CN106502052B - 一种耐刻蚀性的酚醛系正型光刻胶 - Google Patents
一种耐刻蚀性的酚醛系正型光刻胶 Download PDFInfo
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- CN106502052B CN106502052B CN201611198717.7A CN201611198717A CN106502052B CN 106502052 B CN106502052 B CN 106502052B CN 201611198717 A CN201611198717 A CN 201611198717A CN 106502052 B CN106502052 B CN 106502052B
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- methyl
- photoresist
- phenolic
- compound
- solvent
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 70
- 238000005530 etching Methods 0.000 title claims abstract description 34
- -1 phenolic aldehyde Chemical class 0.000 title claims description 161
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000005011 phenolic resin Substances 0.000 claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 claims description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 2
- SNBMUFIWXLUTIH-UHFFFAOYSA-N 2h-naphthalene-1,1,3-triol Chemical compound C1=CC=C2C(O)(O)CC(O)=CC2=C1 SNBMUFIWXLUTIH-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical class [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 claims description 2
- 229950011260 betanaphthol Drugs 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 238000000206 photolithography Methods 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 150000003739 xylenols Chemical class 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 238000001312 dry etching Methods 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000001259 photo etching Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- GJQIMXVRFNLMTB-UHFFFAOYSA-N nonyl acetate Chemical compound CCCCCCCCCOC(C)=O GJQIMXVRFNLMTB-UHFFFAOYSA-N 0.000 description 4
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 2
- 125000006034 1,2-dimethyl-1-propenyl group Chemical group 0.000 description 2
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 2
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 2
- 125000006030 1-methyl-3-butenyl group Chemical group 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- 125000006078 2-ethyl-3-butenyl group Chemical group 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 description 2
