JP2004046206A - Chemically amplified photoresist composition, acrylic or methacrylic ester copolymer used therefor, and acrylic or methacrylic ester used for producing the copolymer - Google Patents
Chemically amplified photoresist composition, acrylic or methacrylic ester copolymer used therefor, and acrylic or methacrylic ester used for producing the copolymer Download PDFInfo
- Publication number
- JP2004046206A JP2004046206A JP2003207338A JP2003207338A JP2004046206A JP 2004046206 A JP2004046206 A JP 2004046206A JP 2003207338 A JP2003207338 A JP 2003207338A JP 2003207338 A JP2003207338 A JP 2003207338A JP 2004046206 A JP2004046206 A JP 2004046206A
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- JP
- Japan
- Prior art keywords
- acrylic
- copolymer
- photoresist composition
- chemically amplified
- acid
- 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.)
- Granted
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 21
- 229920001577 copolymer Polymers 0.000 title claims description 19
- 229920006243 acrylic copolymer Polymers 0.000 title abstract 2
- 229920003146 methacrylic ester copolymer Polymers 0.000 title abstract 2
- 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 title 1
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 36
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 238000001312 dry etching Methods 0.000 abstract description 14
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- -1 acrylic ester Chemical class 0.000 description 26
- 239000000178 monomer Substances 0.000 description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QHGUPRQTQITEPO-UHFFFAOYSA-N oxan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCO1 QHGUPRQTQITEPO-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 2
- 0 *[N+]([N-])[N+]([O-])OC1C2OC2OCC1 Chemical compound *[N+]([N-])[N+]([O-])OC1C2OC2OCC1 0.000 description 2
- 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 2
- 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 2
- FWIBCWKHNZBDLS-UHFFFAOYSA-N 3-hydroxyoxolan-2-one Chemical compound OC1CCOC1=O FWIBCWKHNZBDLS-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- VGZKCAUAQHHGDK-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 VGZKCAUAQHHGDK-UHFFFAOYSA-M 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-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
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 2
- FGWRVVZMNXRWDQ-UHFFFAOYSA-N oxan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCO1 FGWRVVZMNXRWDQ-UHFFFAOYSA-N 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- MCJPJAJHPRCILL-UHFFFAOYSA-N (2,6-dinitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O MCJPJAJHPRCILL-UHFFFAOYSA-N 0.000 description 1
- MCVVDMSWCQUKEV-UHFFFAOYSA-N (2-nitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1[N+]([O-])=O MCVVDMSWCQUKEV-UHFFFAOYSA-N 0.000 description 1
- CVBASHMCALKFME-UHFFFAOYSA-N (4-methoxyphenyl)-diphenylsulfanium Chemical compound C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 CVBASHMCALKFME-UHFFFAOYSA-N 0.000 description 1
- YXSLFXLNXREQFW-UHFFFAOYSA-M (4-methoxyphenyl)-phenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC)=CC=C1[I+]C1=CC=CC=C1 YXSLFXLNXREQFW-UHFFFAOYSA-M 0.000 description 1
- RLAWXWSZTKMPQQ-UHFFFAOYSA-M (4-tert-butylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 RLAWXWSZTKMPQQ-UHFFFAOYSA-M 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OESYNCIYSBWEQV-UHFFFAOYSA-N 1-[diazo-(2,4-dimethylphenyl)sulfonylmethyl]sulfonyl-2,4-dimethylbenzene Chemical compound CC1=CC(C)=CC=C1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=C(C)C=C1C OESYNCIYSBWEQV-UHFFFAOYSA-N 0.000 description 1
