to the entire area of the back surface Wb of the substrate W, and the entire area of the front surface Wa of the substrate W is cooled.
  • the solidified film forming step (S7) includes a step of evaporating the first solvent from the mixed sublimation agent contained in the thin film 72 on the surface Wa of the substrate W.
  • a sublimable substance is deposited by evaporation of the first solvent.
  • the surface Wa of the substrate W decreases in temperature due to the heat of vaporization taken away by evaporation of the first solvent, whereby the sublimable substance solidifies (first process).
  • the content ratio of the first solvent (IPA) contained in the mixed sublimation thin film 72 decreases.
  • the freezing point T FM see FIG.
  • the freezing point T FM mixtures sublimation agent exceeds the room temperature, the sublimable material contained in the mixed sublimation agent is solidified (third process).
  • the solidification of the mixed sublimation agent proceeds, and a solidified film 73 of the mixed sublimation agent is formed.
  • the solidified film 73 formed in the solidified film forming step (S7) contains a solid sublimable substance and a liquid second solvent.
  • the solidified film 73 does not include the first solvent.
  • the vapor pressure at room temperature of IPA used as the first solvent is very high, the evaporation of IPA is promoted well. As a result, a solidified film 73 containing a solid sublimable substance is formed in a short time.
  • the formation rate of the solidified film 73 in the solidified film forming step (S7) is determined based on a liquid that contains the sublimable substance and the first solvent at the same content but does not contain the second. It is slower than the forming speed when forming. This also promotes the formation of the solidified film 73 in a short time.
  • the heating step is performed in a state where the blocking member 10 is disposed at the blocking position and an inert gas flow is formed above the substrate W, the heating fluid (for example, heating) supplied to the back surface Wb of the substrate W Liquid) can be reliably prevented from scattering on the surface Wa of the substrate W and adhering to the surface Wa of the substrate W.
  • the heating fluid for example, heating
  • the mixing ratio (content ratio) between the sublimable substance (1,3,5-trioxane) and the first solvent (IPA) in the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 is as follows.
  • the content of the first solvent is higher than the content of the sublimable substance (about 9: 1).
  • the solidified film 73 does not contain the first solvent.
  • the thickness W13 of the solidified film 73 becomes smaller than the film thickness W12 of the thin film 72 at the start of the solidified film forming step (S7). It is desirable that the thickness of the solidified film 73 be set as thin as possible, that is, set as low as possible within a range higher than the height T of the pattern 100.
  • the thickness of the solidified film 73 is adjusted by adjusting the thickness of the thin film 72, the temperature of the heating fluid supplied to the substrate W, or the sublimable substance and the first solvent in the mixed sublimation agent discharged from the mixing sublimation agent nozzle 46. It is adjusted by the mixing ratio with
  • the thickness reduction step (S6) before the start of the solidified film formation step (S7), the thickness reduction step (S6) is performed, and the content of the first solvent is larger than the content of the sublimable substance.
  • the liquid film (thin film 72) can be made thinner just before the start of the step (S7).
  • the solidified film 73 formed on the surface Wa of the substrate W includes the solid sublimable substance (1,3,5-trioxane) and the liquid second solvent (PGMEA).
  • the content of the second solvent in the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 is extremely small. Therefore, in the solidified film 73, the content ratio of the sublimable substance is smaller than the content ratio of the second solvent. Then, the second solvent exists in a state of being dispersed in a large amount of the sublimable substance. Specifically, as shown in FIG. 8C, a liquid layer 75 of the second solvent (liquid layer of the solvent) is dispersedly disposed in the solid layer 74 of the sublimable substance.
  • the growth can be inhibited by the second solvent (the liquid layer 75 of the second solvent).
  • the second solvent the liquid layer 75 of the second solvent.
  • the sublimable substance contained in the solidified film 73 is sublimated from a solid to a gas.
  • control device 3 performs a substrate high rotation step (spin-off) of rotating the substrate W at a high speed, And a gas blowing step of blowing gas.
  • the substrate W is rotated at a predetermined high rotation speed (for example, a predetermined speed of 300 to 1200 rpm).
  • This high rotation speed is desirably higher than the rotation speed of the substrate W in the solidified film forming step (S7).
  • the control device 3 controls the blocking plate rotation unit 26 to rotate the blocking plate 20 in the same direction as the rotation of the substrate W at the same speed.
