CN114326333B - A polyvinyl cinnamate type KPR photoresist etching residue stripping agent composition - Google Patents
A polyvinyl cinnamate type KPR photoresist etching residue stripping agent composition Download PDFInfo
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- CN114326333B CN114326333B CN202111669888.4A CN202111669888A CN114326333B CN 114326333 B CN114326333 B CN 114326333B CN 202111669888 A CN202111669888 A CN 202111669888A CN 114326333 B CN114326333 B CN 114326333B
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- mixture
- ether
- fluoride
- photoresist etching
- etching residue
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- 238000005530 etching Methods 0.000 title claims abstract description 31
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229940114081 cinnamate Drugs 0.000 title claims abstract description 12
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 title claims description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 48
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 11
- 239000012498 ultrapure water Substances 0.000 claims abstract description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims abstract description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940102253 isopropanolamine Drugs 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 8
- 235000010234 sodium benzoate Nutrition 0.000 claims description 8
- 239000004299 sodium benzoate Substances 0.000 claims description 8
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 abstract description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 abstract description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 abstract description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 3
- 239000008103 glucose Substances 0.000 abstract description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000600 sorbitol Substances 0.000 abstract description 3
- 239000000811 xylitol Substances 0.000 abstract description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 abstract description 3
- 229960002675 xylitol Drugs 0.000 abstract description 3
- 235000010447 xylitol Nutrition 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 abstract description 2
- 150000001565 benzotriazoles Chemical class 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 34
- 229910052581 Si3N4 Inorganic materials 0.000 description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000004380 ashing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005468 ion implantation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- PUTCXBJUWNRWJH-UHFFFAOYSA-N cyclohexa-3,5-diene-1,1,2-triol Chemical compound OC1C=CC=CC1(O)O PUTCXBJUWNRWJH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Cleaning Or Drying Semiconductors (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
本发明公开了一种聚乙烯醇肉桂酸酯型KPR光刻胶蚀刻残留剥离剂组合物，包括：有机溶剂40~70%，有机胺1~20%，缓蚀剂0.5~10%，表面活性剂0.2~5%，氟化物1~5%以及其余的超纯水，其中：所述表面活性剂为乙二醇、丙三醇、葡萄糖、山梨醇、季戊四醇、木糖醇、AEO‑7中的一种或多种的混合；所述有机胺为单乙醇胺、三乙醇胺、异丙醇胺中的一种或多种的混合；所述缓蚀剂为酚类、羧酸类、苯并三氮唑类中的一种或多种的混合。本发明剥离剂具有更高清洗效率，清洗时间较同类产品显著地缩短，且清洗效果和对晶圆基材的保护效果更好，能显著地降低半导体工厂的运营成本。The present invention discloses a polyvinyl alcohol cinnamate type KPR photoresist etching residue stripper composition, including: organic solvent 40-70%, organic amine 1-20%, corrosion inhibitor 0.5-10%, surfactant 0.2-5%, fluoride 1-5% and the rest of ultrapure water, wherein: the surfactant is a mixture of one or more of ethylene glycol, glycerol, glucose, sorbitol, pentaerythritol, xylitol, AEO-7; the organic amine is a mixture of one or more of monoethanolamine, triethanolamine, isopropanolamine; the corrosion inhibitor is a mixture of one or more of phenols, carboxylic acids, and benzotriazoles. Stripper of the present invention has higher cleaning efficiency, cleaning time is significantly shortened compared with similar products, and cleaning effect and protection effect on wafer substrate are better, which can significantly reduce the operating cost of semiconductor factories.
Description
Technical Field
The invention belongs to the technical field of semiconductor photoresist stripping agents, and particularly relates to a rapid stripping agent for removing KPR photoresist etching residues by using fluorine.
Background
In the production of semiconductor chips, it is necessary to transfer the designed pattern from the mask to the wafer by photolithography and etching to finally produce ultra-high integration chips. The method comprises the steps of depositing a film (comprising silicon dioxide, silicon nitride, polysilicon, silicon carbide, gallium nitride, titanium nitride, cobalt, tungsten, copper, aluminum, nickel and the like), photoresist coating, exposing, developing, ion implantation or etching, ashing and cleaning on a wafer. During ion implantation or etching process, photoresist is hard to remove because of ion bombardment becoming hardened, and a large amount of polymer byproducts remain on the wafer during etching process, so that even in the subsequent ashing step, photoresist layers can only be removed, and the remaining byproducts can only rely on a cleaning process to clean the wafer thoroughly.
