TWI805541B - Photoresist stripper - Google Patents
Photoresist stripper Download PDFInfo
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- TWI805541B TWI805541B TW105132973A TW105132973A TWI805541B TW I805541 B TWI805541 B TW I805541B TW 105132973 A TW105132973 A TW 105132973A TW 105132973 A TW105132973 A TW 105132973A TW I805541 B TWI805541 B TW I805541B
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- Taiwan
- Prior art keywords
- weight
- photoresist
- stripping solution
- photoresist stripping
- ammonium hydroxide
- Prior art date
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 83
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 25
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 25
- -1 alkylene amine Chemical class 0.000 claims abstract description 23
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 claims description 24
- 229940109239 creatinine Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 claims description 9
- 239000000845 maltitol Substances 0.000 claims description 9
- 235000010449 maltitol Nutrition 0.000 claims description 9
- 229940035436 maltitol Drugs 0.000 claims description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002123 temporal effect Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 37
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910000881 Cu alloy Inorganic materials 0.000 description 10
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229940043353 maltol Drugs 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- FVRSWMRVYMPTBU-UHFFFAOYSA-M 1-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCC(O)[N+](C)(C)C FVRSWMRVYMPTBU-UHFFFAOYSA-M 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical group CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical group NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- MPAYEWNVIPXRDP-UHFFFAOYSA-N ethanimine Chemical compound CC=N MPAYEWNVIPXRDP-UHFFFAOYSA-N 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
本發明之目的在於提供一種維持充分之光阻剝離性並且氫氧化四級銨之溶解性及經時穩定性優異之光阻剝離液。 An object of the present invention is to provide a resist stripping solution that maintains sufficient resist stripping properties and is excellent in solubility and temporal stability of quaternary ammonium hydroxide.
本發明係關於一種光阻剝離液，其含有：二甲基亞碸、氫氧化四級銨、伸烷基胺、以及多元醇及/或分子量100以下之二醇醚。伸烷基胺較佳為下述通式(1)所表示之伸乙基胺(通式(1)中，n表示1~5之整數)。 The present invention relates to a photoresist stripping solution, which contains: dimethyl sulfide, quaternary ammonium hydroxide, alkylene amine, polyhydric alcohol and/or glycol ether with molecular weight below 100. The alkylene amine is preferably an ethylidene amine represented by the following general formula (1) (in the general formula (1), n represents an integer of 1 to 5).
Description
本發明係關於一種光阻剝離液。 The invention relates to a photoresist stripping solution.
半導體基板等具有實施了微細之配線之電極構造，於其製造步驟中使用有光阻。電極構造例如以如下方式而製造：於形成於基板上之鋁等導電性金屬層或SiO2膜等絕緣膜上塗佈光阻，並對其實施曝光、顯影之處理而形成光阻圖案，將該經圖案化之光阻作為遮罩對導電性金屬層或絕緣膜等進行蝕刻，形成微細之配線後，利用光阻剝離液去除無用之光阻。 Semiconductor substrates and the like have an electrode structure on which fine wiring is implemented, and photoresist is used in the manufacturing process. The electrode structure is manufactured, for example, by coating a photoresist on a conductive metal layer such as aluminum or an insulating film such as a SiO2 film formed on a substrate, and exposing and developing it to form a photoresist pattern. The patterned photoresist is used as a mask to etch the conductive metal layer or insulating film to form fine wiring, and then the useless photoresist is removed with a photoresist stripper.
作為此種光阻剝離液，專利文獻1及專利文獻2中提出有一種含有二甲基亞碸、氫氧化四級銨、及烷醇胺之剝離溶液。專利文獻1及專利文獻2中，由於氫氧化四級銨難以溶解於二甲基亞碸中，故而使用烷醇胺作為溶解劑。然而，烷醇胺之作為溶解劑之性能並不充分，根據剝離溶液之溫度，存在剝離溶液產生白濁或剝離溶液中之氫氧化四級銨固化之情況，而存在無法獲得經時穩定性較高且均勻之光阻剝離液之問題。 As such a photoresist stripping solution, Patent Document 1 and Patent Document 2 propose a stripping solution containing dimethylsulfoxide, quaternary ammonium hydroxide, and alkanolamine. In Patent Document 1 and Patent Document 2, since quaternary ammonium hydroxide is difficult to dissolve in dimethylsulfoxide, alkanolamine is used as a dissolving agent. However, the performance of alkanolamine as a dissolving agent is not sufficient. Depending on the temperature of the stripping solution, the stripping solution may become cloudy or the quaternary ammonium hydroxide in the stripping solution may solidify, and high stability over time may not be obtained. And the problem of uniform photoresist stripping solution.
