TW201734675A - Substrate treatment device and substrate treatment method - Google Patents
Substrate treatment device and substrate treatment method Download PDFInfo
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- TW201734675A TW201734675A TW106118891A TW106118891A TW201734675A TW 201734675 A TW201734675 A TW 201734675A TW 106118891 A TW106118891 A TW 106118891A TW 106118891 A TW106118891 A TW 106118891A TW 201734675 A TW201734675 A TW 201734675A
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- 239000000758 substrate Substances 0.000 title claims abstract description 247
- 238000000034 method Methods 0.000 title claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 342
- 239000007788 liquid Substances 0.000 claims abstract description 169
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000009835 boiling Methods 0.000 claims abstract description 40
- 238000003672 processing method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 150
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 43
- 229920002120 photoresistant polymer Polymers 0.000 description 25
- 238000003860 storage Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 9
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005468 ion implantation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67023—Apparatus for fluid treatment for general liquid treatment, e.g. etching followed by cleaning
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
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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
- H01L21/02096—Cleaning only mechanical cleaning
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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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02557—Sulfides
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- 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
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- 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
- H01L21/67126—Apparatus for sealing, encapsulating, glassing, decapsulating or the like
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- H01L21/67005—Apparatus not specifically provided for elsewhere
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- H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like
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- 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
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- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01016—Sulfur [S]
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- Manufacturing & Machinery (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
本發明之實施形態係有關基板處理裝置及基板處理方法。 Embodiments of the present invention relate to a substrate processing apparatus and a substrate processing method.
在半導體或液晶面板等之製造工程中，加以使用於晶圓或液晶基板等之基板的處理對象面，供給處理液，而將處理對象面進行處理之基板處理裝置。對於此基板處理裝置之中，係加以開發有以水平狀態而使基板旋轉，供給處理液至處理對象面的略中央，經由離心力而將其處理液擴散於處理對象面之旋轉處理裝置。更且，亦加以開發有回收一度利用之處理液而進行再利用之旋轉處理裝置。 In a manufacturing process such as a semiconductor or a liquid crystal panel, a substrate processing apparatus that processes a processing target surface by supplying a processing liquid to a processing target surface of a substrate such as a wafer or a liquid crystal substrate. In the substrate processing apparatus, a rotation processing apparatus that rotates the substrate in a horizontal state, supplies the processing liquid to the center of the processing target surface, and diffuses the processing liquid to the processing target surface via centrifugal force is developed. Further, a rotary processing apparatus that recovers the treatment liquid once used and reuses it has been developed.
經由如此之基板處理裝置，例如，對於除去基板之處理對象面上的光阻劑之情況，係加以利用作為處理液而使用SPM(硫酸溶液及過氧化氫水的混合液)之SPM處理。在使用此SPM處理之基板的枚葉處理中，有著混合硫酸溶液及過氧化氫水之後，供給至基板上之方法，或在基板上而混合硫酸溶液及過氧化氫水之方法等。然而，光阻劑除去後之基板係被加以水洗及乾燥，或者在其水洗 後，以另外的處理液加以處理，再次加以水洗及乾燥之後，運送至接下來的工程。 In the substrate processing apparatus, for example, in the case of removing the photoresist on the surface to be processed of the substrate, SPM (SFC (mixture of sulfuric acid solution and hydrogen peroxide)) is used as the treatment liquid. In the leaf processing using the SPM-treated substrate, there is a method of supplying a sulfuric acid solution and hydrogen peroxide water to the substrate, or a method of mixing a sulfuric acid solution and hydrogen peroxide water on the substrate. However, the substrate after removal of the photoresist is washed with water and dried, or washed in water. Thereafter, it is treated with another treatment liquid, washed again with water, and then transferred to the next work.
在僅使用前述SPM之SPM處理中，有著處理成為不充分之情況。例如，對於加以進行離子注入至基板之處理對象面的情況，於其離子注入後，光阻膜之表面則產生硬化(變質)之故，再經由SPM處理而除去此硬化之光阻劑之情況係為困難，而對於基板上係產生有光阻劑之殘渣。因此，為了提升處理性能，而有使用高溫(例如，160℃等)之SPM而處理基板者。 In the SPM process using only the aforementioned SPM, there is a case where the processing is insufficient. For example, in the case where ion implantation is performed on the surface of the substrate to be processed, after the ion implantation, the surface of the photoresist film is hardened (deteriorated), and the hardened photoresist is removed by SPM treatment. It is difficult, and a residue of a photoresist is generated on the substrate. Therefore, in order to improve the processing performance, there is a case where the substrate is processed using a high temperature (for example, 160 ° C or the like) SPM.
但過氧化氫水係越成為高溫，而壽命則變短之故，當加以混合於硫酸容易而成為高溫時，於到達至基板上之前，分解則進行，處理性能的提升則成為不充分。因此，呈殘存有過氧化氫水地，將大量的過氧化氫水混合於硫酸溶液時，硫酸溶液則變稀之故，再利用處理液之情況則變為困難，而總和之處理液使用量則增加。另外，當混合高溫的硫酸溶液，和過氧化氫水時，此等則未充分地被混合而引起過氧化氫水之突沸，即H2O2之H2O的突沸(激烈沸騰)，而過氧化氫水則消失。詳細係由高溫的硫酸溶液(160℃)則與過氧化氫水接觸者，以硫酸溶液之溫度而過氧化氫水之成分的H2O則急遽地產生沸騰。經由此現象，於與硫酸溶液混合之前，過氧化氫水則消失之故，因未加以生成過氧一硫酸及過氧二硫酸，也就是貢獻於光阻劑剝離之氧化性物質之故，處理性能的提升則成為不充分者。從如此之情況，處理性能之提升及處理液使用量的降 低為佳。 However, the hydrogen peroxide water system has a high temperature and the life is shortened. When it is mixed with sulfuric acid and becomes high temperature, it decomposes before reaching the substrate, and the improvement of the processing performance is insufficient. Therefore, when hydrogen peroxide water remains, and a large amount of hydrogen peroxide water is mixed in the sulfuric acid solution, the sulfuric acid solution becomes thin, and it becomes difficult to reuse the treatment liquid, and the total amount of the treatment liquid is used. Then increase. Further, when the mixing temperature of the sulfuric acid solution, and when the aqueous hydrogen peroxide, such is not sufficiently mixed to cause over the water of hydrogen peroxide bumping, i.e. H H 2 O 2 of the 2 O bumping (fierce boiling), and Hydrogen peroxide water disappears. In detail, a high-temperature sulfuric acid solution (160 ° C) is contacted with hydrogen peroxide water, and H 2 O, which is a component of hydrogen peroxide water at a temperature of a sulfuric acid solution, is rapidly boiled. According to this phenomenon, the hydrogen peroxide water disappears before mixing with the sulfuric acid solution, because the peroxymonosulfuric acid and peroxodisulfuric acid are not formed, that is, the oxidizing substance contributing to the stripping of the photoresist is processed. Performance improvements are not sufficient. From such a situation, the improvement in processing performance and the reduction in the amount of the treatment liquid are preferred.
欲解決本發明之課題係可提供：可實現處理性能之提升及處理液使用量的降低者之基板處理裝置及基板處理方法。 In order to solve the problems of the present invention, it is possible to provide a substrate processing apparatus and a substrate processing method which are capable of achieving an improvement in processing performance and a reduction in the amount of processing liquid used.
有關實施形態基板處理裝置係具備：將過氧化氫水之沸點以上的第1溫度之硫酸溶液，供給至基板之第1液供給部，和將硫酸溶液及過氧化氫水的混合液，係較第1溫度為低之第2溫度之混合液，供給至基板之處理對象面的第2液供給部，和將基板的溫度，呈作為過氧化氫水之沸點以上地，使第1溫度之硫酸溶液供給至第1液供給部，而基板的溫度則成為第2溫度以上之情況，對於第1液供給部停止第1溫度之硫酸溶液的供給，而使第2溫度之混合液供給至第2液供給部的控制部。 The substrate processing apparatus according to the embodiment includes a first liquid supply unit that supplies a sulfuric acid solution having a first temperature equal to or higher than a boiling point of hydrogen peroxide water, and a mixed solution of a sulfuric acid solution and hydrogen peroxide water. The second liquid supply unit that supplies the second temperature to the second temperature is supplied to the second liquid supply unit of the processing target surface of the substrate, and the temperature of the substrate is equal to or higher than the boiling point of the hydrogen peroxide water, and the sulfuric acid at the first temperature is set. When the solution is supplied to the first liquid supply unit and the temperature of the substrate is equal to or higher than the second temperature, the first liquid supply unit stops supplying the sulfuric acid solution at the first temperature, and supplies the mixed liquid at the second temperature to the second temperature. The control unit of the liquid supply unit.
有關實施形態之基板處理方法係具有：將過氧化氫水之沸點以上的第1溫度之硫酸溶液供給至基板，而將基板的溫度作為過氧化氫水之沸點以上的工程，和基板的溫度則成為過氧化氫水之沸點以上之情況，停止第1溫度之硫酸溶液的供給，而將硫酸溶液及過氧化氫水之混合液，較第1溫度為低的第2溫度之混合液，供給至基板之處理對象面的工程。 The substrate processing method according to the embodiment has a method in which a sulfuric acid solution having a first temperature equal to or higher than a boiling point of hydrogen peroxide water is supplied to a substrate, and a temperature of the substrate is equal to or higher than a boiling point of hydrogen peroxide water, and a temperature of the substrate is used. When the boiling point of the hydrogen peroxide water is equal to or higher than the boiling point of the hydrogen peroxide water, the supply of the sulfuric acid solution at the first temperature is stopped, and the mixed solution of the sulfuric acid solution and the hydrogen peroxide water is supplied to the second temperature lower than the first temperature. The engineering of the processing target surface of the substrate.
如根據有關上述實施形態之基板處理裝置及基板處理方法，可實現處理性能之提升或處理液使用量的降低者。 According to the substrate processing apparatus and the substrate processing method according to the above embodiment, it is possible to improve the processing performance or the amount of the processing liquid used.
