KR101739587B1 - Positive resist composition and process for formation of resist pattern using the same - Google Patents
Positive resist composition and process for formation of resist pattern using the same Download PDFInfo
- Publication number
- KR101739587B1 KR101739587B1 KR1020090128797A KR20090128797A KR101739587B1 KR 101739587 B1 KR101739587 B1 KR 101739587B1 KR 1020090128797 A KR1020090128797 A KR 1020090128797A KR 20090128797 A KR20090128797 A KR 20090128797A KR 101739587 B1 KR101739587 B1 KR 101739587B1
- Authority
- KR
- South Korea
- Prior art keywords
- carbon atoms
- group
- benzotriazole
- alkyl group
- resist composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 75
- 239000012964 benzotriazole Substances 0.000 claims abstract description 29
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920003986 novolac Polymers 0.000 claims abstract description 18
- 238000011161 development Methods 0.000 claims abstract description 15
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- -1 aldehyde compound Chemical class 0.000 description 40
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 16
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000004925 Acrylic resin Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000018109 developmental process Effects 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 8
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000005194 fractionation Methods 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229940079877 pyrogallol Drugs 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- CDNVEXPWPDKNHN-UHFFFAOYSA-N (3-cyclohexylphenyl)methanol Chemical compound OCC1=CC=CC(C2CCCCC2)=C1 CDNVEXPWPDKNHN-UHFFFAOYSA-N 0.000 description 2
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- CPEXFJVZFNYXGU-UHFFFAOYSA-N 2,4,6-trihydroxybenzophenone Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=CC=C1 CPEXFJVZFNYXGU-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- CLAQXRONBVEWMK-UHFFFAOYSA-N 4-[(2-hydroxyphenyl)-(4-hydroxy-2,3,5-trimethylphenyl)methyl]-2,3,6-trimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C=2C(=CC=CC=2)O)C=2C(=C(C)C(O)=C(C)C=2)C)=C1C CLAQXRONBVEWMK-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XNWPXDGRBWJIES-UHFFFAOYSA-N Maclurin Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=C(O)C(O)=C1 XNWPXDGRBWJIES-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
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- 230000032050 esterification Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
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- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- GBQZZLQKUYLGFT-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O GBQZZLQKUYLGFT-UHFFFAOYSA-N 0.000 description 1
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
- XLBGWOVCPLFKCQ-UHFFFAOYSA-N (2-methylphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=C(O)C(O)=C1O XLBGWOVCPLFKCQ-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- JHVQWALHXJPODC-ALCCZGGFSA-N (z)-2-[2-(2-methylprop-2-enoyloxy)ethyl]but-2-enedioic acid Chemical compound CC(=C)C(=O)OCC\C(C(O)=O)=C\C(O)=O JHVQWALHXJPODC-ALCCZGGFSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
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- 238000000059 patterning Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
과제 미세한 레지스트 패턴을 형성하기 위해서 레지스트막과 기판의 밀착성을 양호하게 유지하면서도, 레지스트막의 현상 후의 잔사(殘渣)의 발생을 적게 억제할 수 있는 포지티브형 레지스트 조성물 및 이것을 이용한 레지스트 패턴의 형성 방법을 제공하는 것이다. PROBLEMS Provided is a positive resist composition capable of suppressing the generation of residues after development of a resist film while maintaining good adhesion between the resist film and the substrate to form a fine resist pattern and a method of forming a resist pattern using the same .
해결 수단 (A) 알칼리 가용성 노볼락 수지, (B) 감광제 및 소정의 (C) 벤조트리아졸계 화합물을 함유하는 포지티브형 레지스트 조성물은 소정의 벤조트리아졸계 화합물을 함유하기 때문에 레지스트막과 기판의 밀착성이 양호하게 유지되어 미세한 레지스트 패턴을 형성할 수 있는 동시에, 레지스트막의 현상 후에 있어서도 잔사의 발생을 적게 억제할 수 있다. SOLUTION Since the positive resist composition containing (A) the alkali-soluble novolak resin, (B) the photosensitizer and the predetermined (C) benzotriazole-based compound contains a predetermined benzotriazole-based compound, the adhesion between the resist film and the substrate Fine resist patterns can be formed and the occurrence of residues can be suppressed even after development of the resist film.
Description
본 발명은 미세한 레지스트 패턴을 형성할 수 있고, 레지스트막의 현상 후에 잔사의 발생이 적은 포지티브형 레지스트 조성물 및 이것을 이용한 레지스트 패턴의 형성 방법에 관한 것이다.The present invention relates to a positive resist composition which is capable of forming a fine resist pattern and is less likely to generate residues after development of the resist film, and a method of forming a resist pattern using the same.
기판 상에 미세한 패턴을 형성하고, 이것을 마스크로 하여 에칭을 실시함으로써 해당 패턴의 하층을 가공하는 기술(패턴 형성 기술)이나, 도금에 의해 배선, 범프 등을 형성하는 기술은 반도체 산업의 집적회로 작성 등에 널리 채용되며 큰 주목을 받고 있다.A technique of forming a fine pattern on a substrate and etching it using the pattern as a mask to fabricate a lower layer of the pattern (a pattern forming technique) and a technique of forming a wiring, a bump or the like by plating, And has been receiving great attention.
여기서 이 패턴 형성 기술에 있어서 미세 패턴은 통상 유기 재료로 이루어지고, 예를 들면 리소그래피법이나 나노임프린트법 등의 기술에 의해서 형성된다. 리소그래피법에 있어서는 기판 등의 지지체 상에 수지 등을 포함하는 레지스트 조성물로 이루어지는 레지스트막을 형성하고, 해당 레지스트막에 대해 소정의 패턴이 형성된 마스크(마스크 패턴)를 통하여 빛, 전자선 등의 활성선을 조사하여 선택적 노광을 실시하고, 현상 처리를 실시함으로써 레지스트막에 소정 형상의 레지스트 패턴을 형성하는 공정이 실시된다.In this pattern formation technique, the fine pattern is usually made of an organic material and is formed by a technique such as a lithography method or a nanoimprint method. In the lithography method, a resist film made of a resist composition containing a resin or the like is formed on a support such as a substrate, and an active line such as light or electron beam is irradiated through a mask (mask pattern) A selective exposure is performed, and a developing process is performed to form a resist pattern of a predetermined shape on the resist film.
레지스트막에 있어서 노광된 부분이 현상액에 용해하는 특성을 갖도록 변화하는 레지스트 조성물을 포지티브형 레지스트 조성물, 노광된 부분이 현상액에 용해하지 않는 특성을 갖도록 변화하는 레지스트 조성물을 네가티브형 레지스트 조성물이라고 한다.A positive resist composition which changes so that the exposed portions of the resist film have properties dissolving in a developing solution is referred to as a positive resist composition and a resist composition which is changed so as to have a property that the exposed portion does not dissolve in the developing solution is referred to as a negative resist composition.
근래 휴대 전화, 디지털 카메라 등의 전자기기의 소형화ㆍ경량화가 진행되고 있다. 이에 수반하여, 종래의 패키지 기술의 연장선상에 있는 SiP(System in Package)나 CSP(Chip Size Package)의 개발이 활발히 실시되고 있다. CSP는 칩의 크기로 패키지를 마무리하기 위해 칩 상부에 재(再)배선 실장을 실시할 필요가 있고, 배선 피치에는 미세화가 요구된다. 이 배선 형성은 주로 레지스트를 패터닝한 후, 레지스트 패턴에 따라서 구리 도금이나 구리를 에칭함으로써 실시되기 때문에 배선 피치의 미세화에는 레지스트의 고해상화가 불가결하다. 이와 같은 상황으로부터 레지스트 패턴의 고해상화에 대한 시장으로부터의 요구가 높아지고 있다.2. Description of the Related Art In recent years, electronic devices such as mobile phones and digital cameras have been made smaller and lighter. Along with this, the development of SiP (System in Package) and CSP (Chip Size Package), which is an extension of the conventional package technology, has been actively carried out. In order to finish the package with the size of the CSP, the CSP needs to be re-wired on the chip, and the wiring pitch is required to be miniaturized. This wiring formation is mainly performed by patterning a resist and then etching copper plating or copper in accordance with the resist pattern, so it is indispensable to increase the resolution of the resist in order to miniaturize the wiring pitch. From such a situation, there is an increasing demand from the market for the high resolution of the resist pattern.
또, 레지스트 조성물의 고해상화에 수반하여 레지스트 패턴과 기판의 접촉 면적이 작아지기 때문에 기판 밀착성의 향상도 요구된다. 밀착성이 약하면 현상시나 에칭시, 도금시에 레지스트 패턴의 박리가 생기는 문제가 있다. 기판 밀착성을 향상시키는 수단으로는 벤조트리아졸 등의 밀착 향상제의 사용을 들 수 있다(예를 들면 특허 문헌 1 참조).In addition, since the contact area between the resist pattern and the substrate becomes smaller as the resist composition becomes higher in resolution, it is also required to improve the substrate adhesion. When the adhesion is weak, there is a problem that the resist pattern peels off during plating or etching at the time of development or etching. As a means for improving substrate adhesion, use of adhesion improver such as benzotriazole (see, for example, Patent Document 1).
[선행 기술 문헌][Prior Art Literature]
[특허 문헌][Patent Literature]
[특허 문헌 1] 일본 특개 2008-158157호 공보[Patent Document 1] Japanese Unexamined Patent Publication No. 2008-158157
그렇지만, 종래의 첨가제(밀착 향상제)로는 레지스트 패턴과 기판의 밀착성이 향상하는 것의 대상으로서 현상 후에 레지스트막에서 유래하는 잔사(殘渣) 등이 레지스트 패턴 사이에 잔사(스컴)로서 잔존하기 쉽다고 하는 문제가 있었다.However, as a conventional additive (adhesion-improving agent), there is a problem that the adhesion between the resist pattern and the substrate is improved, and residues or the like derived from the resist film after the development are likely to remain as residue (scum) between the resist patterns there was.
