JP4187879B2 - Radiation sensitive resist composition - Google Patents
Radiation sensitive resist composition Download PDFInfo
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- JP4187879B2 JP4187879B2 JP22375099A JP22375099A JP4187879B2 JP 4187879 B2 JP4187879 B2 JP 4187879B2 JP 22375099 A JP22375099 A JP 22375099A JP 22375099 A JP22375099 A JP 22375099A JP 4187879 B2 JP4187879 B2 JP 4187879B2
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- Japan
- Prior art keywords
- group
- acid
- unit
- alkali
- radiation
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 40
- 230000005855 radiation Effects 0.000 title claims description 31
- -1 siloxane unit Chemical group 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 238000004090 dissolution Methods 0.000 claims description 17
- 230000002401 inhibitory effect Effects 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical group O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 5
- 229910020487 SiO3/2 Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JDQNYWYMNFRKNQ-UHFFFAOYSA-N 3-ethyl-4-methylpyridine Chemical compound CCC1=CN=CC=C1C JDQNYWYMNFRKNQ-UHFFFAOYSA-N 0.000 description 2
- KNCHDRLWPAKSII-UHFFFAOYSA-N 4-ethyl-2-methylpyridine Chemical compound CCC1=CC=NC(C)=C1 KNCHDRLWPAKSII-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical group 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 125000004979 cyclopentylene group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 2
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000005054 phenyltrichlorosilane Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 2
- CDVJPOXUZPVGOJ-UHFFFAOYSA-N trichloro-[(4-methoxyphenyl)methyl]silane Chemical compound COC1=CC=C(C[Si](Cl)(Cl)Cl)C=C1 CDVJPOXUZPVGOJ-UHFFFAOYSA-N 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 2
- 239000012953 triphenylsulfonium Substances 0.000 description 2
- QSUJHKWXLIQKEY-UHFFFAOYSA-N (2-oxooxolan-3-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCOC1=O QSUJHKWXLIQKEY-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- WLCIEDPHMBLQBV-UHFFFAOYSA-N (4-methylphenyl)sulfanium;trifluoromethanesulfonate Chemical compound CC1=CC=C([SH2+])C=C1.[O-]S(=O)(=O)C(F)(F)F WLCIEDPHMBLQBV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- WWWFHFGUOIQNJC-UHFFFAOYSA-N 2-hydroxy-3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1O WWWFHFGUOIQNJC-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- FMUGJGVGEWHETE-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl(trichloro)silane Chemical compound C1CC2C([Si](Cl)(Cl)Cl)CC1C2 FMUGJGVGEWHETE-UHFFFAOYSA-N 0.000 description 1
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 239000003613 bile acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DNFSNYQTQMVTOK-UHFFFAOYSA-N bis(4-tert-butylphenyl)iodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DNFSNYQTQMVTOK-UHFFFAOYSA-N 0.000 description 1
- LUEHNHVFDCZTGL-UHFFFAOYSA-N but-2-ynoic acid Chemical compound CC#CC(O)=O LUEHNHVFDCZTGL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- NFJPGAKRJKLOJK-UHFFFAOYSA-N chembl1901631 Chemical compound CCCCOP(=O)OCCCC NFJPGAKRJKLOJK-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000018109 developmental process Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- YWTJTYXQYJSKNB-UHFFFAOYSA-N methyl propaneperoxoate Chemical compound CCC(=O)OOC YWTJTYXQYJSKNB-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- RQKYHDHLEMEVDR-UHFFFAOYSA-N oxo-bis(phenylmethoxy)phosphanium Chemical compound C=1C=CC=CC=1CO[P+](=O)OCC1=CC=CC=C1 RQKYHDHLEMEVDR-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- KTNLYTNKBOKXRW-UHFFFAOYSA-N phenyliodanium Chemical compound [IH+]C1=CC=CC=C1 KTNLYTNKBOKXRW-UHFFFAOYSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ZJEYUFMTCHLQQI-UHFFFAOYSA-N triethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OCC)(OCC)OCC)=CC=CC2=C1 ZJEYUFMTCHLQQI-UHFFFAOYSA-N 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、感放射線レジスト組成物に関するものである。
【０００２】
【従来の技術】
近年、半導体素子の集積度はますます高まり、既にデザインルール０．２０μｍのＬＳＩの量産は開始され、１９９９年末にはデザインルール０．１８μｍのＬＳＩの量産が始まろうとしている。
このような半導体リソグラフィーでは、レジストに基剤樹脂成分としてケイ素原子を含まない樹脂、例えばヒドロキシスチレン系樹脂や（メタ）アクリル酸エステル系樹脂と酸発生剤を主要成分とする化学増幅型のポジ又はネガ型レジストを採用することにより、或いはこれと有機又は無機の反射防止膜を組み合わせることにより、さらにはハーフトーンマスクやレベンソンマスクなどの露光用マスクの工夫や輪帯照明、スキャン方式、レンズの高ＮＡ（ＮＡ：レンズの開口数）化などの露光装置の工夫によりデザインルール０．１３μｍ付近迄実用化されようとしている。
【０００３】
一方、基剤樹脂成分にケイ素原子を含有する樹脂を用いたシリコン含有レジストは、耐ドライエッチング性に優れることから古くより多数の報告がなされている。例えば：
（１）特開平２−２３３５５号公報には、シリル化フェノールノボラック樹脂と架橋剤と酸発生剤からなるネガ型レジストを用いるパターン形成方法；
（２）特開平４−２１２１６０号公報には、ポリシルセスキオキサンと酸発生剤からなる感光性樹脂組成物；
（３）特開平４−３３８９５８号公報には、特定のポリシロキサンと酸発生剤からなるレジスト材料；