- GYQQFWWMZYBCIB-UHFFFAOYSA-N 1-[diazo-(4-methylphenyl)sulfonylmethyl]sulfonyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=C(C)C=C1 GYQQFWWMZYBCIB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DBZKLCIHFPDWMJ-UHFFFAOYSA-N 1-ethoxyethyl prop-2-enoate Chemical compound CCOC(C)OC(=O)C=C DBZKLCIHFPDWMJ-UHFFFAOYSA-N 0.000 description 1
- RDGGDLYJSYBBID-UHFFFAOYSA-N 1-methoxypropyl prop-2-enoate Chemical compound CCC(OC)OC(=O)C=C RDGGDLYJSYBBID-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BVBUVHZVGAXBJX-UHFFFAOYSA-N 2,4,6-tris(2,3-dibromopropyl)-1,3,5-triazine Chemical compound BrCC(Br)CC1=NC(CC(Br)CBr)=NC(CC(Br)CBr)=N1 BVBUVHZVGAXBJX-UHFFFAOYSA-N 0.000 description 1
- BFQFFNWLTHFJOZ-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=C3OCOC3=CC=2)=N1 BFQFFNWLTHFJOZ-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
- FVNIIPIYHHEXQA-UHFFFAOYSA-N 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 FVNIIPIYHHEXQA-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- ZJRNXDIVAGHETA-UHFFFAOYSA-N 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZJRNXDIVAGHETA-UHFFFAOYSA-N 0.000 description 1
- XOPKKHCDIAYUSK-UHFFFAOYSA-N 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound O1C(C)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 XOPKKHCDIAYUSK-UHFFFAOYSA-N 0.000 description 1
- PNDRGJCVJPHPOZ-UHFFFAOYSA-N 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=CC=2OC=CC=2)=N1 PNDRGJCVJPHPOZ-UHFFFAOYSA-N 0.000 description 1
- SAFWZKVQMVOANB-UHFFFAOYSA-N 2-[tert-butylsulfonyl(diazo)methyl]sulfonyl-2-methylpropane Chemical compound CC(C)(C)S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C(C)(C)C SAFWZKVQMVOANB-UHFFFAOYSA-N 0.000 description 1
- GGXVWQGJAWFVRI-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 GGXVWQGJAWFVRI-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- VZRRCQOUNSHSGB-UHFFFAOYSA-N 4-hydroxy-4,6,6-trimethylbicyclo[3.1.1]heptan-3-one Chemical compound C1C2C(C)(C)C1CC(=O)C2(O)C VZRRCQOUNSHSGB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- LFJLNVUGIWJQCX-UHFFFAOYSA-N [[(4-bromophenyl)-cyanomethylidene]amino] methanesulfonate Chemical compound CS(=O)(=O)ON=C(C#N)C1=CC=C(Br)C=C1 LFJLNVUGIWJQCX-UHFFFAOYSA-N 0.000 description 1
- XDHUWCBFSRIEEC-UHFFFAOYSA-N [[cyano(phenyl)methylidene]amino] methanesulfonate Chemical compound CS(=O)(=O)ON=C(C#N)C1=CC=CC=C1 XDHUWCBFSRIEEC-UHFFFAOYSA-N 0.000 description 1
- PEJLVNJVORRJOP-UHFFFAOYSA-N [[cyano(phenyl)methylidene]amino] trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)ON=C(C#N)C1=CC=CC=C1 PEJLVNJVORRJOP-UHFFFAOYSA-N 0.000 description 1
- UPXATANHGSYTNL-UHFFFAOYSA-N [[cyano-(4-methoxyphenyl)methylidene]amino] ethanesulfonate Chemical compound CCS(=O)(=O)ON=C(C#N)C1=CC=C(OC)C=C1 UPXATANHGSYTNL-UHFFFAOYSA-N 0.000 description 1
- BADIYTSGNBSILF-UHFFFAOYSA-N [[cyano-(4-methoxyphenyl)methylidene]amino] methanesulfonate Chemical compound COC1=CC=C(C(=NOS(C)(=O)=O)C#N)C=C1 BADIYTSGNBSILF-UHFFFAOYSA-N 0.000 description 1
- ZMIGBWNVUSOGIL-UHFFFAOYSA-N [[cyano-(4-methoxyphenyl)methylidene]amino] trifluoromethanesulfonate Chemical compound COC1=CC=C(C(=NOS(=O)(=O)C(F)(F)F)C#N)C=C1 ZMIGBWNVUSOGIL-UHFFFAOYSA-N 0.000 description 1
- WVCAZSUCPKYBCC-UHFFFAOYSA-N [[cyano-(4-methylphenyl)methylidene]amino] propane-1-sulfonate Chemical compound CCCS(=O)(=O)ON=C(C#N)C1=CC=C(C)C=C1 WVCAZSUCPKYBCC-UHFFFAOYSA-N 0.000 description 1
- GLGXSTXZLFQYKJ-UHFFFAOYSA-N [cyclohexylsulfonyl(diazo)methyl]sulfonylcyclohexane Chemical compound C1CCCCC1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1CCCCC1 GLGXSTXZLFQYKJ-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- XRLHGXGMYJNYCR-UHFFFAOYSA-N acetic acid;2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)=O.CC(O)COC(C)CO XRLHGXGMYJNYCR-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ＡｒＦエキシマレーザーに対する透明性が高く、パターン特性、特に耐ドライエッチング性及び密着性の優れたレジストパターンを与える化学増幅型ホトレジスト組成物、その樹脂成分として用いられるアクリル酸若しくはメタクリル酸エステル共重合体及びその共重合体製造用単量体として用いられるアクリル酸若しくはメタクリル酸エステルに関するものである。
