TW201914695A - Substrate treatment method and substrate treatment apparatus capable of suppressing liquid from being blown out of a discharge port of a nozzle - Google Patents

Substrate treatment method and substrate treatment apparatus capable of suppressing liquid from being blown out of a discharge port of a nozzle Download PDF

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TW201914695A
TW201914695A TW107119194A TW107119194A TW201914695A TW 201914695 A TW201914695 A TW 201914695A TW 107119194 A TW107119194 A TW 107119194A TW 107119194 A TW107119194 A TW 107119194A TW 201914695 A TW201914695 A TW 201914695A
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hydrogen peroxide
substrate
peroxide water
liquid
sulfuric acid
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TWI666064B (en
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西出基
伊豆田崇
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日商斯庫林集團股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02307—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a liquid
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02343—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a liquid
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/30604—Chemical 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like

Abstract

A substrate treatment method according to the present invention is capable of suppressing liquid from being blown out of a discharge port of a nozzle. The substrate treatment method of the present invention includes a first step and a second step. In the first step, a mixed liquid of sulfuric acid and hydrogen peroxide water is discharged from the nozzle toward a substrate through a pipe. In the second step after the first step, the hydrogen peroxide water is discharged from the nozzle toward the substrate via the pipe. The first step includes: (A) a mixed liquid introduction starting step for starting the introduction of the mixed liquid into the pipe; (B) a mixed liquid introduction stopping step for stopping the introduction of sulfuric acid into the pipe after the step (A); (C) a gas layer forming step for forming a gas layer at a boundary between the mixed liquid and the hydrogen peroxide water; and (D) a moderation step for decreasing the flow rate of the hydrogen peroxide water introduced into the pipe or setting the flow rate to zero at the same time as or after the step (B).

Description

基板處理方法及基板處理裝置    Substrate processing method and substrate processing device   

本發明係關於基板處理方法及基板處理裝置，特別係將利用第1液與第2液的混合而生成氣體的混合液供應給基板表面的技術。 The present invention relates to a substrate processing method and a substrate processing apparatus, and particularly relates to a technology of supplying a mixed liquid that generates a gas by mixing a first liquid and a second liquid to a substrate surface.

例如半導體裝置的製造步驟中，已知有將屬於硫酸與過氧化氫水之混合液的SPM(Sulfuric Acid-Hydrogen Peroxide Mixture，硫酸-過氧化氫混合物)供應給基板表面，利用SPM所含之過氧硫酸(Peroxymonosulfuric acid)的強氧化力，從基板表面上除去光阻的手法。 For example, in the manufacturing process of a semiconductor device, it is known to supply SPM (Sulfuric Acid-Hydrogen Peroxide Mixture), which is a mixed solution of sulfuric acid and hydrogen peroxide water, to the surface of a substrate. The strong oxidizing power of Peroxymonosulfuric acid removes the photoresist from the surface of the substrate.

例如下述專利文獻1所記載的基板處理裝置，係具備有：旋轉夾具、供對由旋轉夾具所保持之基板的上表面供應SPM用的SPM噴嘴、對SPM噴嘴供應硫酸的硫酸供應管以及對SPM噴嘴供應過氧化氫水的過氧化氫水供應管。 For example, the substrate processing apparatus described in the following Patent Document 1 includes a rotary jig, an SPM nozzle for supplying SPM to the upper surface of a substrate held by the rotary jig, a sulfuric acid supply pipe for supplying sulfuric acid to the SPM nozzle, and a The hydrogen peroxide water supply pipe from which the SPM nozzle supplies hydrogen peroxide water.

[先前技術文獻]     [Prior technical literature]     [專利文獻]     [Patent Literature]    

[專利文獻1]日本專利特開2015-106699號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2015-106699

當停止對基板表面供應SPM時，首先可認為停止硫酸供應，然後再停止過氧化氫水的供應。依此，藉由停止硫酸後仍供應過氧化氫水，便利用過氧化氫水取代基板表面上的SPM，便可將SPM從基板表面上除去。又，在將SPM噴嘴內的硫酸全部吐出之狀態時，便可結束處理。依此可避免因硫酸殘留於SPM噴嘴內而造成的不良情況。 When the supply of SPM to the substrate surface is stopped, it can be considered that the supply of sulfuric acid is stopped first, and then the supply of hydrogen peroxide water is stopped. Accordingly, by stopping the supply of hydrogen peroxide water after the sulfuric acid is stopped, it is convenient to replace the SPM on the substrate surface with the hydrogen peroxide water, and the SPM can be removed from the substrate surface. When the sulfuric acid in the SPM nozzle is completely discharged, the process can be terminated. In this way, the undesirable situation caused by sulfuric acid remaining in the SPM nozzle can be avoided.

然而，若停止硫酸供應後仍供應過氧化氫水，例如SPM噴嘴內在SPM與過氧化氫水邊界處的過氧化氫水濃度獲提高。藉此，在該邊界處促進硫酸與過氧化氫水的反應。若硫酸與過氧化氫水進行反應，便會產生氣體(蒸氣)，所以藉由促進該反應便會增加氣體(蒸氣)產生量。而，若該氣體混雜於SPM中再從SPM噴嘴吐出時，SPM便會被強勢吹飛(所謂「吹沸」)，並附著於其他構件(例如頂板)上。 However, if the hydrogen peroxide water is still supplied after the sulfuric acid supply is stopped, for example, the concentration of the hydrogen peroxide water in the SPM nozzle at the boundary between the SPM and the hydrogen peroxide water is increased. This promotes the reaction between sulfuric acid and hydrogen peroxide water at the boundary. When sulfuric acid reacts with hydrogen peroxide water, gas (vapor) is generated. Therefore, the amount of gas (vapor) generated is increased by promoting the reaction. However, if the gas is mixed in the SPM and then discharged from the SPM nozzle, the SPM will be strongly blown away (so-called "boil") and adhere to other components (such as the top plate).

緣是，本發明目的在於提供：能抑制從噴嘴吐出口吹飛液體的基板處理方法及基板處理裝置。 The reason is that it is an object of the present invention to provide a substrate processing method and a substrate processing apparatus capable of suppressing the flying of liquid from a nozzle discharge port.

為解決上述課題，基板處理方法的第1態樣，係包括有：將硫酸與過氧化氫水的混合液，經由配管從噴嘴朝基板吐出的第1步 驟；以及在上述第1步驟後，將過氧化氫水經由上述配管從上述噴嘴朝基板吐出的第2步驟；其中，上述第1步驟係包括有：(A)：開始將上述混合液導入於上述配管的混合液導入開始步驟；(B)：在(A)之後，停止將上述硫酸導入上述配管的混合液導入停止步驟；(C)：在上述混合液與上述過氧化氫水的邊界處形成氣體層的氣體層形成步驟；以及(D)：在與(B)之同時或更完成後，便降低導入於上述配管中的上述過氧化氫水流量或將流量設為零的緩和步驟。 In order to solve the above problems, the first aspect of the substrate processing method includes a first step of discharging a mixed solution of sulfuric acid and hydrogen peroxide water from a nozzle toward a substrate through a pipe; and after the first step, The second step in which the hydrogen peroxide water is discharged from the nozzle to the substrate through the piping; the first step includes: (A): a mixed liquid introduction start step of starting to introduce the mixed liquid into the piping; (B) ): After (A), stop the step of introducing the mixed solution for introducing the sulfuric acid into the piping; (C): a step of forming a gas layer at the boundary between the mixed solution and the hydrogen peroxide water; and ( D): At the same time as (B) or after completion, the easing step of reducing the flow rate of the hydrogen peroxide water introduced into the piping or setting the flow rate to zero.

基板處理方法的第2態樣係第1態樣的基板處理方法，其中，在(D)中，將上述過氧化氫水的流量在中斷期間內設為零，而上述中斷期間係設定為在上述基板表面不會生成沒有被液體覆蓋之斷液區域程度的時間。 The second aspect of the substrate processing method is the substrate processing method of the first aspect, in (D), the flow rate of the hydrogen peroxide water is set to zero during the interruption period, and the interruption period is set to The substrate surface does not generate a period of time that is not covered by the liquid.

基板處理方法的第3態樣係對基板施行處理的基板處理方法，其包括有：將硫酸與過氧化氫水的混合液，經由配管從噴嘴朝基板吐出的第1步驟；以及在上述第1步驟後，將過氧化氫水經由上述配管從上述噴嘴朝基板吐出的第2步驟；其中，上述第1步驟係包括有：(A)：開始將上述混合液導入至上述配管的混合液導入開始步驟；(B)：在(A)之後，停止上述硫酸導入至上述配管的混合液導入停止步驟；以及(C)：在與(B)之同時或完成後，將氣體導入上述配管，而在上述混合液與上述過氧化氫水的邊界處形成氣體層的氣體層形成步驟。 A third aspect of the substrate processing method is a substrate processing method for processing a substrate, which includes a first step of discharging a mixed solution of sulfuric acid and hydrogen peroxide water from a nozzle toward a substrate through a pipe; and the first step After the step, the second step of discharging hydrogen peroxide water from the nozzle to the substrate through the pipe; the first step includes: (A): the introduction of the mixed liquid into the pipe is started; Steps; (B): after (A), stop the mixed liquid introduction stopping step of introducing the sulfuric acid into the piping; and (C): introduce gas into the piping at the same time or after completion of (B), and A gas layer forming step of forming a gas layer at the boundary between the mixed liquid and the hydrogen peroxide water.

基板處理方法的第4態樣係第3態樣的基板處理方法，其中，上述第1步驟係更進一步包括有(D)：在與(B)之同時或其完成後，降低導入至上述配管中的上述過氧化氫水流量或將流量設為零的緩和步驟。 The fourth aspect of the substrate processing method is the third aspect of the substrate processing method, wherein the first step further includes (D): at the same time as (B) or after completion, the introduction is reduced to the piping The above-mentioned hydrogen peroxide water flow rate or the relaxation step of setting the flow rate to zero.

基板處理方法的第5態樣係第3或第4態樣的基板處理方法，其中，上述氣體係惰性氣體。 The fifth aspect of the substrate processing method is the third or fourth aspect of the substrate processing method, wherein the gas system is an inert gas.

基板處理方法的第6態樣係第1至第5態樣中之任一態樣的基板處理方法，其中，上述混合液係依上述硫酸體積大於上述過氧化氫水體積的混合比，由上述硫酸與上述過氧化氫水進行混合。 The sixth aspect of the substrate processing method is the substrate processing method of any one of the first to fifth aspects, wherein the mixed solution is based on a mixing ratio of the sulfuric acid volume greater than the hydrogen peroxide water volume. Sulfuric acid is mixed with the above-mentioned hydrogen peroxide water.

基板處理裝置的第7態樣係具備有：基板保持手段、第1液供應手段、第2液供應手段、第3液供應手段及控制手段；而，該基板保持手段係保持著基板；該第1液供應手段係供應硫酸；該第2液供應手段係依可變流量供應過氧化氫水；該第3液供應手段係具備有：配管與噴嘴，該配管係流動著分別由上述第1液供應手段與上述第2液供應手段所導入之上述硫酸與上述過氧化氫水的混合液，該噴嘴係將來自上述配管的上述混合液朝上述基板表面吐出；該控制手段係使上述第1液供應手段與上述第2液供應手段分別供應上述硫酸與上述過氧化氫水，再將上述混合液朝上述基板吐出後，使上述第1液供應手段停止上述硫酸之供應，在上述混合液與上述過氧化氫水的邊界處形成氣體層，在上述硫酸之供應停止之同時或剛停止後，使上述第2液供應手段的上述過氧化氫水流量降低 或降為零。 A seventh aspect of the substrate processing apparatus includes a substrate holding means, a first liquid supplying means, a second liquid supplying means, a third liquid supplying means, and a control means; and the substrate holding means holds the substrate; the first The one-liquid supply means supplies sulfuric acid; the second-liquid supply means supplies hydrogen peroxide water at a variable flow rate; and the third-liquid supply means includes: a pipe and a nozzle, and the piping system flows through the first liquid The supply means and the mixed liquid of the sulfuric acid and the hydrogen peroxide water introduced by the second liquid supply means, the nozzle discharges the mixed liquid from the piping toward the surface of the substrate; the control means makes the first liquid The supply means and the second liquid supply means respectively supply the sulfuric acid and the hydrogen peroxide water, and after the mixed liquid is ejected toward the substrate, the first liquid supply means stops the supply of the sulfuric acid. A gas layer is formed at the boundary of the hydrogen peroxide water, and at the same time or immediately after the supply of the sulfuric acid is stopped, the flow of the hydrogen peroxide water in the second liquid supply means is caused. Decrease or decrease to zero.