본 발명은 이상의 과제를 감안하여 이루어진 것이며, 미세한 레지스트 패턴을 형성하기 위해서 레지스트막과 기판의 밀착성을 양호하게 유지하면서도 레지스트막의 현상 후의 잔사의 발생을 적게 억제할 수 있는 포지티브형 레지스트 조성물 및 이것을 이용한 레지스트 패턴의 형성 방법을 제공하는 것을 목적으로 한다.SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a positive resist composition capable of suppressing the generation of a residue of a resist film after development of a resist film while maintaining good adhesion between the resist film and the substrate in order to form a fine resist pattern, And a method of forming a pattern.
본 발명자들은 상기 과제를 감안하여 예의 연구를 실시하였다. 그 결과, 알칼리 가용성 노볼락 수지, 감광제 및 소정의 벤조트리아졸계 화합물을 함유하는 포지티브형 레지스트 조성물이 상기 과제를 해결할 수 있는 것을 찾아내어 본 발명을 완성하기에 이르렀다.The present inventors have conducted extensive research in view of the above problems. As a result, they found that a positive resist composition containing an alkali-soluble novolak resin, a photosensitizer and a predetermined benzotriazole-based compound can solve the above problems, and accomplished the present invention.
구체적으로는 본 발명은 이하의 것을 제공한다.Specifically, the present invention provides the following.
본 발명의 제1 형태는 (A) 알칼리 가용성 노볼락 수지, (B) 감광제 및 (C) 벤조트리아졸계 화합물을 함유하고, 상기 벤조트리아졸계 화합물이 하기 일반식 (1)로 표시되는 화합물인 포지티브형 레지스트 조성물이다.A first aspect of the present invention is a positive resist composition comprising (A) an alkali-soluble novolac resin, (B) a photosensitizer, and (C) a benzotriazole-based compound, wherein the benzotriazole- Type resist composition.
[일반식 (1)에 있어서 R1은 탄소수 1 이상 10 이하의 알킬기, 수산기, 카르복실기, 수소 원자 또는 -COOR'(R'는 탄소수 1 이상 5 이하의 알킬기)를 나타내고, R2 및 R3는 각각 독립적으로 수소 원자, 탄소수 1 이상 6 이하의 알킬기, 또는 탄소수 1 이상 6 이하의 히드록시알킬기를 나타낸다. 단, R2 및 R3로부터 선택되는 적어도 1종은 탄소수 1 이상 6 이하의 히드록시알킬기이다.]R 1 represents an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, a hydrogen atom or -COOR '(R' is an alkyl group having 1 to 5 carbon atoms), R 2 and R 3 are Each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. Provided that at least one kind selected from R 2 and R 3 is a hydroxyalkyl group having 1 to 6 carbon atoms.
본 발명의 제2 형태는 (A') 페놀성 수산기가 갖는 수소 원자 중 적어도 일부가 1,2-나프토퀴논 디아지드술포닐기로 치환된 알칼리 가용성 노볼락 수지 및 (C) 벤조트리아졸계 화합물을 함유하고, 상기 벤조트리아졸계 화합물이 하기 일반식 (1)로 표시되는 화합물인 포지티브형 레지스트 조성물이다.(A ') an alkali-soluble novolac resin in which at least a part of the hydrogen atoms of the phenolic hydroxyl group are substituted with a 1,2-naphthoquinone diazide sulfonyl group and (C) a benzotriazole-based compound And the benzotriazole-based compound is a compound represented by the following general formula (1).
[일반식 (1)에 있어서 R1은 탄소수 1 이상 10 이하의 알킬기, 수산기, 카르복실기, 수소 원자 또는 -COOR'(R'는 탄소수 1 이상 5 이하의 알킬기)를 나타내고, R2 및 R3는 각각 독립적으로 수소 원자, 탄소수 1 이상 6 이하의 알킬기, 또는 탄소 수 1 이상 6 이하의 히드록시알킬기를 나타낸다. 단, R2 및 R3로부터 선택되는 적어도 1종은 탄소수 1 이상 6 이하의 히드록시알킬기이다.]R 1 represents an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, a hydrogen atom or -COOR '(R' is an alkyl group having 1 to 5 carbon atoms), R 2 and R 3 are Each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. Provided that at least one kind selected from R 2 and R 3 is a hydroxyalkyl group having 1 to 6 carbon atoms.
본 발명의 제3 형태는 기판 상에 본 발명의 포지티브형 레지스트 조성물을 도포하여 레지스트막을 얻는 도포 공정과 상기 레지스트막에 선택적으로 활성선을 조사하여 노광하는 노광 공정과 상기 노광 공정 후에 현상을 실시하여 레지스트 패턴을 얻는 현상 공정을 갖는 레지스트 패턴의 형성 방법이다.A third aspect of the present invention is a resist pattern forming method comprising: a coating step of applying a positive resist composition of the present invention onto a substrate to obtain a resist film; an exposure step of selectively irradiating the resist film with an active ray to expose the resist film; And a developing step of obtaining a resist pattern.
본 발명의 포지티브형 레지스트 조성물에 의하면, 포지티브형 레지스트 조성물이 소정의 벤조트리아졸계 화합물을 함유하므로, 레지스트막과 기판의 밀착성이 양호하게 유지되어 미세한 레지스트 패턴을 형성 가능함과 동시에, 레지스트막의 현상 후에 있어서도 잔사의 발생을 적게 억제할 수 있다.According to the positive resist composition of the present invention, since the positive resist composition contains a predetermined benzotriazole-based compound, the adhesion between the resist film and the substrate can be kept good and a fine resist pattern can be formed, The occurrence of residues can be suppressed to a small extent.
이하, 본 발명의 실시 형태에 대해 상세하게 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
＜포지티브형 레지스트 조성물＞≪ Positive Resist Composition >
본 발명의 제1 형태에서의 포지티브형 레지스트 조성물은 (A) 알칼리 가용성 노볼락 수지(이하, 「(A) 성분」이라고도 한다), (B) 감광제 및 소정의 (C) 벤조트리아졸계 화합물을 함유한다.The positive resist composition according to the first embodiment of the present invention is a positive resist composition comprising (A) an alkali-soluble novolak resin (hereinafter, also referred to as "component (A)"), (B) a photosensitizer, do.
또, 본 발명의 제2 형태에서의 포지티브형 레지스트 조성물은 (A') 페놀성 수산기가 갖는 수소 원자 중 적어도 일부가 1,2-나프토퀴논 디아지드술포닐기로 치 환된 알칼리 가용성 노볼락 수지(이하 「(A') 성분」이라고도 한다) 및 소정의 (C) 벤조트리아졸계 화합물을 함유한다.In the positive resist composition according to the second embodiment of the present invention, (A ') an alkali-soluble novolak resin in which at least a part of the hydrogen atoms of the phenolic hydroxyl group is substituted with a 1,2-naphthoquinone diazide sulfonyl group Hereinafter also referred to as "component (A ')") and a predetermined (C) benzotriazole-based compound.
[(A) 알칼리 가용성 노볼락 수지][(A) Alkali-soluble novolak resin]
본 발명의 제1 형태에서의 포지티브형 레지스트 조성물에 함유되는 (A) 성분으로는 특별히 한정되지 않으나, 페놀성 수산기를 갖는 방향족 화합물(이하, 단순히 「페놀류」라고 한다)과 알데히드류를 산 촉매하에서 부가 축합시킴으로써 얻어지는 것이 바람직하다.The component (A) contained in the positive resist composition of the first embodiment of the present invention is not particularly limited, but an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenol") and an aldehyde compound Is preferably obtained by addition condensation.
(페놀류)(Phenols)
상기 페놀류로는 예를 들면 페놀, o-크레졸, m-크레졸, p-크레졸 등의 크레졸류; 2,3-크실레놀, 2,4-크실레놀, 2,5-크실레놀, 2,6-크실레놀, 3,4-크실레놀, 3,5-크실레놀 등의 크실레놀류; o-에틸 페놀, m-에틸 페놀, p-에틸 페놀, 2-이소프로필 페놀, 3-이소프로필 페놀, 4-이소프로필 페놀, o-부틸 페놀, m-부틸 페놀, p-부틸 페놀, p-tert-부틸 페놀 등의 알킬 페놀류; 2,3,5-트리메틸 페놀, 3,4,5-트리메틸 페놀 등의 트리알킬 페놀류; 레조르시놀, 카테콜, 하이드로퀴논, 하이드로퀴논 모노메틸 에테르, 피로갈롤, 플루오로글리시놀 등의 다가 페놀류; 알킬레조르신, 알킬 카테콜, 알킬 하이드로퀴논 등의 알킬 다가 페놀류(어느 쪽의 알킬기도 탄소수 1 이상 4 이하이다); α-나프톨; β-나프톨; 히드록시 디페닐; 비스페놀 A 등을 들 수 있다. 이러한 페놀류는 단독으로 이용해도 되고, 2종 이상을 조합하여 이용해도 된다.Examples of the phenols include cresols such as phenol, o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Sileenol; butylphenol, p-butylphenol, p-methylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, alkylphenols such as tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; Alkyl-substituted phenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (both of the alkyl groups having 1 to 4 carbon atoms); alpha -naphthol; ? -naphthol; Hydroxy diphenyl; Bisphenol A, and the like. These phenols may be used alone or in combination of two or more.
