JP4289121B2 - Chemically amplified positive resist composition - Google Patents
Chemically amplified positive resist composition Download PDFInfo
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- JP4289121B2 JP4289121B2 JP2003367050A JP2003367050A JP4289121B2 JP 4289121 B2 JP4289121 B2 JP 4289121B2 JP 2003367050 A JP2003367050 A JP 2003367050A JP 2003367050 A JP2003367050 A JP 2003367050A JP 4289121 B2 JP4289121 B2 JP 4289121B2
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- carbon atoms
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- acid
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- 239000000203 mixture Substances 0.000 title claims description 39
- -1 3-hydroxy-1-adamantyl Chemical group 0.000 claims description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 37
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- MWMWRSCIFDZZGW-UHFFFAOYSA-N (2-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCOC1=O MWMWRSCIFDZZGW-UHFFFAOYSA-N 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000002596 lactones Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 208000024891 symptom Diseases 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 21
- 239000000178 monomer Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 150000001450 anions Chemical group 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001459 lithography Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RCOCMILJXXUEHU-UHFFFAOYSA-N (4-methylphenyl)-diphenylsulfanium Chemical compound C1=CC(C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 RCOCMILJXXUEHU-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 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 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 0 OC(C1CC2C3C1)*3OC2=O Chemical compound OC(C1CC2C3C1)*3OC2=O 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DCTVCFJTKSQXED-UHFFFAOYSA-N (2-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C(C)=C)C2C3 DCTVCFJTKSQXED-UHFFFAOYSA-N 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 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
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N 4-hydroxy-4-methyl-2-oxanone Chemical compound CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-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
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-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
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 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
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- MXHVVCUYXQKCCL-UHFFFAOYSA-M silver;3-nitro-2,4,6-tri(propan-2-yl)benzenesulfonate Chemical compound [Ag+].CC(C)C1=CC(C(C)C)=C(S([O-])(=O)=O)C(C(C)C)=C1[N+]([O-])=O MXHVVCUYXQKCCL-UHFFFAOYSA-M 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 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
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HUDHSZARDMJQOQ-UHFFFAOYSA-N (1-methylcyclohexyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1C(=O)OC1(C)CCCCC1 HUDHSZARDMJQOQ-UHFFFAOYSA-N 0.000 description 1
- WDKWRJUAIFFOII-UHFFFAOYSA-N (2-ethyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C1C4CC(C=C4)C1)C2C3 WDKWRJUAIFFOII-UHFFFAOYSA-N 0.000 description 1
- OJGSGTWNQWAFBE-UHFFFAOYSA-N (2-methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C2)CC3CC1C(C)(OC(=O)C1C4CC(C=C4)C1)C2C3 OJGSGTWNQWAFBE-UHFFFAOYSA-N 0.000 description 1
- UGVRGVIRHLMDHI-UHFFFAOYSA-N (3,5-dihydroxy-1-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3(O)CC1(O)CC2(OC(=O)C=C)C3 UGVRGVIRHLMDHI-UHFFFAOYSA-N 0.000 description 1
- DKDKCSYKDZNMMA-UHFFFAOYSA-N (3-hydroxy-1-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1(O)CC2(OC(=O)C=C)C3 DKDKCSYKDZNMMA-UHFFFAOYSA-N 0.000 description 1
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- FRULOWHFMKCMSZ-UHFFFAOYSA-N (3-methyl-2-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1(C)CCOC1=O FRULOWHFMKCMSZ-UHFFFAOYSA-N 0.000 description 1
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- JJRDPNRWFSHHKJ-UHFFFAOYSA-N n-methyl-n-pentylpentan-1-amine Chemical compound CCCCCN(C)CCCCC JJRDPNRWFSHHKJ-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical class C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OXDRMTKMIYRQLY-UHFFFAOYSA-N octylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[NH3+] OXDRMTKMIYRQLY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
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- 239000001230 potassium iodate Substances 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- JCJNUSDBRRKQPC-UHFFFAOYSA-M tetrahexylazanium;hydroxide Chemical compound [OH-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC JCJNUSDBRRKQPC-UHFFFAOYSA-M 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
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- BFPOZPZYPNVMHU-UHFFFAOYSA-M trimethyl-[3-(trifluoromethyl)phenyl]azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC(C(F)(F)F)=C1 BFPOZPZYPNVMHU-UHFFFAOYSA-M 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Description
本発明は、半導体の微細加工に用いられる化学増幅型のレジスト組成物及び該組成物に用いることができるアクリル樹脂に関するものである。 The present invention relates to a chemically amplified resist composition used for fine processing of semiconductors and an acrylic resin that can be used for the composition.
半導体の微細加工には、通常、レジスト組成物を用いたリソグラフィプロセスが採用されており、リソグラフィにおいては、レイリー(Rayleigh)の回折限界の式で表されるように、原理的には露光波長が短いほど解像度を上げることが可能である。半導体の製造に用いられるリソグラフィ用露光光源は、波長436nmのg線、波長365nmのi線、波長248nmのKrFエキシマレーザー、波長193nmのArFエキシマレーザーと、年々短波長になってきており、次世代の露光光源として、波長157nmのF2エキシマレーザーが有望視され、その後は波長13nm以下の軟X線(EUV)が光源として提案されている。 In microfabrication of semiconductors, a lithography process using a resist composition is usually employed. In lithography, in principle, the exposure wavelength is expressed as expressed by the Rayleigh diffraction limit equation. The shorter the resolution, the higher the resolution. The exposure light source for lithography used in the manufacture of semiconductors has become a shorter wavelength year by year: g-line with a wavelength of 436 nm, i-line with a wavelength of 365 nm, KrF excimer laser with a wavelength of 248 nm, ArF excimer laser with a wavelength of 193 nm As an exposure light source, an F 2 excimer laser with a wavelength of 157 nm is considered promising, and thereafter soft X-rays (EUV) with a wavelength of 13 nm or less have been proposed as a light source.
エキシマレーザー等の、g線、i線より短い波長の光源は、照度が低いため、レジストの感度を高める必要があることから、スルホニウム塩等の塩から露光により発生する酸の触媒作用を利用し、その酸により解裂する基を有するアクリル樹脂を含有するいわゆる化学増幅型レジストが用いられている(例えば、特許文献1参照)。
しかしながら、従来公知の化学増幅型レジスト組成物より、露光時間をさらに短くするために、感度の高いものが必要となった。
Since light sources with wavelengths shorter than g-line and i-line, such as excimer laser, have low illuminance, it is necessary to increase the sensitivity of the resist. Therefore, the catalytic action of acid generated by exposure from a salt such as sulfonium salt is used. A so-called chemically amplified resist containing an acrylic resin having a group that can be cleaved by the acid is used (see, for example, Patent Document 1).
However, in order to further shorten the exposure time than conventionally known chemically amplified resist compositions, those having high sensitivity are required.
本発明の目的は、ArFやKrFなどのエキシマレーザーリソグラフィに適した、解像度などの各種のレジスト性能が良好であるとともに、特に改善された感度を与える化学増幅型のポジ型レジスト組成物及び該組成物に好適に用いられるアクリル樹脂を提供することにある。 An object of the present invention is to provide a chemically amplified positive resist composition suitable for excimer laser lithography such as ArF and KrF, which has various resist performances such as resolution, and gives particularly improved sensitivity, and the composition It is providing the acrylic resin used suitably for a thing.
本発明者らは、鋭意検討を加えた結果、特定の重合単位を有し、それ自身はアルカリ水溶液に不溶又は難溶であるが、酸の作用でアルカリ水溶液に可溶となる樹脂と、酸発生剤とを含有する化学増幅型ポジ型レジスト組成物が、解像度などの各種のレジスト性能が良好であるとともに、特に改善された感度を与えることを見出し、かつ特定の構造のアクリル樹脂が該組成物に好適に用いることができることを見出し、本発明を完成した。 As a result of intensive studies, the present inventors have a specific polymer unit, which is itself insoluble or hardly soluble in an alkaline aqueous solution, but is soluble in an alkaline aqueous solution by the action of an acid, and an acid. It has been found that a chemically amplified positive resist composition containing a generator has various resist performances such as resolution and provides particularly improved sensitivity, and an acrylic resin having a specific structure is used in the composition. The present invention was completed by finding out that it can be suitably used for products.
すなわち、本発明は、〔1〕下式(I)で示される重合単位を有するアクリル樹脂に係るものである。
(式中、R1は、炭素数1〜4の分岐していてもよいアルキレン基を表し、R2は、炭素数1〜4の分岐していてもよいアルキル基を表し、R3は水素原子又はメチル基を表す。)
That is, the present invention relates to [1] an acrylic resin having a polymerization unit represented by the following formula (I).
(Wherein R 1 represents an optionally branched alkylene group having 1 to 4 carbon atoms, R 2 represents an optionally branched alkyl group having 1 to 4 carbon atoms, and R 3 represents hydrogen. Represents an atom or a methyl group.)
さらに、本発明は、〔2〕前記式(I)で示される重合単位を有し、それ自身はアルカリ水溶液に不溶又は難溶であるが、酸の作用でアルカリ水溶液に可溶となる樹脂、並びに酸発生剤を含有するレジスト組成物に係るものである。 Furthermore, the present invention provides [2] a resin having a polymerization unit represented by the formula (I), which itself is insoluble or hardly soluble in an aqueous alkali solution, but becomes soluble in an aqueous alkali solution by the action of an acid, In addition, the present invention relates to a resist composition containing an acid generator.
本発明の化学増幅型のポジ型レジスト組成物は、改善された感度を与え、解像度などのレジスト諸性能も良好である。したがって、この組成物は、ArFやKrFなどのエキシマレーザーリソグラフィに適しており、それによって高い性能のレジストパターンを与える。 The chemically amplified positive resist composition of the present invention provides improved sensitivity and good resist performance such as resolution. Therefore, this composition is suitable for excimer laser lithography such as ArF and KrF, thereby giving a high performance resist pattern.
本発明のアクリル樹脂について説明する。
この樹脂は、式(I)で示される重合単位を有することを特徴とする。
(式中、R1は、炭素数1〜4の分岐していてもよいアルキレン基を表し、R2は、炭素数1〜4の分岐していてもよいアルキル基を表し、R3は水素原子又はメチル基を表す。)
The acrylic resin of the present invention will be described.
This resin is characterized by having polymerized units represented by the formula (I).
(Wherein R 1 represents an optionally branched alkylene group having 1 to 4 carbon atoms, R 2 represents an optionally branched alkyl group having 1 to 4 carbon atoms, and R 3 represents hydrogen. Represents an atom or a methyl group.)
式(I)においてR1で示される炭素数1〜4の分岐してもよい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、イソプロピレン基、ブチレン基、tert−ブチレン基などが挙げられる。
式(I)においてR2で示される炭素数1〜4の分岐してもよいアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert−ブチル基などが挙げられる。
Examples of the alkylene group having 1 to 4 carbon atoms, which is represented by R 1 in the formula (I), include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a tert-butylene group. .
Examples of the optionally branched alkyl group having 1 to 4 carbon atoms represented by R 2 in the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group.