1‧‧‧基板處理裝置 1‧‧‧Substrate processing unit
2‧‧‧基板處理槽 2‧‧‧Substrate processing tank
2a‧‧‧杯狀物 2a‧‧‧ cup
2b‧‧‧平台 2b‧‧‧ platform
2c‧‧‧旋轉機構 2c‧‧‧Rotating mechanism
3‧‧‧液供給裝置 3‧‧‧Liquid supply device
3a‧‧‧第1液供給部 3a‧‧‧1st liquid supply department
3b‧‧‧第2液供給部 3b‧‧‧Second liquid supply department
3c‧‧‧第3液供給部 3c‧‧‧3rd liquid supply department
3d‧‧‧液循環部 3d‧‧‧Liquid circulation department
4‧‧‧液返回部 4‧‧‧Liquid return
4a‧‧‧回收管 4a‧‧‧Recycling tube
5‧‧‧控制部 5‧‧‧Control Department
11‧‧‧第1噴嘴 11‧‧‧1st nozzle
12，32‧‧‧供給管 12,32‧‧‧Supply tube
14，34，25，26‧‧‧開關閥 14,34,25,26‧‧‧ switch valve
15，27，28，35‧‧‧逆止閥 15,27,28,35‧‧‧ check valve
21‧‧‧第2噴嘴 21‧‧‧2nd nozzle
22‧‧‧供給管 22‧‧‧Supply tube
23，41‧‧‧貯留部 23,41‧‧‧Storage Department
24‧‧‧混合管 24‧‧‧ Mixing tube
29，45‧‧‧幫浦 29,45‧‧‧
31‧‧‧第3噴嘴 31‧‧‧3rd nozzle
13，33，43‧‧‧加熱部 13,33,43‧‧・heating department
42‧‧‧循環管 42‧‧‧Circulation tube
44‧‧‧調整閥 44‧‧‧Adjustment valve
圖1係顯示有關實施一形態之基板處理裝置之概略構成的圖。 Fig. 1 is a view showing a schematic configuration of a substrate processing apparatus according to an embodiment.
圖2係為了說明有關實施一形態之硫酸溶液之硫酸濃度及沸點之關係的說明圖。 Fig. 2 is an explanatory view for explaining the relationship between the sulfuric acid concentration and the boiling point of the sulfuric acid solution of the embodiment.
圖3係為了說明有關實施一形態之光阻劑剝離之實驗結果的說明圖。 Fig. 3 is an explanatory view for explaining an experimental result of peeling off a photoresist of a form.
圖4係顯示有關實施一形態之基板處理裝置之液吐出時間的說明圖。 Fig. 4 is an explanatory view showing a liquid discharge time of the substrate processing apparatus of the embodiment.
對於實施一形態，參照圖面加以說明。 The implementation of one embodiment will be described with reference to the drawings.
如圖1所示，有關實施形態之基板處理裝置1係具備：經由處理液而處理基板W之基板處理槽2，和供給處理液至其基板處理槽2之液供給裝置3，和將自基板處理槽2所排出之處理液，返回至液供給裝置3之液返回部4，和控制各部2、3及4之控制部5。然而，在本實施形態中，作為處理液而使用硫酸溶液及過氧化氫水的混合液(以下，單稱作SPM)。 As shown in FIG. 1, the substrate processing apparatus 1 according to the embodiment includes a substrate processing tank 2 that processes the substrate W via a processing liquid, and a liquid supply device 3 that supplies the processing liquid to the substrate processing tank 2, and the substrate is supplied from the substrate. The treatment liquid discharged from the treatment tank 2 is returned to the liquid return unit 4 of the liquid supply device 3, and the control unit 5 for controlling the respective units 2, 3 and 4 is controlled. However, in the present embodiment, a mixed solution of sulfuric acid solution and hydrogen peroxide water (hereinafter, simply referred to as SPM) is used as the treatment liquid.
基板處理槽2係具備：加以設置於槽內部之杯狀物2a，和在其杯狀物2a內以水平狀態而支持基板W的平台2b，和在水平面內此其平台2b旋轉之旋轉機構2c。 The substrate processing tank 2 includes a cup 2a provided inside the groove, and a stage 2b for supporting the substrate W in a horizontal state in the cup 2a, and a rotating mechanism 2c for rotating the stage 2b in the horizontal plane. .
杯狀物2a係加以形成為圓筒形狀，而將平台2b，自 周圍圍繞而收容於內部。杯狀物2a之周壁的上部係朝向於口徑方向內側而傾斜，而平台2b上之基板W的處理對象面Wa則呈露出地進行開口。此杯狀物2a係接收自旋轉的基板W的處理對象面Wa流下的處理液，更且，自基板W之處理對象面Wa或其相反面Wb飛散的處理液等。 The cup 2a is formed into a cylindrical shape, and the platform 2b is self-contained Surrounded by the surrounding and contained inside. The upper portion of the peripheral wall of the cup 2a is inclined toward the inner side in the diameter direction, and the processing target surface Wa of the substrate W on the stage 2b is exposed to be exposed. The cup 2a is a processing liquid that is discharged from the processing target surface Wa of the substrate W that is rotated, and a processing liquid that is scattered from the processing target surface Wa of the substrate W or the opposite surface Wb thereof.
平台2b係加以附上位置於杯狀物2a內之中央附近，可在水平面內旋轉地加以設置。此平台2b係具有複數銷等之支持構件2b1，而經由此等支持構件2b1，呈夾持晶圓或液晶基板等之基板W地支持。此基板W係於處理對象面Wa具有光罩用等之光阻劑(光阻層)。 The platform 2b is attached to the vicinity of the center in the cup 2a and is rotatably disposed in the horizontal plane. The platform 2b is a support member 2b1 having a plurality of pins or the like, and is supported by a substrate W such as a wafer or a liquid crystal substrate via the support members 2b1. This substrate W is a photoresist (photoresist layer) having a mask or the like on the processing target surface Wa.
旋轉機構2c係將平台2b之中央作為旋轉中心而使平台2b旋轉。此旋轉機構2c係具備：加以連結於平台2b中央之旋轉軸或使其旋轉軸旋轉之馬達(均未圖示)等。此馬達係加以電性連接於控制部5，而其驅動則經由控制部5而加以控制。 The rotating mechanism 2c rotates the platform 2b by using the center of the stage 2b as a center of rotation. The rotation mechanism 2c includes a rotation shaft that is coupled to the center of the platform 2b or a motor that rotates the rotation shaft (none of which is shown). The motor is electrically connected to the control unit 5, and the drive is controlled via the control unit 5.
液供給裝置3係具備：供給第1溫度之硫酸溶液至基板W之處理對象面Wa的第1液供給部3a，和供給第2溫度之SPM至基板W之處理對象面Wa的第2液供給部3b，和供給第3溫度之硫酸溶液至基板W之處理對象面Wa的相反面Wb之第3液供給部3c，和使供給至各部3a、3b及3c之硫酸溶液循環之液循環部3d。 The liquid supply device 3 includes a first liquid supply unit 3a that supplies the first temperature sulfuric acid solution to the processing target surface Wa of the substrate W, and a second liquid supply that supplies the second temperature SPM to the processing target surface Wa of the substrate W. The third portion 3b and the third liquid supply portion 3c that supplies the sulfuric acid solution at the third temperature to the opposite surface Wb of the processing target surface Wa of the substrate W, and the liquid circulation portion 3d that circulates the sulfuric acid solution supplied to the respective portions 3a, 3b, and 3c .
在此，第1溫度係過氧化氫水之沸點以上的特定之基板處理溫度，而第2溫度係較第1溫度為低之溫度。另外，第3溫度係第1溫度以上的溫度。特定之基板處理溫 度的範圍係經由SPM而處理基板W時之溫度範圍，例如，加以設定為150℃以上308℃以下之範圍內(詳細係後述之)。作為一例，對於將特定之基板處理溫度決定為150℃之情況，第1溫度係成為150℃，而第2溫度係成為不足150℃，第3溫度係成為150℃以上。另外，例如，對於將特定之基板處理溫度則決定為200℃之情況，第1溫度係200℃及第3溫度係成為200℃以上，但第2溫度係保持不足150℃。 Here, the first temperature is a specific substrate processing temperature equal to or higher than the boiling point of the hydrogen peroxide water, and the second temperature is a temperature lower than the first temperature. Further, the third temperature is a temperature equal to or higher than the first temperature. Specific substrate processing temperature The range of the degree is a temperature range when the substrate W is processed by SPM, and is set, for example, in a range of 150 ° C or more and 308 ° C or less (details will be described later). As an example, when the specific substrate processing temperature is determined to be 150 ° C, the first temperature system is 150 ° C, the second temperature system is less than 150 ° C, and the third temperature system is 150 ° C or higher. Further, for example, when the specific substrate processing temperature is determined to be 200 ° C, the first temperature system 200 ° C and the third temperature system are 200 ° C or higher, but the second temperature system is kept less than 150 ° C.
第1液供給部3a係具有：供給第1溫度之硫酸溶液於平台2b上之基板W的處理對象面Wa之第1噴嘴11，和連接其第1噴嘴11與液循環部3d之供給管12，和加熱流動在其供給管12之硫酸溶液的加熱部13，和開閉供給管12之開閉閥14，和將硫酸溶液的流動方向，限定為自液循環部3d至第1噴嘴11之一方向的逆止閥15。 The first liquid supply unit 3a includes a first nozzle 11 that supplies a sulfuric acid solution having a first temperature to the processing target surface Wa of the substrate W on the stage 2b, and a supply tube 12 that connects the first nozzle 11 and the liquid circulation portion 3d. And heating the heating portion 13 of the sulfuric acid solution flowing through the supply pipe 12, and opening and closing the opening and closing valve 14 of the supply pipe 12, and limiting the flow direction of the sulfuric acid solution to one of the liquid circulation portion 3d to the first nozzle 11 Check valve 15.
第1噴嘴11係朝向平台2b上之基板W的處理對象面Wa而吐出第1溫度之硫酸溶液。此第1噴嘴11係可沿著平台2b上之基板W的處理對象面Wa移動地加以設置，而沿著平台2b上之基板W的處理對象面Wa移動之同時，或者，自對向於處理對象面Wa之略中央的特定位置，朝向處理對象面Wa而吐出硫酸溶液。 The first nozzle 11 discharges the sulfuric acid solution of the first temperature toward the processing target surface Wa of the substrate W on the stage 2b. The first nozzle 11 is movably disposed along the processing target surface Wa of the substrate W on the stage 2b, and moves along the processing target surface Wa of the substrate W on the stage 2b, or is self-aligned. At a specific position in the center of the object surface Wa, the sulfuric acid solution is discharged toward the processing target surface Wa.