이러한 페놀류 중에서도, m-크레졸 및 p-크레졸이 바람직하고, m-크레졸과 p-크레졸을 병용하는 것이 보다 바람직하다. 이 경우 양자의 배합 비율을 조정함으로써 포지티브형 레지스트 조성물로서의 감도, 내열성 등의 여러 특성을 조절할 수 있다. m-크레졸과 p-크레졸의 배합 비율은 특별히 한정되는 것은 아니지만, m-크레졸/p-크레졸의 비로 3/7 이상 8/2 이하(중량비)가 바람직하다. m-크레졸의 비율을 3/7 이상으로 함으로써 감도를 향상시킬 수 있고, 8/2 이하로 함으로써 내열성을 향상시킬 수 있다.Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as sensitivity and heat resistance as a positive resist composition can be controlled by adjusting the blending ratio of the two. The blending ratio of m-cresol and p-cresol is not particularly limited, but is preferably 3/7 to 8/2 (weight ratio) by the ratio of m-cresol / p-cresol. When the ratio of m-cresol is 3/7 or more, the sensitivity can be improved. When the ratio is 8/2 or less, the heat resistance can be improved.
(알데히드류)(Aldehydes)
알데히드류로는 예를 들면 포름알데히드, 파라포름알데히드, 푸르푸랄, 벤즈 알데히드, 니트로 벤즈 알데히드, 아세트알데히드 등을 들 수 있다. 이러한 알데히드류는 단독으로 이용해도 되고, 2종 이상을 조합하여 이용해도 된다.The aldehydes include, for example, formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes may be used alone, or two or more aldehydes may be used in combination.
(산 촉매)(Acid catalyst)
산 촉매로는 예를 들면 염산, 황산, 질산, 인산, 아인산 등의 무기산류; 포름산, 옥살산, 아세트산, 디에틸 황산, 파라톨루엔술폰산 등의 유기산류; 아세트산 아연 등의 금속 염류 등을 들 수 있다. 이러한 산 촉매는 단독으로 이용해도 되고, 2종 이상을 조합하여 이용해도 된다.Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and phosphorous acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid and para-toluenesulfonic acid; And metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.
(분자량)(Molecular Weight)
(A) 성분의 중량 평균 분자량은 포지티브형 레지스트 조성물의 현상성, 해상성 및 내도금액성의 관점으로부터 1000 이상 50000 이하로 하는 것이 바람직하다.The weight average molecular weight of the component (A) is preferably from 1,000 to 50,000 from the viewpoints of developability, resolution and resistance to water resistance of the positive resist composition.
(분별 처리)(Fractionation treatment)
(A) 성분은 분별 처리에 의해 저핵체의 함유량이 해당 분별 처리 전의 80 중 량% 이하, 보다 바람직하게는 50 중량% 이하로 저감되어 있는 분별 수지인 것이 바람직하다. 여기서 저핵체란 상기의 페놀류, 즉 페놀계 모노머와 해당 페놀계 모노머 2 분자로부터 얻어지는 다이머, 해당 페놀계 모노머 3 분자로부터 얻어지는 트리머 등을 의미한다. 이와 같은 분별 수지를 이용함으로써 레지스트 패턴 단면 형상의 수직성이 더욱 양호하게 되며, 현상시에 레지스트 잔사(스컴)가 발생하기 어렵고, 해상성이 향상함과 동시에 내열성이 뛰어난 것으로도 된다.The component (A) is preferably a fractionation resin in which the content of the low-molecular-weight compound by fractionation is reduced to 80% by weight or less, more preferably 50% by weight or less, before the fractionation treatment. Herein, the lower core means the above-mentioned phenol, namely, a phenol-based monomer, a dimer obtained from two molecules of the phenol-based monomer, and a trimmer obtained from three molecules of the phenol-based monomer. By using such a fractionating resin, the verticality of the cross-sectional shape of the resist pattern becomes better, resist residues (scum) are hardly generated at the time of development, the resolution is improved, and the heat resistance is excellent.
분별 처리는 예를 들면 이하와 같은 공지의 분별 침전 처리에 의해서 실시할 수 있다. 우선, 상술한 바와 같이 페놀류와 알데히드류의 부가 축합 반응을 실시한 후, 얻어진 부가 축합 생성물(노볼락 수지)을 극성 용매에 용해하고, 이 용액에 대해 물, 헵탄, 헥산, 펜탄, 시클로 헥산 등의 빈용매를 더한다. 이 때, 저핵체는 비교적 용해도가 높기 때문에 빈용매에 용해한 채로 있으므로 석출물을 여취(濾取)함으로써 저핵체의 함유량이 저감된 분별 수지를 얻을 수 있다.The fractionation treatment can be carried out, for example, by a known fractional precipitation treatment as follows. First, as described above, an addition condensation reaction of phenols and an aldehyde is carried out, then the resulting addition condensation product (novolak resin) is dissolved in a polar solvent, and water, heptane, hexane, pentane, cyclohexane Add the poor solvent. At this time, since the low-molecular-weight core has a relatively high solubility, it remains dissolved in a poor solvent. Thus, the precipitate can be filtered out to obtain a fractionated resin in which the content of the low-molecular-weight core is reduced.
상기 극성 용매로는 예를 들면 메탄올, 에탄올 등의 알코올류; 아세톤, 메틸 에틸 케톤 등의 케톤류; 에틸렌글리콜 모노에틸 에테르 아세테이트 등의 글리콜 에테르 에스테르류; 테트라히드로 푸란 등의 환상 에테르류 등을 들 수 있다.Examples of the polar solvent include alcohols such as methanol and ethanol; Ketones such as acetone and methyl ethyl ketone; Glycol ether esters such as ethylene glycol monoethyl ether acetate; And cyclic ethers such as tetrahydrofuran.
(A) 성분 중의 저핵체의 함유량은 GPC 측정의 결과로부터 확인할 수 있다. 즉, GPC 차트로부터는 합성한 페놀 노볼락 수지의 분자량 분포를 확인할 수 있어, 저핵체의 용출시간에 해당 하는 피크의 강도비를 측정함으로써 그 함유량을 산출할 수 있다. 또한, 저핵체의 용출시간은 측정 수단에 따라 다르기 때문에, 컬럼, 용리액, 유량, 온도, 검출기, 샘플 농도, 주입량, 측정기 등의 특정이 중요하다.The content of the lower core in the component (A) can be confirmed from the results of GPC measurement. That is, the molecular weight distribution of the synthesized phenol novolac resin can be confirmed from the GPC chart, and the content thereof can be calculated by measuring the intensity ratio of the peak corresponding to the elution time of the lower nucleus. Since elution time of the low-molecular-weight nucleic acid differs depending on the measurement means, it is important to specify the column, eluent, flow rate, temperature, detector, sample concentration, injection amount,
분별 수지의 분산도[중량 평균 분자량(Mw)/수평균 분자량(Mn)]는 30 이하가 바람직하고, 15 이상 25 이하가 보다 바람직하다.The dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the fractionation resin is preferably 30 or less, more preferably 15 or more and 25 or less.
[(A') 페놀성 수산기가 갖는 수소 원자 중 적어도 일부가 1,2-나프토퀴논 디아지드술포닐기로 치환된 알칼리 가용성 노볼락 수지] [(A ') an alkali-soluble novolak resin in which at least a part of the hydrogen atoms of the phenolic hydroxyl group is substituted with a 1,2-naphthoquinone diazide sulfonyl group]
본 발명의 제2 형태에서의 포지티브형 레지스트 조성물에 함유되는 (A') 성분으로는 특별히 한정되지 않으나, 상기 (A) 성분에 포함되는 전(全)페놀성 수산기의 수소 원자의 일부가 1,2-나프토퀴논 디아지드술포닐기로 치환된 것이 바람직하다. (A') 성분을 이용하는 경우 (A') 성분 자체가 적은 나프토퀴논 디아지드술포닐로 감광성을 갖기 때문에 포지티브형 레지스트 조성물의 감도를 보다 향상시킬 수 있다.The component (A ') contained in the positive resist composition of the second embodiment of the present invention is not particularly limited, but it is preferable that part of the hydrogen atoms of all the phenolic hydroxyl groups contained in the component (A) It is preferably substituted with a 2-naphthoquinone diazide sulfonyl group. When the component (A ') is used, the sensitivity of the positive resist composition can be further improved because the component (A') has photosensitivity to naphthoquinonediazide sulfonyl having a small amount of the component (A ').
1,2-나프토퀴논 디아지드술포닐기로의 치환은 (A) 성분과 1,2-나프토퀴논 디아지드술폰산 화합물의 에스테르화 반응에 의해 실시할 수 있다. 1,2-나프토퀴논 디아지드술폰산 화합물로는 예를 들면 1,2-나프토퀴논 디아지드-4-술폰산 클로라이드, 1,2-나프토퀴논 디아지드-5-술폰산 클로라이드 등의 퀴논 디아지드 화합물의 할로겐화물을 들 수 있다.Substitution with the 1,2-naphthoquinone diazidesulfonyl group can be carried out by esterification reaction of the component (A) and the 1,2-naphthoquinone diazidesulfonic acid compound. Examples of the 1,2-naphthoquinonediazidesulfonic acid compound include quinonediazides such as 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Halides of compounds.
(A') 성분에 있어서 페놀성 수산기가 갖는 수소 원자가 1,2-나프토퀴논 디아지드술포닐기로 치환되어 있는 비율, 즉 에스테르화 반응의 반응율은 2 몰% 이상 10 몰% 이하인 것이 바람직하고, 3 몰% 이상 7 몰% 이하인 것이 보다 바람직하고, 3 몰% 이상 5 몰% 이하인 것이 더욱 바람직하다. 반응율을 2 몰% 이상으로 함으로써 미노광 부분의 막 감소를 억제할 수 있고, 10 몰% 이하로 함으로써 감도를 향상 시킴과 동시에 레지스트 패턴 단면 형상의 수직성을 양호하게 할 수 있다.The proportion of the hydrogen atom of the phenolic hydroxyl group in the component (A ') substituted with the 1,2-naphthoquinone diazide sulfonyl group, that is, the reaction rate of the esterification reaction, is preferably from 2 mol% to 10 mol% More preferably 3 mol% or more and 7 mol% or less, and still more preferably 3 mol% or more and 5 mol% or less. When the reaction rate is 2 mol% or more, the film thickness of the unexposed portion can be suppressed. When it is 10 mol% or less, the sensitivity can be improved and the perpendicularity of the cross-sectional shape of the resist pattern can be improved.
