TW202225862A - Substrate processing method and substrate processing apparatus - Google Patents

Substrate processing method and substrate processing apparatus Download PDF

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TW202225862A
TW202225862A TW110122856A TW110122856A TW202225862A TW 202225862 A TW202225862 A TW 202225862A TW 110122856 A TW110122856 A TW 110122856A TW 110122856 A TW110122856 A TW 110122856A TW 202225862 A TW202225862 A TW 202225862A
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substrate
liquid
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treatment liquid
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TWI804897B (en
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田原香奈
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日商斯庫林集團股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • 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
    • H01L21/02—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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • 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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • 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
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H01L21/6708—Apparatus for fluid treatment for etching for wet etching using mainly spraying means, e.g. nozzles

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Abstract

This substrate processing method comprises: a first processing liquid supply step wherein a first processing liquid, which contains one of sulfuric acid and a hydrogen peroxide solution, is applied to the surface of a substrate; a second processing liquid supply step wherein a second processing liquid, which contains the other one of the sulfuric acid and the hydrogen peroxide solution and has a lower viscosity than the first processing liquid, is applied to the surface of the substrate, to said surface the first processing liquid having been applied; a solution mixture processing step wherein the surface of the substrate is processed with a sulfuric acid-hydrogen peroxide solution mixture, which is produced by mixing of the first processing liquid and the second processing liquid on the surface of the substrate; and a rinsing step wherein the sulfuric acid-hydrogen peroxide solution mixture is rinsed away from the surface of the substrate by supplying a rinsing liquid to the substrate after the solution mixture processing step.

Description

基板處理方法以及基板處理裝置Substrate processing method and substrate processing apparatus

本發明係有關於一種用以處理基板之裝置以及方法。成為處理對象之基板係例如包括半導體晶圓、液晶顯示裝置用基板、有機EL(electroluminescence；電致發光)顯示裝置等平面顯示器(FPD；flat panel display)用基板、光碟用基板、磁碟用基板、光磁碟用基板、光罩(photomask)用基板、陶瓷基板、太陽電池用基板等。The present invention relates to an apparatus and method for processing substrates. The substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for flat panel displays (FPDs) such as organic EL (electroluminescence) display devices, substrates for optical discs, and substrates for magnetic discs , Optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates, etc.

已知有一種方法，係在基板上使第一處理液與第二處理液混合並反應，並利用反應生成物質對基板進行處理。具體而言，在用以剝離殘留於乾蝕刻(dry etching)後的基板上的阻劑(resist)之阻劑剝離處理中，會有使用SPM(sulfuric acid hydrogen peroxide mixture；硫酸過氧化氫水混合液)之情形，SPM係使硫酸與過氧化氫水混合從而生成。There is known a method in which a first treatment liquid and a second treatment liquid are mixed and reacted on a substrate, and the substrate is treated with a reaction product. Specifically, in the resist stripping process for stripping the resist remaining on the substrate after dry etching, SPM (sulfuric acid hydrogen peroxide mixture; sulfuric acid hydrogen peroxide mixture) is used. In the case of liquid), SPM is produced by mixing sulfuric acid and hydrogen peroxide water.

於專利文獻1揭示一種基板處理，係在噴嘴內混合硫酸與過氧化氫水並調製SPM，並將SPM供給至基板的表面。於專利文獻2揭示一種基板處理，係從其他的噴嘴將硫酸以及過氧化氫水供給至基板上，使硫酸以及過氧化氫水在基板上混合從而生成SPM。 [先前技術文獻] [專利文獻] Patent Document 1 discloses a substrate treatment in which sulfuric acid and hydrogen peroxide water are mixed in a nozzle to prepare SPM, and the SPM is supplied to the surface of the substrate. Patent Document 2 discloses a substrate treatment in which sulfuric acid and hydrogen peroxide water are supplied onto the substrate from another nozzle, and the sulfuric acid and the hydrogen peroxide water are mixed on the substrate to generate SPM. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2019-207948號公報。 [專利文獻2]日本特開2004-349669號公報。 [Patent Document 1] Japanese Patent Laid-Open No. 2019-207948. [Patent Document 2] Japanese Patent Laid-Open No. 2004-349669.

[發明所欲解決之課題][The problem to be solved by the invention]

在專利文獻1的基板處理中，由於一邊流動處理液一邊進行處理，因此處理液的消耗量變多。具體而言，需要以0.5公升／分鐘至2公升／分鐘左右的流量從噴嘴噴出SPM。因此，針對基板處理的成本以及環境負荷會有改善的餘地。In the substrate processing of Patent Document 1, since the processing is performed while the processing liquid is flowing, the consumption of the processing liquid increases. Specifically, it is necessary to eject the SPM from the nozzle at a flow rate of about 0.5 liters/minute to 2 liters/minute. Therefore, there is room for improvement in the cost and environmental load of substrate processing.

於專利文獻2揭示一種基板處理，係將硫酸的液膜形成於基板上，並對硫酸的液膜霧狀地供給過氧化氫水。此種處理雖然在減少硫酸的消耗量之點來說較佳，然而難以形成均勻地覆蓋基板的表面的全域之液膜，且難以維持液膜覆蓋基板的表面的全域的狀態。因此，針對處理的均勻性有改善的餘地。Patent Document 2 discloses a substrate treatment in which a liquid film of sulfuric acid is formed on a substrate, and hydrogen peroxide water is supplied in a mist form to the liquid film of sulfuric acid. Although this type of treatment is preferable in terms of reducing the consumption of sulfuric acid, it is difficult to form a liquid film uniformly covering the entire surface of the substrate, and it is difficult to maintain a state where the liquid film covers the entire surface of the substrate. Therefore, there is room for improvement with regard to the uniformity of the process.

因此，本發明的實施形態之一係提供一種基板處理方法以及基板處理裝置，係能均勻地處理基板表面且能減少處理液的消耗量。 [用以解決課題的手段] Therefore, one of the embodiments of the present invention provides a substrate processing method and a substrate processing apparatus capable of uniformly processing the substrate surface and reducing the consumption of the processing liquid. [means to solve the problem]

本發明的實施形態之一提供一種基板處理方法，係包含：第一處理液供給步驟，係將包含硫酸以及過氧化氫水中的一方之第一處理液塗布至基板的表面；第二處理液供給步驟，係將包含硫酸以及過氧化氫水中的另一方且黏度比前述第一處理液還低之第二處理液供給至塗布有前述第一處理液的前述基板的表面；混合液處理步驟，係以硫酸過氧化氫水混合液處理前述基板的表面，前述硫酸過氧化氫水混合液為前述第一處理液以及前述第二處理液在前述基板的表面混合從而生成；以及清洗(rinse)步驟，係在前述混合液處理步驟之後，對前述基板供給清洗液，從前述基板的表面沖洗前述硫酸過氧化氫水混合液。One embodiment of the present invention provides a substrate processing method, which includes: a first processing liquid supply step of applying a first processing liquid containing one of sulfuric acid and hydrogen peroxide to a surface of a substrate; supplying a second processing liquid The step is to supply the second treatment liquid containing the other one of sulfuric acid and hydrogen peroxide water and the viscosity is lower than the first treatment liquid to the surface of the substrate coated with the first treatment liquid; the mixed liquid treatment step is to The surface of the substrate is treated with a sulfuric acid and hydrogen peroxide water mixture, and the sulfuric acid and hydrogen peroxide water mixture is the first treatment liquid and the second treatment liquid to be mixed on the surface of the substrate to generate; and a rinse step, After the mixed solution treatment step, a cleaning solution is supplied to the substrate to rinse the sulfuric acid-hydrogen peroxide-water mixed solution from the surface of the substrate.

依據此基板處理方法，由於將黏度較高的第一處理液塗布至基板的表面，因此能抑制第一處理液的消耗量，並能使第一處理液均勻地遍及且密著於基板的表面。對塗布有第一處理液的基板的表面供給第二處理液。藉此，第一處理液以及第二處理液係在基板的表面上混合從而生成硫酸過氧化氫水混合液。由於第一處理液均勻地遍及且密著於基板的表面，因此能使硫酸過氧化氫水混合液無遺漏地均勻地遍及至基板的表面。由於第二處理液的黏度較低，因此第一處理液以及第二處理液的混合迅速地進行。由於第一處理液以及第二處理液在基板上混合，因此能有效地活用因為混合時的反應所產生的發熱，從而能處理基板的表面。在硫酸過氧化氫水混合液所為之處理後，能對基板的表面供給清洗液並沖洗硫酸過氧化氫水混合液並停止處理。According to this substrate treatment method, since the first treatment liquid with high viscosity is applied to the surface of the substrate, the consumption of the first treatment liquid can be suppressed, and the first treatment liquid can be uniformly spread and adhered to the surface of the substrate . The second treatment liquid is supplied to the surface of the substrate to which the first treatment liquid has been applied. Thereby, the first treatment liquid and the second treatment liquid are mixed on the surface of the substrate to generate a sulfuric acid-hydrogen peroxide mixed liquid. Since the first treatment liquid spreads uniformly and adheres to the surface of the substrate, the mixed liquid of sulfuric acid and hydrogen peroxide can be uniformly spread to the surface of the substrate without omission. Since the viscosity of the second treatment liquid is low, the mixing of the first treatment liquid and the second treatment liquid proceeds rapidly. Since the first processing liquid and the second processing liquid are mixed on the substrate, the heat generated by the reaction at the time of mixing can be effectively utilized, and the surface of the substrate can be processed. After the treatment with the sulfuric acid-hydrogen peroxide mixed solution, a cleaning solution can be supplied to the surface of the substrate to rinse the sulfuric acid-hydrogen peroxide mixed solution, and the treatment can be stopped.

如此，能提供一種基板處理方法，係能對基板的表面施予均勻的處理且減少處理液的消耗量。In this way, it is possible to provide a substrate processing method capable of applying uniform processing to the surface of the substrate and reducing the consumption of the processing liquid.

對於基板的處理之一例為去除存在於基板的表面的異物。異物的具體例為殘渣、膜。膜的去除係可為膜的剝離，亦可為膜的一部分的蝕刻。膜的一個例子為阻劑膜。An example of the treatment of the substrate is to remove foreign matter present on the surface of the substrate. Specific examples of the foreign matter are residues and films. The removal of the film may be peeling of the film or etching of a part of the film. An example of a film is a resist film.

在本發明的實施形態之一中，前述第一處理液係包含增黏劑。藉此，由於能藉由增黏劑調整第一處理液的黏度，因此能以適合處理的黏度將第一處理液塗布至基板的表面。In one embodiment of the present invention, the first treatment liquid system contains a thickener. Thereby, since the viscosity of the 1st processing liquid can be adjusted by a tackifier, the 1st processing liquid can be apply|coated to the surface of a board|substrate with the viscosity suitable for processing.

本發明的實施形態之一提供一種基板處理方法，係包含：第一處理液供給步驟，係將包含有增黏劑的第一處理液塗布至基板的表面；第二處理液供給步驟，係將第二處理液供給至塗布有前述第一處理液的前述基板的表面；混合液處理步驟，係以硫酸過氧化氫水混合液處理前述基板的表面，前述硫酸過氧化氫水混合液為前述第一處理液以及前述第二處理液在前述基板的表面混合從而生成；以及清洗步驟，係在前述混合液處理步驟之後，對前述基板供給清洗液並從前述基板的表面沖洗前述硫酸過氧化氫水混合液。One of the embodiments of the present invention provides a substrate processing method, which includes: a first processing liquid supply step of applying a first processing liquid containing a tackifier to the surface of the substrate; and a second processing liquid supply step of applying The second treatment solution is supplied to the surface of the substrate coated with the first treatment solution; in the mixed solution treatment step, the surface of the substrate is treated with a sulfuric acid and hydrogen peroxide mixed solution, and the sulfuric acid and hydrogen peroxide mixed solution is the first A treatment liquid and the second treatment liquid are mixed on the surface of the substrate to generate; and a cleaning step is performed after the mixed liquid treatment step, supplying a cleaning liquid to the substrate and rinsing the sulfuric acid hydrogen peroxide solution from the surface of the substrate mixture.

依據此基板處理方法，能抑制包含增黏劑的第一處理液的消耗量，並能使第一處理液均勻地遍及且密著於基板的表面。對塗布有第一處理液的基板的表面供給第二處理液。藉此，第一處理液以及第二處理液係在基板的表面上混合從而生成硫酸過氧化氫水混合液。由於第一處理液均勻地遍及且密著於基板的表面，因此能使硫酸過氧化氫水混合液無遺漏地均勻地遍及至基板的表面。此外，由於第一處理液以及第二處理液在基板上混合，因此能有效地活用因為混合時的反應所產生的發熱，從而能處理基板的表面。在硫酸過氧化氫水混合液所為之處理後，能對基板的表面供給清洗液並沖洗硫酸過氧化氫水混合液，停止處理。According to this substrate processing method, the consumption of the first processing liquid containing the tackifier can be suppressed, and the first processing liquid can be uniformly spread and adhered to the surface of the substrate. The second treatment liquid is supplied to the surface of the substrate to which the first treatment liquid has been applied. Thereby, the first treatment liquid and the second treatment liquid are mixed on the surface of the substrate to generate a sulfuric acid-hydrogen peroxide mixed liquid. Since the first treatment liquid spreads uniformly and adheres to the surface of the substrate, the mixed liquid of sulfuric acid and hydrogen peroxide can be uniformly spread to the surface of the substrate without omission. In addition, since the first treatment liquid and the second treatment liquid are mixed on the substrate, the heat generated by the reaction at the time of mixing can be effectively utilized, and the surface of the substrate can be treated. After the treatment by the sulfuric acid-hydrogen peroxide mixed solution, a cleaning solution can be supplied to the surface of the substrate to rinse the sulfuric acid-hydrogen peroxide mixed solution, and the treatment can be stopped.

與前述實施形態之情形相同，對於基板的處理之一例為去除存在於基板的表面的異物。異物的具體例為殘渣、膜。膜的去除係可為膜的剝離，亦可為膜的一部分的蝕刻。膜的一個例子為阻劑膜。As in the case of the aforementioned embodiment, one example of the treatment of the substrate is to remove foreign matter existing on the surface of the substrate. Specific examples of the foreign matter are residues and films. The removal of the film may be peeling of the film or etching of a part of the film. An example of a film is a resist film.

本發明的實施形態之一提供一種基板處理方法，係包含：第一處理液供給步驟，係將包含過氧化氫水以及增黏劑的第一處理液塗布至基板的表面；第二處理液供給步驟，係將包含硫酸的第二處理液供給至塗布有前述第一處理液的前述基板的表面；混合液處理步驟，係以硫酸過氧化氫水混合液處理前述基板的表面，前述硫酸過氧化氫水混合液為前述第一處理液以及前述第二處理液在前述基板的表面混合從而生成；以及清洗步驟，係在前述混合液處理步驟之後，對前述基板供給清洗液並從前述基板的表面沖洗前述硫酸過氧化氫水混合液。One embodiment of the present invention provides a substrate processing method, comprising: a first processing liquid supply step of applying a first processing liquid containing hydrogen peroxide water and a tackifier to the surface of the substrate; supplying a second processing liquid In the step, the second treatment solution containing sulfuric acid is supplied to the surface of the substrate coated with the first treatment solution; the mixed solution treatment step is to treat the surface of the substrate with a mixed solution of sulfuric acid and hydrogen peroxide, and the sulfuric acid is peroxidized The hydrogen-water mixed solution is generated by mixing the first treatment solution and the second treatment solution on the surface of the substrate; and a cleaning step is performed after the mixed solution treatment step, and a cleaning solution is supplied to the substrate and removed from the surface of the substrate. Rinse the aforementioned sulfuric acid hydrogen peroxide water mixture.