供給管12係連接第1噴嘴11與液循環部3d之配管，於此供給管12加以設置有開閉閥14及逆止閥15。作為開閉閥14係例如，可使用電磁閥等者。此開閉閥14係加以電性連接於控制部5，而因應經由其控制部5之控 制而開閉供給管12的流路。 The supply pipe 12 is connected to a pipe of the first nozzle 11 and the liquid circulation portion 3d, and the supply pipe 12 is provided with an opening and closing valve 14 and a check valve 15. As the opening and closing valve 14, for example, an electromagnetic valve or the like can be used. The on-off valve 14 is electrically connected to the control unit 5, and is controlled by the control unit 5 thereof. The flow path of the supply pipe 12 is opened and closed.
加熱部13係可加熱流動在其供給管12之硫酸溶液地加以設置於供給管12之途中。此加熱部13係加以電性連接於控制部5，而因應經由其控制部5之控制而加熱流動在供給管12的硫酸溶液。作為此加熱部13係例如，可使用加熱器者。加熱溫度係流動在供給管12之硫酸溶液的溫度則呈成為第1溫度地加以設定。 The heating unit 13 can heat the flow of the sulfuric acid solution flowing through the supply pipe 12 to the supply pipe 12. The heating unit 13 is electrically connected to the control unit 5, and the sulfuric acid solution flowing through the supply tube 12 is heated by the control of the control unit 5. As the heating unit 13, for example, a heater can be used. The heating temperature is set so as to be the first temperature when the temperature of the sulfuric acid solution flowing through the supply pipe 12 is reached.
第2液供給部3b係具有：供給第2溫度之SPM於平台2b上之基板W的處理對象面Wa的第2噴嘴21，和連接其第2噴嘴21與液循環部3d之供給管22，和貯留過氧化氫水之貯留部23，和與其貯留部23與供給管22連接之混合管24，和開閉供給管22之開閉閥25，和開閉混合管24之開閉閥26，和將硫酸溶液的流動方向，限制為自液循環部3d至第2噴嘴21之一方向的逆止閥27，和將過氧化氫水的流動方向，限定為自貯留部23至供給管22之一方向的逆止閥28，和使送液力產生的幫浦29。然而，第2液供給部3b係作為混合硫酸溶液及過氧化氫水而生成SPM之混合液生成部而發揮機能。 The second liquid supply unit 3b includes a second nozzle 21 that supplies the SPM of the second temperature to the processing target surface Wa of the substrate W on the stage 2b, and a supply tube 22 that connects the second nozzle 21 and the liquid circulation unit 3d. And a storage pipe 23 for storing hydrogen peroxide water, a mixing pipe 24 connected to the storage portion 23 and the supply pipe 22, an opening and closing valve 25 for opening and closing the supply pipe 22, and an opening and closing valve 26 for opening and closing the mixing pipe 24, and a sulfuric acid solution. The flow direction is limited to the check valve 27 in the direction from the liquid circulation portion 3d to the second nozzle 21, and the flow direction of the hydrogen peroxide water is limited to the direction from one of the reservoir portion 23 to the supply tube 22. The check valve 28, and the pump 29 for generating the hydraulic force. However, the second liquid supply unit 3b functions as a mixed liquid generating unit that generates a SPM by mixing a sulfuric acid solution and hydrogen peroxide water.
第2噴嘴21係朝向平台2b上之基板W的處理對象面Wa而吐出第2溫度之SPM。此第2噴嘴21係可沿著平台2b上之基板W的處理對象面Wa移動地加以設置，而沿著平台2b上之基板W的處理對象面Wa移動之同時，或者，自對向於處理對象面Wa之略中央的特定位置，朝向處理對象面Wa而吐出SPM。 The second nozzle 21 discharges the SPM of the second temperature toward the processing target surface Wa of the substrate W on the stage 2b. The second nozzle 21 is movably disposed along the processing target surface Wa of the substrate W on the stage 2b, and moves along the processing target surface Wa of the substrate W on the stage 2b, or is self-aligned. The specific position at the center of the object surface Wa is discharged to the processing target surface Wa to discharge the SPM.
供給管22係連接第2噴嘴21與液循環部3d之配管，於此供給管22加以設置有開閉閥25及逆止閥27。作為開閉閥25係例如，可使用電磁閥等者。此開閉閥25係加以電性連接於控制部5，而因應經由其控制部5之控制而開閉供給管22的流路。 The supply pipe 22 is connected to a pipe of the second nozzle 21 and the liquid circulation portion 3d, and the supply pipe 22 is provided with an opening and closing valve 25 and a check valve 27. As the opening and closing valve 25, for example, an electromagnetic valve or the like can be used. The on-off valve 25 is electrically connected to the control unit 5, and the flow path of the supply pipe 22 is opened and closed by the control of the control unit 5.
貯留部23係貯留常溫(例如，20~30℃程度)之過氧化氫水的液槽。此貯留部23內之過氧化氫水係經由幫浦29的驅動而傳送至混合管24，流動在此混合管24內。幫浦29係加以電性連接於控制部5，因應經由其控制部5之控制而輸送貯留部23內之過氧化氫水於混合管24。 The storage portion 23 is a liquid tank for storing hydrogen peroxide water at a normal temperature (for example, about 20 to 30 ° C). The hydrogen peroxide water in the storage portion 23 is sent to the mixing tube 24 via the driving of the pump 29, and flows into the mixing tube 24. The pump 29 is electrically connected to the control unit 5, and the hydrogen peroxide water in the storage unit 23 is sent to the mixing tube 24 via the control of the control unit 5.
混合管24係連接較開關閥25為下流側之供給管22與貯留部23的配管，於此混合管24加以設置有開關閥26及逆止閥28。作為開關閥26係例如，可使用電磁閥等者。此開關閥26係加以電性連接於控制部5，而因應經由其控制部5之控制而開閉混合管24的流路。 The mixing pipe 24 is connected to a pipe in which the switching valve 25 is a supply pipe 22 and a storage portion 23 on the downstream side, and the mixing pipe 24 is provided with an on-off valve 26 and a check valve 28. As the on-off valve 26, for example, an electromagnetic valve or the like can be used. The on-off valve 26 is electrically connected to the control unit 5, and the flow path of the mixing tube 24 is opened and closed by the control of the control unit 5.
此混合管24係供給過氧化氫水於供給管22，混合所供給之過氧化氫水與供給管22內之硫酸溶液。此時，加以混合硫酸溶液與過氧化氫水時，經由此時之反應熱而SPM之溫度係變高而成為第2溫度(詳細係後述之)。 The mixing tube 24 supplies hydrogen peroxide water to the supply pipe 22, and mixes the supplied hydrogen peroxide water with the sulfuric acid solution in the supply pipe 22. At this time, when the sulfuric acid solution and the hydrogen peroxide water are mixed, the temperature of the SPM becomes higher through the reaction heat at this time, and becomes the second temperature (details will be described later).
第3液供給部3c係具有：供給第3溫度之硫酸溶液於平台2b上之基板W的處理對象面Wa之相反面Wb之第3噴嘴31，和連接其第3噴嘴31與液循環部3d之供給管32，和加熱流動在其供給管32之硫酸溶液的加熱部33，和開閉供給管32之開關閥34，和將硫酸溶液的流動 方向，限定為自液循環部3d至第3噴嘴31之一方向的逆止閥35。 The third liquid supply unit 3c includes a third nozzle 31 that supplies a sulfuric acid solution having a third temperature to the opposite surface Wb of the processing target surface Wa of the substrate W on the stage 2b, and a third nozzle 31 and a liquid circulation portion 3d. The supply pipe 32, and the heating portion 33 for heating the sulfuric acid solution flowing in the supply pipe 32, and the opening and closing valve 34 of the supply pipe 32, and the flow of the sulfuric acid solution The direction is limited to the check valve 35 in the direction from the liquid circulation portion 3d to the third nozzle 31.
第3噴嘴31係朝向平台2b上之基板W的處理對象面Wa之背面的相反面Wb而吐出第3溫度之硫酸溶液。此第3噴嘴31係可將硫酸溶液吐出成放射狀，或者，改變吐出角度同時而進行吐出者，而自對向於處理對象面Wa之相反面Wb之略中央的特定位置，吐出硫酸溶液。 The third nozzle 31 discharges the sulfuric acid solution of the third temperature toward the opposite surface Wb of the back surface of the processing target surface Wa of the substrate W on the stage 2b. In the third nozzle 31, the sulfuric acid solution can be discharged into a radial state, or the discharge rate can be changed while the discharge angle is changed, and the sulfuric acid solution can be discharged from a specific position in the center of the opposite surface Wb opposite to the processing target surface Wa.
供給管32係連接第3噴嘴31與液循環部3d之配管，於此供給管32加以設置有開關閥34及逆止閥35。作為開關閥34係例如，可使用電磁閥等者。此開關閥34係加以電性連接於控制部5，而因應經由其控制部5之控制而開閉供給管32的流路。 The supply pipe 32 is connected to a pipe of the third nozzle 31 and the liquid circulation portion 3d, and the supply pipe 32 is provided with an on-off valve 34 and a check valve 35. As the on-off valve 34, for example, an electromagnetic valve or the like can be used. The on-off valve 34 is electrically connected to the control unit 5, and the flow path of the supply pipe 32 is opened and closed by the control of the control unit 5.
加熱部33係可加熱流動在其供給管32之硫酸溶液地加以設置於供給管32之途中。此加熱部33係加以電性連接於控制部5，而因應經由其控制部5之控制而加熱流動在供給管32的硫酸溶液。作為此加熱部33係例如，可使用加熱器者。加熱溫度係流動在供給管32之硫酸溶液的溫度則呈成為第3溫度地加以設定。 The heating unit 33 can heat the flow of the sulfuric acid solution flowing through the supply pipe 32 to the supply pipe 32. The heating unit 33 is electrically connected to the control unit 5, and the sulfuric acid solution flowing through the supply pipe 32 is heated by the control of the control unit 5. As the heating unit 33, for example, a heater can be used. The heating temperature is set so that the temperature of the sulfuric acid solution flowing through the supply pipe 32 becomes the third temperature.