本発明に用いられる式(I)で示される重合単位に導く化合物は、例えば、以下のように合成することができる。先ず、対応するハライドアルキルアルカン(ハライドとして、Cl、Br、I)にリチウムもしくはマグネシウムを作用させ、アルキル化剤とし、2−アダマンタノンと作用させ、対応する2−(アルコキシアルキル)−2−アダマンタノールを合成する。その後、このアルコールを、トリエチルアミン等のアミン存在下に(メタ)アクリル酸ハライドを作用させて合成することができる。 The compound leading to the polymerization unit represented by the formula (I) used in the present invention can be synthesized, for example, as follows. First, lithium or magnesium is allowed to act on a corresponding alkyl halide alkane (as a halide, Cl, Br, I), an alkylating agent is allowed to act on 2-adamantanone, and the corresponding 2- (alkoxyalkyl) -2-adaman Synthesizes tanol. Thereafter, this alcohol can be synthesized by reacting a (meth) acrylic acid halide in the presence of an amine such as triethylamine.
例として、(メタ)アクリル酸−2−(4−メトキシブタニル)−2−アダマンタンの場合は、以下のように合成することができる。先ず、1−ブロモ−4−メトキシブタンにリチウムを作用させ、4−メトキシブチルリチウムとし、2−アダマンタノンと作用させ、2−(4−メトキシブタニル)−2−アダマンタノールを合成する。その後、このアルコールを、1−メチルピペリジン存在下に(メタ)アクリル酸クロライドと作用させて合成することができる。 As an example, in the case of (meth) acrylic acid-2- (4-methoxybutanyl) -2-adamantane, it can be synthesized as follows. First, lithium is allowed to act on 1-bromo-4-methoxybutane to form 4-methoxybutyllithium, which is then reacted with 2-adamantanone to synthesize 2- (4-methoxybutanyl) -2-adamantanol. Thereafter, this alcohol can be synthesized by reacting with (meth) acrylic acid chloride in the presence of 1-methylpiperidine.
式(I)で示される重合単位に導くモノマーとして、具体的には下式のようなモノマーが挙げられる。
Specific examples of the monomer leading to the polymerization unit represented by the formula (I) include monomers represented by the following formula.
本発明のレジスト組成物は、前記式(I)で示される重合単位を有し、それ自身はアルカリ水溶液に不溶又は難溶であるが、酸の作用でアルカリ水溶液に可溶となる樹脂、並びに酸発生剤を含有することを特徴とする。
該樹脂は、具体的には、酸の作用により一部の基が解裂し、解裂後はアルカリ水溶液に可溶性となるものである。
The resist composition of the present invention has a polymer unit represented by the above formula (I) and is itself insoluble or hardly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution by the action of an acid, and It contains an acid generator.
Specifically, in the resin, some groups are cleaved by the action of an acid and become soluble in an alkaline aqueous solution after cleavage.
また、本発明のレジスト組成物に用いる樹脂の原料として、前記式(I)で示される重合単位を導くモノマーと共に、必要に応じて従来から知られている酸に不安定な基を持つ他のモノマーを用いてもよい。
このような、アルカリ現像液に対しては溶解抑止能を持つが、酸に対しては不安定な基は、公知の各種保護基であることができる。例えば、tert−ブチル;tert−ブトキシカルボニルもしくはtert−ブトキシカルボニルメチルのような4級炭素が酸素原子に結合する基;テトラヒドロ−2−ピラニル、テトラヒドロ−2−フリル、1−エトキシエチル、1−(2−メチルプロポキシ)エチル、1−(2−メトキシエトキシ)エチル、1−(2−アセトキシエトキシ)エチル、1−〔2−(1−アダマンチルオキシ)エトキシ〕エチルもしくは1−〔2−(1−アダマンタンカルボニルオキシ)エトキシ〕エチルのようなアセタール型の基;又は3−オキソシクロヘキシル、4−メチルテトラヒドロ−2−ピロン−4−イル(メバロニックラクトンから導かれる)もしくは2−メチル−2−アダマンチル、2−エチル−2−アダマンチルのような非芳香族環状化合物の残基などが挙げられる。
これらの基がフェノール性水酸基の水素原子又はカルボキシル基の水素原子に置換することになる。これらの保護基は、公知の保護基導入反応によって、フェノール性水酸基又はカルボキシル基を有するアルカリ可溶性樹脂に導入することができる。また、このような基を有する不飽和化合物を一つのモノマーとする共重合によって、上記の樹脂を得ることもできる。
In addition, as a raw material for the resin used in the resist composition of the present invention, together with a monomer that leads to the polymerization unit represented by the formula (I), other known acid-labile groups may be used as necessary. Monomers may be used.
Such a group capable of inhibiting dissolution with an alkali developer but unstable with respect to an acid can be various known protecting groups. For example, tert-butyl; a group in which a quaternary carbon such as tert-butoxycarbonyl or tert-butoxycarbonylmethyl is bonded to an oxygen atom; tetrahydro-2-pyranyl, tetrahydro-2-furyl, 1-ethoxyethyl, 1- ( 2-methylpropoxy) ethyl, 1- (2-methoxyethoxy) ethyl, 1- (2-acetoxyethoxy) ethyl, 1- [2- (1-adamantyloxy) ethoxy] ethyl or 1- [2- (1- Acetal type groups such as adamantanecarbonyloxy) ethoxy] ethyl; or 3-oxocyclohexyl, 4-methyltetrahydro-2-pyron-4-yl (derived from mevalonic lactone) or 2-methyl-2-adamantyl , Residues of non-aromatic cyclic compounds such as 2-ethyl-2-adamantyl, etc. It is below.
These groups are substituted with a hydrogen atom of a phenolic hydroxyl group or a hydrogen atom of a carboxyl group. These protecting groups can be introduced into an alkali-soluble resin having a phenolic hydroxyl group or a carboxyl group by a known protecting group introduction reaction. Moreover, said resin can also be obtained by the copolymerization which uses the unsaturated compound which has such a group as one monomer.
本発明の組成物における樹脂は、前記式(I)で示される重合単位の他に、酸の作用により解裂しないか又は解裂しにくい他の重合単位を含有することも可能である。含有し得る他の重合単位としては、例えば、アクリル酸やメタクリル酸のような遊離のカルボン酸基を有するモノマーの重合単位、無水マレイン酸や無水イタコン酸のような脂肪族不飽和ジカルボン酸無水物の重合単位、2−ノルボルネンの重合単位、(メタ)アクリロニトリルの重合単位、各種(メタ)アクリル酸エステル類の重合単位などを挙げることができる。
ArF露光の場合は光吸収が大きくて好ましくはないが、KrF露光の場合は光吸収の問題が無いので、ヒドロキシスチレンの重合単位を用いることができる。
The resin in the composition of the present invention may contain other polymerized units that are not cleaved or hardly cleaved by the action of an acid in addition to the polymerized units represented by the formula (I). Examples of other polymer units that can be contained include polymer units of monomers having a free carboxylic acid group such as acrylic acid and methacrylic acid, and aliphatic unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Polymerization units, 2-norbornene polymerization units, (meth) acrylonitrile polymerization units, various (meth) acrylic acid ester polymerization units, and the like.
In the case of ArF exposure, light absorption is large, which is not preferable. However, in the case of KrF exposure, there is no problem of light absorption, so that a polymerized unit of hydroxystyrene can be used.
特に、本発明における樹脂において、式(I)で示される重合単位のほかに、(メタ)アクリル酸3−ヒドロキシ−1−アダマンチルから導かれる重合単位、(メタ)アクリル酸3、5−ジヒドロキシ−1−アダマンチルから導かれる重合単位、ラクトン環がアルキルで置換されていてもよい(メタ)アクリロイロキシ−γ−ブチロラクトンから導かれる重合単位、下式(IIa)で示される重合単位及び(IIb)で示される重合単位からなる群から選ばれた少なくとも1種の重合単位を含有することは、レジストの基板への接着性の点で好ましい。 In particular, in the resin in the present invention, in addition to the polymerization unit represented by the formula (I), a polymerization unit derived from 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acrylic acid 3,5-dihydroxy- Polymer units derived from 1-adamantyl, polymer units derived from (meth) acryloyloxy-γ-butyrolactone, the lactone ring of which may be substituted with alkyl, polymer units represented by the following formula (IIa) and (IIb) It is preferable from the viewpoint of the adhesiveness of the resist to the substrate that it contains at least one polymer unit selected from the group consisting of polymer units.
(式中、R4、R6は、互いに独立に水素原子又はメチル基を表し、R5、R7は、メチル基を表し、nは0〜3の整数を表す。) (In the formula, R 4 and R 6 each independently represent a hydrogen atom or a methyl group, R 5 and R 7 represent a methyl group, and n represents an integer of 0 to 3.)
(メタ)アクリル酸3−ヒドロキシ−1−アダマンチル、(メタ)アクリル酸3、5−ジヒドロキシ−1−アダマンチルは、市販されているが、例えば対応するヒドロキシアダマンタンを(メタ)アクリル酸又はそのハライドと反応させることにより、製造することもできる。
また、(メタ)アクリロイロキシ−γ−ブチロラクトンは、ラクトン環がアルキルで置換されていてもよいα−もしくはβ−ブロモ−γ−ブチロラクトンにアクリル酸もしくはメタクリル酸を反応させるか、又はラクトン環がアルキルで置換されていてもよいα−もしくはβ−ヒドロキシ−γ−ブチロラクトンにアクリル酸ハライドもしくはメタクリル酸ハライドを反応させることにより製造できる。
式(IIa)、(IIb)で示される重合単位に導くためのモノマーは、具体的には例えば、次のような水酸基を有する脂環式ラクトンの(メタ)アクリル酸エステル、それらの混合物等が挙げられる。これらのエステルは、例えば対応する水酸基を有する脂環式ラクトンと(メタ)アクリル酸類との反応により製造し得る(例えば特開2000−26446号公報)。
(Meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid 3,5-dihydroxy-1-adamantyl are commercially available. For example, the corresponding hydroxyadamantane is converted to (meth) acrylic acid or a halide thereof. It can also be produced by reacting.
In addition, (meth) acryloyloxy-γ-butyrolactone is obtained by reacting α- or β-bromo-γ-butyrolactone, in which the lactone ring may be substituted with alkyl, with acrylic acid or methacrylic acid, or the lactone ring is alkyl. It can be produced by reacting an optionally substituted α- or β-hydroxy-γ-butyrolactone with an acrylic acid halide or methacrylic acid halide.
Specific examples of the monomer for leading to the polymerization units represented by the formulas (IIa) and (IIb) include, for example, (meth) acrylic acid esters of alicyclic lactones having the following hydroxyl groups, and mixtures thereof. Can be mentioned. These esters can be produced, for example, by reacting an alicyclic lactone having a corresponding hydroxyl group with (meth) acrylic acids (for example, JP-A No. 2000-26446).