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 2
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 2
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000006031 2-methyl-3-butenyl group Chemical group 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- 125000006041 3-hexenyl group Chemical group 0.000 description 2
- 125000006042 4-hexenyl group Chemical group 0.000 description 2
- 125000006043 5-hexenyl group Chemical group 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- XAOGXQMKWQFZEM-UHFFFAOYSA-N isoamyl propanoate Chemical compound CCC(=O)OCCC(C)C XAOGXQMKWQFZEM-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
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- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- IMXBRVLCKXGWSS-UHFFFAOYSA-N methyl 2-cyclohexylacetate Chemical compound COC(=O)CC1CCCCC1 IMXBRVLCKXGWSS-UHFFFAOYSA-N 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- GXOHBWLPQHTYPF-UHFFFAOYSA-N pentyl 2-hydroxypropanoate Chemical compound CCCCCOC(=O)C(C)O GXOHBWLPQHTYPF-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HHYVKZVPYXHHCG-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C HHYVKZVPYXHHCG-UHFFFAOYSA-M 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- 125000006061 1,2-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006062 1,2-dimethyl-2-butenyl group Chemical group 0.000 description 1
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- 125000006063 1,2-dimethyl-3-butenyl group Chemical group 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 125000006064 1,3-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006065 1,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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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
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
本发明公开一种耐刻蚀性的酚醛系正型光刻胶,其主要成分为酚醛树脂、光敏化合物和溶剂,特点在于,所述酚醛系正型光刻胶中还含0.5~30 wt%的可溶于所述溶剂的金属化合物。本发明所述的光刻胶在光刻后的干法刻蚀工序中,等离子体对胶膜图形进行物理轰击和化学反应双重作用刻蚀,胶层中的碳氧成分形成挥发性反应物被去除,而金属成分则会慢慢沉积下来,并在胶膜表面形成新的金属保护层,从而达到提高光刻胶耐刻蚀的目的。本发明所述光刻胶可广泛应用于需要干法刻蚀的微电子元器件生产的领域。