專利文獻1：日本特表2009-514026號公報 Patent Document 1: Japanese PCT Publication No. 2009-514026
專利文獻2：日本特表2010-507835號公報 Patent Document 2: Japanese PCT Publication No. 2010-507835
本發明之目的在於提供一種維持充分之光阻剝離性並且氫氧化四級銨之溶解性及經時穩定性優異之光阻剝離液。 An object of the present invention is to provide a resist stripping solution that maintains sufficient resist stripping properties and is excellent in solubility and temporal stability of quaternary ammonium hydroxide.
本發明者進行努力研究之結果發現：代替作為溶解劑之烷醇胺，而含有伸烷基胺、以及多元醇及/或分子量100以下之二醇醚之光阻剝離液會維持充分之光阻剝離性並且氫氧化四級銨之溶解性及經時穩定性優異，從而完成本發明。 As a result of diligent research by the present inventors, it was found that instead of alkanolamine as a dissolving agent, a photoresist stripping solution containing alkylene amines, polyhydric alcohols and/or glycol ethers with a molecular weight of 100 or less can maintain sufficient photoresist The present invention has been completed because of its excellent peelability, solubility and temporal stability of quaternary ammonium hydroxide.
即，本發明係關於一種光阻剝離液，其含有：二甲基亞碸、氫氧化四級銨、伸烷基胺、以及多元醇及/或分子量100以下之二醇醚。 That is, the present invention relates to a photoresist stripping solution, which contains: dimethyl sulfide, quaternary ammonium hydroxide, alkylene amine, and polyhydric alcohol and/or glycol ether with a molecular weight of 100 or less.
於本發明之光阻剝離液中，伸烷基胺較佳為下述通式(1)所表示之伸乙基胺。 In the photoresist stripping solution of the present invention, the alkylene amine is preferably ethylidene amine represented by the following general formula (1).
(通式(1)中，n表示1~5之整數) (In general formula (1), n represents an integer from 1 to 5)
本發明之光阻剝離液較佳為水之含量為1~10重量%，且用於負型乾膜光阻之剝離。 The photoresist stripping solution of the present invention preferably has a water content of 1-10% by weight, and is used for stripping negative dry film photoresists.
本發明之光阻剝離液較佳為進而含有麥芽醇及肌酸酐。 It is preferable that the photoresist stripping liquid of this invention further contains maltitol and creatinine.
本發明之光阻剝離液由於含有二甲基亞碸、氫氧化四級銨、伸烷基胺、以及多元醇及/或分子量100以下之二醇醚，故而會維持充分之光阻剝離性並且氫氧化四級銨之溶解性及經時穩定性優異。 The photoresist stripping solution of the present invention maintains sufficient photoresist stripping properties and Quaternary ammonium hydroxide has excellent solubility and stability over time.
本發明之光阻剝離液之特徵在於含有：二甲基亞碸、氫氧化四級銨、伸烷基胺、以及多元醇及/或分子量100以下之二醇醚。 The photoresist stripping solution of the present invention is characterized in that it contains: dimethyl sulfide, quaternary ammonium hydroxide, alkylene amine, and polyhydric alcohol and/or glycol ether with a molecular weight of 100 or less.
於本發明之光阻剝離液中，二甲基亞碸之含量並無特別限定，較佳為50~90重量%，更佳為73~84重量%。於二甲基亞碸之含量未達50重量%之情形或超過90重量%之情形時，存在光阻剝離性降低之情況。 In the photoresist stripping solution of the present invention, the content of dimethylsulfoxide is not particularly limited, but is preferably 50-90% by weight, more preferably 73-84% by weight. When the content of dimethylsulfene is less than 50% by weight or exceeds 90% by weight, resist peelability may decrease.
作為氫氧化四級銨，例如可使用下述通式(2)所表示之化合物。 As quaternary ammonium hydroxide, for example, a compound represented by the following general formula (2) can be used.
通式(2)中，R1~R4表示碳數1~3之烷基、或碳數1~3之經羥基取代之烷基，且可相同亦可不同。 In the general formula (2), R 1 to R 4 represent an alkyl group having 1 to 3 carbons, or an alkyl group having 1 to 3 carbons substituted with a hydroxyl group, and may be the same or different.
