JPH02187764A - Far ultraviolet ray-sensitive resin composition - Google Patents
Far ultraviolet ray-sensitive resin compositionInfo
- Publication number
- JPH02187764A JPH02187764A JP1007322A JP732289A JPH02187764A JP H02187764 A JPH02187764 A JP H02187764A JP 1007322 A JP1007322 A JP 1007322A JP 732289 A JP732289 A JP 732289A JP H02187764 A JPH02187764 A JP H02187764A
- Authority
- JP
- Japan
- Prior art keywords
- far
- hydroxystyrenes
- copolymer
- resist
- sensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 150000003440 styrenes Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 abstract description 6
- -1 α-cyclohexyl-p-hydroxystyrene Chemical compound 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001312 dry etching Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YNGIFMKMDRDNBQ-UHFFFAOYSA-N 3-ethenylphenol Chemical compound OC1=CC=CC(C=C)=C1 YNGIFMKMDRDNBQ-UHFFFAOYSA-N 0.000 description 2
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229940022663 acetate Drugs 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- YTMCUIACOKRXQA-UHFFFAOYSA-N (2-aminoacetyl) 2-aminoacetate Chemical class NCC(=O)OC(=O)CN YTMCUIACOKRXQA-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- BJTXPZYDJTYEBV-UHFFFAOYSA-N 1,13-bis(2,3,4-trihydroxyphenyl)tridecan-7-one Chemical compound OC1=C(O)C(O)=CC=C1CCCCCCC(=O)CCCCCCC1=CC=C(O)C(O)=C1O BJTXPZYDJTYEBV-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical class C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- BOGFHOWTVGAYFK-UHFFFAOYSA-N 1-[2-(2-propoxyethoxy)ethoxy]propane Chemical compound CCCOCCOCCOCCC BOGFHOWTVGAYFK-UHFFFAOYSA-N 0.000 description 1
- MXLWBXNCIZQWNB-UHFFFAOYSA-N 1-cyclohexylethenylbenzene Chemical compound C=1C=CC=CC=1C(=C)C1CCCCC1 MXLWBXNCIZQWNB-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- NGEWQZIDQIYUNV-UHFFFAOYSA-M 2-hydroxy-3-methylbutyrate Chemical compound CC(C)C(O)C([O-])=O NGEWQZIDQIYUNV-UHFFFAOYSA-M 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 description 1
- OCPPVWQQXKOCMP-UHFFFAOYSA-N 4-but-1-en-2-ylphenol Chemical compound CCC(=C)C1=CC=C(O)C=C1 OCPPVWQQXKOCMP-UHFFFAOYSA-N 0.000 description 1
- NGKPMOSDLRDYDI-UHFFFAOYSA-N 4-hex-1-en-2-ylphenol Chemical compound CCCCC(=C)C1=CC=C(O)C=C1 NGKPMOSDLRDYDI-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- FBOSKQVOIHEWAX-UHFFFAOYSA-N benzothiazine Chemical class C1=CC=C2N=CCSC2=C1 FBOSKQVOIHEWAX-UHFFFAOYSA-N 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- YJSSCAJSFIGKSN-UHFFFAOYSA-N hex-1-en-2-ylbenzene Chemical compound CCCCC(=C)C1=CC=CC=C1 YJSSCAJSFIGKSN-UHFFFAOYSA-N 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は、遠紫外線に感応する感遠紫外線樹脂組成物に
関し、さらに詳しくはＫｒＦエキシマレーザ−などに対
して感度が良く、特に高密度化集積回路作製のためのレ
ジストとして使用した場合に、現像による膜減りが小さ
く、ドライエツチング耐性が良く、解像度およびパター
ンプロファイルが優れたレジストパターンを得ることが
できる感遠紫外線樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a far ultraviolet-sensitive resin composition sensitive to far ultraviolet rays, more specifically, it is sensitive to KrF excimer laser, etc., and is particularly sensitive to high density. This invention relates to a sensitive ultraviolet ray resin composition which, when used as a resist for producing integrated circuits, can provide a resist pattern with little film loss due to development, good dry etching resistance, and excellent resolution and pattern profile.