Description
技术领域
本发明属于光刻胶领域,具体涉及一种耐刻蚀性的酚醛系正型光刻胶。
背景技术
光刻胶是微电子技术发展最为关键的基础材料,又称光致抗蚀剂,是通过紫外光、电子束、离子束、准分子激光束、X射线等曝光源的照射或辐射,使其溶解度发生变化的耐蚀刻的薄膜材料。光刻胶膜经过曝光显影形成光刻图形后,会进行干法或湿法刻蚀。没有胶膜覆盖的部分衬底材料被直接刻蚀,而有胶膜覆盖的衬底表面则受光刻胶膜保护而免被刻蚀。耐蚀刻性能是光刻胶非常重要的评价指标,优良的耐刻蚀性可以保障刻蚀工艺中光刻胶能保护衬底表面不受损坏,并有效的简化刻蚀工艺,大大提高刻蚀成品良率。
酚醛系正型光刻胶因其具有感光度高、产出率高、工艺宽容度高、去胶容易等显著优点,广泛应用于MEMS、LED、IC、LCD等光刻制程中。但现有酚醛系正型光刻胶在耐刻蚀性能方面的表现非常一般,在深度刻蚀工艺中通常采用加大光刻胶膜厚以及提高刻蚀前的光刻胶坚膜温度以期提高其耐刻蚀性,但效果并不理想,且高温对光刻胶的耐温性要求也更高。另有报道的采用在光刻胶图案与被蚀刻的衬底之间涂布一层具有高抗蚀刻性的无机或有机层,也即“抗蚀剂下层”或“硬掩膜”,以达到耐刻蚀目的的,如CN103906740A、CN105612459A,但该方案的不足在于二层膜或多层膜工艺操作复杂,效率低,制作成本高,国内在常规干法刻蚀工艺中基本没有使用的。
发明内容
本发明要解决的技术问题是克服现有的缺陷,提供了一种高耐刻蚀性的酚醛体系正型光刻胶,在深度刻蚀中避免了多层膜工艺,且有效的降低了光刻胶膜厚、增大了坚膜温度的工艺宽容度,使工艺流程更为简单。
为了解决上述技术问题,本发明提供了如下的技术方案:
一种耐刻蚀性的酚醛系正型光刻胶,主要成分为酚醛树脂、光敏化合物和溶剂,其特点在于,所述酚醛系正型光刻胶中含0.5~30 wt%的可溶于所述溶剂的金属化合物。优选地,所述酚醛系正型光刻胶中含1~20 wt%的可溶于所述溶剂的金属化合物。更优选地,所述酚醛系正型光刻胶中含2~10 wt%的可溶于所述溶剂的金属化合物。
优选地,所述金属化合物是由选自包括镁、钙、钡、钛、锆、铪、钒、铬、钼、钨、锰、铁、钴、镍、铜、锌、镉、铟、锡、锑中的至少一种与选自包括烷基、烯基、烷氧基、酰氧基、β-二酮类配体、C≡O、卤素、硝基、硝酸根中的至少一种所形成的配合物或盐。
所述的烷基可以是直链、具有支链或环状的碳数1~10的烷基,例如:甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、1-乙基-正丙基、正己基、1-甲基-正戊基、2-甲基-正戊基、3-甲基-正戊基、4-甲基-正戊基、1,1-二甲基-正丁基、1,2-二甲基-正丁基、1,3-二甲基-正丁基、2,2-二甲基-正丁基、2,3-二甲基-正丁基、3,3-二甲基-正丁基、1-乙基-正丁基、2-乙基-正丁基、1,1,2-三甲基-正丙基、1,2,2-三甲基-正丙基、1-乙基-1-甲基-正丙基及1-乙基-2-甲基-正丙基、环丙基、环丁基、1-甲基-环丙基、2-甲基-环丙基、环戊基、1-甲基-环丁基、2-甲基-环丁基、3-甲基-环丁基、1,2-二甲基-环丙基、2,3-二甲基-环丙基、1-乙基-环丙基、2-乙基-环丙基、环己基、1-甲基-环戊基、2-甲基-环戊基、3-甲基-环戊基、1-乙基-环丁基、2-乙基-环丁基、3-乙基-环丁基、1,2-二甲基-环丁基、1,3-二甲基-环丁基、2,2-二甲基-环丁基、2,3-二甲基-环丁基、2,4-二甲基-环丁基、3,3-二甲基-环丁基、1-正丙基-环丙基、2-正丙基-环丙基、1-异丙基-环丙基、2-异丙基-环丙基、1,2,2-三甲基-环丙基、1,2,3-三甲基-环丙基、2,2,3-三甲基-环丙基、1-乙基-2-甲基-环丙基、2-乙基-1-甲基-环丙基、2-乙基-2-甲基-环丙基及2-乙基-3-甲基-环丙基等。
所述的烯基可以是直链、具有支链或环状的碳数2~10的烯基,例如:乙烯基、1-丙烯基、2-丙烯基、1-甲基-1-乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、1-乙基乙烯基、1-甲基-1-丙烯基、1-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-正丙基乙烯基、1-甲基-1-丁烯基、1-甲基-2-丁烯基、1-甲基-3-丁烯基、2-乙基-2-丙烯基、2-甲基-1-丁烯基、2-甲基-2-丁烯基、2-甲基-3-丁烯基、3-甲基-1-丁烯基、3-甲基-2-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1-异丙基乙烯基、1,2-二甲基-1-丙烯基、1,2-二甲基-2-丙烯基、1-环戊烯基、2-环戊烯基、3-环戊烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