（４）特開平８−１８１１３２号公報には、梯子状ポリフェニルシロキサンやポリヒドロキシベンジルシルセスキオキサンのようなシロキサン樹脂のみをレジストに用いるパターン形成方法；及び
（５）特開平８−３３４９００号公報、特開平８−３３４９０１号公報及び特開平９−８７３９１号公報には、ポリヒドロキシベンジルシルセスキオキサンのヒドロキシル基の一部を酸不安定基で保護したポリシロキサンと酸発生剤を含有する化学増幅型ポジ型レジスト組成物などが提案されている。
【０００４】
しかしながら、このようなシリコン含有レジストでは、解像性やレジストパターン形状において十分とは言えず、改善が望まれている。
また、ＫｒＦエキシマレーザー（２４８ｎｍ）の次世代の露光光はＡｒＦエキシマレーザー（１９３ｎｍ）、次〃世代の露光光はＦ2レーザー（１５７ｎｍ）のような真空紫外線（ＶＵＶ１９０〜１０５ｎｍ）と言われているが、これまでＫｒＦポジレジストの基剤樹脂として広く利用されてきたヒドロキシスチレン系樹脂やＡｒＦポジレジストの基剤樹脂として知られている（メタ）アクリル酸エステル系樹脂では、Ｆ2レーザーに対する透過性が低く高解像性のレジストパターンが得られないため、さらに該レーザーに対する透過性の高い感放射線レジスト組成物が望まれている。
【０００５】
【発明が解決しようとする課題】
従って、本発明においては、高解像性で断面形状の良好なレジストパターンが形成可能であり、またＦ2レーザーに対する透過性が高く、Ｆ2レーザーを用いる０．１５μｍ以下の超微細レジストパターン形成のリソグラフィープロセスに有効な感放射線レジスト組成物の提供を目的とする。
【０００６】
【課題を解決するための手段】
本発明は、（Ａ）（ａ１）アルカリ可溶性基含有シロキサン単位、（ａ２）（ａ１）のアルカリ可溶性基を酸解離性の溶解抑制基で置換したシロキサン単位及び（ａ３）酸解離性基を有しないアルカリ不溶性基含有シロキサン単位を含むポリシロキサン樹脂、及び（Ｂ）放射線の照射により酸を発生する化合物からなる酸発生剤を含有してなり、前記（ａ１）のアルカリ可溶性基とシロキサン基のケイ素原子とを連結する基が、アリーレン基及びアラルキレン基から選ばれる少なくとも一つである感放射線レジスト組成物を提供するものである。また本発明は、（ａ１）のアルカリ可溶性基がヒドロキシル基及びカルボキシル基から選ばれる少なくとも一つである前記の感放射線レジスト組成物を提供するものである。また本発明は、（ａ１）がヒドロキシベンジルシルセスキオキサン単位である前記の感放射線レジスト組成物を提供するものである。また本発明は、（ａ２）が前記（ａ１）のアルカリ可溶性基を酸解離性の溶解抑制基で置換したシロキサン単位である前記の感放射線レジスト組成物を提供するものである。また本発明は、（ａ３）の酸解離性基を有しないアルカリ不溶性基がアルキル基、アリール基、アラルキル基から選ばれる少なくとも一つである前記の感放射線レジスト組成物を提供するものである。また本発明は、（ａ３）がアルキルシルセスキオキサン単位、アリールシルセスキオキサン単位、アラルキルシルセスキオキサン単位から選ばれる少なくとも一つである前記の感放射線レジスト組成物を提供するものである。また本発明は、アルキルシルセスキオキサン単位が炭素数１〜４の低級アルキルシルセスキオキサン単位及び環状アルキルシルセスキオキサン単位から選ばれる少なくとも一つである前記の感放射線レジスト組成物を提供するものである。また本発明は、（ａ３）がメチルシルセスキオキサン単位、ノルボルニルシルセスキオキサン単位、フェニルシルセスキオキサン単位、ナフチルシルセスキオキサン単位及びベンジルシルセスキオキサン単位から選ばれる少なくとも一つである前記の感放射線レジスト組成物を提供するものである。
また本発明は、（Ａ）（ａ１）アルカリ可溶性基含有シロキサン単位（ただし、下記一般式（Ｉ）で表されるものを除く）、（ａ２）（ａ１）のアルカリ可溶性基を酸解離性の溶解抑制基で置換したシロキサン単位及び（ａ３）酸解離性基を有しないアルカリ不溶性基含有シロキサン単位を含むポリシロキサン樹脂、及び（Ｂ）放射線の照射により酸を発生する化合物からなる酸発生剤を含有してなり、前記（ａ３）の酸解離性基を有しないアルカリ不溶性基が、アリール基及びアラルキル基から選ばれる少なくとも一つである感放射線レジスト組成物を提供するものである。また本発明は、（ａ１）のアルカリ可溶性基とシロキサン基のケイ素原子とを連結する基が、アルキレン基、アリーレン基及びアラルキレン基から選ばれる少なくとも一つである前記の感放射線レジスト組成物を提供するものである。
【化３】
【化４】
【０００７】
【発明の実施の形態】
本発明における（Ａ）成分は、上記の（ａ１）、（ａ２）及び（ａ３）の各シロキサン単位を含むポリシロキサン樹脂である。（Ａ）成分は、アルカリ可溶性樹脂における、例えばフェノール性水酸基のようなアルカリ可溶性基の一部を酸解離性の溶解抑制基で置換することにより、アルカリ不溶性となり、酸発生剤から生じた酸の作用により、該溶解抑制基が解離しアルカリ可溶性に変化するという基本的な機能を有し、これは従来の化学増幅型のポジ型レジストに用いられている基剤樹脂の機能と同じである。
【０００８】
本発明における（Ａ）成分は、従来知られている（ａ１）と（ａ２）単位からなるポリシロキサン樹脂に（ａ３）酸解離性基を有しないアルカリ不溶性基含有シロキサン単位を導入した点に特徴を有する。
この単位の導入により、（Ａ）成分のアルカリ溶解性が（ａ３）単位を有しない樹脂に比べ落ちるが、それにより、露光部と未露光部のコントラストが大きくなり、解像性が向上し、レジストパターン形状も良好となる。
また、Ｆ2レーザーに対する透過性が向上し、高解像性のレジストパターンが形成可能となる。
【０００９】
（ａ１）単位はアルカリ可溶性基含有シロキサン単位である。この単位はヒドロキシル基やカルボキシル基などのアルカリ可溶性基を有する有機基の少なくとも一つがシロキサン基のケイ素原子に結合した単位である。
該有機基としては、ヒドロキシル基やカルボキシル基などのアルカリ可溶性基を有するアルキレン基、アリーレン基、アラルキレン基などが挙げられる。
アルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等の低級アルキレン基、シクロへキシレン基、シクロペンチレン基、ノルボルナンから水素原子２原子を省いた基などの環状のアルキレン基が挙げられる。
アリーレン基としては、フェニレン基、ナフチレン基などが挙げられる。
アラルキレン基としては、フェニルメチレン基（−Ｃ6Ｈ4−ＣＨ2−）、フェニルエチレン基（−Ｃ6Ｈ4−Ｃ2Ｈ4−）、ナフチルメチレン基（−Ｃ10Ｈ6−ＣＨ2−）、ナフチルエチレン基（−Ｃ10Ｈ6−ＣＨ4−）などが挙げられる。
これらのうち、特にはアラルキレン基、非環状のアルキレン基が好ましい。
【００１０】
（ａ１）単位のより具体的に好ましいものとして、
一般式（Ｉ）
[（ＨＯ−ｐｈ−ＣＨ2）ＳｉＯ3/2]ｎ
（式中ｐｈはフェニル基、ｎは１以上の整数である）
で表されるヒドロキシベンジルシルセスキオキサン単位又は
一般式（II）
[（ＨＯ−ｐｈ）2ＳｉＯ]ｎ
（式中ｐｈはフェニル基、ｎは１以上の整数である）
で表されるジヒドロキシフェニルシロキサン単位等が挙げられる。
【００１１】
（ａ２）単位は、（ａ１）のアルカリ可溶性基を酸解離性の溶解抑制基で置換したシロキサン単位である。
従って、（ａ２）単位は、ヒドロキシル基やカルボキシル基などのアルカリ可溶性基を有する有機基の少なくとも一つがシロキサン基のケイ素原子に結合した単位であって、該アルカリ可溶性基が酸解離性の溶解抑制基で置換されたものである。
該有機基としては、アルカリ可溶性基が酸解離性の溶解抑制基で置換された以外は（ａ１）と同様なアルキレン基、アリーレン基、アラルキレン基などが挙げられ、アルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等の低級アルキレン基、シクロへキシレン基、シクロペンチレン基、ノルボルナンから水素原子２原子を省いた基などの環状のアルキレン基が挙げられ、アリーレン基としては、フェニレン基、ナフチレン基などが挙げら、アラルキレン基としては、フェニルメチレン基（−Ｃ6Ｈ4−ＣＨ2−）、フェニルエチレン基（−Ｃ6Ｈ4−Ｃ2Ｈ4−）、ナフチルメチレン基（−Ｃ10Ｈ6−ＣＨ2−）、ナフチルエチレン基（−Ｃ10Ｈ6−Ｃ2Ｈ4−）などが挙げられる。
これらのうち、（ａ１）と同様にアラルキレン基、非環状のアルキレン基が好ましい。
【００１２】
酸解離性の溶解抑制基としては、既に化学増幅型のポジレジストにおいて、多種多様なものが知られており特に限定されないが、パターン形状を考慮すると第３級アルキルオキシカルボニル基、第３級アルキル基、環状アセタール残基及び鎖状アセタール残基が好ましい。
第３級アルキルオキシカルボニル基としては、ｔｅｒｔ-ブチルオキシカルボニル基（t-boc基）、ｔｅｒｔ-アミルオキシカルボニル基などが挙げられる。
第３級アルキル基としては、ｔｅｒｔ−ブチル基、ｔｅｒｔ-アミル基などが挙げられる。
環状アセタール残基としては、テトラヒドロピラニル基、テトラヒドロフラニル基などが挙げられる。
鎖状のアセタール残基としては、１−エトキシ−１−エチル基、１−メトキシ−１−プロピル基のような低級のアルコキシアルキル基が挙げられる。
【００１３】
（ａ２）単位のより具体的に好ましいものとして、
一般式（III）
[（ＸＯ−ｐｈ−ＣＨ2）ＳｉＯ3/2]ｎ
（式中Ｘは上記した酸解離性の溶解抑制基であり、ｐｈはフェニル基、ｎは１以上の整数である）
で表されるヒドロキシル基の水素原子を酸解離性の溶解抑制基で置換したヒドロキシベンジルシルセスキオキサン単位又は
一般式（IV）
[（ＸＯ−ｐｈ）2ＳｉＯ]ｎ
（式中Ｘ、ｐｈ及びｎは前記に同じ）
で表されるヒドロキシル基の水素原子を酸解離性の溶解抑制基で置換したジヒドロキシフェニルシロキサン単位等が挙げられる。
【００１４】
（ａ３）単位は酸解離性基を有しないアルカリ不溶性基含有シロキサン単位である。この単位は（ａ２）単位でいう酸解離性の溶解抑制基を有しないと共に（ａ１）単位でいうアルカリ可溶性基も有さない有機基の少なくとも一つがシロキサン基のケイ素原子に結合した単位である。
該有機基としては、アルキル基、アリール基、アラルキル基が挙げられる。
アルキル基としては、メチル基、エチル基、プロピル基、ブチル基などの低級アルキル基、シクロヘキシル基、ノルボルニル基などの環状アルキル基が挙げられる。アリール基としては、フェニル基、ナフチル基が挙げられる。アラルキル基としてはベンジル基、フェネチル基などが挙げられる。