作為氫氧化四級銨，並無特別限定，例如可列舉：氫氧化四甲基銨(TMAH)、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化三甲基乙基銨、氫氧化三甲基(2-羥基乙基)銨、氫氧化三丙基(2-羥基乙基)銨、氫氧化三甲基(1-羥基丙基)銨等。該等可單獨使用，亦可將2種以上併用。該等之中，就光阻剝離性之觀點而言，較佳為氫氧化四甲基銨、氫氧化四乙基銨、氫氧化三甲基(2-羥基乙基)銨。又，就分子量最小、每單位重量之莫耳濃度變高、有效地起作用之方面而言，更佳為氫氧化四甲基銨。 The quaternary ammonium hydroxide is not particularly limited, and examples include: tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, hydrogen Trimethyl(2-hydroxyethyl)ammonium oxide, tripropyl(2-hydroxyethyl)ammonium hydroxide, trimethyl(1-hydroxypropyl)ammonium hydroxide, and the like. These may be used alone or in combination of two or more. Among these, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and trimethyl(2-hydroxyethyl)ammonium hydroxide are preferable from the viewpoint of resist stripping properties. Furthermore, tetramethylammonium hydroxide is more preferable in terms of the smallest molecular weight, high molar concentration per unit weight, and effective functioning.
於本發明之光阻剝離液中，氫氧化四級銨之含量並無特別限定，較佳為3~20重量%，更佳為4~8重量%。若氫氧化四級銨之含量未達3重量%，則存在光阻剝離性降低之情況，若超過20重量%，則存在金屬腐蝕性變高之情況。 In the photoresist stripping solution of the present invention, the content of quaternary ammonium hydroxide is not particularly limited, but is preferably 3-20% by weight, more preferably 4-8% by weight. When the content of the quaternary ammonium hydroxide is less than 3% by weight, the photoresist peelability may be lowered, and if it exceeds 20% by weight, the metal corrosion may be increased.
作為伸烷基胺，並無特別限定，可使用下述通式(3)所表示之化合物，具體而言，可列舉：乙二胺(EDA)、二伸乙基三胺(DETA)、三伸乙基四胺(TETA)、四伸乙基五胺(TEPA)、五伸乙基六胺(PEHA)等下述通式(1)所表示之伸乙基胺、丙二胺等。該等之中，就二氧化碳之吸收性之觀點而言，較佳為下述通式(1)所表示之伸乙基胺，更佳為n=2以上之聚伸乙基胺，進而較佳為三伸乙基四胺、四伸乙基五胺。該等伸烷基胺可單獨使用，亦可將2種以上併用。 The alkylene amine is not particularly limited, and compounds represented by the following general formula (3) can be used. Specifically, ethylenediamine (EDA), diethylenetriamine (DETA), tris Ethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and ethyleneamine represented by the following general formula (1), propylenediamine, and the like. Among them, from the viewpoint of absorbing carbon dioxide, preferred is ethylideneamine represented by the following general formula (1), more preferably polyethylideneamine with n=2 or more, and even more preferred It is triethylenetetramine and tetraethylenepentamine. These alkylene amines may be used alone or in combination of two or more.
(通式(3)中，m、n表示1~5之整數；R5、R6相互分別獨立，表示氫原子或碳數1~3之烷基；於存在多個R5、R6之情形時，分別可相同亦可不同) (In the general formula (3), m and n represent an integer of 1 to 5; R 5 and R 6 are independently independent from each other and represent a hydrogen atom or an alkyl group with 1 to 3 carbons; where there are multiple R 5 and R 6 case, they can be the same or different)
(通式(1)中，n表示1~5之整數) (In general formula (1), n represents an integer from 1 to 5)
於本發明之光阻剝離液中，伸烷基胺之含量並無特別限定，較佳為1~25重量%，更佳為2~20重量%。若伸烷基胺之含量未達1重量%，則存在經時穩定性降低之情況，若超過25重量%，則存在光阻剝離性降低之情況。 In the photoresist stripping solution of the present invention, the content of alkylene amine is not particularly limited, but is preferably 1-25% by weight, more preferably 2-20% by weight. When the content of the alkylene amine is less than 1% by weight, the stability over time may decrease, and when it exceeds 25% by weight, the resist peelability may decrease.
於本發明之光阻剝離液中，伸烷基胺之含量並無特別限定，就經時穩定性之觀點而言，較佳為相對於氫氧化四級銨100重量份為10重量份以上。 In the photoresist stripping solution of the present invention, the content of alkyleneamine is not particularly limited, but it is preferably 10 parts by weight or more based on 100 parts by weight of quaternary ammonium hydroxide from the viewpoint of stability over time.