基板處理裝置的第8態樣係具備有：基板保持手段、第1液供應手段、第2液供應手段、第3液供應手段、氣體供應手段及控制手段；而，該基板保持手段係保持著基板；該第1液供應手段係供應硫酸；該第2液供應手段係依可變流量供應過氧化氫水；該第3液供應手段係具備有：配管與噴嘴，該配管係流動著分別由上述第1液供應手段與上述第2液供應手段所導入之上述硫酸與上述過氧化氫水的混合液的配管，該噴嘴係將來自上述配管的上述混合液，朝上述基板表面吐出；該氣體供應手段係朝上述配管內供應氣體；該控制手段係使上述第1液供應手段與上述第2液供應手段分別供應上述硫酸與上述過氧化氫水，再將上述混合液朝上述基板吐出後，使上述第1液供應手段停止上述硫酸之供應，在上述硫酸之供應停止之同時或剛停止後，使上述氣體供應手段朝上述配管內供應氣體，而在上述混合液與上述過氧化氫水的邊界處形成氣體層。 An eighth aspect of the substrate processing apparatus includes a substrate holding means, a first liquid supplying means, a second liquid supplying means, a third liquid supplying means, a gas supplying means, and a control means; and the substrate holding means is held Substrate; the first liquid supply means is for supplying sulfuric acid; the second liquid supply means is for supplying hydrogen peroxide water at a variable flow rate; the third liquid supply means is provided with: a pipe and a nozzle. The nozzle is a piping of a mixed liquid of the sulfuric acid and the hydrogen peroxide water introduced by the first liquid supply means and the second liquid supply means, and the nozzle discharges the mixed liquid from the piping toward the surface of the substrate; the gas The supply means supplies gas into the piping; the control means causes the first liquid supply means and the second liquid supply means to supply the sulfuric acid and the hydrogen peroxide water respectively, and then the mixed liquid is discharged toward the substrate, Stop the supply of the sulfuric acid from the first liquid supply means, and simultaneously or immediately after the supply of the sulfuric acid is stopped, set the gas supply means toward the distribution. The supply of gas to form the gas boundary layer above the hydrogen peroxide in the liquid mixture.

根據基板處理方法的第1、第3態樣及基板處理裝置的第8、第9態樣，利用氣體的層便可抑制第1液與第2液進行反應，因而可抑制因該反應而生成氣體。所以，能抑制從混合液吐出口的吹飛現象。 According to the first and third aspects of the substrate processing method and the eighth and ninth aspects of the substrate processing apparatus, the reaction between the first liquid and the second liquid can be suppressed by the layer of the gas, so that generation due to the reaction can be suppressed. gas. Therefore, the blow-off phenomenon from the mixed liquid discharge port can be suppressed.

根據基板處理方法的第2態樣，可避免在基板表面發生斷液區域。 According to the second aspect of the substrate processing method, it is possible to avoid the occurrence of a liquid-cut region on the substrate surface.

根據基板處理方法的第3及基板處理裝置的第9態樣，可控制在邊界處所形成之氣體層的體積。 According to the third aspect of the substrate processing method and the ninth aspect of the substrate processing apparatus, the volume of the gas layer formed at the boundary can be controlled.

1、1A‧‧‧基板處理裝置 1. 1A‧‧‧ substrate processing equipment

10‧‧‧基板保持手段(基板保持部) 10‧‧‧ substrate holding means (substrate holding section)

11‧‧‧突起部 11‧‧‧ protrusion

12‧‧‧保持台 12‧‧‧ holding table

13‧‧‧旋轉機構 13‧‧‧rotating mechanism

20‧‧‧第1液供應部 20‧‧‧The first liquid supply department

21‧‧‧液供應源 21‧‧‧Liquid supply source

22‧‧‧第1液供應配管 22‧‧‧The first liquid supply piping

23、33‧‧‧開閉手段(開閉閥) 23, 33‧‧‧ Opening and closing means (opening and closing valve)

24‧‧‧流量調整部 24‧‧‧Flow Adjustment Department

25‧‧‧加熱部 25‧‧‧Heating section

30‧‧‧第2液供應部 30‧‧‧Second liquid supply department

31‧‧‧液供應源 31‧‧‧Liquid supply source

32‧‧‧第2液供應配管 32‧‧‧ 2nd liquid supply piping

34‧‧‧流量調整部 34‧‧‧Flow Adjustment Department

40‧‧‧混合液供應手段(混合液供應部) 40‧‧‧Mixed liquid supply means (Mixed liquid supply department)

41‧‧‧混合部 41‧‧‧ Mixing Department

42‧‧‧混合液供應配管 42‧‧‧ mixed liquid supply piping

43‧‧‧噴嘴 43‧‧‧Nozzle

43a‧‧‧吐出口 43a‧‧‧Eject

43b‧‧‧內部流路 43b‧‧‧Internal flow path

44‧‧‧噴嘴移動機構 44‧‧‧ Nozzle moving mechanism

50‧‧‧控制部 50‧‧‧Control Department

60‧‧‧清洗液供應部 60‧‧‧Cleaning liquid supply department

61‧‧‧液供應源 61‧‧‧Liquid supply source

62‧‧‧液供應配管 62‧‧‧Liquid supply piping

63‧‧‧開閉閥 63‧‧‧Open and close valve

64‧‧‧噴嘴 64‧‧‧ Nozzle

65‧‧‧噴嘴移動機構 65‧‧‧Nozzle moving mechanism

70‧‧‧氣體供應手段(氣體供應部) 70‧‧‧Gas supply means (gas supply department)

71‧‧‧氣體供應源 71‧‧‧Gas supply source

72‧‧‧氣體供應配管 72‧‧‧Gas supply piping

73‧‧‧開閉閥 73‧‧‧Open and close valve

80‧‧‧杯 80‧‧‧ cup

A1‧‧‧氣體 A1‧‧‧Gas

L1‧‧‧過氧化氫水 L1‧‧‧ Hydrogen peroxide water

L2‧‧‧混合液 L2‧‧‧ mixed liquid

P1、P2、P3‧‧‧連接口 P1, P2, P3‧‧‧Connector

Q‧‧‧旋轉軸 Q‧‧‧rotation axis

S1、S3~S6‧‧‧步驟(step) S1, S3 ~ S6‧‧‧ steps

W‧‧‧基板 W‧‧‧ substrate

圖1係基板處理裝置之構成一例的概略圖。 FIG. 1 is a schematic diagram of an example of a configuration of a substrate processing apparatus.

圖2係基板處理裝置的動作一例之流程圖。 FIG. 2 is a flowchart showing an example of the operation of the substrate processing apparatus.

圖3係過氧化氫水與混合液的邊界樣子之一例圖。 FIG. 3 is a diagram showing an example of a boundary state of hydrogen peroxide water and a mixed solution.

圖4係基板處理裝置的動作一例之流程圖。 FIG. 4 is a flowchart of an example of the operation of the substrate processing apparatus.

圖5係過氧化氫水與混合液的邊界樣子之一例圖。 Fig. 5 is a diagram showing an example of a boundary state of hydrogen peroxide water and a mixed solution.

圖6係基板處理裝置的動作一例之流程圖。 FIG. 6 is a flowchart of an example of the operation of the substrate processing apparatus.

圖7係基板處理裝置構成一例的概略圖。 FIG. 7 is a schematic diagram showing an example of a configuration of a substrate processing apparatus.

圖8係混合部附近的構成一例之概略圖。 FIG. 8 is a schematic diagram of an example of a configuration near a mixing section.

圖9係基板處理裝置的動作一例之流程圖。 FIG. 9 is a flowchart showing an example of the operation of the substrate processing apparatus.

以下，參照圖式針對實施形態進行詳細說明。又，在求容易理解目的下，視需要誇張(或簡化)描述各部位尺寸與數量。 Hereinafter, embodiments will be described in detail with reference to the drawings. In addition, for the purpose of easy understanding, the size and quantity of each part are exaggerated (or simplified) as necessary.

[第1實施形態]     [First Embodiment]    

<基板處理裝置> <Substrate Processing Device>

圖1所示係基板處理裝置1的構成一例之概略圖。基板處理裝置1係對基板W表面供應處理液，而對基板W施行根據該處理液進行處理的裝置。該基板處理裝置1係具備有：基板保持部10、第 1液供應部20、第2液供應部30、混合液供應部40及控制部50。另外，基板處理裝置1亦具備未圖示框體(腔)。在該框體中設有未圖示之閘門，該閘門開啟時，基板W便經由該打開的閘門從框體外部被搬入於框體內部，或將框體內部的基板W搬出於框體外部。 FIG. 1 is a schematic view showing an example of a configuration of a substrate processing apparatus 1. The substrate processing apparatus 1 is a device that supplies a processing liquid to the surface of the substrate W and performs processing on the substrate W based on the processing liquid. The substrate processing apparatus 1 includes a substrate holding section 10, a first liquid supply section 20, a second liquid supply section 30, a mixed liquid supply section 40, and a control section 50. The substrate processing apparatus 1 also includes a frame (cavity) (not shown). A gate (not shown) is provided in the frame. When the gate is opened, the substrate W is moved into the frame from the outside of the frame through the opened gate, or the substrate W inside the frame is moved out of the frame. .

基板保持部10係將基板W呈水平保持。例如基板W係半導體基板，俯視具有圓形形狀的板狀基板。但，基板W並不僅侷限於此，可例如：液晶等顯示面板用基板，及俯視具矩形形狀的板狀基板。基板保持部10並無特別限制之必要，但可例如具有保持台12。在保持台12的上表面設有例如複數個突起部(銷)11，由複數個突起部11的前端支撐著基板W的下表面。在突起部11亦可設置與基板W的側面呈相對向，且從外周側進行基板W定位的構件。 The substrate holding portion 10 holds the substrate W horizontally. For example, the substrate W is a semiconductor substrate, and a plate-like substrate having a circular shape in plan view. However, the substrate W is not limited to this, and examples thereof include a substrate for a display panel such as a liquid crystal, and a plate-like substrate having a rectangular shape in plan view. The substrate holding portion 10 is not particularly limited, but may include a holding stage 12, for example. A plurality of protrusions (pins) 11 are provided on the upper surface of the holding table 12, and the lower surface of the substrate W is supported by the tips of the plurality of protrusions 11. A member facing the side surface of the substrate W and positioning the substrate W from the outer peripheral side may be provided on the protrusion 11.

圖1的例中，設置使基板W在水平面內進行旋轉的旋轉機構13。旋轉機構13係設有例如馬達，將通過基板W中心的軸設為旋轉軸Q，使基板保持部10進行旋轉。藉此，由基板保持部10保持的基板W便以旋轉軸Q為中心進行旋轉。由基板保持部10與旋轉機構13構成的構造，亦稱「旋轉夾具」。 In the example of FIG. 1, a rotation mechanism 13 is provided to rotate the substrate W in a horizontal plane. The rotation mechanism 13 is provided with, for example, a motor, and the axis passing through the center of the substrate W is set as the rotation axis Q, and the substrate holding portion 10 is rotated. Thereby, the substrate W held by the substrate holding portion 10 is rotated around the rotation axis Q as a center. The structure composed of the substrate holding portion 10 and the rotating mechanism 13 is also referred to as a "rotary jig".

第1液供應部20係將第1液供應給混合液供應部40。第1液係例如硫酸。第1液供應部20係具備有：液供應源21、液供應配管22、開閉閥23及流量調整部24。液供應配管22的一端連接於液供應源21，另一端連接於混合液供應部40。來自液供應源21的第1液在液供應配管22的內部流動，並供應給混合液供應部40。 The first liquid supply unit 20 supplies the first liquid to the mixed liquid supply unit 40. The first liquid system is, for example, sulfuric acid. The first liquid supply unit 20 includes a liquid supply source 21, a liquid supply pipe 22, an on-off valve 23, and a flow rate adjustment unit 24. One end of the liquid supply pipe 22 is connected to the liquid supply source 21, and the other end is connected to the mixed liquid supply unit 40. The first liquid from the liquid supply source 21 flows inside the liquid supply pipe 22 and is supplied to the mixed liquid supply unit 40.