ｂ、従来の技術
近年、半導体集積回路の高密度化に伴い、その加エサ法
の微細化が進み、サブミクロンのレジストパターンの形
成が必要とされてきている。こうしたサブミクロンのレ
ジストパターンを形成させるために、従来の超高圧水銀
灯から発生するｇ線（−４３６ｎｍ）を光源とする縮小
投影照射方式に代って、ＫｒＰエキシマレーザ−などの
遠紫外線を用いて縮小投影照射を行ない解像度を向上さ
せる方法が提案されている。b. Prior Art In recent years, as the density of semiconductor integrated circuits has increased, processing methods have become increasingly finer, and it has become necessary to form submicron resist patterns. In order to form such submicron resist patterns, far ultraviolet rays such as KrP excimer lasers are used instead of the conventional reduced projection irradiation method using the g-line (-436 nm) emitted from an ultra-high pressure mercury lamp as a light source. A method of improving resolution by performing reduced projection irradiation has been proposed.
Ｃ１発明が解決しようとする課題
ＫｒＦエキシマレーザ−などの遠紫外線を照射源とする
場合、レジストに使用する樹脂としては、ポリメチルメ
タクリレート、ポリグリシジルメタクリレート、ノボラ
ック樹脂、ポリヒドロキシスチレンなどが提案されてい
る。しかし、ポリメチルメタクリレート、およびポリグ
リシジルメタクリレートはドライエツチング耐性が悪い
うえに、非常に感度が悪く、ノボラック樹脂はドライエ
ツチング耐性は良いが、遠紫外線、例えばＫｒＦエキシ
マレーザ−の発振波長（２４８ｎｍ）における吸光度が
大きく、レジストの深部まで遠紫外線が十分到達せず、
その結果アルカリ性水溶液からなる現像液によって現像
する際に得られるレジストパターンのプロファイルが悪
いという欠点を有している。また、ポリヒドロキシスチ
レンは、ドライエツチング耐性が良く、２４８ｎｍにお
ける吸光度がノボラック樹脂よりも小さいが、アルカリ
性水溶液に対する溶解性が大きいため現像によるレジス
トパターンの膜減りが大きすぎて基板をエツチングする
際にレジストとしての機能を十分果せないという欠点が
ある。C1 Problems to be Solved by the Invention When far ultraviolet rays such as KrF excimer laser are used as an irradiation source, polymethyl methacrylate, polyglycidyl methacrylate, novolak resin, polyhydroxystyrene, etc. have been proposed as resins to be used in the resist. There is. However, polymethyl methacrylate and polyglycidyl methacrylate have poor dry etching resistance and very low sensitivity, while novolac resins have good dry etching resistance, but at the oscillation wavelength (248 nm) of deep ultraviolet rays, such as KrF excimer laser. The absorbance is high, and far ultraviolet rays do not reach deep into the resist.
As a result, it has the disadvantage that the profile of the resist pattern obtained when developing with a developer consisting of an alkaline aqueous solution is poor. In addition, polyhydroxystyrene has good dry etching resistance and has a lower absorbance at 248 nm than novolac resin, but because it has a high solubility in alkaline aqueous solutions, the resist pattern film is reduced too much by development, so it is difficult to remove the resist when etching the substrate. It has the disadvantage of not being able to fully perform its functions.
本発明の目的は、上記課題を解決し、エキシマレーザ−
などの遠紫外線を照射源として用いても、現像による膜
減りが小さく、ドライエツチング耐性が良く、良好なプ
ロファイルを有するレジストパターンを高解像度にて得
ることのできる感遠紫外線樹脂組成物を提供することに
ある。The purpose of the present invention is to solve the above problems and to improve excimer laser
To provide a far-ultraviolet-sensitive resin composition capable of obtaining a resist pattern with small film loss due to development, good dry etching resistance, and a good profile at high resolution even when using far-ultraviolet rays such as UV rays as an irradiation source. There is a particular thing.
６１課題を解決するための手段
すなわち本発明は、ヒドロキシスチレン＠（Ａ）とヒド
ロキシスチレン類以外のスチレン類（Ｂ）の共重合体（
以下、単に「共重合体」という）からなるアルカリ可溶
性樹脂を含有することを特徴とする感遠紫外線樹脂組成
物を提供するものであり、特に前記共重合体からなるア
ルカリ可溶性樹脂と、下記−紋穴（１）、（ＴＩ）また
は（ＩＩＩ）、で表わされる構造を分子中に少くとも一
つ含む感遠紫外線化合物を含有することを特徴とする感
遠紫外線樹脂組成物を提供するものである。61 Means for solving the problem, that is, the present invention is a copolymer of hydroxystyrene@(A) and styrenes (B) other than hydroxystyrenes (
The present invention provides a far-ultraviolet-sensitive resin composition characterized by containing an alkali-soluble resin consisting of the copolymer (hereinafter simply referred to as a "copolymer"), and in particular an alkali-soluble resin consisting of the copolymer and the following - The present invention provides an ultraviolet-sensitive resin composition containing an ultraviolet-sensitive compound containing at least one structure represented by Mongan (1), (TI), or (III) in its molecule. be.