(メタ)アクリル酸3−ヒドロキシ−1−アダマンチル、(メタ)アクリル酸3、5−ジヒドロキシ−1−アダマンチルから導かれる重合単位、α−(メタ)アクリロイロキシ−γ−ブチロラクトンから導かれる重合単位、β−(メタ)アクリロイロキシ−γ−ブチロラクトンから導かれる重合単位、式(IIa)、(IIb)で示される重合単位は、それらのいずれかを樹脂中に存在させることにより、それを含むレジストの基板への接着性が向上するだけでなく、レジストの解像性の向上にも寄与する。 Polymer unit derived from 3-hydroxy-1-adamantyl (meth) acrylate, 3, methacrylic acid 3,5-dihydroxy-1-adamantyl, polymer unit derived from α- (meth) acryloyloxy-γ-butyrolactone, β -A polymer unit derived from (meth) acryloyloxy-γ-butyrolactone, a polymer unit represented by the formulas (IIa) and (IIb), is present in the resin by containing any of them in the resin. This not only improves the adhesion of the resist, but also contributes to the improvement of the resolution of the resist.
ここで、(メタ)アクリロイロキシ−γ−ブチロラクトンとしては、例えば、α−アクリロイロキシ−γ−ブチロラクトン、α−メタクリロイロキシ−γ−ブチロラクトン、α−アクリロイロキシ−β,β−ジメチル−γ−ブチロラクトン、α−メタクリロイロキシ−β,β−ジメチル−γ−ブチロラクトン、α−アクリロイロキシ−α−メチル−γ−ブチロラクトン、α−メタクリロイロキシ−α−メチル−γ−ブチロラクトン、β−アクリロイロキシ−γ−ブチロラクトン、β−メタクリロイロキシ−γ−ブチロラクトン、β−メタクリロイロキシ−α−メチル−γ−ブチロラクトンなどが挙げられる。 Here, as (meth) acryloyloxy-γ-butyrolactone, for example, α-acryloyloxy-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, α-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α- Methacryloyloxy-β, β-dimethyl-γ-butyrolactone, α-acryloyloxy-α-methyl-γ-butyrolactone, α-methacryloyloxy-α-methyl-γ-butyrolactone, β-acryloyloxy-γ-butyrolactone, β- Examples include methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-α-methyl-γ-butyrolactone, and the like.
また、2−ノルボルネンの重合単位を含む樹脂は、その主鎖に直接脂環基を有するために頑丈な構造となり、ドライエッチング耐性に優れるという特性を示す。2−ノルボルネンの重合単位は、例えば対応する2−ノルボルネンの他に無水マレイン酸や無水イタコン酸のような脂肪族不飽和ジカルボン酸無水物を併用したラジカル重合により主鎖へ導入し得る。したがって、2−ノルボルネンの重合単位は、その二重結合が開いて形成されるものであり式(V)で表すことができる。また、脂肪族不飽和ジカルボン酸無水物の重合単位である無水マレイン酸の重合単位、無水イタコン酸の重合単位は、それらの二重結合が開いて形成されるものであり、それぞれ式(VI)及び(VII)で表すことができる。 Moreover, since the resin containing the polymerization unit of 2-norbornene has an alicyclic group directly in the main chain, it has a sturdy structure and exhibits excellent dry etching resistance. The polymer unit of 2-norbornene can be introduced into the main chain by radical polymerization using, in addition to the corresponding 2-norbornene, an aliphatic unsaturated dicarboxylic acid anhydride such as maleic anhydride or itaconic anhydride. Therefore, the polymerization unit of 2-norbornene is formed by opening the double bond, and can be represented by the formula (V). In addition, a polymerization unit of maleic anhydride, a polymerization unit of itaconic anhydride, which is a polymerization unit of an aliphatic unsaturated dicarboxylic acid anhydride, is formed by opening their double bond, and each has formula (VI) And (VII).
ここで、式(V)中のR8及びR9は、互いに独立に、水素原子、炭素数1〜3のアルキル、炭素数1〜3のヒドロキシアルキル、カルボキシル、シアノもしくは基−COOZ(Zはアルコール残基である)を表すか、又はR8とR9が結合して、−C(=O)OC(=O)−で示されるカルボン酸無水物残基を形成することもできる。
R8及び/又はR9がアルキルである場合の具体例としては、メチル、エチル、プロピルなどが挙げられ、同じくヒドロキシアルキルである場合の具体例としては、ヒドロキシメチル、2−ヒドロキシエチルなどが挙げられる。
R8及び/又はR9が基−COOZである場合は、カルボキシルがエステルとなったものであり、Zに相当するアルコール残基としては、例えば、置換されていてもよい炭素数1〜8程度のアルキル、2−オキソオキソラン−3−又は−4−イルなどを挙げることができ、ここにアルキルの置換基としては、水酸基や脂環式炭化水素残基などが挙げられる。
そこで、R8及び/又はR9が−COOZで示されるカルボン酸エステル残基である場合の具体例としては、メトキシカルボニル、エトキシカルボニル、2−ヒドロキシエトキシカルボニル、tert−ブトキシカルボニル、2−オキソオキソラン−3−イルオキシカルボニル、2−オキソオキソラン−4−イルオキシカルボニル、1,1,2−トリメチルプロポキシカルボニル、1−シクロヘキシル−1−メチルエトキシカルボニル、1−(4−メチルシクロヘキシル)−1−メチルエトキシカルボニル、1−(1−アダマンチル)−1−メチルエトキシカルボニルなどが挙げられる。
Here, R 8 and R 9 in formula (V) are each independently a hydrogen atom, alkyl having 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, carboxyl, cyano, or a group —COOZ (Z is Which is an alcohol residue), or R 8 and R 9 can be combined to form a carboxylic acid anhydride residue represented by —C (═O) OC (═O) —.
Specific examples of when R 8 and / or R 9 are alkyl include methyl, ethyl, propyl and the like, and specific examples of the case where R 8 and / or R 9 are also hydroxyalkyl include hydroxymethyl, 2-hydroxyethyl and the like. It is done.
When R 8 and / or R 9 is a group —COOZ, carboxyl is an ester, and the alcohol residue corresponding to Z is, for example, about 1 to 8 carbon atoms that may be substituted. Alkyl, 2-oxooxolan-3- or -4-yl, and the like. Examples of the alkyl substituent include a hydroxyl group and an alicyclic hydrocarbon residue.
Thus, specific examples of R 8 and / or R 9 being a carboxylate residue represented by —COOZ include methoxycarbonyl, ethoxycarbonyl, 2-hydroxyethoxycarbonyl, tert-butoxycarbonyl, 2-oxooxo Lan-3-yloxycarbonyl, 2-oxooxolan-4-yloxycarbonyl, 1,1,2-trimethylpropoxycarbonyl, 1-cyclohexyl-1-methylethoxycarbonyl, 1- (4-methylcyclohexyl) -1 -Methylethoxycarbonyl, 1- (1-adamantyl) -1-methylethoxycarbonyl and the like.
また式(V)で示される重合単位に導くためのモノマーとして、具体的には例えば、次のような化合物を挙げることができる。 Specific examples of the monomer for leading to the polymerization unit represented by the formula (V) include the following compounds.
2−ノルボルネン、
2−ヒドロキシ−5−ノルボルネン、
5−ノルボルネン−2−カルボン酸、
5−ノルボルネン−2−カルボン酸メチル、
5−ノルボルネン−2−カルボン酸−t−ブチル、
5−ノルボルネン−2−カルボン酸1−シクロヘキシル−1−メチルエチル、
5−ノルボルネン−2−カルボン酸1−(4−メチルシクロヘキシル)−1−メチルエチル、
5−ノルボルネン−2−カルボン酸1−(4−ヒドロキシシクロヘキシル)−1−メチルエチル、
5−ノルボルネン−2−カルボン酸1−メチル−1−(4−オキソシクロヘキシル)エチル、
5−ノルボルネン−2−カルボン酸1−(1−アダマンチル)−1−メチルエチル、
5−ノルボルネン−2−カルボン酸1−メチルシクロヘキシル、
5−ノルボルネン−2−カルボン酸2−メチル−2−アダマンチル、
5−ノルボルネン−2−カルボン酸2−エチル−2−アダマンチル、
5−ノルボルネン−2−カルボン酸2−ヒドロキシ−1−エチル、
5−ノルボルネン−2−メタノール、
5−ノルボルネン−2,3−ジカルボン酸無水物など。
2-norbornene,
2-hydroxy-5-norbornene,
5-norbornene-2-carboxylic acid,
Methyl 5-norbornene-2-carboxylate,
5-norbornene-2-carboxylic acid-t-butyl,
1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate,
1- (4-methylcyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate,
1- (4-hydroxycyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate,
1-methyl-1- (4-oxocyclohexyl) ethyl 5-norbornene-2-carboxylate,
1- (1-adamantyl) -1-methylethyl 5-norbornene-2-carboxylate,
1-methylcyclohexyl 5-norbornene-2-carboxylate,
2-methyl-2-adamantyl 5-norbornene-2-carboxylate,
2-ethyl-2-adamantyl 5-norbornene-2-carboxylate,
2-hydroxy-1-ethyl 5-norbornene-2-carboxylate,
5-norbornene-2-methanol,
5-norbornene-2,3-dicarboxylic anhydride and the like.
本発明で用いる樹脂は、パターニング露光用の放射線の種類や酸に不安定な基の種類などによっても変動するが、一般には、樹脂の全重合単位中の式(I)で示される重合単位を10〜80%の範囲で含有することが好ましい。
そして、酸に不安定な基として式(I)の重合単位を用いる場合は、該重合単位が樹脂の全重合単位のうち15%以上となるようにすることが有利である。
また、式(I)で示される重合単位に加えて、酸の作用で解裂しにくい他の重合単位、例えば、(メタ)アクリル酸3−ヒドロキシ−1−アダマンチルから導かれる重合単位、(メタ)アクリル酸3、5−ジヒドロキシ−1−アダマンチル、α−(メタ)アクリロイロキシ−γ−ブチロラクトンから導かれる重合単位、β−(メタ)アクリロイロキシ−γ−ブチロラクトンから導かれる重合単位、式(IIa)、(IIb)で示される重合単位、式(V)で示される重合単位、脂肪族不飽和ジカルボン酸無水物から導かれる重合単位である式(VI)で示される無水マレイン酸から導かれる重合単位、式(VII)で示される無水イタコン酸から導かれる重合単位などを存在させる場合は、それらの重合単位と式(I)で示される重合単位との合計が、樹脂の全重合単位のうち20〜90%の範囲となるようにすることが好ましい。
The resin used in the present invention varies depending on the type of radiation used for patterning exposure and the type of acid-labile group, but in general, the polymer units represented by the formula (I) in all polymer units of the resin are used. It is preferable to contain in 10 to 80% of range.
When the polymerized unit of the formula (I) is used as the acid labile group, it is advantageous that the polymerized unit is 15% or more of the total polymerized units of the resin.
Further, in addition to the polymer unit represented by the formula (I), other polymer units that are not easily cleaved by the action of an acid, for example, polymer units derived from 3-hydroxy-1-adamantyl (meth) acrylate, (meta ) 3,5-dihydroxy-1-adamantyl acrylate, polymerized units derived from α- (meth) acryloyloxy-γ-butyrolactone, polymerized units derived from β- (meth) acryloyloxy-γ-butyrolactone, formula (IIa), A polymerization unit represented by (IIb), a polymerization unit represented by formula (V), a polymerization unit derived from maleic anhydride represented by formula (VI) which is a polymerization unit derived from an aliphatic unsaturated dicarboxylic acid anhydride, When polymerized units derived from itaconic anhydride represented by the formula (VII) are present, these polymerized units and polymerized units represented by the formula (I) Meter is preferably to be 20 to 90 percent range of the total polymerization units of the resin.