作為多元醇，並無特別限定，例如可列舉：三乙二醇(TEG)、甘油、二乙二醇、1,3-丁二醇、1,4-丁二醇、丙二醇、乙二醇等。作為分子量100以下之二醇醚，並無特別限定，例如可列舉乙二醇單甲醚、乙二醇單乙醚等。該等之中，就提高氫氧化四級銨之溶解性之觀點而言，較佳為使用三乙二醇、甘油。該等多元醇及/或分子量100以下之二醇醚可單獨使用， 亦可將2種以上併用。 The polyhydric alcohol is not particularly limited, and examples thereof include triethylene glycol (TEG), glycerin, diethylene glycol, 1,3-butanediol, 1,4-butanediol, propylene glycol, and ethylene glycol. . It does not specifically limit as a glycol ether with a molecular weight of 100 or less, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. are mentioned. Among them, it is preferable to use triethylene glycol and glycerin from the viewpoint of improving the solubility of quaternary ammonium hydroxide. These polyols and/or glycol ethers with molecular weight below 100 can be used alone, You may use 2 or more types together.
多元醇及/或分子量100以下之二醇醚之SP值並無特別限定，較佳為δ D=15.8~17.6、δ P=9.0~15.5且δ H=16.2~30.0，更佳為δ D=17.0~17.4、δ P=10.2~14.2且δ H=26.0~29.3。若δ D、δ P、δ H之值偏離上述範圍，則存在氫氧化四級銨之溶解性降低之情況。再者，於本說明書中，所謂SP值，係指漢森(Hansen)之溶解參數，係將物質之溶解性以分散項δ D、極性項δ P、氫鍵項δ H之3個參數而表現者。分散項δ D、極性項δ P、氫鍵項δ H為物質固有之物性值，例如示於「Hansen Solubility Parameters：A User's Handbook,HSPiP 3rd Edition ver.3.0.20」。再者，氫鍵項δ H可使用上述文獻中記載之值，於無記載之情形時，可藉由使用被稱為Y-MB法之神經網絡法之推算方法算出氫鍵項δ H。 The SP value of polyols and/or glycol ethers with molecular weights below 100 is not particularly limited, preferably δ D=15.8~17.6, δ P=9.0~15.5 and δ H=16.2~30.0, more preferably δ D= 17.0~17.4, δP=10.2~14.2 and δH=26.0~29.3. When the values of δD, δP, and δH deviate from the above ranges, the solubility of quaternary ammonium hydroxide may decrease. Furthermore, in this specification, the so-called SP value refers to the dissolution parameter of Hansen (Hansen), which refers to the solubility of the substance based on the three parameters of dispersion item δD, polarity item δP, and hydrogen bond item δH. performer. Dispersion term δ D, polarity term δ P, and hydrogen bond term δ H are intrinsic physical properties of the substance, for example, they are shown in "Hansen Solubility Parameters: A User's Handbook, HSPiP 3rd Edition ver.3.0.20". In addition, the hydrogen bond term δ H can use the value described in the above-mentioned literature, and when there is no description, the hydrogen bond term δ H can be calculated by an estimation method using a neural network method called the Y-MB method.
於本發明之光阻剝離液中，多元醇及/或分子量100以下之二醇醚之含量並無特別限定，較佳為1.0~20.0重量%，更佳為2.0~10.0重量%。若多元醇及/或分子量100以下之二醇醚之含量未達1.0重量%，則存在氫氧化四級銨之溶解性降低之情況，若超過20.0重量%，則存在光阻剝離性降低之情況。 In the photoresist stripping solution of the present invention, the content of polyhydric alcohol and/or glycol ether with a molecular weight of 100 or less is not particularly limited, but is preferably 1.0-20.0% by weight, more preferably 2.0-10.0% by weight. If the content of polyol and/or glycol ether with a molecular weight of 100 or less is less than 1.0% by weight, the solubility of quaternary ammonium hydroxide may decrease, and if it exceeds 20.0% by weight, the photoresist stripping property may decrease .
於本發明之光阻剝離液中，多元醇及/或分子量100以下之二醇醚之含量並無特別限定，就經時穩定性之觀點而言，較佳為相對於氫氧化四級銨100重量份為10重量份以上。 In the photoresist stripping solution of the present invention, the content of polyhydric alcohol and/or glycol ether with a molecular weight of 100 or less is not particularly limited, but from the viewpoint of stability over time, it is preferably 100 or less than quaternary ammonium hydroxide. The weight part is 10 weight parts or more.
