CN116203795A - Application of sulfoacid imine compound as KrF thick film photoresist photoacid generator - Google Patents
Application of sulfoacid imine compound as KrF thick film photoresist photoacid generator Download PDFInfo
- Publication number
- CN116203795A CN116203795A CN202111444525.0A CN202111444525A CN116203795A CN 116203795 A CN116203795 A CN 116203795A CN 202111444525 A CN202111444525 A CN 202111444525A CN 116203795 A CN116203795 A CN 116203795A
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- China
- Prior art keywords
- monomer
- krf
- thick film
- weight
- solvent
- 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
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 65
- 150000002466 imines Chemical class 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims description 44
- -1 sulphonic acid imine compound Chemical class 0.000 claims description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 238000011161 development Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 238000012644 addition polymerization Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002313 adhesive film Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 239000002253 acid Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 125000006239 protecting group Chemical group 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JHVQWALHXJPODC-ALCCZGGFSA-N (z)-2-[2-(2-methylprop-2-enoyloxy)ethyl]but-2-enedioic acid Chemical compound CC(=C)C(=O)OCC\C(C(O)=O)=C\C(O)=O JHVQWALHXJPODC-ALCCZGGFSA-N 0.000 description 2
- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- YGBVAGIVGBLKFE-UHFFFAOYSA-N 2-phenylbut-1-en-1-ol Chemical compound CCC(=CO)C1=CC=CC=C1 YGBVAGIVGBLKFE-UHFFFAOYSA-N 0.000 description 2
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 2
- MKHXOKALQIHXPI-UHFFFAOYSA-N 2-phenylprop-1-en-1-ol Chemical compound OC=C(C)C1=CC=CC=C1 MKHXOKALQIHXPI-UHFFFAOYSA-N 0.000 description 2
- DWTKNKBWDQHROK-UHFFFAOYSA-N 3-[2-(2-methylprop-2-enoyloxy)ethyl]phthalic acid Chemical compound CC(=C)C(=O)OCCC1=CC=CC(C(O)=O)=C1C(O)=O DWTKNKBWDQHROK-UHFFFAOYSA-N 0.000 description 2
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical group CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000007824 aliphatic compounds 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
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- QPMIVFWZGPTDPN-UHFFFAOYSA-N Tetrabromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C(C(Br)=C(Br)C(Br)=C2Br)=C2S(=O)(=O)O1 QPMIVFWZGPTDPN-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006229 isopropoxyethyl group Chemical group [H]C([H])([H])C([H])(OC([H])([H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses an application of a sulfoacid imine compound as a KrF thick film photoresist photoacid generator. Specifically, the invention discloses an application of a sulfoacid imine compound shown in a formula I as a KrF thick film photoresist photoacid generator, and a photoresist composition prepared by using the sulfoacid imine compound shown in the formula I as the photoacid generator has good rectangular adhesive film.
Description
Technical Field
The invention relates to an application of a sulfoacid imine compound as a KrF thick film photoresist photoacid generator.
Background
In the field of semiconductor manufacturing, in the manufacturing process of chips such as LCD (liquid crystal display)/BUMP BUMP/MEMS micro electro mechanical system/3D-NAND memory, a thick film photoresist of a KrF light source is used, and the photoresist is different from a conventional thin layer photoresist of KrF and a photoresist of an ArF light source, and has unique performance.
Although the manufacturing technology of integrated circuit semiconductor chips is rapidly developed at present, the technology of thick film photoresist matched with the KrF light source is not fully mature, and is the hot spot field of the research of the KrF photoresist at present. In particular, the photoacid generator market for KrF thick film photoresists is relatively scarce and development is needed.
Disclosure of Invention
The invention provides application of a sulfoacid imine compound as a photoacid generator of a KrF thick film photoresist. The photoresist composition prepared by taking the sulfoacid imine compound as the photoacid generator has good rectangular adhesive film.
The invention solves the technical problems through the following technical proposal.