上記共重合体のポリスチレン換算の重量平均分子量（以
下、ｒＭｗという）は、通常、５００〜５０，０００、
好ましくは７００〜３０，０００である。πＷが５００
未満では十分な強度を有するレジスト膜が得られず、５
０．０００を超えるとレジストとしての解像度が悪くな
る。The weight average molecular weight (hereinafter referred to as rMw) of the above copolymer in terms of polystyrene is usually 500 to 50,000,
Preferably it is 700-30,000. πW is 500
If it is less than 5, a resist film with sufficient strength cannot be obtained;
If it exceeds 0.000, the resolution of the resist will deteriorate.
上記ヒドロキシスチレン！ （Ａ）としては、例えばｐ
−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、α−
メチル−ｐ−ヒドロキシスチレン、α−メチルｍ−ヒド
ロキシスチレン、α−エチル−ｐ−ヒドロキシスチレン
、α−ブチル−ｐ−ヒドロキシスチレン、α−ブチル−
ｍ−ヒドロキシスチレン、αシクロヘキシル−ｐ−ヒド
ロキシスチレン、α−シクロヘキシル−ｍ−ヒドロキシ
スチレンなどが挙ケられるが、好ましくはｐ−ヒドロキ
シスチレンおよびα−メチル−ｐ−ヒドロキシスチレン
である。The above hydroxystyrene! As (A), for example, p
-Hydroxystyrene, m-hydroxystyrene, α-
Methyl-p-hydroxystyrene, α-methyl m-hydroxystyrene, α-ethyl-p-hydroxystyrene, α-butyl-p-hydroxystyrene, α-butyl-
Examples include m-hydroxystyrene, α-cyclohexyl-p-hydroxystyrene, α-cyclohexyl-m-hydroxystyrene, and the like, with p-hydroxystyrene and α-methyl-p-hydroxystyrene being preferred.
上記ヒドロキシスチレン類以外のスチレンＩ （Ｂ）と
しては、例えばスチレン、α−メチルスチレン、α−エ
チルスチレン、α−ブチルスチレン、α−シクロへキシ
ルスチレン、０−メチルスチレン、ｍメチルスチレン、
ｐ−メチルスチレン、２，４．６トリメチルスチレンな
どが挙げられるが、好ましくはスチレンおよびα−メチ
ルスチレンである。Examples of styrene I (B) other than the above-mentioned hydroxystyrenes include styrene, α-methylstyrene, α-ethylstyrene, α-butylstyrene, α-cyclohexylstyrene, 0-methylstyrene, m-methylstyrene,
Examples include p-methylstyrene and 2,4.6-trimethylstyrene, with styrene and α-methylstyrene being preferred.
ヒドロキシスチレン［（Ａ）とスチレン１１ （Ｂ）の
共重合割合は、モル比で通常、（Ａ） ／ （Ｂ） ＝
５５／４５〜９５１５であり、好ましくは６０／４０
〜９０／１０である。（Ａ）／（Ｂ）づ
が５５／４５未満では、得られる共重合体がアルカリ性
水溶液からなる現像液に溶けにくくなりレジストパター
ンが形成しにくくなる。また、（Ａ） ／ （Ｂ）が９
５７５を超えると、得られる共重合体のアルカリ性水溶
液からなる現像液に対する溶解性が高すぎるため形成さ
れるレジストパターの膜減りが著しくなる。The copolymerization ratio of hydroxystyrene [(A) and styrene 11 (B) is usually expressed as a molar ratio, (A) / (B) =
55/45 to 9515, preferably 60/40
~90/10. If the ratio (A)/(B) is less than 55/45, the resulting copolymer will be difficult to dissolve in a developer consisting of an alkaline aqueous solution, making it difficult to form a resist pattern. Also, (A) / (B) is 9
If it exceeds 575, the resulting copolymer has too high solubility in a developer consisting of an alkaline aqueous solution, resulting in significant film thinning of the formed resist pattern.
上記共重合体は、ランダム共重合体でもブロック共重合
体でもよいが、通常はランダム共重合体が用いられる。The above copolymer may be a random copolymer or a block copolymer, but usually a random copolymer is used.
本発明の組成物には、感度およびコントラストを向上さ
せるために、下記−紋穴（Ｉ）、（ｎ）または（ＩＩＩ
）で表わされる構造を分子中に少くとも１つ含む悠遠紫
外線化合物が必要に応じて用いられる。In order to improve sensitivity and contrast, the composition of the present invention may include the following - pattern holes (I), (n) or (III).