依據此基板處理方法，由於過氧化氫水係以包含增黏劑的第一處理液的形態被塗布至基板的表面，因此能抑制過氧化氫水的消耗量，並能使過氧化氫水遍及且密著於基板的表面。對塗布有第一處理液(過氧化氫水)的基板的表面供給包含硫酸的第二處理液。藉此，過氧化氫水以及硫酸係在基板的表面上混合從而生成硫酸過氧化氫水混合液。由於第一處理液均勻地遍及且密著於基板的表面，因此能使硫酸過氧化氫水混合液無遺漏地均勻地遍及至基板的表面。此外，由於硫酸以及過氧化氫水在基板上混合，因此能有效地活用因為混合時的反應所產生的發熱，從而能處理基板的表面。在硫酸過氧化氫水混合液所為之處理後，能對基板的表面供給清洗液並沖洗硫酸過氧化氫水混合液，停止處理。According to this substrate processing method, since the aqueous hydrogen peroxide system is applied to the surface of the substrate in the form of the first treatment liquid containing the tackifier, the consumption of the aqueous hydrogen peroxide can be suppressed and the aqueous hydrogen peroxide can be permeated. and adhered to the surface of the substrate. The second treatment liquid containing sulfuric acid was supplied to the surface of the substrate to which the first treatment liquid (hydrogen peroxide water) was applied. Thereby, the aqueous hydrogen peroxide and the sulfuric acid are mixed on the surface of the substrate to generate a mixed solution of sulfuric acid and hydrogen peroxide. Since the first treatment liquid spreads uniformly and adheres to the surface of the substrate, the mixed liquid of sulfuric acid and hydrogen peroxide can be uniformly spread to the surface of the substrate without omission. In addition, since sulfuric acid and hydrogen peroxide water are mixed on the substrate, the heat generated by the reaction at the time of mixing can be effectively utilized, and the surface of the substrate can be treated. After the treatment by the sulfuric acid-hydrogen peroxide mixed solution, a cleaning solution can be supplied to the surface of the substrate to rinse the sulfuric acid-hydrogen peroxide mixed solution, and the treatment can be stopped.

與前述實施形態之情形相同，對於基板的處理之一例為去除存在於基板的表面的異物。異物的具體例為殘渣、膜。膜的去除係可為膜的剝離，亦可為膜的一部分的蝕刻。膜的一個例子為阻劑膜。As in the case of the aforementioned embodiment, one example of the treatment of the substrate is to remove foreign matter existing on the surface of the substrate. Specific examples of the foreign matter are residues and films. The removal of the film may be peeling of the film or etching of a part of the film. An example of a film is a resist film.

在本發明的實施形態之一中，前述增黏劑係包含從由聚乙烯吡咯烷酮(polyvinyl pyrrolidone)、聚丙烯酸(polyacrylic acid)、聚丙烯酸鈉(sodium polyacrylate)、聚丙烯酸銨(polyacrylic acid ammonium)、交聯型聚丙烯酸、交聯型聚丙烯酸鈉、交聯型丙烯系聚合物以及羧酸系共聚物(carboxylic acid copolymer)所組成的群組所選擇的至少一種。In one embodiment of the present invention, the aforementioned tackifier is composed of polyvinyl pyrrolidone, polyacrylic acid, sodium polyacrylate, polyacrylic acid ammonium, At least one selected from the group consisting of cross-linked polyacrylic acid, cross-linked sodium polyacrylate, cross-linked propylene-based polymer, and carboxylic acid copolymer.

較佳為，增黏劑係例如具有下述耐熱性：在被供給至基板的表面時之第一處理液的溫度中，第一處理液的黏度能保持於所需的值以上。此情形中所謂所需的值係指能無遺漏且均勻地將第一處理液塗布至基板的表面且將此種塗布狀態至少維持一定時間之值，較佳為例如30mPa．s至3000mPa．s的範圍。較佳為，增黏劑係例如具有下述耐熱性：在混合液處理步驟中的硫酸過氧化氫水混合液的溫度中，能將硫酸過氧化氫水混合液的黏度保持於所需的值以上。此情形中所謂所需的值係指能將硫酸過氧化氫水混合液已無遺漏地擴展至基板的表面的狀態至少維持一定時間之值，較佳為例如30mPa．s至3000mPa．s的範圍。Preferably, the tackifier system has, for example, heat resistance such that the viscosity of the first treatment liquid can be maintained at a desired value or higher at the temperature of the first treatment liquid when supplied to the surface of the substrate. The so-called required value in this case refers to the value that can apply the first treatment liquid to the surface of the substrate without omission and uniformly and maintain this coating state for at least a certain period of time, preferably, for example, 30mPa. s to 3000mPa. range of s. Preferably, the tackifier system has, for example, the following heat resistance: at the temperature of the sulfuric acid and hydrogen peroxide mixed solution in the mixed solution treatment step, the viscosity of the sulfuric acid and hydrogen peroxide mixed solution can be maintained at a desired value. above. The so-called required value in this case refers to the value that can maintain the state in which the sulfuric acid-hydrogen peroxide aqueous mixture has been completely extended to the surface of the substrate for at least a certain period of time, preferably, for example, 30mPa. s to 3000mPa. range of s.

在本發明的實施形態之一中，前述第二處理液係不包含增黏劑。藉由第二處理液不包含增黏劑，能以黏度低的狀態將第二處理液供給至基板的表面。藉此，能在基板上促進第一處理液與第二處理液的混合。In one embodiment of the present invention, the second treatment liquid system does not contain a thickener. Since the second treatment liquid does not contain a tackifier, the second treatment liquid can be supplied to the surface of the substrate in a state of low viscosity. Thereby, the mixing of the first processing liquid and the second processing liquid can be promoted on the substrate.

在第一處理液包含有增黏劑之情形中，該增黏劑係存在於在基板上所生成的硫酸過氧化氫水混合液中，故提高硫酸過氧化氫水的黏度。因此，能在已使硫酸過氧化氫水混合液密著於基板的表面的狀態下使硫酸過氧化氫水混合液所為之處理持續進展。藉此，能對基板表面進行均勻的處理。In the case where the first treatment liquid contains a tackifier, the tackifier is present in the sulfuric acid-hydrogen peroxide water mixture generated on the substrate, thereby increasing the viscosity of the sulfuric acid-hydrogen peroxide water. Therefore, the treatment by the aqueous sulfuric acid and hydrogen peroxide mixture can be continued in a state where the aqueous mixture of sulfuric acid and hydrogen peroxide is made to adhere to the surface of the substrate. Thereby, the substrate surface can be uniformly processed.

為了減少第二處理液的消耗量，亦可於第二處理液包含有增黏劑。然而，較佳為增黏劑的含有量控制在不會阻礙與第一處理液混合的程度。In order to reduce the consumption of the second treatment liquid, a thickener may also be included in the second treatment liquid. However, it is preferable that the content of the thickener is controlled so as not to hinder mixing with the first treatment liquid.

在本發明的實施形態之一中，在前述第一處理液供給步驟中，前述第一處理液被塗布至前述基板的表面，從而形成覆蓋前述基板的表面的全域之前述第一處理液的塗布膜。In one embodiment of the present invention, in the step of supplying the first treatment liquid, the first treatment liquid is applied to the surface of the substrate, thereby forming the application of the first treatment liquid covering the entire surface of the substrate. membrane.

在此種基板處理方法中，由於第一處理液的塗布膜(例如凝膠(gel)狀塗布膜)覆蓋基板的表面的全域，因此能使第一處理液密著於基板的表面的全域。因此，能使第一處理液以及第二處理液混合而成的硫酸過氧化氫水混合液密著於基板的表面的全域，從而能均勻地處理基板的表面的全域。In such a substrate processing method, since the coating film (eg, a gel-like coating film) of the first processing liquid covers the entire surface of the substrate, the first processing liquid can be adhered to the entire surface of the substrate. Therefore, the mixed liquid of sulfuric acid and hydrogen peroxide in which the first treatment liquid and the second treatment liquid are mixed can be adhered to the entire surface of the substrate, and the entire surface of the substrate can be uniformly processed.

在本發明的實施形態之一中，在前述第二處理液供給步驟中，對前述第一處理液的塗布膜的表面供給前述第二處理液。在此種基板處理方法中，於基板的表面形成有第一處理液的塗布膜，並對前述第一處理液的塗布膜的表面供給第二處理液。因此，能抑制因為第二處理液的流動將第一處理液推流至基板外部，並能減少第一處理液的消耗量。In one embodiment of the present invention, in the second treatment liquid supply step, the second treatment liquid is supplied to the surface of the coating film of the first treatment liquid. In such a substrate processing method, the coating film of the first processing liquid is formed on the surface of the substrate, and the second processing liquid is supplied to the surface of the coating film of the first processing liquid. Therefore, it is possible to suppress the flow of the first processing liquid to the outside of the substrate due to the flow of the second processing liquid, and to reduce the consumption of the first processing liquid.

在本發明的實施形態之一中，前述第二處理液供給步驟係在停止朝前述基板的表面供給前述第一處理液的狀態下開始。In one embodiment of the present invention, the second processing liquid supply step is started in a state where the supply of the first processing liquid to the surface of the substrate is stopped.

在此種基板處理方法中，停止供給第一處理液(更具體而言為供給新的液體)，開始供給第二處理液。因此，由於能抑制因為低黏度的第二處理液的流動將第一處理液推流至基板外部，因此能減少第一處理液的消耗量。In such a substrate processing method, the supply of the first processing liquid (more specifically, the supply of a new liquid) is stopped, and the supply of the second processing liquid is started. Therefore, since the flow of the first processing liquid to the outside of the substrate due to the flow of the low-viscosity second processing liquid can be suppressed, the consumption amount of the first processing liquid can be reduced.

在本發明的實施形態之一中，前述混合液處理步驟的至少一部分的期間係與前述第二處理液供給步驟的至少一部分的期間重複。In one embodiment of the present invention, at least a part of the period of the mixed liquid treatment step is overlapped with at least a part of the period of the second treatment liquid supply step.

在基板的表面存在有第一處理液的狀態下將第二處理液供給至基板的表面，藉此開始混合第一處理液以及第二處理液。因此，會有在第二處理液供給步驟的執行中開始硫酸過氧化氫水混合液所為之基板表面的處理之情形。The mixing of the first processing liquid and the second processing liquid is started by supplying the second processing liquid to the surface of the substrate in a state where the first processing liquid exists on the surface of the substrate. Therefore, there are cases in which the treatment of the substrate surface by the sulfuric acid-hydrogen peroxide mixed solution is started during the execution of the second treatment solution supplying step.

在本發明的實施形態之一中，在前述混合液處理步驟的至少一部分的期間中停止朝前述基板的表面供給前述第二處理液。In one embodiment of the present invention, supply of the second treatment liquid to the surface of the substrate is stopped during at least a part of the mixed liquid treatment step.

在此種基板處理方法中，在停止供給第二處理液(具體而言為供給新的液體)的狀態下存在進行硫酸過氧化氫水混合液所為之基板表面的處理之期間。In such a substrate treatment method, there is a period in which the treatment of the substrate surface by the sulfuric acid-hydrogen peroxide mixed solution is performed in a state in which the supply of the second treatment liquid (specifically, the supply of a new liquid) is stopped.

例如，在將基板的表面朝向上方水平地保持的狀態下對形成有第一處理液的塗布膜之基板的表面供給第二處理液後停止供給第二處理液，藉此能作成於基板的表面保持有硫酸過氧化氫水混合液的液膜之覆液(paddle)狀態。藉由維持此種覆液狀態，無須供給第一處理液以及第二處理液即能使硫酸過氧化氫水混合液所為之基板處理持續進展。在此種覆液處理期間中，亦可因應需要將第一處理液以及第二處理液的一方或者雙方補充至基板的表面。For example, the surface of the substrate can be formed by supplying the second treatment liquid to the surface of the substrate on which the coating film of the first treatment liquid is formed, and then stopping the supply of the second treatment liquid with the surface of the substrate held horizontally upward. The paddle state of the liquid film containing the aqueous mixture of sulfuric acid and hydrogen peroxide is maintained. By maintaining such a liquid-covered state, the substrate processing by the sulfuric acid-hydrogen peroxide-water mixture can continue to progress without supplying the first processing liquid and the second processing liquid. During such a liquid coating treatment period, one or both of the first treatment liquid and the second treatment liquid may be supplemented to the surface of the substrate as needed.

在本發明的實施形態之一中，交互地反復執行前述第一處理液供給步驟以及前述第二處理液供給步驟。藉由此種基板處理方法，能因應需要一邊交互地反復供給第一處理液以及第二處理液，一邊在基板上使硫酸過氧化氫水混合液所為之處理持續進展。因此，能以不會處理不足之方式充分地處理基板的表面。In one embodiment of the present invention, the first treatment liquid supply step and the second treatment liquid supply step are alternately and repeatedly executed. According to such a substrate processing method, the treatment by the sulfuric acid-hydrogen peroxide-water mixture can be continuously advanced on the substrate while supplying the first processing liquid and the second processing liquid alternately and repeatedly as needed. Therefore, the surface of the substrate can be sufficiently treated without insufficient treatment.

亦可在第二處理液供給步驟之後，在再次進行第一處理液供給步驟時於這些步驟之間夾著其他的步驟。亦即，亦可在第二處理液供給步驟之後，在不供給第一處理液以及第二處理液地進行之混合液處理步驟之後供給第一處理液。此外，亦可在進行前述清洗步驟後再進行第一處理液供給步驟。After the second treatment liquid supply step, when the first treatment liquid supply step is performed again, other steps may be sandwiched between these steps. That is, after the second treatment liquid supply step, the first treatment liquid may be supplied after the mixed liquid treatment step performed without supplying the first treatment liquid and the second treatment liquid. In addition, the first treatment liquid supply step may be performed after the aforementioned cleaning step.

本發明的實施形態之一係提供用以實施上述般的基板處理方法之基板處理裝置。此基板處理裝置係包含：基板保持單元(基板固持具)，係保持基板；第一處理液噴嘴，係對被前述基板保持單元保持的基板供給前述第一處理液；第二處理液噴嘴，係對被前述基板保持單元保持的基板供給前述第二處理液；清洗液噴嘴，係對被前述基板保持單元保持的基板供給前述清洗液；以及控制單元(控制器)。前述控制單元係控制從前述第一處理液噴嘴供給前述第一處理液並執行前述第一處理液供給步驟，控制前述第二處理液噴嘴供給前述第二處理液並執行前述第二處理液供給步驟，控制前述清洗液噴嘴供給前述清洗液並執行前述清洗步驟。One embodiment of the present invention provides a substrate processing apparatus for implementing the above-described substrate processing method. This substrate processing apparatus includes: a substrate holding unit (substrate holder) for holding a substrate; a first processing liquid nozzle for supplying the first processing liquid to the substrate held by the substrate holding unit; and a second processing liquid nozzle for The second processing liquid is supplied to the substrate held by the substrate holding unit; a cleaning liquid nozzle is used to supply the cleaning liquid to the substrate held by the substrate holding unit; and a control unit (controller). The control unit controls the supply of the first treatment liquid from the first treatment liquid nozzle and executes the first treatment liquid supply step, and controls the second treatment liquid nozzle to supply the second treatment liquid and executes the second treatment liquid supply step , control the cleaning liquid nozzle to supply the cleaning liquid and execute the cleaning step.

藉由此種構成，能實施前述基板處理方法。因此，能提供一種對基板的表面施予均勻的處理且能減少處理液的消耗量之基板處理裝置。With such a configuration, the aforementioned substrate processing method can be implemented. Therefore, it is possible to provide a substrate processing apparatus which can uniformly process the surface of the substrate and can reduce the consumption of the processing liquid.

在本發明的實施形態之一中，前述基板保持單元係包含：自轉夾具(spin chuck)，係將基板的表面朝向上方水平地保持並旋轉。在此情形中，較佳為前述控制單元係在前述第一處理液供給步驟中控制從前述第一處理液噴嘴供給前述第一處理液並控制前述自轉夾具的旋轉，並將前述第一處理液旋轉塗布(spin coating)至前述基板的表面。In one embodiment of the present invention, the substrate holding unit includes a spin chuck for horizontally holding and rotating the surface of the substrate upward. In this case, it is preferable that the control unit controls the supply of the first treatment liquid from the first treatment liquid nozzle and the rotation of the rotation jig in the first treatment liquid supply step, and feeds the first treatment liquid Spin coating is applied to the surface of the aforementioned substrate.

藉由此種構成，能藉由所謂的旋轉塗布對基板的表面塗布第一處理液。藉此，由於能將少量的第一處理液均勻地擴展塗布至基板的表面，因此能減少第一處理液的消耗量並均勻地處理基板的表面。With such a configuration, the first treatment liquid can be applied to the surface of the substrate by so-called spin coating. Thereby, since a small amount of the first treatment liquid can be uniformly spread and applied to the surface of the substrate, the consumption of the first treatment liquid can be reduced and the surface of the substrate can be treated uniformly.