液循環部3d係具備：貯留硫酸溶液之貯留部41，和使其貯留部41內之硫酸溶液循環的循環管42，和加熱流動在其循環管42之硫酸溶液的加熱部43，和調整循環管42之開度(即，所循環之處理液的流量)之調整閥44，和使送液力產生的幫浦45。 The liquid circulation unit 3d includes a storage portion 41 for storing the sulfuric acid solution, a circulation pipe 42 for circulating the sulfuric acid solution in the storage portion 41, and a heating portion 43 for heating the sulfuric acid solution flowing through the circulation pipe 42, and an adjustment cycle. The adjustment valve 44 of the opening degree of the tube 42 (i.e., the flow rate of the circulating treatment liquid) and the pump 45 for generating the liquid supply force.
貯留部41係例如，貯留60℃以上120℃以下之硫酸 溶液的液槽。此貯留部41內之硫酸溶液係經由幫浦45的驅動而傳送至循環管42，流動在此循環管42內。幫浦45係加以電性連接於控制部5，因應經由其控制部5之控制而輸送貯留部41內之硫酸溶液於循環管42。 The storage portion 41 is, for example, a sulfuric acid having a temperature of 60 ° C or more and 120 ° C or less. The tank of the solution. The sulfuric acid solution in the storage portion 41 is sent to the circulation pipe 42 via the driving of the pump 45, and flows into the circulation pipe 42. The pump 45 is electrically connected to the control unit 5, and the sulfuric acid solution in the storage unit 41 is transported to the circulation pipe 42 by the control of the control unit 5.
循環管42係自貯留部41延伸而返回至其貯留部41，使硫酸溶液循環的配管，於此循環管42加以設置調整閥44。作為調整閥44係例如，可使用電磁閥等者。此調整閥44係加以電性連接於控制部5，而因應經由其控制部5之控制而調整循環管42的開度，即調整流量。另外，對於循環管42係個別地加以連接第1液供給部3a之供給管12，第2液供給部3b之供給管22及第3液供給部3c之供給管32。 The circulation pipe 42 is a pipe that extends from the storage portion 41 and returns to the storage portion 41 to circulate the sulfuric acid solution, and the circulation pipe 42 is provided with the adjustment valve 44. As the adjustment valve 44, for example, an electromagnetic valve or the like can be used. The adjustment valve 44 is electrically connected to the control unit 5, and the opening degree of the circulation pipe 42 is adjusted by the control of the control unit 5, that is, the flow rate is adjusted. Further, the circulation pipe 42 is connected to the supply pipe 12 of the first liquid supply unit 3a, the supply pipe 22 of the second liquid supply unit 3b, and the supply pipe 32 of the third liquid supply unit 3c.
加熱部43係加以設置於循環管42之途中，成為可加熱流動在其循環管42之硫酸溶液者。此加熱部43係加以電性連接於控制部5，而因應經由其控制部5之控制而加熱流動在循環管42的硫酸溶液。作為此加熱部43係例如，可使用加熱器者。加熱溫度係流動在循環管42之硫酸溶液的溫度則較硫酸溶液的沸點為小，例如，60℃以上120℃以下的範圍內，作為一例而呈成為80℃地加以設定。 The heating unit 43 is provided on the way of the circulation pipe 42, and is a person who can heat the sulfuric acid solution flowing through the circulation pipe 42. The heating unit 43 is electrically connected to the control unit 5, and the sulfuric acid solution flowing through the circulation pipe 42 is heated by the control of the control unit 5. As the heating unit 43, for example, a heater can be used. The temperature of the sulfuric acid solution flowing through the circulation pipe 42 at the heating temperature is smaller than the boiling point of the sulfuric acid solution, for example, in the range of 60° C. or more and 120° C. or less, and is set to 80° C. as an example.
液返回部4係具備：自基板處理槽2之杯狀物2a回收液體之回收管4a，和冷卻流動在其回收管4a之回收液的冷卻部4b。回收管4a係連接杯狀物2a底面與液循環部3d之貯留部41的管，而於此回收管4a加以設置冷卻部 4b。作為冷卻部4b係例如，可使用泊耳帖元件或熱交換器等者。此冷卻部4b係加以電性連接於控制部5，而因應經由其控制部5之控制而冷卻流動在回收管4a內的回收液。冷卻溫度係回收液則例如60℃以上120℃以下之範圍內，作為一例而呈成為80℃地加以設定。然而，SPM則在基板W之處理對象面Wa上產生反應時，過氧化氫水則分解，而成為過氧一硫酸(過硫酸)、過氧二硫酸之故，回收液係成為硫酸溶液。 The liquid returning unit 4 includes a recovery pipe 4a that recovers liquid from the cup 2a of the substrate processing tank 2, and a cooling unit 4b that cools the recovered liquid flowing through the recovery pipe 4a. The recovery pipe 4a is a pipe that connects the bottom surface of the cup 2a and the storage portion 41 of the liquid circulation portion 3d, and the recovery pipe 4a is provided with a cooling portion. 4b. As the cooling unit 4b, for example, a Pole member, a heat exchanger or the like can be used. The cooling unit 4b is electrically connected to the control unit 5, and the recovered liquid flowing in the recovery pipe 4a is cooled by the control of the control unit 5. The cooling temperature-based recovery liquid is, for example, in the range of 60° C. or more and 120° C. or less, and is set to 80° C. as an example. However, when SPM reacts on the processing target surface Wa of the substrate W, the hydrogen peroxide water is decomposed to become peroxymonosulfuric acid (persulfuric acid) or peroxodisulfuric acid, and the recovered liquid is a sulfuric acid solution.
在此，硫酸溶液及過氧化氫水的反應熱係變高之故，如前述，設置冷卻部4b，但並不限定於此者，而硫酸溶液及過氧化氫水之反應熱則未成為問題程度，即對於回收液則例如成為60℃以上120℃以下之範圍內的情況，係成為無須冷卻回收液之故，未設置冷卻部4b亦可。 Here, although the reaction heat of the sulfuric acid solution and the hydrogen peroxide water is increased, the cooling unit 4b is provided as described above, but the invention is not limited thereto, and the reaction heat of the sulfuric acid solution and the hydrogen peroxide water is not a problem. In the case where the recovery liquid is in the range of, for example, 60° C. or more and 120° C. or less, the cooling portion 4b may not be provided, and the cooling unit 4b may not be provided.
控制部5係具備：集中地控制各部之微電腦，和記憶關於基板處理之基板處理資訊或各種程式等之記憶部(均未圖示)。此控制部5係依據基板處理資訊或各種程式而控制基板處理槽2或液供給裝置3，液返回部4等之各部。例如，進行經由基板處理槽2及液供給裝置3之基板處理或液循環，經由液返回部4之液回收等之控制。 The control unit 5 includes a microcomputer that collectively controls each unit, and a memory unit (none of which is shown) that memorizes substrate processing information or various programs for substrate processing. The control unit 5 controls each of the substrate processing tank 2, the liquid supply device 3, the liquid returning unit 4, and the like in accordance with the substrate processing information or various programs. For example, control of the substrate processing or liquid circulation through the substrate processing tank 2 and the liquid supply device 3, liquid recovery via the liquid returning portion 4, and the like is performed.
在此，前述之處理液係為SPM之故，而特定之基板處理溫度範圍成為150℃以上308℃以下者為佳，但對於此範圍之上限溫度及下限溫度加以說明。 Here, the above-mentioned processing liquid is SPM, and the specific substrate processing temperature range is preferably 150° C. or higher and 308° C. or lower. However, the upper limit temperature and the lower limit temperature in this range will be described.
如圖2所示，加以顯示硫酸溶液之硫酸濃度(wt%：質量百分率濃度)與沸點(℃)之關係。然而，質量百分 率濃度係指(溶質之質量/溶液之質量)×100。此硫酸溶液之硫酸濃度與沸點之關係則作為圖表A1而顯示於圖3，而光阻劑剝離之實驗結果(○印或×印)則對於每硫酸溶液之硫酸濃度及SPM之溫度的組合加以顯示。 As shown in Fig. 2, the relationship between the sulfuric acid concentration (wt%: mass percentage concentration) and the boiling point (°C) of the sulfuric acid solution is shown. However, the mass percentage The concentration concentration means (mass of solute/mass of solution) × 100. The relationship between the sulfuric acid concentration and the boiling point of the sulfuric acid solution is shown in Fig. 3 as the graph A1, and the experimental result of the photoresist stripping (○ printing or x printing) is applied to the combination of the sulfuric acid concentration per sulfuric acid solution and the temperature of the SPM. display.
如圖3所示，對於可光阻劑剝離之情況，係(剝離可能)，顯示、○印(圈印)，而對於殘留有光阻劑而光阻劑剝離不完全之情況，係(剝離殘留)，加以顯×印(叉印)。硫酸濃度則約65wt%至約96wt%之範圍以內，而SPM之温度則如為150℃以上，光阻劑剝離則成為可能。然而，硫酸濃度則為65wt%時，硫酸溶液之沸點係150℃，而SPM之沸點亦相同為150℃。從此實驗結果，特定之基板處理溫度範圍之下限溫度係150℃以上為佳。 As shown in Fig. 3, in the case where the photoresist can be peeled off, it is possible (peeling), display, ○ printing (ring printing), and in the case where the photoresist is left and the photoresist is not completely peeled off, Residual), printed and printed (fork). The sulfuric acid concentration is in the range of about 65 wt% to about 96 wt%, and the temperature of the SPM is 150 ° C or more, and the photoresist stripping is possible. However, when the sulfuric acid concentration is 65 wt%, the boiling point of the sulfuric acid solution is 150 ° C, and the boiling point of the SPM is also 150 ° C. From the results of this experiment, the lower limit temperature of the specific substrate treatment temperature range is preferably 150 ° C or more.