) A far-UV compound containing at least one structure represented by the following in its molecule may be used as necessary.
この感遠紫外線化合物としては、例えば下記の構造式で
示される化合物が挙げられる。Examples of this ultraviolet-sensitive compound include compounds represented by the following structural formula.
また、感遠紫外線化合物としては、上記化合物の中でＲ
１，ＲＺ、Ｒ３およびＲ４のうち少くとも１つがゾール
、ｍ−クレゾール、ｐ−フレ ゾール、レゾルシノール
、ピロガロール、フロログルシノールなどの（ポリ）ヒ
ドロキシベンゼン、２．４−ジヒドロキシフェニル−ｎ
−へキシルケトン、２，３．４トリヒドロキシフェニル
−ｎ−ヘキシルケトン、２．３．４−）リヒドロキシベ
ンゾフェノン、２゜３．４．４’ −テトラヒドロキ
シベンゾフェノンなどの（ポリ）ヒドロキシフェニルア
ルキルケトンまたは（ポリ）ヒドロキシアリールケトン
とを反応させることにより得られるエステル類を例示す
ることもできる。In addition, among the above-mentioned compounds, R
At least one of 1, RZ, R3 and R4 is (poly)hydroxybenzene such as sol, m-cresol, p-fresol, resorcinol, pyrogallol, phloroglucinol, 2,4-dihydroxyphenyl-n
(Poly)hydroxyphenylalkyl ketones such as -hexylketone, 2,3.4-trihydroxyphenyl-n-hexylketone, 2.3.4-)lyhydroxybenzophenone, and 2°3.4.4'-tetrahydroxybenzophenone. Alternatively, esters obtained by reacting with (poly)hydroxyarylketone can also be exemplified.
本発明の組成物を用いると、通常のアルカリ性水溶液、
例えばテトラメチルアンモニウムヒドロキシド水溶液に
よる現像ではネガ型パターンが得られる。When using the composition of the present invention, ordinary alkaline aqueous solutions,
For example, a negative pattern can be obtained by development with an aqueous solution of tetramethylammonium hydroxide.
上記感遠紫外線化合物の配合量は、上記共重合体１００
重量部に対して、通常、２００重量部以下であり、好ま
しくは１００重量部以下、特に好ましくは１０〜６０重
量部である。The blending amount of the far-ultraviolet-sensitive compound is 100% of the above copolymer.
It is usually 200 parts by weight or less, preferably 100 parts by weight or less, particularly preferably 10 to 60 parts by weight.
この配合量が２００重量部を越える場合には、レジスト
の強度が不十分となる。If this amount exceeds 200 parts by weight, the strength of the resist will be insufficient.
本発明の組成物には、レジストとして使用する際のアル
カリ性水溶液からなる現像液による膜減りを減小させる
ためにアルカリ溶解抑制剤を配合することができる。ア
ルカリ溶解抑制剤としては、などを挙げることができる
。アルカリ溶解抑制剤の配合量は、感遠紫外線化合物１
００重量部に対して、通常、１００重量部以下、好まし
くは５〜５０重量部である。The composition of the present invention may contain an alkaline dissolution inhibitor in order to reduce film loss due to a developer comprising an alkaline aqueous solution when used as a resist. Examples of the alkali dissolution inhibitor include the following. The blending amount of the alkali dissolution inhibitor is 1 part of the far-ultraviolet-sensitive compound.
The amount is usually 100 parts by weight or less, preferably 5 to 50 parts by weight.
また、本発明の組成物には、レジストとしての感度を向
上させるため、増感剤を配合することができる。増感剤
としては、例えば２Ｈ−ピリド〔３，２ｂ）−１，４−
オキサジン−３（４Ｈ）オン類、ＩＯＨピリド［３，２
−ｂ）（１，４）−ベンゾチアジン類、ウラゾール類、
ヒダントイン類、バルビッール酸類、グリシン無水物類
、１−ヒドロキシベンゾトリアゾール類、アロキサン類
、マレイミド類などを挙げることができる。増感剤の配
合量は、感遠紫外線化合物１００重量部に対し、通常、
１００重量部以下、好ましくは５〜５０重量部である。Further, the composition of the present invention may contain a sensitizer in order to improve the sensitivity as a resist. As a sensitizer, for example, 2H-pyrido[3,2b)-1,4-
Oxazin-3(4H)ones, IOH pyrido[3,2
-b) (1,4)-benzothiazines, urazoles,
Examples include hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The blending amount of the sensitizer is usually 100 parts by weight of the ultraviolet-sensitive compound.
The amount is 100 parts by weight or less, preferably 5 to 50 parts by weight.