In the front-end cleaning process (i.e., prior to formation of the metal interconnect layer), a mixture of sulfuric acid and hydrogen peroxide is typically used to remove residues after etching or ion implantation. However, after the metal interconnection layer is formed, neither the aluminum interconnection process nor the copper interconnection process can be performed by using the front-end cleaning process, and a special stripper is necessary to clean the wafer. Obviously, the special stripper used in the back-end process must take into account that, in addition to completely cleaning the residues after etching, the substrate of the wafer itself, in particular metallic aluminum or copper, and also silicon dioxide and silicon nitride, must not be damaged too much.
At present, the most main photoresist of our company is KPR series photoresist of polyvinyl alcohol cinnamate, which has the advantages of high resolution, etching resistance, strong adhesiveness and the like, but after etching-ashing, the conventional back-stage stripping liquid still has residues easily after cleaning, so the cleaning time is often longer, generally more than 20 minutes is required, and the corrosion damage of a wafer substrate can be caused along with the extension of the cleaning time. With the development of advanced processes, the complexity of metal interconnection processes is higher and higher, the number of layers is also higher and the number of cleaning times required for single wafer production is also higher and higher. Longer cleaning times can lead to higher occupancy of cleaning equipment, thereby forcing semiconductor factories to purchase more equipment and occupy more clean rooms to meet the growing cleaning demands. Purchase of semiconductor equipment, use of stripping agents, and clean room operation are all important components of the cost of operating a semiconductor factory. Therefore, reducing the cleaning time and improving the cleaning efficiency are one of the important means for reducing the cost of the semiconductor factory.
Disclosure of Invention
The invention aims to solve the problems and the defects of the prior art and provide a polyvinyl alcohol cinnamate type KPR photoresist etching residue stripper composition.
The technical scheme is that the polyvinyl alcohol cinnamate type KPR photoresist etching residue stripper composition comprises the following components in parts by weight:
and the rest of ultrapure water, wherein the sum of the mass percentages of the components is 100 percent, and the components are as follows:
the surfactant is one or more of glycol, glycerol, glucose, sorbitol, pentaerythritol, xylitol and AEO-7;
The organic solvent is one or a mixture of more of ether, ketone and amide organic solvents;
the organic amine is one or more of monoethanolamine, triethanolamine and isopropanolamine;
The corrosion inhibitor is one or a mixture of more of phenols, carboxylic acids and benzotriazole;
The fluoride is one or more of ammonium bifluoride, tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, hydrogen fluoride and ammonium fluoride.
Preferably, the surfactant is one or more of AEO-7, glycerol, pentaerythritol, sorbitol, ethylene glycol, glucose and xylitol.
Preferably, the surfactant is a mixture of glycerol and pentaerythritol.
Preferably, the ether organic solvent is one or more of diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether.
Preferably, the ketone organic solvent is one or more of acetone, imidazolidone, pyrrolidone and imidazolinone.
Preferably, the amide-based organic solvent is dimethylformamide and/or dimethylacetamide.
Preferably, the corrosion inhibitor is one or more of sodium benzoate, methyl benzotriazole, sebacic acid, ethylenediamine tetraacetic acid, sodium nitrite, gallic acid and 1, 2-dihydroxyphenol.
Preferably, the corrosion inhibitor is any one of combination of benzoic acid and methyl benzotriazol, sodium benzoate and sebacic acid, and sebacic acid/sodium nitrite.
Preferably, the polyvinyl alcohol cinnamate type KPR photoresist etching residual stripper composition comprises the following components in percentage by mass:
and the rest of ultrapure water, wherein the sum of the mass percentages of the components is 100 percent, and the components are as follows:
The corrosion inhibitor is any combination of sodium benzoate and methyl benzotriazol, sodium benzoate and sebacic acid, and sebacic acid and sodium nitrite in a mass ratio of 1:1;
The surfactant adopts glycerol and pentaerythritol with the mass ratio of 1:1, or adopts fatty alcohol polyoxyethylene ether AE0-7.