The invention provides an application of a sulfoacid imine compound as a photoacid generator in a KrF thick film photoresist composition, wherein the sulfoacid imine compound is shown as a formula I;
in the formula I, n is 0, 1, 2 or 3;
R 1 is-COOR 1-1 Or C 1-4 An alkyl group; r is R 1-1 Is C 1-4 An alkyl group;
R 2 is C 1-4 An alkyl group.
In a preferred embodiment, n is 0, 1 or 2.
In a preferred embodiment, R 1 is-COOR 1-1 Wherein R is 1-1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably ethyl.
In a preferred embodiment, R 1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably methyl.
In a preferred embodiment, R 2 Is methyl, ethyl, n-propyl, isopropyl, n-propylButyl, isobutyl, sec-butyl or tert-butyl, preferably methyl.
The sulfoacid imine compound is preferably any one of the following compounds:
the KrF thick film photoresist composition comprises the sulfoacid imine compound.
The KrF thick film photoresist composition comprises the following components: the sulfoacid imine compound, a photosensitive polymer, triethanolamine and a solvent;
the photopolymer may be a polymer that can be used for Deep Ultraviolet (DUV) light to perform photochemical reactions. For example, the photopolymer may be a polymer that chemically reacts when a photoacid generator (PAG) mixed with the photopolymer is exposed to light such as deep ultraviolet light to generate an acid, and the acid thus generated chemically reacts the polymer to increase its hydrophilicity or hydrophobicity. It should be appreciated that the photopolymer need not be directly sensitive to light (e.g., exposure of the photopolymer to light does not necessarily change the chemical composition of the photopolymer, although the chemical composition of the photopolymer may change due to the acid created by the exposed PAG that is mixed with the photopolymer). In some embodiments, the solubility of the photopolymer in the base may be increased due to photochemical reactions. In some embodiments, the photopolymer may have a structure in which a protecting group is bonded to the repeating unit, and the protecting group may be deprotected during exposure so that the photopolymer dissolves well in the base. The photoresist may be a positive photoresist in which the portions of the photoresist that are removed by subsequent photoresist development are exposed to light (e.g., DUV light). The deprotected protecting group may generate a new acid for chemical amplification.
In a preferred embodiment of the present invention, the KrF thick film photoresist composition consists of the sulfoximine compound, the photopolymer, triethanolamine and a solvent.
The photopolymer may be a phenolic resin, a polyhydroxystyrene resin, an acrylic resin, or a combination thereof.
The phenolic resin may be a resin having a repeating unit represented by formula (IV),
in the formula (IV), R 5a Is an acid dissociating protecting group, and R 5b And R is 5c Each of which is a hydrogen atom or C 1 -C 6 An alkyl group. R is R 5a Is C 1 -C 6 Straight-chain, branched or cyclic alkyl, vinyloxyethyl, tetrahydropyranyl, tetrahydrofuranyl, trialkylsilyl, isonorbornyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 3-tetrahydrofuranyl, 3-oxocyclohexyl, gamma-butyrolactone-3-yl, mevalonolactone, gamma-butyrolactone-2-yl, 3-methyl-gamma-butyrolactone-3-yl, 2-tetrahydropyranyl, 2-tetrahydrofuranyl, 2, 3-propylene carbonate-1-yl, 1-methoxyethyl, 1-ethoxyethyl, 1- (2-methoxyethoxy) ethyl, 1- (2-acetoxyethoxy) ethyl, t-butoxycarbonylmethyl, methoxymethyl, ethoxymethyl, trimethoxysilyl or triethoxysilyl, and may be methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, t-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxymethyl-carbonyl (t-butoxycarbonyl) or t-butoxymethyl. The straight or branched alkyl group may include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, or neopentyl. The cyclic alkyl group may include, for example, cyclopentyl or cyclohexyl.