中でもメチル基、ノルボルニル基、フェニル基、ナフチル基、ベンジル基がそれらのシルセスキオキサン単位を容易に得られ、好ましい。
【００１５】
より具体的には、
一般式（Ｖ）
[（Ｒ）ＳｉＯ3/2]ｎ
（式中Ｒはアルキル基、アリール基またはアラルキル基、ｎは１以上の整数である）
で表されるアルキルシルセスキオキサン単位、アリールシルセスキオキサン単位またはアラルキルシルセスキオキサン単位又は
一般式（VI）
[（Ｒ）2ＳｉＯ]ｎ
（式中Ｒとｎは前記に同じである）
で表されるジアルキルシロキサン単位、ジアリールシロキサン単位、ジアラルキルシロキサン単位等が挙げられる。
【００１６】
本発明（Ａ）成分における（ａ１）、（ａ２）及び（ａ３）の各単位の割合は、（Ａ）成分のアルカリ可溶性を考慮すると、２．３８重量％テトラメチルアンモニウムヒドロキシド水溶液に対する溶解性（単位時間当たりの膜減り量）で０〜１０００Å／minが好ましいことから（ａ１）１０〜７０モル％、好ましくは２０〜６０モル％、（ａ２）２０〜６０モル％、好ましくは３０〜４０モル％、（ａ３）５〜５０モル％、好ましくは１０〜４５モル％がよい。
【００１７】
また、（Ａ）成分の重量平均分子量は１０００〜５００００、好ましくは５０００〜１００００がよい。
【００１８】
なお、本発明の（Ａ）成分は、まず（ａ１）と（ａ３）単位を有するコポリマーを準備し、これに化学増幅型ポジ型レジストの基剤樹脂成分の調製と同様にしてヒドロキシル基やカルボキシル基などのアルカリ可溶性基を酸解離性の溶解抑制基（例えば、t-boc基）にて置換する公知の反応により得られる。
（ａ１）と（ａ３）のコポリマーは市販品を用いることもできるし、特許２５６７９８４号公報に記載された合成法により得ることができる。その一例を示すと、ｐ−メトキシベンジルトリクロロシランとベンジルトリクロロシランを出発物質としてｐ−メトキシベンジルシルセスキオキサンとベンジルシルセスキオキサンのコポリマーを合成し、このメトキシ基をヒドロキシル基に置換することにより、ｐ−ヒドロキシベンジルシルセスキオキサンとベンジルシルセスキオキサンのコポリマーが得られる。
なお、この場合、（ａ３）としてベンジルシルセスキオキサンを例示したが、それ以外にもメチルトリクロロシラン、エチルトリクロロシラン、２−ノルボニルトリクロロシラン、フェニルトリクロロシラン、１−ナフチルトリエトキシシランなどが市販品として購入できることから、同様にしてベンジル基以外の（ａ３）も合成できる。
【００１９】
本発明における（Ｂ）成分は、放射線の照射により酸を発生する化合物からなる酸発生剤である。
（Ｂ）成分は、放射線の照射により酸を発生する化合物であればよく特に限定されず、これまで公知の酸発生剤を使用できるが、好ましくはアニオンが炭素数１〜１０のフルオロアルキルスルホン酸イオンのオニウム塩である。
オニウム塩のカチオンとしてはメチル基、エチル基、プロピル、ｎ−ブチル基、ｔｅｒｔ−ブチルのような低級アルキル基またはメトキシ基、エトキシ基のような低級アルコキシ基で置換されていてもよいフェニルヨードニウムまたはスルホニウムが挙げられる。
アニオンとしては炭素数１〜１０のアルキル基の水素原子の一部または全部がフッ素化されたフルオロアルキルスルホン酸イオンである。炭素数が長くなるほど、またフッ素化率（アルキル基中のフッ素原子の割合）が小さくなるほどスルホン酸としての強度が落ちることから、炭素数１〜５のアルキル基の水素原子の全部がフッ素化されたフルオロアルキルスルホン酸が好ましい。
具体的にはジフェニルヨードニウムのトリフルオロメタンスルホネートまたはノナフルオロブタンスルホネート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムのトリフルオロメタンスルホネートまたはノナフルオロブタンスルホネート、トリフェニルスルホニウムのトリフルオロメタンスルホネートまたはノナフルオロブタンスルホネート、トリ（４−メチルフェニル）スルホニウムのトリフルオロメタンスルホネートまたはノナフルオロブタンスルホネート等が挙げられる。これらのうちトリフェニルスルホニウムのメタンスルホネートまたはノナフルオロブタンスルホネートが好ましい。
これらは１種または２種以上同時に用いてもよい。
（Ｂ）成分は、（Ａ）成分に対し、０．１〜２０重量％、好ましくは１〜１０重量％の割合で用いることができる。（Ａ）成分がこの範囲より少ないと像形成ができないし、逆に多いと均一なレジスト溶液とならずに好ましくない。
【００２０】
本発明の組成物には、必要に応じて上記以外の各種添加剤を配合することができる。添加剤としては、例えば有機カルボン酸、燐のオキソ酸若しくはその誘導体、有機アミン、胆汁酸と酸解離性基のエステル等が挙げられる。
【００２１】
有機カルボン酸としては、飽和または不飽和脂肪族カルボン酸、脂環式カルボン酸、芳香族カルボン酸等の有機カルボン酸を挙げることができるが、特に限定されるものではない。飽和脂肪族カルボン酸としては、蟻酸、酢酸、プロピオン酸、酪酸、イソ酪酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸等の１価または多価カルボン酸が挙げられる。不飽和脂肪族カルボン酸としては、アクリル酸、クロトン酸、イソクロトン酸、３−ブテン酸、メタクリル酸、４−ペンテン酸、プロピオル酸、２−ブチン酸、マレイン酸、フマル酸、アセチレンカルボン酸等が挙げられる。脂環式カルボン酸としては、１，１−シクロヘキサンジカルボン酸、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、１，１−シクロヘキシルジ酢酸等が挙げられる。芳香族カルボン酸としては、ｐ−ヒドロキシ安息香酸、ｏ−ヒドロキシ安息香酸、２−ヒドロキシ−３−ニトロ安息香酸、フタル酸、テレフタル酸、イソフタル酸等の水酸基、ニトロ基、カルボキシル基等の置換基を有する芳香族カルボン酸が挙げられる。
【００２２】
燐のオキソ酸若しくはその誘導体としては、具体的にはリン酸、亜リン酸、リン酸ジｎ−ブチルエステル、リン酸ジフェニルエステル等のリン酸または亜リン酸あるいはそれらのエステルのような誘導体、ホスホン酸、ホスホン酸ジメチルエステル、ホスホン酸ジｎ−ブチルエステル、フェニルホスホン酸、ホスホン酸ジフェニルエステル、ホスホン酸ジベンジルエステル等のホスホン酸およびそれらのエステルのような誘導体、ホスフィン酸、フェニルホスフィン酸等のホスフィン酸およびそれらのエステルのような誘導体が挙げられるがこれらに限定されるものではない。
【００２３】
有機アミンとしては、例えば、脂肪族アミン、芳香族アミン、複素環式アミンが挙げられるがこれらに限定されるものではない。脂肪族アミンとしては、ジエチルアミン、トリエチルアミン、ｎ−プロピルアミン、ジ−ｎ−プロピルアミン、トリ−ｎ−プロピルアミン、トリイソプロパノールアミン、イソプロピルアミン、ジブチルアミン、トリブチルアミン、トリペンチルアミン、トリエタノールアミン、ジプロパノールアミン、トリプロパノールアミン等が挙げられる。芳香族アミンとしては、ベンジルアミン、アニリン、Ｎ−メチルアニリン、Ｎ，Ｎ−ジメチルアニリン、ｏ−メチルアニリン、ｍ−メチルアニリン、ｐ−メチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ジフェニルアミン、ジ−ｐ−トリルアミン等が挙げられる。複素環式アミンとしては、ピリジン、ｏ−メチルピリジン、ｏ−エチルピリジン、２，３−ジメチルピリジン、４−エチル−２−メチルピリジン、３−エチル−４−メチルピリジン等が挙げられる。
【００２４】
これらの中で、トリエタノールアミン等の脂肪族アミンが引置き経時特性に優れるので好ましい。
【００２５】
有機カルボン酸または燐のオキソ酸若しくはその誘導体の配合割合は（Ａ）成分に対し、０．０１〜５重量％、好ましくは０．０２〜０．２重量％の範囲である。この範囲であると、解像性および感度が向上し好ましい。
【００２６】
有機アミンの配合割合は（Ａ）成分に対し、０．０１〜５重量％、好ましくは、０．０２〜０．２重量％の範囲である。この範囲であると、レジストパターン形状および感度が向上し好ましい。
【００２７】
また本発明の組成物には、さらに必要に応じて、相容性のある添加物、例えばハレーション防止剤や塗布性を向上させる界面活性剤等を適宜配合することができる。
【００２８】
本発明の組成物は、上記した各成分を適当な溶剤に溶解して溶液の形で用いるのが好ましい。このような溶剤の例としては、従来のレジスト組成物に用いられる溶剤を挙げることができ、例えばアセトン、メチルエチルケトン、シクロヘキサノン、メチルイソアミルケトン、２−ヘプタノン等のケトン類；エチレングリコール、プロピレングリコール、ジエチレングリコール、エチレングリコールモノアセテート、プロピレングリコールモノアセテート、ジエチレングリコールモノアセテート、あるいはこれらのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテルまたはモノフェニルエーテル等の多価アルコール類およびその誘導体；ジオキサンのような環式エーテル類；および乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル等のエステル類を挙げることができる。これらは単独で用いてもよいし、２種以上を混合して用いてもよい。
【００２９】
本発明の組成物の好適な使用方法について一例を示すと、まず、シリコンウェーハ等の基板上に、組成物の溶液をスピンナー等で塗布し、乾燥して感光層を形成させ、次いでパターンが描かれたホトマスクを介して露光する。次にこれを露光後加熱（ＰＥＢ）した後、現像液、例えば１〜１０重量％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液のようなアルカリ性水溶液で現像すると、露光部が溶解除去されてマスクパターンに忠実な画像（レジストパターン）を得ることができる。なお、レジストパターンの解像性をさらに高めるためには、感光層の膜厚を０．０５〜０．２μｍと薄膜化し、基板と本発明の組成物を用いて得られる感光層との間に従来のポジ型レジストやネガ型レジスト或いは反射防止膜を膜厚０．３５〜０．７μｍで介在させるとよい。なお、露光光としては、ＫｒＦレーザーなどの遠紫外線、Ｆ2レーザーなどの真空紫外線、ＥＵＶ、ＥＢ、Ｘ線などを用いることができる。
【００３０】
【実施例】
以下、本発明を実施例および比較例により説明するが、本発明は下記例に限定されるものではない。
製造例１