開閉閥23係設置於液供應配管22的途中。開閉閥23係具有切換第1液供應/停止的切換手段機能。具體而言，藉由開啟開閉閥23，第1液便在液供應配管22的內部流動並供應給混合液供應部40，藉由關閉開閉閥23，便停止對混合液供應部40的第1液供應。 The on-off valve 23 is provided in the middle of the liquid supply pipe 22. The on-off valve 23 has a switching means function for switching the supply / stop of the first liquid. Specifically, when the on-off valve 23 is opened, the first liquid flows inside the liquid supply pipe 22 and is supplied to the mixed liquid supply unit 40. When the on-off valve 23 is closed, the first liquid to the mixed liquid supply unit 40 is stopped. Fluid supply.

流量調整部24係例如流量調整閥，設置於液供應配管22的途中。流量調整部24係調整在液供應配管22內部流動的第1液流量。具體而言，藉由調整流量調整部24的開度，便調整第1液的流量。另外，藉由關閉開閉閥23，便可將硫酸流量設為零，因而開閉閥23亦可視為一種流量調整手段。 The flow rate adjustment unit 24 is, for example, a flow rate adjustment valve and is provided in the middle of the liquid supply pipe 22. The flow rate adjustment unit 24 adjusts a first liquid flow rate flowing inside the liquid supply pipe 22. Specifically, by adjusting the opening degree of the flow rate adjustment unit 24, the flow rate of the first liquid is adjusted. In addition, by closing the on-off valve 23, the sulfuric acid flow rate can be set to zero, so the on-off valve 23 can also be regarded as a flow rate adjustment means.

第2液供應部30係將第2液供應給混合液供應部40。第2液係藉由與第1液進行會合，而與第1液產生反應並生成氣體的液體。當第1液係採用硫酸時，第2液係可採用例如過氧化氫水。藉由硫酸與過氧化氫水混合進行反應，便生成具強氧化力的過氧硫酸，且例如利用其反應熱使混合液中的水蒸發而生成氣體(蒸氣)。此處，作為其中一例針對第1液與第2液分別為硫酸與過氧化氫水的情況進行說明。 The second liquid supply unit 30 supplies the second liquid to the mixed liquid supply unit 40. The second liquid is a liquid that reacts with the first liquid and generates a gas by meeting the first liquid. When sulfuric acid is used as the first liquid system, for example, hydrogen peroxide water may be used as the second liquid system. Sulfuric acid and hydrogen peroxide water are mixed and reacted to generate peroxysulfuric acid with strong oxidizing power. For example, the reaction heat is used to evaporate water in the mixed liquid to generate a gas (vapor). Here, as an example, a case where the first liquid and the second liquid are sulfuric acid and hydrogen peroxide water, respectively will be described.

第2液供應部30係具備有：液供應源31、液供應配管32、開閉閥33及流量調整部34。液供應配管32的一端連接於液供應源31，另一端連接於混合液供應部40。來自液供應源31的過氧化氫水在液供應配管32的內部流動，並供應給混合液供應部40。 The second liquid supply unit 30 includes a liquid supply source 31, a liquid supply pipe 32, an on-off valve 33, and a flow rate adjustment unit 34. One end of the liquid supply pipe 32 is connected to the liquid supply source 31 and the other end is connected to the mixed liquid supply unit 40. The hydrogen peroxide water from the liquid supply source 31 flows inside the liquid supply pipe 32 and is supplied to the mixed liquid supply unit 40.

開閉閥33係設置於液供應配管32的途中。開閉閥33係具有切換過氧化氫水供應/停止的切換手段機能。具體而言，藉由開啟開閉閥33，過氧化氫水便在液供應配管32的內部流動並供應給混合液供應部40，而藉由關閉開閉閥33，便停止對混合液供應部40的過氧化氫水供應。 The on-off valve 33 is provided in the middle of the liquid supply pipe 32. The on-off valve 33 has a function of a switching means for switching the supply / stop of hydrogen peroxide water. Specifically, when the on-off valve 33 is opened, the hydrogen peroxide water flows inside the liquid supply pipe 32 and is supplied to the mixed liquid supply unit 40. When the on-off valve 33 is closed, the supply of the mixed liquid supply unit 40 is stopped. Hydrogen peroxide water supply.

流量調整部34係例如流量調整閥，設置於液供應配管32的途中。流量調整部34係調整在液供應配管32內部流動的過氧化氫水流量。具體而言，藉由調整流量調整部34的開度，便調整過氧化氫水的流量。另外，藉由關閉開閉閥33，便可將過氧化氫水的流量設為零，因而開閉閥33亦可視為一種流量調整手段。 The flow rate adjustment unit 34 is, for example, a flow rate adjustment valve, and is provided in the middle of the liquid supply pipe 32. The flow rate adjustment unit 34 adjusts the flow rate of the hydrogen peroxide water flowing inside the liquid supply pipe 32. Specifically, the flow rate of the hydrogen peroxide water is adjusted by adjusting the opening degree of the flow rate adjustment unit 34. In addition, by closing the on-off valve 33, the flow rate of the hydrogen peroxide water can be set to zero, so the on-off valve 33 can also be regarded as a kind of flow rate adjustment means.

圖1所示例中，在第1液供應部20中設有加熱部25。加熱部25係例如加熱器，設置於液供應配管22的途中。加熱部25係可將在液供應配管22內部流動的硫酸予以加熱。藉此，可使硫酸與過氧化氫水進行混合時的反應呈良好。加熱部25係將硫酸溫度升溫至例如150度以上。 In the example shown in FIG. 1, a heating section 25 is provided in the first liquid supply section 20. The heating section 25 is, for example, a heater and is provided in the middle of the liquid supply pipe 22. The heating section 25 is capable of heating the sulfuric acid flowing inside the liquid supply pipe 22. Thereby, the reaction when sulfuric acid and hydrogen peroxide water are mixed can be made favorable. The heating section 25 raises the temperature of the sulfuric acid to, for example, 150 degrees or more.

混合液供應部40係分別將第1液供應部20及第2液供應部30導入的硫酸與過氧化氫水予以混合，再將該混合液(SPM)當作處理液供應給基板W的表面。在該混合液中，由硫酸與過氧化氫水產生反應生成過氧硫酸。在基板W的表面(上表面)上形成光阻，藉由該過氧硫酸的強氧化力除去該光阻。所以，此情況，基板處理裝置 1便成為光阻除去裝置。 The mixed liquid supply unit 40 mixes sulfuric acid and hydrogen peroxide water introduced by the first liquid supply unit 20 and the second liquid supply unit 30, respectively, and then supplies the mixed liquid (SPM) as a processing liquid to the surface of the substrate W. . In this mixed solution, sulfuric acid and hydrogen peroxide water react to produce peroxysulfuric acid. A photoresist is formed on the surface (upper surface) of the substrate W, and the photoresist is removed by the strong oxidizing power of the peroxy sulfuric acid. Therefore, in this case, the substrate processing apparatus 1 becomes a photoresist removal apparatus.

混合液供應部40係具備有：混合部41、混合液供應配管42及噴嘴43。混合部41連接於液供應配管22、32的另一端。更具體而言，混合部41係具有內部空間，該內部空間連通於液供應配管22、32的另一端。另外，混合部41亦可視同配管。在該混合部41中，硫酸與過氧化氫水會進行混合。硫酸與過氧化氫水的混合比係設定成硫酸之體積大於過氧化氫水之體積的狀態，混合比(=硫酸體積/過氧化氫水體積)設定為例如10以上。該混合比係藉由流量調整部24、34進行硫酸與過氧化氫水的流量調整便可實現。 The mixed liquid supply unit 40 includes a mixing unit 41, a mixed liquid supply pipe 42, and a nozzle 43. The mixing section 41 is connected to the other ends of the liquid supply pipes 22 and 32. More specifically, the mixing section 41 has an internal space that communicates with the other ends of the liquid supply pipes 22 and 32. In addition, the mixing section 41 may be regarded as a pipe. In the mixing section 41, sulfuric acid and hydrogen peroxide water are mixed. The mixing ratio of sulfuric acid and hydrogen peroxide water is set such that the volume of sulfuric acid is larger than the volume of hydrogen peroxide water, and the mixing ratio (= sulfuric acid volume / hydrogen peroxide water volume) is set to, for example, 10 or more. This mixing ratio can be achieved by adjusting the flow rates of sulfuric acid and hydrogen peroxide water by the flow rate adjusting units 24 and 34.

混合部41亦連接於混合液供應配管42之一端。即，混合部41的內部空間連通於混合液供應配管42的一端。混合液供應配管42的另一端連接於噴嘴43。噴嘴43的前端面設有吐出口43a，且設有將該吐出口43a與混合液供應配管42的另一端相連通之內部流路43b。來自混合部41的混合液係經由混合液供應配管42流入於噴嘴43的內部流路43b，再從噴嘴43的吐出口43a吐出。 The mixing section 41 is also connected to one end of the mixed liquid supply pipe 42. That is, the internal space of the mixing section 41 communicates with one end of the mixed liquid supply pipe 42. The other end of the mixed liquid supply pipe 42 is connected to a nozzle 43. The front end surface of the nozzle 43 is provided with a discharge port 43a, and an internal flow path 43b that communicates the discharge port 43a with the other end of the mixed liquid supply pipe 42 is provided. The mixed liquid from the mixing section 41 flows into the internal flow path 43 b of the nozzle 43 through the mixed liquid supply pipe 42, and is then discharged from the discharge port 43 a of the nozzle 43.

該噴嘴43至少在混合液吐出時，位於基板W的上方。所以，混合液係從噴嘴43的吐出口43a吐出於基板W的表面。 This nozzle 43 is located above the substrate W at least when the mixed liquid is discharged. Therefore, the mixed liquid is discharged from the surface of the substrate W from the discharge port 43 a of the nozzle 43.

在混合部41與噴嘴43的吐出口43a間之流路長度係可設定為如下。即，依過氧硫酸濃度成為在基板W表面能充分除去光阻的值之方式，設定該流路長度。藉此，可效率佳地除去基板W的光 阻。 The length of the flow path between the mixing section 41 and the discharge port 43a of the nozzle 43 can be set as follows. That is, the length of the flow path is set so that the concentration of peroxysulfuric acid becomes a value capable of sufficiently removing photoresist on the surface of the substrate W. This makes it possible to efficiently remove the photoresist of the substrate W.

於此種基板處理裝置1中，第1液供應部20與第2液供應部30一組成為從噴嘴43經由混合液供應配管42朝基板W供應混合液的供應部。又，因為在混合部41中流動著硫酸與過氧化氫水，因而混合部41亦可視為配管之一部分。 In such a substrate processing apparatus 1, a set of the first liquid supply unit 20 and the second liquid supply unit 30 is a supply unit that supplies the mixed liquid to the substrate W from the nozzle 43 through the mixed liquid supply pipe 42. Moreover, since sulfuric acid and hydrogen peroxide water flow through the mixing section 41, the mixing section 41 can also be regarded as a part of the piping.

再者，如圖1所例示，噴嘴43的內部流路43b之延伸方向係可在吐出口43a中傾斜於基板W的表面，或者亦可不同於圖1所例示，該延伸方向係略垂直於基板W的表面。 Moreover, as illustrated in FIG. 1, the extending direction of the internal flow path 43 b of the nozzle 43 may be inclined to the surface of the substrate W in the discharge port 43 a, or may be different from that illustrated in FIG. 1, and the extending direction is slightly perpendicular to The surface of the substrate W.