【０００２】
【従来の技術】
これまで、化学増幅型レジストの樹脂成分としては、ＫｒＦエキシマレーザー（２４８ｎｍ）に対し高い透明性を有するポリヒドロキシスチレンやこのヒドロキシル基を酸解離性の溶解抑制基で保護したものが主に用いられてきた。
しかしながら、近年半導体素子の微細化に対する要求はますます高まり、その光源もＫｒＦエキシマレーザーからより短波長のＡｒＦエキシマレーザー（１９３ｎｍ）を用いるプロセスに移行しつつある。
【０００３】
ところで、ＡｒＦエキシマレーザー（１９３ｎｍ）を光源とするプロセスにおいては、従来用いていたポリヒドロキシスチレンのような芳香族環をもつ樹脂では、このＡｒＦエキシマレーザーに対する透明性が不十分で使用できないため、これに代わるものとして芳香族環をもたないアクリル系樹脂が注目されるようになってきたが、このアクリル系樹脂は、耐ドライエッチング性が劣るという欠点を有している。
【０００４】
そして、このような耐ドライエッチング性を向上させるために、アクリル酸と脂環式アルキルとのエステルを樹脂中の構成単位に導入することが有効であることが知られ、これまでエステル部にアダマンタン骨格をもつアクリル酸エステルの重合体（特許文献１参照）や、エステル部にアダマンタン骨格をもつアクリル酸エステルとアクリル酸テトラヒドロピラニルエステルとの共重合体（特許文献２参照）などが提案されている。
【０００５】
しかしながら、このようなアダマンタン骨格をもつアクリル酸エステルを構成単位として導入すれば、透明性及び耐ドライエッチング性については、ある程度の向上効果が認められるが、その効果は必ずしも満足しうるものではない上に、アダマンタン骨格をもつアクリル酸エステル自体容易に入手しうるものではないためコスト高になるのを免れず、また感度の点でも不十分で、良好なパターン形状が得られないという欠点がある。
【０００６】
一方、ＡｒＦエキシマレーザーを用いるプロセスにおいては、０．２μｍ以下の超微細パターンを解像性よく形成させることが重要な目的となっているが、このような超微細パターンを形成させる場合、基板とレジスト層との密着性が不足し、パターン倒れを生じるという問題を伴う。
このため、アクリル酸の３‐オキソシクロヘキシルエステル（特許文献３参照）や、γ‐ブチロラクトン（特許文献４参照）のような含酸素複素環基をもつアクリル酸エステルを構成単位として導入したものが提案されている。
【０００７】
しかしながら、このような含酸素複素環基をもつアクリル酸エステル単位を導入したアクリル系樹脂をＡｒＦエキシマレーザーに対して使用すると、密着性の点では幾分改善が認められるものの、現像液として用いられるアルカリ水溶液に対する親和性が不十分で、半導体素子製造の主流となっているパドル現像においては、忠実なレジストパターンが形成できない。このため、基板に対する密着性が優れ、しかもパドル現像可能なアルカリ水溶液に対する親和性を有するＡｒＦエキシマレーザー用レジストを実現させることが、この分野における重要な課題となっている。
【０００８】
【特許文献１】
特開平４−３９６６５号公報（特許請求の範囲その他）
【特許文献２】
特開平５−２６５２１２号公報（特許請求の範囲その他）
【特許文献３】
特開平５−３４６６６８号公報（特許請求の範囲その他）
【特許文献４】
特開平７−１８１６７７号公報（特許請求の範囲その他）
【０００９】
【発明が解決しようとする課題】
本発明は、このような事情のもとで、ＡｒＦエキシマレーザーに対する透明性が高く、かつ優れた感度、レジストパターン形状、耐ドライエッチング性及び密着性を示すとともに、アルカリに対する親和性が高く、パドル現像により良好なレジストパターンを与えうる化学増幅型ホトレジスト組成物と、その樹脂成分として用いるアクリル酸若しくはメタクリル酸エステル共重合体と、その製造原料となるアクリル酸若しくはメタクリル酸エステルを提供することを目的としてなされたものである。
【００１０】
【課題を解決するための手段】
本発明者らは、ＡｒＦエキシマレーザー用の化学増幅型ホトレジスト組成物、特にポジ型ホトレジスト組成物について種々研究を重ねた結果、特定のブチロラクトン環をもつ単量体から製造された共重合体を樹脂成分として用いることにより、ＡｒＦエキシマレーザーに対して良好な透明性を有し、かつ優れた感度、レジストパターン形状、耐ドライエッチング性及び密着性を示す上に、アルカリに対し高い親和性を有する化学増幅型ホトレジスト組成物が得られることを見出し、この知見に基づいて本発明をなすに至った。
【００１１】
すなわち、本発明は、（Ａ）酸の作用によりアルカリに対する溶解性が変化するアクリル系樹脂及び（Ｂ）酸発生剤を含有するポジ型レジスト組成物において、（Ａ）成分がその構成単位の少なくとも一部として一般式
【化４】
で表わされる構成単位を有するアクリル酸若しくはメタクリル酸エステル共重合体であることを特徴とする化学増幅型ホトレジスト組成物、前記一般式（Ｉ）で表わされる構成単位を有するアクリル酸又はメタクリル酸エステル共重合体、及び一般式
【化５】
で表わされるアクリル酸又はメタクリル酸エステルを提供するものである。
【００１２】
【発明の実施の形態】
本発明の化学増幅型ホトレジスト組成物においては、（Ａ）酸の作用によりアルカリに対する溶解性が変化するアクリル系樹脂及び（Ｂ）酸発生剤を必須成分として含有するものである。
【００１３】
ところで、一般に化学増幅型ホトレジスト組成物の樹脂成分としては、（ａ）耐ドライエッチング性向上基や酸解離性保護基を有するアクリル酸若しくはメタクリル酸誘導体と（ｂ）エチレン性二重結合をもつ不飽和カルボン酸及び（ｃ）他の単量体から選ばれる少なくとも１種との共重合体が用いられているが、本発明においても、（Ａ）成分としてこのような共重合体が用いられる。
【００１４】
そして、この（ａ）のアクリル酸若しくはメタクリル酸誘導体としては、これまで知られている化学増幅型ホトレジストにおいて、耐ドライエッチング性を向上させるために用いられているもの、あるいは酸解離性保護基を導入させるために用いられているものの中から任意に選ぶことができる。
【００１５】
このようなものとしては、例えば（ａ−１）アクリル酸若しくはメタクリル酸のカルボキシル基の水素原子をｔｅｒｔ‐ブチル基、２‐テトラヒドロピラニル基、２‐テトラヒドロフラニル基、１‐メチルシクロヘキシル基、１‐メチルアダマンチル基、１‐エトキシエチル基及び１‐メトキシプロピル基などにより置換したもの又はアクリル酸若しくはメタクリル酸と２‐ヒドロキシ‐３‐ピナノンとのエステルのようなカルボキシル基を酸解離性置換基で保護したアクリル酸若しくはメタクリル酸や、（ａ−２）アクリル酸若しくはメタクリル酸のカルボキシル基の水素原子をアダマンチル基、シクロヘキシル基、ナフチル基、ベンジル基、３‐オキソシクロヘキシル基、ビシクロ［２，２，１］ヘプチル基、トリシクロデカニル基及びアセトニル基などにより置換したもの又はアクリル酸若しくはメタクリル酸とテルピネオールとのエステルのようなカルボキシル基を酸非解離性置換基で保護したアクリル酸若しくはメタクリル酸がある。
【００１６】
次に（ｂ）のエチレン性二重結合をもつ不飽和カルボン酸は、アルカリ可溶性を付与するために用いられるものであって、例えばアクリル酸、メタクリル酸、マレイン酸、フマル酸などがあるが、これらの中で特にアクリル酸及びメタクリル酸が好ましい。
【００１７】
また、（ｃ）の他の単量体は、（ａ）又は、（ａ）及び（ｂ）の単量体と共重合させるものであって、このようなものとしては、アクリル酸又はメタクリル酸のアルキルエステル、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ｎ‐ブチル、アクリル酸イソブチル、アクリル酸ｎ‐ヘキシル、アクリル酸オクチル、アクリル酸２‐エチルヘキシル、アクリル酸ラウリル、アクリル酸２‐ヒドロキシエチル、アクリル酸２‐ヒドロキシプロピル及び対応するメタクリル酸アルキルや、アクリル酸若しくはメタクリル酸のアミド類、例えばアクリルアミド、Ｎ‐メチロールアクリルアミド、ジアセトンアクリルアミド及び対応するメタクリルアミドや、アクリロニトリル、メタクリロニトリル、塩化ビニル、エチルビニルエーテルのようなエチレン結合をもつ化合物などが挙げられる。