  • the contact speed between the solidified film 73 and the surrounding atmosphere can be increased. Thereby, as shown in FIG. 8D, the solidified film 73 can be sublimated in a short period of time.
  • the gas blowing step performed in parallel with the removing step (S8) is the same as the gas blowing step included in the coagulated film forming step (S7). That is, the discharge of the inert gas from the discharge port 21a of the upper surface nozzle 21 is continuously performed also in the removing step (S8). By blowing such a gas, the sublimation of the sublimable substance contained in the solidified film 73 is promoted.
  • the surface Wa of the substrate W is dried by sublimating the sublimable substance contained in the mixed sublimation agent (that is, by vaporizing without passing through the liquid state), so that the pattern collapse is effectively performed.
  • the surface Wa of the substrate W can be dried while suppressing or preventing it.
  • the liquid film 76 of the second solvent remains on the upper surface of the pattern 100 (each structure 101) on the surface Wa of the substrate W as shown in FIG. 8E.
  • the thickness W14 of the liquid film 76 of the second solvent is extremely thin (for example, several tens nm to several hundreds nm). That is, the thickness of the liquid film 76 of the second solvent remaining after the removing step (S8) is smaller than the height T of the pattern 100 (see FIG. 5).
  • the control device 3 executes a solvent evaporation step (S9) for evaporating the second solvent from the surface Wa of the substrate W.
  • the substrate high rotation step (spin-off) which has been performed in parallel with the removing step (S8), and the gas blowing step of blowing gas to the surface Wa of the substrate W are continuously performed, so that A solvent evaporation step (S9) is performed.
  • the second solvent contained in the liquid film 76 of the second solvent remaining on the surface Wa of the substrate W evaporates. Is removed (see FIG. 7F).
  • the second The surface tension of the solvent is small. This makes it possible to remove the second solvent from the surface Wa of the substrate W while suppressing pattern collapse.
  • the control device 3 controls the spin motor 16 to stop the rotation of the spin chuck 5. Further, the control device 3 closes the gas valve 25. Further, the control device 3 controls the blocking member lifting / lowering unit 27 to raise the blocking member 10 to the retracted position.
  • the substrate transport robot CR enters the processing unit 2 and unloads the processed substrate W out of the processing unit 2 (S10 in FIG. 6: unloading the substrate W).
  • the unloaded substrate W is transferred from the substrate transfer robot CR to the indexer robot IR, and is stored in the substrate container C by the indexer robot IR.
  • a mixed sublimation in which the sublimable substance, the first solvent, and the second solvent are mixed with each other is supplied to the surface Wa of the substrate W.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the sublimable substance and the vapor pressure of the second solvent. Therefore, the first solvent is preferentially evaporated from the mixed drying auxiliary substance present on the surface Wa of the substrate W, whereby the solidified film 73 containing the sublimable substance is formed.
  • the vapor pressure of the sublimable substance is higher than the vapor pressure of the second solvent. Therefore, the second solvent does not evaporate from the mixed drying auxiliary substance present on the surface Wa of the substrate W.
  • the solidified film 73 contains not only the sublimable substance but also the second solvent, even if a crack due to a crystal defect occurs in the solidified film 73, its growth can be inhibited by the second solvent. Thereby, crack growth in the solidified film 73 can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • a mixed sublimation agent composed of a mixture of the sublimable substance, the first solvent, and the second solvent is supplied to the surface Wa of the substrate W. Since the sublimable substance has a freezing point TF0 of room temperature or higher, part or all of the sublimable substance is in a solid state at room temperature. In this embodiment, the freezing point T FM mixtures sublimation agent is set lower than the room temperature. Therefore, at room temperature, the mixed sublimation agent maintains a liquid state. Therefore, the surface Wa of the substrate W can be favorably dried while avoiding unintended solidification of the sublimable substance without a large increase in cost.
  • the solidified film forming step (S7) may include a heating step of heating the surface Wa of the substrate W by a heating unit instead of the cooling step. That is, the solidified film forming step (S7) includes a gas blowing step, a heating step, and a substrate rotating step.
  • the heating unit includes a heating fluid pipe 53 connected to the lower surface supply pipe 51, and a heating fluid valve 57 for opening and closing the heating fluid pipe 53.