本製造例１では、特許２５６７９８４号に記載の方法を使用して、本発明における（Ａ）成分であるポリシロキサン樹脂を製造した。
かき混ぜ機還流冷却器、滴下ロート及び温度計を備えた５００ｍｌ三つ口フラスコに、炭酸水素ナトリウム８４．０ｇ（１．０ｍｏｌ）と水４００ｍｌを投入したのち、滴下ロートより、ｐ−メトキシベンジルトリクロロシラン５１．１ｇ（０．２ｍｏｌ）、フェニルトリクロロシラン１９．７ｇ（０．１０ｍｏｌ）及びジエチルエーテル１００ｍｌの混合液を２時間で滴下し、さらに１時間熟成した。反応終了後、反応混合物をエーテルで抽出し、エーテルを減圧下留去したのち、得られた加水分解生成物へ水酸化カリウムの１０重量％溶液０．２ｇを加え、２００℃で２時間熟成することにより、コポリ（ｐ−メトキシベンジルシルセスキオキサン・フェニルシルセスキオキサンを得た。得られたポリマーを１５０ｍｌのアセトニトリルに溶解し、ここへトリメチルシリルヨード８０ｇ（０．４０ｍｏｌ）を加え、還流下に２４時間かきまぜたのち、水５０ｍｌを加え、さらに１２時間還流下にかきまぜた。冷却後、亜硫酸水素ナトリウム水溶液で遊離のヨウ素を還元したのち、有機層を分離し、溶媒を減圧下に留去し、ついで得られたポリマーをアセトンとｎ−ヘキサンで再沈し減圧加熱乾燥することで、目的とするアルカリ可溶性ラダーシリコーン重合体である、下記式で示されるｐ−ヒドロキシベンジルシルセスキオキサンとフェニルシルセスキオキサンのコポリマー（重量平均分子量＝６７００）を得た。
【００３１】
【化１】
[（ＨＯ−ｐｈ−ＣＨ2）ＳｉＯ3/2]ｎ・[（ｐｈ）ＳｉＯ3/2]ｍ
（式中、ｎ／（ｎ＋ｍ）=０．６、ｍ／（ｎ＋ｍ）=０．４、ｐｈはフェニル基である）
【００３２】
次に該コポリマー３０ｇを１，４−ジオキサン５００ｇに溶解し、この溶液の中にジ−ｔｅｒｔ−ブチル−ジ−カーボネート２０ｇを加え、かき混ぜて完全に溶解したのち、かき混ぜながらトリエチルアミン５０ｇを約１５分間かけて滴下した。滴下終了後、そのまま約４時間かき混ぜた。次いで、得られた溶液に対して２０倍量の純水を加え、かき混ぜることでヒドロキシル基がｔｅｒｔ−ブトキシカルボニルオキシ基で置換されたポリシロキサンを析出させた。この樹脂を純水で洗浄、脱水、乾燥することにより、ポリシロキサン樹脂３０ｇを得た。なお、各シロキサン単位の割合を分析したところ、（ａ１）ヒドロキシベンジルシルセスキオキサン単位４０モル％、（ａ３）フェニルシルセスキオキサン単位４０モル％及び（ａ２）ｔｅｒｔ−ブトキシカルボニルオキシベンジルシルセスキオキサン単位２０モル％であった。
【００３３】
実施例１
（Ａ）成分
製造例で得たポリシロキサン１００重量部
（Ｂ）成分
トリフェニルスルホニウムトリフルオロメタンスルホネート２重量部
（添加剤）
トリエタノールアミン０．１重量部
上記（Ａ）、（Ｂ）及び添加剤をプロピレングリコールモノメチルエーテルモノアセテート２０００重量部に溶解した後、孔径０．１μｍのメンブレンフィルターを通してろ過し、ポジ型レジスト溶液を得た。
６インチシリコンウェーハに上記ポジ型レジスト溶液をスピンコートし、ホットプレート上９０℃で９０秒間乾燥することにより、膜厚０．１μmのレジスト層を形成した。
次いで、縮小投影露光装置ＦＰＡ−３０００ＥＸ３（キヤノン社製）により、ＫｒＦエキシマレーザー（２４８ｎｍ）を選択的に照射したのち、１１０℃で９０秒間加熱（ＰＥＢ）処理し、２．３８重量％テトラメチルアンモニウムヒドロキシド水溶液で２３℃にて６０秒間パドル現像した。次いで純水で３０秒間リンスし、最後に１００℃で６０秒間ポストベークし、ポジ型のレジストパターンを得た。
このようにして０．２５μｍラインアンドスペースパターンが得られる露光量は１０ｍＪ／ｃｍ2であり、その際の限界解像度は０．２０μｍで矩形に近い断面形であった。
【００３４】
実施例２
６インチシリコンウェーハに下層レジスト膜としてＯＦＰＲ８００を塗布、乾燥後、ホットプレート上で２２０℃で３００秒間加熱して膜厚０．５６μｍの有機層を設けた。次いで、該レジスト層の上に上記ポジ型レジスト溶液をスピンコートし、ホットプレート上９０℃で９０秒間乾燥することにより、膜厚０．１μｍのレジスト層を形成した。
以下実施例１と同様にしてレジストパターニングを行ったところ、０．２５μｍラインアンドスペースパターンが得られる露光量は１０ｍＪ／ｃｍ2であり、その際の限界解像度は０．２０μｍで矩形に近い断面形であった。
次いで、平行平板型スパッタエッチング装置にて酸素ガスをエッチャントとして、下層レジストをリアクティブイオンエッチングを行ったところ、０．２０μｍの多層レジストパターンが良好な形状で形成された。
【００３５】
参考例
製造例で調製したポリシロキサン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に溶解した後、スピンナー法によりＭｇＦ2基板（１ｍｍ厚）に回転塗布し、９０℃で９０秒間乾燥し、膜厚０．１μｍの塗膜を設けた。次いで、真空紫外分光光度計ＶＵＶ−２０１（日本分光社製）を用いてＦ2レーザー（１５７ｎｍ）における透過率を測定した。その結果、吸光度は５．２３μｍ-1であった。
なお、比較のためにヒドロキシスチレン系樹脂として、ヒドロキシスチレン６５モル％とスチレン２１．５モル％とｔｅｒｔ−ブチルアクリレート１３．５モル％の共重合体（重量平均分子量１３０００、Ｍｎ／Ｍｗ＝２．０）の樹脂を同様にして測定したところ、吸光度は６．５０μｍ-1であった。
また、メタアクリル酸エステル系樹脂として、メタクリル酸アダマンチル４０モル％とα−メタクリロイキシ−γ−ブチロラクトン５０モル％とアクリル酸１０モル％の共重合体（重量平均分子量２００００、Ｍｎ／Ｍｗ＝１．８）の樹脂を同様にして測定したところ、吸光度は８．０５μｍ-1であった。
【００３６】
【発明の効果】
本発明によれば、高解像性で断面形状の良好なレジストパターンが形成可能であり、またＦ2レーザーに対する透過性が高く、Ｆ2レーザーを用いる０．１５μｍ以下の超微細レジストパターン形成のリソグラフィープロセスに有効な感放射線レジスト組成物が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a radiation sensitive resist composition.
[0002]
[Prior art]
In recent years, the degree of integration of semiconductor elements has further increased, and mass production of LSIs with a design rule of 0.20 μm has already started, and mass production of LSIs with a design rule of 0.18 μm is about to begin at the end of 1999.
In such semiconductor lithography, a resin that does not contain a silicon atom as a base resin component in a resist, for example, a chemically amplified positive or negative resin mainly composed of a hydroxystyrene resin, a (meth) acrylic acid ester resin, and an acid generator. By adopting a negative resist, or by combining this with an organic or inorganic anti-reflection film, it is possible to further devise exposure masks such as halftone masks and Levenson masks, as well as annular illumination, scanning methods, and lens heights. The design rule is about to be put to practical use up to the vicinity of 0.13 μm by devising the exposure apparatus such as NA (NA: numerical aperture of lens).
[0003]
On the other hand, many silicon-containing resists using a resin containing a silicon atom as a base resin component have been reported for a long time because of their excellent dry etching resistance. For example:
(1) JP-A-2-23355 discloses a pattern forming method using a negative resist comprising a silylated phenol novolak resin, a crosslinking agent and an acid generator;
(2) JP-A-4-212160 discloses a photosensitive resin composition comprising polysilsesquioxane and an acid generator;
(3) JP-A-4-338958 discloses a resist material comprising a specific polysiloxane and an acid generator;
(4) JP-A-8-181132 discloses a pattern forming method using only a siloxane resin such as a ladder-like polyphenylsiloxane or polyhydroxybenzylsilsesquioxane as a resist; and