なお、2−ノルボルネン類及び脂肪族不飽和ジカルボン酸無水物を共重合モノマーとする場合には、これらは重合しにくい傾向があるので、この点を考慮し、これらは過剰に使用することが好ましい。 In addition, when 2-norbornenes and aliphatic unsaturated dicarboxylic acid anhydrides are used as copolymerization monomers, they tend to be difficult to polymerize. Therefore, in consideration of this point, it is preferable to use them excessively. .
本発明のレジスト組成物を構成する酸発生剤としては、その物質自体に、あるいはその物質を含むレジスト組成物に、光や電子線などの放射線を作用させることにより、その物質が分解して酸を発生する。酸発生剤から発生する酸が前記樹脂に作用して、その樹脂中に存在する酸の作用で開裂する基を開裂させることになる。 As the acid generator constituting the resist composition of the present invention, the substance is decomposed by the action of radiation such as light or electron beam on the substance itself or on the resist composition containing the substance. Is generated. The acid generated from the acid generator acts on the resin and cleaves the group that is cleaved by the action of the acid present in the resin.
本発明における酸発生剤として、下式(IIIa)、(IIIb)又は(IIIc)が挙げられる。
(式中、P1〜P3は、互いに独立に、水素原子、水酸基、炭素数1〜6のアルキル基又は炭素数1〜6のアルコキシ基を表す。Z−は、対イオンを表す。)
(式中、P4、P5は、互いに独立に、水素原子、水酸基、炭素数1〜6のアルキル基又は炭素数1〜6のアルコキシ基を表す。Z−は、前記と同じ定義である。)
(式中、P6、P7は、互いに独立に、炭素数1〜6のアルキル基、炭素数3〜10のシクロアルキル基、又はP6とP7とが結合して炭素数3〜7の二価の脂肪族炭化水素基を表し、隣接するS+と共に環を形成する。該脂肪式炭化水素基は、該脂環式炭化水素基の少なくとも1個の−CH2−がカルボニル基、酸素原子もしくは硫黄原子に置換されていてもよい。P8が水素原子を表し、P9が炭素数1〜6のアルキル基、炭素数3〜10のシクロアルキル基もしくは置換されていても良い芳香環基を表すか、又はP8とP9とが結合して二価の脂肪族炭化水素基を表し、隣接する−CHCO−と共に環を形成する。Z−は、前記と同じ定義である。)
Examples of the acid generator in the present invention include the following formula (IIIa), (IIIb), or (IIIc).
(Wherein, P 1 to P 3 are each independently, .Z representing hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms - represents a counter ion.)
(In the formula, P 4 and P 5 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z − has the same definition as described above. .)
(Wherein P 6 and P 7 are independently of each other an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or P 6 and P 7 bonded to each other to form 3 to 7 carbon atoms. The divalent aliphatic hydrocarbon group is formed together with adjacent S + , and the aliphatic hydrocarbon group is a group in which at least one —CH 2 — of the alicyclic hydrocarbon group is a carbonyl group, May be substituted by an oxygen atom or a sulfur atom, P 8 represents a hydrogen atom, and P 9 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an optionally substituted fragrance Represents a cyclic group, or P 8 and P 9 are bonded to each other to represent a divalent aliphatic hydrocarbon group, and form a ring together with the adjacent —CHCO—, where Z − is as defined above. )
式(IIIa)におけるP1、P2、P3が、アルキル基又はアルコキシ基である場合に、炭素数3以上のときは直鎖でも分岐していてもよい。
式(IIIb)におけるP4及びP5が、アルキル基又はアルコキシ基である場合に、炭素数3以上のときは直鎖でも分岐していてもよい。
P1、P2、P3、P4及びP5の具体的なアルキル基の例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert−ブチル基、ペンチル基、ヘキシル基などが挙げられ、アルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などが挙げられる。
When P 1 , P 2 , and P 3 in formula (IIIa) are an alkyl group or an alkoxy group, they may be linear or branched when they have 3 or more carbon atoms.
When P 4 and P 5 in formula (IIIb) are an alkyl group or an alkoxy group, they may be linear or branched when they have 3 or more carbon atoms.
Examples of specific alkyl groups of P 1 , P 2 , P 3 , P 4 and P 5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
P6、P7、P9がアルキル基の場合には、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert−ブチル基、ペンチル基、ヘキシル基などが挙げられ、またP6、P7、P9がシクロアルキル基の場合には具体的にはシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基などが挙げられる。
また、式(IIIc)において、P6とP7とが結合して炭素数3〜7の二価の脂肪族炭化水素基を表し、隣接するS+と共に環を形成する場合には、ペンタメチレンスルホニオ基、テトラメチレンスルホニオ基、オキシビスエチレンスルホニオ基が挙げられる。
P9において、芳香環基としては、フェニル、トリル、キシリル、ナフチル等が挙げられる。P8とP9とが結合して二価の脂肪族炭化水素基を表し、隣接する−CHCO−と共に環を形成する場合には、2−オキソシクロヘキシル基、2−オキソシクロヘンチル基等が挙げられる。
When P 6 , P 7 and P 9 are alkyl groups, specific examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, and hexyl groups. When P 6 , P 7 and P 9 are cycloalkyl groups, specific examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like.
In formula (IIIc), when P 6 and P 7 are bonded to each other to represent a divalent aliphatic hydrocarbon group having 3 to 7 carbon atoms and form a ring with adjacent S + , pentamethylene Examples thereof include a sulfonio group, a tetramethylene sulfonio group, and an oxybisethylene sulfonio group.
In P 9, the aromatic ring group, phenyl, tolyl, xylyl, naphthyl and the like. When P 8 and P 9 are combined to represent a divalent aliphatic hydrocarbon group and form a ring with the adjacent —CHCO—, a 2-oxocyclohexyl group, a 2-oxocyclohenethyl group, etc. Can be mentioned.
また、式(IIIa)、(IIIb)、(IIIc)で示される対イオンの具体的な例としては、次のようなイオンを挙げることができる。
Specific examples of the counter ion represented by the formulas (IIIa), (IIIb), and (IIIc) include the following ions.
本発明における酸発生剤のZ-は、対イオンであり、該対イオンとしては、アルカンスルホネート、ハロアルカンスルホネート、ハロホスフェート、ハロボレートハロアンチモネート、Z-が下式(IV)で示されるアニオン等が挙げられる。
(式中、Q1、Q2、Q3、Q4及びQ5は、互いに独立に、水素原子、炭素数1〜16個の分岐していてもよいアルキル基、炭素数1〜16個の分岐していてもよいアルコキシ基、ハロゲン原子、炭素数6〜12個のアリール基、炭素数7〜12のアラルキル基、シアノ基、スルフィド基、ヒドロキシ基、ニトロ基又は下式(IV')で示される基を表す。
式中、Xは、アルキレン基、又はチオエーテル結合もしくはエーテル結合を含んでいても良いアルキレン基を表し、Cy1は、炭素数3〜20個の脂環式炭化水素基を表す。)
炭素数1〜16の分岐していてもよいアルキル基の例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、ヘキサデシル基などが挙げられる。
炭素数1〜16の分岐していてもよいアルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、tert−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、イソペンチルオキシ基、デシルオキシ基、ドデシルオキシ基、ヘキサデシルオキシ基などが挙げられる。
ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。
炭素数6〜12個のアリール基としては、フェニル基、トリル基、メトキシフェニル基、ナフチル基などが挙げられる。
炭素数7〜12のアラルキル基としては、ベンジル基、クロロベンジル基、メトキシベンジル基などが挙げられる。
Z of the acid generator in the present invention - is a counterion, the counterion, alkanesulfonate, haloalkanesulfonate, halophosphates, Ha Robo rate halo antimonate, Z - anion which is represented by the following formula (IV) Is mentioned.
(In the formula, Q 1 , Q 2 , Q 3 , Q 4 and Q 5 are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms which may be branched, or a group having 1 to 16 carbon atoms. An alkoxy group which may be branched, a halogen atom, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cyano group, a sulfide group, a hydroxy group, a nitro group or the following formula (IV ′) Represents the group shown.
In the formula, X represents an alkylene group, or an alkylene group which may contain a thioether bond or an ether bond, and Cy 1 represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms. )
Examples of the alkyl group having 1 to 16 carbon atoms which may be branched include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and decyl group. , Dodecyl group, hexadecyl group and the like.
Examples of the alkoxy group having 1 to 16 carbon atoms which may be branched include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and an isopentyl group. Examples thereof include an oxy group, a decyloxy group, a dodecyloxy group, and a hexadecyloxy group.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a chlorobenzyl group, and a methoxybenzyl group.
また、式(IV')で示される基が、式(IV)において、複数存在する場合は、それらは互いに異なっても同一でもよい。 When a plurality of groups represented by the formula (IV ′) are present in the formula (IV), they may be different from each other or the same.
Xとしては、次のようなものが挙げられる。
上記式において、好ましくは(a-1)〜(a-7)のアルキレン基が挙げられる。
Examples of X include the following.
In the above formula, an alkylene group of (a-1) to (a-7) is preferable.
Cy1としては、次のようなものが挙げられる。
上記式において、好ましくはシクロヘキシル基(b−4)、2−ノルボルナン基(b−21)、1−アダマンチル基(b−24)、2−アダマンチル基(b−23)が挙げられる。
Examples of Cy 1 include the following.
In said formula, Preferably a cyclohexyl group (b-4), 2-norbornane group (b-21), 1-adamantyl group (b-24), 2-adamantyl group (b-23) is mentioned.
また、式(IV)で表される塩において、アニオン部の具体的な例として次のようなイオンを挙げることができる。 Moreover, in the salt represented by the formula (IV), the following ions can be given as specific examples of the anion moiety.
また、酸発生剤のアニオン部Z-としては、式(IV)で示されるアニオン以外に、
具体的な例として、次のようなイオンを挙げることができる。
トリフルオロメタンスルホネート、
パーフルオロブタンスルホネート、
パーフルオロオクタンスルホネート、
ヘキサフルオロアンチモネート、
テトラフルオロボレート、
ヘキサフルオロホスフェートなど。
Moreover, as an anion part Z − of the acid generator, in addition to the anion represented by the formula (IV),
Specific examples include the following ions.
Trifluoromethanesulfonate,
Perfluorobutanesulfonate,
Perfluorooctane sulfonate,
Hexafluoroantimonate,
Tetrafluoroborate,
Hexafluorophosphate etc.