  • the heating fluid may be a heating liquid such as hot water or a heating gas. Heating fluid has a higher liquid temperature than the freezing point T FM mixtures sublimation agent discharged from the mixing sublimation agent nozzle 46.
  • the heating fluid from the heating fluid supply source is supplied to the lower nozzle 11 via the heating fluid pipe 53 and the lower supply pipe 51.
  • the heating fluid supplied to the lower nozzle 11 is discharged almost vertically upward from the discharge port 11a.
  • the heating liquid discharged from the lower surface nozzle 11 is incident on the substrate W held by the spin chuck 5 substantially perpendicularly to the center of the lower surface.
  • a heating unit is constituted by the lower surface nozzle 11, the heating fluid pipe 53, and the heating fluid valve 57.
  • the control device 3 opens the heating fluid valve 57 while closing the cooling fluid valve 56.
  • the heating fluid is supplied from the lower surface nozzle 11 to the center of the back surface Wb of the substrate W in the rotating state.
  • the heating fluid supplied to the back surface Wb of the substrate W receives centrifugal force due to the rotation of the substrate W and spreads toward the outer peripheral portion of the substrate W.
  • the heating fluid is supplied to the entire area of the back surface Wb of the substrate W, and the liquid film (thin film 72) of the mixed sublimation agent is heated over the entire area of the front surface Wa of the substrate W.
  • the first solvent (IPA) having a high vapor pressure is given priority to the mixed sublimation agent contained in the liquid film (thin film 72) of the mixed sublimation agent. Evaporate.
  • the heating step is provided as the solidified film forming step (S7). It is effective.
  • the heating unit that heats the front surface Wa of the substrate W in the solidified film forming step (S7) of the above-described substrate processing example is limited to a configuration that supplies a heating fluid to the rear surface Wb of the substrate W as in the above-described embodiment. I can't.
  • a hot plate 201 facing and disposed below the back surface Wb of the substrate W may be used as a heating unit.
  • the heating unit that heats the front surface Wa of the substrate W in the solidified film forming step (S7) of the above-described substrate processing example is limited to a configuration that supplies a heating fluid to the rear surface Wb of the substrate W as in the above-described embodiment. I can't. As shown in FIG.
  • a hot plate 201 facing and disposed below the back surface Wb of the substrate W may be used as a heating unit.
  • the hot plate 201 is provided instead of the lower surface nozzle 11.
  • the hot plate 201 has a built-in heater 202 built therein.
  • the built-in heater 202 is, for example, a heating wire that generates heat when energized.
  • the hot plate 201 is arranged above the spin base 18 and below the substrate W held by the holding member 19.
  • the hot plate 201 has an upper surface 201a facing the whole area of the back surface Wb of the substrate W. Even if the spin chuck 5 rotates, the hot plate 201 does not rotate.
  • the temperature of the hot plate 201 is changed by the control device 3.
  • the temperature of the upper surface 201a of the hot plate 201 is uniform within the surface. When the controller 3 raises the temperature of the hot plate 201, the entire surface Wa of the substrate W is uniformly heated.
  • heating unit for heating the surface Wa of the substrate W includes a configuration in which a heater is built in the blocking member 10 as shown in FIG.
  • the built-in heater 301 is disposed inside the blocking plate 20 of the blocking member 10.
  • the built-in heater 301 moves up and down together with the blocking member 10.
  • the substrate W is arranged below the built-in heater 301.
  • the built-in heater 301 is, for example, a heating wire that generates heat when energized.
  • the temperature of the built-in heater 301 is changed by the control device 3.
  • the temperature of the substrate facing surface 20a is uniform within the surface.
  • the control device 3 heats the surface Wa of the substrate W by increasing the temperature of the built-in heater 301 to a temperature higher than room temperature, as shown in FIG. You may do so. Thereby, the first solvent contained in the mixed sublimation agent on the surface Wa of the substrate W can be satisfactorily evaporated.
  • the pressure reduction step is performed as follows.
  • the exhaust device 99 (see FIG. 2) is provided so that its exhaust force (suction force) can be adjusted.
  • the exhaust device 99 is provided with an exhaust power adjustment unit (decompression unit) 401.
  • the exhaust power adjustment unit 401 is, for example, a regulator or an opening adjustment valve.
  • control device 3 can satisfactorily evaporate the first solvent contained in the mixed sublimation agent on the surface Wa of the substrate W by reducing the pressure inside the chamber 4.