、1-甲基-2-戊烯基、1-甲基-3-戊烯基、1-甲基-4-戊烯基、1-正丁基乙烯基、2-甲基-1-戊烯基、2-甲基-2-戊烯基、2-甲基-3-戊烯基、2-甲基-4-戊烯基、2-正丙基-2-丙烯基、3-甲基-1-戊烯基、3-甲基-2-戊烯基、3-甲基-3-戊烯基、3-甲基-4-戊烯基、3-乙基-3-丁烯基、4-甲基-1-戊烯基、4-甲基-2-戊烯基、4-甲基-3-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-1-丁烯基、1,2-二甲基-2-丁烯基、1,2-二甲基-3-丁烯基、1-甲基-2-乙基-2-丙烯基、1-s-丁基乙烯基、1,3-二甲基-1-丁烯基、1,3-二甲基-2-丁烯基、1,3-二甲基-3-丁烯基、1-异丁基乙烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-1-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、2-异丙基-2-丙烯基、3,3-二甲基-1-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、1-正丙基-1-丙烯基、1-正丙基-2-丙烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-叔丁基乙烯基、1-甲基-1-乙基-2-丙烯基、1-乙基-2-甲基-1-丙烯基、1-乙基-2-甲基-2-丙烯基、1-异丙基-1-丙烯基、1-异丙基-2-丙烯基、1-甲基-2-环戊烯基、1-甲基-3-环戊烯基、2-甲基-1-环戊烯基、2-甲基-2-环戊烯基、2-甲基-3-环戊烯基、2-甲基-4-环戊烯基、2-甲基-5-环戊烯基、2-亚甲基-环戊基、3-甲基-1-环戊烯基、3-甲基-2-环戊烯基、3-甲基-3-环戊烯基、3-甲基-4-环戊烯基、3-甲基-5-环戊烯基、3-亚甲基-环戊基、1-环己烯基、2-环己烯基及3-环己烯基、1-甲基-2,4-环戊二烯等。
所述的烷氧基为碳数1~10的烷氧基,例如:甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、1-甲基-正丁氧基、2-甲基-正丁氧基、3-甲基-正丁氧基、1,1-二甲基-正丙氧基、1,2-二甲基-正丙氧基、2,2-二甲基-正丙氧基、1-乙基-正丙氧基、正己基氧基、1-甲基-正戊氧基、2-甲基-正戊氧基、3-甲基-正戊氧基、4-甲基-正戊氧基、1,1-二甲基-正丁氧基、1,2-二甲基-正丁氧基、1,3-二甲基-正丁氧基、2,2-二甲基-正丁氧基、2,3-二甲基-正丁氧基、3,3-二甲基-正丁氧基、1-乙基-正丁氧基、2-乙基-正丁氧基、1,1,2-三甲基-正丙氧基、1,2,2-三甲基-正丙氧基、1-乙基-1-甲基-正丙氧基及1-乙基-2-甲基-正丙氧基等。
所述的酰氧基为碳数1~10的酰基氧基,例如:甲酰氧基、乙酰氧基、正丙基羰基氧基、异丙基羰基氧基、环丙基羰基氧基、正丁基羰基氧基、异丁基羰基氧基、s-丁基羰基氧基、叔丁基羰基氧基、环丁基羰基氧基、1-甲基-环丙基羰基氧基、2-甲基-环丙基羰基氧基、正戊基羰基氧基、1-甲基-正丁基羰基氧基、2-甲基-正丁基羰基氧基、3-甲基-正丁基羰基氧基、1,1-二甲基-正丙基羰基氧基、1,2-二甲基-正丙基羰基氧基、2,2-二甲基-正丙基羰基氧基、1-乙基-正丙基羰基氧基、环戊基羰基氧基、1-甲基-环丁基羰基氧基、2-甲基-环丁基羰基氧基、3-甲基-环丁基羰基氧基、1,2-二甲基-环丙基羰基氧基、2,3-二甲基-环丙基羰基氧基、1-乙基-环丙基羰基氧基、2-乙基-环丙基羰基氧基、正己基羰基氧基、1-甲基-正戊基羰基氧基、2-甲基-正戊基羰基氧基、3-甲基-正戊基羰基氧基、4-甲基-正戊基羰基氧基、1,1-二甲基-正丁基羰基氧基、1,2-二甲基-正丁基羰基氧基、1,3-二甲基-正丁基羰基氧基、2,2-二甲基-正丁基羰基氧基、2,3-二甲基-正丁基羰基氧基、3,3-二甲基-正丁基羰基氧基、1-乙基-正丁基羰基氧基、2-乙基-正丁基羰基氧基、1,1,2-三甲基-正丙基羰基氧基、1,2,2-三甲基-正丙基羰基氧基、1-乙基-1-甲基-正丙基羰基氧基、1-乙基-2-甲基-正丙基羰基氧基、环己基羰基氧基、1-甲基-环戊基羰基氧基、2-甲基-环戊基羰基氧基、3-甲基-环戊基羰基氧基、1-乙基-环丁基羰基氧基、2-乙基-环丁基羰基氧基、3-乙基-环丁基羰基氧基、1,2-二甲基-环丁基羰基氧基、1,3-二甲基-环丁基羰基氧基、2,2-二甲基-环丁基羰基氧基、2,3-二甲基-环丁基羰基氧基、2,4-二甲基-环丁基羰基氧基、3,3-二甲基-环丁基羰基氧基、1-正丙基-环丙基羰基氧基、2-正丙基-环丙基羰基氧基、1-异丙基-环丙基羰基氧基、2-异丙基-环丙基羰基氧基、1,2,2-三甲基-环丙基羰基氧基、1,2,3-三甲基-环丙基羰基氧基、2,2,3-三甲基-环丙基羰基氧基、1-乙基-2-甲基-环丙基羰基氧基、2-乙基-1-甲基-环丙基羰基氧基、2-乙基-2-甲基-环丙基羰基氧基及2-乙基-3-甲基-环丙基羰基氧基等。