本発明の組成物における酸発生剤は、市販品を用いることもでき、また公知の方法により製造することもできる。例えば、Zが式(IV)のアニオンである場合に、式(IIIa)のスルホニウム塩、式(IIIb)のヨードニウム塩、式(IIIc)のスルホニウム塩は、次に示す方法で製造することができる。
式(IIIa)のトリフェニルスルホニウム塩は、例えば、相当するトリフェニルスルホニウムブロマイドを目的とする化合物の陰イオンと同じスルホン酸の銀塩と反応させる方法や、Chem.Pharm.Bull.,Vol.29,3753(1981)の記載に準じて、相当するジフェニルスルホキシドとベンゼン系化合物とパーフルオロアルカンスルホン酸とを、トリフルオロ酢酸無水物の存在下で反応させる方法、特開平8−311018号公報の記載に準じて、相当するアリールグリニヤル試薬を塩化チオニルと反応させ、次いでトリオルガノシリルハライドと反応させてトリアリールスルホニウムハライドとした後、目的とする化合物の陰イオンと同じスルホン酸の銀塩と反応させる方法などにより製造できる。
また、式(IIIa)中のP1、P2及び/又はP3が水酸基である化合物は、上記特開平8−157451号公報の記載に準じて、ベンゼン環上にtert−ブトキシ基を有するトリフェニルスルホニウム塩を、その化合物の陰イオンと同じスルホン酸で処理してtert−ブチル基を脱離させることにより製造できる。
A commercial item can also be used for the acid generator in the composition of this invention, and it can also manufacture it by a well-known method. For example, when Z is an anion of the formula (IV), a sulfonium salt of the formula (IIIa), an iodonium salt of the formula (IIIb), or a sulfonium salt of the formula (IIIc) can be produced by the following method. .
The triphenylsulfonium salt of the formula (IIIa) can be prepared by reacting the corresponding triphenylsulfonium bromide with the same silver salt of sulfonic acid as the anion of the target compound, Chem. Pharm. Bull. , Vol. 29, 3753 (1981), a method of reacting the corresponding diphenyl sulfoxide, a benzene compound and perfluoroalkanesulfonic acid in the presence of trifluoroacetic anhydride, JP-A-8-311018 According to the description, the corresponding aryl Grignard reagent is reacted with thionyl chloride and then reacted with triorganosilyl halide to give triarylsulfonium halide, and then the same sulfonic acid silver salt as the anion of the target compound It can be produced by a method of reacting.
Further, a compound in which P 1 , P 2 and / or P 3 in the formula (IIIa) is a hydroxyl group is a trimethyl group having a tert-butoxy group on the benzene ring in accordance with the description in JP-A-8-157451. A phenylsulfonium salt can be produced by treating with the same sulfonic acid as the anion of the compound to remove the tert-butyl group.
また、式(IIIb)のジフェニルヨードニウム塩は、例えば、J.Am.Chem.Soc.,vol.81,342(1959)の記載に準じて、ヨージル硫酸と相当するアリール化合物を反応させた後、目的とする化合物の陰イオンと同じスルホン酸を加える方法や、無水酢酸と発煙硝酸の混合液中にヨウ素とトリフルオロ酢酸を加えて得られる反応生成物と相当するアリール化合物を反応させた後目的とする化合物の陰イオンと同じスルホン酸酸を加える方法、特開平9−179302号公報の記載に準じて、相当するアリール化合物と無水酢酸、ヨウ素酸カリウムの混合物に濃硫酸を滴下して反応させた後、目的とする化合物の陰イオンと同じスルホン酸を加える方法などにより製造できる。 Moreover, the diphenyl iodonium salt of the formula (IIIb) is, for example, J.I. Am. Chem. Soc. , Vol. 81,342 (1959), after reacting iodoylsulfuric acid with the corresponding aryl compound, adding the same sulfonic acid as the anion of the target compound, or in a mixture of acetic anhydride and fuming nitric acid In the method described in JP-A-9-179302, a reaction product obtained by adding iodine and trifluoroacetic acid is reacted with the corresponding aryl compound and then the same sulfonic acid as the anion of the target compound is added. Similarly, it can be produced by a method in which concentrated sulfuric acid is added dropwise to a mixture of the corresponding aryl compound, acetic anhydride and potassium iodate to cause the reaction, and then the same sulfonic acid as the anion of the target compound is added.
また、式(IIIc)のスルホニウム塩は、例えば、J.Polymer Science,Polymer Chemistry Edition,Vol.17,2877−2892(1979)writtern by J.V.Crivello et al.に準じて、相当するβ−ハロケトンと相当するスルフィド化合物とを反応させ、相当するスルホニウムハライドを得て、該スルホニウムハライドと目的とするスルホニウム塩のアニオン部分の同じ構造を有する相当するスルホン酸又はスルホン酸金属塩とを反応させることなどにより製造できる。 The sulfonium salt of the formula (IIIc) is, for example, J. Polymer Science, Polymer Chemistry Edition, Vol. 17, 2877-2892 (1979) writtern by J. et al. V. Crivello et al. According to the above, the corresponding β-haloketone and the corresponding sulfide compound are reacted to obtain the corresponding sulfonium halide, and the corresponding sulfonic acid or sulfone having the same structure of the anion portion of the sulfonium salt and the target sulfonium salt is obtained. It can be produced by reacting with an acid metal salt.
また、本発明の化学増幅型ポジ型レジストにおいては、有機塩基化合物をクエンチャーとして添加することにより、露光後の引き置きに伴う酸の失活による性能劣化を改良できる。このような含窒素塩基性有機化合物の具体的な例としては、以下の各式で示されるアミン類を挙げることができる。 In addition, in the chemically amplified positive resist of the present invention, by adding an organic base compound as a quencher, it is possible to improve performance deterioration due to acid deactivation accompanying holding after exposure. Specific examples of such nitrogen-containing basic organic compounds include amines represented by the following formulas.
式中、R12、R13及びR18は、それぞれ独立に、水素原子、アルキル、シクロアルキル又はアリールを表す。該アルキル、シクロアルキル又はアリールは、それぞれ独立に、水酸基、アミノ基、又は炭素数1〜6のアルコキシ基で置換されていてもよい。該アミノ基は、炭素数1〜4のアルキル基で置換されていてもよい。また、該アルキルは、炭素数1〜6程度が好ましく、該シクロアルキルは、炭素数5〜10程度が好ましく、該アリールは、炭素数6〜10程度が好ましい。
R14、R15及びR16は、それぞれ独立に、水素原子、アルキル、シクロアルキル、アリール又はアルコキシを表す。該アルキル、シクロアルキル、アリール、又はアルコキシは、それぞれ独立に、水酸基、アミノ基、又は炭素数1〜6のアルコキシ基、で置換されていてもよい。該アミノ基は、炭素数1〜4のアルキル基で置換されていてもよい。また、該アルキルは、炭素数1〜6程度が好ましく、該シクロアルキルは、炭素数5〜10程度が好ましく、該アリールは、炭素数6〜10程度が好ましく、該アルコキシは、炭素数1〜6程度が好ましい。
R17は、アルキル又はシクロアルキルを表す。該アルキル又はシクロアルキルは、それぞれ独立に、水酸基、アミノ基、炭素数1〜6のアルコキシ基、で置換されていてもよい。該アミノ基は、炭素数1〜4のアルキル基で置換されていてもよい。また、該アルキルは、炭素数1〜6程度が好ましく、該シクロアルキルは、炭素数5〜10程度が好ましい。
Aは、アルキレン、カルボニル、イミノ、スルフィド又はジスルフィドを表す。該アルキレンは、炭素数2〜6程度であることが好ましい。
また、R12〜R18において、直鎖構造と分岐構造の両方をとり得るものについては、そのいずれでもよい。
但し、前記式[3]化合物におけるR12、R13およびR18は何れも水素原子であることはない。
R19〜R21は同一でも異なっていてもよく、水素原子、炭素数1〜6個のアルキル基、炭素数1〜6個のアミノアルキル基、炭素数1〜6個のヒドロキシアルキル基または6〜20個の置換もしくは非置換のアリール基を表し、ここで
R19とR20は互いに結合して環を形成していてもよい。
In the formula, R 12 , R 13 and R 18 each independently represent a hydrogen atom, alkyl, cycloalkyl or aryl. The alkyl, cycloalkyl, or aryl may be each independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, the cycloalkyl preferably has about 5 to 10 carbon atoms, and the aryl preferably has about 6 to 10 carbon atoms.
R 14 , R 15 and R 16 each independently represents a hydrogen atom, alkyl, cycloalkyl, aryl or alkoxy. The alkyl, cycloalkyl, aryl, or alkoxy may be each independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. In addition, the alkyl preferably has about 1 to 6 carbon atoms, the cycloalkyl preferably has about 5 to 10 carbon atoms, the aryl preferably has about 6 to 10 carbon atoms, and the alkoxy has 1 to about carbon atoms. About 6 is preferable.
R 17 represents alkyl or cycloalkyl. The alkyl or cycloalkyl may each independently be substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, and the cycloalkyl preferably has about 5 to 10 carbon atoms.
A represents alkylene, carbonyl, imino, sulfide or disulfide. The alkylene preferably has about 2 to 6 carbon atoms.
Further, in R 12 to R 18 , any of those that can take both a linear structure and a branched structure may be used.
However, none of R 12 , R 13 and R 18 in the compound of the formula [3] is a hydrogen atom.
R 19 to R 21 may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or 6 Represents -20 substituted or unsubstituted aryl groups, wherein R 19 and R 20 may be bonded to each other to form a ring;
このような化合物として、具体的には、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、アニリン、2−,3−又は4−メチルアニリン、4−ニトロアニリン、1−又は2−ナフチルアミン、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、4,4′−ジアミノ−1,2−ジフェニルエタン、4,4′−ジアミノ−3,3′−ジメチルジフェニルメタン、4,4′−ジアミノ−3,3′−ジエチルジフェニルメタン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、ジノニルアミン、ジデシルアミン、N−メチルアニリン、ピペリジン、ジフェニルアミン、トリエチルアミン、トリメチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、トリヘプチルアミン、トリオクチルアミン、トリノニルアミン、トリデシルアミン、メチルジブチルアミン、メチルジペンチルアミン、メチルジヘキシルアミン、メチルジシクロヘキシルアミン、メチルジヘプチルアミン、メチルジオクチルアミン、メチルジノニルアミン、メチルジデシルアミン、エチルジブチルアミン、エチルジペンチルアミン、エチルジヘキシルアミン、エチルジヘプチルアミン、エチルジオクチルアミン、エチルジノニルアミン、エチルジデシルアミン、ジシクロヘキシルメチルアミン、トリス〔2−(2−メトキシエトキシ)エチル〕アミン、トリイソプロパノールアミン、N,N−ジメチルアニリン、2,6−イソプロピルアニリン、イミダゾール、ピリジン、4−メチルピリジン、4−メチルイミダゾール、ビピリジン、2,2′−ジピリジルアミン、ジ−2−ピリジルケトン、1,2−ジ(2−ピリジル)エタン、1,2−ジ(4−ピリジル)エタン、1,3−ジ(4−ピリジル)プロパン、1,2−ビス(2−ピリジル)エチレン、1,2−ビス(4−ピリジル)エチレン、1,2−ビス(4−ピリジルオキシ)エタン、4,4′−ジピリジルスルフィド、4,4′−ジピリジルジスルフィド、1,2−ビス(4−ピリジル)エチレン、2,2′−ジピコリルアミン、3,3′−ジピコリルアミン、テトラメチルアンモニウムヒドロキシド、テトライソプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、テトラ−n−ヘキシルアンモニウムヒドロキシド、テトラ−n−オクチルアンモニウムヒドロキシド、フェニルトリメチルアンモニウムヒドロキシド、3−(トリフルオロメチル)フェニルトリメチルアンモニウムヒドロキシド、コリン、N−メチルピロリドン、ジメチルイミダゾールなどを挙げることができる。 Specific examples of such compounds include hexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, 1- or 2-naphthylamine, and ethylenediamine. Tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'- Diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine , Tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine , Methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, N, N-dimethylaniline, 2,6-isopropylaniline, imidazole, pyridine, -Methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4 , 4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine, 3,3'-dipicolylamine, tetramethylammonium hydroxide Tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n- Examples include octylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, choline, N-methylpyrrolidone, and dimethylimidazole.