在本發明的實施形態之一中，前述基板處理裝置係進一步包含：噴嘴移動單元，係在處理位置與待機位置之間移動前述第一處理液噴嘴，前述處理位置為用以對被前述基板保持單元保持的基板供給處理液之位置，前述待機位置為已從前述處理位置退避之位置；以及洗淨埠，係在前述待機位置中使前述第一處理液噴嘴的噴出口浸漬於噴嘴洗淨液中。In one embodiment of the present invention, the substrate processing apparatus further includes: a nozzle moving unit for moving the first processing liquid nozzle between a processing position and a standby position, the processing position being used to hold the substrate on the substrate. a position where the substrate held by the unit is supplied with the processing liquid, the standby position is a position that has been evacuated from the processing position; and the cleaning port is in the standby position so that the discharge port of the first processing liquid nozzle is immersed in the nozzle cleaning liquid middle.

藉由此種構成，能在不使用第一處理液噴嘴時在第一處理液的待機位置處洗淨噴出口。藉此，能抑制或者防止高黏度的第一處理液導致噴出口阻塞。With this configuration, when the first processing liquid nozzle is not used, the discharge port can be cleaned at the standby position of the first processing liquid. Thereby, it is possible to suppress or prevent the clogging of the discharge port due to the high-viscosity first processing liquid.

參照隨附的圖式並藉由以下所進行的本發明的詳細的說明，更明瞭上述目的以及其他的目的、特徵、態樣以及優點。The above object and other objects, features, aspects, and advantages will become more apparent from the following detailed description of the present invention with reference to the accompanying drawings.

圖1A至圖1H係用以說明本發明的實施形態之一的基板處理方法之步驟圖。基板處理方法係包含第一處理液塗布步驟S1(第一處理液供給步驟，圖1A至圖1B)、第二處理液供給步驟S2(圖1C)、混合液處理步驟S3(圖1C至圖1D)、清洗步驟S4(圖1E)、殘渣去除步驟S5(圖1F至圖1G)以及乾燥步驟S6(圖1H)。處理對象的基板W為於表面(在本實施形態中為上表面)形成有阻劑膜(未圖示)之基板。基板W係能為半導體基板、液晶顯示裝置用基板。典型而言，阻劑膜為作為乾蝕刻用的遮罩(mask)來使用後的阻劑膜。本實施形態的基板處理方法係進行用以剝離基板W的表面的阻劑膜之阻劑剝離處理。更具體而言，藉由硫酸過氧化氫水混合液從基板W的表面剝離並去除阻劑。1A to 1H are step diagrams for explaining a substrate processing method according to one embodiment of the present invention. The substrate processing method includes a first processing liquid coating step S1 (a first processing liquid supply step, FIGS. 1A to 1B ), a second processing liquid supply step S2 ( FIG. 1C ), and a mixed liquid processing step S3 ( FIGS. 1C to 1D ) ), cleaning step S4 (FIG. 1E), residue removal step S5 (FIG. 1F to 1G), and drying step S6 (FIG. 1H). The substrate W to be processed is a substrate on which a resist film (not shown) is formed on the surface (in this embodiment, the upper surface). The substrate W can be a semiconductor substrate or a substrate for a liquid crystal display device. Typically, the resist film is used as a mask for dry etching. The substrate processing method of this embodiment performs the resist peeling process for peeling the resist film on the surface of the board|substrate W. More specifically, the resist is peeled off and removed from the surface of the substrate W by a sulfuric acid-hydrogen peroxide mixed solution.

於表面形成有阻劑膜之基板W被搬入至處理腔室(processing chamber)1(參照圖3)，該基板W係被自轉夾具5保持。藉此，基板W係被自轉夾具5保持成水平姿勢並在此種狀態下繞著通過中央部之鉛直的旋轉軸線A旋轉。基板W係以將形成有阻劑膜之基板W的表面朝上的姿勢下被自轉夾具5保持。The substrate W on which the resist film is formed on the surface is carried into a processing chamber 1 (see FIG. 3 ), and the substrate W is held by the rotation jig 5 . Thereby, the substrate W is held in a horizontal posture by the rotation jig 5, and in this state is rotated about the vertical rotation axis A passing through the central portion. The substrate W is held by the rotation jig 5 with the surface of the substrate W on which the resist film is formed facing upward.

第一處理液塗布步驟S1為下述步驟：一邊藉由自轉夾具5旋轉基板W一邊對基板W的表面(上表面)供給第一處理液L1，將該第一處理液L1塗布(所謂的旋轉塗布)至基板W的表面。在本實施形態中，第一處理液L1係包含屬於SPM的原料之硫酸以及過氧化氫水中的一方且不包含另一方。在本實施形態中，第一處理液L1為進一步包含增黏劑(高黏度化劑)之高黏度的處理液。The first treatment liquid application step S1 is a step of supplying the first treatment liquid L1 to the surface (upper surface) of the substrate W while rotating the substrate W by the rotation jig 5, and applying the first treatment liquid L1 (so-called spinning). coating) to the surface of the substrate W. In the present embodiment, the first treatment liquid L1 contains one of sulfuric acid and aqueous hydrogen peroxide, which are raw materials of SPM, and does not contain the other. In the present embodiment, the first treatment liquid L1 is a high-viscosity treatment liquid that further contains a thickener (high-viscosity agent).

如圖1A所示，在第一處理液塗布步驟S1中，從第一處理液噴嘴N1對基板W的中央附近供給第一處理液L1達至預定供給量。供給達至預定供給量後，停止從第一處理液噴嘴N1供給第一處理液L1。被供給至基板W的表面之第一處理液L1係藉由伴隨著基板W的旋轉之離心力而在基板W的表面朝周緣部擴展。藉此，如圖1B所示，能形成覆蓋基板W的表面(上表面)的全域之第一處理液L1的塗布膜F1。第一處理液L1的預定供給量係被制定成充分的量，俾能藉由基板W的旋轉形成覆蓋基板W的表面(上表面)的全域之塗布膜F1。較佳為此預定供給量係進一步被制定成形成覆蓋基板W的表面(上表面)的全域之塗布膜F1所需的量，藉此能將第一處理液L1的消耗量設定成最低限度。As shown in FIG. 1A , in the first processing liquid application step S1 , the first processing liquid L1 is supplied to the vicinity of the center of the substrate W from the first processing liquid nozzle N1 to a predetermined supply amount. After the supply reaches the predetermined supply amount, the supply of the first processing liquid L1 from the first processing liquid nozzle N1 is stopped. The first processing liquid L1 supplied to the surface of the substrate W spreads toward the peripheral portion on the surface of the substrate W by the centrifugal force accompanying the rotation of the substrate W. Thereby, as shown to FIG. 1B, the coating film F1 of the 1st processing liquid L1 which covers the whole area of the surface (upper surface) of the board|substrate W can be formed. The predetermined supply amount of the first treatment liquid L1 is determined to be a sufficient amount so that the coating film F1 covering the entire surface (upper surface) of the substrate W can be formed by the rotation of the substrate W. Preferably, the predetermined supply amount for this purpose is further determined to be an amount required to form the coating film F1 covering the entire surface (upper surface) of the substrate W, whereby the consumption of the first processing liquid L1 can be minimized.

第二處理液供給步驟S2係在第一處理液塗布步驟S1之後進行。亦即，在於基板W的表面(上表面)的全域形成有第一處理液L1的塗布膜F1的狀態下開始。在本實施形態中，第二處理液L2係包含屬於SPM的原料之硫酸以及過氧化氫水中之未被包含於第一處理液L1之另一方且不包含已被包含於第一處理液L1之一方。較佳為第二處理液L2為黏度比第一處理液L1還低之低黏度的處理液。雖然較佳為第二處理液L2不包含增黏劑，然而亦可因應需要包含有微量的增黏劑。The second treatment liquid supply step S2 is performed after the first treatment liquid application step S1. That is, it starts in a state in which the coating film F1 of the 1st processing liquid L1 is formed in the whole area|region of the surface (upper surface) of the board|substrate W. In the present embodiment, the second treatment liquid L2 contains sulfuric acid, which is a raw material of SPM, and hydrogen peroxide water, which is not included in the first treatment liquid L1, and does not include the first treatment liquid L1. one side. Preferably, the second processing liquid L2 is a low-viscosity processing liquid having a viscosity lower than that of the first processing liquid L1. Although it is preferable that the second treatment liquid L2 does not contain a tackifier, it can also contain a trace amount of tackifier as required.

如圖1C所示，在第二處理液供給步驟S2中，一邊藉由自轉夾具5將基板W繞著旋轉軸線A旋轉，一邊從第二處理液噴嘴N2將第二處理液L2供給至形成於基板W的表面(上表面)的全域的第一處理液L1的塗布膜F1上。此供給亦可以預定流量連續地供給。如圖1C所示，第二處理液噴嘴N2亦可為直式噴嘴(straight nozzle)，用以在柱狀的連續流動的狀態下噴出第二處理液L2。此外，第二處理液噴嘴N2亦可為噴霧噴嘴(spray nozzle)，用以以呈現錐(cone)狀的輪廓(profile)之方式噴霧第二處理液L2。此外，第二處理液噴嘴N2係可在第二處理液供給步驟S2中進行固定式噴出，亦可在第二處理液供給步驟S2中進行移動式噴出，固定式噴出係在基板W上的著液位置實質性地被保持在固定位置(例如旋轉軸線A上)，移動式噴出係基板W上的著液位置會移動。在移動式噴出之情形中，較佳為從第二處理液噴嘴N2噴出的第二處理液L2的著液位置係在基板W的表面上於從旋轉中心至周緣部為止的範圍內移動，藉此著液位置係掃描基板W的表面。第二處理液供給步驟S2係進行預定時間。As shown in FIG. 1C , in the second processing liquid supply step S2 , the second processing liquid L2 is supplied from the second processing liquid nozzle N2 to the surface formed in the On the coating film F1 of the 1st processing liquid L1 in the whole area of the surface (upper surface) of the board|substrate W. This supply can also be supplied continuously at a predetermined flow rate. As shown in FIG. 1C , the second treatment liquid nozzle N2 can also be a straight nozzle, which is used to eject the second treatment liquid L2 in a columnar continuous flow state. In addition, the second treatment liquid nozzle N2 may also be a spray nozzle, which is used to spray the second treatment liquid L2 in a manner of presenting a cone-shaped profile. In addition, the second processing liquid nozzle N2 may perform fixed type discharge in the second processing liquid supply step S2, or may perform movable type discharge in the second processing liquid supply step S2, and the fixed type discharge is fixed on the substrate W. The liquid position is substantially held at a fixed position (for example, on the rotation axis A), and the liquid impinging position on the substrate W of the mobile ejection system moves. In the case of the movable ejection, it is preferable that the impingement position of the second treatment liquid L2 ejected from the second treatment liquid nozzle N2 is moved on the surface of the substrate W within the range from the rotation center to the peripheral portion, by The liquid impingement position scans the surface of the substrate W. As shown in FIG. The second treatment liquid supply step S2 is performed for a predetermined time.

混合液處理步驟S3為下述步驟：藉由第一處理液L1以及第二處理液L2在基板W上混合而成的混合液亦即SPM，剝離基板W的表面的阻劑膜。具體而言，硫酸以及過氧化氫水係在基板W上彼此混合並引起發熱反應從而成為SPM，該SPM係使基板W的表面的阻劑膜腐蝕。當開始供給第二處理液L2時，由於第一處理液L1以及第二處理液L2開始混合，因此第二處理液供給步驟S2的至少一部分的期間亦可與混合液處理步驟S3的至少一部分的期間重複(參照圖1C)。The mixed liquid processing step S3 is a step of peeling off the resist film on the surface of the substrate W with SPM, which is a mixed liquid obtained by mixing the first processing liquid L1 and the second processing liquid L2 on the substrate W. Specifically, sulfuric acid and aqueous hydrogen peroxide are mixed with each other on the substrate W to cause an exothermic reaction to become SPM, and this SPM corrodes the resist film on the surface of the substrate W. When the supply of the second treatment liquid L2 is started, since the first treatment liquid L1 and the second treatment liquid L2 start to mix, at least a part of the second treatment liquid supplying step S2 may be combined with at least a part of the mixed liquid treatment step S3. The period repeats (see FIG. 1C ).

如圖1D所示，在第二處理液供給步驟S2之後，亦即在停止供給第二處理液L2之後，第一處理液L1以及第二處理液L2的混合反應(SPM反應)亦在基板W的表面上持續進展，且SPM所致使之阻劑膜的腐蝕亦持續進展。在停止供給第二處理液L2之後，亦可停止基板W的旋轉，亦可以能於基板W上保持第一處理液L1、第二處理液L2以及該第一處理液L1與該第二處理液L2混合而成的SPM之程度的低速旋轉基板W(參照圖1D)。藉此，成為於第一處理液L1的塗布膜F1上保持有第二處理液L2之覆液狀態。因此，成為在基板W上保持有第一處理液L1與第二處理液L2混合而成的SPM之覆液狀態。藉由維持此種覆液狀態，皆無須供給第一處理液L1以及第二處理液L2即能使SPM所致使之阻劑腐蝕處理持續進展。As shown in FIG. 1D , after the second processing liquid supply step S2 , that is, after the supply of the second processing liquid L2 is stopped, the mixing reaction (SPM reaction) of the first processing liquid L1 and the second processing liquid L2 also occurs on the substrate W On the surface, the corrosion of the resist film caused by SPM continued to progress. After the supply of the second processing liquid L2 is stopped, the rotation of the substrate W may be stopped, and the first processing liquid L1, the second processing liquid L2, the first processing liquid L1 and the second processing liquid may be held on the substrate W. The substrate W is rotated at a low speed of the level of SPM in which L2 is mixed (see FIG. 1D ). Thereby, the coating film F1 of the 1st processing liquid L1 becomes the liquid-coated state in which the 2nd processing liquid L2 is hold|maintained. Therefore, the substrate W is kept in a liquid-covered state in which the SPM in which the first processing liquid L1 and the second processing liquid L2 are mixed is maintained. By maintaining such a liquid-covered state, it is possible to continuously progress the resist corrosion treatment by SPM without supplying the first processing liquid L1 and the second processing liquid L2.

在停止供給第二處理液L2之後的混合液處理步驟S3中，亦可因應需要從第一處理液噴嘴N1對基板W的表面補充第一處理液L1，亦可從第二處理液噴嘴N2對基板W的表面補充第二處理液L2。亦可因應需要僅補充第一處理液L1以及第二處理液L2的一方，亦可補充第一處理液L1以及第二處理液L2雙方。此外，亦可不停止供給第二處理液L2，而是在混合液處理步驟S3的整個期間中持續地供給第二處理液L2。In the mixed liquid processing step S3 after the supply of the second processing liquid L2 is stopped, the first processing liquid L1 may be supplied to the surface of the substrate W from the first processing liquid nozzle N1 as required, or the surface of the substrate W may be supplied from the second processing liquid nozzle N2 The surface of the substrate W is supplemented with the second treatment liquid L2. As needed, only one of the first treatment liquid L1 and the second treatment liquid L2 may be replenished, or both the first treatment liquid L1 and the second treatment liquid L2 may be replenished. Further, the supply of the second treatment liquid L2 may not be stopped, but the second treatment liquid L2 may be continuously supplied throughout the entire period of the mixed liquid treatment step S3.

清洗步驟S4係在已藉由混合液處理步驟S3使基板W上的阻劑膜充分地腐蝕後再進行。具體而言，如圖1E所示，一邊藉由自轉夾具5使基板W旋轉，一邊從清洗液噴嘴NR供給純水(去離子水)、碳酸水等之清洗液R，將已在基板W腐蝕的阻劑膜以及SPM朝基板W的表面外部沖洗。較佳為基板W係以比混合液處理步驟S3時還高速地旋轉，利用離心力於基板W的表面形成從旋轉中心朝向周緣之清洗液R的流動。The cleaning step S4 is performed after the resist film on the substrate W has been sufficiently etched by the mixed solution processing step S3. Specifically, as shown in FIG. 1E , while the substrate W is rotated by the rotation jig 5, a cleaning solution R such as pure water (deionized water) and carbonated water is supplied from the cleaning solution nozzle NR, and the substrate W is etched. The resist film and SPM are flushed toward the outside of the surface of the substrate W. Preferably, the substrate W is rotated at a higher speed than that in the mixed solution processing step S3, and a flow of the cleaning solution R from the rotation center toward the periphery is formed on the surface of the substrate W by centrifugal force.