[(B) 감광제][(B) Photosensitizer]
본 발명의 포지티브형 레지스트 조성물에 함유되는 감광제로는 특별히 한정되지 않으나 퀴논 디아지드기 함유 화합물이 바람직하다. 이 퀴논 디아지드기 함유 화합물로는 예를 들면 2,3,4-트리히드록시벤조페논, 2,4,4'-트리히드록시벤조페논, 2,4,6-트리히드록시벤조페논, 2,3,6-트리히드록시벤조페논, 2,3,4-트리히드록시-2'-메틸벤조페논, 2,3,4,4'-테트라히드록시벤조페논, 2,2',4,4'-테트라히드록시벤조페논, 2,3',4,4',6-펜타히드록시벤조페논, 2,2',3,4,4'-펜타히드록시벤조페논, 2,2',3,4,5-펜타히드록시벤조페논, 2,3',4,4',5',6-헥사히드록시벤조페논, 2,3,3',4,4',5'-헥사히드록시벤조페논 등의 폴리히드록시벤조페논류; 비스(2,4-디히드록시 페닐)메탄, 비스(2,3,4-트리히드록시 페닐)메탄, 2-(4-히드록시 페닐)-2-(4'-히드록시 페닐)프로판, 2-(2,4-디히드록시 페닐)-2-(2',4'-디히드록시 페닐)프로판, 2-(2,3,4-트리히드록시 페닐)-2-(2',3',4'-트리히드록시 페닐)프로판, 4,4'-｛1-[4-〔2-(4-히드록시 페닐)-2-프로필〕페닐]에틸리덴｝비스페놀, 3,3'-디메틸-｛1-[4-〔2-(3-메틸-4-히드록시 페닐)-2-프로필〕페닐]에틸리덴｝비스페놀 등의 비스[(폴리)히드록시 페닐]알칸류; 트리스(4-히드록시 페닐)메탄, 비스(4-히드록시-3,5-디메틸 페닐)-4-히드록시 페닐 메탄, 비스(4-히드록시-2,5-디메틸 페닐)-4-히드록시 페닐 메탄, 비스(4-히드록시-3,5-디메틸 페닐)-2-히드록시 페닐 메탄, 비스(4-히드록시-2,5-디메틸 페닐)-2-히드록시 페닐 메탄, 비스(4-히드록시-2,5-디메틸 페닐)-3,4-디히드록시 페닐 메탄, 비스(4-히드록시-3,5-디메틸 페닐)-3,4-디히 드록시 페닐 메탄 등의 트리스(히드록시 페닐)메탄류 또는 그 메틸 치환체; 비스(3-시클로헥실-4-히드록시 페닐)-3-히드록시 페닐 메탄, 비스(3-시클로헥실-4-히드록시 페닐)-2-히드록시 페닐 메탄, 비스(3-시클로헥실-4-히드록시 페닐)-4-히드록시 페닐 메탄, 비스(5-시클로헥실-4-히드록시-2-메틸 페닐)-2-히드록시 페닐 메탄, 비스(5-시클로헥실-4-히드록시-2-메틸 페닐)-3-히드록시 페닐 메탄, 비스(5-시클로헥실-4-히드록시-2-메틸 페닐)-4-히드록시 페닐 메탄, 비스(3-시클로헥실-2-히드록시 페닐)-3-히드록시 페닐 메탄, 비스(5-시클로헥실-4-히드록시-3-메틸 페닐)-4-히드록시 페닐 메탄, 비스(5-시클로헥실-4-히드록시-3-메틸 페닐)-3-히드록시 페닐 메탄, 비스(5-시클로헥실-4-히드록시-3-메틸 페닐)-2-히드록시 페닐 메탄, 비스(3-시클로헥실-2-히드록시 페닐)-4-히드록시 페닐 메탄, 비스(3-시클로헥실-2-히드록시 페닐)-2-히드록시 페닐 메탄, 비스(5-시클로헥실-2-히드록시-4-메틸 페닐)-2-히드록시 페닐 메탄, 비스(5-시클로헥실-2-히드록시-4-메틸 페닐)-4-히드록시 페닐 메탄 등의 비스(시클로헥실 히드록시 페닐)(히드록시 페닐)메탄류 또는 그 메틸 치환체; 페놀, p-메톡시 페놀, 디메틸 페놀, 히드로퀴논, 나프톨, 피로카테콜, 피로갈롤, 피로갈롤 모노메틸 에테르, 피로갈롤-1,3-디메틸 에테르, 갈산, 아닐린, p-아미노 디페닐 아민, 4,4'-디아미노벤조페논 등의 수산기 또는 아미노기를 갖는 화합물; 노볼락, 피로갈롤-아세톤 수지, p-히드록시 스티렌의 호모폴리머 또는 이것과 공중합할 수 있는 모노머의 공중합체; 등과 나프토퀴논-1,2-디아지드-5-술폰산, 나프토퀴논-1,2-디아지드-4-술폰산, 오르토안트라퀴논 디아지드술폰산 등의 퀴논 디아지드기 함유 술폰산의 완전 에스테르 화합물, 부분 에스테르 화합물, 아미 드화물 또는 부분 아미드화물 등을 들 수 있다. 이러한 감광제는 단독으로 이용해도 되고, 2종 이상을 조합하여 이용해도 된다.The photosensitizer contained in the positive resist composition of the present invention is not particularly limited, but is preferably a quinonediazide group-containing compound. Examples of the quinone diazide group-containing compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2 , 3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ' Tetra hydroxybenzophenone, 2,3 ', 4,4', 6-pentahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2' 3,4,5-pentahydroxybenzophenone, 2,3 ', 4,4', 5 ', 6-hexahydroxybenzophenone, 2,3,3', 4,4 ', 5'- Polyhydroxybenzophenones such as hydroxybenzophenone; Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- 2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2' 3 ', 4'-trihydroxyphenyl) propane, 4,4' - {1- [4- [2- (4- hydroxyphenyl) -2- propylphenyl] ethylidene} - [(poly) hydroxyphenyl] alkanes such as dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol; Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) Dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (Hydroxyphenyl) methanes or methyl substituents thereof; Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl- Methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4- hydroxyphenylmethane, bis (3-cyclohexyl- Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl- Hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5- (Cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane and bis (5-cyclohexyl-2-hydroxy- Hexylhydroxyphenyl) (hydroxyphenyl) methanes or methyl substituents thereof; Phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine , 4'-diaminobenzophenone, and other compounds having a hydroxyl group or an amino group; Novolak, pyrogallol-acetone resins, homopolymers of p-hydroxystyrene or monomers copolymerizable therewith; And the like, and a complete ester compound of a quinone diazide group-containing sulfonic acid such as naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinone diazidesulfonic acid, A partial ester compound, an amide compound or a partial amide compound. These photosensitizers may be used alone or in combination of two or more.
이러한 감광제 중에서도, 하기 일반식 (B-1) 및 (B-2)으로 표시되는 화합물의 퀴논 디아지드술폰산 에스테르가 바람직하다.Among these photosensitizers, quinonediazidesulfonic acid esters of the compounds represented by the following general formulas (B-1) and (B-2) are preferred.
[일반식 (B-1) 및 (B-2) 중, R1b 내지 R7b는 각각 독립적으로 수소 원자, 치환기를 가지고 있어도 되는 탄소수 1 이상 5 이하의 알킬기, 또는 치환기를 가지고 있어도 되는 탄소수 4 이상 8 이하의 시클로 알킬기를 나타낸다.][In formulas (B-1) and (B-2), R 1b to R 7b each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, 8 or less cycloalkyl groups.]
상기 일반식 (B-1) 및 (B-2)으로 표시되는 화합물의 퀴논 디아지드술폰산 에스테르 중에서도, 하기 화학식 (B-3)으로 표시되는 화합물의 퀴논 디아지드술폰산 에스테르가 특히 바람직하다.Among the quinonediazidesulfonic acid esters of the compounds represented by the general formulas (B-1) and (B-2), quinonediazidesulfonic acid ester of the compound represented by the following general formula (B-3) is particularly preferable.
여기서 상기 일반식 (B-1) 및 (B-2) 및 화학식 (B-3)으로 표시되는 화합물의 퀴논 디아지드술폰산 에스테르에 있어서 나프토퀴논-1,2-디아지드술포닐기는 4 위치 또는 5 위치에 술포닐기가 결합하고 있는 것이 바람직하다. 이러한 화합물은 포지티브형 레지스트 조성물을 용액으로서 사용할 때에 통상 이용되는 용제에 잘 용해되고, 또한 (A) 성분이나 (A') 성분과의 상용성이 양호하며, 포지티브형 레지스트 조성물의 감광제로서 사용하면 고감도이고, 화상 콘트라스트 및 단면 형상이 뛰어나며, 또한 내열성도 뛰어날 뿐만 아니라, 용액으로서 이용하는 경우에 있어서도 이물의 발생이 없는 포지티브형 레지스트 조성물을 부여한다.The naphthoquinone-1,2-diazidesulfonyl group in the quinonediazidesulfonic acid ester of the compound represented by the general formulas (B-1) and (B-2) It is preferable that a sulfonyl group is bonded to the 5-position. Such a compound is well soluble in a solvent usually used when a positive resist composition is used as a solution and has good compatibility with the component (A) or the component (A '), and when used as a photosensitizer of a positive resist composition, , Excellent in image contrast and sectional shape and excellent in heat resistance, and also provides a positive resist composition free from the generation of foreign matter even when used as a solution.