圖1所示例中，在基板處理裝置1中設有噴嘴移動機構44。噴嘴移動機構44係可使噴嘴43在基板W上方的處理位置、與從基板W上方退縮的待機位置之間移動。藉由噴嘴43移動至待機位置，因為基板保持部10的上方便空出空間，因而可輕易在基板保持部10與基板處理裝置1外部之間進行基板W的讓渡。 In the example shown in FIG. 1, a nozzle moving mechanism 44 is provided in the substrate processing apparatus 1. The nozzle moving mechanism 44 moves the nozzle 43 between a processing position above the substrate W and a standby position retracted from above the substrate W. By moving the nozzle 43 to the standby position, it is easy to free up the space on the substrate holding portion 10, so that the transfer of the substrate W between the substrate holding portion 10 and the outside of the substrate processing apparatus 1 can be easily performed.

噴嘴移動機構44並無特別的限制，例如亦可設有未圖示的柱部、機械臂及旋轉機構。柱部係沿鉛直方向延伸，且基端固定於旋轉機構上。機械臂係從柱部前端朝水平延伸。機械臂的前端連結於噴嘴43。旋轉機構係設有例如馬達，使該柱部以柱部中心軸(鉛直方向的平行中心軸)為旋轉軸進行旋轉。藉由使柱部旋轉，噴嘴43便沿圓弧上進行移動。處理位置及待機位置設定於該圓弧上。藉此，噴嘴移動機構44便可使噴嘴43在處理位置與待機位置之間進 行移動。 The nozzle moving mechanism 44 is not particularly limited, and for example, a column portion, a robot arm, and a rotating mechanism (not shown) may be provided. The column part extends in the vertical direction, and the base end is fixed on the rotating mechanism. The robot arm extends horizontally from the front end of the column. The tip of the robot arm is connected to the nozzle 43. The rotation mechanism is provided with, for example, a motor, and the column portion is rotated with the column portion central axis (parallel central axis in the vertical direction) as a rotation axis. By rotating the column, the nozzle 43 moves along the arc. The processing position and the standby position are set on the arc. Thereby, the nozzle moving mechanism 44 can move the nozzle 43 between the processing position and the standby position.

再者，噴嘴移動機構44亦可設有為使噴嘴43沿鉛直方向移動的升降機構。升降機構係可採用例如氣缸、滾珠螺桿機構或單軸平台等。藉此，便可調整噴嘴43與基板W間的間隔。 The nozzle moving mechanism 44 may be provided with a lifting mechanism for moving the nozzle 43 in the vertical direction. The lifting mechanism can be, for example, an air cylinder, a ball screw mechanism, or a single-axis platform. Thereby, the interval between the nozzle 43 and the substrate W can be adjusted.

於圖1所示之例中，在基板處理裝置1設有杯80。杯80係設計呈包圍基板W周緣的狀態。杯80係供將從基板W周緣流出至外側的處理液予以回收的構件。該杯80係具有例如筒狀之形狀。隨基板W旋轉而從基板W周緣飛散的處理液，碰撞到杯80的內周面並流入杯80的底面。在杯80的底面形成有處理液回收用的孔(未圖示)，經由該孔回收處理液。 In the example shown in FIG. 1, the substrate processing apparatus 1 is provided with a cup 80. The cup 80 is designed to surround the periphery of the substrate W. The cup 80 is a member for recovering the processing liquid flowing from the periphery of the substrate W to the outside. The cup 80 has a cylindrical shape, for example. The processing liquid scattered from the periphery of the substrate W as the substrate W rotates hits the inner peripheral surface of the cup 80 and flows into the bottom surface of the cup 80. A hole (not shown) for recovering the processing liquid is formed on the bottom surface of the cup 80, and the processing liquid is recovered through the hole.

控制部50係針對由第1液供應部20進行的硫酸之供應、由第2液供應部30進行的過氧化氫水之供應予以控制。具體而言，控制部50係控制著：開閉閥23、33的開閉、流量調整部24、34的開度、及加熱部25的發熱量。又，控制部50亦可控制著旋轉機構13的旋轉速度及噴嘴移動機構44。 The control unit 50 controls the supply of sulfuric acid by the first liquid supply unit 20 and the supply of hydrogen peroxide water by the second liquid supply unit 30. Specifically, the control unit 50 controls the opening and closing of the on-off valves 23 and 33, the opening degrees of the flow rate adjusting units 24 and 34, and the heat generation amount of the heating unit 25. The control unit 50 may also control the rotation speed of the rotation mechanism 13 and the nozzle moving mechanism 44.

控制部50係電子電路機器，亦可設有例如資料處理裝置及記憶媒體。資料處理裝置係可為例如CPU(Central Processor Unit，中央處理器)等運算處理裝置。記憶部亦可具有：非暫時性記憶媒體(例如ROM(Read Only Memory，唯讀記憶體)或硬碟)、及暫時性記憶媒體(例如RAM(Random Access Memory，隨機存取記憶體))。非暫 時性記憶媒體亦可記憶著例如規定由控制部50所執行之處理的程式。藉由處理裝置執行該程式，控制部50便可執行程式所規定的處理。當然，控制部50所執行之處理的其中一部分或全部，亦可由硬體執行。 The control unit 50 is an electronic circuit device, and may be provided with, for example, a data processing device and a memory medium. The data processing device may be an arithmetic processing device such as a CPU (Central Processor Unit, central processing unit). The memory unit may include a non-transitory memory medium (such as a ROM (Read Only Memory) or a hard disk) and a temporary memory medium (such as a RAM (Random Access Memory)). The non-transitory memory medium may also memorize a program that specifies a process to be executed by the control unit 50, for example. When the program is executed by the processing device, the control unit 50 can execute the processing prescribed by the program. Of course, some or all of the processing executed by the control unit 50 may be executed by hardware.

於圖1所示之例中，在基板處理裝置1中亦設有清洗液供應部60。清洗液供應部60係朝基板W的表面供應清洗液。清洗液係可採用例如純水(DIW：DeIonized Water，去離子水)。或者，清洗液亦可採用碳酸水、電解離子水、臭氧水、稀釋濃度(例如10~100ppm程度)鹽酸水、還原水(氫水)等。 In the example shown in FIG. 1, the substrate processing apparatus 1 is also provided with a cleaning liquid supply unit 60. The cleaning liquid supply unit 60 supplies a cleaning liquid to the surface of the substrate W. As the cleaning liquid system, for example, pure water (DIW: DeIonized Water) can be used. Alternatively, the cleaning solution may be carbonated water, electrolytic ion water, ozone water, dilute concentration (for example, about 10 to 100 ppm) hydrochloric acid water, reduced water (hydrogen water), or the like.

清洗液供應部60係例如具備有：液供應源61、液供應配管62、開閉閥63、噴嘴64及噴嘴移動機構65。液供應配管62的一端係連接於液供應源61，另一端連接於噴嘴64。來自液供應源61的清洗液在液供應配管62的內部流向於噴嘴64，再從噴嘴64的吐出口中吐出。 The cleaning liquid supply unit 60 includes, for example, a liquid supply source 61, a liquid supply pipe 62, an on-off valve 63, a nozzle 64, and a nozzle moving mechanism 65. One end of the liquid supply pipe 62 is connected to the liquid supply source 61 and the other end is connected to the nozzle 64. The cleaning liquid from the liquid supply source 61 flows into the nozzle 64 inside the liquid supply pipe 62 and is then discharged from the discharge port of the nozzle 64.

開閉閥63係設置於液供應配管62的途中。開閉閥63係作為切換清洗液之供應/停止的切換手段而發揮機能。具體而言，藉由開啟開閉閥63，清洗液便在液供應配管62的內部流動，而藉由關閉開閉閥63，便停止清洗液的供應。開閉閥63的開閉係由控制部50進行控制。 The on-off valve 63 is provided in the middle of the liquid supply pipe 62. The on-off valve 63 functions as a switching means for switching the supply / stop of the cleaning liquid. Specifically, by opening the on-off valve 63, the cleaning liquid flows inside the liquid supply pipe 62, and by closing the on-off valve 63, the supply of the cleaning liquid is stopped. The opening and closing of the on-off valve 63 is controlled by the control unit 50.

噴嘴64係至少在清洗液吐出時，位於基板W的上方。清洗液 係從噴嘴64朝基板W的表面吐出，便可沖洗基板W的表面。 The nozzle 64 is located above the substrate W at least when the cleaning liquid is discharged. The cleaning liquid is discharged from the nozzle 64 toward the surface of the substrate W, and the surface of the substrate W can be rinsed.

噴嘴移動機構65係可使噴嘴64在基板W上方的處理位置、與從基板W上方退縮的待機位置之間移動。藉由噴嘴64移動至待機位置，便可避免噴嘴64、43的物理性干擾，且可在基板保持部10與基板處理裝置1的外部之間輕易地進行基板W之讓渡。噴嘴移動機構65的構成之一例係與噴嘴移動機構44同樣。 The nozzle moving mechanism 65 moves the nozzle 64 between a processing position above the substrate W and a standby position retracted from above the substrate W. By moving the nozzle 64 to the standby position, physical interference of the nozzles 64 and 43 can be avoided, and the substrate W can be easily transferred between the substrate holding portion 10 and the outside of the substrate processing apparatus 1. An example of the configuration of the nozzle moving mechanism 65 is the same as that of the nozzle moving mechanism 44.

<基板處理裝置之動作> <Operation of Substrate Processing Device>

圖2所示係基板處理裝置1的動作一例之流程圖。於步驟S1，配置表面已形成光阻的基板W。具體而言，控制部50控制著噴嘴移動機構44、65，在使噴嘴43、64分別停止於各自待機位置的狀態下，開啟框體的閘門。然後，未圖示之搬送機器人便使已載置基板W的機械手部，進入基板處理裝置1(框體)的內部，而將基板W讓渡給基板保持部10上。然後，搬送機器人從基板處理裝置1中抽出空的機械手部。藉此，基板W便由基板保持部10保持。 FIG. 2 is a flowchart showing an example of the operation of the substrate processing apparatus 1. In step S1, a substrate W having a photoresist formed on the surface is disposed. Specifically, the control unit 50 controls the nozzle moving mechanisms 44 and 65 to open the shutters of the housing in a state where the nozzles 43 and 64 are stopped at their respective standby positions. Then, a transfer robot (not shown) moves the robot arm portion on which the substrate W has been placed into the substrate processing apparatus 1 (frame), and passes the substrate W to the substrate holding portion 10. Then, the transfer robot extracts the empty robot hand from the substrate processing apparatus 1. Thereby, the substrate W is held by the substrate holding portion 10.

接著，步驟S2，由控制部50控制著旋轉機構13，使基板W依既定的旋轉速度進行旋轉。既定的旋轉速度係可採用例如300[rpm]~1500[rpm]範圍內的值。 Next, in step S2, the control unit 50 controls the rotation mechanism 13 to rotate the substrate W at a predetermined rotation speed. The predetermined rotation speed is, for example, a value in a range of 300 [rpm] to 1500 [rpm].

其次，步驟S3，執行朝基板W表面吐出混合液(SPM)的混合液供應步驟。具體而言，由控制部50控制著噴嘴移動機構44，使噴嘴43移動至處理位置。在使噴嘴43移動至處理位置後，控制部 50略同時開啟開閉閥23、33。藉此，硫酸與過氧化氫水便分別在液供應配管22、32內部流向於混合部41。 Next, in step S3, a mixed liquid supply step of discharging a mixed liquid (SPM) toward the surface of the substrate W is performed. Specifically, the nozzle moving mechanism 44 is controlled by the control unit 50 to move the nozzle 43 to the processing position. After moving the nozzle 43 to the processing position, the control unit 50 opens the on-off valves 23 and 33 at the same time. Thereby, the sulfuric acid and the hydrogen peroxide water flow into the mixing section 41 in the liquid supply pipes 22 and 32, respectively.

再者，控制部50係依硫酸與過氧化氫水的混合比成為既定比的方式，控制著流量調整部24、34的開度。例如該既定比係設定呈硫酸量大於過氧化氫水量的狀態，例如設定為硫酸：過氧化氫水=10：1程度。藉由將硫酸的混合比設定為較高，經回收後的混合液便可輕易再利用。即若硫酸的混合比較高，則因為經回收後的混合液中，硫酸濃度仍高，因而經回收後的混合液可輕易地再作為硫酸利用。 The control unit 50 controls the openings of the flow rate adjustment units 24 and 34 so that the mixing ratio of sulfuric acid and hydrogen peroxide water becomes a predetermined ratio. For example, the predetermined ratio is set to a state where the amount of sulfuric acid is greater than the amount of hydrogen peroxide water. For example, the predetermined ratio is set to approximately 10: 1 sulfuric acid: hydrogen peroxide water. By setting the mixing ratio of sulfuric acid to be high, the recovered mixed liquid can be easily reused. That is, if the mixing of sulfuric acid is relatively high, the sulfuric acid concentration in the recovered mixed liquid is still high, so the recovered mixed liquid can be easily reused as sulfuric acid.