本發明之光阻剝離液除二甲基亞碸、氫氧化四級銨、伸烷基胺、多元醇及/或分子量100以下之二醇醚以外，亦可任意地含有其他成分。作為 其他成分，並無特別限定，可列舉：水、防蝕劑、二甲基亞碸以外之有機溶劑、界面活性劑(例如，烷基苯磺酸鹽、聚氧乙烯烷基醚)、消泡劑(例如聚矽氧油)等。 The photoresist stripping solution of the present invention may optionally contain other components besides dimethylsulfoxide, quaternary ammonium hydroxide, alkylene amine, polyhydric alcohol and/or glycol ether with molecular weight below 100. as Other components are not particularly limited, and examples include: water, corrosion inhibitors, organic solvents other than dimethylsulfone, surfactants (for example, alkylbenzene sulfonates, polyoxyethylene alkyl ethers), and defoamers (such as silicone oil) and so on.
於本發明之光阻剝離液含有水之情形時，其含量並無特別限定，就光阻剝離性之觀點而言，較佳為30重量%以下，就負型光阻剝離性之觀點而言，較佳為20重量%以下。尤其是將本發明之光阻剝離液用於負型乾膜光阻之剝離之情形時，水之含量更佳為10重量%以下，進而較佳為1~10重量%，尤佳為3~10重量%。若水之含量未達1重量%，則存在氫氧化四級銨之溶解性降低之情況，若超過10重量%，則存在光阻剝離性降低之情況。 When the photoresist stripping solution of the present invention contains water, its content is not particularly limited, but it is preferably 30% by weight or less from the viewpoint of photoresist stripping performance, and from the viewpoint of negative photoresist stripping performance , preferably 20% by weight or less. Especially when the photoresist stripping solution of the present invention is used for stripping the negative dry film photoresist, the water content is more preferably 10% by weight or less, further preferably 1-10% by weight, and especially preferably 3-10% by weight. 10% by weight. If the content of water is less than 1% by weight, the solubility of quaternary ammonium hydroxide may decrease, and if it exceeds 10% by weight, the resist peeling property may decrease.
作為防蝕劑，並無特別限定，例如可列舉麥芽醇、肌酸酐等。該等可單獨使用，亦可將2種以上併用，就對多種金屬之防蝕性之觀點而言，較理想為含有麥芽醇及肌酸酐。 It does not specifically limit as a corrosion inhibitor, For example, maltitol, creatinine, etc. are mentioned. These may be used alone or in combination of two or more. From the viewpoint of corrosion resistance to multiple metals, maltitol and creatinine are preferably contained.
於本發明之光阻剝離液含有麥芽醇作為防蝕劑之情形時，其含量並無特別限定，較佳為0.1~0.5重量%，更佳為0.2~0.4重量%。若麥芽醇之含量未達0.1重量%，則存在錫-銀合金之防蝕性變得不充分之情況，若超過0.5重量%，則存在銅之防蝕性變得不充分之情況。 When the photoresist stripper of the present invention contains maltol as an anti-corrosion agent, its content is not particularly limited, but is preferably 0.1-0.5% by weight, more preferably 0.2-0.4% by weight. When the content of maltitol is less than 0.1% by weight, the corrosion resistance of the tin-silver alloy may become insufficient, and when it exceeds 0.5% by weight, the corrosion resistance of copper may become insufficient.
於本發明之光阻剝離液含有肌酸酐作為防蝕劑之情形時，其含量並無特別限定，較佳為0.01~1.0重量%，更佳為0.1~0.5重量%。若肌酸酐之含量未達0.01重量%，則存在銅之防蝕性變得不充分之情況，若超過1.0重量%，則存在銅及錫-銀合金之防蝕性變得不充分之情況。 When the photoresist stripper of the present invention contains creatinine as an anti-corrosion agent, its content is not particularly limited, but is preferably 0.01-1.0% by weight, more preferably 0.1-0.5% by weight. If the content of creatinine is less than 0.01% by weight, the corrosion resistance of copper may become insufficient, and if it exceeds 1.0% by weight, the corrosion resistance of copper and tin-silver alloy may become insufficient.
於本發明之光阻剝離液含有麥芽醇及肌酸酐作為防蝕劑之 情形時，麥芽醇及肌酸酐之總含量並無特別限定，較佳為1.0重量%以下，更佳為0.7重量%以下，進而較佳為0.6重量%以下。若麥芽醇及肌酸酐之總含量超過1.0重量%，則存在光阻剝離性降低之情況。 The photoresist stripping solution of the present invention contains maltitol and creatinine as corrosion inhibitors In some cases, the total content of maltitol and creatinine is not particularly limited, but is preferably at most 1.0% by weight, more preferably at most 0.7% by weight, and still more preferably at most 0.6% by weight. When the total content of maltitol and creatinine exceeds 1.0% by weight, resist peelability may decrease.