(5) In JP-A-8-334900, JP-A-8-334901 and JP-A-9-87391, a part of hydroxyl groups of polyhydroxybenzylsilsesquioxane is protected with an acid labile group. A chemically amplified positive resist composition containing polysiloxane and an acid generator has been proposed.
[0004]
However, such a silicon-containing resist is not sufficient in terms of resolution and resist pattern shape, and improvements are desired.
The next generation exposure light of KrF excimer laser (248 nm) is ArF excimer laser (193 nm), and the next generation exposure light is F.2It is said to be a vacuum ultraviolet ray (VUV 190-105 nm) such as laser (157 nm), but it is known as a base resin for hydroxystyrene resins and ArF positive resists that have been widely used as a base resin for KrF positive resists. In the (meth) acrylic ester resin used, F2Since a resist pattern with low laser transparency and high resolution cannot be obtained, a radiation sensitive resist composition with further high laser transparency is desired.
[0005]
[Problems to be solved by the invention]
Therefore, in the present invention, it is possible to form a resist pattern having a high resolution and a good cross-sectional shape.2High transparency to laser, F2An object of the present invention is to provide a radiation-sensitive resist composition effective in a lithography process for forming an ultrafine resist pattern of 0.15 μm or less using a laser.
[0006]
[Means for Solving the Problems]
The present invention comprises (A) (a1) an alkali-soluble group-containing siloxane unit, (a2) a siloxane unit obtained by substituting the alkali-soluble group of (a1) with an acid-dissociable, dissolution-inhibiting group, and (a3) an acid-dissociable group. A polysiloxane resin containing an alkali-insoluble group-containing siloxane unit, and (B) an acid generator composed of a compound that generates an acid upon irradiation with radiation.And the group that links the alkali-soluble group (a1) and the silicon atom of the siloxane group is at least one selected from an arylene group and an aralkylene group.A radiation-sensitive resist composition is provided. The present invention also provides the radiation-sensitive resist composition as described above, wherein the alkali-soluble group (a1) is at least one selected from a hydroxyl group and a carboxyl group.. MaThe present invention also provides the radiation sensitive resist composition described above, wherein (a1) is a hydroxybenzylsilsesquioxane unit. The present invention also provides the radiation sensitive resist composition, wherein (a2) is a siloxane unit in which the alkali-soluble group of (a1) is substituted with an acid dissociable, dissolution inhibiting group. The present invention also provides the radiation sensitive resist composition described above, wherein the alkali-insoluble group having no acid dissociable group (a3) is at least one selected from an alkyl group, an aryl group, and an aralkyl group. The present invention also provides the radiation sensitive resist composition described above, wherein (a3) is at least one selected from an alkylsilsesquioxane unit, an arylsilsesquioxane unit, and an aralkylsilsesquioxane unit. . The present invention also provides alkylsilsesquioxane units.1 to 4 carbon atomsThe radiation-sensitive resist composition is at least one selected from lower alkyl silsesquioxane units and cyclic alkyl silsesquioxane units. In the present invention, (a3) is at least one selected from a methylsilsesquioxane unit, a norbornylsilsesquioxane unit, a phenylsilsesquioxane unit, a naphthylsilsesquioxane unit, and a benzylsilsesquioxane unit. The radiation sensitive resist composition is provided.
The present invention also provides (A) (a1) an alkali-soluble group-containing siloxane unit (excluding those represented by the following general formula (I)), (a2) an alkali-soluble group of (a1) having an acid-dissociable property. An acid generator comprising a siloxane unit substituted with a dissolution inhibiting group and (a3) a polysiloxane resin containing an alkali-insoluble group-containing siloxane unit having no acid-dissociable group, and (B) a compound that generates an acid upon irradiation with radiation. The radiation-sensitive resist composition comprising (a3) the alkali-insoluble group having no acid-dissociable group is at least one selected from an aryl group and an aralkyl group. The present invention also provides the radiation sensitive resist composition as described above, wherein the group (a1) linking the alkali-soluble group and the silicon atom of the siloxane group is at least one selected from an alkylene group, an arylene group, and an aralkylene group. To do.