再者，控制部50係控制著加熱部25，使硫酸升溫至既定溫度(例如150度以上)。藉此，可提升硫酸與過氧化氫水的反應性。 The control unit 50 controls the heating unit 25 to raise the sulfuric acid temperature to a predetermined temperature (for example, 150 degrees or more). Thereby, the reactivity of sulfuric acid and hydrogen peroxide water can be improved.

在混合部41中，將經加熱的硫酸、與過氧化氫水相混合，然後使該混合液在混合液供應配管42的內部及噴嘴43的內部流路43b流動，再從噴嘴43的吐出口43a吐出於基板W的表面。經吐出於基板W表面的混合液，會因承接由基板W旋轉造成的離心力而擴散。藉此，混合液便覆蓋基板W的表面全面。然後，混合液中所含的過氧硫酸會與基板W表面的光阻產生化學性反應，且從基板W表面上除去該光阻。 In the mixing section 41, the heated sulfuric acid and the hydrogen peroxide water are mixed, and then the mixed liquid is caused to flow in the mixed liquid supply pipe 42 and the internal flow path 43 b of the nozzle 43, and then flows from the discharge port of the nozzle 43 43a is ejected from the surface of the substrate W. The mixed liquid discharged from the surface of the substrate W is diffused by receiving the centrifugal force caused by the rotation of the substrate W. Thereby, the mixed liquid covers the entire surface of the substrate W. Then, the peroxy sulfuric acid contained in the mixed solution will chemically react with the photoresist on the surface of the substrate W, and the photoresist will be removed from the surface of the substrate W.

另外，該混合液供應步驟，亦可在固定噴嘴43的位置狀態下，將混合液供應給基板W，亦可一邊使噴嘴43移動一邊將混合液供 應給基板W。例如控制部50亦可控制噴嘴移動機構44，使混合液對基板W的落滴位置在基板W中心部與周緣部間進行移動(例如往復移動)。若使落滴位置在基板W中心部與周緣部之間移動，便可對基板W表面的全面施行均勻處理。 In this mixed liquid supply step, the mixed liquid may be supplied to the substrate W with the nozzle 43 fixed, or the mixed liquid may be supplied to the substrate W while the nozzle 43 is moved. For example, the control unit 50 may control the nozzle moving mechanism 44 to move the dropping position of the mixed liquid on the substrate W between the center portion and the peripheral portion of the substrate W (for example, reciprocating movement). If the drop position is moved between the central portion and the peripheral portion of the substrate W, the entire surface of the substrate W can be uniformly processed.

若從混合液開始供應起經既定期間，便結束混合液供應步驟，接著在步驟S4中，由控制部50停止硫酸供應。具體而言，控制部50係藉由關閉開閉閥23而停止硫酸供應。藉此，停止對混合部41導入硫酸，而僅導入過氧化氫水。又，此時控制部50結束由加熱部25進行的加熱。 When a predetermined period has elapsed from the start of the supply of the mixed liquid, the mixed liquid supply step is ended, and in step S4, the control unit 50 stops the sulfuric acid supply. Specifically, the control unit 50 stops the sulfuric acid supply by closing the on-off valve 23. Thereby, the introduction of sulfuric acid into the mixing section 41 is stopped, and only the hydrogen peroxide water is introduced. At this time, the control unit 50 ends the heating by the heating unit 25.

再者，當停止供應硫酸且仍維持過氧化氫水之供應時，在混合液供應部40之內部(即由混合部41起至噴嘴43的流路內)所存在的混合液，會被來自第1液供應部20的過氧化氫水擠壓，而被從噴嘴43吐出。然後，若混合液全部由噴嘴43的吐出口43a吐出，之後從噴嘴43的吐出口43a便僅吐出過氧化氫水。 Furthermore, when the supply of sulfuric acid is stopped and the supply of hydrogen peroxide water is still maintained, the mixed liquid existing inside the mixed liquid supply section 40 (that is, in the flow path from the mixing section 41 to the nozzle 43) will be derived The hydrogen peroxide water in the first liquid supply unit 20 is squeezed and is discharged from the nozzle 43. Then, if all the mixed liquid is discharged from the discharge port 43a of the nozzle 43, only hydrogen peroxide water is discharged from the discharge port 43a of the nozzle 43 after that.

但是，在混合液供應部40的內部，於過氧化氫水與混合液邊界處的過氧化氫水濃度，較邊界處以外的混合液中之過氧化氫水濃度高。理由係因為已停止硫酸的供應。另外，此處所謂邊界處係指混合液(例如混合比10：1)與過氧化氫水相混雜的部分，在成分上係與混合液相同。但，如上述般，邊界處的過氧化氫水濃度較高。 However, the concentration of the hydrogen peroxide water at the boundary between the hydrogen peroxide water and the mixed liquid in the mixed liquid supply unit 40 is higher than the concentration of the hydrogen peroxide water in the mixed liquid outside the boundary. The reason is because the supply of sulfuric acid has been stopped. Here, the term “boundary” refers to a portion where a mixed liquid (for example, a mixing ratio of 10: 1) and an aqueous hydrogen peroxide phase are mixed, and the components are the same as the mixed liquid. However, as described above, the concentration of hydrogen peroxide water at the boundary is high.

依此，因為邊界處的過氧化氫水濃度增加，因而便促進該邊界處的硫酸與過氧化氫水之反應，而增加反應熱量，使氣體(蒸氣)的生成量增加。例如邊界處的溫度可上升至200度左右。 Accordingly, since the concentration of the hydrogen peroxide water at the boundary is increased, the reaction between sulfuric acid and the hydrogen peroxide water at the boundary is promoted, the reaction heat is increased, and the amount of gas (vapor) generated is increased. For example, the temperature at the boundary can rise to about 200 degrees.

而，若過氧化氫水持續供應給邊界處，則過氧化氫水與混合液相混合的邊界處便擴大，結果在廣範圍內分散式生成氣體。圖3所示係此現象的示意圖，表示噴嘴43的內部。 On the other hand, if the hydrogen peroxide water is continuously supplied to the boundary, the boundary where the hydrogen peroxide water and the mixed liquid phase are mixed will be enlarged, and as a result, the gas will be generated in a dispersed manner over a wide range. FIG. 3 is a schematic diagram of this phenomenon, and shows the inside of the nozzle 43.

另外，此處雖示意性圖示在噴嘴43內部發生上述現象，但實際上，該現象係在剛停止硫酸供應後的混合部41內發生，但因過氧化氫水的供應，隨時間經過，邊界處與氣體會在混合液供應配管42內部移動，最終到達噴嘴43的吐出口43a。於圖3所示之例中，噴嘴43內部的混合液L2位於吐出口43a側，而過氧化氫水L1則位於較混合液L2更靠上游側(吐出口43a的對向側)，氣體A1呈廣範圍分散。另外，該混合液L2係包含邊界處在內。 In addition, although the above phenomenon is schematically shown inside the nozzle 43, this phenomenon actually occurs in the mixing section 41 immediately after the sulfuric acid supply is stopped, but due to the supply of hydrogen peroxide water, over time, The boundary and the gas move inside the mixed liquid supply pipe 42 and finally reach the discharge port 43 a of the nozzle 43. In the example shown in FIG. 3, the mixed liquid L2 inside the nozzle 43 is located on the discharge outlet 43a side, and the hydrogen peroxide water L1 is located on the upstream side (the opposite side of the discharge outlet 43a) than the mixed liquid L2, and the gas A1 Widely dispersed. The mixed liquid L2 includes a boundary.

再者，藉由該氣體A1從噴嘴43的吐出口43a一起與混合液L2被吐出，混合液L2便被吹飛(飛散)，而落滴於不同於所需落滴位置處的位置。被吹飛的混合液L2亦會落滴於基板W以外的地方(例如頂板)。圖3所示例中，被吹飛的混合液L2統籌示意式依圓圈表示，又飛散方向則依箭頭示意式表示。 In addition, the gas A1 is ejected from the discharge port 43a of the nozzle 43 together with the mixed liquid L2, and the mixed liquid L2 is blown away (scattered), and the drop is at a position different from the desired drop position. The blown-off mixed liquid L2 also drops to a place other than the substrate W (for example, the top plate). In the example shown in FIG. 3, the blown-off mixed liquid L2 is indicated by a circle as a whole, and the scattering direction is indicated by an arrow.

且，當由混合液供應步驟(步驟S3)所供應的混合液中，硫酸混合比設定為較高時、即過氧化氫水的混合比設定為較低時，邊界處 的過氧化氫水之混合比，明顯較混合液的過氧化氫水之混合比增加。藉此，可認為較能輕易促進邊界處的硫酸與過氧化氫水之反應。即，硫酸混合比(=硫酸體積/過氧化氫水體積)較高時，邊界處的氣體生成量較多。所以，若提高硫酸混合比而提高回收後的混合液再利用性，則硫酸停止供應後的混合液容易發生吹飛現象。例如硫酸混合比(=硫酸/過氧化氫水)達10以上時，較容易發生混合液吹飛現象。 In addition, when the sulfuric acid mixing ratio is set to be high in the mixed liquid supplied in the mixed liquid supply step (step S3), that is, when the mixing ratio of hydrogen peroxide water is set to be low, the amount of hydrogen peroxide water at the boundary is reduced. The mixing ratio is significantly higher than the mixing ratio of the hydrogen peroxide water in the mixed liquid. By this, it can be considered that it is easier to promote the reaction between sulfuric acid and hydrogen peroxide water at the boundary. That is, when the sulfuric acid mixing ratio (= sulfuric acid volume / hydrogen peroxide water volume) is high, the amount of gas generated at the boundary is large. Therefore, if the sulfuric acid mixing ratio is increased to improve the reusability of the mixed liquid after recovery, the mixed liquid after the supply of sulfuric acid is stopped is liable to blow off. For example, when the mixing ratio of sulfuric acid (= sulfuric acid / hydrogen peroxide water) is more than 10, the phenomenon of mixed liquid blowing off is more likely to occur.

再者，本實施形態可抑制因硫酸的停止供應而衍生之混合液吹飛情形，在步驟S5中，於過氧化氫水與混合液的邊界處形成氣體層。圖4所示係為形成氣體層的處理順序一例之流程圖。步驟S51，控制部50暫時停止(中斷)供應過氧化氫水。步驟S51亦可與步驟S4同時執行。即，控制部50係在關閉開閉閥23之同時或剛關閉後，便暫時關閉開閉閥33。藉此，混合液供應部40之內部由過氧化氫水進行的擠壓便暫時消失。換言之，在停止硫酸導入於混合液供應部40之同時或停止供應後，便將過氧化氫水的流量設為零。藉由該擠壓的消失，在邊界處生成的氣體便容易滯留於邊界處附近，氣體糾結形成於該邊界處，結果便形成氣體層。圖5所示係該現象的示意圖，與圖3同樣地均表示噴嘴43之內部。該氣體層可降低過氧化氫水L1與混合液L2的接觸區域。該氣體層可具有過氧化氫水L1與混合液L2的隔離區域機能。另外，此處雖示意式圖示在噴嘴43內部發生上述現象，但與圖3同樣，實際上該現象係在剛停止供應硫酸後的混合部41中發生。 Furthermore, this embodiment can suppress the blow-off of the mixed liquid derived from the stop of the supply of sulfuric acid. In step S5, a gas layer is formed at the boundary between the hydrogen peroxide water and the mixed liquid. FIG. 4 is a flowchart showing an example of a processing sequence for forming a gas layer. In step S51, the control unit 50 temporarily stops (interrupts) the supply of hydrogen peroxide water. Step S51 may also be performed simultaneously with step S4. That is, the control unit 50 temporarily closes the on-off valve 33 at the same time as or immediately after closing the on-off valve 23. Thereby, the inside of the mixed liquid supply part 40 is temporarily disappeared by the hydrogen peroxide water. In other words, the flow rate of the hydrogen peroxide water is set to zero when the introduction of sulfuric acid is stopped at the same time as the introduction of the sulfuric acid into the mixed liquid supply unit 40 or after the supply is stopped. With the disappearance of the compression, the gas generated at the boundary is easily retained near the boundary, and the gas is tangled at the boundary, and a gas layer is formed as a result. FIG. 5 is a schematic diagram of this phenomenon, and both show the inside of the nozzle 43 similarly to FIG. 3. This gas layer can reduce the contact area between the hydrogen peroxide water L1 and the mixed liquid L2. The gas layer may have a function of a separation region between the hydrogen peroxide water L1 and the mixed liquid L2. In addition, although the above-mentioned phenomenon occurs inside the nozzle 43 schematically, as in FIG. 3, this phenomenon actually occurs in the mixing section 41 immediately after the supply of sulfuric acid is stopped.