然而，從圖2了解到，對於為了將硫酸溶液之沸點作為150℃以上，係必須將硫酸溶液之硫酸濃度作為65wt%以上，但在硫酸溶液之硫酸濃度則較65wt%為薄為止，回收自基板處理槽2所排出之排液，可將其回收液作為硫酸溶液而使用。 However, it is understood from Fig. 2 that in order to set the boiling point of the sulfuric acid solution to 150 ° C or higher, the sulfuric acid concentration of the sulfuric acid solution must be 65 wt% or more, but the sulfuric acid concentration of the sulfuric acid solution is thinner than 65 wt%, and is recovered from The liquid discharged from the substrate processing tank 2 can be used as a sulfuric acid solution.
接著，特定之基板處理溫度範圍之上限溫度係自可剝離光阻劑之溫度所決定。在此，光阻劑剝離可能之範圍係在圖3中附上○印之範圍。附上○印之範圍的硫酸濃度係65wt%至96wt%之範圍。此時，如圖2所示，硫酸溶液之沸點的溫度範圍係成為150℃以上308℃以下之範圍，伴隨於此，SPM之溫度範圍亦與硫酸溶液之沸點同樣，成為150℃以上308℃以下。從此硫酸溶液之沸點與SPM之溫 度範圍之上限值，特定之基板處理溫度範圍之上限溫度係成為308℃。因此，特定之基板處理溫度範圍之上限溫度係308℃以下者為佳。 Next, the upper limit temperature of the particular substrate processing temperature range is determined by the temperature of the strippable photoresist. Here, the range in which the photoresist is peeled off is in the range of ○ printed in FIG. The sulfuric acid concentration in the range of ○print is in the range of 65 wt% to 96 wt%. In this case, as shown in FIG. 2, the temperature range of the boiling point of the sulfuric acid solution is in the range of 150 ° C to 308 ° C. Accordingly, the temperature range of SPM is also the same as the boiling point of the sulfuric acid solution, and is 150 ° C or more and 308 ° C or less. . From the boiling point of the sulfuric acid solution and the temperature of SPM The upper limit of the degree range, the upper limit temperature of the specific substrate processing temperature range is 308 °C. Therefore, the upper limit temperature of the specific substrate processing temperature range is preferably 308 ° C or less.
但，前述之硫酸溶液及過氧化氫水之混合液的比率係經由除去處理而產生變化，但過氧化氫水之濃度減少時，剝離性則降低故，例如，在硫酸溶液：過氧化氫水之體積比為100：1~3：1的比率(硫酸溶液之體積係對於過氧化氫水之體積而言，例如為3倍以上100倍以下)。另外，更理想係H2SO4(98wt%)：H2O2(35wt%)=7：3~20：1之比率。 However, the ratio of the above-mentioned mixed solution of the sulfuric acid solution and the hydrogen peroxide water is changed by the removal treatment. However, when the concentration of the hydrogen peroxide water is decreased, the peelability is lowered, for example, in a sulfuric acid solution: hydrogen peroxide water. The volume ratio is a ratio of 100:1 to 3:1 (the volume of the sulfuric acid solution is, for example, 3 times or more and 100 times or less for the volume of hydrogen peroxide water). Further, it is more desirable to be a ratio of H 2 SO 4 (98 wt%): H 2 O 2 (35 wt%) = 7:3 to 20:1.
然而，在第2液供給部3b中，由改變供給管22或混合管24之粗度，或者將供給管22之開關閥25或混合管24之開關閥26更換為調整閥而調整管的開度者，可改變硫酸溶液及過氧化氫水之混合液的比率者。 However, in the second liquid supply unit 3b, the thickness of the supply pipe 22 or the mixing pipe 24 is changed, or the on-off valve 25 of the supply pipe 22 or the on-off valve 26 of the mixing pipe 24 is replaced with a regulating valve to adjust the opening of the pipe. In addition, the ratio of the mixture of the sulfuric acid solution and the hydrogen peroxide water can be changed.
接著，對於前述之基板處理裝置1所進行之基板處理動作，參照圖4加以說明。控制部5係依據基板處理資訊或各種程式等而執行基板處理。作為一例，特定之基板處理溫度係加以決定為150℃。此時，第1溫度係成為150℃，而第2溫度係成為不足150℃，第3溫度係成為150℃以上。另外，硫酸溶液之硫酸濃度係65wt%以上。 Next, the substrate processing operation performed by the substrate processing apparatus 1 described above will be described with reference to FIG. 4 . The control unit 5 performs substrate processing in accordance with substrate processing information, various programs, and the like. As an example, the specific substrate processing temperature is determined to be 150 °C. At this time, the first temperature system is 150 ° C, the second temperature system is less than 150 ° C, and the third temperature system is 150 ° C or higher. Further, the sulfuric acid concentration of the sulfuric acid solution is 65 wt% or more.
首先，平台2b上之基板W則經由旋轉機構2c而以特定的旋轉速度進行旋轉，之後，如圖4所示，在步驟S1中，自第1液供給部3a之第1噴嘴(第1噴嘴)11，加以吐出第1溫度之硫酸溶液於基板W的處理對象面 Wa，更且，自第3液供給部3c之第3噴嘴(第3噴嘴)31，加以吐出第3溫度之硫酸溶液於基板W的處理對象面Wa相反面Wb。 First, the substrate W on the stage 2b is rotated at a specific rotation speed via the rotation mechanism 2c, and then, as shown in FIG. 4, the first nozzle (first nozzle) from the first liquid supply unit 3a is shown in step S1. 11), the sulfuric acid solution of the first temperature is discharged to the surface of the substrate W In addition, the third nozzle (third nozzle) 31 of the third liquid supply unit 3c discharges the sulfuric acid solution of the third temperature on the opposite surface Wb of the processing target surface Wa of the substrate W.
此時，自第1噴嘴11加以供給硫酸溶液至基板W的處理對象面Wa之略中央時，經由基板W之旋轉的離心力而擴散於基板W的處理對象面Wa全體，加以形成液膜於其表面。同樣地，自第3噴嘴31加以供給硫酸溶液至基板W的處理對象面Wa之相反面Wb之略中央時，經由基板W之旋轉的離心力而擴散於基板W的處理對象面Wa之相反面Wb全體，加以形成液膜於其表面。然而，將第3噴嘴31設置於對向於第1噴嘴11之位置，但並不限於此等，而例如，對於基板W之旋轉軸而言對稱性地設置亦可。 At this time, when the sulfuric acid solution is supplied from the first nozzle 11 to the center of the processing target surface Wa of the substrate W, the entire processing target surface Wa of the substrate W is diffused by the centrifugal force of the rotation of the substrate W, and a liquid film is formed thereon. surface. In the same manner, when the sulfuric acid solution is supplied from the third nozzle 31 to the center of the opposite surface Wb of the processing target surface Wa of the substrate W, it is diffused on the opposite surface Wb of the processing target surface Wa of the substrate W by the centrifugal force of the rotation of the substrate W. Whole, a liquid film is formed on the surface. However, the third nozzle 31 is provided at a position facing the first nozzle 11, but the present invention is not limited thereto. For example, the rotation axis of the substrate W may be symmetrically provided.
在此，對於進行供給處理液至自基板W的處理對象面Wa之中心偏差的位置之偏移之情況，當與供給處理液於基板W的處理對象面Wa之中心的情況做比較時，處理液則經常地未加以供給相同基板W上之位置，而也就是由基板W旋轉者，到達至基板W之處理液的位置產生變化，可加熱基板W之廣範圍者。更且，如將處理液吐出成放射狀，因處理液則加以供給至基板W之範圍則被擴大之故，可使自基板W的處理對象面Wa之中心至外周之加熱均一性提升者。 Here, when the processing liquid is supplied to the position of the center deviation of the processing target surface Wa of the substrate W, the processing is performed when compared with the case where the processing liquid is supplied to the center of the processing target surface Wa of the substrate W. The liquid is often not supplied to the position on the same substrate W, that is, the position of the processing liquid reaching the substrate W is changed by the rotation of the substrate W, and a wide range of the substrate W can be heated. In addition, when the processing liquid is discharged to the radial direction, the range in which the processing liquid is supplied to the substrate W is enlarged, so that the heating uniformity from the center to the outer circumference of the processing target surface Wa of the substrate W can be improved.
在第1液供給部3a中，經由加熱部13而加以加熱硫酸溶液，而第1溫度係成為150℃，同樣地，在第3液供 給部3c中，經由加熱部33而加以加熱硫酸溶液，而其第3溫度係成為150℃以上。如此之第1溫度之硫酸溶液及第3溫度之硫酸溶液則朝向基板W而加以吐出，經由此等之硫酸溶液而加溫基板W。 In the first liquid supply unit 3a, the sulfuric acid solution is heated via the heating unit 13, and the first temperature system is 150 ° C, and similarly, the third liquid is supplied. In the feeding portion 3c, the sulfuric acid solution is heated via the heating portion 33, and the third temperature system is 150 °C or higher. The sulfuric acid solution at the first temperature and the sulfuric acid solution at the third temperature are discharged toward the substrate W, and the substrate W is heated via the sulfuric acid solution.
自步驟S1之液供給開始經過特定時間t1，基板W則充分加溫而為特定之基板處理溫度，即成為150℃時，在步驟S2中，停止自第1噴嘴11之硫酸溶液吐出，而在第2液供給部3b中加以混合硫酸溶液及過氧化氫水，自第2噴嘴(第2噴嘴)21將第2溫度之SPM，則加以吐出至基板W的處理對象面Wa上。 When the liquid supply in step S1 is started for a predetermined time t1, the substrate W is sufficiently heated to a specific substrate processing temperature, that is, at 150 ° C, in step S2, the sulfuric acid solution from the first nozzle 11 is stopped, and The sulfuric acid solution and the hydrogen peroxide water are mixed in the second liquid supply unit 3b, and the SPM of the second temperature is discharged from the second nozzle (second nozzle) 21 to the processing target surface Wa of the substrate W.
此時，當自第2噴嘴21加以供給SPM於基板W之處理對象面Wa之略中央時，經由基板W之旋轉的離心力而擴散於基板W的處理對象面Wa全體，加以形成液膜於其表面。然而，自第3噴嘴31之硫酸溶液吐出係加以持續進行。 At this time, when SPM is supplied from the second nozzle 21 to the center of the processing target surface Wa of the substrate W, the entire processing target surface Wa of the substrate W is diffused by the centrifugal force of the rotation of the substrate W, and a liquid film is formed thereon. surface. However, the discharge of the sulfuric acid solution from the third nozzle 31 is continued.