[Chemical 3]
[Formula 4]
[0007]
DETAILED DESCRIPTION OF THE INVENTION
(A) component in this invention is polysiloxane resin containing each siloxane unit of said (a1), (a2), and (a3). The component (A) is made insoluble in an alkali-soluble resin by substituting a part of an alkali-soluble group such as a phenolic hydroxyl group with an acid-dissociable, dissolution-inhibiting group. By the action, the dissolution inhibiting group has a basic function of dissociating and changing to alkali-soluble, which is the same as the function of the base resin used in the conventional chemical amplification type positive resist.
[0008]
The component (A) in the present invention is characterized in that (a3) an alkali-insoluble group-containing siloxane unit having no acid-dissociable group is introduced into a conventionally known polysiloxane resin comprising (a1) and (a2) units. Have
By introducing this unit, the alkali solubility of the component (A) is lower than that of the resin not having the unit (a3), whereby the contrast between the exposed portion and the unexposed portion is increased, and the resolution is improved. The resist pattern shape is also good.
F2The transparency to the laser is improved, and a resist pattern with high resolution can be formed.
[0009]
The unit (a1) is an alkali-soluble group-containing siloxane unit. This unit is a unit in which at least one organic group having an alkali-soluble group such as a hydroxyl group or a carboxyl group is bonded to a silicon atom of a siloxane group.
Examples of the organic group include an alkylene group having an alkali-soluble group such as a hydroxyl group and a carboxyl group, an arylene group, and an aralkylene group.
Examples of the alkylene group include lower alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group, a cyclic alkylene group such as a cyclohexylene group, a cyclopentylene group, and a group in which two hydrogen atoms are omitted from norbornane. It is done.
Examples of the arylene group include a phenylene group and a naphthylene group.
As the aralkylene group, a phenylmethylene group (—C6HFour-CH2-), Phenylethylene group (-C6HFour-C2HFour-), A naphthylmethylene group (-CTenH6-CH2-), Naphthylethylene group (-CTenH6-CHFour-).
Of these, an aralkylene group and an acyclic alkylene group are particularly preferable.
[0010]
(A1) More specifically preferred units are:
Formula (I)
[(HO-ph-CH2) SiO3/2] n
(Wherein ph is a phenyl group and n is an integer of 1 or more)
Or a hydroxybenzylsilsesquioxane unit represented by
Formula (II)
[(HO-ph)2SiO] n
(Wherein ph is a phenyl group and n is an integer of 1 or more)
And the like, and the like.
[0011]
The unit (a2) is a siloxane unit obtained by substituting the alkali-soluble group of (a1) with an acid dissociable, dissolution inhibiting group.
Accordingly, the unit (a2) is a unit in which at least one organic group having an alkali-soluble group such as a hydroxyl group or a carboxyl group is bonded to the silicon atom of the siloxane group, and the alkali-soluble group suppresses acid dissociable dissolution. It is substituted with a group.
Examples of the organic group include the same alkylene group, arylene group, and aralkylene group as in (a1) except that an alkali-soluble group is substituted with an acid dissociable, dissolution inhibiting group. Examples of the alkylene group include a methylene group, Examples include lower alkylene groups such as ethylene group, propylene group and butylene group, cyclohexylene group, cyclopentylene group and cyclic alkylene groups such as norbornane in which 2 hydrogen atoms are omitted. Group, naphthylene group and the like. As the aralkylene group, a phenylmethylene group (—C6HFour-CH2-), Phenylethylene group (-C6HFour-C2HFour-), A naphthylmethylene group (-CTenH6-CH2-), Naphthylethylene group (-CTenH6-C2HFour-).
Of these, an aralkylene group and an acyclic alkylene group are preferable as in (a1).
[0012]
As the acid dissociable, dissolution inhibiting group, a wide variety of chemical amplification type positive resists are already known and are not particularly limited. However, in consideration of the pattern shape, a tertiary alkyloxycarbonyl group and a tertiary alkyl are considered. Groups, cyclic acetal residues and chain acetal residues are preferred.
Examples of the tertiary alkyloxycarbonyl group include a tert-butyloxycarbonyl group (t-boc group) and a tert-amyloxycarbonyl group.
Examples of the tertiary alkyl group include a tert-butyl group and a tert-amyl group.
Examples of the cyclic acetal residue include a tetrahydropyranyl group and a tetrahydrofuranyl group.
Examples of the chain acetal residue include lower alkoxyalkyl groups such as 1-ethoxy-1-ethyl group and 1-methoxy-1-propyl group.
[0013]
(A2) More specifically preferred units are:
General formula (III)
[(XO-ph-CH2) SiO3/2] n
(Wherein X is an acid dissociable, dissolution inhibiting group, ph is a phenyl group, and n is an integer of 1 or more)
A hydroxybenzylsilsesquioxane unit in which a hydrogen atom of a hydroxyl group represented by the above is substituted with an acid dissociable, dissolution inhibiting group, or
Formula (IV)
[(XO-ph)2SiO] n
(Wherein X, ph and n are the same as above)
And dihydroxyphenylsiloxane units in which the hydrogen atom of the hydroxyl group represented by the formula (1) is substituted with an acid dissociable, dissolution inhibiting group.
[0014]
The unit (a3) is an alkali-insoluble group-containing siloxane unit having no acid-dissociable group. This unit is a unit in which at least one organic group having no acid dissociable, dissolution inhibiting group as referred to in the unit (a2) and having no alkali-soluble group as defined in the unit (a1) is bonded to the silicon atom of the siloxane group. .
Examples of the organic group include an alkyl group, an aryl group, and an aralkyl group.
Examples of the alkyl group include lower alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, and cyclic alkyl groups such as cyclohexyl group and norbornyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.
Of these, a methyl group, a norbornyl group, a phenyl group, a naphthyl group, and a benzyl group are preferable because these silsesquioxane units can be easily obtained.
[0015]
More specifically,
General formula (V)
[(R) SiO3/2] n
(Wherein R is an alkyl group, aryl group or aralkyl group, and n is an integer of 1 or more)
An alkylsilsesquioxane unit, an arylsilsesquioxane unit or an aralkylsilsesquioxane unit represented by
General formula (VI)
[(R)2SiO] n
(Wherein R and n are the same as above)
And a dialkylsiloxane unit, a diarylsiloxane unit, a diaralkylsiloxane unit, and the like.
[0016]
The proportion of each unit of (a1), (a2) and (a3) in the component (A) of the present invention is considered to be soluble in 2.38 wt% tetramethylammonium hydroxide aqueous solution in consideration of alkali solubility of component (A). (A1) 10 to 70 mol%, preferably 20 to 60 mol%, (a2) 20 to 60 mol%, preferably 30 to 40 because 0 to 1000% / min is preferable in terms of (film reduction amount per unit time). Mol%, (a3) 5-50 mol%, preferably 10-45 mol%.
[0017]
The weight average molecular weight of the component (A) is 1000 to 50000, preferably 5000 to 10000.
[0018]
In addition, as the component (A) of the present invention, first, a copolymer having units (a1) and (a3) is prepared, and a hydroxyl group and a carboxyl group are prepared in the same manner as the preparation of the base resin component of the chemically amplified positive resist. It is obtained by a known reaction in which an alkali-soluble group such as a group is substituted with an acid dissociable, dissolution inhibiting group (for example, a t-boc group).
As the copolymer of (a1) and (a3), a commercially available product can be used, or it can be obtained by the synthesis method described in Japanese Patent No. 2567984. As an example, a copolymer of p-methoxybenzylsilsesquioxane and benzylsilsesquioxane is synthesized using p-methoxybenzyltrichlorosilane and benzyltrichlorosilane as starting materials, and this methoxy group is substituted with a hydroxyl group. Gives a copolymer of p-hydroxybenzylsilsesquioxane and benzylsilsesquioxane.
In this case, benzylsilsesquioxane is exemplified as (a3), but other than that, methyltrichlorosilane, ethyltrichlorosilane, 2-norbornyltrichlorosilane, phenyltrichlorosilane, 1-naphthyltriethoxysilane, and the like. Since it can be purchased as a commercial product, (a3) other than the benzyl group can be synthesized in the same manner.
[0019]
(B) component in this invention is an acid generator which consists of a compound which generate | occur | produces an acid by irradiation of a radiation.
The component (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation, and a known acid generator can be used so far. Preferably, the anion is a fluoroalkylsulfonic acid having 1 to 10 carbon atoms. Ion onium salt.