  • spontaneous evaporation at room temperature and normal pressure, or the evaporation of the substrate W is performed in addition to or instead of at least one of the cooling step, the heating step, the gas blowing step, and the depressurizing step.
  • the first solvent contained in the mixed sublimation agent on the surface Wa of the substrate W may be evaporated.
  • the cooling unit that cools the front surface Wa of the substrate W is not limited to the configuration that supplies the cooling fluid to the rear surface Wb of the substrate W as in the above-described embodiment.
  • a cooling plate 501 that is disposed below the back surface Wb of the substrate W so as to be opposed can be used as a cooling unit.
  • the cooling plate 501 is provided instead of the lower surface nozzle 11.
  • the cooling plate 501 is arranged above the spin base 18 and below the substrate W held by the holding member 19.
  • the cooling plate 501 has an upper surface 501a facing the whole area of the back surface Wb of the substrate W. Even if the spin chuck 5 rotates, the cooling plate 501 does not rotate.
  • the temperature of the cooling plate 501 is changed by the control device 3.
  • the temperature of the upper surface 501a of the cooling plate 501 is uniform in the plane. When the control device 3 lowers the temperature of the cooling plate 501, the entire surface Wa of the substrate W is uniformly cooled.
  • the substrate high rotation step and the gas blowing step are described as being performed.
  • a heating step may be performed in addition to or instead of at least one of the steps. Further, a part or all of the substrate high rotation step, the gas blowing step and the heating step may be omitted.
  • the substrate W may be rotated at a rotating speed to shake off and dry the back surface Wb of the substrate W after the removing step (S8).
  • the substrate high rotation step is performed in parallel with the removal step (S8), the back surface Wb of the substrate W after the removal step (S8) is dry, and thus the shake-off drying is performed after the removal step (S8). Is unnecessary.
  • a cooling step of cooling the surface Wa of the substrate W may be performed in parallel with the removing step (S8).
  • a method similar to the cooling step performed in the solidified film forming step (S7) described above may be applied. Examples of such a method include a method of supplying a cooling fluid to the back surface Wb of the substrate W, and a method of disposing the cooling plate 501 (see FIG. 12) close to the back surface Wb of the substrate W.
  • the solidified film 73 is cooled over the entire surface Wa of the substrate W. Since the solidified film 73 on the surface Wa of the substrate W is maintained below the freezing point (melting point), the sublimable substance contained in the solidified film 73 can be sublimated while suppressing or preventing melting.
  • the film thickness reducing step (S6) is described as being performed prior to the solidified film forming step (S7), but the film thickness reducing step (S6) and the solidified film forming step (S7) are performed. ) May be performed in parallel with each other (that is, simultaneously). In this case, the time required for the processing can be reduced.
  • the thickness reducing step (S6) may be performed after the solidified film forming step (S7) of the above-described substrate processing example.
  • a solvent for dissolving the solidified first sublimable substance (and the second sublimable substance) may be supplied onto the solidified film 73 and a part of the solidified film may be dissolved to reduce the thickness.
  • the thickness of the solidified film 73 may be reduced by physical removal such as scraping off a part of the solidified film 73 from above the solidified film 73 with a blade or the like.
  • the replacement step (S4 in FIG. 6) is performed between the rinsing liquid supply step (S3 in FIG. 6) and the mixed sublimation agent supply step (S5 in FIG. 6).
  • the substitution step (S4) may be omitted.
  • the configuration of the solvent supply unit 8 of the processing unit 2 may be omitted.
  • the blocking plate 20 in parallel with the solidified film forming step (S7) and / or the removing step (S8) has been described.
  • the heating fluid or the cooling fluid is not supplied to the back surface Wb of the substrate W, the blocking plate 20 can be omitted.
  • the freezing point T FM mixtures sublimation agent supplied from the mixing sublimation agent supply unit 9 may be above room temperature and not less than room temperature.
  • a device (temperature control device) for maintaining the mixed sublimation agent in a liquid state inside the mixed sublimation agent supply unit 9 is required.
  • the freezing point T FM of the mixed sublimation agent is lower than the freezing point T F0 of the sublimable substance due to the freezing point depression, the amount of heat for maintaining the mixed subliming agent in a liquid state can be reduced.