상기 일반식 (B-1)로 표시되는 화합물은 예를 들면 1-히드록시-4-[1,1-비스(4-히드록시 페닐) 에틸]벤젠과 나프토퀴논-1,2-디아지드-술포닐클로라이드를 디옥산과 같은 용매 중에 있어서 트리에탄올 아민, 탄산 알칼리, 탄산수소 알칼리 등의 알칼리의 존재하에서 축합시켜, 완전 에스테르화 또는 부분 에스테르화함으로써 제조할 수 있다. 또, 상기 일반식 (B-2)로 표시되는 화합물은 예를 들면 1-[1-(4-히드록시 페닐)이소프로필]-4-[1,1-비스(4-히드록시 페닐) 에틸]벤젠과 나프토퀴논 -1,2-디아지드-술포닐클로라이드를 디옥산과 같은 용매 중에 있어서 트리에탄올 아민, 탄산 알칼리, 탄산수소 알칼리 등의 알칼리의 존재하에서 축합시켜, 완전 에스테르화 또는 부분 에스테르화함으로써 제조할 수 있다.The compound represented by the above general formula (B-1) is, for example, 1-hydroxy-4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and naphthoquinone- - sulfonyl chloride in a solvent such as dioxane in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogen carbonate or the like to complete esterification or partial esterification. The compound represented by the above general formula (B-2) is, for example, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ ] Benzene and naphthoquinone-1,2-diazide-sulfonyl chloride are condensed in a solvent such as dioxane in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogen carbonate or the like to obtain a completely esterified or partially esterified .
또한, 나프토퀴논-1,2-디아지드-술포닐클로라이드로는 나프토퀴논-1,2-디아지드-4-술포닐클로라이드나 나프토퀴논-1,2-디아지드-5-술포닐클로라이드를 이용하는 것이 바람직하다.As the naphthoquinone-1,2-diazide-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide- It is preferable to use chloride.
감광제의 함유량은 베이스 수지로서 (A) 성분을 이용하는 경우 (A) 성분 100 중량부에 대해 5 중량부 이상 100 중량부 이하 이용하는 것이 바람직하고, 10 중량부 이상 50 중량부 이하 이용하는 것이 보다 바람직하다. 함유량을 5 중량부 이상으로 함으로써 원하는 레지스트 패턴을 얻을 수 있게 되고, 100 중량부 이하로 함으로써 충분한 감도를 유지할 수 있다.When the component (A) is used as the base resin, the content of the photosensitizer is preferably 5 parts by weight or more and 100 parts by weight or less, more preferably 10 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the component (A). When the content is 5 parts by weight or more, a desired resist pattern can be obtained. When the amount is 100 parts by weight or less, sufficient sensitivity can be maintained.
한편, 베이스 수지로서 (A') 성분을 이용하는 경우 감광제는 필수는 아니지만 감광제를 함유시키는 경우에는 (A') 성분 100 중량부에 대해 1 중량부 이상 30 중량부 이하 이용하는 것이 바람직하고, 5 중량부 이상 20 중량부 이하 이용하는 것이 보다 바람직하다.On the other hand, when the component (A ') is used as the base resin, the photosensitive agent is not essential, but when it contains a photosensitive agent, it is preferably used in an amount of 1 part by weight to 30 parts by weight with respect to 100 parts by weight of the component (A'), By weight or more and 20 parts by weight or less.
[(C) 벤조트리아졸계 화합물][(C) benzotriazole-based compound]
본 발명의 포지티브형 레지스트 조성물에 포함되는 벤조트리아졸계 화합물은 이하의 일반식 (1)로 표시되는 것이다.The benzotriazole-based compound contained in the positive resist composition of the present invention is represented by the following general formula (1).
[일반식 (1)에 있어서 R1은 탄소수 1 이상 10 이하의 알킬기, 수산기, 카르복실기, 수소 원자 또는 -COOR'(R'는 탄소수 1 이상 5 이하의 알킬기)를 나타내고, R2 및 R3는 각각 독립적으로 수소 원자, 탄소수 1 이상 6 이하의 알킬기, 또는 탄소수 1 이상 6 이하의 히드록시알킬기를 나타낸다. 단, R2 및 R3로부터 선택되는 적어도 1종은 탄소수 1 이상 6 이하의 히드록시알킬기이다.]R 1 represents an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, a hydrogen atom or -COOR '(R' is an alkyl group having 1 to 5 carbon atoms), R 2 and R 3 are Each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. Provided that at least one kind selected from R 2 and R 3 is a hydroxyalkyl group having 1 to 6 carbon atoms.
포지티브형 레지스트 조성물이 상기 일반식 (1)로 표시되는 벤조트리아졸계 화합물을 함유함으로써 레지스트막과 기판의 밀착성이 양호하게 유지되어 미세한 레지스트 패턴을 형성 가능함과 동시에 레지스트막의 현상 후에 있어서도 잔사의 발생을 적게 억제할 수 있다.The positive resist composition contains a benzotriazole-based compound represented by the above-mentioned general formula (1), whereby the adhesion between the resist film and the substrate can be maintained favorably so that a fine resist pattern can be formed. In addition, .
여기서 R1에서의 탄소수 1 이상 10 이하의 알킬기로는 특별히 한정되는 것이 아니고, 메틸기, 에틸기, n-프로필기, 이소프로필기, 노닐기, 데실기 등을 들 수 있다. 본 발명의 포지티브형 레지스트 조성물에 있어서는 R1이 탄소수 1 이상 3 이하의 알킬기인 것이 바람직하고, 메틸기인 것이 더욱 바람직하다.The alkyl group having 1 to 10 carbon atoms in R 1 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a nonyl group and a decyl group. In the positive resist composition of the present invention, R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
R2 및 R3인 탄소수 1 이상 6 이하의 알킬기로는 메틸기, 에틸기, n-프로필 기, 이소프로필기, n-부틸기, sec-부틸기, tert-부틸기, n-헵틸기, n-헥실기 등을 들 수 있다. 또, 탄소수 1 이상 6 이하의 히드록시알킬기로는 상기 탄소수 1 이상 6 이하의 알킬기 중 적어도 하나의 수소 원자를 히드록실기로 치환한 기를 들 수 있다.Examples of the alkyl group having 1 to 6 carbon atoms represented by R 2 and R 3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Hexyl group and the like. Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include groups in which at least one hydrogen atom in the alkyl group having 1 to 6 carbon atoms is substituted with a hydroxyl group.
상술한 바와 같이, R2 및 R3로부터 선택되는 적어도 1종은 탄소수 1 이상 6 이하의 히드록시알킬기이다. R2 또는 R3로서 상기 히드록시알킬기를 갖음으로써 상기 벤조트리아졸계 화합물의 포지티브형 레지스트 조성물에 대한 용해성을 충분히 유지할 수 있고, 포지티브형 레지스트 조성물과 기판의 밀착성을 충분히 유지할 수 있다. R2 및 R3는 공히 탄소수 1 이상 6 이하의 히드록시알킬기인 것이 바람직하고, 공히 2-히드록시 에틸기인 것이 더욱 바람직하다.As described above, at least one selected from R 2 and R 3 is a hydroxyalkyl group having 1 to 6 carbon atoms. By having the hydroxyalkyl group as R 2 or R 3 , the solubility of the benzotriazole-based compound in the positive resist composition can be sufficiently maintained, and the adhesion between the positive resist composition and the substrate can be sufficiently maintained. R 2 and R 3 are preferably a hydroxyalkyl group having 1 to 6 carbon atoms, and more preferably a 2-hydroxyethyl group.
구체적으로는 이하의 화학식 (C-1)으로부터 (C-4)로 나타내는 벤조트리아졸계 화합물을 바람직하게 이용할 수 있다.Specifically, benzotriazole-based compounds represented by the following formulas (C-1) to (C-4) can be preferably used.
상기 일반식 (1)로 표시되는 벤조트리아졸계 화합물은 예를 들면 이하에 나타내는 방법에 의해 제조할 수 있다(예를 들면 일본 특개 2000-044549호 공보 참조).The benzotriazole-based compound represented by the above general formula (1) can be produced, for example, by the following method (for example, see Japanese Patent Application Laid-Open No. 2000-044549).
메틸-1H-벤조트리아졸 등의 하기 화학식 (2)로 표시되는 화합물과 디에탄올 아민 등의 2급 알코올 아민과 포름알데히드를 1:1:1의 몰비로 넣고, 메탄올 환류하에서 5시간 반응시킨다. 반응 후 증류에 의해 메탄올, 물을 없앰으로써 목적 화합물을 얻는다.Methyl-1H-benzotriazole, a secondary alcohol amine such as diethanolamine and formaldehyde in a molar ratio of 1: 1: 1 and reacted for 5 hours under methanol reflux. After the reaction, the desired compound is obtained by removing methanol and water by distillation.
[일반식 (2)에 있어서 R1은 상기와 같다.][In the general formula (2), R 1 is as defined above.]
상기 일반식 (1)로 표시되는 벤조트리아졸계 화합물은 (A) 성분 또는 (A') 성분 100 중량부당 0.1 중량부 이상 5 중량부 이하 첨가되는 것이 바람직하고, 0.2 중량부 이상 2 중량부 이하 첨가되는 것이 더욱 바람직하다. 상기 벤조트리아졸계 화합물의 첨가량이 0.1 중량부 이상인 것에 의해 본 발명의 포지티브형 레지스트 조성물로부터 얻어지는 레지스트막과 기판의 밀착성을 충분히 높은 것으로 할 수 있다. 또, 상기 벤조트리아졸계 화합물의 첨가량이 5 중량부 이하인 것에 의해 상기 레지스트막의 현상 후에 있어서도 잔사가 적은 양호한 레지스트 패턴을 얻을 수 있다.The benzotriazole-based compound represented by the general formula (1) is preferably added in an amount of 0.1 part by weight to 5 parts by weight per 100 parts by weight of the component (A) or (A '), more preferably 0.2 parts by weight or more and 2 parts by weight or less . When the addition amount of the benzotriazole compound is 0.1 parts by weight or more, the adhesion between the resist film and the substrate obtained from the positive resist composition of the present invention can be made sufficiently high. When the addition amount of the benzotriazole-based compound is 5 parts by weight or less, a good resist pattern with less residue even after development of the resist film can be obtained.