第一處理液塗布步驟S1、第二處理液供給步驟S2、混合液處理步驟S3以及清洗步驟S4亦可循環地複數次反復地進行。亦即，亦可在清洗步驟S4之後再次進行第一處理液塗布步驟S1、第二處理液供給步驟S2、混合液處理步驟S3以及清洗步驟S4。在此情形中，在第二次以後的第一處理液塗布步驟S1所供給的第一處理液的黏度亦可比在第一次的第一處理液塗布步驟S1所使用的第一處理液的黏度還小。The first treatment liquid application step S1 , the second treatment liquid supply step S2 , the mixed liquid treatment step S3 , and the cleaning step S4 may be repeated several times in a cycle. That is, the first treatment liquid application step S1, the second treatment liquid supply step S2, the mixed liquid treatment step S3, and the cleaning step S4 may be performed again after the cleaning step S4. In this case, the viscosity of the first treatment liquid supplied in the second and subsequent first treatment liquid application steps S1 may be higher than the viscosity of the first treatment liquid used in the first first treatment liquid application step S1 for the first time still small.

此外，亦可循環地複數次反復地進行第一處理液塗布步驟S1、第二處理液供給步驟S2以及混合液處理步驟S3。而且，亦可在反復預定次數後進行清洗步驟S4。在此情形中，在第二次以後的第一處理液塗布步驟S1所供給的第一處理液的黏度亦可比在第一次的第一處理液塗布步驟S1所使用的第一處理液的黏度還小。Further, the first treatment liquid application step S1 , the second treatment liquid supply step S2 , and the mixed liquid treatment step S3 may be repeatedly performed in a cycle. Furthermore, the cleaning step S4 may be performed after being repeated a predetermined number of times. In this case, the viscosity of the first treatment liquid supplied in the second and subsequent first treatment liquid application steps S1 may be higher than the viscosity of the first treatment liquid used in the first first treatment liquid application step S1 for the first time still small.

殘渣去除步驟S5為用以去除在清洗步驟S4中未去除乾淨的異物之洗淨步驟。更具體而言，殘渣去除步驟S5係從基板W的表面去除混合液處理步驟S3中的生成物(處理殘渣)、微粒(particle)。殘渣去除步驟S5係包含圖1F所示的洗淨液供給步驟S51以及圖1G所示的清洗步驟S52。亦可因應所需的處理內容省略殘渣去除步驟S5。The residue removal step S5 is a cleaning step for removing the foreign matter not removed in the cleaning step S4. More specifically, the residue removal step S5 removes the product (processing residue) and particles (particles) from the surface of the substrate W in the mixed solution processing step S3 . The residue removal step S5 includes the cleaning solution supply step S51 shown in FIG. 1F and the cleaning step S52 shown in FIG. 1G . The residue removal step S5 may also be omitted according to the desired processing content.

洗淨液供給步驟S51係一邊藉由自轉夾具5使基板W旋轉，一邊從藥液噴嘴NC對基板W的表面供給洗淨液C(更具體而言為洗淨藥液)。洗淨液供給步驟S51亦可為鹼洗淨步驟，用以使用氨過氧化氫水混合液(例如SC1(Standard clean-1；第一標準清洗液))作為洗淨液C來洗淨基板W。The cleaning liquid supply step S51 is to supply the cleaning liquid C (more specifically, cleaning chemical liquid) to the surface of the substrate W from the chemical liquid nozzle NC while rotating the substrate W by the rotation jig 5 . The cleaning solution supplying step S51 may also be an alkaline cleaning step for cleaning the substrate W using an aqueous ammonia hydrogen peroxide solution (eg SC1 (Standard clean-1; first standard cleaning solution)) as the cleaning solution C .

清洗步驟S52為下述步驟：在洗淨液供給步驟S51之後以清洗液R置換基板W的表面的洗淨液C，並從基板W的表面沖洗洗淨液C。清洗步驟S52係一邊藉由自轉夾具5使基板W旋轉，一邊從清洗液噴嘴NR朝基板W的表面供給清洗液R。The cleaning step S52 is a step of rinsing the cleaning solution C from the surface of the substrate W by replacing the cleaning solution C on the surface of the substrate W with the cleaning solution R after the cleaning solution supplying step S51 . In the cleaning step S52 , the cleaning liquid R is supplied to the surface of the substrate W from the cleaning liquid nozzle NR while the substrate W is rotated by the rotation jig 5 .

乾燥步驟S6係在殘渣去除步驟S5的清洗步驟S52(參照圖1G)之後進行。在省略殘渣去除步驟S5之情形中則在清洗步驟S4(參照圖1E)之後進行。亦即，乾燥步驟S6係在停止朝基板W的表面供給清洗液R之後進行。如圖1H所示，乾燥步驟S6亦可為旋乾(spin drying)步驟，用以藉由自轉夾具5使基板W高速地旋轉，並藉由離心力甩離基板W上的液體。藉由此乾燥步驟S6完成一連串的基板處理，從處理腔室1(參照圖3)搬出處理完畢的基板W，亦即從處理腔室1(參照圖3)搬出已從表面剝離阻劑膜且表面已被洗淨以及乾燥的基板W。The drying step S6 is performed after the cleaning step S52 (see FIG. 1G ) of the residue removing step S5 . In the case where the residue removal step S5 is omitted, it is performed after the cleaning step S4 (see FIG. 1E ). That is, the drying step S6 is performed after the supply of the cleaning liquid R to the surface of the substrate W is stopped. As shown in FIG. 1H , the drying step S6 can also be a spin drying step, which is used to rotate the substrate W at a high speed by the spin jig 5 and to spin off the liquid on the substrate W by centrifugal force. In this drying step S6, a series of substrate processing is completed, and the processed substrate W is unloaded from the processing chamber 1 (see FIG. 3 ), that is, the resist film has been removed from the surface of the processing chamber 1 (see FIG. 3 ). The surface of the substrate W has been cleaned and dried.

圖2A至圖2D係用以說明主要的步驟中的基板表面的狀態的例子之圖解性的剖視圖。在此例子中，第一處理液L1為高黏度的過氧化氫水，亦即為包含增黏劑的過氧化氫水。此外，第二處理液L2為硫酸。第二處理液L2較佳為比第一處理液L1還低黏度的硫酸。例如，第二處理液L2為不包含增黏劑的硫酸。在被供給至基板W的表面時之溫度(例如室溫)的第一處理液L1的黏度為30mPa．s以上，較佳為50mPa．s以上，更佳為100mPa．s以上，再更佳為200mPa．s以上。針對第一處理液L1的黏度的上限，只要在能旋轉塗布至基板W的表面之範圍即可，例如為3000mPa．s。2A to 2D are schematic cross-sectional views for explaining an example of the state of the substrate surface in the main steps. In this example, the first treatment liquid L1 is high-viscosity hydrogen peroxide water, that is, hydrogen peroxide water containing a thickening agent. In addition, the second treatment liquid L2 is sulfuric acid. The second treatment liquid L2 is preferably sulfuric acid having a lower viscosity than the first treatment liquid L1. For example, the second treatment liquid L2 is sulfuric acid that does not contain a thickener. The viscosity of the first processing liquid L1 at the temperature (eg, room temperature) supplied to the surface of the substrate W is 30 mPa. s above, preferably 50mPa. s or more, more preferably 100mPa. s above, and then more preferably 200mPa. s or more. For the upper limit of the viscosity of the first treatment liquid L1, as long as it can be spin-coated to the surface of the substrate W, for example, it is 3000 mPa. s.

作為增黏劑的例子，能例舉聚乙烯吡咯烷酮、鹼系增黏劑等。作為鹼系增黏劑，除了聚丙烯酸、聚丙烯酸鈉、聚丙烯酸銨、交聯型聚丙烯酸、交聯型聚丙烯酸鈉等之聚丙烯酸系增黏劑之外，亦可包含交聯型丙烯系聚合物、羧酸系共聚物(銨鹽或者鈉鹽)等。亦可使用這些增黏劑的一種以上，亦即亦可使用一種或者兩種以上。增黏劑係能以粉末、水溶液或者乳液(emulsion)的形態來提供。As an example of a thickener, polyvinylpyrrolidone, an alkaline-type thickener, etc. can be mentioned. As the alkali-based tackifier, in addition to polyacrylic acid-based tackifiers such as polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, cross-linked polyacrylic acid, cross-linked sodium polyacrylate, etc., cross-linked propylene-based tackifiers may also be included. Polymers, carboxylic acid-based copolymers (ammonium salt or sodium salt), etc. One or more of these tackifiers may be used, that is, one or two or more may be used. The tackifier system can be provided in the form of powder, aqueous solution or emulsion.

在第一處理液塗布步驟S1(參照圖2A)中，於基板W的表面形成有高黏度的過氧化氫水(第一處理液L1)的塗布膜F1(例如膠(jelly)狀的膜)。塗布膜F1係密著於基板W的表面的全域。In the first treatment liquid coating step S1 (see FIG. 2A ), a coating film F1 (eg, a jelly-like film) of the high-viscosity hydrogen peroxide water (first treatment liquid L1 ) is formed on the surface of the substrate W . The coating film F1 adheres to the entire surface of the substrate W.

在第二處理液供給步驟S2(參照圖2B)中，將例如黏度較低的硫酸(第二處理液L2)供給至高黏度過氧化氫水的塗布膜(第一處理液L1的塗布膜F1)上並形成硫酸的液層。接著，高黏度過氧化氫水(第一處理液L1)與硫酸(第二處理液L2)開始混合。In the second treatment liquid supply step S2 (see FIG. 2B ), for example, sulfuric acid (the second treatment liquid L2 ) having a relatively low viscosity is supplied to the coating film of the high-viscosity hydrogen peroxide water (the coating film F1 of the first treatment liquid L1 ) and formed a liquid layer of sulfuric acid. Next, mixing of the high-viscosity hydrogen peroxide water (first treatment liquid L1) and sulfuric acid (second treatment liquid L2) is started.

在混合液處理步驟S3(參照圖2C)中，藉由高黏度過氧化氫水與硫酸的混合從而生成SPM。該SPM到達至基板W的表面，藉此使形成於基板W的表面的阻劑膜腐蝕。由於過氧化氫水在高黏度的狀態下存在於基板W的表面，因此在抑制或者防止SPM從基板W上流出的狀態下反應持續進展。藉此，能藉由供給少量的高黏度過氧化氫水以及少量的硫酸而使基板W的表面的阻劑膜腐蝕。在過氧化氫水以及／或者硫酸不足之情形中，如上所述亦可補充過氧化氫水以及硫酸。由於高黏度過氧化氫水的塗布膜F1係密著於基板W的全域，因此能在基板W的全域使處理均勻地持續進展，結果能實現均勻性佳的基板處理(阻劑剝離處理)。In the mixed solution processing step S3 (see FIG. 2C ), SPM is generated by mixing high-viscosity hydrogen peroxide water and sulfuric acid. The SPM reaches the surface of the substrate W, whereby the resist film formed on the surface of the substrate W is corroded. Since the hydrogen peroxide water exists on the surface of the substrate W in a state of high viscosity, the reaction continues to progress in a state in which the outflow of SPM from the substrate W is suppressed or prevented. Thereby, the resist film on the surface of the substrate W can be corroded by supplying a small amount of high-viscosity hydrogen peroxide water and a small amount of sulfuric acid. In the case of insufficient hydrogen peroxide water and/or sulfuric acid, hydrogen peroxide water and sulfuric acid may also be supplemented as described above. Since the coating film F1 of the high-viscosity hydrogen peroxide water adheres to the entire area of the substrate W, the process can continue to progress uniformly over the entire area of the substrate W, and as a result, a substrate treatment (resist stripping treatment) with excellent uniformity can be realized.

第一處理液L1中所含有的增黏劑係用以將第一處理液L1以及第二處理液L2在基板W上混合從而生成SPM時之SPM的黏度控制在30mPa．s以上，較佳為控制在50mPa．s以上，更佳為控制在100mPa．s以上，再更佳為控制在200mPa．s以上。藉此，由於容易在基板W上以覆液狀態保持SPM，因此能有效地減少第一處理液L1以及第二處理液L2的消耗量且容易地實現均勻的基板處理。The viscosity enhancer contained in the first processing liquid L1 is used to mix the first processing liquid L1 and the second processing liquid L2 on the substrate W to generate the SPM when the viscosity of the SPM is controlled at 30mPa. s above, preferably controlled at 50mPa. s above, more preferably controlled at 100mPa. s above, it is better to control at 200mPa. s or more. As a result, since the SPM is easily held on the substrate W in a liquid-covered state, the consumption of the first processing liquid L1 and the second processing liquid L2 can be effectively reduced, and uniform substrate processing can be easily achieved.

在混合液處理步驟S3之後，藉由清洗步驟S4(參照圖2D)將基板W上的SPM置換成清洗液R並與已腐蝕的阻劑膜一起從基板W的表面去除。After the mixed solution processing step S3, the SPM on the substrate W is replaced with the cleaning solution R by the cleaning step S4 (see FIG. 2D) and removed from the surface of the substrate W together with the etched resist film.

在第一處理液L1使用高黏度的硫酸亦即添加了增黏劑的硫酸且第二處理液L2使用過氧化氫水(較佳為比第一處理液L1還低黏度的過氧化氫水)之情形的處理係只要置換上述說明中的「過氧化氫水」與「硫酸」即可。在此情形中亦能實現均勻性佳的基板處理(阻劑剝離處理)。The first treatment liquid L1 uses high-viscosity sulfuric acid, that is, sulfuric acid to which a thickening agent is added, and the second treatment liquid L2 uses hydrogen peroxide water (preferably, hydrogen peroxide water with a lower viscosity than the first treatment liquid L1) In this case, it is sufficient to replace the "hydrogen peroxide water" and "sulfuric acid" in the above description. Also in this case, a substrate treatment (resist stripping treatment) with excellent uniformity can be realized.

圖3係用以說明用以執行前述基板處理方法的基板處理裝置100(處理單元)的構成例之圖解性的剖視圖。基板處理裝置100係包含屬於基板保持單元(基板固持具)的一例之自轉夾具5、第一處理液噴嘴N1、第二處理液噴嘴N2、藥液噴嘴NC、清洗液噴嘴NR以及待機埠3，且將這些構件收容於處理腔室1內。基板處理裝置100係進一步包含配置於處理腔室1外的第一處理液供給源15以及第二處理液供給源25。基板處理裝置100係進一步包含配置於處理腔室1外的藥液供給源35。FIG. 3 is a schematic cross-sectional view for explaining a configuration example of a substrate processing apparatus 100 (processing unit) for performing the aforementioned substrate processing method. The substrate processing apparatus 100 includes a rotation jig 5 which is an example of a substrate holding unit (substrate holder), a first processing liquid nozzle N1, a second processing liquid nozzle N2, a chemical liquid nozzle NC, a cleaning liquid nozzle NR, and a standby port 3, And these components are accommodated in the processing chamber 1 . The substrate processing apparatus 100 further includes a first processing liquid supply source 15 and a second processing liquid supply source 25 disposed outside the processing chamber 1 . The substrate processing apparatus 100 further includes a chemical solution supply source 35 disposed outside the processing chamber 1 .

自轉夾具5為基板保持旋轉裝置，用以在處理腔室1內以水平姿勢保持一片基板W，並使基板W繞著通過基板W的中心之鉛直的旋轉軸線A旋轉。自轉夾具5係包含：旋轉軸51，係沿著旋轉軸線A延伸；自轉基座52，係接合於旋轉軸51的上端；以及自轉馬達53，係用以使旋轉軸51旋轉。自轉基座52係具有以水平姿勢被保持於旋轉軸51的上端之圓盤形狀。複數個夾持銷54係隔著間隔配置於自轉基座52的周緣部的周方向。複數個夾持銷54係構成為抵接至基板W的周端面並夾持基板W。亦可採用真空型夾具來取代此種機械夾具，真空型夾具係吸附並保持基板W的下表面中央。The rotation jig 5 is a substrate holding and rotating device for holding a substrate W in a horizontal position in the processing chamber 1 and rotating the substrate W around a vertical rotation axis A passing through the center of the substrate W. The rotation jig 5 includes: a rotation shaft 51 extending along the rotation axis A; a rotation base 52 connected to the upper end of the rotation shaft 51 ; and a rotation motor 53 for rotating the rotation shaft 51 . The rotation base 52 has a disk shape that is held by the upper end of the rotating shaft 51 in a horizontal position. The plurality of clamping pins 54 are arranged at intervals in the circumferential direction of the peripheral edge portion of the rotation base 52 . The plurality of clamping pins 54 are configured to abut on the peripheral end surface of the substrate W and clamp the substrate W. As shown in FIG. Instead of such a mechanical jig, a vacuum-type jig can also be used, and the vacuum-type jig attracts and holds the center of the lower surface of the substrate W. As shown in FIG.