在第2液供給部3b中，當加以混合60℃以上120℃以下之硫酸溶液與常溫(例如，20~30℃程度)之過氧化氫水時，經由此時之反應熱而SPM的溫度係變高，成為第2溫度，但此第2溫度係特定之基板處理溫度，即因成為較SPM之沸點為低之故，可防止突沸者。加上，SPM則到達至基板W的處理對象面Wa為止，可抑制過氧化氫水的分解，即過氧一硫酸及過氧二硫酸之反應的促進者。另外，在基板W的處理對象面Wa上中，因經由所加熱之基板W的溫度而過氧化氫水產生分解，而促進氧化力強 之過氧一硫酸及過氧二硫酸之反應之故，可使光阻劑剝離性提升者。 In the second liquid supply unit 3b, when a sulfuric acid solution of 60° C. or more and 120° C. or less is mixed with hydrogen peroxide water at a normal temperature (for example, about 20 to 30° C.), the temperature of the SPM is passed through the reaction heat at this time. When it becomes high, it becomes a 2nd temperature, but this 2nd temperature system is a board|substrate processing temperature, and it is set as the point which becomes the boiling point rather than SPM, and can prevent a bumper. In addition, the SPM reaches the processing target surface Wa of the substrate W, and can suppress the decomposition of hydrogen peroxide water, that is, the promoter of the reaction of peroxymonosulfuric acid and peroxodisulfuric acid. Further, in the processing target surface Wa of the substrate W, hydrogen peroxide water is decomposed by the temperature of the heated substrate W, and the oxidation resistance is promoted. The reaction of peroxymonosulfuric acid and peroxodisulfuric acid can improve the peelability of the photoresist.
然而，即使加以停止自第1噴嘴11之硫酸溶液吐出，因亦加以繼續自第3噴嘴31之硫酸溶液吐出之故，第3溫度之硫酸溶液則加以持續供給於基板W的處理對象面Wa的相反面Wb，而持續基板W的溫度。因此，經由自第2噴嘴21所吐出之第2溫度的SPM，可抑制基板W之溫度下降者。 However, even if the sulfuric acid solution from the first nozzle 11 is stopped, the sulfuric acid solution of the third temperature is continuously discharged from the sulfuric acid solution of the third nozzle 31, and the sulfuric acid solution of the third temperature is continuously supplied to the processing target surface Wa of the substrate W. The opposite side Wb, while continuing the temperature of the substrate W. Therefore, the temperature drop of the substrate W can be suppressed by the SPM of the second temperature discharged from the second nozzle 21 .
但自第3噴嘴31之硫酸溶液吐出係未必需要者，而例如，即使經由自第2噴嘴21所吐出之第2溫度的SPM而基板W的溫度下降，亦可不執行其基板W的溫度成為特定之基板處理溫度以上之情況等，自第3噴嘴31之硫酸溶液吐出者。 However, the sulfuric acid solution from the third nozzle 31 is not necessarily required. For example, even if the temperature of the substrate W is lowered by the SPM of the second temperature ejected from the second nozzle 21, the temperature of the substrate W may not be specified. When the substrate processing temperature is equal to or higher than the above, the sulfuric acid solution from the third nozzle 31 is discharged.
在此，第2溫度係較過氧化氫水之沸點為低者為佳，但並不限定於此，而第2溫度係即使較過氧化氫水的沸點為高而如較第1溫度為低即可。 Here, the second temperature system is preferably lower than the boiling point of the hydrogen peroxide water, but the second temperature system is not lower than the boiling point of the hydrogen peroxide water, and is lower than the first temperature. Just fine.
接著，自步驟S2之液供給開始，經過特定時間t2，基板W的處理對象面Wa全體則自硫酸溶液加以置換為SPM時，在步驟S3中，加以停止自第2噴嘴21之SPM吐出。更且，基板W之旋轉速度則作為成慢於未經由旋轉之離心力而處理對象面Wa上之SPM產生飛散程度，而基板W的處理對象面Wa上之SPM則作為成漿狀態(液貯留狀態)。 Then, when the entire processing target surface Wa of the substrate W is replaced with SPM from the sulfuric acid solution from the supply of the liquid in the step S2, the SPM discharge from the second nozzle 21 is stopped in the step S3. Further, the rotation speed of the substrate W is caused to be slower than the SPM on the processing target surface Wa which is slower than the centrifugal force that has not been rotated, and the SPM on the processing target surface Wa of the substrate W is used as the slurry state (liquid storage state). ).
在此漿狀態中，加以停止對於基板W的處理對象面 Wa而言之SPM的供給之故，基板W的處理對象面Wa上之SPM的溫度係確實上升至基板W的溫度。另外，對於基板W的處理對象面Wa之相反面Wb係因自第3噴嘴31持續加以吐出硫酸溶液之故，加以維持基板W之溫度，而防止基板W之溫度下降。 In this state of the slurry, the processing target surface for the substrate W is stopped. In the case of the supply of SPM by Wa, the temperature of the SPM on the processing target surface Wa of the substrate W does rise to the temperature of the substrate W. In addition, since the sulfuric acid solution is continuously discharged from the third nozzle 31 in the opposite surface Wb of the processing target surface Wa of the substrate W, the temperature of the substrate W is maintained to prevent the temperature of the substrate W from dropping.
當自步驟S3之液供給停止，經過特定時間t3時，在步驟S4中，再次自第2噴嘴21而加以吐出第2溫度之SPM於基板W的處理對象面Wa。更且，基板W之旋轉速度則作為成快於經由旋轉之離心力而處理對象面Wa上之SPM產生飛散程度，而基板W的處理對象面Wa上之SPM則置換為新的SPM。然而，亦未可提升基板W之旋轉數，例如，亦可以新的SPM，沖出位於基板上之SPM。 When the liquid supply from step S3 is stopped and the predetermined time t3 elapses, in step S4, the second temperature SPM is again ejected from the second nozzle 21 to the processing target surface Wa of the substrate W. Further, the rotation speed of the substrate W is caused to be faster than the SPM on the processing target surface Wa by the centrifugal force of the rotation, and the SPM on the processing target surface Wa of the substrate W is replaced with a new SPM. However, the number of rotations of the substrate W is not increased. For example, a new SPM can be used to punch out the SPM on the substrate.
之後，自步驟S4之液供給開始，經過特定時間t2，基板W的處理對象面Wa上之漿狀態的SPM則加以置換為新的SPM時，在步驟S5中，加以停止自第2噴嘴21之SPM吐出。更且，再次，基板W之旋轉速度則作為成慢於未經由旋轉之離心力而處理對象面Wa上之SPM產生飛散程度，而基板W的處理對象面Wa上之SPM則作為成漿狀態(液貯留狀態)。 Then, when the SPM of the slurry state on the processing target surface Wa of the substrate W is replaced with a new SPM after the liquid supply of the step S4 is elapsed, the second nozzle 21 is stopped in the step S5. SPM spit out. Further, again, the rotational speed of the substrate W is generated as a degree of scattering as the SPM on the processing target surface Wa is slower than the centrifugal force that has not been rotated, and the SPM on the processing target surface Wa of the substrate W is used as a slurry state (liquid) Storage status).
如此，加以反覆n回(n=1以上)SPM之吐出及漿狀態，當自步驟S5之液供給停止，經過特定時間t3時，在步驟S6中，加以停止自第3噴嘴31之硫酸溶液吐出。更且，基板W之旋轉速度則作為成快於經由旋轉之離心力 而處理對象面Wa上之SPM產生飛散程度，而加以飛散基板W的處理對象面Wa上之SPM，之後加以停止基板W的旋轉。 In this way, the discharge and the slurry state of the SPM are reversed n (n=1 or more), and when the liquid supply from the step S5 is stopped and the specific time t3 elapses, the sulfuric acid solution from the third nozzle 31 is stopped in step S6. . Moreover, the rotational speed of the substrate W is taken to be faster than the centrifugal force via rotation. On the other hand, the SPM on the processing target surface Wa is scattered, and the SPM on the processing target surface Wa of the substrate W is scattered, and then the rotation of the substrate W is stopped.
然而，在前述中，在特定時間而決定液供給之開始及停止，但作為其他的手段，測定加以供給至基板W之處理液的液膜厚，做為呈因應其液膜厚而實施亦可。例如，供給處理液而膜厚如成為特定膜厚時，停止液供給，成為較特定膜厚為低時，進行液供給。另外，經由溫度計而測定加以供給至基板W上之處理液的溫度，做為呈因應液溫度而進行液供給之開始及停止亦可。 However, in the above, the start and stop of the supply of the liquid are determined at a specific time, but the liquid film thickness of the treatment liquid supplied to the substrate W is measured as another means, and may be implemented in accordance with the thickness of the liquid film. . For example, when the processing liquid is supplied and the film thickness is a specific film thickness, the liquid supply is stopped, and when the specific film thickness is low, the liquid supply is performed. Further, the temperature of the treatment liquid supplied to the substrate W is measured by a thermometer, and the liquid supply may be started and stopped at the temperature of the reaction solution.
在此，第2溫度之SPM係自基板W加以排出時，與至少加以吐出於相反面Wb之溫度為高之硫酸溶液混合之故，過氧化氫水的分解則進行，而成為硫酸溶液。此硫酸溶液係自杯狀物2a流動在回收管4a而經由冷卻部4b加以冷卻，之後，加以回收於貯留部41。然而，在SPM中，當加以生成有過氧一硫酸及過氧二硫酸時，過氧化氫水係加以分解於水。對於光阻劑剝離時，過氧一硫酸及過氧二硫酸之氧化力則作動，但經由高溫狀態(基板溫度)而加以促進反應而消失。也就是，殘留的硫酸與水則自基板表面飛散，與吐出於基板W之相反面的硫酸溶液混合。 Here, when the SPM of the second temperature is discharged from the substrate W, it is mixed with at least a sulfuric acid solution having a temperature at which the opposite surface Wb is discharged, and the decomposition of the hydrogen peroxide water proceeds to form a sulfuric acid solution. This sulfuric acid solution flows from the cup 2a to the recovery pipe 4a, is cooled by the cooling unit 4b, and is then collected in the storage unit 41. However, in SPM, when peroxymonosulfuric acid and peroxodisulfuric acid are formed, hydrogen peroxide is decomposed into water. When the photoresist is peeled off, the oxidizing power of peroxymonosulfuric acid and peroxodisulfuric acid is activated, but the reaction is accelerated by the high temperature state (substrate temperature). That is, the residual sulfuric acid and water are scattered from the surface of the substrate and mixed with the sulfuric acid solution which is discharged on the opposite side of the substrate W.