[(D) 증감제][(D) sensitizer]
본 발명의 포지티브형 레지스트 조성물은 필요에 따라서 증감제를 함유한다. 본 발명에서 이용할 수 있는 증감제로는 특별히 한정되는 것이 아니고, 포지티브형 레지스트 조성물에 있어서 통상 이용되는 증감제 중에서 임의로 선택할 수 있다. 구체적으로는 하기 일반식 (D-1)로 표시되는 페놀 화합물을 사용할 수 있다.The positive resist composition of the present invention contains a sensitizer if necessary. The sensitizer that can be used in the present invention is not particularly limited, and may be selected arbitrarily from the sensitizers commonly used in the positive resist composition. Specifically, a phenol compound represented by the following general formula (D-1) can be used.
[일반식 (D-1)에 있어서 R41 내지 R48는 각각 독립적으로, 수소 원자, 할로겐 원자, 탄소수 1 이상 6 이하의 알킬기, 탄소수 1 이상 6 이하의 알콕시기 또는 시클로 알킬기를 나타내고; R49 내지 R51는 각각 독립적으로 수소 원자 또는 탄소수 1 이상 6 이하의 알킬기를 나타내며; Q는 수소 원자, 탄소수 1 이상 6 이하의 알킬기, R49와 결합하여 형성되는 탄소쇄 수 3 이상 6 이하의 시클로환 또는 하기의 화학식 (D-2)로 표시되는 잔기를 나타내고; w, s는 1 이상 3 이하의 정수를 나타내며; u는 0 이상 3 이하의 정수를 나타내고; ｖ는 0 이상 3 이하의 정수를 나타낸다.][In the formula (D-1), R 41 to R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group; R 49 to R 51 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclo ring having 3 to 6 carbon atoms formed by combining with R 49 , or a residue represented by the following formula (D-2); w and s represent an integer of 1 or more and 3 or less; u represents an integer of 0 to 3; and v represents an integer of 0 or more and 3 or less.]
[일반식 (D-2)에 있어서 R52 및 R53는 각각 독립적으로, 수소 원자, 할로겐 원자, 탄소수 1 이상 6 이하의 알킬기, 탄소수 1 이상 6 이하의 알콕시기 또는 시클로 알킬기를 나타내고; t는 1 이상 3 이하의 정수를 나타낸다.]In the general formula (D-2), R 52 and R 53 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group; and t represents an integer of 1 or more and 3 or less.]
상기 일반식 (D-1)로 표시되는 페놀 화합물로는 예를 들면 비스(4-히드록시-2,3,5-트리메틸 페닐)-2-히드록시 페닐 메탄, 1, 4-비스[1-(3,5-디메틸-4-히드록시 페닐)이소프로필]벤젠, 2,4-비스(3,5-디메틸-4-히드록시 페닐 메틸)-6-메틸 페놀, 비스(4-히드록시-3,5-디메틸 페닐)-2-히드록시 페닐 메탄, 비스(4-히드록시-2,5-디메틸 페닐)-2-히드록시 페닐 메탄, 비스(4-히드록시-3,5-디메틸 페닐)-3,4-디히드 록시 페닐 메탄, 1-[1-(4-히드록시 페닐)이소프로필]-4-[1,1-비스(4-히드록시 페닐) 에틸]벤젠, 1-[1-(3-메틸-4-히드록시 페닐)이소프로필]-4-[1,1-비스(3-메틸-4-히드록시 페닐) 에틸]벤젠, 2,6-비스[1-(2,4-디히드록시 페닐)이소프로필]-4-메틸 페놀, 4,6-비스[1-(4-히드록시 페닐)이소프로필]레조르신, 4,6-비스(3,5-디메톡시-4-히드록시페닐메틸)피로갈롤, 4,6-비스(3,5-디메틸-4-히드록시 페닐 메틸)피로갈롤, 2,6-비스(3-메틸-4,6-디히드록시 페닐 메틸)-4-메틸 페놀, 2,6-비스(2,3,4-트리히드록시 페닐 메틸)-4-메틸 페놀, 1,1-비스(4-히드록시 페닐)시클로 헥산 등을 들 수 있다. 또, 그 외 6-히드록시-4a-(2,4-디히드록시 페닐)-9-1'-스피로 시클로헥실-1,2,3,4,4a,9a-헥사히드로크산텐, 6-히드록시-5-메틸-4a-(2,4-디히드록시-3-메틸 페닐)-9-1'-스피로 시클로헥실-1,2,3,4,4a,9a-헥사히드로크산텐 등도 이용할 수 있다. 이러한 증감제는 단독으로 이용해도 되고, 2종 이상을 혼합하여 이용해도 되나, 그 중에서도 1-[1-(4-히드록시 페닐)이소프로필]-4-[1,1-비스(4-히드록시 페닐)에틸]벤젠과 비스(4-히드록시-2,3,5-트리메틸 페닐)-2-히드록시 페닐 메탄의 조합이 고감도화와 스페이스 패턴의 수직성이 뛰어난 점에서 바람직하다.Examples of the phenol compound represented by the above general formula (D-1) include bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, 1,4- Bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis (4-hydroxy- Bis (4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) ) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2,6-bis [1- , 4-dihydroxyphenyl) isopropyl] -4-methylphenol, 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin, 4,6- 4-hydroxyphenylmethyl) pyrogallol, 4,6-bis (3,5-dimethyl-4-hydroxyphenyl (3-methyl-4,6-dihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (2,3,4-trihydroxyphenylmethyl) - 4-methylphenol, and 1,1-bis (4-hydroxyphenyl) cyclohexane. In addition, other 6-hydroxy-4a- (2,4-dihydroxyphenyl) -9-1'-spirocyclohexyl-1,2,3,4,4a, 9a-hexahydroxanthene, 6- (2,4-dihydroxy-3-methylphenyl) -9-1'-spirocyclohexyl-1,2,3,4,4a, 9a-hexahydroxanthone and the like Can be used. These sensitizers may be used alone or in combination of two or more. Among them, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1- Hydroxyphenyl) ethyl] benzene and bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane are preferable because of high sensitivity and excellent perpendicularity of the space pattern.
또, 증감제로는 하기 일반식 (D-3)로 표시되는 페놀 화합물을 사용할 수 있다.As the sensitizer, a phenol compound represented by the following formula (D-3) may be used.
[일반식 (D-3)에 있어서 R61 내지 R63는 각각 독립적으로, 저급 알킬기, 시클로 알킬기 또는 저급 알콕시기를 나타내고; q 및 r는 각각 독립적으로, 1 이상 3 이하, 바람직하게는 1 이상 2 이하의 정수를 나타내고; l, o 및 p는 각각 독립적으로, 0 이상 3 이하의 정수를 나타낸다.][In the formula (D-3), R 61 to R 63 each independently represent a lower alkyl group, a cycloalkyl group or a lower alkoxy group; q and r each independently represent an integer of 1 or more and 3 or less, preferably 1 or more and 2 or less; l, o and p each independently represent an integer of 0 or more and 3 or less.
여기서 R61 내지 R63가 나타내는 저급 알킬기 및 저급 알콕시기는 직쇄상이어도 분기쇄상이어도 되고, 바람직하게는 탄소수 1 이상 5 이하이며, 보다 바람직하게는 탄소수 1 이상 3 이하이다. 또, R61 내지 R63가 나타내는 시클로 알킬기는 바람직하게는 탄소수 5 이상 7 이하이다.Here, the lower alkyl group and lower alkoxy group represented by R 61 to R 63 may be straight chain or branched chain, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. The cycloalkyl group represented by R 61 to R 63 preferably has 5 or more and 7 or less carbon atoms.
일반식 (D-3)로 표시되는 화합물로는 보다 구체적으로는 하기 화학식 (D-4) 내지 (D-8)로 표시되는 화합물을 들 수 있다.Examples of the compound represented by the general formula (D-3) include compounds represented by the following general formulas (D-4) to (D-8).
또, 증감제로는 하기 일반식 (D-9)로 표시되는 페놀 화합물을 사용할 수 있다.As the sensitizer, a phenol compound represented by the following general formula (D-9) can be used.
[일반식 (D-9)에 있어서 R71 내지 R79는 각각 독립적으로, 수소 원자, 알킬기, 할로겐 원자 또는 수산기를 나타내고, R71 내지 R79 중 적어도 하나는 수산기이다. R80 내지 R85는 각각 독립적으로, 수소 원자, 알킬기, 알케닐기, 시클로 알킬기 또는 아릴기를 나타낸다.]In the general formula (D-9), R 71 to R 79 each independently represent a hydrogen atom, an alkyl group, a halogen atom or a hydroxyl group, and at least one of R 71 to R 79 is a hydroxyl group. R 80 to R 85 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.
여기서 R71 내지 R74 중 적어도 하나와 R75 내지 R79 중 적어도 하나가 수산기인 것이 바람직하다. 또, R71 내지 R79가 나타내는 알킬기는 직쇄상이어도 분기쇄상이어도 되고, 바람직하게는 탄소수 1 이상 5 이하이며, 보다 바람직하게는 탄소수 1 이상 3 이하이다. 또한, R80 내지 R85가 나타내는 알킬기는 직쇄상이어도 분기쇄상이어도 되고, 탄소수 1 이상 10 이하인 것이 바람직하고, R80 내지 R85가 나타내는 알케닐기로는 탄소수 1 이상 4 이하인 것이 바람직하다.It is preferable that at least one of R 71 to R 74 and at least one of R 75 to R 79 is a hydroxyl group. The alkyl groups represented by R 71 to R 79 may be straight chain or branched chain, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. The alkyl group represented by R 80 to R 85 may be linear or branched and preferably has 1 to 10 carbon atoms and the alkenyl group represented by R 80 to R 85 preferably has 1 to 4 carbon atoms.