【００１８】
そのほか、一般式
【化６】
で表わされるアクリル酸若しくはメタクリル酸エステル及び一般式
【化７】
で表わされるアクリル酸若しくはメタクリル酸エステルも用いることができる。
【００１９】
前記一般式（ＩＩＩ）で表わされるアクリル酸若しくはメタクリル酸エステルとしては、アクリル酸の２‐オキサシクロペンタン‐４‐オン‐１‐イルエステル、３‐メチル‐２‐オキサシクロペンタン‐４‐オン‐１‐イルエステル又は３，３‐ジメチル‐２‐オキサシクロペンタン‐４‐オン‐１‐イルエステル及び対応するメタクリル酸のエステルを挙げることができる。
【００２０】
また、前記一般式（ＩＶ）で表わされるアクリル酸若しくはメタクリル酸エステルとしては、アクリル酸の２，４‐ジオキサシクロヘキサ‐５‐オン‐１‐イルエステル、３‐メチル‐２，４‐ジオキサシクロヘキサ‐５‐オン‐１‐イルエステル、３，３‐ジメチル‐２，４‐ジオキサシクロヘキサ‐５‐オン‐１‐イルエステル、１‐メチル‐２‐オキサシクロヘキサ‐３，５‐ジオン‐１‐イルエステル、１‐メチル‐４‐アセチル‐２‐オキサシクロヘキサ‐３，５‐ジオン‐１‐イルエステル及び対応するメタクリル酸のエステルを挙げることができる。
【００２１】
そして、本発明組成物の（Ａ）成分は、上記の（ａ）、（ｂ）及び（ｃ）の中から選ばれる少なくとも１種の単量体に加えて、さらに前記一般式（ＩＩ）で表わされるアクリル酸若しくはメタクリル酸エステルを単量体として用いて誘導されたもの、すなわち前記一般式（Ｉ）で表わされる構成単位を有する共重合体であることが必要である。この前記一般式（ＩＩ）で表わされるアクリル酸若しくはメタクリル酸エステルは、新規化合物でこれまで化学増幅型ホトレジストの樹脂成分である、酸の作用によりアルカリに対する溶解性が増加するアクリル系樹脂を製造する際の単量体として使用されることが未だ知られていなかった化合物である。
【００２２】
この一般式（ＩＩ）で表わされる単量体は、例えばアクリル酸又はメタクリル酸に、慣用のエステル化方法に従い、式
【化８】
【００２３】
本発明の（Ａ）成分は、これらの単量体により構成されるが、特に好ましいのは、前記一般式（ＩＩ）で表わされるアクリル酸若しくはメタクリル酸エステルとともにアクリル酸２‐テトラヒドロピラニル、アクリル酸２‐テトラヒドロフラニル、アクリル酸１‐エトキシエチル、アクリル酸１‐メトキシプロピル及び対応するメタクリル酸エステルのようなカルボキシル基の水酸基をアセタール系の酸解離性置換基で保護したアクリル酸及びメタクリル酸特にアクリル酸若しくはメタクリル酸の２‐テトラヒドロピラニルエステルを単量体として用いた共重合体が酸解離性が高く、露光後加熱処理による依存性が少ないので有利である。
【００２４】
本発明においては、このように、（Ａ）成分の構成単位の一部が前記一般式（Ｉ）で表わされる構成単位であることが必要であるが、この構成単位の割合としては、全構成単位の２０〜８０モル％、特に５０〜８０モル％の範囲が、耐ドライエッチング性、密着性、未露光部とのコントラストが良好になる点で好ましい。
【００２５】
次に、本発明の（Ｂ）成分としては、これまで化学増幅型レジストの酸発生剤として知られている化合物の中から任意に選んで用いることができる。
このような化合物としては、例えば次に示すものを挙げることができる。
【００２６】
（イ）ビススルホニルジアゾメタン；
ビス（ｐ‐トルエンスルホニル）ジアゾメタン、ビス（１，１‐ジメチルエチルスルホニル）ジアゾメタン、ビス（シクロヘキシルスルホニル）ジアゾメタン、ビス（２，４‐ジメチルフェニルスルホニル）ジアゾメタンなど。
【００２７】
（ロ）ニトロベンジル誘導体；
ｐ‐トルエンスルホン酸２‐ニトロベンジル、ｐ‐トルエンスルホン酸２，６‐ジニトロベンジルなど。
【００２８】
（ハ）スルホン酸エステル；
ピロガロールトリメシレート、ピロガロールトリトシレートなど。
【００２９】
（ニ）オニウム塩；
ジフェニルヨードニウムヘキサフルオロフェスフェート、（４‐メトキシフェニル）フェニルヨードニウムトリフルオロメタンスルホネート、ビス（ｐ‐ｔｅｒｔ‐ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムヘキサフルオロフェスフェート、（４‐メトキシフェニル）ジ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、（ｐ‐ｔｅｒｔ‐ブチルフェニル）ジ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など。
【００３０】
（ホ）ベンゾイントシレート及びそのアルキル置換体；
ベンゾイントシレート、α‐メチルベンゾイントシレートなど。
【００３１】
（ヘ）ハロゲン含有トリアジン化合物；
２‐（４‐メトキシフェニル）‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２‐（４‐メトキシナフチル）‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２‐［２‐（２‐フリル）エテニル］‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２‐［２‐（５‐メチル‐２‐フリル）エテニル］‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２‐［２‐（３，５‐ジメトキシフェニル）エテニル］‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２‐［２‐（３，４‐ジメトキシフェニル）エテニル］‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２‐（３，４‐メチレンジオキシフェニル）‐４，６‐ビス（トリクロロメチル）‐１，３，５‐トリアジン、２，４，６‐トリス（２，３‐ジブロモプロピル）‐１，３，５‐トリアジンなど。
【００３２】
（ト）シアノ基を有するオキシムスルホネート；
α‐（メチルスルホニルオキシイミノ）フェニルアセトニトリル、α‐（メチルスルホニルオキシイミノ）‐４‐メトキシフェニルアセトニトリル、α‐（トリフルオロメチルスルホニルオキシイミノ）フェニルアセトニトリル、α‐（トリフルオロメチルスルホニルオキシイミノ）‐４‐メトキシフェニルアセトニトリル、α‐（エチルスルホニルオキシイミノ）‐４‐メトキシフェニルアセトニトリル、α‐（プロピルスルホニルオキシイミノ）‐４‐メチルフェニルアセトニトリル、α‐（メチルスルホニルオキシイミノ）‐４‐ブロモフェニルアセトニトリル、α‐（メチルスルホニルオキシイミノ）‐１‐シクロペンテニルアセトニトリル、α‐［１‐（又は２‐）ナフチルスルホニルオキシイミノ］‐４‐メトキシベンジルシアニド、α‐（１０‐カンファースルホニルオキシイミノ）‐４‐メトキシベンジルシアニドなど。
【００３３】
これらの酸発生剤の中で特に好ましいのは、オニウム塩及びシアノ基を有するオキシムスルホネートである。（Ａ）成分と（Ｂ）成分の配合割合は、（Ａ）成分１００重量部に対し、（Ｂ）成分０．５〜３０重量部、好ましくは、１〜１０重量部である。この範囲よりも少なくなると像形成ができないし、多くなると、均一な溶液とならず、保存安定性が低下する。
【００３４】
本発明のホトレジスト組成物には、所望に応じ、（Ａ）成分及び（Ｂ）成分に加えて、通常の化学増幅型ホトレジストに慣用されている添加成分、例えば、ハレーション防止剤、酸化防止剤、熱安定剤、密着性向上剤、可塑剤、着色剤、界面活性剤、付加的樹脂、有機カルボン酸、アミン類など本発明組成物の特性が阻害されない範囲の量で配合することができる。
【００３５】
本発明のホトレジスト組成物は、その使用に当たっては上記各成分を溶剤に溶解した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、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‐ヘプタノンなどのケトン類や、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、ジエチレングリコール、ジ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、プロピレングリコールモノアセテート、ジプロピレングリコール、又はジプロピレングリコールモノアセテート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又はモノフェニルエーテルなどの多価アルコール類及びその誘導体や、ジオキサンのような環式エーテル類や、乳酸メチル、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など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種以上混合して用いてもよい。