因為該氣體層會抑制過氧化氫水與混合液的接觸，因而可更進一步抑制反應，甚至可更進一步抑制氣體生成。即可降低氣體生成量。 Because the gas layer inhibits the contact between the hydrogen peroxide water and the mixed liquid, the reaction can be further suppressed, and even the gas generation can be further suppressed. This reduces the amount of gas generated.

若開閉閥33關閉後經既定期間(以下稱「中斷期間」)，便在步驟S52中，由控制部50再度開始過氧化氫水的供應。具體而言，控制部50係藉由開啟開閉閥33，而再度開始過氧化氫水的供應。藉此，過氧化氫水會將氣體層與混合液朝噴嘴43的吐出口43a方向擠壓，所以從任一噴嘴43的吐出口43a均僅將過氧化氫水吐出於基板W的表面。 When a predetermined period of time (hereinafter referred to as a "discontinued period") has passed after the on-off valve 33 is closed, the control unit 50 restarts the supply of hydrogen peroxide water in step S52. Specifically, the control unit 50 restarts the supply of hydrogen peroxide water by opening and closing the on-off valve 33. Thereby, the hydrogen peroxide water squeezes the gas layer and the mixed liquid toward the discharge port 43a of the nozzle 43, so that only the hydrogen peroxide water is discharged from the surface of the substrate W from the discharge port 43a of any of the nozzles 43.

但是，在剛由步驟S51停止過氧化氫水之供應後，將混合液朝噴嘴43的吐出口43a方向擠壓的力，主要係利用在邊界處所形成之氣體層的壓力實現。換言之，在開閉閥23、33雙方剛關閉後，便利用氣體層的壓力維持從噴嘴43的吐出口43a吐出混合液。因為該由氣體層壓力進行的混合液吐出並無法維持長期間，因而在尚未再度開始過氧化氫水供應的前提下，從噴嘴43的混合液吐出均會中斷。基板W表面上的混合液利用基板W的旋轉，從中央處朝周緣處移動，因而在尚未再度開始從噴嘴43的吐出前提下，基板W的中心區域均將成為斷液區域。所謂斷液區域係指基板W表面上的區域中，未被液體覆蓋的區域。該斷液區域會有發生水痕、或附著微塵等的情況。 However, immediately after the supply of hydrogen peroxide water is stopped in step S51, the force for pressing the mixed liquid toward the discharge port 43a of the nozzle 43 is mainly achieved by the pressure of the gas layer formed at the boundary. In other words, immediately after both the on-off valves 23 and 33 are closed, it is convenient to maintain the pressure of the gas layer to discharge the mixed liquid from the discharge port 43 a of the nozzle 43. Since the discharge of the mixed liquid by the gas layer pressure cannot be maintained for a long period of time, the discharge of the mixed liquid from the nozzle 43 is interrupted without the supply of hydrogen peroxide water being restarted. The mixed liquid on the surface of the substrate W is moved from the center to the periphery by the rotation of the substrate W. Therefore, the center region of the substrate W will be a liquid-cut region unless the discharge from the nozzle 43 is started again. The term “liquid cutoff region” refers to a region on the surface of the substrate W that is not covered by the liquid. There may be water marks on the fluid cutoff area, or fine dust may be attached.

此處，開閉閥23、33雙方均關閉的中斷期間較佳為設定為基 板W表面不會出現斷液區域程度的時間。即，控制部50在基板W之表面出現斷液區域之前，便由步驟S52再度開始過氧化氫水之供應。藉此，可避免基板W表面上出現斷液區域。該中斷期間係可利用例如實驗等進行設定。 Here, the interruption period in which both of the on-off valves 23 and 33 are closed is preferably set to a time such that a liquid-interrupted area does not appear on the surface of the substrate W. That is, before the liquid-interrupted area appears on the surface of the substrate W, the control unit 50 restarts the supply of hydrogen peroxide water in step S52. Thereby, the liquid-interrupted area on the surface of the substrate W can be avoided. This interruption period can be set using, for example, experiments.

另外，藉由再度開始過氧化氫水的供應，氣體層便因過氧化氫水的擠壓而朝噴嘴43方向移動。即便氣體層被從噴嘴43的吐出口43a吐出時，仍不易發生混合液吹飛現象。理由係在邊界處生成的氣體量減少。又，因為亦可抑制氣體分散，因而就此觀點亦可抑制吹飛之情形。 In addition, when the supply of hydrogen peroxide water is started again, the gas layer is moved toward the nozzle 43 due to the compression of the hydrogen peroxide water. Even when the gas layer is discharged from the discharge port 43 a of the nozzle 43, the mixed liquid blow-off phenomenon is unlikely to occur. The reason is that the amount of gas generated at the boundary is reduced. In addition, since gas dispersion can also be suppressed, the blow-off situation can also be suppressed from this viewpoint.

再者，氣體層被從噴嘴43的吐出口43a吐出時，可中斷從噴嘴43的吐出口43a吐出液體。然而，因為氣體層的體積並不大，因而在氣體層吐出後便迅速吐出過氧化氫水。所以，基板W的表面不易發生斷液區域。 When the gas layer is discharged from the discharge port 43 a of the nozzle 43, the discharge of the liquid from the discharge port 43 a of the nozzle 43 can be interrupted. However, because the volume of the gas layer is not large, the hydrogen peroxide water is quickly discharged after the gas layer is discharged. Therefore, the surface of the substrate W is less likely to have a liquid-cut region.

若過氧化氫水從噴嘴43的吐出口43a朝基板W表面的中央處吐出，便承接由基板W旋轉所衍生的離心力，朝外周擴展。藉此，過氧化氫水便將基板W表面的混合液朝外周方向推出並被從基板W的周緣排出。所以，基板W表面上的混合液被取代為過氧化氫水。過氧化氫水供應經過既定期間後，便在步驟S6中，由控制部50關閉開閉閥33，而停止過氧化氫水的供應(圖2)。 When the hydrogen peroxide water is discharged from the outlet 43a of the nozzle 43 toward the center of the surface of the substrate W, it receives the centrifugal force derived from the rotation of the substrate W and expands toward the outer periphery. Thereby, the hydrogen peroxide water pushes the mixed liquid on the surface of the substrate W toward the outer peripheral direction and is discharged from the peripheral edge of the substrate W. Therefore, the mixed liquid on the surface of the substrate W is replaced with hydrogen peroxide water. After the supply of the hydrogen peroxide water has passed a predetermined period, the control unit 50 closes the on-off valve 33 in step S6 to stop the supply of the hydrogen peroxide water (FIG. 2).

接著，在步驟S7中執行清洗液供應步驟。具體而言，由控制 部50控制著噴嘴移動機構44，使噴嘴43移動至待機位置，然後控制著噴嘴移動機構65，使噴嘴64移動至處理位置。之後，由控制部50開啟開閉閥63，從噴嘴64的吐出口將清洗液吐出於基板W的表面。 Next, a cleaning liquid supply step is performed in step S7. Specifically, the control unit 50 controls the nozzle moving mechanism 44 to move the nozzle 43 to the standby position, and then controls the nozzle moving mechanism 65 to move the nozzle 64 to the processing position. Thereafter, the on-off valve 63 is opened by the control unit 50, and the cleaning liquid is discharged from the discharge port of the nozzle 64 onto the surface of the substrate W.

清洗液滴至基板W表面的中央處，承接由基板W旋轉所衍生的離心力而朝外周擴展。藉此，清洗液將基板W表面上的過氧化氫水朝外周方向推出，並從基板W的周緣排出。所以，基板W表面上的過氧化氫水便被清洗液取代。即，基板W表面全面的過氧化氫水將被沖洗掉。持續供應清洗液既定期間後，便於步驟S8中，由控制部50關閉開閉閥63而停止清洗液供應。 The cleaning liquid drops to the center of the surface of the substrate W, and receives the centrifugal force derived from the rotation of the substrate W to expand toward the outer periphery. Thereby, the cleaning solution pushes the hydrogen peroxide water on the surface of the substrate W toward the outer peripheral direction, and is discharged from the peripheral edge of the substrate W. Therefore, the hydrogen peroxide water on the surface of the substrate W is replaced by the cleaning liquid. That is, the entire surface of the substrate W is flushed with hydrogen peroxide. After the cleaning liquid is continuously supplied for a predetermined period, in step S8, the control unit 50 closes the on-off valve 63 to stop the cleaning liquid supply.

接著，在步驟S9中，執行乾燥步驟。乾燥步驟係例如由控制部50控制著旋轉機構13，增加基板W的旋轉速度。藉此，對基板W表面上的清洗液作用更大的離心力，清洗液便從基板W的周緣部朝外側而被甩乾。藉此，清洗液被除去而使基板W乾燥。控制部50經既定期間使基板W旋轉後，控制著旋轉機構13，使基板W停止旋轉。 Next, in step S9, a drying step is performed. In the drying step, for example, the control unit 50 controls the rotation mechanism 13 to increase the rotation speed of the substrate W. Thereby, a greater centrifugal force is applied to the cleaning liquid on the surface of the substrate W, and the cleaning liquid is dried from the peripheral edge portion of the substrate W to the outside. Thereby, the cleaning liquid is removed and the substrate W is dried. After the control unit 50 rotates the substrate W over a predetermined period, the control unit 50 controls the rotation mechanism 13 to stop the rotation of the substrate W.

如上所述，根據基板處理裝置1，在因停止對混合液供應部40的硫酸之供應而生成的混合液與過氧化氫水之邊界處，形成氣體層。上述具體例中，當停止供應硫酸時，藉由暫時停止(中斷)過氧化氫水對混合液供應部40的供應，便在邊界處形成氣體層。藉此，可降低氣體生成量，因而能抑制從噴嘴43之吐出口43a的混合液 吹飛情形。又，藉由中斷過氧化氫水的供應，亦能抑制氣體之分散，就此觀點亦能抑制混合液的吹飛情形。 As described above, according to the substrate processing apparatus 1, a gas layer is formed at the boundary between the mixed liquid and the hydrogen peroxide water generated by stopping the supply of sulfuric acid to the mixed liquid supply unit 40. In the above specific example, when the supply of sulfuric acid is stopped, the supply of the hydrogen peroxide water to the mixed liquid supply unit 40 is temporarily stopped (interrupted), thereby forming a gas layer at the boundary. Thereby, the amount of generated gas can be reduced, and the blow-off of the mixed liquid from the discharge port 43a of the nozzle 43 can be suppressed. In addition, by interrupting the supply of hydrogen peroxide water, the dispersion of the gas can also be suppressed, and the blow-off of the mixed liquid can also be suppressed from this viewpoint.

再者，於上述例中，過氧化氫水的供應中斷期間係可設定為在基板W表面上不會出現斷液區域程度的時間。藉此可避免基板W表面上發生斷液區域，能避免因該斷液區域造成的水痕與微塵等不良情況。 Further, in the above-mentioned example, the period during which the supply of hydrogen peroxide water is interrupted may be set to a time such that a liquid-cut region does not occur on the surface of the substrate W. Thereby, a liquid-interrupted area on the surface of the substrate W can be avoided, and problems such as water marks and fine dust caused by the liquid-interrupted area can be avoided.