さらに本発明の組成物には、塗布性、例えばストリエー
ションや現像性を改良するために、界面活性剤を配合す
ることができる。界面活性剤としては、例えばポリオキ
シエチレンラウリルエーテル、ポリオキシエチレンステ
アリルエーテル、ポリオキシエチレンオレイルエーテル
などのポリオキシエチレンアルキルエーテル類、ポリオ
キシエチレンオクチルフェノールエーテル、ポリオキシ
エチレンノニルフェノールエーテルなどのポリオキシエ
チレンアルキルフェノールエーテル類、およびポリエチ
レングリコールジラウレート、ポリエチレングリコール
ジステアレートなどのポリエチレングリコールジアルキ
ルエーテル類のノニオン系界面活性剤、エフトップＥＦ
３０１ 、ＥＦ３０３ 、ＥＦ３５２（新秋田化成■製
）、メガファックＦ１７１、Ｆ１７２、Ｆ１７３ （大
日本インキ■製）、フロラードＦＣ４３０、ｐｃ４３１
（住友スリーエム■製）、アサヒガードへＧ７１０
、サーフロンＳ −３８２，５ＣＩＯＩ 。Furthermore, a surfactant may be added to the composition of the present invention in order to improve coating properties, such as striation and developability. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene alkyl phenols such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether. FTOP EF, a nonionic surfactant of ethers and polyethylene glycol dialkyl ethers such as polyethylene glycol dilaurate and polyethylene glycol distearate
301, EF303, EF352 (manufactured by Shin Akita Kasei ■), Megafac F171, F172, F173 (manufactured by Dainippon Ink ■), Florado FC430, pc431
(manufactured by Sumitomo 3M), G710 to Asahi Guard
, Surflon S-382,5CIOI.
５Ｃ１０２，５Ｃ１０３，５Ｃ１０４，５Ｃ１０５，５
Ｃ１０６（旭硝子■製）などのフッ素系界面活性剤、オ
ルガノシロキサンポリマーＫＰ３４１ （信越化学工
業■製）やアクリル酸系またはメタクリル酸系（共）重
合体ポリフローＮｏ、７５、Ｎｏ、９５ （共栄社油脂
化学工業■製）などが挙げられる。界面活性剤の配合量
は、上記共重合体および悠遠紫外線化合物の合計量１０
０重量部当たり、通常、２重量部以下である。5C102, 5C103, 5C104, 5C105, 5
Fluorine surfactants such as C106 (manufactured by Asahi Glass), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical), and acrylic or methacrylic acid (co)polymers Polyflow No. 75, No. 95 (Kyoeisha Yushi Chemical) Industrial products), etc. The blending amount of the surfactant is the total amount of the above copolymer and the ultraviolet ray compound: 10
It is usually 2 parts by weight or less per 0 parts by weight.
さらに本発明の組成物には、必要に応じてハレーション
防止剤、接着助剤、保存安定剤、消泡剤などを適宜配合
することができる。Further, the composition of the present invention may contain an antihalation agent, an adhesion aid, a storage stabilizer, an antifoaming agent, and the like, if necessary.
本発明の組成物は、溶剤に上記共重合体、悠遠紫外線化
合物、アルカリ溶解抑制剤および上記各種の配合剤を所
定量ずつ溶解させ、例えば孔径０．２μ丑程度のフィル
ターで濾過することにより調製することができる。The composition of the present invention is prepared by dissolving predetermined amounts of the above-mentioned copolymer, far-UV compound, alkali dissolution inhibitor, and various above-mentioned ingredients in a solvent, and filtering the solution through a filter with a pore size of about 0.2 μm, for example. can do.