The polyhydroxystyrene resin may be a resin having a repeating unit represented by the formula (V),
in the formula (V), R 7a Is a hydrogen atom or C 1-6 Alkyl, and R 7b Is a protecting group for acid dissociation. The definition of the acid dissociating protecting group is as described above.
The polyhydroxystyrene resin may include another polymerizable compound as a repeating unit. Examples of the polymerizable compound may include, but are not limited to: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl-containing aromatic compounds such as styrene, alpha-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, alpha-methylhydroxystyrene and alpha-ethylhydroxystyrene; vinyl-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and polymerizable compounds containing an amide bond, such as acrylamide and methacrylamide.
The acrylic resin may be a resin having a repeating unit represented by formula (VI);
in the formula (VI), R 8a Is a hydrogen atom, C 1 -C 6 Straight-chain or branched alkyl, fluorine or C 1 -C 6 A linear or branched fluorinated alkyl group, and R 8b Is a protecting group for acid dissociation. The definition of the acid dissociating protecting group is as described above.
In one embodiment of the photoresist composition, the photosensitive polymer may include a (meth) acrylate-based polymer. The (meth) acrylate-based polymer may be an aliphatic (meth) acrylate-based polymer, and may include, for example, polymethyl methacrylate (PMMA), poly (t-butyl methacrylate), poly (methacrylic acid), poly (norbornyl methacrylate), a binary or ternary copolymer photopolymer of the repeating units of the above (meth) acrylate-based polymer, or a combination thereof.
The acrylic resin may include another polymerizable compound as a repeating unit. Examples of the polymerizable compound may include, but are not limited to: acrylic esters having an ether bond such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl-containing aromatic compounds such as styrene, alpha-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, alpha-methylhydroxystyrene and alpha-ethylhydroxystyrene; vinyl-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and polymerizable compounds containing an amide bond, such as acrylamide and methacrylamide.
In one embodiment of the photoresist composition, the photopolymer may have the structure:
The photopolymer may be obtained by polyaddition of the polymer monomers as is conventional in the art. In one embodiment of the photoresist composition, the photopolymer is obtained by addition polymerization of monomer A, monomer B, and monomer C, wherein monomer A is
The monomer B is->
The monomer C is
Wherein the molar ratio of the monomer A to the monomer B to the monomer C is 66.5:8.5:25.
In one embodiment, the solvent for the polyaddition reaction is an ester solvent, preferably ethyl acetate.
In one embodiment, the polyaddition reaction is carried out at a temperature of 75 to 80℃and preferably 78 ℃.
In one embodiment, the polyaddition reaction is carried out for a period of from 6 to 10 hours, preferably 8 hours.
In one embodiment, after the polyaddition reaction has ended, it can be treated by the following work-up steps: 1) Mixing the reaction solution with an alcohol solvent to generate a precipitate, and mixing the precipitate with an ester solvent for dissolution; 2) Repeating the operation 1) for 3 times, mixing with alcohol solvent to obtain precipitate, and drying.
In the post-treatment step, the alcohol solvent is preferably methanol.
In the post-treatment step, the ester solvent is preferably ethyl acetate.
In one embodiment of the photoresist composition, the weight average molecular weight (Mw) of the photosensitive polymer may be 10,000 to 600,000; for example 20,000 to 400,000; and for example 22,000. Wherein the Mw value may be a value measured using Gel Permeation Chromatography (GPC) by setting polystyrene as a standard.
In one embodiment of the photoresist composition, the photosensitive polymer may have a polydispersity index (PDI) of 1 to 3, for example 2.1.