上述的β-二酮类配体具有如下结构式:
上述的卤素可列举的如:氟、氯、溴、碘。
本发明所述的酚醛树脂是指由例如苯酚、邻甲酚、间甲酚、对甲酚、二甲苯酚、三甲基苯酚、叔丁基苯酚、乙基苯酚、2-萘酚、1,3-二羟基萘酚等酚类的一种或二种以上与醛类在酸性或碱性催化剂存在下缩聚而成的树脂性聚合物。具体地可以采用已知的被用于传统酚醛系正型光刻胶的酚醛树脂。
本发明所述的光敏化合物可以采用已知的被用于传统酚醛系正型光刻胶的光敏化合物,包括重氮盐、铵盐、碘鎓盐、锍盐、鏻盐、鉮盐、氧鎓盐、卤代有机化合物、醌二叠氮化合物、二(磺酰基)重氮甲烷化合物、砜化合物、有机酸酯化合物、有机酸酰亚胺化合物中的至少一种。
所述光敏化合物具体可列举的如下:二苯基碘鎓六氟磷酸酯、二苯基碘鎓三氟甲烷磺酸酯、二苯基碘鎓九氟正丁烷磺酸酯、二苯基碘鎓全氟正辛烷磺酸酯、二苯基碘鎓樟脑磺酸酯、双(4-叔丁基苯基)碘鎓樟脑磺酸酯及双(4-叔丁基苯基)碘鎓三氟甲烷磺酸酯、双(三氟甲基磺酰基)重氮甲烷、双(环己基磺酰基)重氮甲烷、双(对甲苯磺酰基)重氮甲烷、双(2,4-二甲基苯基磺酰基)重氮甲烷、2,1,4-重氮萘醌磺酸酯、2,1,5-重氮萘醌磺酸酯、2,3,4-三羟基二苯甲酮、1,2-苯醌二叠氮-4-磺酸、1,2-萘醌二叠氮-5-磺酸等。
本发明所用的溶剂可以是能够溶解本发明光刻胶组合物以产生均匀溶液的任何溶剂,可以是已用作传统酚醛系正型光刻胶溶剂中的已知溶剂中的一种或多种溶剂的组合。所述溶剂可列举如下:二乙基碳酸酯、乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、乙酸甲基环己基酯、乙酸正壬酯、乙酰乙酸甲酯、乙酰乙酸乙酯、乙二醇甲醚醋酸酯、乙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯、丙二醇苯醚醋酸酯、乙二醇二乙酸酯、丙酸乙酯、丙酸正丁酯、丙酸异戊酯、乳酸甲酯、乳酸乙酯、乳酸正丁酯、乳酸正戊酯、丙二酸二乙酯、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、N-甲基甲酰胺、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、乙酰胺、N-甲基乙酰胺、N,N-二甲基乙酰胺、N-甲基丙酰胺、N-甲基吡咯烷酮、二甲基硫、二乙基硫、噻吩、四氢噻吩、二甲基亚砜、环丁砜、1,3-丙烷磺内酯、甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正戊烷、异戊烷、正己烷、异己烷、正庚烷、异庚烷、苯、甲苯、二甲苯、丙酮、甲基乙基酮、乙二醇、丙二醇、乙醚、乙二醇乙醚等。
优选地,所述酚醛系正型光刻胶含:
10~70wt%的酚醛树脂;
0.5~20wt%的光敏化合物;
0.5~30wt%的可溶于所述溶剂的金属化合物;
10~80wt%的溶剂。
优选地,所述酚醛系正型光刻胶还含0.05~10wt%的助粘剂、表面活性剂、阻溶剂、增塑剂和/或防光晕剂。
一种光刻蚀的方法,包括:(1)在基底上涂布酚醛系正型光刻胶,(2)曝光、显影,(3)刻蚀,其特点在于,在所述酚醛系正型光刻胶中溶解有0.5~30 wt%的金属化合物。
优选地,所述金属化合物是由选自包括镁、钙、钡、钛、锆、铪、钒、铬、钼、钨、锰、铁、钴、镍、铜、锌、镉、铟、锡、锑中的至少一种与选自包括烷基、烯基、烷氧基、酰氧基、β-二酮类配体、C≡O、卤素、硝基、硝酸根中的至少一种所形成的配合物或盐。
本发明所述的光刻胶组合物中,金属化合物完全溶于传统酚醛系正型光刻胶,在光刻工艺中,光刻胶涂布烘干成膜后,金属化合物均匀分布于胶膜中,经过曝光后显影,显影时曝光反应部分的金属化合物与胶膜一起溶解于显影液中,未曝光反应部分的胶膜及金属化合物一起留存在衬底表面形成光刻图形。在后续的干法刻蚀中,等离子体对含有金属化合物的光刻胶膜进行物理轰击和化学反应双重作用刻蚀,其中的碳氧成分形成挥发性反应物被去除,而金属成分则会慢慢沉积下来,并在胶膜表面形成新的保护层,起到阻碍刻蚀的作用,从而达到提高光刻胶耐刻蚀的目的。
与现有通过增加光刻胶膜厚和提高坚膜温度来提高耐刻蚀性,以及采用涂布“抗蚀剂下层”或“硬掩膜”来提高光刻胶耐刻蚀的方法相比,采用本发明的光刻胶可以省去涂布“抗蚀剂下层”或“硬掩膜”,操作流程更为简单,优异的耐蚀刻性能可以有效的简化刻蚀工艺,增加成品良率,同时降低光刻胶的使用成本。本发明所述光刻胶可广泛应用于需要干法刻蚀的微电子元器件生产的领域。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1