さらには、特開平11−52575号公報に開示されているような、ピペリジン骨格を有するヒンダードアミン化合物をクエンチャーとすることもできる。 Furthermore, a hindered amine compound having a piperidine skeleton as disclosed in JP-A-11-52575 can be used as a quencher.
本発明のレジスト組成物は、樹脂と酸発生剤の合計重量に対して、樹脂を80〜99.9重量%、酸発生剤を20〜0.1重量%の範囲で含有することが好ましい。
本発明の組成物において、塩基性化合物を用いる場合は、該樹脂100重量部に対して、0.001〜1重量部の範囲、さらには0.01〜0.3重量部の範囲で含有することが好ましい。
本発明の組成物は、必要に応じて、増感剤、溶解抑止剤、他の樹脂、界面活性剤、安定剤、染料など、各種の添加物を少量含有することもできる。
The resist composition of the present invention preferably contains 80 to 99.9% by weight of the resin and 20 to 0.1% by weight of the acid generator with respect to the total weight of the resin and the acid generator.
In the composition of the present invention, when a basic compound is used, it is contained in the range of 0.001 to 1 part by weight, and further in the range of 0.01 to 0.3 part by weight with respect to 100 parts by weight of the resin. It is preferable.
The composition of the present invention can contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, and dyes as necessary.
本発明のレジスト組成物は、通常、上記の各成分が溶剤に溶解された状態でレジスト液組成物とされ、シリコンウェハーなどの基体上に、スピンコーティングなどの常法に従って塗布される。ここで用いる溶剤は、各成分を溶解し、適当な乾燥速度を有し、溶剤が蒸発した後に均一で平滑な塗膜を与えるものであればよく、この分野で一般に用いられている溶剤が使用しうる。
例えば、エチルセロソルブアセテート、メチルセロソルブアセテート及びプロピレングリコールモノメチルエーテルアセテートのようなグリコールエーテルエステル類;乳酸エチル、酢酸ブチル、酢酸アミル及びピルビン酸エチルのようなエステル類;アセトン、メチルイソブチルケトン、2−ヘプタノン及びシクロヘキサノンのようなケトン類;γ−ブチロラクトンのような環状エステル類などを挙げることができる。これらの溶剤は、それぞれ単独で、又は2種以上組み合わせて用いることができる。
The resist composition of the present invention is usually made into a resist solution composition in a state where each of the above components is dissolved in a solvent, and is applied on a substrate such as a silicon wafer according to a conventional method such as spin coating. The solvent used here may be any solvent that dissolves each component, has an appropriate drying rate, and gives a uniform and smooth coating film after the solvent evaporates, and a solvent generally used in this field is used. Yes.
For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; acetone, methyl isobutyl ketone, 2-heptanone And ketones such as cyclohexanone; cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more.
基体上に塗布され、乾燥されたレジスト膜には、パターニングのための露光処理が施され、次いで脱保護基反応を促進するための加熱処理を行った後、アルカリ現像液で現像される。ここで用いるアルカリ現像液は、この分野で用いられる各種のアルカリ性水溶液であることができるが、一般には、テトラメチルアンモニウムヒドロキシドや(2−ヒドロキシエチル)トリメチルアンモニウムヒドロキシド(通称コリン)の水溶液が用いられることが多い。
上記において、本発明の実施の形態について説明を行なったが、上記に開示された本発明の実施の形態は、あくまで例示であって、本発明の範囲はこれらの実施の形態に限定されない。本発明の範囲は、特許請求の範囲によって示され、さらに特許請求の範囲の記載と均等の意味及び範囲内でのすべての変更を含むものである。
The resist film coated and dried on the substrate is subjected to an exposure process for patterning, followed by a heat treatment for promoting a deprotecting group reaction, and then developed with an alkali developer. The alkaline developer used here can be various alkaline aqueous solutions used in this field, but in general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline) is used. Often used.
While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope.
次に実施例を挙げて、本発明をさらに具体的に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。例中、含有量ないし使用量を表す%及び部は、特記ないかぎり重量基準である。また重量平均分子量は、ポリスチレンを標準品として、ゲルパーミュエーションクロマトグラフィーにより求めた値である。 EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified. The weight average molecular weight is a value obtained by gel permeation chromatography using polystyrene as a standard product.
酸発生剤合成例1(酸発生剤B1の合成)
フラスコに2,4,6−トリイソプロピル−3−ニトロベンゼンスルホン酸20部、アセトニトリル80部、アセトン40部を仕込み、室温で16時間攪拌した。ここへ酸化銀7.46部を加え16時間攪拌した。これをろ過し、濃縮することで23.68部の2,4,6−トリイソプロピル3−ニトロベンゼンスルホン酸銀を得た。
フラスコに2,4,6−トリイソプロピル3−ニトロベンゼンスルホン酸銀20部とメタノール185.35部を仕込み、ここへp−トリルジフェニルスルホニウムヨーダート18.53部とメタノール185.35部の混合溶液を滴下した。滴下後16時間攪拌し、濾過後濾液を濃縮した。ここへクロロホルム300部を加え、イオン交換水75部で3度洗浄した。その後濃縮し、攪拌後t−ブチルメチルエーテルで晶析を行い、22.07部の目的物を得た。
この化合物が次式で示される4−メチルフェニルジフェニルスルホニウム 2,4,6−トリイソプロピル3−ニトロベンゼンスルホナートであることを、NMR(日本電子製“GX-270”)で確認した。
Acid generator synthesis example 1 (Synthesis of acid generator B1)
The flask was charged with 20 parts of 2,4,6-triisopropyl-3-nitrobenzenesulfonic acid, 80 parts of acetonitrile and 40 parts of acetone, and stirred at room temperature for 16 hours. 7.46 parts of silver oxide was added here, and it stirred for 16 hours. This was filtered and concentrated to obtain 23.68 parts of silver 2,4,6-triisopropyl 3-nitrobenzenesulfonate.
A flask is charged with 20 parts of silver 2,4,6-triisopropyl 3-nitrobenzenesulfonate and 185.35 parts of methanol, and a mixed solution of 18.53 parts of p-tolyldiphenylsulfonium iodide and 185.35 parts of methanol is added thereto. It was dripped. After dropping, the mixture was stirred for 16 hours, and after filtration, the filtrate was concentrated. To this, 300 parts of chloroform was added and washed three times with 75 parts of ion-exchanged water. After concentration, the mixture was stirred and crystallized with t-butyl methyl ether to obtain 22.07 parts of the desired product.
It was confirmed by NMR (“GX-270” manufactured by JEOL Ltd.) that this compound was 4-methylphenyldiphenylsulfonium 2,4,6-triisopropyl 3-nitrobenzenesulfonate represented by the following formula.
1H−NMR(ジメチルスルホキシド−d6、内部標準物質テトラメチルシラン):δ(ppm)
1.10-1.19 (m, 18H); 2.44 (s, 3H); 2.46−2.56 (m, 1H) ; 4.61−4.71 (m, 1H) ; 4.972 (br, 1H); 7.32 (s, 1H); 7.59−7.62 (m, 2H) ; 7.74−7.88 (m, 12H)
1 H-NMR (dimethyl sulfoxide-d 6 , internal standard substance tetramethylsilane): δ (ppm)
1.10-1.19 (m, 18H); 2.44 (s, 3H); 2.46−2.56 (m, 1H); 4.61−4.71 (m, 1H); 4.972 (br, 1H); 7.32 (s, 1H); 7.59− 7.62 (m, 2H); 7.74−7.88 (m, 12H)
酸発生剤合成例2:酸発生剤B2の合成
フラスコに5-スルホイソフタル酸6部、シクロヘキサンエタノール50部を仕込み、135℃〜140℃で9時間撹拌した。冷却後、ジメチルスルホキシド50部、メタノール10部、ノルマルヘプタン200部を加え、撹拌・静置すると、二層に分離し、下層をさらにノルマルヘプタンで2度洗浄した。得られた溶液を濃縮し、ノルマルヘプタン、メタノールを除去した。得られた溶液に酸化銀を3.0部添加し、室温で16時間攪拌した。その後、ろ過し、ろ液を撹拌しながら、p−トリルジフェニルスルホニウム アイオダイド8.67部とメタノール86.7部の混合溶液を添加した。滴下後16時間攪拌し、ろ過後、ろ液に酢酸エチル200部を加え、イオン交換水100部で5回洗浄し、得られた有機層を濃縮した。ここへノルマルヘプタン200部を加え、リパルプ、デカント、濃縮の操作を2回繰り返し、さらにノルマルヘプタン200部を加え、リパルプ、ろ過によって淡黄色結晶を6.24部得た。
この化合物が次式で示される構造を有することを、NMR(日本電子製“GX−270”)、質量分析(LCはHP製1100、MASSはHP製LC/MSD)で確認した。
Acid generator synthesis example 2: Synthesis of acid generator B2 6 parts of 5-sulfoisophthalic acid and 50 parts of cyclohexaneethanol were placed in a flask and stirred at 135 ° C to 140 ° C for 9 hours. After cooling, 50 parts of dimethyl sulfoxide, 10 parts of methanol, and 200 parts of normal heptane were added and stirred and allowed to stand to separate into two layers, and the lower layer was further washed twice with normal heptane. The resulting solution was concentrated to remove normal heptane and methanol. To the obtained solution, 3.0 parts of silver oxide was added and stirred at room temperature for 16 hours. Thereafter, the mixture was filtered, and a mixed solution of 8.67 parts of p-tolyldiphenylsulfonium iodide and 86.7 parts of methanol was added while stirring the filtrate. After dropping, the mixture was stirred for 16 hours, filtered, 200 parts of ethyl acetate was added to the filtrate, washed 5 times with 100 parts of ion-exchanged water, and the obtained organic layer was concentrated. To this, 200 parts of normal heptane was added, and repulping, decanting, and concentration were repeated twice. Further, 200 parts of normal heptane was added, and 6.24 parts of pale yellow crystals were obtained by repulping and filtration.
It was confirmed by NMR (JEOL “GX-270”) and mass spectrometry (LC: 1100 made by HP, MASS: LC / MSD made by HP) that this compound had a structure represented by the following formula.