The invention also provides a method for removing photoresist etching residues by using the stripping agent composition, which comprises the steps of carrying out contact cleaning on the stripping agent and the etched and ashed semiconductor chip in a spraying mode at the temperature of 20-60 ℃, then carrying out oscillation treatment in an ultrasonic wave, megasonic wave, shaking or rotating oscillation mode, then rinsing with pure water or ultrapure water at the temperature of 10-30 ℃, and finally carrying out centrifugal drying and/or IPA steam drying.
Compared with the prior art, the stripping agent can be applied to a semiconductor chip cleaning process adopting a KRP photoresist structure as aluminum interconnection or copper interconnection, can rapidly clean photoresist residues after etching and ashing of semiconductor chips, has obviously shortened cleaning time compared with similar products, has good cleaning effect and good protection effect on wafer substrates, and can obviously reduce the operation cost of a semiconductor factory.
Detailed Description
The present application is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the application and not limiting the scope of the application, and that modifications of the application, which are equivalent to those skilled in the art to which the application pertains, fall within the scope of the application defined in the appended claims after reading the application.
Examples 1 to 39
The KPR photoresist etching residue stripper described in examples 1-39 of the present invention was formulated by mixing the components and proportions shown in tables 1 and 2. The method comprises the steps of testing the influence of different surfactants on the cleaning effect in examples 1-10, testing the influence of different corrosion inhibitor combinations on the cleaning effect and the corrosion condition of a test piece in examples 11-21, and discussing the influence of other components and proportions on the cleaning effect of KPR photoresist residues.
Table 1 shows the components of the stripping agent of examples 1 to 33
Table 2 the mass percent content of each component and the cleaning time in examples 1 to 33.
Comparative examples 1 to 17:
The photoresist components and proportions of comparative examples D1 to D17 of the present invention are shown in tables 3 and 4. Wherein, comparative examples 1 to 12 are mainly used for evaluating the influence of the cleaning effect of the stripping agent of the invention under the condition of no surfactant, and comparative examples 13 to 17 are used for the cleaning effect under the condition of non-polyol surfactant.
Table 3 shows the components of the photoresists of comparative examples D1 to D17
Table 4 shows the contents of the components in the photoresists of comparative examples D1 to D15
Stripping agent cleaning test method and evaluation:
1. The stripper cleaning and cleaning effect test of the semiconductor chip after etching and ashing comprises the steps of uniformly mixing the above examples and comparative examples according to a proportion, filtering, placing 5L of the mixture into spray cleaning equipment, placing the semiconductor chip after etching and ashing by using KPR photoresist sold in Jiangsu nan large photoelectric market into the cleaning equipment, cleaning by using a spray method, rinsing by using ultrapure water after cleaning, and drying by using a centrifugal drying mode after rinsing. And finally, detecting the cleaning effect by using SEM. The washing time of each example and comparative example was 1 minute and 30 minutes for each piece, and the washing results are shown in tables 5 and 6.
2. Different blank wafer corrosion effect test:
the method for testing the corrosion conditions of the blank wafer metal aluminum, the blank wafer metal copper, the blank wafer metal titanium and the blank wafer metal tungsten comprises the following steps:
The front value of the film thickness can be obtained by measuring the surface resistance of a blank wafer with the thickness of 4x4cm by using a four-point probe instrument, immersing the wafer with the measured front value into a stripping agent with the constant temperature of 30-60 ℃, taking out the wafer after 30 minutes, rinsing the wafer by ultrapure water, drying the wafer by high-purity nitrogen, measuring the thickness back value of the cleaned film by using the four-point probe instrument, and calculating the corrosion rate of the stripping agent to the metal aluminum film.