この際に用いられる溶剤としては、例えばエチレングリ
コールモノメチルエーテル、エチレングリコールモノエ
チルエーテル、エチレングリコールモノプロビルエーテ
ル、エチレングリコールモノブチルエーテルなどのエチ
レングリコールアルキルエーテル類；ジエチレングリコ
ールジメチルエーテル、ジエチレングリコールジエチル
エーテル、ジエチレングリコールジプロピルエーテル、
ジエチレングリコールジブチルエーテルなどのジエチレ
ングリコールジアルキルエーテル類；メチルセロソルブ
アセテート、エチルセロソルブアセテートなどのエチレ
ングリコールアルキルアセテート類；プロピレングリコ
ールモノメチルエーテルアセテート、プロピレングリコ
ールモノエチルエーテルアセテート、プロピレングリコ
ールプロピルエーテルアセテートなどのプロピレングリ
コールアルキルエーテルアセテート類；トルエン、キシ
レンなどの芳香族炭化水素類；メチルエチルケトン、シ
クロヘキサノンなどのケトン類；２−ヒドロキシプロピ
オン酸メチル、２−ヒドロキシプロピオン酸エチル、２
−ヒドロキシ−２−メチルプロピオン酸エチル、エトキ
シ酢酸エチル、オキシ酢酸エチル、２−ヒドロキシ−３
−メチルブタン酸メチル、３−メトキシブチルアセテー
ト、３−メチル−３−メトキシブチルアセテート、３−
メチル３−メトキシブチルプロピオネート、３−メチル
３−メトキシブチルブチレート、酢酸エチル、酢酸ブチ
ル、アセト酢酸メチル、アセト酢酸エチルなどのエステ
ル類；ジメチルホルムアミド、ジメチルアセトアミドな
どのアミド類を用いることができる。Solvents used in this case include, for example, ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether,
Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone and cyclohexanone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate,
-Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3
-Methyl butanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-
Esters such as methyl 3-methoxybutylpropionate, 3-methyl 3-methoxybutylbutyrate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate; amides such as dimethylformamide and dimethylacetamide can be used. can.
また必要に応じてベンジルエチルエーテル、ジヘキシル
エーテル、ジエチレングリコールモノメチルエーテル、
ジエチレングリコールモノメチルエーテル、アセトニル
アセトン、イソホロン、カプロン酸、カプリル酸、１−
オクタツール、ｌ−ノナノール、ベンジルアルコール、
酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マ
レイン酸ジエチル、Ｔ−ブチロラクトン、炭酸エチレン
、炭酸プロピレン、フェニルセロソルブアセテートなど
のような高沸点溶剤を添加することもできる。In addition, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monomethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-
octatool, l-nonanol, benzyl alcohol,
High boiling solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, T-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. can also be added.
本発明の組成物をシリコンウェハーなどの基板に塗布す
る方法としては、本発明の組成物を、例えば固形分濃度
が５〜５０重量％となるように調製し、これを回転塗布
、流し塗布、ロール塗布などにより塗布する方法が挙げ
られる。As a method for applying the composition of the present invention to a substrate such as a silicon wafer, the composition of the present invention is prepared to have a solid content concentration of, for example, 5 to 50% by weight, and the composition is applied by spin coating, flow coating, etc. Examples include a method of applying by roll coating.
本発明の組成物の現像液としては、例えば水酸化ナトリ
ウム、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウ
ム、メタ珪酸ナトリウム、アンモニア水などの無機アル
カリ類、エチルアミン、ｎ−プロピルアミンなどの第１
級アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン
などの第２級アミン類、トリエチルアミン、メチルジエ
チルアミンなどの第３級アミン類、ジメチルエタノール
アミン、トリエタノールアミンなどのアルコールアミン
類、テトラメチルアンモニウムヒドロキシド、テトラエ
チルアンモニウムヒドロキシドなどの第４級アンモニウ
ムヒドロキシド、またはピロール、ピペリジン、１．８
ジアザビシクロ（５，４，０）−７〜ウンデセン、１．
５−ジアザビシクロ（４，３，０）−５−ノナンなどの
環状アミン類を溶解してなるアルカリ性水溶液などが使
用できる。Examples of the developer for the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia;
secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetramethylammonium hydroxide. , quaternary ammonium hydroxide such as tetraethylammonium hydroxide, or pyrrole, piperidine, 1.8
Diazabicyclo(5,4,0)-7~undecene, 1.
An alkaline aqueous solution prepared by dissolving a cyclic amine such as 5-diazabicyclo(4,3,0)-5-nonane can be used.
また上記現像液に水溶性有機溶媒、例えばメタノール、
エタノールなどのアルコール類や界面活性剤を適宜添加
したアルカリ性水溶液を現像液として使用することもで
きる。In addition, a water-soluble organic solvent such as methanol,
An alkaline aqueous solution to which an alcohol such as ethanol or a surfactant is appropriately added can also be used as the developer.
上記現像液で現像したのちは、通常、水でリンスし、乾
燥する。After developing with the above developer, it is usually rinsed with water and dried.
本発明の感遠紫外線樹脂組成物は、例えばＸｅＣｉ！、
、ＫｒＦ 、＾ｒＦなどを光源とするエキシマレーザを
用いてレジストパターンを形成する場合において、特に
好ましく用いられる組成物である。The far-ultraviolet-sensitive resin composition of the present invention is, for example, XeCi! ,
, KrF 2 , ^rF, etc., is a composition particularly preferably used when forming a resist pattern using an excimer laser as a light source.