於本發明之光阻剝離液含有麥芽醇及肌酸酐作為防蝕劑之情形時，麥芽醇與肌酸酐之含有重量比率(重量比)並無特別限定，較佳為3：1~1：3，更佳為3：1~1：1。若麥芽醇之含有重量比率未達1：3，則存在錫-銀合金之防蝕性變得不充分之情況，若肌酸酐之含有重量比率未達3：1，則存在銅之防蝕性變得不充分之情況。 When the photoresist stripping solution of the present invention contains maltol and creatinine as corrosion inhibitors, the weight ratio (weight ratio) of maltol and creatinine is not particularly limited, preferably 3:1~1: 3. More preferably 3:1~1:1. If the weight ratio of maltitol is less than 1:3, the corrosion resistance of tin-silver alloy may become insufficient, and if the weight ratio of creatinine is less than 3:1, the corrosion resistance of copper may be deteriorated. Insufficient situation.
除水及防蝕劑以外之其他任意成分之含量取決於其種類，故而不可一概而論，例如較佳為0.001~5重量%，更佳為0.01~1重量%。 The content of other arbitrary components other than water and anti-corrosion agent depends on the type, so it cannot be generalized. For example, it is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight.
本發明之光阻剝離液可藉由利用常規方法將上述各成分進行混合而製備。 The photoresist stripping solution of the present invention can be prepared by mixing the above-mentioned components by a conventional method.
本發明之光阻剝離液可於半導體基板或FPD基板等之製造步驟中用於將金屬配線等之蝕刻處理後變得無用之光阻進行剝離。本發明之光阻剝離液除常溫以外亦可例如加熱至30℃~80℃而使用。剝離所需要之時間取決於光阻之變質程度等，一般而言，例如為30秒~10分鐘左右。處理後，可視需要進行水洗、空氣吹乾等。 The photoresist stripping solution of the present invention can be used for stripping photoresists that become useless after etching of metal wiring and the like in the manufacturing steps of semiconductor substrates, FPD substrates, and the like. The photoresist stripping solution of the present invention can also be used by heating to, for example, 30° C. to 80° C. besides normal temperature. The time required for the stripping depends on the degree of deterioration of the photoresist, etc. Generally speaking, it is about 30 seconds to 10 minutes, for example. After the treatment, water washing, air drying, etc. may be performed as necessary.
為了使用本發明之光阻剝離液將具有銅層或銅合金層之金屬配線基板之光阻剝離，於使用光阻於基板上形成具有銅層或銅合金層之金屬配線時，為了防止銅層或銅合金層之腐蝕，只要使用本發明之光阻剝離液將變得無用之光阻剝離去除即可。更具體而言，於本發明之光阻剝離液中，例如於室溫~80℃浸漬1~30分鐘。此時，亦可視需要對光阻剝離液 進行攪拌、或振動基板。或亦可將本發明之光阻剝離液利用噴淋器或噴霧器等吹送至基板。此時，亦可藉由併用刷洗使光阻剝離性提昇。於溶解或剝離光阻後，較佳為利用純水將含有已溶解之光阻之光阻剝離液進行洗淨去除，而將光阻自基板上去除。其後，利用氣刀等將基板上之液體吹散，使基板乾燥。 In order to use the photoresist stripping solution of the present invention to strip the photoresist of the metal wiring substrate having a copper layer or a copper alloy layer, when using a photoresist to form metal wiring with a copper layer or a copper alloy layer on the substrate, in order to prevent the copper layer Or corrosion of the copper alloy layer, as long as the useless photoresist is stripped and removed using the photoresist stripping solution of the present invention. More specifically, in the photoresist stripping solution of the present invention, for example, immerse at room temperature to 80° C. for 1 to 30 minutes. At this time, the photoresist stripper can also be adjusted as needed. Agitation, or vibration of the substrate is performed. Alternatively, the photoresist stripping solution of the present invention may be blown onto the substrate by a shower or a sprayer. At this time, the photoresist peelability can also be improved by using the brush together. After dissolving or stripping the photoresist, it is preferable to use pure water to wash and remove the photoresist stripping solution containing the dissolved photoresist, so as to remove the photoresist from the substrate. Thereafter, the liquid on the substrate is blown away by using an air knife or the like to dry the substrate.