當經由如此之SPM的光阻劑除去結束時，接著進行水洗。對於在相同之基板處理槽2而進行光阻劑除去與水洗之情況，呈未加以混合自基板W所排出之硫酸溶液與 水洗用的水地，設置兩個液接受部及切換此等液接受部之機構，因應處理液而切換液接受部者為佳。對於水洗後，在同一之基板處理槽2內進行以另外的處理液之處理亦可，此時，係設置呈未混合有處理液地切換處理液之處理液切換機構者為佳。另外，於另外的基板處理槽，移動基板W，在此進行以其他的處理液之處理亦可。最終，水洗後，使基板W進行乾燥而處理結束。 When the removal of the photoresist via such SPM is completed, water washing is then performed. In the case where the photoresist is removed and washed in the same substrate processing tank 2, the sulfuric acid solution discharged from the substrate W is not mixed. In the water for washing, it is preferable to provide two liquid receiving portions and a mechanism for switching the liquid receiving portions, and to switch the liquid receiving portions in accordance with the processing liquid. After the water washing, it is also possible to carry out the treatment with another treatment liquid in the same substrate processing tank 2. In this case, it is preferable to provide a treatment liquid switching mechanism that switches the treatment liquid without mixing the treatment liquid. Further, the substrate W may be moved in another substrate processing tank, and treatment with another processing liquid may be performed here. Finally, after washing with water, the substrate W is dried and the treatment is completed.
如以上說明地，如根據實施形態，於供給SPM於基板W的處理對象面Wa之前，基板W則經由過氧化氫水之沸點以上的第1溫度之硫酸溶液而加溫為過氧化氫水的沸點以上。隨之，較第1溫度為低之第2溫度的SPM則加以供給至基板W的處理對象面Wa上時，在其處理對象面Wa上加溫為過氧化氫水之沸點以上。此時，SPM中之過氧化氫水則效率佳而進行分解，加以生成具有強氧化力之過氧一硫酸及過氧二硫酸之故，可確實地除去光阻劑，而使處理性能提升者。 As described above, according to the embodiment, before the SPM is supplied to the processing target surface Wa of the substrate W, the substrate W is heated to hydrogen peroxide by a sulfuric acid solution having a first temperature equal to or higher than the boiling point of the hydrogen peroxide water. Above the boiling point. In the meantime, when the SPM having the second temperature lower than the first temperature is supplied to the processing target surface Wa of the substrate W, the processing target surface Wa is heated to a temperature higher than the boiling point of the hydrogen peroxide water. At this time, the hydrogen peroxide water in the SPM is efficiently decomposed to form a peroxidic sulfuric acid and a peroxydisulfuric acid having a strong oxidizing power, so that the photoresist can be surely removed, and the treatment performance is improved. .
更且，混合硫酸溶液及過氧化氫水之後而加以供給至基板W的處理對象面Wa，但SPM則到達至基板W的處理對象面Wa上為止，SPM的溫度係較第1溫度為低之第2溫度之故，成為SPM則到達至基板W的處理對象面Wa上為止可抑制過氧化氫水的分解者。也就是，由將SPM的溫度作為成較第1溫度為低之第2溫度者，成為SPM則到達至基板W的處理對象面Wa上為止可防止過氧化氫水之消失，加上，成為SPM則到達至基板W的處理對象 面Wa上為止可抑制過氧化氫水的分解，即過氧一硫酸及過氧二硫酸之反應的促進者。因此，成為無須混合大量的過氧化氫水於硫酸溶液，而過氧化氫水之使用量則減少，更且，因加以抑制硫酸濃度下降而再利用成為容易之故，可降低總和之處理液使用量者。 Further, after the sulfuric acid solution and the hydrogen peroxide water are mixed and supplied to the processing target surface Wa of the substrate W, the SPM reaches the processing target surface Wa of the substrate W, and the temperature of the SPM is lower than the first temperature. When the SPM reaches the processing target surface Wa of the substrate W, the decomposition of the hydrogen peroxide water can be suppressed. In other words, when the temperature of the SPM is set to be the second temperature lower than the first temperature, the SPM is prevented from reaching the processing target surface Wa of the substrate W, and the disappearance of the hydrogen peroxide water is prevented. Then reach the processing target of the substrate W The decomposition of hydrogen peroxide water, that is, the promoter of the reaction of peroxymonosulfuric acid and peroxodisulfuric acid, can be suppressed up to the surface Wa. Therefore, it is not necessary to mix a large amount of hydrogen peroxide water in a sulfuric acid solution, and the amount of hydrogen peroxide water used is reduced, and further, it is easy to reuse the sulfuric acid concentration, and the total amount of the treatment liquid can be reduced. Quantity.
然而，如前述，經由硫酸溶液而加熱基板W者則為重要。例如，以加熱器而加熱基板W之情況，加熱器係照射紅外線而進行加熱，但基板W(半導體晶圓)係未吸收紅外線而透過。基板W則由未吸收光而透過時，未加以加熱基板W自體。另外，當於基板W上有處理液時，處理液則成為吸收自加熱器之紅外線者。也就是，未加以加熱基板W，而僅加以加熱處理液。隨之，基板W係將所加熱之處理液作為媒介而加以加熱。但，如此情況，為了加熱基板W，而將處理液加熱為高溫為止需要時間。另外，處理液如為SPM時，為加以加熱基板W而先行加以加熱SPM。對於此情況，促進了SPM之過氧一硫酸及過氧二硫酸之反應之故，而強氧化力則在一瞬間而消失，無法剝離光阻劑者。 However, as described above, it is important to heat the substrate W via a sulfuric acid solution. For example, when the substrate W is heated by a heater, the heater is heated by irradiation of infrared rays, but the substrate W (semiconductor wafer) is transmitted without absorbing infrared rays. When the substrate W is transmitted without being absorbed by light, the substrate W is not heated and is self-contained. Further, when there is a treatment liquid on the substrate W, the treatment liquid becomes an infrared ray that is absorbed from the heater. That is, the substrate W is not heated, but only the heat treatment liquid is applied. Accordingly, the substrate W is heated by using the heated processing liquid as a medium. However, in this case, it takes time to heat the substrate W to heat the processing liquid to a high temperature. Further, when the treatment liquid is SPM, the SPM is heated first to heat the substrate W. In this case, the reaction of peroxymonosulfuric acid and peroxodisulfuric acid of SPM is promoted, and the strong oxidizing power disappears in an instant, and the photoresist cannot be peeled off.
但將高溫的硫酸溶液作為加熱媒體而使用時，因硫酸溶液的熱則傳達至基板W之故，而無須時間而可加熱基板W自體者。其結果，基板W係成為高溫狀態，對於加以供給至其上方之低溫的SPM，係傳達有基板W的熱，由加以促進反應者，可良好地剝離光阻劑。如此，經由硫酸溶液而加溫基板W者，則貢獻於光阻劑剝離。如從此 點而考量時，作為加熱媒體，除了硫酸溶液以外，亦可使用高溫的液體者。另外，作為加熱媒體而使用液體，經由直接供給高溫的液體於基板W之處理對象面Wa之時，可直接加熱基板W之處理對象面Wa者。隨之，比較於經由加熱器等之間接加熱，可使基板W之處理對象面Wa之加熱效率提升者。 However, when a high-temperature sulfuric acid solution is used as a heating medium, the heat of the sulfuric acid solution is transmitted to the substrate W, and the substrate W can be heated without time. As a result, the substrate W is in a high temperature state, and the heat of the substrate W is transmitted to the low temperature SPM supplied thereto, and the photoresist can be favorably peeled off by promoting the reaction. As described above, when the substrate W is heated via the sulfuric acid solution, the photoresist is released. As ever since When considering the point, as the heating medium, a high-temperature liquid can be used in addition to the sulfuric acid solution. In addition, when the liquid is used as the heating medium and the high-temperature liquid is directly supplied to the processing target surface Wa of the substrate W, the processing target surface Wa of the substrate W can be directly heated. Accordingly, the heating efficiency of the processing target surface Wa of the substrate W can be improved by comparing the heating by the heater or the like.
在此，對於加熱媒體使用硫酸溶液的理由係在基板W之處理對象面Wa上而使SPM反應時，因過氧化氫水則產生分解而成為水或過氧一硫酸(過硫酸)，過氧二硫酸，而可將SPM作為硫酸溶液而回收者之故。也就是，將此硫酸溶液作為加熱媒體，或者，可作為為了SPM生成之硫酸溶液而進行再利用者。例如，作為加熱媒體而使用硫酸溶液以外之加熱液之情況，對於為了排液之再利用，有必要將排液分離為加熱液與硫酸溶液而進行回收。但，由如前述作為加熱媒體而使用硫酸溶液者，排液則成為硫酸溶液之故，成為無須分離排液而進行回收。經由此，僅由設置硫酸溶液用之配管者，因成為無須設置分離回收機構之故，可實現裝置之簡略化者。 Here, the reason why the sulfuric acid solution is used for the heating medium is to react with the SPM in the treatment target surface Wa of the substrate W, and it is decomposed by hydrogen peroxide water to become water or peroxymonosulfuric acid (persulfuric acid), and peroxygen. Disulfuric acid, and SPM can be recovered as a sulfuric acid solution. That is, the sulfuric acid solution is used as a heating medium, or it can be reused as a sulfuric acid solution for SPM production. For example, when a heating liquid other than a sulfuric acid solution is used as a heating medium, it is necessary to separate the liquid discharge into a heating liquid and a sulfuric acid solution for recycling. However, when the sulfuric acid solution is used as the heating medium as described above, the liquid discharge is a sulfuric acid solution, and the liquid is recovered without separating the liquid. As a result, only the piping for the sulfuric acid solution is provided, and since it is not necessary to provide a separation and recovery mechanism, the device can be simplified.