第一處理液噴嘴N1為下述噴嘴：用以對被保持於自轉夾具5的基板W的表面(上表面)供給第一處理液L1。第一處理液噴嘴N1係具有在處理位置(以實線所示的位置)與待機位置(以二點鏈線所示的位置)之間移動之移動噴嘴的形態，處理位置為用以對被保持於自轉夾具5的基板W的表面噴出第一處理液L1之位置，待機位置為已被設定至自轉夾具5的側方之位置。更具體而言，第一處理液噴嘴N1係藉由第一噴嘴移動單元11而移動。第一噴嘴移動單元11係包含例如水平地延伸的第一擺動臂12，且於第一擺動臂12的擺動端結合有第一處理液噴嘴N1。雖然省略詳細的圖示，然而第一噴嘴移動單元11係進一步包含結合於第一擺動臂12的基端部之擺動驅動機構，擺動驅動機構係使第一擺動臂12繞著通過第一擺動臂12的基端部之鉛直的擺動軸線擺動。藉此，第一處理液噴嘴N1係在處理位置與待機位置之間移動。如上所述，第一處理液L1為高黏度的處理液。處理位置亦可為第一處理液L1著液至基板W的旋轉中心之位置。已著液至基板W的旋轉中心的第一處理液L1係藉由因為基板W的旋轉所產生的離心力而被延伸塗布至基板W的表面的全域。The first processing liquid nozzle N1 is a nozzle for supplying the first processing liquid L1 to the surface (upper surface) of the substrate W held by the rotation jig 5 . The first processing liquid nozzle N1 has the form of a moving nozzle that moves between a processing position (position shown by a solid line) and a standby position (position shown by a two-dot chain line), and the processing position is used to The position where the first processing liquid L1 is ejected from the surface of the substrate W held by the rotation jig 5 and the standby position is set to the side of the rotation jig 5 . More specifically, the first processing liquid nozzle N1 is moved by the first nozzle moving unit 11 . The first nozzle moving unit 11 includes, for example, a first swing arm 12 extending horizontally, and a first treatment liquid nozzle N1 is coupled to the swing end of the first swing arm 12 . Although detailed illustration is omitted, the first nozzle moving unit 11 further includes a swing drive mechanism coupled to the base end of the first swing arm 12 , and the swing drive mechanism makes the first swing arm 12 pass around the first swing arm The vertical swing axis of the base end portion of 12 swings. Thereby, the first processing liquid nozzle N1 is moved between the processing position and the standby position. As described above, the first processing liquid L1 is a high-viscosity processing liquid. The processing position may be a position where the first processing liquid L1 is applied to the rotation center of the substrate W. As shown in FIG. The first processing liquid L1 having reached the rotation center of the substrate W is spread over the entire surface of the substrate W by the centrifugal force generated by the rotation of the substrate W.

第二處理液噴嘴N2為下述噴嘴：用以對被自轉夾具5保持的基板W的表面(上表面)供給第二處理液L2。第二處理液噴嘴N2係具有在處理位置與待機位置之間移動之移動噴嘴的形態，處理位置為用以對被保持於自轉夾具5的基板W的表面噴出第二處理液L2之位置，待機位置為已被設定至自轉夾具5的側方之位置。更具體而言，第二處理液噴嘴N2係藉由第二噴嘴移動單元21而移動。第二噴嘴移動單元21係具有例如與第一噴嘴移動單元11同樣的構成。亦即，第二噴嘴移動單元21係包含例如水平地延伸的第二擺動臂22，且於第二擺動臂22的擺動端結合有第二處理液噴嘴N2。與第一噴嘴移動單元11同樣地，第二噴嘴移動單元21係具備用以使第二擺動臂22擺動之擺動驅動機構。第二處理液噴嘴N2亦可作為掃描噴嘴而動作，掃描噴嘴係一邊噴出第二處理液L2一邊使基板W上的著液位置掃描。在此情形中，處理位置係在基板W的旋轉中心與周緣之間變動。The second processing liquid nozzle N2 is a nozzle for supplying the second processing liquid L2 to the surface (upper surface) of the substrate W held by the rotation jig 5 . The second processing liquid nozzle N2 has the form of a moving nozzle that moves between a processing position and a standby position. The processing position is a position for ejecting the second processing liquid L2 to the surface of the substrate W held by the rotation jig 5, and is on standby. The position is the position set to the side of the rotation jig 5 . More specifically, the second processing liquid nozzle N2 is moved by the second nozzle moving unit 21 . The second nozzle moving unit 21 has, for example, the same configuration as that of the first nozzle moving unit 11 . That is, the second nozzle moving unit 21 includes, for example, a second swing arm 22 extending horizontally, and the second treatment liquid nozzle N2 is coupled to the swing end of the second swing arm 22 . Like the first nozzle moving unit 11 , the second nozzle moving unit 21 includes a swing drive mechanism for swinging the second swing arm 22 . The second processing liquid nozzle N2 may also operate as a scanning nozzle that scans the liquid impingement position on the substrate W while ejecting the second processing liquid L2. In this case, the processing position is fluctuated between the rotation center and the peripheral edge of the substrate W. As shown in FIG.

藥液噴嘴NC為下述噴嘴：對被保持於自轉夾具5的基板W的表面(上表面)供給洗淨液C(洗淨用的藥液)。藥液噴嘴NC係具有在處理位置與待機位置之間移動之移動噴嘴的形態，處理位置為用以對被保持於自轉夾具5的基板W的表面噴出洗淨液C之位置，待機位置為已被設定至自轉夾具5的側方之位置。更具體而言，藥液噴嘴NC係藉由第三噴嘴移動單元31而移動。第三噴嘴移動單元31係具有例如與第一噴嘴移動單元11同樣的構成。亦即，第三噴嘴移動單元31係包含例如水平地延伸的第三擺動臂32，且於第三擺動臂32的擺動端結合有藥液噴嘴NC。與第一噴嘴移動單元11同樣地，第三噴嘴移動單元31係具備用以使第三擺動臂32擺動之擺動驅動機構。如上所述，洗淨液C係例如為氨過氧化氫水混合液(例如為SC1)。藥液噴嘴NC亦可作為掃描噴嘴而動作，掃描噴嘴係一邊噴出洗淨液C一邊使基板W上的著液位置掃描。在此情形中，處理位置亦可在基板W的旋轉中心與周緣之間移動。The chemical liquid nozzle NC is a nozzle for supplying the cleaning liquid C (chemical liquid for cleaning) to the surface (upper surface) of the substrate W held by the rotation jig 5 . The chemical liquid nozzle NC is in the form of a movable nozzle that moves between a processing position and a standby position. The processing position is a position for spraying the cleaning liquid C on the surface of the substrate W held by the rotation jig 5, and the standby position is a ready position. It is set to the position on the side of the rotation jig 5 . More specifically, the chemical liquid nozzle NC is moved by the third nozzle moving unit 31 . The third nozzle moving unit 31 has, for example, the same configuration as that of the first nozzle moving unit 11 . That is, the third nozzle moving unit 31 includes, for example, a third swing arm 32 extending horizontally, and the chemical liquid nozzle NC is coupled to the swing end of the third swing arm 32 . Like the first nozzle moving unit 11 , the third nozzle moving unit 31 includes a swing drive mechanism for swinging the third swing arm 32 . As described above, the cleaning solution C is, for example, an ammonia-hydrogen peroxide-water mixed solution (for example, SC1). The chemical liquid nozzle NC may also operate as a scan nozzle that scans the liquid impingement position on the substrate W while ejecting the cleaning liquid C. In this case, the processing position can also be moved between the center of rotation of the substrate W and the peripheral edge.

清洗液噴嘴NR為下述噴嘴：對被保持於自轉夾具5的基板W的表面(上表面)供給清洗液R。在本實施形態中，清洗液噴嘴NR係具有位置固定的固定噴嘴的形態。當然，清洗液噴嘴NR亦可具有在處理位置與待機位置之間移動之移動噴嘴的形態，處理位置為用以對被保持於自轉夾具5的基板W的表面噴出清洗液R之位置，待機位置為已被設定至自轉夾具5的側方之位置。在本實施形態中，清洗液噴嘴NR係以朝基板W的旋轉中心噴出清洗液R之方式被固定。典型而言清洗液R為純水(去粒子水)。The cleaning liquid nozzle NR is a nozzle for supplying the cleaning liquid R to the surface (upper surface) of the substrate W held by the rotation jig 5 . In the present embodiment, the cleaning liquid nozzle NR is a fixed nozzle having a fixed position. Of course, the cleaning liquid nozzle NR may have the form of a moving nozzle that moves between the processing position and the standby position. The processing position is a position for ejecting the cleaning liquid R to the surface of the substrate W held by the rotation jig 5, and the standby position It is the position set to the side of the rotation jig 5 . In the present embodiment, the cleaning liquid nozzle NR is fixed so as to eject the cleaning liquid R toward the rotation center of the substrate W. As shown in FIG. Typically, the cleaning liquid R is pure water (de-particle water).

待機埠3為洗淨埠的一例，配置於第一處理液噴嘴N1的待機位置(圖3中以二點鏈線所示)且用以洗淨第一處理液噴嘴N1的噴出口10。待機埠3亦可具有用以儲留用以洗淨第一處理液噴嘴N1的噴出口10的噴嘴洗淨液之容器的形態。第一處理液噴嘴N1係在待機位置處使第一處理液噴嘴N1的噴出口10浸漬於待機埠3內的噴嘴洗淨液中。藉此，能抑制高黏度的第一處理液L1的固化從而防止第一處理液噴嘴N1的噴出口10阻塞。The standby port 3 is an example of a cleaning port, and is disposed at the standby position of the first processing liquid nozzle N1 (indicated by a two-dot chain line in FIG. 3 ) and used to clean the discharge port 10 of the first processing liquid nozzle N1 . The standby port 3 may have the form of a container for storing the nozzle cleaning liquid for cleaning the discharge port 10 of the first processing liquid nozzle N1. In the first processing liquid nozzle N1, the discharge port 10 of the first processing liquid nozzle N1 is immersed in the nozzle cleaning liquid in the standby port 3 at the standby position. Thereby, solidification of the high-viscosity first processing liquid L1 can be suppressed, and clogging of the discharge port 10 of the first processing liquid nozzle N1 can be prevented.

第一處理液噴嘴N1係經由第一處理液配管13連接於第一處理液供給源15。於第一處理液配管13的中途夾設有第一處理液閥14。第一處理液閥14係將第一處理液配管13的流路予以開閉。The first processing liquid nozzle N1 is connected to the first processing liquid supply source 15 via the first processing liquid piping 13 . A first processing liquid valve 14 is interposed in the middle of the first processing liquid piping 13 . The first processing liquid valve 14 opens and closes the flow path of the first processing liquid piping 13 .

第二處理液噴嘴N2係經由第二處理液配管23連接於第二處理液供給源25。於第二處理液配管23的中途夾設有第二處理液閥24。第二處理液閥24係將第二處理液配管23的流路予以開閉。The second processing liquid nozzle N2 is connected to the second processing liquid supply source 25 via the second processing liquid piping 23 . A second processing liquid valve 24 is interposed in the middle of the second processing liquid piping 23 . The second processing liquid valve 24 opens and closes the flow path of the second processing liquid piping 23 .

藥液噴嘴NC係經由藥液配管33連接於藥液供給源35。於藥液配管33的中途夾設有藥液閥34。藥液閥34係將藥液配管33的流路予以開閉。雖然省略圖示，然而藥液供給源35係包含：藥液槽，係儲留洗淨藥液(例如為氨過氧化氫水混合液)；以及藥液泵，係從藥液槽朝藥液噴嘴NC往藥液配管33送出藥液。於藥液槽儲留有洗淨液。更具體而言，包含氨水與過氧化氫水之洗淨用的藥液係以預定的比率被混合並調製成洗淨液且儲留於藥液槽。亦可因應需要於藥液槽或者藥液配管33配置有用以將藥液加熱至適當的溫度之加熱器。The chemical liquid nozzle NC is connected to the chemical liquid supply source 35 via the chemical liquid piping 33 . A chemical liquid valve 34 is interposed in the middle of the chemical liquid piping 33 . The chemical solution valve 34 opens and closes the flow path of the chemical solution pipe 33 . Although not shown, the chemical solution supply source 35 includes: a chemical solution tank for storing a cleaning chemical solution (for example, an aqueous mixture of ammonia and hydrogen peroxide); and a chemical solution pump for sending the chemical solution from the chemical solution tank to the chemical solution The nozzle NC sends the chemical solution to the chemical solution pipe 33 . The cleaning solution is stored in the liquid medicine tank. More specifically, a chemical solution for cleaning containing ammonia water and hydrogen peroxide water is mixed at a predetermined ratio to prepare a cleaning solution and stored in a chemical solution tank. A heater for heating the chemical solution to an appropriate temperature may also be arranged in the chemical solution tank or the chemical solution piping 33 as required.

清洗液噴嘴NR係經由清洗液配管43連接於清洗液供給源45。於清洗液配管43的中途夾設有清洗液閥44。清洗液閥44係將清洗液配管43的流路予以開閉。清洗液供給源45亦可為用以供給去離子水等清洗液之工廠內的公用設施(utility)。The cleaning liquid nozzle NR is connected to the cleaning liquid supply source 45 via the cleaning liquid piping 43 . A cleaning fluid valve 44 is interposed in the middle of the cleaning fluid piping 43 . The cleaning fluid valve 44 opens and closes the flow path of the cleaning fluid piping 43 . The cleaning liquid supply source 45 may also be a utility in the factory for supplying cleaning liquids such as deionized water.

圖4係用以說明第一處理液供給源15的構成例之圖。第一處理液供給源15係包含：第一處理液槽16，係儲留第一處理液L1；以及第一處理液泵17，係從第一處理液槽16朝第一處理液噴嘴N1往第一處理液配管13送出第一處理液L1。亦可於第一處理液配管13夾設有用以去除第一處理液L1中的異物之第一過濾器18。於第一處理液槽16儲留有預先調製的高黏度的第一處理液L1。高黏度的第一處理液L1係混合硫酸以及過氧化氫水中的一方與增黏劑調製而成。在第一處理液L1包含硫酸之情形中，較佳為於第一處理液槽16或者第一處理液配管13配置有第一處理液加熱器19。藉此，第一處理液L1被加熱至比室溫還高溫(例如120℃至130℃左右)。在第一處理液L1包含過氧化氫水之情形中，無須此種第一處理液加熱器19，室溫(環境溫度，一般而言為0℃至30℃，例如為25℃左右)的第一處理液L1係被供給至第一處理液噴嘴N1並從第一處理液噴嘴N1噴出。FIG. 4 is a diagram for explaining a configuration example of the first processing liquid supply source 15 . The first treatment liquid supply source 15 includes: a first treatment liquid tank 16 for storing the first treatment liquid L1; and a first treatment liquid pump 17 for going from the first treatment liquid tank 16 to the first treatment liquid nozzle N1. The first processing liquid pipe 13 sends out the first processing liquid L1. The first filter 18 for removing foreign matter in the first treatment liquid L1 may be interposed in the first treatment liquid pipe 13 . A preliminarily prepared high-viscosity first treatment liquid L1 is stored in the first treatment liquid tank 16 . The high-viscosity first treatment liquid L1 is prepared by mixing one of sulfuric acid and hydrogen peroxide with water and a thickener. When the first treatment liquid L1 contains sulfuric acid, it is preferable to arrange the first treatment liquid heater 19 in the first treatment liquid tank 16 or the first treatment liquid piping 13 . Thereby, the first processing liquid L1 is heated to a higher temperature than room temperature (for example, about 120° C. to 130° C.). In the case where the first treatment liquid L1 contains hydrogen peroxide water, such a first treatment liquid heater 19 is not required, and the first treatment liquid heater 19 at room temperature (ambient temperature, generally, 0°C to 30°C, for example, about 25°C) is not required. A processing liquid L1 is supplied to the first processing liquid nozzle N1 and ejected from the first processing liquid nozzle N1.