In one embodiment, the photopolymer is prepared as follows:
(1) About 80g of monomer A, about 9g of monomer B and about 32g of monomer C are added into a reaction kettle filled with nitrogen, then 110g of ethyl acetate is added into the reaction kettle, the reaction kettle is heated to 78 ℃ after being uniformly stirred, and then a mixed solution of ethyl acetate (25 g) and benzoyl peroxide (2.2 g) is dropwise added into the reaction kettle for 10 minutes. Reacting at 78 ℃ for 8 hours, stopping the reaction, and cooling the temperature of the reaction liquid to room temperature; (2) Methanol (1000 g) was then added to the reaction vessel to produce a precipitate. After 1h, liquid in the reaction kettle is led out, and ethyl acetate (150 g) is added into the reaction kettle until precipitation and dissolution are carried out; (3) Repeating the operation of the step (2) for 3 times, adding methanol (1000 g) into the reaction kettle to obtain a solid precipitate, and drying the solid precipitate in a vacuum drying oven to obtain the photopolymer. Wherein the monomer A, the monomer B and the monomerThe molar ratio of C was about 66.5:8.5:25. The structural formula of the finally prepared photosensitive polymer is
Wherein x is 1 :y 1 :z 1 =66.5:8.5:25; its weight average molecular weight (Mw) was 22,000; its polydispersity index (PDI) is 2.1.
In the KrF thick film photoresist composition, the solvent may be a solvent conventional in the art for such reactions, preferably an ester solvent such as propylene glycol monomethyl ether acetate.
In the KrF thick film photoresist composition, the weight part of the photosensitive polymer may be 100 parts.
In the KrF thick film photoresist composition, the weight part of the sulfoximine compound may be 5 parts, based on 100 parts by weight of the photopolymer.
In the KrF thick film photoresist composition, the weight part of the triethanolamine may be 0.1 part based on 100 parts by weight of the photopolymer.
In the KrF thick film photoresist composition, the solvent may be 800 parts by weight based on 100 parts by weight of the photopolymer.
In a preferred embodiment of the present invention, the KrF thick film photoresist composition is prepared by dissolving 5 parts by weight of the above-mentioned sulfoacid imine compound, 100 parts by weight of the above-mentioned photopolymer, and 0.1 part by weight of triethanolamine to 800 parts by weight of propylene glycol monomethyl ether acetate; wherein the photosensitive polymer is obtained by carrying out addition polymerization on the monomer A, the monomer B and the monomer C; the conditions and operation of the polyaddition reaction are as described previously, the molar ratio of the monomer A, the monomer B and the monomer C being 66.5:8.5:25, the final prepared photopolymer having a weight average molecular weight (Mw) of 22,000; its polydispersity index (PDI) is 2.1.
The preparation method of the KrF thick film photoresist composition can comprise the following steps: and uniformly mixing the sulfoacid imine compound, the photosensitive polymer, the triethanolamine and the solvent.
The mixing is a procedure conventional in the art. Wherein the temperature of the mixing is room temperature.
After the mixing is finished, the operation of filtering can be further included. The filtration mode is a conventional filtration mode in the field, preferably a filter is adopted for filtration, and the pore diameter of a filter membrane of the filter is preferably 150 nm-250 nm, and more preferably 200nm.
The invention also provides a using method of the photoresist composition, which comprises the following steps:
step 1: coating the KrF thick film photoresist composition on a substrate surface to form a photoresist layer;
step 2: pre-baking the photoresist layer;
step 3: copying the pattern on the mask plate onto the pre-baked photoresist layer through exposure;
step 4: baking the exposed photoresist layer;
step 5: and (5) applying a developer to the baked photoresist layer for development, thus obtaining the photoetching pattern.