As the cation of the onium salt, phenyliodonium which may be substituted with a lower alkyl group such as methyl group, ethyl group, propyl, n-butyl group or tert-butyl, or a lower alkoxy group such as methoxy group or ethoxy group, or Examples include sulfonium.
The anion is a fluoroalkylsulfonic acid ion in which part or all of the hydrogen atoms of an alkyl group having 1 to 10 carbon atoms are fluorinated. The longer the carbon number and the smaller the fluorination rate (ratio of fluorine atoms in the alkyl group), the lower the strength of the sulfonic acid. Therefore, all the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are fluorinated. Fluoroalkylsulfonic acid is preferred.
Specifically, trifluoromethanesulfonate or nonafluorobutanesulfonate of diphenyliodonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of bis (4-tert-butylphenyl) iodonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of triphenylsulfonium, Examples include (4-methylphenyl) sulfonium trifluoromethane sulfonate or nonafluorobutane sulfonate. Of these, methanesulfonate or nonafluorobutanesulfonate of triphenylsulfonium is preferable.
These may be used alone or in combination of two or more.
The component (B) can be used at a ratio of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the component (A). If the component (A) is less than this range, image formation cannot be achieved, and if it is too large, a uniform resist solution is not preferable.
[0020]
Various additives other than the above can be blended in the composition of the present invention as necessary. Examples of the additive include organic carboxylic acids, phosphorus oxo acids or derivatives thereof, organic amines, esters of bile acids and acid-dissociable groups, and the like.
[0021]
Examples of the organic carboxylic acid include organic carboxylic acids such as saturated or unsaturated aliphatic carboxylic acids, alicyclic carboxylic acids, and aromatic carboxylic acids, but are not particularly limited. Examples of the saturated aliphatic carboxylic acid include monovalent or polyvalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Examples of unsaturated aliphatic carboxylic acids include acrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, methacrylic acid, 4-pentenoic acid, propiolic acid, 2-butynoic acid, maleic acid, fumaric acid, and acetylene carboxylic acid. Can be mentioned. Examples of the alicyclic carboxylic acid include 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cyclohexyldiacetic acid, and the like. It is done. As aromatic carboxylic acids, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2-hydroxy-3-nitrobenzoic acid, phthalic acid, terephthalic acid, isophthalic acid and other hydroxyl groups, nitro groups, carboxyl groups and other substituents An aromatic carboxylic acid having
[0022]
Specific examples of phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphorous acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester, and other phosphoric acid or phosphorous acid or derivatives thereof. Phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and other phosphonic acids and derivatives such as phosphinic acid, phenylphosphinic acid, etc. But are not limited to derivatives such as phosphinic acids and esters thereof.
[0023]
Examples of organic amines include, but are not limited to, aliphatic amines, aromatic amines, and heterocyclic amines. Aliphatic amines include diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, triisopropanolamine, isopropylamine, dibutylamine, tributylamine, tripentylamine, triethanolamine, Examples include dipropanolamine and tripropanolamine. Aromatic amines include benzylamine, aniline, N-methylaniline, N, N-dimethylaniline, o-methylaniline, m-methylaniline, p-methylaniline, N, N-diethylaniline, diphenylamine, di-p. -Tolylamine and the like. Examples of the heterocyclic amine include pyridine, o-methylpyridine, o-ethylpyridine, 2,3-dimethylpyridine, 4-ethyl-2-methylpyridine, 3-ethyl-4-methylpyridine and the like.
[0024]
Among these, aliphatic amines such as triethanolamine are preferable because they have excellent retention time characteristics.
[0025]
The proportion of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is 0.01 to 5% by weight, preferably 0.02 to 0.2% by weight, based on component (A). Within this range, resolution and sensitivity are preferably improved.
[0026]
The compounding ratio of the organic amine is 0.01 to 5% by weight, preferably 0.02 to 0.2% by weight, based on the component (A). Within this range, the resist pattern shape and sensitivity are preferably improved.
[0027]
Further, in the composition of the present invention, if necessary, a compatible additive such as an antihalation agent or a surfactant for improving coating properties can be appropriately blended.
[0028]
The composition of the present invention is preferably used in the form of a solution by dissolving the above-described components in a suitable solvent. Examples of such solvents include solvents used in conventional resist compositions, such as ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol. , Ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; rings such as dioxane Formula ethers; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionate Can be exemplified Le, esters such as ethyl ethoxypropionate. These may be used alone or in combination of two or more.
[0029]
An example of a preferred method of using the composition of the present invention is as follows. First, a solution of the composition is applied on a substrate such as a silicon wafer with a spinner and dried to form a photosensitive layer, and then a pattern is drawn. Exposure through the photomask. Next, after this is heated after exposure (PEB), and developed with a developer, for example, an alkaline aqueous solution such as an aqueous solution of 1 to 10% by weight of tetramethylammonium hydroxide (TMAH), the exposed portion is dissolved and removed to form a mask pattern. A faithful image (resist pattern) can be obtained. In order to further improve the resolution of the resist pattern, the thickness of the photosensitive layer is reduced to 0.05 to 0.2 μm, and the gap between the substrate and the photosensitive layer obtained by using the composition of the present invention is used. A conventional positive resist, negative resist, or antireflection film may be interposed at a film thickness of 0.35 to 0.7 μm. As exposure light, far ultraviolet rays such as KrF laser, F2A vacuum ultraviolet ray such as a laser, EUV, EB, X-ray or the like can be used.
[0030]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to the following example.
Production Example 1
In Production Example 1, a polysiloxane resin as component (A) in the present invention was produced using the method described in Japanese Patent No. 2567984.
A 500 ml three-necked flask equipped with a stirrer reflux condenser, a dropping funnel and a thermometer was charged with 84.0 g (1.0 mol) of sodium hydrogen carbonate and 400 ml of water, and then p-methoxybenzyltrichlorosilane from the dropping funnel. A mixture of 51.1 g (0.2 mol), phenyltrichlorosilane 19.7 g (0.10 mol) and diethyl ether 100 ml was added dropwise over 2 hours, followed by further aging for 1 hour. After completion of the reaction, the reaction mixture is extracted with ether, the ether is distilled off under reduced pressure, 0.2 g of a 10 wt% potassium hydroxide solution is added to the obtained hydrolysis product, and the mixture is aged at 200 ° C. for 2 hours. As a result, copoly (p-methoxybenzylsilsesquioxane / phenylsilsesquioxane was obtained. The obtained polymer was dissolved in 150 ml of acetonitrile, and 80 g (0.40 mol) of trimethylsilyl iodide was added thereto, and the mixture was refluxed. After stirring for 24 hours, 50 ml of water was added, and the mixture was further stirred for 12 hours under reflux.After cooling, free iodine was reduced with an aqueous sodium hydrogen sulfite solution, the organic layer was separated, and the solvent was distilled off under reduced pressure. Then, the obtained polymer is reprecipitated with acetone and n-hexane and dried by heating under reduced pressure. It is a silicone polymer, to obtain a p- hydroxybenzyl silsesquioxane and phenyl silsesquioxane copolymer represented by the following formula (weight-average molecular weight = 6700).
[0031]
[Chemical 1]
[(HO-ph-CH2) SiO3/2] n ・ [(ph) SiO3/2] m
(Where n / (n + m) = 0.6, m / (n + m) = 0.4, ph is a phenyl group)
[0032]
Next, 30 g of the copolymer is dissolved in 500 g of 1,4-dioxane, 20 g of di-tert-butyl-dicarbonate is added to this solution, and the mixture is completely dissolved by stirring. Then, 50 g of triethylamine is stirred for about 15 minutes. It was dripped over. After completion of dropping, the mixture was stirred as it was for about 4 hours. Next, 20 times the amount of pure water was added to the resulting solution, and the mixture was stirred to precipitate polysiloxane having hydroxyl groups substituted with tert-butoxycarbonyloxy groups. This resin was washed with pure water, dehydrated and dried to obtain 30 g of a polysiloxane resin. In addition, when the ratio of each siloxane unit was analyzed, (a1) hydroxybenzylsilsesquioxane unit 40 mol%, (a3) phenylsilsesquioxane unit 40 mol%, and (a2) tert-butoxycarbonyloxyBenzylThe silsesquioxane unit was 20 mol%.