圖5係用以說明第二處理液供給源25的構成例之圖。第二處理液供給源25係包含：第二處理液槽26，係儲留第二處理液L2；以及第二處理液泵27，係從第二處理液槽26朝第二處理液噴嘴N2往第二處理液配管23送出第二處理液L2。亦可於第二處理液配管23夾設有用以去除第二處理液L2中的異物之第二過濾器28。於第二處理液槽26儲留有第二處理液L2(較佳為比第一處理液L1還低黏度的第二處理液L2)。在本實施形態中，第二處理液L2係包含硫酸以及過氧化氫水中的另一方且不包含增黏劑。在第二處理液L2包含硫酸之情形中，於第二處理液槽26或者第二處理液配管23配置有第二處理液加熱器29。藉此，第二處理液L2被加熱至比室溫還高溫(例如120℃至130℃左右)。在第二處理液L2包含過氧化氫水之情形中，無須此種第二處理液加熱器29，室溫(環境溫度，一般而言為0℃至30℃，例如為25℃左右)的第二處理液L2係被供給至第二處理液噴嘴N2並從第二處理液噴嘴N2噴出。FIG. 5 is a diagram for explaining a configuration example of the second processing liquid supply source 25 . The second treatment liquid supply source 25 includes: a second treatment liquid tank 26 for storing the second treatment liquid L2; and a second treatment liquid pump 27 for going from the second treatment liquid tank 26 to the second treatment liquid nozzle N2 The second processing liquid piping 23 sends out the second processing liquid L2. The second filter 28 for removing foreign matter in the second processing liquid L2 may be interposed in the second processing liquid piping 23 . A second treatment liquid L2 (preferably, a second treatment liquid L2 having a lower viscosity than the first treatment liquid L1 ) is stored in the second treatment liquid tank 26 . In the present embodiment, the second treatment liquid L2 contains the other one of sulfuric acid and aqueous hydrogen peroxide, and does not contain a thickener. When the second treatment liquid L2 contains sulfuric acid, a second treatment liquid heater 29 is arranged in the second treatment liquid tank 26 or the second treatment liquid piping 23 . Thereby, the second processing liquid L2 is heated to a higher temperature than room temperature (for example, about 120° C. to 130° C.). In the case where the second treatment liquid L2 contains hydrogen peroxide water, such a second treatment liquid heater 29 is not required, and the first treatment liquid heater 29 at room temperature (ambient temperature, generally, 0°C to 30°C, for example, about 25°C) is unnecessary. The second processing liquid L2 is supplied to the second processing liquid nozzle N2 and discharged from the second processing liquid nozzle N2.

圖6係用以說明與基板處理裝置100的各個部分的控制相關的構成之方塊圖。基板處理裝置100係包含控制器2作為用以控制基板處理裝置100的各個部分之控制單元。控制器2係包含處理器(CPU(Central Processing Unit；中央處理單元))2a以及記憶體2b。處理器2a係執行儲存於記憶體2b的程式，藉此實現控制器2的各種功能。換言之，控制器2係以實現各種功能之方式所構成(程式)。控制器2係控制第一處理液閥14、第二處理液閥24、藥液閥34以及清洗液閥44的開閉。再者，控制器2係控制自轉夾具5的旋轉、第一噴嘴移動單元11、第二噴嘴移動單元21以及第三噴嘴移動單元31的動作等。此外，控制器2係控制第一處理液供給源15、第二處理液供給源25以及藥液供給源35的動作。FIG. 6 is a block diagram for explaining the configuration related to the control of each part of the substrate processing apparatus 100 . The substrate processing apparatus 100 includes the controller 2 as a control unit for controlling various parts of the substrate processing apparatus 100 . The controller 2 includes a processor (Central Processing Unit (CPU)) 2a and a memory 2b. The processor 2a executes the programs stored in the memory 2b, thereby realizing various functions of the controller 2. FIG. In other words, the controller 2 is constituted (programmed) so as to realize various functions. The controller 2 controls the opening and closing of the first processing liquid valve 14 , the second processing liquid valve 24 , the chemical liquid valve 34 , and the cleaning liquid valve 44 . In addition, the controller 2 controls the rotation of the rotation jig 5, the operations of the first nozzle moving unit 11, the second nozzle moving unit 21, and the third nozzle moving unit 31, and the like. Further, the controller 2 controls the operations of the first processing liquid supply source 15 , the second processing liquid supply source 25 , and the chemical liquid supply source 35 .

藉此，控制器2係控制第一處理液L1、第二處理液L2、洗淨液C以及清洗液R的供給以及停止供給。此外，控制器2係控制基板W的旋轉(旋轉、停止旋轉、旋轉速度等)。再者，控制器2係控制第一處理液噴嘴N1、第二處理液噴嘴N2以及藥液噴嘴NC的位置。藉由此種控制，控制器2係執行上面所說明的第一處理液塗布步驟S1、第二處理液供給步驟S2、混合液處理步驟S3、清洗步驟S4、殘渣去除步驟S5以及乾燥步驟S6。Thereby, the controller 2 controls the supply and stop of the first processing liquid L1, the second processing liquid L2, the cleaning liquid C, and the cleaning liquid R. In addition, the controller 2 controls the rotation of the substrate W (rotation, stop of rotation, rotation speed, etc.). Furthermore, the controller 2 controls the positions of the first processing liquid nozzle N1, the second processing liquid nozzle N2, and the chemical liquid nozzle NC. By such control, the controller 2 executes the first treatment liquid application step S1 , the second treatment liquid supply step S2 , the mixed liquid treatment step S3 , the cleaning step S4 , the residue removal step S5 , and the drying step S6 described above.

當藉由未圖示的基板搬運機器人將未處理的基板W傳遞至自轉夾具5時，控制器2係執行第一處理液塗布步驟S1(參照圖1A以及圖1B)。亦即，控制器2係一邊以第一處理液塗布速度(例如500rpm至1500rpm)使自轉夾具5旋轉，一邊將第一處理液噴嘴N1配置於處理位置並打開第一處理液閥14，從第一處理液噴嘴N1朝基板W的表面(上表面)的旋轉中心噴出預定量的第一處理液L1。已接觸至基板W的表面的第一處理液L1係藉由離心力而朝基板W的周緣擴展，藉此擴展塗布至基板W的整面。藉此，形成有覆蓋基板W的表面的全域之第一處理液L1的塗布膜F1。When the unprocessed substrate W is transferred to the rotation jig 5 by the substrate transfer robot (not shown), the controller 2 executes the first processing liquid application step S1 (see FIGS. 1A and 1B ). That is, the controller 2 arranges the first processing liquid nozzle N1 at the processing position and opens the first processing liquid valve 14 while rotating the rotation jig 5 at the first processing liquid application speed (for example, 500 rpm to 1500 rpm). A processing liquid nozzle N1 ejects a predetermined amount of the first processing liquid L1 toward the center of rotation of the surface (upper surface) of the substrate W. As shown in FIG. The first treatment liquid L1 that has come into contact with the surface of the substrate W spreads toward the peripheral edge of the substrate W by centrifugal force, thereby spreading and coating the entire surface of the substrate W. Thereby, the coating film F1 of the 1st processing liquid L1 which covers the whole surface of the board|substrate W is formed.

在第一處理液塗布步驟S1之後，控制器2係執行第二處理液供給步驟S2(參照圖1C)。亦即，控制器2係使第一處理液噴嘴N1移動至待機位置(圖3中以二點鏈線所示)，並使第二處理液噴嘴N2移動至處理位置。第一處理液噴嘴N1係在待機位置處將噴出口10浸漬於待機埠3內的噴嘴洗淨液，藉此洗淨噴出口10。控制器2係以第二處理液處理速度(例如300rpm至800rpm)使自轉夾具5旋轉。較佳為第二處理液處理速度係與第一處理液塗布速度相等或者比第一處理液塗布速度還低速。再者，控制器2係例如以第二處理液L2著液至基板W的表面的旋轉中心之方式配置第二處理液噴嘴N2。After the first treatment liquid application step S1, the controller 2 executes the second treatment liquid supply step S2 (see FIG. 1C ). That is, the controller 2 moves the first processing liquid nozzle N1 to the standby position (indicated by a two-dot chain line in FIG. 3 ), and moves the second processing liquid nozzle N2 to the processing position. The first processing liquid nozzle N1 cleans the discharge port 10 by immersing the discharge port 10 in the nozzle cleaning liquid in the standby port 3 at the standby position. The controller 2 rotates the rotation jig 5 at the second processing liquid processing speed (eg, 300 rpm to 800 rpm). Preferably, the treatment speed of the second treatment liquid is equal to or lower than the application speed of the first treatment liquid. In addition, the controller 2 arranges the second processing liquid nozzle N2, for example, so that the second processing liquid L2 is applied to the rotation center of the surface of the substrate W. As shown in FIG.

控制器2亦可在第二處理液L2著液至基板W的表面的旋轉中心的狀態下使第二處理液噴嘴N2靜止，並進行第二處理液供給步驟S2。此外，控制器2亦可以使第二處理液L2的著液位置在基板W的表面的旋轉中心與周緣之間掃描之方式，一邊使第二處理液噴嘴N2移動一邊進行第二處理液供給步驟S2。在第二處理液噴嘴N2為噴霧噴嘴時，會有使著液位置靜止並進行第二處理液供給步驟S2之事宜是適當的之情形。此外，在第二處理液噴嘴N2為直式噴嘴時，會有使著液位置掃描並進行第二處理液供給步驟S2之事宜是適當的之情形。The controller 2 may stop the second processing liquid nozzle N2 in a state in which the second processing liquid L2 is applied to the rotation center of the surface of the substrate W, and perform the second processing liquid supply step S2. In addition, the controller 2 may perform the second processing liquid supply step while moving the second processing liquid nozzle N2 in such a manner that the impregnating position of the second processing liquid L2 is scanned between the rotation center and the peripheral edge of the surface of the substrate W S2. When the second processing liquid nozzle N2 is a spray nozzle, it may be appropriate to perform the second processing liquid supply step S2 with the liquid application position still. In addition, when the second processing liquid nozzle N2 is a straight nozzle, it may be appropriate to perform the second processing liquid supply step S2 by scanning the liquid position.

在第二處理液供給步驟S2之後，控制器2係使第二處理液噴嘴N2停止供給第二處理液L2，並將第二處理液噴嘴N2移動至待機位置。此外，控制器2係將自轉夾具5的旋轉速度設定成混合液處理速度(例如0rpm至50rpm)。混合液處理速度較佳為比第二處理液供給速度還低速，亦可為零(亦即停止旋轉)。將第二處理液L2供給至第一處理液L1的塗布膜F1上，藉此使第一處理液L1以及第二處理液L2混合從而生成SPM。因此，從供給第二處理液L2後立即開始SPM所為之處理步驟，亦即開始混合液處理步驟S3(參照圖1C以及圖1D)。由於在停止供給第二處理液L2後高黏度的第一處理液L1與第二處理液L2仍然在基板W的表面上持續混合，因此在停止供給第二處理液L2後亦持續混合液處理步驟S3。After the second processing liquid supply step S2, the controller 2 stops the supply of the second processing liquid L2 to the second processing liquid nozzle N2, and moves the second processing liquid nozzle N2 to the standby position. In addition, the controller 2 sets the rotation speed of the autorotation jig 5 to the mixed solution processing speed (eg, 0 rpm to 50 rpm). The mixed solution treatment speed is preferably lower than the second treatment solution supply speed, and may be zero (ie, the rotation is stopped). The SPM is generated by mixing the first processing liquid L1 and the second processing liquid L2 by supplying the second processing liquid L2 onto the coating film F1 of the first processing liquid L1. Therefore, immediately after the supply of the second processing liquid L2, the processing step by the SPM, that is, the mixed liquid processing step S3 (refer to FIGS. 1C and 1D ) is started. Since the high-viscosity first processing liquid L1 and the second processing liquid L2 continue to be mixed on the surface of the substrate W after the supply of the second processing liquid L2 is stopped, the mixed liquid processing step is continued even after the supply of the second processing liquid L2 is stopped. S3.

當停止供給第二處理液L2後經過預先設定的反應時間時，控制器2係執行清洗步驟S4(參照圖1E)。亦即，控制器2係將清洗液噴嘴NR移動至處理位置。接著，控制器2係以預定的清洗速度(例如300rpm至1000rpm)使自轉夾具5旋轉。在此狀態下，控制器2係打開清洗液閥44，使清洗液噴嘴NR朝基板W噴出清洗液R。在本實施形態中，基板W的表面中的清洗液R的著液位置係固定於基板W的中心。然而，亦可使用移動噴嘴的形態的清洗液噴嘴NR將清洗液R的著液位置在基板W的中心與周緣之間移動(掃描)。When the preset reaction time elapses after the supply of the second treatment liquid L2 is stopped, the controller 2 executes the cleaning step S4 (see FIG. 1E ). That is, the controller 2 moves the cleaning liquid nozzle NR to the processing position. Next, the controller 2 rotates the rotation jig 5 at a predetermined cleaning speed (eg, 300 rpm to 1000 rpm). In this state, the controller 2 opens the cleaning solution valve 44 and causes the cleaning solution nozzle NR to eject the cleaning solution R toward the substrate W. As shown in FIG. In the present embodiment, the impingement position of the cleaning liquid R on the surface of the substrate W is fixed at the center of the substrate W. As shown in FIG. However, the cleaning liquid nozzle NR in the form of a moving nozzle may be used to move (scan) the impingement position of the cleaning liquid R between the center and the periphery of the substrate W.

經過預先設定的清洗處理時間後，控制器2係停止從清洗液噴嘴NR噴出清洗液R，結束清洗步驟S4，將清洗液噴嘴NR移動至待機位置。After the preset cleaning processing time has elapsed, the controller 2 stops spraying the cleaning liquid R from the cleaning liquid nozzle NR, ends the cleaning step S4, and moves the cleaning liquid nozzle NR to the standby position.

接著，控制器2係執行殘渣去除步驟S5(參照圖1F以及圖1G)。亦即，控制器2係將藥液噴嘴NC移動至處理位置。接著，控制器2係以預定的洗淨液處理速度(例如500rpm至1500rpm)使自轉夾具5旋轉。在此種狀態下，控制器2係打開藥液閥34，使洗淨液C(例如氨過氧化氫水混合液)朝基板W噴出，執行洗淨液供給步驟S51(參照圖1F)。基板W的表面中的洗淨液C的著液位置係可固定於基板W的中心，亦可在基板W的中心與周緣之間移動(掃描)。在供給洗淨液C達至預先設定的時間後，控制器2係停止從藥液噴嘴NC噴出洗淨液C，使藥液噴嘴NC移動至待機位置。Next, the controller 2 executes the residue removal step S5 (see FIGS. 1F and 1G ). That is, the controller 2 moves the chemical liquid nozzle NC to the processing position. Next, the controller 2 rotates the rotation jig 5 at a predetermined cleaning liquid processing speed (for example, 500 rpm to 1500 rpm). In this state, the controller 2 opens the chemical solution valve 34 to eject the cleaning solution C (eg, a mixture of ammonia and hydrogen peroxide) toward the substrate W, and executes the cleaning solution supply step S51 (see FIG. 1F ). The impingement position of the cleaning solution C on the surface of the substrate W may be fixed at the center of the substrate W, or may be moved (scanned) between the center and the periphery of the substrate W. When the cleaning liquid C is supplied for a predetermined time, the controller 2 stops the spraying of the cleaning liquid C from the chemical liquid nozzle NC, and moves the chemical liquid nozzle NC to the standby position.

接著，控制器2係執行洗淨液處理後的清洗步驟S52(參照圖1G)。清洗步驟S52亦可實質性地與混合液處理步驟S3後的清洗步驟S4(參照圖1E)相同。Next, the controller 2 executes the cleaning step S52 after the cleaning liquid processing (see FIG. 1G ). The cleaning step S52 may be substantially the same as the cleaning step S4 (see FIG. 1E ) after the mixed solution processing step S3 .