In step 1, the substrate is preferably a silicon wafer;
in step 1, the coating mode is preferably spin coating;
in step 1, the thickness of the composition layer is preferably 8.5 to 11.5 μm, more preferably 10 μm;
in the step 2, the temperature of the pre-baking is preferably 95-125 ℃, and more preferably 110 ℃;
in step 3, the wavelength of the exposure is preferably 248nm;
in the step 4, the baking temperature is preferably 110-130 ℃, and more preferably 120 ℃;
in step 5, the developer is preferably an aqueous solution of tetramethylammonium hydroxide, for example, an aqueous solution of tetramethylammonium hydroxide having a mass percent of 2.38%;
in the step 5, the temperature of the development is preferably 20 to 25 ℃, and more preferably 23 ℃;
in step 5, the development time is preferably 0.5 to 2 minutes, more preferably 1 minute.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the adhesive film formed by the photoresist composition has the advantage of good rectangle.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
1. Photo-acid-producing function test of sulfoacid imine compound as photo-acid-producing agent
The acetonitrile solution of the photoacid generator was prepared to have a concentration of 0.05mol/L, placed in a quartz optical cell having an optical path length of 1cm, irradiated with light (290 nm) split by a xenon lamp, and subjected to radiation measurement of acid production. The acid yield was observed by absorption of tetrabromophenol blue at 610 nm. The quantum yield was determined by measuring the amount of light using potassium ferrite oxalate.
2. Solubility test of sulfoacid imine compounds as photoacid generators
1.0g of photoacid generator was weighed, added to 100g of propylene glycol monomethyl ether acetate, magnetically stirred for 20 minutes, and the solubility was observed.
3. Use of sulfoacid imine compounds as photoacid generators (process for preparing photoresist compositions)
5 parts by weight of a photoacid generator, 100 parts by weight of a photopolymer, and 0.1 part by weight of triethanolamine were dissolved to 800 parts by weight of propylene glycol monomethyl ether acetate, and uniformly mixed to prepare a photoresist composition.
The preparation method of the photosensitive polymer comprises the following steps:
(1) About 80g of monomer A, about 9g of monomer B and about 32g of monomer C were charged into a reaction vessel filled with nitrogen, and then 110g were charged into the reaction vesselAfter the ethyl acetate was stirred uniformly, the reaction vessel was heated to 78 ℃, and then a mixture of ethyl acetate (25 g) and benzoyl peroxide (2.2 g) was added dropwise to the reaction vessel, followed by completion of the addition for 10 minutes. Reacting at 78 ℃ for 8 hours, stopping the reaction, and cooling the temperature of the reaction liquid to room temperature; (2) Methanol (1000 g) was then added to the reaction vessel to produce a precipitate. After 1h, liquid in the reaction kettle is led out, and ethyl acetate (150 g) is added into the reaction kettle until precipitation and dissolution are carried out; (3) Repeating the operation of the step (2) for 3 times, adding methanol (1000 g) into the reaction kettle to obtain a solid precipitate, and drying the solid precipitate in a vacuum drying oven to obtain the photopolymer. Wherein the molar ratio of monomer A, monomer B and monomer C is about 66.5:8.5:25. The structural formula of the finally prepared photosensitive polymer is
Wherein x is 1 :y 1 :z 1 =66.5:8.5:25; its weight average molecular weight (Mw) was 22,000; its polydispersity index (PDI) is 2.1.
Monomer A:
monomer B:>
monomer C:>
4. use of photoresist composition
The photoresist composition was filtered using a 0.2 μm membrane filter to prepare a photoresist solution. Next, a thick film photoresist having a thickness of 10 μm was prepared by spin-coating a photoresist solution on a silicon wafer. After prebaking at 110 ℃, exposure was performed through a photomask 248nm ultraviolet, and then post-exposure baking was performed at 120 ℃. Then, development was performed at 23℃for 1 minute using a 2.38 wt% aqueous tetramethylammonium hydroxide solution. The resin compatibility and pattern shape were observed.