【００３６】
本発明のホトレジスト組成物を用いれば、例えば次のようにしてパターン形成することができる。すなわち、このホトレジスト組成物を、シリコンウエーハなどの基板上に塗布し、７０〜１５０℃で３０〜１５０秒間プリベイクを行い、レジスト層を形成したのち、マスクを介してＡｒＦエキシマレーザーなどの放射線を照射し、７０〜１５０℃程度の加熱を３０秒から１５０秒行い、次いで現像を行う。レジストの現像液としては、アルカリ性水溶液を用いることができ現像により、露光部がアルカリ性水溶液に溶解し、ポジ型のパターンが得られる。アルカリ性水溶液としては例えばテトラメチルアンモニウムヒドロキシド、コリンなどの水溶液を用いることができる。
【００３７】
【実施例】
次に実施例により本発明をさらに詳細に説明する。
【００３８】
参考例１
３‐ヒドロキシ‐１‐オキサシクロペンタン‐２‐オン５５．１ｇ（０．５４モル）、トリエチルアミン６０ｇ（０．６０モル）をテトラヒドロフラン２００ミリリットルに溶解し、十分撹拌した後、これにメタクリロイルクロリド６２．４ｇ（０．６０モル）を２５℃で１時間にわたって滴下した。
次いで、２５℃にて２４時間反応させた後、反応液をろ過した。そのろ液の溶媒を留去し、残存生成物をジエチルエーテル３００ミリリットルに溶解し、１０重量％水酸化ナトリウム溶液で１０回洗浄した。次いで、ｎ‐ヘプタンを溶媒としてカラムクロマトグラフィーにより精製し、無色の液体として、式
【化９】
この生成物の１Ｈ−ＮＭＲ（溶媒：アセトン−ｄ６）を測定した結果、１．９２ｐｐｍ、２．３０〜２．５０ｐｐｍ、３．９０〜４．１０ｐｐｍ、５．２０ｐｐｍ、５．６０ｐｐｍ、６．１２ｐｐｍにピークが認められた。
【００３９】
このようにして得たメタクリル酸エステル１７．４ｇ（０．０９４モル、全モノマーに対するモル％は７５モル％）、メタクリル酸２‐テトラヒドロピラニル５．３ｇ（０．０３１モル、全モノマーに対するモル％は２５モル％）をテトラヒドロフラン５６０ｇに溶解し、反応開始剤としてアゾビスイソブチロニトリル０．８１ｇを加え、７５℃で３時間重合反応させた。反応終了後、反応物をｎ‐ヘプタン５リットル中に注加して重合体を析出させ、得られた共重合体を室温下で減圧乾燥した。このようにして、上記のメタクリル酸エステルとメタクリル酸２‐テトラヒドロピラニルの共重合体（Ａ−１）を得た。この共重合体の収量は１４．９ｇであり、重量平均分子量は１３，５００で、分散度は２．０１であった。
【００４０】
参考例２
参考例１における重合性モノマーの代りに、全モノマーに対するモル％が５０モル％となる量のメタクリル酸アダマンチルを用い、参考例１と同様にして、式
【化１０】
【００４１】
参考例３
参考例１における重合性モノマーの代りに、式
【化１１】
【００４２】
実施例
参考例１で得た重合体（Ａ−１）１００重量部、ビス（ｐ‐ｔｅｒｔ‐ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート２重量部をプロピレングリコールモノメチルエーテルアセテート６８０重量部に溶解してポジ型レジスト溶液を得た。
次いで、このレジスト溶液をスピンナーを用いてシリコンウエーハ上に塗布し、ホットプレート上で１００℃で９０秒間乾燥することにより、膜厚０．５μｍのレジスト層を形成した。次いで、ＡｒＦ露光装置（ニコン社製）により、ＡｒＦエキシマレーザー（１９３ｎｍ）を選択的に照射したのち、１１０℃９０秒間ＰＥＢ処理し、次いで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６５秒間パドル現像し、３０秒間水洗して乾燥した。
【００４３】
このような操作で形成された０．２５μｍのラインアンドスペースが１：１に形成される露光時間を感度としてｍＪ／ｃｍ２（エネルギー量）単位で測定したところ、６．０ｍＪ／ｃｍ２であった。
また、このようにして形成された０．２５μｍのレジストパターンの断面形状をＳＥＭ（走査型電子顕微鏡）写真により、観察したところ、基板に対して垂直な矩形のレジストパターンであった。
また、このような操作で０．２０μｍのレジストパターンまで解像され、パターン倒れはなかった。
次いで、テトラフルオロメタンガスをエッチングガスとして、エッチング装置ＯＡＰＭ−４０６（東京応化工業株式会社製）でドライエッチングし、耐ドライエッチング性を単位時間当たりの膜減り量で評価し、ポリヒドロキシスチレンを１．０とした場合、１．１であった。
【００４４】
比較例１
実施例１において、重合体（Ａ−１）を同量の参考例２で得た重合体（Ａ−２）に代えた以外は実施例１と同様にして、ポジ型レジスト溶液を調製し、次いで実施例と同様な条件でレジストパターンを形成した。
その際の実施例と同様な定義の感度は、１５ｍＪ／ｃｍ２であり、０．３０μｍ以下のレジストパターンは解像することができなかった。
また、実施例と同様な定義の耐ドライエッチング性を調べたところ、１．０であった。
【００４５】
比較例２
実施例において、重合体（Ａ−１）を同量の参考例３で得た重合体（Ａ−３）に代えた以外は実施例と同様にして、ポジ型レジスト溶液を調製し、次いで実施例と同様な条件でレジストパターンを形成した。
その際の実施例と同様な定義の感度は、５．０ｍＪ／ｃｍ２であり、このような操作で０．２５μｍのレジストパターンまで解像され、パターン倒れはなかったものの、形成された０．３０μｍのレジストパターンの断面形状をＳＥＭ（走査型電子顕微鏡）写真により、観察したところ、基板に対して台形状のレジストパターンであった。
また、同様にして、耐ドライエッチング性を調べたところ、１．５であった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a chemically amplified photoresist composition which provides a resist pattern having high transparency to an ArF excimer laser and excellent pattern characteristics, especially dry etching resistance and adhesion, acrylic acid or methacrylic acid ester used as a resin component thereof The present invention relates to a copolymer and an acrylic acid or methacrylic acid ester used as a monomer for producing the copolymer.
[0002]
[Prior art]
Heretofore, as a resin component of a chemically amplified resist, polyhydroxystyrene having high transparency to a KrF excimer laser (248 nm) or a resin in which this hydroxyl group is protected by an acid dissociable, dissolution inhibiting group has been mainly used. Have been.
However, in recent years, the demand for miniaturization of semiconductor elements has been increasing more and more, and the light source thereof has been shifting from a KrF excimer laser to a process using an ArF excimer laser (193 nm) having a shorter wavelength.