再者，如上所述，控制部50亦可關閉開閉閥23之同時，亦停止開閉閥33。藉此，因過氧化氫水所造成之朝過氧化氫水與混合液邊界處的擠壓將迅速消失。所以，因該擠壓造成的邊界處將擴大，甚而能迅速抑制氣體分散。藉此便可更輕易地形成氣體層。 In addition, as described above, the control unit 50 may close the on-off valve 23 and stop the on-off valve 33 at the same time. As a result, the squeezing caused by the hydrogen peroxide water toward the boundary between the hydrogen peroxide water and the mixed liquid will quickly disappear. Therefore, the boundary due to the compression will be enlarged, and even gas dispersion can be quickly suppressed. This makes it easier to form a gas layer.

<第2液(過氧化氫水)流量> <Second liquid (hydrogen peroxide water) flow rate>

上述例中，藉由控制部50暫時停止(中斷)過氧化氫水，而在混合液與過氧化氫水的邊界處形成氣體層。然而，為能形成氣體層，並無一定要中斷過氧化氫水的供應之必要。 In the above-mentioned example, the hydrogen peroxide water is temporarily stopped (interrupted) by the control unit 50 to form a gas layer at the boundary between the mixed liquid and the hydrogen peroxide water. However, in order to form a gas layer, it is not necessary to interrupt the supply of hydrogen peroxide water.

圖6所示係為形成氣體層的處理順序之另一例的流程圖。步驟S51A，由控制部50控制著流量調整部34，降低過氧化氫水的流量。該步驟S51A係與步驟S4同時或剛完成後便執行。即，控制部50係在關閉開閉閥23之同時或剛關閉後，便降低過氧化氫水的流量。藉由降低該流量，由過氧化氫水所造成朝過氧化氫水與混合液間之邊界處的擠壓便受抑制。所以，可抑制邊界處擴大與氣體分散，甚 而可輕易由氣體糾結形成氣體層。反言之，步驟S51A的過氧化氫水流量係設定為會形成氣體層之程度的值。該氣體層可減少過氧化氫水與混合液的接觸區域。所以，能抑制過氧化氫水與硫酸的進一步反應，而能更進一步抑制氣體生成。 FIG. 6 is a flowchart showing another example of a processing procedure for forming a gas layer. In step S51A, the flow rate adjusting unit 34 is controlled by the control unit 50 to reduce the flow rate of the hydrogen peroxide water. This step S51A is executed at the same time as step S4 or immediately after completion. That is, the control unit 50 reduces the flow rate of the hydrogen peroxide water at the same time as the on-off valve 23 is closed or immediately after closing. By reducing the flow rate, the squeeze caused by the hydrogen peroxide water toward the boundary between the hydrogen peroxide water and the mixed liquid is suppressed. Therefore, expansion at the boundary and gas dispersion can be suppressed, and even a gas layer can be easily tangled by the gas. In other words, the hydrogen peroxide water flow rate in step S51A is set to a value to the extent that a gas layer is formed. The gas layer can reduce the contact area between the hydrogen peroxide water and the mixed liquid. Therefore, further reaction of hydrogen peroxide water and sulfuric acid can be suppressed, and gas generation can be further suppressed.

然後，從過氧化氫水的流量開始降低起經既定期間(以下亦稱「降低期間」)後，便於步驟S52A中，由控制部50增加過氧化氫水的流量。例如由控制部50控制著流量調整部34，將過氧化氫水的流量回復至降低期間(步驟S51A)前的流量。 Then, after a predetermined period of time (hereinafter also referred to as a "reduction period") from the start of the decrease in the flow rate of the hydrogen peroxide water, it is convenient for the controller 50 to increase the flow rate of the hydrogen peroxide water in step S52A. For example, the control unit 50 controls the flow rate adjustment unit 34 to restore the flow rate of the hydrogen peroxide water to the flow rate before the reduction period (step S51A).

因為上述動作亦可抑制邊界處的氣體生成，因而能抑制噴嘴43吐出口43a的混合液之吹飛情形。 Since the above operation can also suppress the generation of gas at the boundary, it is possible to suppress the blow-off of the mixed liquid from the nozzle 43 outlet 43a.

再者，根據上述動作，因為即便停止供應硫酸後仍持續供應過氧化氫水，因而從噴嘴43的液體吐出不易中斷。藉此，便可降低基板W表面出現斷液區域的可能性。 Furthermore, according to the above-mentioned operation, since the supply of hydrogen peroxide water is continued even after the supply of sulfuric acid is stopped, the liquid discharge from the nozzle 43 is not easily interrupted. Thereby, the possibility of a liquid-interrupted area on the surface of the substrate W can be reduced.

[第2實施形態]     [Second Embodiment]    

於第1實施形態中，利用由硫酸與過氧化氫水的化學反應所生成之氣體，在過氧化氫水與混合液的邊界處形成氣體層。於第2實施形態，企圖藉由對混合液供應部40另外供應與該氣體不同的氣體，而形成氣體層。 In the first embodiment, a gas layer is formed at the boundary between the hydrogen peroxide water and the mixed liquid using a gas generated by a chemical reaction between sulfuric acid and hydrogen peroxide water. In the second embodiment, an attempt is made to form a gas layer by separately supplying a gas different from the gas to the mixed liquid supply unit 40.

圖7所示係第2實施形態的基板處理裝置1A之構成一例之概 略圖。基板處理裝置1A係就有無設置氣體供應部70之處不同於基板處理裝置1。換言之，基板處理裝置1A相較於基板處理裝置1之下，更進一步具備有氣體供應部70。氣體供應部70係對混合液供應部40供應氣體，而在過氧化氫水與混合液間的邊界處形成氣體層。該氣體係可採用例如氮或氬等惰性氣體。 Fig. 7 is a schematic diagram showing an example of the configuration of a substrate processing apparatus 1A according to the second embodiment. The substrate processing apparatus 1A differs from the substrate processing apparatus 1 in that a gas supply unit 70 is not provided. In other words, the substrate processing apparatus 1A further includes a gas supply unit 70 than the substrate processing apparatus 1. The gas supply unit 70 supplies gas to the mixed liquid supply unit 40 and forms a gas layer at the boundary between the hydrogen peroxide water and the mixed liquid. The gas system may use an inert gas such as nitrogen or argon.

氣體供應部70係具備有：氣體供應源71、氣體供應配管72及開閉閥73。氣體供應配管72的一端連接於氣體供應源71，另一端連接於混合部41。來自氣體供應源71的氣體在氣體供應配管72的內部流動並供應給混合部41。 The gas supply unit 70 includes a gas supply source 71, a gas supply pipe 72, and an on-off valve 73. One end of the gas supply pipe 72 is connected to the gas supply source 71 and the other end is connected to the mixing section 41. The gas from the gas supply source 71 flows inside the gas supply pipe 72 and is supplied to the mixing section 41.

圖8所示係混合部41附近的構成一例之概略圖。混合部41連接於液供應配管22、32、及氣體供應配管72。圖8所示例中，液供應配管22與混合部41的連接口P2係相對於液供應配管32與混合部41的連接口P3，位於較靠噴嘴43側(下游側)，而氣體供應配管72與混合部41的連接口P1則位於連接口P2、P3之間。 FIG. 8 is a schematic diagram showing an example of a configuration in the vicinity of the mixing section 41. The mixing section 41 is connected to the liquid supply pipes 22 and 32 and the gas supply pipe 72. In the example shown in FIG. 8, the connection port P2 of the liquid supply pipe 22 and the mixing section 41 is located closer to the nozzle 43 (downstream side) than the connection port P3 of the liquid supply pipe 32 and the mixing section 41, and the gas supply pipe 72 The connection port P1 with the mixing section 41 is located between the connection ports P2 and P3.

開閉閥73係設置於氣體供應配管72的途中。開閉閥73作為切換氣體供應/停止的切換手段而發揮機能。具體而言，藉由開啟開閉閥73，來自氣體供應源71的氣體在氣體供應配管72的內部流動並供應給混合液供應部40，而藉由關閉開閉閥73，便停止對混合液供應部40的氣體供應。 The on-off valve 73 is provided in the middle of the gas supply pipe 72. The on-off valve 73 functions as a switching means for switching gas supply / stop. Specifically, when the on-off valve 73 is opened, the gas from the gas supply source 71 flows inside the gas supply pipe 72 and is supplied to the mixed liquid supply unit 40. When the on-off valve 73 is closed, the mixed liquid supply unit is stopped. 40 gas supply.

該開閉閥73的開閉係由控制部50進行控制。具體而言，控制 部50係當關閉開閉閥23而停止硫酸供應時，便開啟開閉閥73將氣體供應給混合液供應部40。藉此，對因停止供應硫酸而生成的過氧化氫水與混合液邊界處供應氣體，並形成氣體層。 The opening and closing of the on-off valve 73 is controlled by the control unit 50. Specifically, when the control unit 50 closes the on-off valve 23 to stop the sulfuric acid supply, the control unit 50 opens the on-off valve 73 to supply the gas to the mixed liquid supply unit 40. As a result, a gas is supplied to the boundary between the hydrogen peroxide water and the mixed liquid generated by the supply of sulfuric acid, and a gas layer is formed.

圖9所示係基板處理裝置1A的氣體層形成步驟具體處理順序一例之流程圖。圖9中，步驟S51B，由控制部50在步驟S4之同時或剛完成後，開啟開閉閥73而朝混合部41供應氣體。藉此，在混合部41中會於過氧化氫水與混合液的邊界處形成氣體層。即，在步驟S4中，若關閉開閉閥23，則在混合部41會形成過氧化氫水與混合液的邊界處，因而控制部50藉由關閉開閉閥23，同時開啟開閉閥73，而將氣體供應給混合部41，便在該邊界處形成氣體層。換言之，控制部50係在停止供應硫酸之同時或剛停止後，便對氣體供應部70供應氣體而形成氣體層。 FIG. 9 is a flowchart showing an example of a specific processing sequence of a gas layer forming step of the substrate processing apparatus 1A. In step S51B in FIG. 9, at the same time as step S4 or immediately after completion of step S4, the control unit 50 opens the on-off valve 73 to supply the gas to the mixing unit 41. As a result, a gas layer is formed at the boundary between the hydrogen peroxide water and the mixed liquid in the mixing section 41. That is, in step S4, when the on-off valve 23 is closed, the boundary between the hydrogen peroxide water and the mixed liquid is formed in the mixing section 41. Therefore, the control section 50 closes the on-off valve 23 and simultaneously opens the on-off valve 73, thereby When the gas is supplied to the mixing section 41, a gas layer is formed at the boundary. In other words, the control unit 50 supplies gas to the gas supply unit 70 at the same time as or immediately after the supply of sulfuric acid is stopped, thereby forming a gas layer.

從氣體開始供應起經既定期間(以下亦稱「氣體供應期間」)時，便於步驟S52B中，由控制部50關閉開閉閥73，停止氣體供應。利用步驟S52B所形成的氣體層體積，係藉由調整氣體壓力與氣體供應期間便可控制。 When a predetermined period of time (hereinafter also referred to as a "gas supply period") has passed from the start of gas supply, it is convenient in step S52B to close the on-off valve 73 by the control unit 50 to stop the gas supply. The volume of the gas layer formed in step S52B can be controlled by adjusting the gas pressure and the gas supply period.

藉由在邊界處形成氣體層，便與第1實施形態同樣，可抑制邊界處的過氧化氫水與硫酸進行反應，便能抑制氣體分散。所以，可抑制來自噴嘴43吐出口43a的液體吹飛情形。又，氣體層在從噴嘴43吐出口43a吐出的期間內，可中斷吐出液體。所以，較佳為依不要因該中斷而導致在基板W表面上形成斷液區域的方式，調整氣體 層的體積。氣體壓力及氣體供應期間係可預先利用實驗等決定。 By forming a gas layer at the boundary, as in the first embodiment, the reaction of hydrogen peroxide water and sulfuric acid at the boundary can be suppressed, and gas dispersion can be suppressed. Therefore, it is possible to suppress the flying of the liquid from the discharge port 43a of the nozzle 43. In addition, during the period when the gas layer is discharged from the nozzle 43 discharge port 43a, the discharge of the liquid can be interrupted. Therefore, it is preferable to adjust the volume of the gas layer in such a manner that a liquid-tight region is not formed on the surface of the substrate W due to the interruption. The gas pressure and gas supply period can be determined in advance through experiments and the like.