상기 일반식 (D-9)로 표시되는 페놀 화합물로서 보다 구체적으로는 하기 일반식 (D-10)로 표시되는 화합물을 들 수 있다.More specific examples of the phenol compound represented by the general formula (D-9) include the compounds represented by the following general formula (D-10).
[일반식 (D-10)에 있어서 R86 및 R87는 각각 독립적으로 알킬기를 나타내고, f 및 g는 1 이상 3 이하, 바람직하게는 1 이상 2 이하의 정수를 나타내고, j 및 z는 0 이상 3 이하의 정수를 나타낸다.]In the general formula (D-10), R 86 and R 87 each independently represents an alkyl group, f and g each represent an integer of 1 or more and 3 or less, preferably 1 or more and 2 or less, Represents an integer of 3 or less.]
여기서 R86 및 R87로 표시되는 알킬기는 직쇄상이어도 분기쇄상이어도 되고, 바람직하게는 탄소수 1 이상 5 이하이며, 보다 바람직하게는 탄소수 1 이상 3 이하이다.The alkyl group represented by R 86 and R 87 may be straight chain or branched chain, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
상기 일반식 (D-9)로 표시되는 페놀 화합물로는 보다 구체적으로는 하기 화학식 (D-11) 및 (D-12)로 표시되는 화합물을 들 수 있다.Examples of the phenol compound represented by the general formula (D-9) include compounds represented by the following formulas (D-11) and (D-12).
증감제의 배합량은 상기(A) 성분 또는 (A') 성분에 대해서 1 중량% 이상 30 중량% 이하인 것이 바람직하고, 3 중량% 이상 25 중량% 이하인 것이 더욱 바람직하다.The blending amount of the sensitizer is preferably 1% by weight or more and 30% by weight or less, more preferably 3% by weight or more and 25% by weight or less with respect to the component (A) or the component (A ').
[그 외의 성분][Other components]
(용제)(solvent)
본 발명의 포지티브형 레지스트 조성물은 상기의 각 성분을 적당한 용제에 용해하여 용액의 형태로 이용하는 것이 바람직하다. 이와 같은 용제의 예로는 에틸렌글리콜 모노메틸 에테르, 에틸렌글리콜 모노에틸 에테르, 에틸렌글리콜 모노프로필 에테르, 에틸렌글리콜 모노부틸 에테르 등의 에틸렌글리콜 알킬 에테르류; 디에틸렌글리콜 디메틸 에테르, 디에틸렌글리콜 디에틸 에테르, 디에틸렌글리콜 디프로필 에테르, 디에틸렌글리콜 디부틸 에테르 등의 디에틸렌글리콜 디알킬 에테르류; 메틸 셀로솔브 아세테이트, 에틸 셀로솔브 아세테이트 등의 에틸렌글리콜 알킬 에테르 아세테이트류; 프로필렌 글리콜 모노메틸 에테르 아세테이트, 프로필렌 글리콜 모노에틸 에테르 아세테이트, 프로필렌 글리콜 모노프로필 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류; 아세톤, 메틸 에틸 케톤, 시클로 헥산온, 메틸 아밀 케톤 등의 케톤류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 디옥산 등의 환식 에테르류; 2-히드록시 프로피온산 메틸, 2-히드록시 프로피온산 에틸, 2-히드록시-2-메틸 프로피온산 에틸, 에톡시 아세트산 에틸, 옥시 아세트산 에틸, 2-히드록시-3-메틸 부탄산 메틸, 3-메톡시 부틸 아세테이트, 3-메틸-3-메톡시 부틸 아세테이트, 포름산 에틸, 아세트산 에틸, 아세트산 부틸, 아세토 아세트산 메틸, 아세토 아세트산 에틸 등의 에스테르류 등을 들 수 있다. 이러한 용제는 단독으로 이용해도 되고, 2종 이상을 혼합하여 이용해도 된다.The positive resist composition of the present invention is preferably used in the form of a solution in which each of the above components is dissolved in a suitable solvent. Examples of such a solvent include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; Aromatic hydrocarbons such as toluene and xylene; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3- Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate. These solvents may be used alone or in combination of two or more.
또한, 스핀 코트법을 이용하여 예를 들면 3㎛ 이상의 막 두께를 얻기 위해서는 포지티브형 레지스트 조성물에서의 고형분 농도가 20 중량% 이상 65 중량% 이하가 되는 양의 용제를 사용하는 것이 바람직하다.Further, in order to obtain a film thickness of 3 m or more, for example, by spin coating, it is preferable to use a solvent in which the solid concentration in the positive resist composition is 20 wt% or more and 65 wt% or less.
(계면활성제)(Surfactants)
또, 본 발명의 포지티브형 레지스트 조성물은 도포성, 소포성, 레벨링성 등을 향상시키기 위해 계면활성제를 함유하고 있어도 된다. 계면활성제로는 예를 들면 BM-1000, BM-1100(BM 케미사제), 메가파크 F142D, 메가파크 F172, 메가파크 F173, 메가파크 F183(대일본 잉크 화학공업사제), 플로라드 FC-135, 플로라로 FC-170C, 플로라드 FC-430, 플로라드 FC-431(스미토모 쓰리엠사제), 서프론 S-112, 서프론 S-113, 서프론 S-131, 서프론 S-141, 서프론 S-145(아사히 가라스사제), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428(토오레 실리콘사제) 등의 명칭으로 시판되고 있는 불소계 계면활성제를 사용할 수 있다.In addition, the positive resist composition of the present invention may contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM Chemie), Mega Park F142D, Mega Park F172, Mega Park F173, Mega Park F183 Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-113, Florad FC-430, Florad FC-431 (manufactured by Sumitomo 3M Company) Fluorinated surfactants commercially available under the trade names of -145 (manufactured by Asahi Glass), SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428 (manufactured by Toray Silicone Co., Ltd.)
계면활성제의 함유량은 (A) 성분 또는 (A') 성분 100 중량부당 5 중량부 이하인 것이 바람직하다.The content of the surfactant is preferably 5 parts by weight or less per 100 parts by weight of the component (A) or the component (A ').
(가소제)(Plasticizer)
본 발명의 포지티브형 레지스트 조성물에는 크랙의 발생 등의 내도금성을 더욱 향상시키기 위해서 가소제로서 알칼리 가용성 아크릴 수지를 배합해도 된다. 알칼리 가용성 아크릴 수지로는 일반적으로 가소제로서 포지티브형 포토 레지스트 조성물에 배합되어 있는 것을 사용할 수 있다.The positive resist composition of the present invention may be blended with an alkali-soluble acrylic resin as a plasticizer in order to further improve resistance to corrosion such as cracking. As the alkali-soluble acrylic resin, those which are generally mixed with a positive photoresist composition as a plasticizer can be used.
알칼리 가용성 아크릴 수지로는 보다 구체적으로는 에테르 결합을 갖는 중합성 화합물로부터 유도된 구성 단위를 30 중량% 이상 90 중량% 이하와 카르복실기를 갖는 중합성 화합물로부터 유도된 구성 단위를 2 중량부 이상 50 중량부 이하를 함유하는 것을 들 수 있다.More specifically, as the alkali-soluble acrylic resin, 30 to 90% by weight of constituent units derived from a polymerizable compound having an ether bond and 2 to 50% by weight of a constituent unit derived from a polymerizable compound having a carboxyl group By weight or less.
에테르 결합을 갖는 중합성 화합물로는 2-메톡시 에틸 (메타)아크릴레이트, 메톡시 트리에틸렌 글리콜 (메타)아크릴레이트, 3-메톡시 부틸 (메타)아크릴레이트, 에틸 카르비톨 (메타)아크릴레이트, 페녹시 폴리에틸렌 글리콜 (메타)아크릴레이트, 메톡시 폴리프로필렌 글리콜 (메타)아크릴레이트, 테트라히드로 푸르푸릴 (메타)아크릴레이트 등의 에테르 결합과 에스테르 결합을 갖는 (메타)아크릴산 유도체 등의 라디칼 중합성 화합물을 들 수 있다. 이들 중에서도 2-메톡시 에틸 아크릴레이트 및 메톡시 트리에틸렌 글리콜 아크릴레이트를 이용하는 것이 바람직하다. 이러한 화합물은 단독으로 이용해도 되고, 2종 이상 혼합하여 이용해도 된다.Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (Meth) acrylic acid derivatives having an ether bond and an ester bond such as phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Compounds. Of these, 2-methoxyethyl acrylate and methoxy triethylene glycol acrylate are preferably used. These compounds may be used alone or in combination of two or more.
카르복실기를 갖는 중합성 화합물로는 아크릴산, 메타크릴산, 크로톤산 등의 모노카르본산; 말레산, 푸마르산, 이타콘산 등의 디카르본산; 2-메타크릴로일 옥시 에틸 숙신산, 2-메타크릴로일 옥시 에틸 말레산, 2-메타크릴로일 옥시 에틸 프탈산, 2-메타크릴로일 옥시 에틸 헥사히드로 프탈산 등의 카르복실기와 에스테르 결합을 갖는 메타크릴산 유도체 등의 라디칼 중합성 화합물을 들 수 있다. 이들 중에서도 아크릴산 및 메타크릴산을 이용하는 것이 바람직하다. 이러한 화합물은 단독으로 이용해도 되고, 2종 이상을 혼합하여 이용해도 된다.Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; Having an ester bond with a carboxyl group such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid, And radically polymerizable compounds such as methacrylic acid derivatives. Of these, acrylic acid and methacrylic acid are preferably used. These compounds may be used alone or in combination of two or more.