1H−NMR(クロロホルム−d、内部標準物質テトラメチルシラン):δ(ppm)
0.94-1.00 (m, 4H); 1.14-1.26 (m, 6H); 1.41-1.44 (m, 2H); 1.62-1.76 (m, 14H); 2.44 (s, 3H); 4.32-4.34(t, 4H); 7.46−7.47 (m, 2H) ; 7.65−7.77 (m, 12H) ; 8.61 (s, 1H);8.77(d, 2H)
MS(ESI(+)Spectrum):M+ 277.2
MS(ESI(−)Spectrum):M− 465.2
1 H-NMR (chloroform-d, internal standard substance tetramethylsilane): δ (ppm)
0.94-1.00 (m, 4H); 1.14-1.26 (m, 6H); 1.41-1.44 (m, 2H); 1.62-1.76 (m, 14H); 2.44 (s, 3H); 4.32-4.34 (t, 4H ); 7.46-7.47 (m, 2H); 7.65-7.77 (m, 12H); 8.61 (s, 1H); 8.77 (d, 2H)
MS (ESI (+) Spectrum): M + 277.2
MS (ESI (-) Spectrum): M-465.2
樹脂合成例1:樹脂A1の合成
下式(VIII)のモノマーを9.18g、5−メタクリロイルオキシ−2,6−ノルボルネンラクトンを3.33g、α−メタクリロイロキシ−γ−ブチロラクトンを4.73g仕込み(モル比 50:25:25)、全モノマーの2.5重量倍のメチルイソブチルケトンを加えた後、窒素雰囲気で80℃に昇温した。そこに、開始剤としてアゾビスイソブチロニトリルを全モノマー量に対して3モル%添加し、85℃で約5時間加熱した。その後、反応液を大量のメタノールに注いで沈殿させる操作を3回行って、分子量が5500、分散が1.79の共重合体を11.3g(収率65.6%)得た。これを樹脂A1とする。
Resin Synthesis Example 1: Synthesis of Resin A1 9.18 g of the following formula (VIII) monomer, 3.33 g of 5-methacryloyloxy-2,6-norbornenelactone, and 4.73 g of α-methacryloyloxy-γ-butyrolactone After charging (molar ratio 50:25:25) and adding 2.5 times the methyl isobutyl ketone of all monomers, the temperature was raised to 80 ° C. in a nitrogen atmosphere. Thereto, 3 mol% of azobisisobutyronitrile as an initiator was added with respect to the total amount of monomers and heated at 85 ° C. for about 5 hours. Then, the operation of pouring the reaction solution into a large amount of methanol and precipitating was performed three times to obtain 11.3 g (yield 65.6%) of a copolymer having a molecular weight of 5500 and a dispersion of 1.79. This is designated as resin A1.
樹脂合成例2:樹脂A2の合成
式(VIII)のモノマーを10.0g、5−メタクリロイルオキシ−2,6−ノルボルネンラクトンを7.25g仕込み(モル比 50:50)、全モノマーの2.5重量倍のメチルイソブチルケトンを加えた後、窒素雰囲気で80℃に昇温した。そこに、開始剤としてアゾビスイソブチロニトリルを全モノマー量に対して3モル%添加し、85℃で約5時間加熱した。その後、反応液を大量のメタノールに注いで沈殿させる操作を3回行って、分子量が19000、分散が2.02の共重合体を11.5g(収率66.7%)得た。これを樹脂A2とする。
Resin Synthesis Example 2: Synthesis of Resin A2
10.0 g of the monomer of formula (VIII) and 7.25 g of 5-methacryloyloxy-2,6-norbornenelactone were charged (molar ratio 50:50), and 2.5 times by weight of methyl isobutyl ketone was added to all monomers. Thereafter, the temperature was raised to 80 ° C. in a nitrogen atmosphere. Thereto, 3 mol% of azobisisobutyronitrile as an initiator was added with respect to the total amount of monomers and heated at 85 ° C. for about 5 hours. Thereafter, the reaction solution was poured into a large amount of methanol and precipitated three times to obtain 11.5 g (yield 66.7%) of a copolymer having a molecular weight of 19000 and a dispersion of 2.02. This is called Resin A2.
樹脂合成例3:樹脂A3の合成
式(VIII)のモノマーを9.18g、アクリル酸3−ヒドロキシ−1−アダマンチルを2.22g、5−アクリロイルオキシ−2,6−ノルボルネンラクトンを12.48g仕込み(モル比 30:10:60)、全モノマーの2.5重量倍のメチルイソブチルケトンを加えた後、窒素雰囲気で80℃に昇温した。そこに、開始剤としてアゾビスイソブチロニトリルを全モノマー量に対して3モル%添加し、85℃で約5時間加熱した。その後、反応液を大量のメタノールに注いで沈殿させる操作を3回行って、分子量が7300、分散が1.77の共重合体を21.4g(収率89.6%)得た。これを樹脂A3とする。
Resin Synthesis Example 3: Synthesis of Resin A3 9.18 g of the monomer of formula (VIII), 2.22 g of 3-hydroxy-1-adamantyl acrylate, and 12.48 g of 5-acryloyloxy-2,6-norbornenelactone were charged. After adding methyl isobutyl ketone (molar ratio 30:10:60) 2.5 times the weight of all monomers, the temperature was raised to 80 ° C. in a nitrogen atmosphere. Thereto, 3 mol% of azobisisobutyronitrile as an initiator was added with respect to the total amount of monomers and heated at 85 ° C. for about 5 hours. Then, the operation of pouring the reaction solution into a large amount of methanol and precipitating it was performed three times to obtain 21.4 g (yield: 89.6%) of a copolymer having a molecular weight of 7300 and a dispersion of 1.77. This is designated as resin A3.
樹脂合成例4:樹脂A4の合成
メタクリル酸2−エチル−2−アダマンチル、5−メタクリロイルオキシ−2,6−ノルボルネンラクトンおよびα−メタクリロイルオキシ−γ−ブチロラクトンを2:1:1のモル比(11.1g:5.0g:3.8g)で混合し、1.4−ジオキサン50gを加え溶液とした。そこに開始剤としてアゾビスイソブチロニトリルを0.30g加え、85℃に昇温し、5時間攪拌を続けた。その後、大量のn−ヘプタンに注ぎこむことで晶析する操作を3回繰り返すことで精製したところ分子量9100、分散1.72の共重合体を得た。これを樹脂A4とする。
Resin Synthesis Example 4: Synthesis of Resin A4 2-ethyl-2-adamantyl methacrylate, 5-methacryloyloxy-2,6-norbornenelactone and α-methacryloyloxy-γ-butyrolactone were mixed at a molar ratio of 11: 1 (11 0.1 g: 5.0 g: 3.8 g), and 50 g of 1.4-dioxane was added to obtain a solution. Thereto was added 0.30 g of azobisisobutyronitrile as an initiator, the temperature was raised to 85 ° C., and stirring was continued for 5 hours. Then, when it refine | purified by repeating operation which crystallizes by pouring into a lot of n-heptane three times, the copolymer of molecular weight 9100 and dispersion | distribution 1.72 was obtained. This is called Resin A4.
樹脂合成例5:樹脂A5の合成
メタクリル酸2−エチル−2−アダマンチル、5−メタクリロイロキシ−2、6−ノルボルナンカルボラクトンをモル比1:1(12.42g:11.11g)を仕込み、1、4−ジオキサン47gを加え溶液とした。そこに開始剤としてアゾビスイソブチロニトリルを全モノマーの3モル%加えた後、80℃に昇温して6時間攪拌を続けた。その後、反応マスを大量のメタノールに注ぎ結晶化する操作を3回繰り返し、樹脂を精製したところ分子量9600の共重合体15.8g(収率67.1%)を得た。これを樹脂A5とする。
Resin Synthesis Example 5: Synthesis of Resin A5 2-ethyl-2-adamantyl methacrylate, 5-methacryloyloxy-2, 6-norbornanecarbolactone was charged at a molar ratio of 1: 1 (12.42 g: 11.11 g). 47 g of 1,4-dioxane was added to make a solution. After adding 3 mol% of azobisisobutyronitrile as an initiator thereto, the temperature was raised to 80 ° C. and stirring was continued for 6 hours. Thereafter, the operation of pouring the reaction mass into a large amount of methanol and crystallization was repeated three times, and the resin was purified to obtain 15.8 g (yield 67.1%) of a copolymer having a molecular weight of 9600. This is called Resin A5.
以下の各成分を混合して溶解し、さらに孔径0.2μmのフッ素樹脂製フィルターで濾過して、レジスト液を調製した。 The following components were mixed and dissolved, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist solution.
<酸発生剤>
B1:4−メチルフェニルジフェニルスルホニウム 2,4,6−トリイソプロピル3−ニトロベンゼンスルホナート 0.22部
B2:4−メチルフェニルジフェニルスルホニウム 3,5−ビス(2−シクロヘキシルエトキシカルボニル)ベンゼンスルホナート 0.27部
B3:p-トリルジフェニルスルホニウム パーフルオロオクタンスルホネート 0.2部
<樹脂>
種類は、表1に記載:10部
<クエンチャー>
2、6−ジイソプロピルアニリン 0.0075部
<溶剤>
プロピレングリコールモノメチルエーテルアセテート 33.25部
2−ヘプタノン 33.25部
γ−ブチロラクトン 3.5部
<Acid generator>
B1: 4-methylphenyldiphenylsulfonium 2,4,6-triisopropyl 3-nitrobenzenesulfonate 0.22 parts B2: 4-methylphenyldiphenylsulfonium 3,5-bis (2-cyclohexylethoxycarbonyl) benzenesulfonate 0. 27 parts B3: p-tolyldiphenylsulfonium perfluorooctane sulfonate 0.2 part <resin>
Types listed in Table 1: 10 parts <quencher>
2,6-diisopropylaniline 0.0075 part <solvent>
Propylene glycol monomethyl ether acetate 33.25 parts 2-heptanone 33.25 parts γ-butyrolactone 3.5 parts
シリコンウェハーにBrewer社製の有機反射防止膜用組成物である“ARC−29A−8”を塗布して215℃、60秒の条件でベークすることによって厚さ780Åの有機反射防止膜を形成させ、次いでこの上に、上記のレジスト液を乾燥後の膜厚が表1、表2では、0.30μm、表3、表4では、0.39μmとなるようにスピンコートした。
レジスト液塗布後は、ダイレクトホットプレート上にて、表1、表3の「PB」の欄に示す温度で60秒間プリベークした。こうしてレジスト膜を形成したそれぞれのウェハーに、ArFエキシマステッパー〔(株)ニコン製の“NSR ArF”、表1、表2では、NA=0.55、表3、表4では、NA=0.55 2/3Annular〕用いて、露光量を段階的に変化させてラインアンドスペースパターンを露光した。
露光後は、ホットプレート上にて表1、表3の「PEB」の欄に示す温度で60秒間ポストエキスポジャーベークを行い、さらに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60秒間のパドル現像を行った。
有機反射防止膜基板上のもので現像後のブライトフィールドパターンを走査型電子顕微鏡で観察し、その結果を表2に示した。なお、ここでいうブライトフィールドパターンとは、外枠がクロム層(遮光層)で、その枠の内側にガラス面(透光部)をベースとしてライン状にクロム層(遮光層)が形成されたレチクルを介した露光及び現像によって得られるパターンである。したがって、露光現像後は、ラインアンドスペースパターンの周囲のレジスト層が除去され、さらにその外側に外枠相当のレジスト層が残る。
An organic antireflection film having a thickness of 780 mm is formed by applying “ARC-29A-8”, a composition for organic antireflection film made by Brewer, to a silicon wafer and baking it at 215 ° C. for 60 seconds. Subsequently, the resist solution was spin-coated thereon so that the film thickness after drying was 0.30 μm in Tables 1 and 2, and 0.39 μm in Tables 3 and 4.