5. Examples 1 to 5 and comparative examples 1 to 10 in which the sulfinamide compound was used as the photoacid generator are shown in the following table
Wherein the structure of C1-C10 is as follows:
6. examples of effects of the photo-acid generator of the sulfenamide class and the corresponding photoresist composition
| Effect example | Quantum yield | Solubility of | Compatibility of resins | Pattern shape |
| Example 1 | 0.2 | Completely dissolve | Good quality | Clear rectangle |
| Example 2 | 0.25 | Completely dissolve | Good quality | Clear rectangle |
| Example 3 | 0.2 | Completely dissolve | Good quality | Clear rectangle |
| Example 4 | 0.24 | Completely dissolve | Good quality | Clear rectangle |
| Example 5 | 0.24 | Completely dissolve | Good quality | Clear rectangle |
| Comparative example 1 | 0.16 | Incomplete dissolution of | Slightly worse | Slightly enlarged head shape |
| Comparative example 2 | 0.18 | Incomplete dissolution of | Slightly worse | Slightly enlarged head shape |
| Comparative example 3 | 0.19 | Incomplete dissolution of | Slightly worse | Slightly enlarged head shape |
| Comparative example 4 | 0.21 | Completely dissolve | Slightly worse | Slightly enlarged head shape |
| Comparative example 5 | 0.22 | Completely dissolve | Good quality | Slightly enlarged head shape |
| Comparative example 6 | 0.21 | Completely dissolve | Slightly worse | Slightly enlarged head shape |
| Comparative example 7 | 0.15 | Completely dissolve | Slightly worse | Slightly enlarged head shape |
| Comparative example 8 | 0.23 | Completely dissolve | Slightly worse | Slightly enlarged head shape |
| Comparative example 9 | 0.19 | Completely dissolve | Slightly worse | Slightly enlarged head shape |
| Comparative example 10 | 0.15 | Completely dissolve | Good quality | Slightly enlarged head shape |
。
Claims (11)
1. The application of the sulfoacid imine compound as the photoacid generator in the KrF thick film photoresist composition is characterized in that the sulfoacid imine compound is shown as a formula I;
in the formula I, n is 0, 1, 2 or 3;
R 1 is-COOR 1-1 Or C 1-4 An alkyl group; r is R 1-1 Is C 1-4 An alkyl group;
R 2 is C 1-4 An alkyl group.
2. The use according to claim 1, wherein the sulphonic acid imine compound fulfils one or more of the following conditions:
(1) n is 0, 1 or 2;
(2) When R is 1 is-COOR 1-1 When said R is 1-1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably ethyl;
(3) When R is 1 Is C 1-4 In the case of alkyl, said R 1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably methyl;
(4)R 2 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably methyl.
3. The use according to claim 2, wherein the sulphonic acid imine compound is any one of the following compounds:
4. the use of claim 1, wherein the KrF thick film photoresist composition comprises: a sulphonic acid imine compound according to any one of claims 1 to 3, photopolymer, triethanolamine and solvent; the photosensitive polymer is phenolic resin, polyhydroxystyrene resin, acrylic resin or a combination thereof.
5. The use of claim 4 wherein said KrF thick film photoresist composition consists of said sulfoximine compound, said photopolymer, triethanolamine and a solvent.
6. The use of claim 4 or 5, wherein the KrF thick film photoresist composition meets one or more of the following conditions:
(1) The photosensitive polymer is a single unitThe photosensitive polymer is obtained by carrying out addition polymerization on a body A, a monomer B and a monomer C, wherein the monomer A is
The monomer B is->
The monomer C is->
The molar ratio of the monomer A to the monomer B to the monomer C is 66.5:8.5:25;
(2) The weight average molecular weight of the photopolymer is 10,000 to 600,000; for example 20,000 to 400,000; also for example 22,000;
(3) The polydispersity of the photopolymer is from 1 to 3, for example 2.1;
(4) The solvent is an ester solvent, such as propylene glycol monomethyl ether acetate;
(5) The weight part of the photosensitive polymer is 100 parts;
(6) The weight part of the sulfoacid imine compound is 5 parts, and the weight part of the sulfoacid imine compound is calculated by 100 parts of the photosensitive polymer;
(7) The weight part of the triethanolamine is 0.1 part, and the weight part of the triethanolamine is 100 parts of the photopolymer;
(8) The weight portion of the solvent is 800 parts based on 100 parts by weight of the photopolymer.