The method for testing the corrosion conditions of the blank wafer Tetraethoxysilane (TEOS) and the blank wafer silicon nitride (PE Si 3N4) comprises the following steps:
The etching condition of the blank wafer Tetraethoxysilane (TEOS) is specifically operated by using FE3000 to measure the front value of the thickness of the 4x4cm blank TEOS wafer, immersing the TEOS wafer with the measured front value into a stripping agent with the constant temperature of 30-60 ℃, taking out the TEOS wafer after 30 minutes, rinsing the TEOS wafer with ultrapure water, then drying the TEOS wafer with high-purity nitrogen, testing the rear value of the thickness of the TEOS film by using FE3000, and calculating to obtain the etching rate of the stripping agent to the TEOS film, wherein the etching results are shown in tables 5 and 6.
The corrosion condition of the blank silicon nitride (PE Si 3N4) is specifically carried out by measuring the front value of the thickness of a blank silicon nitride wafer with the thickness of 4x4cm by using an FE3000, immersing the silicon nitride wafer with the front value in a stripping agent with the constant temperature of 30-60 ℃, taking out the silicon nitride wafer after 30 minutes, rinsing the silicon nitride wafer with ultrapure water, drying the silicon nitride wafer by using high-purity nitrogen, testing the rear value of the thickness of the silicon nitride film by using the FE3000, and calculating the corrosion rate of the stripping agent on the silicon nitride film, wherein the corrosion test results are shown in tables 5 and 6.
Table 5 shows the etching effect of different blank wafers after being cleaned by the stripping solution according to various embodiments of the present invention
Table 6 shows the etching effect of different blank wafers after being cleaned by different stripping solutions of comparative examples
The meanings of the symbols in tables 5 and 6
From comparison of the cleaning results of the above examples B1 to B33 and comparative examples D1 to D15, it can be seen that:
From the results of comparative examples D1 to D15, it was found that the stripping solution without the surfactant still had more photoresist residue after 10 minutes of cleaning, and the cleaning effect after the addition of the surfactants such as 5-sulfosalicylic acid, isooctyl alcohol ether phosphate, sodium dodecylbenzenesulfonate, distyrylphenol polyoxyethylene ether, and vinyl distearamide was improved, but the effects of examples 1 to 33 of the present invention were still different from those of examples 1 to 33.
The stripping agents B1-B33 can be completely stripped without residues after being cleaned for 10min, and the stripping agents B10-B21 with glycerol/pentaerythritol combination or AEO-7 surfactants can be completely removed without residues after being cleaned for 1min, so that the cleaning efficiency is greatly improved, and the cleaning time is shortened, and therefore, the stripping agents B1-B33 have obviously improved cleaning effect on etching residual glue. In addition, the cleaning effect of other organic solvents, surfactants and corrosion inhibitors is discussed in the embodiments B23-B33, and the results show that the cleaning effect can be completely removed in 10min of cleaning time. From the test results, the corrosion inhibitor adopting the combination of at least two of sodium benzoate, methyl benzotriazole, sebacic acid and sodium nitrite has the optimal corrosion inhibition effect, and can achieve the basically corrosion-free effect.
The stripping agent can obviously improve the cleaning efficiency of the semiconductor chip, and is beneficial to reducing the occupancy rate of cleaning equipment in a semiconductor factory, thereby achieving the effects of reducing the purchase of the cleaning equipment and reducing the production operation cost.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (6)
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| CN101286016A (en) * | 2007-04-13 | 2008-10-15 | 安集微电子（上海）有限公司 | Low etching photoresist cleaning agent |
| CN107229194A (en) * | 2017-07-25 | 2017-10-03 | 上海新阳半导体材料股份有限公司 | A kind of fluorine-containing plasma etching residue cleaning, its preparation method and application |
| CN108255026A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子（上海）有限公司 | A kind of low etching photoresist residual washing liquid composition |
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| CN101286016A (en) * | 2007-04-13 | 2008-10-15 | 安集微电子（上海）有限公司 | Low etching photoresist cleaning agent |
| CN108255026A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子（上海）有限公司 | A kind of low etching photoresist residual washing liquid composition |
| CN107229194A (en) * | 2017-07-25 | 2017-10-03 | 上海新阳半导体材料股份有限公司 | A kind of fluorine-containing plasma etching residue cleaning, its preparation method and application |
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