[0003]
By the way, in a process using an ArF excimer laser (193 nm) as a light source, a resin having an aromatic ring such as polyhydroxystyrene conventionally used cannot be used because of insufficient transparency to the ArF excimer laser. As an alternative to the above, an acrylic resin having no aromatic ring has been attracting attention, but this acrylic resin has a drawback that its dry etching resistance is inferior.
[0004]
In order to improve such dry etching resistance, it is known that it is effective to introduce an ester of acrylic acid and an alicyclic alkyl into a structural unit in a resin. A polymer of an acrylate having a skeleton (see Patent Document 1), a copolymer of an acrylate having an adamantane skeleton in the ester portion and tetrahydropyranyl acrylate (see Patent Document 2), and the like have been proposed. .
[0005]
However, when such an acrylate having an adamantane skeleton is introduced as a constituent unit, a certain improvement in transparency and dry etching resistance is observed, but the effects are not always satisfactory. In addition, the acrylic ester having an adamantane skeleton itself is not easily available, so that it is unavoidable that the cost is high, the sensitivity is insufficient, and a good pattern shape cannot be obtained.
[0006]
On the other hand, in a process using an ArF excimer laser, it is important to form an ultra-fine pattern of 0.2 μm or less with good resolution. There is a problem that the adhesion to the resist layer is insufficient and the pattern collapses.
For this reason, it has been proposed that acrylic acid esters having an oxygen-containing heterocyclic group, such as 3-oxocyclohexyl ester of acrylic acid (see Patent Document 3) and γ-butyrolactone (see Patent Document 4), are introduced as constituent units. Have been.
[0007]
However, when an acrylic resin into which such an acrylate unit having an oxygen-containing heterocyclic group is introduced is used for an ArF excimer laser, it is used as a developer, although a slight improvement in adhesion is observed. In paddle development, which is the mainstream in semiconductor device production, the affinity for an alkaline aqueous solution is insufficient, so that a faithful resist pattern cannot be formed. Therefore, realizing a resist for an ArF excimer laser having excellent adhesion to a substrate and having an affinity for an aqueous alkali solution capable of paddle development has become an important issue in this field.
[0008]
[Patent Document 1]
JP-A-4-39665 (claims and others)
[Patent Document 2]
JP-A-5-265212 (Claims and others)
[Patent Document 3]
JP-A-5-346668 (Claims and others)
[Patent Document 4]
JP-A-7-181677 (claims and others)
[0009]
[Problems to be solved by the invention]
Under such circumstances, the present invention has high transparency to ArF excimer laser, excellent sensitivity, resist pattern shape, dry etching resistance and adhesion, and high affinity for alkali, The object is to provide a chemically amplified photoresist composition capable of providing a good resist pattern by development, an acrylic acid or methacrylic acid ester copolymer used as a resin component thereof, and an acrylic acid or methacrylic acid ester as a raw material for producing the same. It was done as.
[0010]
[Means for Solving the Problems]
The present inventors have conducted various studies on a chemically amplified photoresist composition for an ArF excimer laser, particularly a positive photoresist composition, and have found that a copolymer produced from a monomer having a specific butyrolactone ring can be used as a resin. By using it as a component, it has good transparency to ArF excimer laser, excellent sensitivity, resist pattern shape, dry etching resistance and adhesion, and also has high affinity to alkali. It has been found that an amplified photoresist composition can be obtained, and the present invention has been accomplished based on this finding.
[0011]
That is, the present invention provides a positive resist composition containing (A) an acrylic resin whose solubility in alkali is changed by the action of an acid and (B) an acid generator, wherein the component (A) has at least one of its constituent units. Partially represented by the general formula
A chemically amplified photoresist composition comprising an acrylic acid or methacrylic acid ester copolymer having a structural unit represented by the formula: and an acrylic acid or methacrylic acid ester having a structural unit represented by the general formula (I). Polymer and general formula
And an acrylic acid or methacrylic acid ester represented by the formula:
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The chemically amplified photoresist composition of the present invention contains (A) an acrylic resin whose solubility in alkali changes due to the action of an acid and (B) an acid generator as essential components.
[0013]
By the way, generally, as the resin component of the chemically amplified photoresist composition, (a) an acrylic acid or methacrylic acid derivative having a group for improving dry etching resistance or an acid dissociable protecting group and (b) a resin having an ethylenic double bond are used. A copolymer with at least one selected from a saturated carboxylic acid and (c) another monomer is used. In the present invention, such a copolymer is used as the component (A).
[0014]
As the acrylic acid or methacrylic acid derivative (a), those which have been used for improving dry etching resistance in a chemically amplified photoresist known so far, or an acid dissociable protecting group can be used. It can be arbitrarily selected from those used for introduction.
[0015]
As such a compound, for example, (a-1) a hydrogen atom of a carboxyl group of acrylic acid or methacrylic acid is replaced with a tert-butyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group, 1-methylcyclohexyl group, Carboxyl groups, such as those substituted with -methyladamantyl, 1-ethoxyethyl and 1-methoxypropyl, or esters of acrylic acid or methacrylic acid with 2-hydroxy-3-pinanone, with acid dissociable substituents Protected acrylic acid or methacrylic acid, or (a-2) an adamantyl group, a cyclohexyl group, a naphthyl group, a benzyl group, a 3-oxocyclohexyl group, a bicyclo [2,2 1] a heptyl group, a tricyclodecanyl group and Setoniru groups include acrylic acid or methacrylic acid carboxyl groups are protected with non-acid-dissociable substituent groups such as esters of those that have been substituted or acrylic acid or methacrylic acid and terpineol and the like.
[0016]
Next, the unsaturated carboxylic acid having an ethylenic double bond (b) is used to impart alkali solubility, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Of these, acrylic acid and methacrylic acid are particularly preferred.
[0017]
The other monomer (c) is copolymerized with the monomer (a) or the monomers (a) and (b), such as acrylic acid or methacrylic acid. Alkyl esters of, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and the corresponding alkyl methacrylates, and amides of acrylic acid or methacrylic acid, such as acrylamide, N-methylolacrylamide, diacetoneacrylamide and the corresponding methacrylamide, acrylonitrile , Methacryloni Lil, vinyl chloride, and compounds having ethylenic bonds such as ethyl vinyl ether and the like.
[0018]
In addition, the general formula
Acrylic acid or methacrylic acid ester represented by the formula and a general formula:
And acrylic acid or methacrylic acid esters represented by
[0019]
As the acrylic acid or methacrylic acid ester represented by the general formula (III), 2-oxacyclopentan-4-one-1-yl ester of acrylic acid, 3-methyl-2-oxacyclopentan-4-one- Mention may be made of 1-yl esters or 3,3-dimethyl-2-oxacyclopentan-4-one-1-yl esters and the corresponding esters of methacrylic acid.