<過氧化氫水之流量> <Flow of hydrogen peroxide water>

控制部50亦可在開啟開閉閥73的期間(即氣體供應期間：步驟S51B)內，降低過氧化氫水的流量。具體而言，控制部50亦可在關閉開閉閥23之同時或剛關閉後，便控制流量調整部34降低過氧化氫水的流量。藉此，因為可抑制由過氧化氫水所造成之朝邊界處的擠壓，因而從氣體供應部70供應的氣體容易集結於邊界處，而容易形成氣體層。 The control unit 50 may reduce the flow rate of the hydrogen peroxide water during the period during which the on-off valve 73 is opened (that is, the gas supply period: step S51B). Specifically, the control unit 50 may control the flow rate adjustment unit 34 to reduce the flow rate of the hydrogen peroxide water at the same time as or immediately after the on-off valve 23 is closed. Thereby, since the squeezing toward the boundary caused by the hydrogen peroxide water can be suppressed, the gas supplied from the gas supply unit 70 is easily gathered at the boundary, and a gas layer is easily formed.

在氣體供應期間經過後，控制部50便控制流量調整部34使過氧化氫水的流量增加。例如由控制部50控制流量調整部34，使過氧化氫水的流量回復至氣體供應期間前的流量。 After the gas supply period has elapsed, the control unit 50 controls the flow rate adjustment unit 34 to increase the flow rate of the hydrogen peroxide water. For example, the control unit 50 controls the flow rate adjustment unit 34 so that the flow rate of the hydrogen peroxide water is returned to the flow rate before the gas supply period.

另外，控制部50為降低過氧化氫水的流量，未必一定要控制流量調整部34。例如控制部50亦可藉由關閉開閉閥33，將過氧化氫水的流量降低至零。藉此，因為由過氧化氫水所造成之朝邊界處的擠壓會消失，因而更容易形成氣體層。在氣體供應期間經過後，由控制部50控制開閉閥33，再度開始供應過氧化氫水。 In addition, the control unit 50 does not necessarily control the flow rate adjustment unit 34 in order to reduce the flow rate of the hydrogen peroxide water. For example, the control unit 50 may reduce the flow rate of the hydrogen peroxide water to zero by closing the on-off valve 33. This makes it easier to form a gas layer because the compression toward the boundary caused by the hydrogen peroxide water disappears. After the gas supply period has elapsed, the on-off valve 33 is controlled by the control unit 50 and the supply of hydrogen peroxide water is started again.

<基板處理裝置1之其他具體例> <Other specific examples of the substrate processing apparatus 1>

上述例中，第1液係採用硫酸，第2液係採用過氧化氫水。然而，第1液與第2液的組合並不僅侷限於此。例如第1液與第2液的組合亦可採用磷酸與水的組合(於此情況下，混合液為熱磷酸)。 於此情況，基板處理裝置1係將熱磷酸供應給基板W的表面，便可蝕刻基板W的表面。第1液與第2液的組合亦可採用硫酸與臭氧水的組合(此情況，混合液便為硫酸臭氧(使臭氧氣體溶解於硫酸中而生成的液體))。此情況，基板處理裝置1係將硫酸臭氧水供應給基板W的表面，便可洗淨基板W的表面。 In the above example, sulfuric acid was used as the first liquid system, and hydrogen peroxide water was used as the second liquid system. However, the combination of the first liquid and the second liquid is not limited to this. For example, the combination of the first liquid and the second liquid may be a combination of phosphoric acid and water (in this case, the mixed liquid is hot phosphoric acid). In this case, the substrate processing apparatus 1 supplies hot phosphoric acid to the surface of the substrate W, and the surface of the substrate W can be etched. The combination of the first liquid and the second liquid may be a combination of sulfuric acid and ozone water (in this case, the mixed liquid is ozone sulfuric acid (a liquid produced by dissolving ozone gas in sulfuric acid). In this case, the substrate processing apparatus 1 can clean the surface of the substrate W by supplying sulfuric acid ozone water to the surface of the substrate W.

Claims (8)

一種基板處理方法，係對基板施行處理的基板處理方法，包括有：第1步驟，其係將硫酸與過氧化氫水的混合液經由配管從噴嘴朝基板吐出；以及第2步驟，其係在上述第1步驟後，將過氧化氫水經由上述配管從上述噴嘴朝基板吐出；其中，上述第1步驟係包括有：(A)：開始將上述混合液導入於上述配管的混合液導入開始步驟；(B)：在(A)之後，停止上述硫酸導入上述配管的混合液導入停止步驟；(C)：在上述混合液與上述過氧化氫水的邊界處形成氣體層的氣體層形成步驟；以及(D)：在與(B)之同時或其完成後，降低導入於上述配管中的上述過氧化氫水流量或將流量設為零的緩和步驟。     A substrate processing method, which is a substrate processing method for processing a substrate, includes: a first step of discharging a mixed solution of sulfuric acid and hydrogen peroxide water from a nozzle toward a substrate through a pipe; and a second step of After the first step, the hydrogen peroxide water is discharged from the nozzle to the substrate through the piping. The first step includes: (A): a mixed liquid introduction start step for starting the introduction of the mixed liquid into the piping. ; (B): after (A), stopping the step of introducing a mixed solution of the sulfuric acid into the piping; (C): a step of forming a gas layer at the boundary between the mixed solution and the hydrogen peroxide water; And (D): at the same time as (B) or after completion, a step of reducing or reducing the flow rate of the hydrogen peroxide water introduced into the piping to zero.     如請求項1之基板處理方法，其中，在(D)中，將上述過氧化氫水的流量在中斷期間內設為零；上述中斷期間係設定為在上述基板表面不會生成沒有被液體覆蓋之斷液區域程度的時間。     For example, in the substrate processing method of claim 1, in (D), the flow rate of the hydrogen peroxide water is set to zero during the interruption period; the interruption period is set so that the surface of the substrate is not covered with liquid The extent of the fluid cutoff time.     一種基板處理方法，係對基板施行處理的基板處理方法，包括有：第1步驟，其係將硫酸與過氧化氫水的混合液經由配管從噴嘴朝基板吐出；以及第2步驟，其係在上述第1步驟後，將過氧化氫水經由上述配管 從上述噴嘴朝基板吐出；其中，上述第1步驟係包括有：(A)：開始將上述混合液導入於上述配管的混合液導入開始步驟；(B)：在(A)之後，停止上述硫酸導入上述配管的混合液導入停止步驟；以及(C)：在與(B)之同時或其完成後，將氣體導入上述配管，而在上述混合液與上述過氧化氫水的邊界處形成氣體層的氣體層形成步驟。     A substrate processing method, which is a substrate processing method for processing a substrate, includes: a first step of discharging a mixed solution of sulfuric acid and hydrogen peroxide water from a nozzle toward a substrate through a pipe; and a second step of After the first step, the hydrogen peroxide water is discharged from the nozzle to the substrate through the piping. The first step includes: (A): a mixed liquid introduction start step for starting the introduction of the mixed liquid into the piping. ; (B): after (A), stop the mixed liquid introduction stopping step of introducing the sulfuric acid into the piping; and (C): introduce gas into the piping at the same time as (B) or after completion, and above A gas layer forming step of forming a gas layer at the boundary between the mixed liquid and the hydrogen peroxide water.     如請求項3之基板處理方法，其中，上述第1步驟係更進一步包括有：(D)：在與(B)之同時或其完成後，降低導入於上述配管中的上述過氧化氫水流量或將流量設為零的緩和步驟。     For example, the substrate processing method of claim 3, wherein the first step further includes: (D): at the same time as (B) or after completion, reducing the flow of the hydrogen peroxide water introduced into the piping; Or a mitigation step that sets the flow to zero.     如請求項3或4之基板處理方法，其中，上述氣體係惰性氣體。     The substrate processing method according to claim 3 or 4, wherein the gas system is an inert gas.     如請求項1至4中任一項之基板處理方法，其中，上述混合液係依上述硫酸之體積大於上述過氧化氫水體積的混合比，由上述硫酸與上述過氧化氫水進行混合。     The substrate processing method according to any one of claims 1 to 4, wherein the mixed liquid is mixed with the sulfuric acid and the hydrogen peroxide water according to a mixing ratio of a volume of the sulfuric acid greater than a volume of the hydrogen peroxide water.     一種基板處理裝置，係具備有：基板保持手段，其係保持著基板；第1液供應手段，其係供應硫酸；第2液供應手段，其係依可變之流量供應過氧化氫水；第3液供應手段，其係具備有：配管與噴嘴，而該配管係流動著分別由上述第1液供應手段與上述第2液供應手段所導入之上述硫酸與上述過氧化氫水的混合液，該噴嘴係將來自上述配管的上述混合液朝上述基板表面吐出；以及 控制手段，其係使上述第1液供應手段與上述第2液供應手段分別供應上述硫酸與上述過氧化氫水，再將上述混合液朝上述基板吐出後，使上述第1液供應手段停止上述硫酸之供應，在上述混合液與上述過氧化氫水的邊界處形成氣體層，在上述硫酸之供應停止之同時或剛停止後，使上述第2液供應手段的上述過氧化氫水流量降低或降為零。     A substrate processing apparatus includes: a substrate holding means for holding a substrate; a first liquid supply means for supplying sulfuric acid; a second liquid supply means for supplying hydrogen peroxide water at a variable flow rate; The three-liquid supply means includes a piping and a nozzle, and the piping is provided with a mixture of the sulfuric acid and the hydrogen peroxide water introduced by the first liquid supply means and the second liquid supply means, respectively. The nozzle discharges the mixed liquid from the piping toward the surface of the substrate; and a control means that causes the first liquid supply means and the second liquid supply means to supply the sulfuric acid and the hydrogen peroxide water, respectively, and then After the mixed liquid is discharged toward the substrate, the first liquid supply means stops the supply of the sulfuric acid, and a gas layer is formed at the boundary between the mixed liquid and the hydrogen peroxide water. At the same time or immediately after the supply of the sulfuric acid is stopped Thereafter, the flow rate of the hydrogen peroxide water in the second liquid supply means is reduced or reduced to zero.     一種基板處理裝置，係具備有：基板保持手段，其係保持著基板；第1液供應手段，其係供應硫酸；第2液供應手段，其係依可變之流量供應過氧化氫水；第3液供應手段，其係具備有：配管與噴嘴，而該配管係流動著分別由上述第1液供應手段與上述第2液供應手段所導入之上述硫酸與上述過氧化氫水的混合液，該噴嘴係將來自上述配管的上述混合液朝上述基板表面吐出；氣體供應手段，其係朝上述配管內供應氣體；以及控制手段，其係使上述第1液供應手段與上述第2液供應手段分別供應上述硫酸與上述過氧化氫水，再將上述混合液朝上述基板吐出後，使上述第1液供應手段停止上述硫酸之供應，在上述硫酸之供應停止之同時或剛停止後，使上述氣體供應手段朝上述配管內供應氣體，而在上述混合液與上述過氧化氫水的邊界處形成氣體層。     A substrate processing apparatus includes: a substrate holding means for holding a substrate; a first liquid supply means for supplying sulfuric acid; a second liquid supply means for supplying hydrogen peroxide water at a variable flow rate; The three-liquid supply means includes a piping and a nozzle, and the piping is a mixture of the sulfuric acid and the hydrogen peroxide water introduced by the first liquid supply means and the second liquid supply means, respectively. The nozzle discharges the mixed liquid from the piping toward the surface of the substrate; a gas supply means for supplying gas into the piping; and a control means for causing the first liquid supply means and the second liquid supply means After supplying the sulfuric acid and the hydrogen peroxide water separately, and then ejecting the mixed liquid toward the substrate, the first liquid supply means stops the supply of the sulfuric acid. When the supply of the sulfuric acid stops or immediately after the supply is stopped, the The gas supply means supplies gas into the piping, and forms a gas layer at a boundary between the mixed liquid and the hydrogen peroxide water.    
TW107119194A 2017-09-22 2018-06-04 Substrate treatment method and substrate treatment apparatus TWI666064B (en)

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