藉由如此進行，可防止銅層或銅合金層受到過度腐蝕而使銅配線或銅合金配線之線寬變窄，且於不損害藉由蝕刻所形成之配線剖面形狀之情況下形成良好之金屬配線。再者，作為金屬配線之多層態樣，可有：自上層依序為銅或銅合金之1層配線、自上層依序為銅或銅合金/與上層不同之組成之銅或銅合金之2層配線、自上層依序為銅或銅合金/鉬、鈦等上覆金屬(cap metal)之2層配線、自上層依序為鉬、鈦等上覆金屬/銅或銅合金/鉬、鈦等上覆金屬之3層配線等。 By doing so, it is possible to prevent the copper layer or the copper alloy layer from being excessively corroded to narrow the line width of the copper wiring or the copper alloy wiring, and to form a good metal without impairing the cross-sectional shape of the wiring formed by etching. Wiring. Furthermore, as a multilayer form of metal wiring, there are: 1 layer wiring of copper or copper alloy sequentially from the upper layer, 2 layers of copper or copper alloy of copper or copper alloy of different composition from the upper layer sequentially from the upper layer Layer wiring, 2-layer wiring of copper or copper alloy/molybdenum, titanium and other cap metals in sequence from the upper layer, cap metal such as molybdenum and titanium in sequence from the upper layer/copper or copper alloy/molybdenum and titanium 3-layer wiring of overlying metal, etc.
本發明之光阻剝離液於正型、負型之任一光阻之剝離中均可使用，就具有較高之光阻剝離性之方面而言，較佳為用於負型乾膜光阻之剝離。 The photoresist stripping solution of the present invention can be used in the stripping of either positive-type or negative-type photoresists, and is preferably used for stripping negative-type dry film photoresists in terms of high photoresist stripping performance.
以下列舉實施例對本發明進行說明，但本發明並不僅限定於該等實施例。 The following examples are given to describe the present invention, but the present invention is not limited to these examples.
以下述表1所示之重量比將各成分混合，而獲得光阻剝離液。針對所獲得之光阻剝離液，藉由後文所述之方法對液體狀態、光阻剝離性及經時穩定性進行評價。將結果示於表1。 Each component was mixed in the weight ratio shown in the following Table 1, and the photoresist stripping liquid was obtained. Regarding the obtained resist stripping liquid, the liquid state, resist stripping property, and temporal stability were evaluated by the method described later. The results are shown in Table 1.
再者，表1中，DMSO表示二甲基亞碸，TMAH表示氫氧化四甲基銨，MEA表示單乙醇胺，MIPA表示1-胺基-2-丙醇，NPA表示正丙醇胺，MMA表示N-甲基乙醇胺，MDA表示N-甲基二乙醇胺。 Furthermore, in Table 1, DMSO represents dimethylsulfoxide, TMAH represents tetramethylammonium hydroxide, MEA represents monoethanolamine, MIPA represents 1-amino-2-propanol, NPA represents n-propanolamine, and MMA represents N-methylethanolamine, MDA means N-methyldiethanolamine.
以下述表2所示之重量比將各成分混合，而獲得光阻剝離液。針對所獲得之光阻剝離液，藉由後文所述之方法對液體狀態、光阻剝離性及經時穩定性進行評價。將結果示於表2。 Each component was mixed in the weight ratio shown in the following Table 2, and the photoresist stripping liquid was obtained. Regarding the obtained resist stripping liquid, the liquid state, resist stripping property, and temporal stability were evaluated by the method described later. The results are shown in Table 2.
再者，表2中，DMSO表示二甲基亞碸，TMAH表示氫氧化四甲基銨，EDA表示乙二胺，DETA表示二伸乙基三胺，TETA表示三伸乙基四胺，TEPA表示四伸乙基五胺，PEHA表示五伸乙基六胺，TEG表示三乙二醇。 Furthermore, in Table 2, DMSO represents dimethylsulfide, TMAH represents tetramethylammonium hydroxide, EDA represents ethylenediamine, DETA represents diethylenetriamine, TETA represents triethylenetetramine, and TEPA represents Tetraethylenepentamine, PEHA means pentaethylenehexamine, and TEG means triethylene glycol.
以下述表3所示之重量比將各成分混合，而獲得光阻剝離液。針對所獲得之光阻剝離液，藉由後文所述之方法對液體狀態、光阻剝離性及經時穩定性進行評價。將結果示於表3。 Each component was mixed in the weight ratio shown in the following Table 3, and the photoresist stripping liquid was obtained. Regarding the obtained resist stripping liquid, the liquid state, resist stripping property, and temporal stability were evaluated by the method described later. The results are shown in Table 3.