在經過預先設定的清洗處理時間後，控制器2係停止從清洗液噴嘴NR噴出清洗液R，結束清洗步驟S52。接著，控制器2係將自轉夾具5加速至乾燥旋轉速度(例如2500rpm至4000rpm)，執行用以甩離基板W上的清洗液R之乾燥步驟S6(旋乾)(參照圖1H)。在進行乾燥步驟S6達至預定時間後，控制器2係停止旋轉自轉夾具5並結束處理。After the preset cleaning processing time has elapsed, the controller 2 stops the spraying of the cleaning liquid R from the cleaning liquid nozzle NR, and ends the cleaning step S52. Next, the controller 2 accelerates the rotation jig 5 to a drying rotation speed (eg, 2500 rpm to 4000 rpm), and executes the drying step S6 (spin-drying) for throwing off the cleaning solution R on the substrate W (refer to FIG. 1H ). After the drying step S6 has been performed for a predetermined time, the controller 2 stops the rotation of the autorotating jig 5 and ends the process.

處理完畢的基板W係被基板搬運機器人(未圖示)從自轉夾具5接取並從處理腔室1搬出。The processed substrate W is picked up from the rotation jig 5 by a substrate transfer robot (not shown) and carried out from the processing chamber 1 .

圖7係用以說明第一處理液供給源15的其他構成例之圖。FIG. 7 is a diagram for explaining another configuration example of the first processing liquid supply source 15 .

在上面所說明的圖4所示的第一處理液供給源15的構成例中，能將調整完畢的第一處理液L1供給至第一處理液槽16或者在第一處理液槽16內調製第一處理液L1。具體而言，將硫酸或者過氧化氫水中的一方與增黏劑混合且調製而成的第一處理液L1供給至第一處理液槽16或者在第一處理液槽16內進行此種調製。In the configuration example of the first processing liquid supply source 15 shown in FIG. 4 described above, the adjusted first processing liquid L1 can be supplied to the first processing liquid tank 16 or prepared in the first processing liquid tank 16 . The first treatment liquid L1. Specifically, the first treatment liquid L1 prepared by mixing one of sulfuric acid or aqueous hydrogen peroxide and a thickener is supplied to the first treatment liquid tank 16 or prepared in the first treatment liquid tank 16 .

相對於此，在圖7所示的第一處理液供給源15的構成例中，硫酸或者過氧化氫水中的一方與增黏劑係在第一處理液配管13的中途混合。On the other hand, in the configuration example of the first treatment liquid supply source 15 shown in FIG. 7 , either sulfuric acid or hydrogen peroxide water and the thickener are mixed in the middle of the first treatment liquid piping 13 .

具體而言，於第一處理液配管13連接有：第一處理液成分配管131，係供給屬於硫酸或者過氧化氫水中的一方之第一處理液成分L1a；以及增黏劑配管132，係供給液體狀的增黏劑。因此，第一處理液成分L1a與增黏劑係在第一處理液配管13合流並混合。為了促進混合，於第一處理液配管13夾設有沿線混合器(in-line mixer)133。Specifically, the first treatment liquid pipe 13 is connected to: a first treatment liquid component distribution pipe 131 for supplying the first treatment liquid component L1a belonging to either sulfuric acid or hydrogen peroxide water; and a thickener pipe 132 for supplying Liquid tackifier. Therefore, the 1st process liquid component L1a and the thickener system merge in the 1st process liquid piping 13, and are mixed. In order to promote mixing, an in-line mixer 133 is interposed between the first treatment liquid piping 13 .

沿線混合器133係具有例如攪拌構件，攪拌於第一處理液配管13流動的流體，藉此使第一處理液成分L1a與增黏劑充分地混合並輔助高黏度的第一處理液L1的生成。不僅是此種攪拌型的沿線混合器，亦可使用下述分散混合型的沿線混合器：在使第一處理液成分L1a與增黏劑合流時，從混合噴嘴對於主流路流動的流體分散地噴出流體從而分散地混合。The mixer 133 along the line has, for example, a stirring member, and agitates the fluid flowing in the first processing liquid piping 13, thereby sufficiently mixing the first processing liquid component L1a with the thickener and assisting the production of the high-viscosity first processing liquid L1 . Not only such a stirring-type in-line mixer, but also a dispersing-mixing-type in-line mixer may be used: when the first treatment liquid component L1a is combined with the thickener, the fluid flowing from the mixing nozzle is dispersed in the main flow path. The fluid is ejected for dispersive mixing.

此構成例的第一處理液供給源15係在增黏劑為液體或者乳液之情形中為適當。在增黏劑為固體(粉體等)之情形中，圖4所示的構成的第一處理液供給源15為適當。The first processing liquid supply source 15 of this configuration example is suitable when the thickener is a liquid or an emulsion. When the thickener is a solid (powder or the like), the first processing liquid supply source 15 having the configuration shown in FIG. 4 is suitable.

如上所述，依據本實施形態，添加了增黏劑作為高黏度的液體之第一處理液L1係被塗布至基板W的表面(上表面)的全域。藉此，能抑制第一處理液L1的消耗量，並能使第一處理液L1均勻地遍及且密著於基板W的表面的全域。對塗布有第一處理液L1的基板W的表面供給第二處理液L2，藉此第一處理液L1以及第二處理液L2在基板W上混合從而生成SPM。由於第一處理液L1均勻且無遺漏地遍及且密著於基板W的表面的全域，因此能使SPM均勻且無遺漏地遍及至基板W的表面的全域。因此，能在基板W的表面的全域使SPM所為之處理(使阻劑腐蝕之處理)均勻地持續進展。而且，由於第一處理液L1以及第二處理液L2在基板W上混合，因此能利用混合時的反應熱，藉此能夠有效率地處理。SPM所為之處理係能藉由對基板W的表面供給清洗液R來置換SPM從而停止。As described above, according to the present embodiment, the first treatment liquid L1 to which the thickener is added as a high-viscosity liquid is applied to the entire surface (upper surface) of the substrate W. Thereby, the consumption amount of the 1st processing liquid L1 can be suppressed, and the 1st processing liquid L1 can be uniformly spread and adhered to the whole area of the surface of the substrate W. As shown in FIG. By supplying the second processing liquid L2 to the surface of the substrate W to which the first processing liquid L1 has been applied, the first processing liquid L1 and the second processing liquid L2 are mixed on the substrate W to generate SPM. Since the first processing liquid L1 spreads and adheres to the entire surface of the substrate W uniformly and without omission, the SPM can be uniformly spread over the entire surface of the substrate W without any omission. Therefore, the processing by SPM (processing of etching the resist) can be uniformly progressed over the entire surface of the substrate W. As shown in FIG. Furthermore, since the first processing liquid L1 and the second processing liquid L2 are mixed on the substrate W, the reaction heat at the time of mixing can be utilized, thereby enabling efficient processing. The processing by the SPM can be stopped by supplying the cleaning liquid R to the surface of the substrate W to replace the SPM.

由於只要第二處理液L2為較低黏度(例如比第一處理液L1還低黏度)則第一處理液L1以及第二處理液L2的混合即能迅速地持續進展，因此能使屬於第一處理液L1以及第二處理液L2的混合液之SPM迅速地生成。藉此，能夠更有效率地處理。Since the mixing of the first treatment liquid L1 and the second treatment liquid L2 can continue to progress rapidly as long as the second treatment liquid L2 has a relatively low viscosity (for example, a viscosity lower than that of the first treatment liquid L1 ), the first treatment liquid L2 can be The SPM of the mixed liquid of the treatment liquid L1 and the second treatment liquid L2 is rapidly generated. Thereby, it can process more efficiently.

由於第一處理液L1的黏度能藉由增黏劑適當地調整，因此能考慮塗布至基板W的表面時的延伸性、基板W的表面中的塗布膜F1的保持性、與第二處理液L2的混合程度等來設定適當的黏度。藉此，能更減少第一處理液L1的消耗量並對基板W施予均勻的處理。Since the viscosity of the first treatment liquid L1 can be appropriately adjusted by a tackifier, the stretchability when applied to the surface of the substrate W, the retention of the coating film F1 on the surface of the substrate W, and the second treatment liquid can be considered. The appropriate viscosity can be set by the mixing degree of L2, etc. Thereby, the consumption amount of the first processing liquid L1 can be further reduced, and the substrate W can be uniformly processed.

尤其，由於藉由使用包含過氧化氫水以及增黏劑的液體作為第一處理液L1且使用於包含硫酸的液體作為第二處理液L2能減少過氧化氫水的消耗量，故較佳。In particular, it is preferable to use a liquid containing hydrogen peroxide water and a thickener as the first treatment liquid L1 and a liquid containing sulfuric acid as the second treatment liquid L2 to reduce the consumption of the hydrogen peroxide water.

只要在第一處理液塗布步驟S1中於基板W的表面形成有塗布膜F1(例如凝膠狀的塗布膜)，即能使第一處理液L1確實地密著於基板W的表面的全域。藉此，由於能使供給第二處理液L2而成的SPM確實地密著於基板W的表面的全域，因此能夠有效率且均勻地處理。When the coating film F1 (eg, a gel-like coating film) is formed on the surface of the substrate W in the first treatment liquid application step S1 , the first treatment liquid L1 can be reliably adhered to the entire surface of the substrate W. Thereby, since the SPM formed by supplying the second processing liquid L2 can be reliably adhered to the entire surface of the substrate W, it can be processed efficiently and uniformly.

較佳為第二處理液供給步驟S2係在停止供給第一處理液L1(供給新的液體)的狀態下進行。藉此，能確實地減少第一處理液L1的消耗量。而且，由於能將第二處理液L2供給至第一處理液L1的塗布膜F1上，因此能抑制因為第二處理液L2的流動將第一處理液L1推流至基板W外部。Preferably, the second treatment liquid supply step S2 is performed in a state in which the supply of the first treatment liquid L1 is stopped (a new liquid is supplied). Thereby, the consumption amount of the 1st processing liquid L1 can be reduced reliably. Furthermore, since the second processing liquid L2 can be supplied onto the coating film F1 of the first processing liquid L1, the first processing liquid L1 can be suppressed from being pushed to the outside of the substrate W due to the flow of the second processing liquid L2.

較佳為在混合液處理步驟S3的至少一部分的期間中停止供給第二處理液L2(供給新的液體)。藉此，能更抑制第二處理液L2的消耗量。亦即，能藉由在第一處理液L1的塗布膜F1上保持有第二處理液L2的液膜的狀態下第一處理液L1以及第二處理液L2的混合持續進展之覆液處理，使屬於第一處理液L1以及第二處理液L2的混合液之SPM所為之基板處理持續進展。此時，由於皆未供給第一處理液L1以及第二處理液L2，因此亦能減少第一處理液L1以及第二處理液L2的消耗量。It is preferable to stop supplying the second processing liquid L2 (supply a new liquid) during at least a part of the mixed liquid processing step S3. Thereby, the consumption amount of the 2nd processing liquid L2 can be suppressed more. That is, by the liquid coating process in which the mixing of the first processing liquid L1 and the second processing liquid L2 continues to progress in a state where the liquid film of the second processing liquid L2 is held on the coating film F1 of the first processing liquid L1, The substrate processing by the SPM, which is the mixed liquid of the first processing liquid L1 and the second processing liquid L2, continues to progress. At this time, since neither the first processing liquid L1 nor the second processing liquid L2 is supplied, the consumption of the first processing liquid L1 and the second processing liquid L2 can also be reduced.

圖8係用以說明本發明的第二實施形態的基板處理方法之步驟圖。在本實施形態中，於第一處理液塗布步驟S1之前執行前處理步驟S0。之後的第一處理液塗布步驟S1至乾燥步驟S6係與前述第一實施形態(參照圖1A至圖1H)同樣。FIG. 8 is a step diagram for explaining the substrate processing method according to the second embodiment of the present invention. In the present embodiment, the preprocessing step S0 is performed before the first treatment liquid application step S1. The subsequent first treatment liquid application step S1 to drying step S6 are the same as those of the aforementioned first embodiment (see FIGS. 1A to 1H ).

前處理步驟S0為下述步驟：在將高黏度的第一處理液L1塗布至基板W的表面之前，將第二處理液(較佳為比第一處理液L1還低黏度的第二處理液L2)供給至基板W的表面。在前處理步驟S0中，基板處理裝置100亦可與第二處理液供給步驟S2實質性同樣地動作。The pre-processing step S0 is a step of: before applying the high-viscosity first processing liquid L1 to the surface of the substrate W, applying a second processing liquid (preferably a second processing liquid with a lower viscosity than the first processing liquid L1) L2) is supplied to the surface of the substrate W. In the preprocessing step S0, the substrate processing apparatus 100 may operate substantially in the same manner as in the second processing liquid supply step S2.

在前處理步驟S0中，由於基板W未存在有第一處理液L1的塗布膜F1，因此第二處理液L2係被供給至基板W的表面而不是被供給至第一處理液L1的塗布膜F1上。控制器2係以第二處理液處理速度使自轉夾具5旋轉，並在此種狀態下使第二處理液噴嘴N2朝基板W的表面噴出第二處理液L2。In the preprocessing step S0, since the coating film F1 of the first processing liquid L1 does not exist on the substrate W, the second processing liquid L2 is supplied to the surface of the substrate W instead of the coating film of the first processing liquid L1. on F1. The controller 2 rotates the rotation jig 5 at the second processing liquid processing speed, and causes the second processing liquid nozzle N2 to eject the second processing liquid L2 toward the surface of the substrate W in this state.

在此種前處理步驟S0之後，第二處理液噴嘴N2移動至待機位置，執行第一處理液塗布步驟S1。由於供給至基板W的表面的第一處理液L1係與已經存在於基板W上的第二處理液L2接觸，因此產生第一處理液L1以及第二處理液L2的混合(SPM反應)。因此，能在供給第一處理液L1後立即在基板W的表面上開始混合液處理步驟S3。After such preprocessing step S0, the second processing liquid nozzle N2 is moved to the standby position, and the first processing liquid application step S1 is executed. Since the first processing liquid L1 supplied to the surface of the substrate W is in contact with the second processing liquid L2 already existing on the substrate W, mixing of the first processing liquid L1 and the second processing liquid L2 (SPM reaction) occurs. Therefore, the mixed liquid processing step S3 can be started on the surface of the substrate W immediately after the supply of the first processing liquid L1.

由於在第一處理液塗布步驟S1之前執行前處理步驟S0，藉此能容易將高黏度的第一處理液L1擴展塗布至基板W的表面的全域且促進基板W的表面中的混合液處理，因此能進行更有效率的阻劑剝離處理。Since the pretreatment step S0 is performed before the first treatment liquid application step S1, the high-viscosity first treatment liquid L1 can be easily spread and applied to the entire surface of the substrate W and the mixed liquid treatment in the surface of the substrate W can be promoted, Therefore, a more efficient resist stripping treatment can be performed.

以上，雖然已經說明本發明的兩個實施形態，然而本發明亦能進一步地以其他的形態來實施。例如，在上述實施形態中，主要說明了將室溫的過氧化氫水以及比過氧化氫水還高溫的硫酸供給至基板W的表面之處理。然而，亦可將室溫的過氧化氫水以及室溫的硫酸供給至基板W的表面。在此情形中，亦能藉由過氧化氫水以及硫酸混合時的發熱反應在基板W上生成高溫的SPM從而使基板W的表面的阻劑腐蝕。為了促進基板W上的反應，亦可藉由加熱器加熱基板W。加熱器係可內置於自轉夾具5，亦可使用鹵加熱器等另外的熱源。As mentioned above, although the two embodiments of the present invention have been described, the present invention can be further implemented in other forms. For example, in the above-described embodiment, the treatment of supplying the surface of the substrate W with hydrogen peroxide water at room temperature and sulfuric acid higher than the hydrogen peroxide water is mainly described. However, room temperature hydrogen peroxide water and room temperature sulfuric acid may also be supplied to the surface of the substrate W. In this case, the resist on the surface of the substrate W can be corroded by generating high-temperature SPM on the substrate W by the exothermic reaction when the hydrogen peroxide water and the sulfuric acid are mixed. In order to promote the reaction on the substrate W, the substrate W may also be heated by a heater. The heater system may be built in the rotation jig 5, or another heat source such as a halogen heater may be used.

此外，在上述實施形態中，雖然已說明用以逐片地保持並處理基板W之葉片式的基板處理，然而本發明亦可應用用以對複數片基板總括處理之批次(batch)式的基板處理。In addition, in the above-mentioned embodiment, although the blade-type substrate processing for holding and processing the substrates W one by one has been described, the present invention can also be applied to a batch-type substrate processing for collectively processing a plurality of substrates. Substrate processing.