ｅ、実施例
以下、実施例により本発明をさらに詳しく説明するが、
本発明はこれらに限定されるものではない。e. Examples The present invention will be explained in more detail by Examples below.
The present invention is not limited to these.
実施例１
ｐ−ヒドロキシスチレンとスチレンの共重合体（モノマ
ーのモル比：ｐ−ヒドロキシスチレン／スチレン−７０
／３０ Ｍマ＝３０００） １００重量部をプロピレ
ングリコールモノメチルエーテルアセテート４５０重量
部によく攪拌して溶解したのち、孔径０．２μｍのメン
ブランフィルタ−で濾過することにより、本発明の組成
物の溶液を調製した。この溶液をシリコンウェーハー上
にスピンナーにて塗布したのち、８０°Ｃにて２分間プ
レベークして０．５ μｍの膜厚のレジスト膜を形成さ
せた。次に遠紫外線コンタクト露光機（キャノン■製Ｐ
ＬＡ５２１Ｆ）を用い、上記のレジスト膜を形成させた
シリコンウェーハにパターンマスクを介し２５３．７ｎ
ｍの遠紫外線を３００ｍＪ／ｃ＋ｆｌ照射し、１．３重
量％のテトラメチルアンモニウムヒドロキシド（以下、
ｒＴＭＡ Ｊという）水溶液を現像液として用い、２分
間現像し、超純水でリンスし乾燥した。。得られたネガ
型レジストパターンの膜厚を測定し、次式により残膜率
を求めたところ８５％と良好な値を得た。Example 1 Copolymer of p-hydroxystyrene and styrene (monomer molar ratio: p-hydroxystyrene/styrene-70
/30M = 3000) was dissolved in 450 parts by weight of propylene glycol monomethyl ether acetate with thorough stirring, and then filtered through a membrane filter with a pore size of 0.2 μm to obtain a solution of the composition of the present invention. Prepared. This solution was applied onto a silicon wafer using a spinner, and then prebaked at 80° C. for 2 minutes to form a resist film with a thickness of 0.5 μm. Next, a far ultraviolet contact exposure machine (Canon P)
LA521F), 253.7nm was applied to the silicon wafer on which the above resist film was formed through a pattern mask.
irradiated with 300mJ/c+fl of far ultraviolet rays of 1.3% by weight of tetramethylammonium hydroxide (hereinafter referred to as
Using an aqueous solution (rTMA J) as a developer, the film was developed for 2 minutes, rinsed with ultrapure water, and dried. . The film thickness of the obtained negative resist pattern was measured, and the remaining film percentage was determined using the following formula, and a good value of 85% was obtained.
また、得られたレジストパターンを走査型電子顕微鏡で
観察したところ、０．６ μｍのラインアンドスペース
が解像できることがわかった。Furthermore, when the obtained resist pattern was observed with a scanning electron microscope, it was found that lines and spaces of 0.6 μm could be resolved.
実施例２〜７および比較例１
表−１に示すＰ−ヒドロキシスチレンとスチレンの共重
合体１００重量部に表−１に示す悠遠紫外線化合物およ
びアルカリ溶解抑制剤を表−１に示す溶媒３５０重量部
によく攪拌して溶解したのち、実施例１と同様に濾過し
、組成物を調製した。次に、この溶液を用いて実施例１
と同様の方法にてレジスト膜を形成後、実施例１と同様
に２５３．７ｎｍの遠紫外線を表１に示す量照射し、次
いで表−１に示す濃度のＴＭＡ水溶液を現像液として１
分間現像し超純水でリンスし乾燥した。得られたネガ型
レジストパターンの残膜率および解像度を実施例１と同
様にして測定したところ、表−１に示す結果を得た。Examples 2 to 7 and Comparative Example 1 100 parts by weight of the copolymer of P-hydroxystyrene and styrene shown in Table 1 were added to 350 parts by weight of the solvent shown in Table 1, and the far-UV compound and alkali dissolution inhibitor shown in Table 1 were added. After thoroughly stirring and dissolving the mixture, it was filtered in the same manner as in Example 1 to prepare a composition. Next, using this solution, Example 1
After forming a resist film in the same manner as in Example 1, it was irradiated with deep ultraviolet rays of 253.7 nm in the amount shown in Table 1, and then a TMA aqueous solution with the concentration shown in Table 1 was used as a developer.
It was developed for a minute, rinsed with ultrapure water, and dried. When the remaining film rate and resolution of the obtained negative resist pattern were measured in the same manner as in Example 1, the results shown in Table 1 were obtained.