[0020]
The acrylic acid or methacrylic acid ester represented by the general formula (IV) includes 2,4-dioxacyclohex-5-one-1-yl ester of acrylic acid and 3-methyl-2,4-diethyl ester. Oxacyclohex-5-one-1-yl ester, 3,3-dimethyl-2,4-dioxacyclohex-5-one-1-yl ester, 1-methyl-2-oxacyclohexa-3,5 Mention may be made of -dione-1-yl ester, 1-methyl-4-acetyl-2-oxacyclohexa-3,5-dione-1-yl ester and the corresponding esters of methacrylic acid.
[0021]
The component (A) of the composition of the present invention further comprises, in addition to at least one monomer selected from the above (a), (b) and (c), a compound represented by the general formula (II) It is necessary that the acrylic acid or methacrylic acid ester represented by the formula (I) be used as a monomer, that is, a copolymer having the structural unit represented by the general formula (I). The acrylic acid or methacrylic acid ester represented by the general formula (II) is a novel compound and produces an acrylic resin, which has been a resin component of a chemically amplified photoresist and has increased solubility in alkali due to the action of an acid. It is a compound that has not yet been known to be used as a monomer at the time.
[0022]
The monomer represented by the general formula (II) can be converted to, for example, acrylic acid or methacrylic acid by a conventional esterification method according to the formula:
[0023]
The component (A) of the present invention is composed of these monomers. Particularly preferred are 2-tetrahydropyranyl acrylate, acrylic acid and acrylic acid or methacrylic acid ester represented by the general formula (II). Acrylic acid and methacrylic acid in which the hydroxyl group of a carboxyl group such as 2-tetrahydrofuranyl acid, 1-ethoxyethyl acrylate, 1-methoxypropyl acrylate and the corresponding methacrylic acid ester is protected with an acetal acid-dissociable substituent. A copolymer using 2-tetrahydropyranyl ester of acrylic acid or methacrylic acid as a monomer is advantageous because it has a high acid dissociation property and is less dependent on heat treatment after exposure.
[0024]
In the present invention, as described above, it is necessary that some of the structural units of the component (A) are structural units represented by the general formula (I). The range of 20 to 80 mol%, especially 50 to 80 mol% of the unit is preferable in that the dry etching resistance, the adhesion, and the contrast with the unexposed portion are improved.
[0025]
Next, the component (B) of the present invention can be arbitrarily selected from compounds known as acid generators for chemically amplified resists.
Examples of such compounds include the following.
[0026]
(A) bissulfonyldiazomethane;
Bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and the like.
[0027]
(B) nitrobenzyl derivatives;
2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate and the like.
[0028]
(C) sulfonic acid ester;
Pyrogallol trimesylate, pyrogallol tritosylate and the like.
[0029]
(D) onium salts;
Diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoro Romethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate and the like.
[0030]
(E) benzoin tosylate and its alkyl-substituted product;
Benzoin tosylate, α-methyl benzoin tosylate and the like.
[0031]
(F) a halogen-containing triazine compound;
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl ] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl ) -1,3,5-triazine, 2,4,6-tris (2,3-dibromopropyl) -1,3,5-triazine.
[0032]
(To) an oxime sulfonate having a cyano group;
α- (methylsulfonyloxyimino) phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino)- 4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile, α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile Α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- [1- (or 2-) naphthylsulfonyloxyimino] -4-methoxybenzyl cyanide, - (10-camphorsulfonyl) -4-methoxybenzyl cyanide and the like.
[0033]
Particularly preferred among these acid generators are onium salts and oxime sulfonates having a cyano group. The mixing ratio of the component (A) and the component (B) is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the component (A). When the amount is less than this range, image formation cannot be performed. When the amount is too large, a uniform solution is not obtained, and storage stability is reduced.
[0034]
In the photoresist composition of the present invention, if necessary, in addition to the components (A) and (B), additional components commonly used in ordinary chemically amplified photoresists, for example, antihalation agents, antioxidants, Heat stabilizers, adhesion improvers, plasticizers, colorants, surfactants, additional resins, organic carboxylic acids, amines, and the like can be added in amounts that do not impair the properties of the composition of the present invention.
[0035]
The photoresist composition of the present invention is preferably used in the form of a solution in which the above components are dissolved in a solvent. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, Dipropylene glycol or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and derivatives thereof, and cyclic ethers such as dioxane, lactic acid Methyl, 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 as a mixture of two or more.
[0036]
Using the photoresist composition of the present invention, a pattern can be formed, for example, as follows. That is, the photoresist composition is applied on a substrate such as a silicon wafer, prebaked at 70 to 150 ° C. for 30 to 150 seconds to form a resist layer, and then irradiated with radiation such as an ArF excimer laser through a mask. Then, heating at about 70 to 150 ° C. is performed for 30 to 150 seconds, and then development is performed. An alkaline aqueous solution can be used as a developing solution for the resist, and the exposed portions are dissolved in the alkaline aqueous solution by development, and a positive pattern is obtained. As the alkaline aqueous solution, for example, an aqueous solution of tetramethylammonium hydroxide, choline or the like can be used.
[0037]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0038]
Reference Example 1
After dissolving 55.1 g (0.54 mol) of 3-hydroxy-1-oxacyclopentan-2-one and 60 g (0.60 mol) of triethylamine in 200 ml of tetrahydrofuran and sufficiently stirring the mixture, methacryloyl chloride was added thereto. 4 g (0.60 mol) were added dropwise at 25 ° C. over 1 hour.
Next, after reacting at 25 ° C. for 24 hours, the reaction solution was filtered. The solvent of the filtrate was distilled off, the remaining product was dissolved in 300 ml of diethyl ether, and washed 10 times with a 10% by weight sodium hydroxide solution. Then, the product is purified by column chromatography using n-heptane as a solvent and converted into a colorless liquid of the formula
As a result of measuring 1 H-NMR (solvent: acetone-d 6 ) of this product, 1.92 ppm, 2.30 to 2.50 ppm, 3.90 to 4.10 ppm, 5.20 ppm, 5.60 ppm, 6 A peak was observed at .12 ppm.
[0039]
The thus obtained methacrylic acid ester (17.4 g, 0.094 mol, mol% based on all monomers is 75 mol%), 5.3 g of 2-tetrahydropyranyl methacrylate (0.031 mol, mol% based on all monomers) Was dissolved in 560 g of tetrahydrofuran, and 0.81 g of azobisisobutyronitrile was added as a reaction initiator, followed by polymerization at 75 ° C. for 3 hours. After the completion of the reaction, the reaction product was poured into 5 liters of n-heptane to precipitate a polymer, and the obtained copolymer was dried under reduced pressure at room temperature. Thus, a copolymer (A-1) of the above methacrylate and 2-tetrahydropyranyl methacrylate was obtained. The yield of this copolymer was 14.9 g, the weight average molecular weight was 13,500, and the degree of dispersion was 2.01.