在前述之實施形態中，經由第1液供給部3a而供給第1溫度之硫酸溶液於基板W之處理對象面Wa，但並不限於此者，而作為呈無對於其基板W之處理對象面Wa而言之硫酸溶液的供給，例如，經由第3液供給部3c，而 於基板W之處理對象面Wa的相反面Wb，供給第3溫度之硫酸溶液，也就是第1溫度以上之硫酸溶液而加溫基板W亦可。即，如為可經由第1溫度以上之硫酸溶液而加溫基板W時，供給硫酸溶液於基板W之處理對象面Wa及其相反面Wb之任一亦可。 In the above-described embodiment, the sulfuric acid solution of the first temperature is supplied to the processing target surface Wa of the substrate W via the first liquid supply unit 3a. However, the present invention is not limited thereto, and the processing target surface for the substrate W is not provided. The supply of the sulfuric acid solution for Wa is, for example, via the third liquid supply unit 3c. The sulfuric acid solution of the third temperature, that is, the sulfuric acid solution of the first temperature or higher, may be supplied to the opposite surface Wb of the processing target surface Wa of the substrate W to warm the substrate W. In other words, when the substrate W is heated by the sulfuric acid solution having the first temperature or higher, the sulfuric acid solution may be supplied to any of the processing target surface Wa of the substrate W and the opposite surface Wb.
另外，在前述實施形態中，經由所加熱之硫酸溶液而加溫基板W，但並不限於此者，而加上於經由其硫酸溶液之加熱，作為加熱基板W之補助，使用照射光的燈或發熱之加熱器，使用電磁波之電磁加熱器，另外，熱板等之加熱部亦可者。然而，較經由硫酸溶液之加熱為先行執行經由加熱部之加熱時，有著基板W之處理對象面Wa上之光阻劑產生碳化而變為除去困難之情況之故，而較經由加熱部之加熱為先行執行經由硫酸溶液之加熱者為佳。 Further, in the above-described embodiment, the substrate W is heated by the heated sulfuric acid solution. However, the substrate W is not limited thereto, and is heated by the sulfuric acid solution, and is used as a heating substrate W. For heating heaters, electromagnetic heaters using electromagnetic waves, and heating units such as hot plates may be used. However, when the heating by the heating portion is performed in advance by the heating of the sulfuric acid solution, the photoresist on the processing target surface Wa of the substrate W is carbonized and becomes difficult to remove, and is heated by the heating portion. It is preferred to perform the heating via the sulfuric acid solution first.
另外，在前述之實施形態中，追加檢出基板處理槽2之杯狀物2a內之硫酸溶液的硫酸濃度，或者流動在液返回部4之回收管4a的硫酸溶液的硫酸濃度之濃度檢出部，呈經由第2液供給部3b之液供給中，因應經由濃度檢出部而加以檢出之硫酸濃度，經由控制部5而控制第1液供給部3a之液供給(即，開關閥14)亦可。例如，控制部5係硫酸濃度則成為較特定值(例如，65wt%)為低之情況，使第1溫度之硫酸溶液供給至第1液供給部3a，而硫酸濃度則成為特定值以上的情況，對於第1液供給部3a，停止第1溫度之硫酸溶液的供給。經由此，可將成為回收液之硫酸溶液的硫酸濃度，即貯留部41內之 硫酸溶液的硫酸濃度，維持成特定值者。 Further, in the above-described embodiment, the sulfuric acid concentration of the sulfuric acid solution in the cup 2a of the substrate processing tank 2 is additionally detected, or the concentration of the sulfuric acid concentration of the sulfuric acid solution flowing in the recovery pipe 4a of the liquid returning portion 4 is detected. In the liquid supply via the second liquid supply unit 3b, the sulfuric acid concentration detected by the concentration detecting unit is controlled by the control unit 5 to control the liquid supply of the first liquid supply unit 3a (that is, the on-off valve 14). ) Yes. For example, when the sulfuric acid concentration of the control unit 5 is lower than a specific value (for example, 65 wt%), the sulfuric acid solution of the first temperature is supplied to the first liquid supply unit 3a, and the sulfuric acid concentration is equal to or higher than a specific value. In the first liquid supply unit 3a, the supply of the sulfuric acid solution at the first temperature is stopped. Thereby, the sulfuric acid concentration of the sulfuric acid solution which is the recovered liquid, that is, the inside of the storage portion 41 can be The sulfuric acid concentration of the sulfuric acid solution is maintained at a specific value.
另外，在前述之實施形態中，在供給第2溫度之SPM於基板W之處理對象面Wa時，對於沿著基板W之處理對象面Wa而使第2噴嘴21移動之情況，使其自基板W之處理對象面Wa的外周，朝向中心而加以移動者為佳。對於此情況，自基板W之處理對象面Wa的外周，依序基板W之溫度下降之故，而與於基板W之處理對象面Wa之略中心，供給第2溫度之SPM情況，或者自基板W之中心，朝向外周而使第2噴嘴21移動之同時，進行供給之情況做比較，可抑止基板W之處理對象面Wa全體則經由第2溫度之SPM而一口氣冷卻之情況者。 In the above-described embodiment, when the SPM of the second temperature is supplied to the processing target surface Wa of the substrate W, the second nozzle 21 is moved along the processing target surface Wa of the substrate W, and the substrate is moved from the substrate. It is preferable that the outer circumference of the processing target surface Wa of W is moved toward the center. In this case, from the outer periphery of the processing target surface Wa of the substrate W, the temperature of the sequential substrate W is lowered, and the SPM of the second temperature is supplied to the center of the processing target surface Wa of the substrate W, or from the substrate. In the center of the W, the second nozzle 21 is moved toward the outer circumference, and the supply of the second nozzle 21 is compared, and the entire processing target surface Wa of the substrate W is prevented from being cooled by the SPM of the second temperature.
以上，雖已說明過本發明之幾個實施形態，但此等實施形態係作為例而提示之構成，未特意限定發明之範圍者。此等新穎之實施形態係可由其他種種形態而加以實施，在不脫離發明的內容範圍，可進行種種省略，置換，變更者。此等實施形態或其變形係與包含於發明範圍或內容之同時，包含於記載於申請專利申請範圍之發明與其均等的範圍。 Although the embodiments of the present invention have been described above, the embodiments are presented as examples and are not intended to limit the scope of the invention. The present invention can be implemented in various other forms, and various omissions, substitutions, and changes can be made without departing from the scope of the invention. The invention and its modifications are intended to be included within the scope of the invention and the scope of the invention.
1‧‧‧基板處理裝置 1‧‧‧Substrate processing unit
2‧‧‧基板處理槽 2‧‧‧Substrate processing tank
2a‧‧‧杯狀物 2a‧‧‧ cup
2b‧‧‧平台 2b‧‧‧ platform
2c‧‧‧旋轉機構 2c‧‧‧Rotating mechanism
2b1‧‧‧支持構件 2b1‧‧‧Support components
3‧‧‧液供給裝置 3‧‧‧Liquid supply device
3a‧‧‧第1液供給部 3a‧‧‧1st liquid supply department
3b‧‧‧第2液供給部 3b‧‧‧Second liquid supply department
3c‧‧‧第3液供給部 3c‧‧‧3rd liquid supply department
3d‧‧‧液循環部 3d‧‧‧Liquid circulation department
4‧‧‧液返回部 4‧‧‧Liquid return
4a‧‧‧回收管 4a‧‧‧Recycling tube
4b‧‧‧冷卻部 4b‧‧‧The Ministry of Cooling
5‧‧‧控制部 5‧‧‧Control Department
11‧‧‧第1噴嘴 11‧‧‧1st nozzle
12，32‧‧‧供給管 12,32‧‧‧Supply tube
13，33，43‧‧‧加熱部 13,33,43‧‧・heating department
14，34，25，26‧‧‧開關閥 14,34,25,26‧‧‧ switch valve
15，27，28，35‧‧‧逆止閥 15,27,28,35‧‧‧ check valve
21‧‧‧第2噴嘴 21‧‧‧2nd nozzle
22‧‧‧供給管 22‧‧‧Supply tube
23，41‧‧‧貯留部 23,41‧‧‧Storage Department
24‧‧‧混合管 24‧‧‧ Mixing tube
29，45‧‧‧幫浦 29,45‧‧‧
31‧‧‧第3噴嘴 31‧‧‧3rd nozzle
42‧‧‧循環管 42‧‧‧Circulation tube
44‧‧‧調整閥 44‧‧‧Adjustment valve
W‧‧‧基板 W‧‧‧Substrate
Wa‧‧‧處理對象面 Wa‧‧‧Processing surface
Wb‧‧‧相反面 Wb‧‧‧ opposite
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| KR20180013327A (en) | 2016-07-29 | 2018-02-07 | 세메스 주식회사 | Substrate treating apparatus and substrate treating method |
| JP6876570B2 (en) * | 2017-07-28 | 2021-05-26 | 株式会社Ｓｃｒｅｅｎホールディングス | Treatment liquid static elimination method, substrate processing method and substrate processing system |
| JP7181764B2 (en) * | 2018-03-26 | 2022-12-01 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing apparatus |
| JP7094147B2 (en) * | 2018-05-30 | 2022-07-01 | 株式会社Ｓｃｒｅｅｎホールディングス | Board processing method and board processing equipment |
| JP7220537B2 (en) | 2018-09-20 | 2023-02-10 | 株式会社Ｓｃｒｅｅｎホールディングス | SUBSTRATE PROCESSING APPARATUS AND SUBSTRATE PROCESSING METHOD |
| KR102012209B1 (en) * | 2018-10-04 | 2019-10-21 | 세메스 주식회사 | Substrate treating apparatus and substrate treating method |
| JP7128099B2 (en) * | 2018-11-27 | 2022-08-30 | 株式会社Ｓｃｒｅｅｎホールディングス | SUBSTRATE PROCESSING APPARATUS AND SUBSTRATE PROCESSING METHOD |
| CN113448186B (en) * | 2020-03-27 | 2024-05-14 | 长鑫存储技术有限公司 | Wafer processing apparatus and wafer processing method |
| KR102622445B1 (en) * | 2020-04-24 | 2024-01-09 | 세메스 주식회사 | Substrate treating apparatus and liquid supplying method |
| JP7421410B2 (en) * | 2020-04-30 | 2024-01-24 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing device, substrate processing method, learning data generation method, learning method, learning device, learned model generation method, and learned model |
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