7. The use of claim 6 wherein said KrF thick film photoresist composition is prepared from 5 parts by weight of said sulfoximine compound, 100 parts by weight of said photopolymer, 0.1 parts by weight of triethanolamine dissolved to 800 parts by weight of propylene glycol monomethyl ether acetate; wherein the photosensitive polymer is obtained by carrying out addition polymerization on the monomer A, the monomer B and the monomer C; the molar ratio of the monomer A to the monomer B to the monomer C is 66.5:8.5:25, and the weight average molecular weight of the finally prepared photosensitive polymer is 22,000; the polydispersity index thereof is 2.1.
8. Use according to claim 6 or 7, characterized in that it fulfils one or more of the following conditions:
(1) The solvent for the polyaddition reaction is an ester solvent, preferably ethyl acetate;
(2) The temperature of the polyaddition reaction is 75-80 ℃, preferably 78 ℃;
(3) The polyaddition reaction time is 6 to 10 hours, preferably 8 hours;
(4) After the polyaddition reaction is finished, the polyaddition reaction can be treated by the following post-treatment steps: 1) Mixing the reaction solution with an alcohol solvent to generate a precipitate, and mixing the precipitate with an ester solvent for dissolution; 2) Repeating the operation 1) for 3 times, mixing with alcohol solvent to obtain precipitate, and drying; the alcohol solvent is preferably methanol; the ester solvent is preferably ethyl acetate.
9. The use according to any one of claims 4 to 7, wherein the KrF thick film photoresist composition is prepared by: uniformly mixing the sulfoacid imine compound, the photosensitive polymer, the triethanolamine and the solvent; preferably, after the mixing is finished, filtering; the filtering is filtering by adopting a filter; the filter membrane pore size of the filter is 150-250 nm, preferably 200nm.
10. The use of claim 9, wherein the method of using the KrF thick film photoresist composition comprises the steps of:
step 1: coating the KrF thick film photoresist on the surface of a substrate to form a photoresist layer;
step 2: pre-baking the photoresist layer;
step 3: copying the pattern on the mask plate onto the pre-baked photoresist layer through exposure;
step 4: baking the exposed photoresist layer;
step 5: and (5) applying a developer to the baked photoresist layer for development, thus obtaining the photoetching pattern.
11. The use of claim 10, wherein the KrF thick film photoresist composition is used in a manner that satisfies one or more of the following conditions:
(1) In the step 1, the substrate is a silicon wafer;
(2) In the step 1, the coating mode is spin coating;
(3) In step 1, the thickness of the composition layer is 8.5 to 11.5. Mu.m, preferably 10. Mu.m;
(4) In the step 2, the temperature of the pre-baking is 95-125 ℃, preferably 110 ℃;
(5) In the step 3, the wavelength of the exposure is 248nm;
(6) In the step 4, the baking temperature is 110-130 ℃, preferably 120 ℃;
(7) In step 5, the developer is an aqueous solution of tetramethylammonium hydroxide, for example, an aqueous solution of tetramethylammonium hydroxide with a mass percentage of 2.38%;
(8) In the step 5, the temperature of the development is 20-25 ℃, preferably 23 ℃;
(9) In step 5, the development time is 0.5 to 2min, preferably 1min.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111444525.0A CN116203795A (en) | 2021-11-30 | 2021-11-30 | Application of sulfoacid imine compound as KrF thick film photoresist photoacid generator |
| KR1020247018789A KR20240096731A (en) | 2021-11-30 | 2021-12-24 | KrF light source thick film photoresist composition, method of making the same, and method of using the same |
| PCT/CN2021/141097 WO2023097826A1 (en) | 2021-11-30 | 2021-12-24 | Krf light source thick film photoresist composition, preparation method therefor and use method thereof |
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| CN202111444525.0A CN116203795A (en) | 2021-11-30 | 2021-11-30 | Application of sulfoacid imine compound as KrF thick film photoresist photoacid generator |
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