  • a fluorinated solvent having a cyclic structure 1,3,5-dioxane, 1,3,5-Trioxane, Camphor, naphthalene, iodine and the like can be used.
  • the first and second solvents are not limited to IPA and PGMEA, and may include, for example, NMP (n-methyl-2-pyrrolidone), acetone (acetone), n-hexane, methanol, ethanol, EG ( Examples include ethylene glycol), HFE (hydrofluoroether), n-butanol, t-butanol, isobutyl alcohol and 2-butanol.
  • NMP n-methyl-2-pyrrolidone
  • acetone acetone
  • n-hexane methanol
  • ethanol ethanol
  • EG examples include ethylene glycol), HFE (hydrofluoroether), n-butanol, t-butanol, isobutyl alcohol and 2-butanol.
  • the one with the higher vapor pressure can be the first solvent
  • the one with the lower vapor pressure can be the second solvent.
  • a combination of 1,3,5-trioxane, IPA and PGMEA has been exemplified, but as another combination, 1,3,5-dioxane , N-Hexane and PGMEA.
  • the freezing point of 1,3,5-dioxane II under normal pressure is 64 ° C.
  • the vapor pressures of 1,3,5-dioxane, n-Hexane and PGMEA are, for example, 6.1 kPa, 17 kPa and 0.5 kPa, respectively.
  • Other combinations of the sublimable substance, the first solvent, and the second solvent include cyclohexane, acetone, and IPA.
  • the freezing point of cyclohexane under normal pressure is 6 ° C.
  • the vapor pressures of cyclohexane and acetone are, for example, 9.6 kPa and 24 kPa, respectively. Various other combinations are also possible.
  • the vapor pressure of the second solvent may be higher than the vapor pressure of the sublimable substance. However, the vapor pressure of the second solvent is lower than the vapor pressure of the first solvent.
  • the first solvent evaporates preferentially, and in the liquid film containing the mixed sublimant containing the sublimable substance and the second solvent, the sublimable substance starts to solidify. The solidification of the mixed sublimation proceeds.
  • the second solvent also evaporates.
  • the solidified film 73 containing the sublimable substance and the second solvent is formed during the period from the start of the solidification of the mixed sublimation agent to the evaporation of the second solvent. Therefore, crack growth in the solidified film 73 can be suppressed or prevented in the entire region of the solidified film 73 from the start of solidification of the mixed sublimation agent to the evaporation of the second solvent.
  • the removing step (S8) of changing the solidified film 73 into a gas without passing through a liquid state may be a plasma irradiation step of irradiating the substrate W with plasma instead of the sublimation step.
  • the removal step it may be changed to a gas without passing through a liquid by decomposition by an oxygen radical or the like or by a chemical reaction.
  • a removal step such as a plasma irradiation step may be performed in another processing unit.
  • FIG. 13 is a schematic diagram for explaining the transfer of the substrate W from the wet processing unit 2W to the dry processing unit 2D that changes the solidified film 73 into a gas without passing through a liquid state. 13, the same components as those shown in FIGS. 1 to 12 are denoted by the same reference numerals as those in FIG. 1 and the like, and description thereof is omitted.
  • the processing unit 2 includes a dry processing unit 2D for processing the substrate W without supplying the processing liquid to the substrate W, in addition to the wet processing unit 2W for supplying the processing liquid to the substrate W.
  • FIG. 13 illustrates an example in which the dry processing unit 2D includes a processing gas pipe 601 that guides a processing gas into a chamber (second chamber) 4D, and a plasma generator 602 that converts the processing gas in the chamber 4D into plasma. Is shown.
  • the plasma generation device 602 includes an upper electrode 603 disposed above the substrate W and a lower electrode 604 disposed below the substrate W.
  • the steps from the loading of the substrate W (step S1 in FIG. 6) to the solidified film formation removing step (step S10 in FIG. 4) shown in FIG. 6 are performed in the chamber (first chamber) 4 of the wet processing unit 2W. . Thereafter, as shown in FIG. 13, the substrate W is unloaded from the chamber 4 of the wet processing unit 2W by the substrate transfer robot CR, and is loaded into the chamber 4D of the dry processing unit 2D.
  • the solidified film 73 remaining on the surface Wa of the substrate W changes into a gas without passing through a liquid due to a chemical reaction and a physical reaction caused by the plasma in the chamber 4D. Thus, the solidified film 73 is removed from the substrate W.