雖然已經詳細地說明本發明的實施形態，然而這些實施形態僅為用以明瞭本發明的技術內容之具體例，本發明不應被解釋成限定在這些具體例，本發明僅被隨附的申請專利範圍所限定。Although the embodiments of the present invention have been described in detail, these embodiments are only specific examples for clarifying the technical content of the present invention, the present invention should not be construed as being limited to these specific examples, and the present invention is only covered by the accompanying application limited by the scope of the patent.

1:處理腔室 2:控制器 2a:處理器 2b:記憶體 3:待機埠 5:自轉夾具 10:噴出口 11:第一噴嘴移動單元 12:第一擺動臂 13:第一處理液配管 14:第一處理液閥 15:第一處理液供給源 16:第一處理液槽 17:第一處理液泵 18:第一過濾器 19:第一處理液加熱器 21:第二噴嘴移動單元 22:第二擺動臂 23:第二處理液配管 24:第二處理液閥 25:第二處理液供給源 26:第二處理液槽 27:第二處理液泵 28:第二過濾器 29:第二處理液加熱器 31:第三噴嘴移動單元 32:第三擺動臂 33:藥液配管 34:藥液閥 35:藥液供給源 43:清洗液配管 44:清洗液閥 45:清洗液供給源 51:旋轉軸 52:自轉基座 53:自轉馬達 54:夾持銷 100:基板處理裝置 131:第一處理液成分配管 132:增黏劑配管 133:沿線混合器 A:旋轉軸線 C:洗淨液 F1:塗布膜 L1:第一處理液 L1a:第一處理液成分 L2:第二處理液 N1:第一處理液噴嘴 N2:第二處理液噴嘴 NC:藥液噴嘴 NR:清洗液噴嘴 R:清洗液 S0:前處理步驟 S1:第一處理液塗布步驟 S2:第二處理液供給步驟 S3:混合液處理步驟 S4:清洗步驟 S5:殘渣去除步驟 S6:乾燥步驟 S51:洗淨液供給步驟 S52:清洗步驟 W:基板 1: Processing chamber 2: Controller 2a: Processor 2b: memory 3: Standby port 5: Rotation fixture 10: spout 11: The first nozzle moving unit 12: The first swing arm 13: The first treatment liquid piping 14: The first treatment fluid valve 15: The first treatment liquid supply source 16: The first treatment tank 17: The first treatment liquid pump 18: First Filter 19: The first treatment liquid heater 21: Second nozzle moving unit 22: Second swing arm 23: Second treatment liquid piping 24: The second treatment fluid valve 25: The second treatment liquid supply source 26: The second treatment liquid tank 27: The second treatment liquid pump 28: Second filter 29: Second treatment liquid heater 31: The third nozzle moving unit 32: Third swing arm 33: Chemical liquid piping 34: liquid medicine valve 35: Liquid supply source 43: Cleaning fluid piping 44: Cleaning fluid valve 45: Cleaning fluid supply source 51: Rotary axis 52: Rotation base 53: Autorotation Motor 54: Clamping pin 100: Substrate processing device 131: The first treatment liquid component distribution pipe 132: Tackifier piping 133: Mixer along the line A: Rotation axis C: cleaning solution F1: Coating film L1: The first treatment liquid L1a: Component of the first treatment liquid L2: The second treatment liquid N1: The first treatment liquid nozzle N2: Second treatment liquid nozzle NC: Liquid Nozzle NR: Cleaning fluid nozzle R: cleaning fluid S0: preprocessing step S1: first treatment liquid coating step S2: second treatment liquid supply step S3: Mixed solution processing step S4: Cleaning step S5: Residue removal step S6: drying step S51: cleaning solution supply step S52: Cleaning step W: substrate

[圖1A至圖1E]係用以說明本發明的實施形態之一的基板處理方法之步驟圖。 [圖1F至圖1H]係用以說明前述基板處理方法之步驟圖。 [圖2A至圖2D]係用以說明主要的步驟中的基板表面的狀態的例子之圖解性的剖視圖。 [圖3]係用以說明用以執行前述基板處理方法的基板處理裝置的構成例之圖解性的剖視圖。 [圖4]係用以說明第一處理液供給源的構成例之圖。 [圖5]係用以說明第二處理液供給源的構成例之圖。 [圖6]係用以說明與前述基板處理裝置的各個部分的控制相關的構成之方塊圖。 [圖7]係用以說明第一處理液供給源的其他構成例之圖。 [圖8]係用以說明本發明的第二實施形態的基板處理方法之步驟圖。 1A to 1E are step diagrams for explaining a substrate processing method according to one embodiment of the present invention. 1F to 1H are step diagrams for explaining the aforementioned substrate processing method. 2A to 2D are schematic cross-sectional views for explaining an example of the state of the substrate surface in the main steps. 3 is a schematic cross-sectional view for explaining a configuration example of a substrate processing apparatus for executing the aforementioned substrate processing method. 4] It is a figure for demonstrating the structural example of a 1st process liquid supply source. 5] It is a figure for demonstrating the structural example of a 2nd process liquid supply source. FIG. 6 is a block diagram for explaining the configuration related to the control of the respective parts of the substrate processing apparatus. [ Fig. 7] Fig. 7 is a diagram for explaining another configuration example of the first processing liquid supply source. 8] It is a process diagram for demonstrating the board|substrate processing method of 2nd Embodiment of this invention.

5:自轉夾具 5: Rotation fixture

A:旋轉軸線 A: Rotation axis

F1:塗布膜 F1: Coating film

L1:第一處理液 L1: The first treatment liquid

L2:第二處理液 L2: The second treatment liquid

N1:第一處理液噴嘴 N1: The first treatment liquid nozzle

N2:第二處理液噴嘴 N2: Second treatment liquid nozzle

NR:清洗液噴嘴 NR: Cleaning fluid nozzle

R:清洗液 R: cleaning fluid

S1:第一處理液塗布步驟 S1: first treatment liquid coating step

S2:第二處理液供給步驟 S2: second treatment liquid supply step

S3:混合液處理步驟 S3: Mixed solution processing step

S4:清洗步驟 S4: Cleaning step

W:基板 W: substrate

Claims (15)

一種基板處理方法，係包含： 第一處理液供給步驟，係將包含硫酸以及過氧化氫水中的一方之第一處理液塗布至基板的表面； 第二處理液供給步驟，係將包含硫酸以及過氧化氫水中的另一方且黏度比前述第一處理液還低之第二處理液供給至塗布有前述第一處理液的前述基板的表面； 混合液處理步驟，係以硫酸過氧化氫水混合液處理前述基板的表面，前述硫酸過氧化氫水混合液為前述第一處理液以及前述第二處理液在前述基板的表面混合從而生成；以及 清洗步驟，係在前述混合液處理步驟之後，對前述基板供給清洗液，從前述基板的表面沖洗前述硫酸過氧化氫水混合液。 A substrate processing method, comprising: The first treatment liquid supply step is to apply a first treatment liquid containing one of sulfuric acid and hydrogen peroxide water to the surface of the substrate; The second treatment liquid supply step is to supply the second treatment liquid containing the other one of sulfuric acid and aqueous hydrogen peroxide and having a lower viscosity than the first treatment liquid to the surface of the substrate coated with the first treatment liquid; The mixed solution treatment step is to treat the surface of the substrate with a sulfuric acid hydrogen peroxide mixed solution, wherein the sulfuric acid hydrogen peroxide mixed solution is generated by mixing the first treatment solution and the second treatment solution on the surface of the substrate; and In the cleaning step, after the mixed solution treatment step, a cleaning solution is supplied to the substrate to rinse the sulfuric acid-hydrogen peroxide-water mixed solution from the surface of the substrate. 如請求項1所記載之基板處理方法，其中前述第一處理液係包含增黏劑。The substrate processing method according to claim 1, wherein the first processing liquid contains a tackifier. 一種基板處理方法，係包含： 第一處理液供給步驟，係將包含有增黏劑的第一處理液塗布至基板的表面； 第二處理液供給步驟，係將第二處理液供給至塗布有前述第一處理液的前述基板的表面； 混合液處理步驟，係以硫酸過氧化氫水混合液處理前述基板的表面，前述硫酸過氧化氫水混合液為前述第一處理液以及前述第二處理液在前述基板的表面混合從而生成；以及 清洗步驟，係在前述混合液處理步驟之後，對前述基板供給清洗液並從前述基板的表面沖洗前述硫酸過氧化氫水混合液。 A substrate processing method, comprising: The first treatment liquid supply step is to apply the first treatment liquid containing the tackifier to the surface of the substrate; The second treatment liquid supply step is to supply the second treatment liquid to the surface of the substrate coated with the first treatment liquid; The mixed solution treatment step is to treat the surface of the substrate with a sulfuric acid hydrogen peroxide mixed solution, wherein the sulfuric acid hydrogen peroxide mixed solution is generated by mixing the first treatment solution and the second treatment solution on the surface of the substrate; and In the cleaning step, after the mixed solution treatment step, a cleaning solution is supplied to the substrate to rinse the sulfuric acid-hydrogen peroxide-water mixed solution from the surface of the substrate. 一種基板處理方法，係包含： 第一處理液供給步驟，係將包含過氧化氫水以及增黏劑的第一處理液塗布至基板的表面； 第二處理液供給步驟，係將包含硫酸的第二處理液供給至塗布有前述第一處理液的前述基板的表面； 混合液處理步驟，係以硫酸過氧化氫水混合液處理前述基板的表面，前述硫酸過氧化氫水混合液為前述第一處理液以及前述第二處理液在前述基板的表面混合從而生成；以及 清洗步驟，係在前述混合液處理步驟之後，對前述基板供給清洗液並從前述基板的表面沖洗前述硫酸過氧化氫水混合液。 A substrate processing method, comprising: The first treatment liquid supply step is to apply the first treatment liquid containing hydrogen peroxide water and a tackifier to the surface of the substrate; The second treatment liquid supply step is to supply a second treatment liquid containing sulfuric acid to the surface of the substrate coated with the first treatment liquid; The mixed solution treatment step is to treat the surface of the substrate with a sulfuric acid hydrogen peroxide mixed solution, wherein the sulfuric acid hydrogen peroxide mixed solution is generated by mixing the first treatment solution and the second treatment solution on the surface of the substrate; and In the cleaning step, after the mixed solution treatment step, a cleaning solution is supplied to the substrate to rinse the sulfuric acid-hydrogen peroxide-water mixed solution from the surface of the substrate. 如請求項2至4中任一項所記載之基板處理方法，其中前述增黏劑係包含從由聚乙烯吡咯烷酮、聚丙烯酸、聚丙烯酸鈉、聚丙烯酸銨、交聯型聚丙烯酸、交聯型聚丙烯酸鈉、交聯型丙烯系聚合物以及羧酸系共聚物所組成的群組所選擇的至少一種。The substrate processing method according to any one of claims 2 to 4, wherein the tackifier comprises polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, cross-linked polyacrylic acid, cross-linked At least one selected from the group consisting of sodium polyacrylate, cross-linked propylene-based polymer and carboxylic acid-based copolymer. 如請求項1至4中任一項所記載之基板處理方法，其中前述第二處理液係不包含增黏劑。The substrate processing method according to any one of claims 1 to 4, wherein the second processing liquid system does not contain a tackifier. 如請求項1至4中任一項所記載之基板處理方法，其中在前述第一處理液供給步驟中，前述第一處理液被塗布至前述基板的表面，從而形成覆蓋前述基板的表面的全域之前述第一處理液的塗布膜。The substrate processing method according to any one of claims 1 to 4, wherein in the first processing liquid supply step, the first processing liquid is applied to the surface of the substrate so as to form an entire area covering the surface of the substrate the coating film of the aforementioned first treatment liquid. 如請求項1至4中任一項所記載之基板處理方法，其中在前述第二處理液供給步驟中，對前述第一處理液的塗布膜的表面供給前述第二處理液。The substrate processing method according to any one of claims 1 to 4, wherein in the second processing liquid supply step, the second processing liquid is supplied to the surface of the coating film of the first processing liquid. 如請求項1至4中任一項所記載之基板處理方法，其中前述第二處理液供給步驟係在停止朝前述基板的表面供給前述第一處理液的狀態下開始。The substrate processing method according to any one of claims 1 to 4, wherein the second processing liquid supply step is started in a state where the supply of the first processing liquid to the surface of the substrate is stopped. 如請求項1至4中任一項所記載之基板處理方法，其中前述混合液處理步驟的至少一部分的期間係與前述第二處理液供給步驟的至少一部分的期間重複。The substrate processing method according to any one of Claims 1 to 4, wherein at least a part of the period of the mixed liquid processing step is overlapped with at least a part of the period of the second processing liquid supply step. 如請求項1至4中任一項所記載之基板處理方法，其中在前述混合液處理步驟的至少一部分的期間中停止朝前述基板的表面供給前述第二處理液。The substrate processing method according to any one of claims 1 to 4, wherein supply of the second processing liquid to the surface of the substrate is stopped during at least a part of the mixed liquid processing step. 如請求項1至4中任一項所記載之基板處理方法，其中交互地反復執行前述第一處理液供給步驟以及前述第二處理液供給步驟。The substrate processing method according to any one of claims 1 to 4, wherein the first processing liquid supply step and the second processing liquid supply step are alternately and repeatedly performed. 一種基板處理裝置，係用以實施如請求項1至4中任一項所記載之基板處理方法，並包含： 基板保持單元，係保持基板； 第一處理液噴嘴，係對被前述基板保持單元保持的基板供給前述第一處理液； 第二處理液噴嘴，係對被前述基板保持單元保持的基板供給前述第二處理液； 清洗液噴嘴，係對被前述基板保持單元保持的基板供給前述清洗液；以及 控制單元，係控制從前述第一處理液噴嘴供給前述第一處理液並執行前述第一處理液供給步驟，控制前述第二處理液噴嘴供給前述第二處理液並執行前述第二處理液供給步驟，控制前述清洗液噴嘴供給前述清洗液並執行前述清洗步驟。 A substrate processing apparatus for implementing the substrate processing method as described in any one of claims 1 to 4, comprising: a substrate holding unit for holding the substrate; a first processing liquid nozzle for supplying the first processing liquid to the substrate held by the substrate holding unit; a second processing liquid nozzle for supplying the second processing liquid to the substrate held by the substrate holding unit; a cleaning liquid nozzle for supplying the cleaning liquid to the substrate held by the substrate holding unit; and A control unit controls the supply of the first treatment liquid from the first treatment liquid nozzle and executes the first treatment liquid supply step, and controls the second treatment liquid nozzle to supply the second treatment liquid and executes the second treatment liquid supply step , control the cleaning liquid nozzle to supply the cleaning liquid and execute the cleaning step. 如請求項13所記載之基板處理裝置，其中前述基板保持單元係包含：自轉夾具，係將基板的表面朝向上方水平地保持並旋轉； 前述控制單元係在前述第一處理液供給步驟中控制從前述第一處理液噴嘴供給前述第一處理液並控制前述自轉夾具的旋轉，並將前述第一處理液旋轉塗布至前述基板的表面。 The substrate processing apparatus according to claim 13, wherein the substrate holding unit comprises: a rotation jig that holds and rotates the surface of the substrate horizontally upward; The control unit controls the supply of the first treatment liquid from the first treatment liquid nozzle and the rotation of the rotation jig in the first treatment liquid supply step, and spin-coats the first treatment liquid on the surface of the substrate. 如請求項13所記載之基板處理裝置，其中進一步包含： 噴嘴移動單元，係在處理位置與待機位置之間移動前述第一處理液噴嘴，前述處理位置為用以對被前述基板保持單元保持的基板供給處理液之位置，前述待機位置為已從前述處理位置退避之位置；以及 洗淨埠，係在前述待機位置中使前述第一處理液噴嘴的噴出口浸漬於噴嘴洗淨液中。 The substrate processing apparatus according to claim 13, further comprising: a nozzle moving unit for moving the first processing liquid nozzle between a processing position, which is a position for supplying the processing liquid to the substrate held by the substrate holding unit, and a standby position, where the processing liquid has been removed from the processing the position of the position retreat; and In the cleaning port, the discharge port of the first processing liquid nozzle is immersed in the nozzle cleaning liquid in the standby position.
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