[0033]
Example 1
(A) component
100 parts by weight of polysiloxane obtained in Production Example
(B) component
2 parts by weight of triphenylsulfonium trifluoromethanesulfonate
(Additive)
0.1 parts by weight of triethanolamine
The above (A), (B) and additives were dissolved in 2000 parts by weight of propylene glycol monomethyl ether monoacetate and then filtered through a membrane filter having a pore size of 0.1 μm to obtain a positive resist solution.
The positive resist solution was spin-coated on a 6-inch silicon wafer and dried at 90 ° C. for 90 seconds on a hot plate to form a resist layer having a thickness of 0.1 μm.
Next, after selectively irradiating KrF excimer laser (248 nm) with a reduced projection exposure apparatus FPA-3000EX3 (manufactured by Canon Inc.), it was heated (PEB) at 110 ° C. for 90 seconds, and 2.38 wt% tetramethylammonium. Paddle development was performed with an aqueous hydroxide solution at 23 ° C. for 60 seconds. Subsequently, it was rinsed with pure water for 30 seconds and finally post-baked at 100 ° C. for 60 seconds to obtain a positive resist pattern.
The exposure amount for obtaining a 0.25 μm line and space pattern in this way is 10 mJ / cm.2In this case, the limiting resolution was 0.20 μm, which was a cross-sectional shape close to a rectangle.
[0034]
Example 2
OFPR800 was applied as a lower resist film to a 6-inch silicon wafer, dried, and then heated on a hot plate at 220 ° C. for 300 seconds to provide an organic layer having a thickness of 0.56 μm. Next, the positive resist solution was spin-coated on the resist layer and dried on a hot plate at 90 ° C. for 90 seconds to form a resist layer having a thickness of 0.1 μm.
When resist patterning was performed in the same manner as in Example 1, the exposure amount for obtaining a 0.25 μm line and space pattern was 10 mJ / cm.2In this case, the limiting resolution was 0.20 μm, which was a cross-sectional shape close to a rectangle.
Subsequently, when the lower layer resist was subjected to reactive ion etching using an oxygen gas as an etchant in a parallel plate type sputter etching apparatus, a 0.20 μm multilayer resist pattern was formed in a good shape.
[0035]
Reference example
After the polysiloxane prepared in the production example is dissolved in propylene glycol monomethyl ether acetate, MgF is prepared by a spinner method.2It spin-coated on the board | substrate (1 mm thickness), and it dried at 90 degreeC for 90 second, and provided the coating film with a film thickness of 0.1 micrometer. Next, using a vacuum ultraviolet spectrophotometer VUV-201 (manufactured by JASCO Corporation), F2The transmittance with a laser (157 nm) was measured. As a result, the absorbance was 5.23 μm.-1Met.
For comparison, as a hydroxystyrene resin, a copolymer of hydroxystyrene 65 mol%, styrene 21.5 mol%, and tert-butyl acrylate 13.5 mol% (weight average molecular weight 13000, Mn / Mw = 2. 0) resin was measured in the same manner, and the absorbance was 6.50 μm.-1Met.
Further, as a methacrylic ester resin, a copolymer of 40 mol% adamantyl methacrylate, 50 mol% α-methacryloyloxy-γ-butyrolactone and 10 mol% acrylic acid (weight average molecular weight 20000, Mn / Mw = 1) .8) was measured in the same manner, and the absorbance was 8.05 μm.-1Met.
[0036]
【The invention's effect】
According to the present invention, it is possible to form a resist pattern having a high resolution and a good cross-sectional shape.2High transparency to laser, F2Provided is a radiation-sensitive resist composition effective in a lithography process for forming an ultrafine resist pattern of 0.15 μm or less using a laser.
Claims (10)
前記（ａ１）のアルカリ可溶性基とシロキサン基のケイ素原子とを連結する基が、アリーレン基及びアラルキレン基から選ばれる少なくとも一つである感放射線レジスト組成物。(A) (a1) an alkali-soluble group-containing siloxane unit, (a2) a siloxane unit obtained by substituting the alkali-soluble group of (a1) with an acid-dissociable, dissolution-inhibiting group, and (a3) an alkali-insoluble group having no acid-dissociable group Ri Na contain an acid generator including the polysiloxane resin, and (B) a compound that generates an acid when exposed to radiation including containing siloxane units,
The alkali-soluble groups as linking the silicon atom of the siloxane group is at least one Der Ru radiation-sensitive resist composition selected from arylene radicals and aralkylene group (a1).
前記（ａ３）の酸解離性基を有しないアルカリ不溶性基が、アリール基及びアラルキル基から選ばれる少なくとも一つである感放射線レジスト組成物。 The radiation-sensitive resist composition, wherein the alkali-insoluble group having no acid dissociable group (a3) is at least one selected from an aryl group and an aralkyl group.
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| JP4141625B2 (en) * | 2000-08-09 | 2008-08-27 | 東京応化工業株式会社 | Positive resist composition and substrate provided with the resist layer |
| KR101004224B1 (en) | 2002-02-01 | 2010-12-27 | 어리어드 파마슈티칼스, 인코포레이티드 | Phosphorus-containing compounds and uses thereof |
| KR20050084283A (en) * | 2002-12-02 | 2005-08-26 | 토쿄오오카코교 가부시기가이샤 | Ladder silicone copolymer |
| JP4361527B2 (en) * | 2002-12-02 | 2009-11-11 | 東京応化工業株式会社 | Chemically amplified silicone-based positive photoresist composition, double-layer resist material using the same, and ladder-type silicone copolymer used therefor |
| JPWO2004111734A1 (en) * | 2003-06-11 | 2006-07-20 | 東京応化工業株式会社 | Positive resist composition, resist laminate, and resist pattern forming method |
| JP5102428B2 (en) * | 2003-11-25 | 2012-12-19 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Waveguide composition and waveguide formed therefrom |
| JP4294521B2 (en) * | 2004-03-19 | 2009-07-15 | 東京応化工業株式会社 | Negative resist composition and pattern forming method using the same |
| JP4494061B2 (en) | 2004-03-30 | 2010-06-30 | 東京応化工業株式会社 | Positive resist composition |
| JP4494060B2 (en) | 2004-03-30 | 2010-06-30 | 東京応化工業株式会社 | Positive resist composition |
| JP4549911B2 (en) * | 2004-03-31 | 2010-09-22 | 東京応化工業株式会社 | Positive resist composition for lift-off |
| WO2008001782A1 (en) * | 2006-06-28 | 2008-01-03 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive resin composition and method of forming pattern |
| EP2094241A4 (en) | 2006-11-14 | 2013-04-17 | Ariad Pharma Inc | Oral formulations |
| US11248086B2 (en) | 2018-05-01 | 2022-02-15 | Tokyo Ohka Kogyo Co., Ltd. | Hard-mask forming composition and method for manufacturing electronic component |
| US11650503B2 (en) | 2018-08-02 | 2023-05-16 | Tokyo Ohka Kogyo Co., Ltd. | Hard mask-forming composition and method for manufacturing electronic component |
| JP7349887B2 (en) | 2019-10-31 | 2023-09-25 | 東京応化工業株式会社 | Composition for forming hard mask and method for producing electronic components |
| JP7361579B2 (en) | 2019-11-22 | 2023-10-16 | 東京応化工業株式会社 | Composition for forming hard masks, method for producing electronic components, and compounds and resins |
| JP7553245B2 (en) | 2020-02-20 | 2024-09-18 | 東京応化工業株式会社 | Composition for forming hard mask, method for producing electronic component, and resin |
| JP7523256B2 (en) | 2020-06-05 | 2024-07-26 | 東京応化工業株式会社 | Composition for forming hard mask and method for producing electronic component |
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| JP3198848B2 (en) * | 1994-12-09 | 2001-08-13 | 信越化学工業株式会社 | Positive resist material |
| JP3505990B2 (en) * | 1997-01-31 | 2004-03-15 | 信越化学工業株式会社 | High molecular silicone compound, chemically amplified positive resist material and pattern forming method |
| JP3533951B2 (en) * | 1997-08-06 | 2004-06-07 | 信越化学工業株式会社 | Polymeric silicone compound, resist material and pattern forming method |
| JP4557328B2 (en) * | 1999-02-01 | 2010-10-06 | 富士フイルム株式会社 | Positive photoresist composition |
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