１０発明の効果
以上述べたように、本発明によれば、ＫｒＦエキシマレ
ーザ−などによる遠紫外線に対して感度が良く、レジス
トとして使用した場合にアルカリ性水溶液からなる現像
液による膜減りが小さく、パターンプロファイルの良好
で解像度が高いレジストパターンを得ることができる悠
遠紫外線樹脂組成物を提供することができる。10 Effects of the Invention As described above, the present invention has good sensitivity to deep ultraviolet rays produced by KrF excimer laser, etc., and when used as a resist, there is little film loss due to a developer consisting of an alkaline aqueous solution, and pattern It is possible to provide a long-range ultraviolet ray resin composition that can obtain a resist pattern with a good profile and high resolution.
Claims (2)
ン類以外のスチレン類（Ｂ）の共重合体からなるアルカ
リ可溶性樹脂を含有することを特徴とする感遠紫外線樹
脂組成物。(1) An ultraviolet-sensitive ultraviolet resin composition comprising an alkali-soluble resin comprising a copolymer of hydroxystyrenes (A) and styrenes other than hydroxystyrenes (B).
ン類以外のスチレン類（Ｂ）の共重合体からなるアルカ
リ可溶性樹脂と、 一般式（ I ）、 ▲数式、化学式、表等があります▼・・・（ I ） 一般式（II）、 ▲数式、化学式、表等があります▼・・・（II） または一般式（III）、 ▲数式、化学式、表等があります▼・・・（III） で表わされる構造を分子中に少くとも一つ含む感遠紫外
線化合物、 を含有することを特徴とする感遠紫外線樹脂組成物。(2) Alkali-soluble resin consisting of a copolymer of hydroxystyrenes (A) and styrenes other than hydroxystyrenes (B), and general formula (I), ▲Mathematical formula, chemical formula, table, etc.▼... (I) General formula (II), ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) Or general formula (III), ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) A far-UV-sensitive resin composition comprising: a far-UV-sensitive compound containing at least one structure in its molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1007322A JPH02187764A (en) | 1989-01-13 | 1989-01-13 | Far ultraviolet ray-sensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1007322A JPH02187764A (en) | 1989-01-13 | 1989-01-13 | Far ultraviolet ray-sensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02187764A true JPH02187764A (en) | 1990-07-23 |
Family
ID=11662736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1007322A Pending JPH02187764A (en) | 1989-01-13 | 1989-01-13 | Far ultraviolet ray-sensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02187764A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02291559A (en) * | 1989-05-01 | 1990-12-03 | Toyo Gosei Kogyo Kk | Photoresist composition for far ultraviolet light |
| JPH03103856A (en) * | 1989-09-09 | 1991-04-30 | Hoechst Ag | Positive processing irradiation sensitive mixture and irradiation sensitive copying material manufactured from the same |
| JPH03103854A (en) * | 1989-09-09 | 1991-04-30 | Hoechst Ag | Positive processing irradiation sensitive mixture and irradiation sensitive copying material manufactured from the same |
| JPH0488348A (en) * | 1990-08-01 | 1992-03-23 | Wako Pure Chem Ind Ltd | Novel resist material |
| US6153733A (en) * | 1998-05-18 | 2000-11-28 | Tokyo Ohka Kogyo Co., Ltd. | (Disulfonyl diazomethane compounds) |
| JP2009216790A (en) * | 2008-03-07 | 2009-09-24 | Nippon Kayaku Co Ltd | Functional element, negative photosensitive resin composition used in the same, and method for manufacturing functional element |
-
1989
- 1989-01-13 JP JP1007322A patent/JPH02187764A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02291559A (en) * | 1989-05-01 | 1990-12-03 | Toyo Gosei Kogyo Kk | Photoresist composition for far ultraviolet light |
| JPH03103856A (en) * | 1989-09-09 | 1991-04-30 | Hoechst Ag | Positive processing irradiation sensitive mixture and irradiation sensitive copying material manufactured from the same |
| JPH03103854A (en) * | 1989-09-09 | 1991-04-30 | Hoechst Ag | Positive processing irradiation sensitive mixture and irradiation sensitive copying material manufactured from the same |
| JPH0488348A (en) * | 1990-08-01 | 1992-03-23 | Wako Pure Chem Ind Ltd | Novel resist material |
| US6153733A (en) * | 1998-05-18 | 2000-11-28 | Tokyo Ohka Kogyo Co., Ltd. | (Disulfonyl diazomethane compounds) |
| JP2009216790A (en) * | 2008-03-07 | 2009-09-24 | Nippon Kayaku Co Ltd | Functional element, negative photosensitive resin composition used in the same, and method for manufacturing functional element |
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