  • FIG. 13 the steps from the loading of the substrate W (step S1 in FIG. 6) to the solidified film formation removing step (step S10 in FIG. 4) shown in FIG. 6 are performed in the chamber (first chamber) 4 of the wet processing unit 2W. .
  • the substrate W is unloaded from the
  • the substrate processing apparatus 1 is an apparatus that processes a substrate W made of a semiconductor wafer, but the substrate processing apparatus may be a substrate for a liquid crystal display device, an organic EL (electroluminescence) display device, or the like.
  • FPD Full Panel Display
  • optical disk substrate magnetic disk substrate
  • magneto-optical disk substrate photomask substrate
  • ceramic substrate solar cell substrate, etc.
  • a substrate holding unit for holding a substrate, On the surface of the substrate held by the substrate holding unit, a drying auxiliary substance, a first solvent, and a mixed drying auxiliary substance in which the drying auxiliary substance and the agent different from the first solvent are mixed with each other.
  • a mixing / drying auxiliary substance supply unit for supplying;
  • a solidified film forming unit for forming a solidified film containing the drying auxiliary substance and the chemical by evaporating the first solvent from the mixed drying auxiliary substance present on the surface of the substrate held by the substrate holding unit
  • a substrate processing apparatus comprising: a removing unit configured to remove the drying aid contained in the solidified film formed on the surface of the substrate held by the substrate holding unit.
  • the mixed drying auxiliary substance in which the drying auxiliary substance, the first solvent, and the chemical are mixed with each other is supplied to the surface of the substrate.
  • the solidified film may contain drugs as well as drying aids. In this case, even if cracks due to crystal defects occur in the solidified film, the growth can be inhibited by the chemical. Thereby, the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • lowering of the freezing point occurs by mixing the drying aid with the first solvent and the drug.
  • the solidification point of the mixed drying auxiliary substance is lower than the solidification point of the drying auxiliary substance, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. This makes it possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying auxiliary material without increasing the cost.
  • a solidified film forming step of forming a solidified film containing the drying auxiliary substance and the solvent Removing the drying auxiliary substance contained in the solidified film.
  • a mixed drying auxiliary substance in which the drying auxiliary substance, the first solvent, and the second solvent are mixed with each other is supplied to the surface of the substrate.
  • the vapor pressure of the first solvent is higher than the vapor pressure of the drying aid and the vapor pressure of the second solvent. Therefore, the first solvent is preferentially evaporated from the mixed and dried auxiliary substance present on the surface of the substrate.
  • the vapor pressure of the drying auxiliary substance is higher than the vapor pressure of the second solvent. Therefore, the second solvent does not evaporate from the mixed drying auxiliary substance present on the surface of the substrate. Therefore, the solidified film contains not only the drying aid but also the second solvent. Thereby, the growth of cracks in the solidified film can be suppressed or prevented. Therefore, occurrence of pattern collapse due to crack growth can be suppressed or prevented.
  • the freezing point drop occurs by mixing the drying aid with the first solvent and the drug.
  • the solidification point of the mixed drying auxiliary substance is lower than the solidification point of the drying auxiliary substance, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. This makes it possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying auxiliary material without increasing the cost.
  • substrate processing apparatus 2 processing unit 3: control apparatus 4: chamber (first chamber) 4D: chamber (second chamber) 5: Spin chuck (substrate holding unit) 6: Chemical liquid supply unit (treatment liquid supply unit) 7: Rinse liquid supply unit (treatment liquid supply unit) 8: solvent supply unit (treatment liquid supply unit) 9: Mixed sublimation agent supply unit (mixed drying auxiliary substance supply unit) 11: Bottom nozzle (heating unit, cooling unit) 16: Spin motor (rotary unit) 21: Top nozzle (gas blowing unit) 24: Gas piping (gas blowing unit) 25: Gas valve (gas blowing unit) 30: shut-off space 52: cooling fluid pipe (cooling unit) 53: Heating fluid piping (heating unit) 56: Cooling fluid valve (cooling unit) 57: Heated fluid valve (heating unit) 71: liquid film 73: solidified film 201: hot plate (heating unit) 301: Built-in heater (heating unit) 401: Exhaust power adjustment unit (decompression unit) 501: Cooling plate

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