After application of the resist solution, pre-baking was performed for 60 seconds on the direct hot plate at the temperature shown in the column “PB” in Tables 1 and 3. ArF excimer stepper [NSR ArF manufactured by Nikon Corporation, NA = 0.55 in Tables 1 and 2, NA = 0.55 in Tables 3 and 4, respectively. 55 2/3 Annular] was used to expose the line and space pattern by changing the exposure stepwise.
After exposure, post-exposure baking is performed for 60 seconds on the hot plate at the temperature indicated in the column of “PEB” in Tables 1 and 3, and then paddles are added for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Development was performed.
The bright field pattern after development on the organic antireflection film substrate was observed with a scanning electron microscope, and the results are shown in Table 2. The bright field pattern here is a chrome layer (light-shielding layer) on the outer frame, and a chrome layer (light-shielding layer) is formed in a line on the inside of the frame with the glass surface (translucent part) as a base. It is a pattern obtained by exposure and development through a reticle. Therefore, after exposure and development, the resist layer around the line and space pattern is removed, and a resist layer corresponding to the outer frame remains on the outer side.
実効感度:
表2:0.13μmのラインアンドスペースパターンが1:1となる露光量で表示した。
表4:0.18μmのラインアンドスペースパターンが1:1となる露光量で表示した。
解像度: 実効感度の露光量で分離するラインアンドスペースパターンの最小寸法で表示した。
Effective sensitivity:
Table 2: A 0.13 μm line and space pattern was displayed at an exposure amount of 1: 1.
Table 4: A 0.18 μm line and space pattern was displayed at an exposure amount of 1: 1.
Resolution: Displayed with the minimum size of the line and space pattern separated by the exposure amount of effective sensitivity.
〔表1〕
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
例 No. 樹脂 酸発生剤 クエンチャー PB PEB
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例1 A1/10部 B1/0.22部 C1/0.0075部 130℃ 125℃
実施例2 A1/10部 B2/0.27部 C1/0.0075部 100℃ 110℃
実施例3 A2/10部 B2/0.27部 C1/0.0075部 130℃ 120℃
比較例1 A5/10部 B2/0.27部 C1/0.0075部 140℃ 120℃
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example No. Resin Acid generator Quencher PB PEB
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 A1 / 10 part B1 / 0.22 part C1 / 0.0075 part 130 ° C 125 ° C
Example 2 A1 / 10 part B2 / 0.27 part C1 / 0.0075 part 100 ° C 110 ° C
Example 3 A2 / 10 part B2 / 0.27 part C1 / 0.0075 part 130 ° C 120 ° C
Comparative Example 1 A5 / 10 part B2 / 0.27 part C1 / 0.0075 part 140 ° C 120 ° C
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
〔表2〕
━━━━━━━━━━━━━━━━━
例 No. 実効感度 解像度
(mJ/cm2) (μm)
━━━━━━━━━━━━━━━━━
実施例1 36 0.12
実施例2 48 0.12
実施例3 45 0.12
比較例1 78 0.12
━━━━━━━━━━━━━━━━━
[Table 2]
━━━━━━━━━━━━━━━━━
Example No. Effective sensitivity Resolution
(mJ / cm 2 ) (μm)
━━━━━━━━━━━━━━━━━
Example 1 36 0.12
Example 2 48 0.12
Example 3 45 0.12
Comparative Example 1 78 0.12
━━━━━━━━━━━━━━━━━
〔表3〕
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
例 No. 樹脂 酸発生剤 クエンチャー PB PEB
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例4 A1/10部 B3/0.20部 C1/0.0075部 130℃ 110℃
実施例5 A2/10部 B3/0.20部 C1/0.0075部 130℃ 110℃
実施例6 A3/10部 B3/0.20部 C1/0.0075部 130℃ 100℃
比較例2 A4/10部 B3/0.20部 C1/0.0075部 130℃ 130℃
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 3]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example No. Resin Acid generator Quencher PB PEB
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 4 A1 / 10 part B3 / 0.20 part C1 / 0.0075 part 130 ° C 110 ° C
Example 5 A2 / 10 part B3 / 0.20 part C1 / 0.0075 part 130 ° C 110 ° C
Example 6 A3 / 10 part B3 / 0.20 part C1 / 0.0075 part 130 ° C 100 ° C
Comparative Example 2 A4 / 10 part B3 / 0.20 part C1 / 0.0075 part 130 ° C 130 ° C
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
〔表4〕
━━━━━━━━━━━━━━━━━
例 No. 実効感度 解像度
(mJ/cm2) (μm)
━━━━━━━━━━━━━━━━━
実施例4 17 0.16
実施例5 13 0.16
実施例6 26 0.16
比較例2 20 0.16
━━━━━━━━━━━━━━━━━
[Table 4]
━━━━━━━━━━━━━━━━━
Example No. Effective sensitivity Resolution
(mJ / cm 2 ) (μm)
━━━━━━━━━━━━━━━━━
Example 4 17 0.16
Example 5 13 0.16
Example 6 26 0.16
Comparative Example 2 20 0.16
━━━━━━━━━━━━━━━━━
本発明の化学増幅型のポジ型レジスト組成物は、解像度などの各種のレジスト性能が良好であるとともに、特に改善された感度を与えるので、ArFやKrFなどのエキシマレーザーリソグラフィ、中でもArFエキシマレーザーリソグラフィに特に好適に用いられる。 The chemical amplification type positive resist composition of the present invention has various resist performances such as resolution and provides particularly improved sensitivity. Therefore, excimer laser lithography such as ArF and KrF, especially ArF excimer laser lithography. Is particularly preferably used.
Claims (7)
(式中、R1は、炭素数1〜4の分岐していてもよいアルキレン基を表し、R2は、炭素数1〜4の分岐していてもよいアルキル基を表し、R3は水素原子又はメチル基を表す。)
(式中、R 4 、R 6 は、互いに独立に水素原子又はメチル基を表し、R 5 、R 7 は、メチル基を表し、nは0〜3の整数を表す。) It has a polymerization unit represented by the following formula (I), a polymerization unit derived from 2-norbornene, and a polymerization unit derived from an aliphatic unsaturated dicarboxylic anhydride, and itself is insoluble or hardly soluble in an aqueous alkali solution. Contains an acid generator that is soluble in an alkaline aqueous solution by the action of an acid , and the resin is derived from 3-hydroxy-1-adamantyl (meth) acrylate in addition to the polymerized units. Polymerized unit, polymerized unit derived from (meth) acrylic acid 3,5-dihydroxy-1-adamantyl, polymerized unit derived from (meth) acryloyloxy-γ-butyrolactone in which the lactone ring may be substituted with alkyl, the following formula that contains at least one polymerization unit selected from the group consisting of polymerized units represented by the polymerized units and represented by (IIa) (IIb) The resist composition according to symptoms.
(Wherein R 1 represents an optionally branched alkylene group having 1 to 4 carbon atoms, R 2 represents an optionally branched alkyl group having 1 to 4 carbon atoms, and R 3 represents hydrogen. Represents an atom or a methyl group.)
(Wherein, R 4, R 6 are independently a hydrogen atom or a methyl group to one another, R 5, R 7 represents a methyl group, n represents an integer of 0 to 3.)
(式中、P1〜P3は、互いに独立に、水素原子、水酸基、炭素数1〜6のアルキル基又は炭素数1〜6のアルコキシ基を表す。Z−は、対イオンを表す。)
(式中、P4、P5は、互いに独立に、水素原子、水酸基、炭素数1〜6のアルキル基又は炭素数1〜6のアルコキシ基を表す。Z−は、前記と同じ定義である。)
(式中、P6、P7は、互いに独立に、炭素数1〜6のアルキル基、炭素数3〜10のシクロアルキル基、又はP6とP7とが結合して炭素数3〜7の二価の脂肪族炭化水素基を表し、隣接するS+と共に環を形成する。該脂肪式炭化水素基は、該脂環式炭化水素基の少なくとも1個の−CH2−がカルボニル基、酸素原子もしくは硫黄原子に置換されていてもよい。P8が水素原子を表し、P9が炭素数1〜6のアルキル基、炭素数3〜10のシクロアルキル基もしくは置換されていても良い芳香環基を表すか、又はP8とP9とが結合して二価の脂肪族炭化水素基を表し、隣接する−CHCO−と共に環を形成する。Z−は、前記と同じ定義である。) The composition according to claim 1 or 2, wherein the acid generator is represented by the following formula (IIIa), (IIIb) or (IIIc).
(Wherein, P 1 to P 3 are each independently, .Z representing hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms - represents a counter ion.)
(In the formula, P 4 and P 5 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z − has the same definition as described above. .)
(Wherein P 6 and P 7 are independently of each other an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or P 6 and P 7 bonded to each other to form 3 to 7 carbon atoms. A divalent aliphatic hydrocarbon group and forming a ring with adjacent S + , wherein the alicyclic hydrocarbon group is a group in which at least one —CH 2 — of the alicyclic hydrocarbon group is a carbonyl group, May be substituted by an oxygen atom or a sulfur atom, P 8 represents a hydrogen atom, and P 9 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an optionally substituted fragrance Represents a cyclic group, or P 8 and P 9 are bonded to each other to represent a divalent aliphatic hydrocarbon group, and form a ring together with the adjacent —CHCO—, where Z − is as defined above. )
(式中、Q1、Q2、Q3、Q4及びQ5は、互いに独立に、水素原子、炭素数1〜16個の分岐していてもよいアルキル基、炭素数1〜16個の分岐していてもよいアルコキシ基、ハロゲン原子、炭素数6〜12個のアリール基、炭素数7〜12のアラルキル基、シアノ基、スルフィド基、ヒドロキシ基、ニトロ基又は下式(IV’)で示される基を表す。
式中、Xは、アルキレン基、又はチオエーテル結合もしくはエーテル結合を含んでいても良いアルキレン基を表し、Cy1は、炭素数3〜20個の脂環式炭化水素基を表す。) The composition of claim 3 which is characterized in that it is a following formula (IV) - anion Z in the acid-generating agent.
(In the formula, Q 1 , Q 2 , Q 3 , Q 4 and Q 5 are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms which may be branched, or a group having 1 to 16 carbon atoms. An alkoxy group which may be branched, a halogen atom, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cyano group, a sulfide group, a hydroxy group, a nitro group or the following formula (IV ′) Represents the group shown.
In the formula, X represents an alkylene group, or an alkylene group which may contain a thioether bond or an ether bond, and Cy 1 represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms. )
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