[0040]
Reference Example 2
In place of the polymerizable monomer in Reference Example 1, adamantyl methacrylate was used in an amount such that the molar percentage based on the total monomer was 50 mol%.
[0041]
Reference Example 3
Instead of the polymerizable monomer in Reference Example 1, the formula
[0042]
EXAMPLE 100 parts by weight of the polymer (A-1) obtained in Reference Example 1 and 2 parts by weight of bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate were dissolved in 680 parts by weight of propylene glycol monomethyl ether acetate to obtain a positive type. A resist solution was obtained.
Next, the resist solution was applied on a silicon wafer using a spinner and dried on a hot plate at 100 ° C. for 90 seconds to form a resist layer having a thickness of 0.5 μm. Next, after selectively irradiating an ArF excimer laser (193 nm) with an ArF exposure apparatus (manufactured by Nikon Corporation), PEB treatment was performed at 110 ° C. for 90 seconds, and then paddle was performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 65 seconds. It was developed, washed with water for 30 seconds and dried.
[0043]
The exposure time, in which a 0.25 μm line and space formed by such an operation was formed at a ratio of 1: 1, was measured in mJ / cm 2 (energy amount) as a sensitivity, and was 6.0 mJ / cm 2. Was.
Further, when the cross-sectional shape of the thus formed resist pattern of 0.25 μm was observed by an SEM (scanning electron microscope) photograph, it was a rectangular resist pattern perpendicular to the substrate.
In addition, the resolution was reduced to a 0.20 μm resist pattern by such an operation, and no pattern collapse occurred.
Next, dry etching was performed with an etching apparatus OAPM-406 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) using tetrafluoromethane gas as an etching gas, and the dry etching resistance was evaluated by the amount of film reduction per unit time. When it was set to 0, it was 1.1.
[0044]
Comparative Example 1
A positive resist solution was prepared in the same manner as in Example 1 except that the polymer (A-1) was replaced with the same amount of the polymer (A-2) obtained in Reference Example 2 in Example 1. Next, a resist pattern was formed under the same conditions as in the example.
At that time, the sensitivity having the same definition as that of the example was 15 mJ / cm 2 , and a resist pattern of 0.30 μm or less could not be resolved.
In addition, when the dry etching resistance having the same definition as in the example was examined, it was 1.0.
[0045]
Comparative Example 2
In the example, a positive resist solution was prepared in the same manner as in the example except that the polymer (A-1) was replaced with the same amount of the polymer (A-3) obtained in Reference Example 3, and then the procedure was repeated. A resist pattern was formed under the same conditions as in the example.
At that time, the sensitivity having the same definition as that of the embodiment is 5.0 mJ / cm 2 , and the resist pattern is resolved to 0.25 μm by such an operation. When the cross-sectional shape of the 30 μm resist pattern was observed by a SEM (scanning electron microscope) photograph, the resist pattern was trapezoidal with respect to the substrate.
In addition, when the dry etching resistance was examined in the same manner, it was 1.5.
Claims (5)
で表わされる構成単位を有するアクリル酸若しくはメタクリル酸エステル共重合体であることを特徴とする化学増幅型ホトレジスト組成物。In a positive resist composition containing (A) an acrylic resin whose solubility in an alkali is changed by the action of an acid and (B) an acid generator, the component (A) has at least a part of a structural unit represented by a general formula:
A chemically amplified photoresist composition comprising an acrylic acid or methacrylate copolymer having a structural unit represented by the formula:
で表わされる構成単位を有するアクリル酸又はメタクリル酸エステル共重合体。General formula
An acrylic acid or methacrylic acid ester copolymer having a structural unit represented by the following formula:
で表わされるアクリル酸又はメタクリル酸エステル。General formula
Acrylic acid or methacrylic acid ester represented by the formula:
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| JP2003207338A JP3719606B2 (en) | 2003-08-12 | 2003-08-12 | Chemically amplified photoresist composition |
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| JP01158197A Division JP3712218B2 (en) | 1997-01-24 | 1997-01-24 | Chemically amplified photoresist composition |
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| JP2003362073A Division JP3793194B2 (en) | 2003-10-22 | 2003-10-22 | Resist pattern forming method |
| JP2005111421A Division JP4104155B2 (en) | 2005-04-07 | 2005-04-07 | Novel (meth) acrylate copolymer and process for producing the same |
| JP2005115109A Division JP4229392B2 (en) | 2005-04-12 | 2005-04-12 | Method for producing acrylic or methacrylic acid ester having oxacyclopentyl group |
| JP2005160656A Division JP4289563B2 (en) | 2005-05-31 | 2005-05-31 | New acrylic acid or methacrylic acid ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007094474A1 (en) * | 2006-02-17 | 2007-08-23 | Kuraray Co., Ltd. | Tertiary alcohol derivative, polymer compound and photoresist composition |
| KR20100117064A (en) | 2008-02-22 | 2010-11-02 | 가부시키가이샤 구라레 | (meth)acrylate derivative, intermediate thereof, and polymer compound |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007094474A1 (en) * | 2006-02-17 | 2007-08-23 | Kuraray Co., Ltd. | Tertiary alcohol derivative, polymer compound and photoresist composition |
| US8105746B2 (en) | 2006-02-17 | 2012-01-31 | Kuraray Co., Ltd. | Tertiary alcohol derivative, polymer compound and photoresist composition |
| JP5118622B2 (en) * | 2006-02-17 | 2013-01-16 | 株式会社クラレ | Tertiary alcohol derivative, polymer compound and photoresist composition |
| US8541606B2 (en) | 2006-02-17 | 2013-09-24 | Kuraray Co., Ltd. | Tertiary alcohol derivative, polymer compound and photoresist composition |
| KR101443394B1 (en) | 2006-02-17 | 2014-09-24 | 가부시키가이샤 구라레 | Tertiary alcohol derivatives, polymer compounds and photoresist compositions |
| KR20100117064A (en) | 2008-02-22 | 2010-11-02 | 가부시키가이샤 구라레 | (meth)acrylate derivative, intermediate thereof, and polymer compound |
| US8492562B2 (en) | 2008-02-22 | 2013-07-23 | Kuraray Co., Ltd. | (Meth)acrylate derivative, intermediate thereof, and polymer compound |
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