将43g线性酚醛树脂、10g 2,1,4-重氮萘醌磺酸酯、16g 2-甲基环戊二烯三羰基锰、1g γ-氨丙基三乙氧基硅烷、100g丙二醇甲醚醋酸酯混合,充分溶解后用0.02微米孔径的滤膜过滤,即得到光刻胶1。
本实施例中线性酚醛树脂的结构如下:
实施例2
将43g线性酚醛树脂、10g 2,1,5-重氮萘醌磺酸酯、16g丙酸锆、1g N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、100g丙二醇甲醚醋酸酯混合,充分溶解后用0.02微米孔径的滤膜过滤,即得到光刻胶2。
本实施例中线性酚醛树脂的结构如下:
实施例3
将65g线性酚醛树脂、15g 1,2-苯醌二叠氮-4-磺酸、8g三氟乙酰丙酮铁(CAS:14526-22-8)、2g γ-氨丙基三乙氧基硅烷、40g苯、80g丙二醇甲醚醋酸酯混合,充分溶解后用0.02微米孔径的滤膜过滤,即得到光刻胶3。
本实施例中线性酚醛树脂的结构如下:
其中R为甲基,n=50。
实施例4
将65g线性酚醛树脂、10g 1,2-萘醌二叠氮-5-磺酸、8g乙酰丙酮铬(CAS:21679-31-2)、 2g N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、40g乙醇、80g丙二醇甲醚醋酸酯混合,充分溶解后用0.02微米孔径的滤膜过滤,即得到光刻胶4。
本实施例中线性酚醛树脂的结构如下:
对比例1
将43g线性酚醛树脂、10g 2,1,4-重氮萘醌磺酸酯、 1g N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、100g丙二醇甲醚醋酸酯混合,充分溶解后用0.02微米孔径的滤膜过滤,即得到对比光刻胶。
本对比例中线性酚醛树脂的结构如下:
测试:
将光刻胶旋涂在洁净处理过后的氮化镓基片上,调节转速使光刻胶膜厚约为8μm,用热板预烘(PAB)100℃/180s,通过i线曝光后,用2.38wt%TMAH进行浸泡显影180s,采用去离子水清洗后用烘箱后烘坚膜120℃/120s。在三氯化硼和氯气的刻蚀气体氛围下进行干法刻蚀60min,测定光刻胶的膜厚损失以及衬底的刻蚀深度,以胶厚损失/衬底刻蚀深度来计算刻蚀比,结果如下表所示。
由上述测试结果可知,本发明所述酚醛系正性光刻胶可以显著提高光刻胶的耐刻蚀性能。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种耐刻蚀性的酚醛系正型光刻胶,主要成分为酚醛树脂、光敏化合物和溶剂,其特征在于,所述酚醛系正型光刻胶中含0.5~30wt%的可溶于所述溶剂的金属化合物;
所述金属化合物是由选自包括镁、钙、钡、钛、锆、铪、钒、铬、钼、钨、锰、铁、钴、镍、铜、锌、镉、铟、锡、锑中的至少一种与选自包括烷基、烯基、烷氧基、酰氧基、β-二酮类配体、C≡O、卤素、硝基、硝酸根中的至少一种所形成的配合物或盐。
2.根据权利要求1所述的酚醛系正型光刻胶,其特征在于,所述酚醛系正型光刻胶中含1~20wt%的可溶于所述溶剂的金属化合物。
3.根据权利要求2所述的酚醛系正型光刻胶,其特征在于,所述酚醛系正型光刻胶中含2~10wt%的可溶于所述溶剂的金属化合物。
4.根据权利要求1所述的酚醛系正型光刻胶,其特征在于,所述酚醛树脂是由苯酚、邻甲酚、间甲酚、对甲酚、二甲苯酚、三甲基苯酚、叔丁基苯酚、乙基苯酚、2-萘酚、1,3-二羟基萘酚中的至少一种与醛在酸性或碱性催化剂存在下缩聚而成的树脂聚合物。
5.根据权利要求1所述的酚醛系正型光刻胶,其特征在于,所述光敏化合物包括重氮盐、铵盐、碘鎓盐、锍盐、鏻盐、鉮盐、氧鎓盐、卤代有机化合物、醌二叠氮化合物、二(磺酰基)重氮甲烷化合物、砜化合物、有机酸酯化合物、有机酸酰亚胺化合物中的至少一种。
6.根据权利要求1所述的酚醛系正型光刻胶,其特征在于,所述酚醛系正型光刻胶含:
10~70wt%的酚醛树脂;
0.5~20wt%的光敏化合物;
0.5~30wt%的可溶于所述溶剂的金属化合物;
10~80wt%的溶剂。
7.根据权利要求6所述的酚醛系正型光刻胶,其特征在于,所述酚醛系正型光刻胶还含0.05~10wt%的助粘剂、表面活性剂、阻溶剂、增塑剂和/或防光晕剂。
8.一种光刻蚀的方法,包括:(1)在基底上涂布酚醛系正型光刻胶,(2)曝光、显影,(3)刻蚀,其特征在于,在所述酚醛系正型光刻胶中溶解有0.5~30wt%的金属化合物;
所述金属化合物是由选自包括镁、钙、钡、钛、锆、铪、钒、铬、钼、钨、锰、铁、钴、镍、铜、锌、镉、铟、锡、锑中的至少一种与选自包括烷基、烯基、烷氧基、酰氧基、β-二酮类配体、C≡O、卤素、硝基、硝酸根中的至少一种所形成的配合物或盐。
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