再者，表3中，DMSO表示二甲基亞碸，TMAH表示氫氧化四甲基銨，TETA表示三伸乙基四胺，TEG表示三乙二醇。 In Table 3, DMSO represents dimethylsulfene, TMAH represents tetramethylammonium hydroxide, TETA represents triethylenetetramine, and TEG represents triethylene glycol.
以下述表4所示之重量比將各成分混合，而獲得光阻剝離液。針對所獲得之光阻剝離液，藉由後文所述之方法對液體狀態、多元醇等之SP值、光阻剝離性及經時穩定性進行評價。將結果示於表4。 Each component was mixed in the weight ratio shown in the following Table 4, and the photoresist stripping liquid was obtained. Regarding the obtained resist stripping liquid, the liquid state, SP values such as polyols, resist stripping property, and temporal stability were evaluated by the method described later. The results are shown in Table 4.
再者，表4中，DMSO表示二甲基亞碸，TMAH表示氫氧化四甲基銨，TETA表示三伸乙基四胺，EDA表示乙二胺，MEA表示單乙醇胺，TEG表示三乙二醇。 Furthermore, in Table 4, DMSO represents dimethylsulfide, TMAH represents tetramethylammonium hydroxide, TETA represents triethylenetetramine, EDA represents ethylenediamine, MEA represents monoethanolamine, and TEG represents triethylene glycol .
1.液體狀態 1. Liquid state
針對光阻剝離液，以目視對析出物之有無、液體之流動性進行觀察，並利用以下基準進行評價。 Regarding the resist stripping liquid, the presence or absence of precipitates and the fluidity of the liquid were observed visually, and evaluated by the following criteria.
○：為無析出物之液狀 ○: Liquid without precipitates
析出：有析出物但有液體流動性 Precipitation: There are precipitates but liquid fluidity
固化：析出物較多且無液體流動性 Curing: more precipitates and no fluidity
2.SP值 2.SP value
光阻剝離液中所使用之多元醇、二醇醚、MEA及EDA之SP值係利用上述方法而求出。 The SP values of the polyols, glycol ethers, MEA, and EDA used in the photoresist stripping solution were obtained by the method described above.
3.光阻剝離性 3. Photoresist stripping
將以如下方式而製成之基板作為評價對象：於Si基板上藉由濺鍍分別形成Ti膜及銅籽晶層，其後以成為膜厚120μm之方式輥式層壓光阻(負型乾膜光阻：東京應化工業股份有限公司製造，MP-112)，並藉由UV曝光及顯影進行光阻之圖案化，其後，藉由電鍍形成銅鍍覆層(膜厚50μm)，藉由無電解鍍覆形成Ni鍍覆層(膜厚1μm)，藉由電鍍形成錫-銀合金鍍覆層(膜厚30μm)。將基板浸漬於調整至60℃之光阻剝離液中，進行100分鐘處理。浸漬處理後，將基板進行水洗及空氣吹乾。使用電子顯微鏡對基板進行觀察，確認光阻之剝離情況。 A substrate manufactured in the following manner was used as an evaluation object: a Ti film and a copper seed layer were formed on a Si substrate by sputtering, and then a roll-laminated photoresist (negative dry film) was formed to have a film thickness of 120 μm. Film photoresist: manufactured by Tokyo Ohka Industry Co., Ltd., MP-112), patterning the photoresist by UV exposure and development, and then forming a copper plating layer (film thickness 50 μm) by electroplating, by A Ni plating layer (film thickness 1 μm) was formed by electroless plating, and a tin-silver alloy plating layer (film thickness 30 μm) was formed by electroplating. The substrate was immersed in a photoresist stripping solution adjusted to 60°C for 100 minutes. After the dipping treatment, the substrate was washed with water and air-dried. Observe the substrate with an electron microscope to confirm the peeling of the photoresist.
○：無剝離殘留 ○: No peeling residue
△：略微存在剝離殘留 △: There is a slight peeling residue
×：存在較多剝離殘留 ×: There are many peeling residues
4.經時穩定性 4. Stability over time
將光阻剝離液於空氣環境下於60℃靜置36小時，使其進行經時變化。其後，以與上述相同之方式進行光阻剝離性之評價。 The photoresist stripping solution was allowed to stand still at 60° C. for 36 hours in an air environment, and was changed over time. Thereafter, evaluation of resist peelability was performed in the same manner as above.
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