알칼리 가용성 아크릴 수지 성분 중에서의 에테르 결합을 갖는 중합성 화합물의 함유량은 30 중량% 이상 90 중량% 이하인 것이 바람직하고, 40 중량% 이상 80 중량% 이하인 것이 더욱 바람직하다. 상기 함유량이 90 중량% 이하인 것에 의해 (A) 성분 또는 (A') 성분의 용액에 대한 상용성이 악화되는 일이 없고, 프리베이크시에 버나드셀(Benard Cell, 중력 또는 표면장력 구배 등에 의해서 도막 표면에 생기는 불균일성을 갖는 5각형에서 7각형의 네트워크 패턴)이 발생하지 않기 때문에 균일한 레지스트막을 얻을 수 있고, 30 중량% 이상인 것에 의해 도금시에 크랙이 발생하지 않는다.The content of the polymerizable compound having an ether bond in the alkali-soluble acrylic resin component is preferably 30 wt% or more and 90 wt% or less, and more preferably 40 wt% or more and 80 wt% or less. When the content is 90% by weight or less, compatibility with the solution of the component (A) or the component (A ') is not deteriorated. When the prebake is applied to the film by a Benard Cell (gravity or surface tension gradient, A hexagonal to hexagonal network pattern having non-uniformity on the surface) does not occur. Thus, a uniform resist film can be obtained, and cracks do not occur during plating because of 30 wt% or more.
또, 알칼리 가용성 아크릴 수지 성분 중에서의 카르복실기를 갖는 중합성 화합물의 함유량은 2 중량% 이상 50 중량% 이하인 것이 바람직하고, 5 중량% 이상 40 중량% 이하인 것이 더욱 바람직하다. 상기 함유량이 2 중량% 이상인 것에 의해 알칼리 가용성 아크릴 수지 성분의 알칼리 용해성이 높게 유지되어 충분한 현상성을 얻을 수 있음과 동시에 박리성이 저하하지 않아 기판 상에 레지스트막이 잔막(殘膜)하지 않는다. 50 중량% 이하인 것에 의해 현상 후의 잔막율이 높게 유지되어 내도금성이 양호하게 유지된다.The content of the polymerizable compound having a carboxyl group in the alkali-soluble acrylic resin component is preferably 2 wt% or more and 50 wt% or less, and more preferably 5 wt% or more and 40 wt% or less. When the content is 2% by weight or more, the alkali solubility of the alkali-soluble acrylic resin component is kept high, sufficient developability can be obtained, and the releasability is not lowered and the resist film does not remain on the substrate. When the content is 50% by weight or less, the residual film ratio after development is maintained at a high level, and thus the gold plating is maintained well.
알칼리 가용성 아크릴 수지 성분의 중량 평균 분자량은 10000 이상 800000 이하인 것이 바람직하고, 30000 이상 500000 이하인 것이 보다 바람직하다. 10000 이상인 것에 의해 레지스트막의 강도가 충분한 것이 되어 도금시의 프로파일의 팽창이나 크랙의 발생이 야기되지 않는다. 800000 이하인 것에 의해 박리성이 저하하지 않는다.The weight average molecular weight of the alkali-soluble acrylic resin component is preferably 10000 or more and 800000 or less, and more preferably 30000 or more and 500000 or less. When it is 10,000 or more, the strength of the resist film becomes sufficient, so that the profile does not expand or cracks are generated at the time of plating. The peelability is not deteriorated by being 800000 or less.
또한, 알칼리 가용성 아크릴 수지 성분 중에는 물리적ㆍ화학적 특성을 적절히 컨트롤할 목적으로, 다른 라디칼 중합성 화합물로부터 유도되는 구성 단위를 포함하고 있어도 된다. 여기서 「다른 라디칼 중합성 화합물」이란 전출의 중합성 화합물 이외의 라디칼 중합성 화합물의 의미이다.Further, the alkali-soluble acrylic resin component may contain a constituent unit derived from another radical polymerizable compound for the purpose of appropriately controlling physical and chemical properties. The term "other radical polymerizable compound" as used herein means a radical polymerizable compound other than the polymerizable compound that is transferred.
이와 같은 라디칼 중합성 화합물로는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 부틸 (메타)아크릴레이트 등의 (메타)아크릴산 알킬 에스테르류; 2-히드록시 에틸 (메타)아크릴레이트, 2-히드록시 프로필 (메타)아크릴레이트 등의 (메타)아크릴산 히드록시알킬 에스테르류; 페닐 (메타)아크릴레이트, 벤질 (메타)아크릴레이트 등의 (메타)아크릴산 아릴 에스테르류; 말레산 디에틸, 푸마르산 디부틸 등의 디카르본산 디에스테르류; 스티렌, α-메틸 스티렌 등의 비닐기 함유 방향족 화합물; 아세트산 비닐 등의 비닐기 함유 지방족 화합물; 부타디엔, 이소프렌 등의 공역 디올레핀류; 아크릴로니트릴, 메타크릴로니트릴 등의 니트릴기 함유 중합성 화합물; 염화 비닐, 염화 비닐리덴 등의 염소 함유 중합성 화합물; 아크릴 아미드, 메타크릴 아미드 등의 아미드 결합 함유 중합성 화합물 등을 이용할 수 있다. 이러한 화합물은 단독으로 이용해도 되고, 2종 이상을 혼합하여 이용해도 된다. 이러한 화합물 중에서도, 특히, n-부틸 아크릴레이트, 벤질 메타크릴레이트, 메틸 메타크릴레이트 등을 이용하는 것이 바람직하다. 알칼리 가용성 아크릴 수지 성분 중에 차지하는 다른 라디칼 중합성 화합물의 함유량은 50 중량% 미만인 것이 바람직하고, 40 중량% 미만인 것이 더욱 바람직하다.Examples of such a radical polymerizable compound include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; Vinyl group-containing aromatic compounds such as styrene and? -Methylstyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; Amide bond-containing polymerizable compounds such as acrylamide, methacrylamide and the like can be used. These compounds may be used alone or in combination of two or more. Among these compounds, n-butyl acrylate, benzyl methacrylate, methyl methacrylate and the like are particularly preferably used. The content of other radical polymerizable compounds in the alkali-soluble acrylic resin component is preferably less than 50% by weight, more preferably less than 40% by weight.
알칼리 가용성 아크릴 수지 성분을 합성할 때에 이용되는 중합 용매로는 예 를 들면 에탄올, 디에틸렌글리콜 등의 알코올류; 에틸렌글리콜 모노메틸 에테르, 디에틸렌글리콜 모노메틸 에테르, 디에틸렌글리콜 에틸 메틸 에테르 등의 다가 알코올의 알킬 에테르류; 에틸렌글리콜 에틸 에테르 아세테이트, 프로필렌 글리콜 메틸 에테르 아세테이트 등의 다가 알코올의 알킬 에테르 아세테이트류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 아세톤, 메틸 이소부틸 케톤 등의 케톤류; 아세트산 에틸, 아세트산 부틸 등의 에스테르류 등을 이용할 수 있다. 이러한 중합성 용매 중에서도 특히 다가 알코올의 알킬 에테르류 및 다가 알코올의 알킬 에테르 아세테이트류를 이용하는 것이 바람직하다.Examples of the polymerization solvent used in synthesizing the alkali-soluble acrylic resin component include alcohols such as ethanol and diethylene glycol; Alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether and diethylene glycol ethyl methyl ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone and methyl isobutyl ketone; Esters such as ethyl acetate and butyl acetate, and the like can be used. Among these polymerizable solvents, alkyl ethers of polyhydric alcohols and alkyl ether acetates of polyhydric alcohols are preferably used.
알칼리 가용성 아크릴 수지 성분을 합성할 때에 이용되는 중합 촉매로는 통상의 라디칼 중합 개시제를 사용할 수 있고, 예를 들면 2,2'-아조비스 이소부티로니트릴 등의 아조 화합물; 벤조일퍼옥시드, 디-tert-부틸퍼옥시드 등의 유기 과산화물 등을 사용할 수 있다.As the polymerization catalyst to be used in synthesizing the alkali-soluble acrylic resin component, a usual radical polymerization initiator can be used, and examples thereof include azo compounds such as 2,2'-azobisisobutyronitrile; Organic peroxides such as benzoyl peroxide and di-tert-butyl peroxide, and the like can be used.
본 발명의 포지티브형 레지스트 조성물에 있어서 알칼리 가용성 아크릴 수지 성분의 배합량은 전술의 (A) 성분 또는 (A') 성분 100 중량부에 대해 30 중량부 이하가 바람직하고, 20 중량부 이하가 보다 바람직하다.In the positive resist composition of the present invention, the amount of the alkali-soluble acrylic resin component is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the component (A) or (A ' .
[포지티브형 레지스트 조성물의 조제][Preparation of Positive Resist Composition]
본 발명의 포지티브형 레지스트 조성물은 통상의 방법으로 혼합, 교반함으로써 조제할 수 있다. 또, 필요에 따라서 추가로 메시(mesh), 멤브레인 필터(membrane filter) 등을 이용하여 여과해도 된다.The positive resist composition of the present invention can be prepared by mixing and stirring in a conventional manner. If necessary, it may be further filtered using a mesh, a membrane filter, or the like.
＜레지스트 패턴의 형성 방법＞≪ Method of forming resist pattern >
본 발명의 레지스트 패턴의 형성 방법은 기판 상에 본 발명의 포지티브형 레지스트 조성물을 도포하여 레지스트막을 얻는 도포 공정과 레지스트막에 선택적으로 활성선을 조사하여 노광하는 노광 공정과 노광 공정 후에 현상을 실시하여 레지스트 패턴을 얻는 현상 공정을 갖는다.A method of forming a resist pattern of the present invention includes a coating step of applying a positive resist composition of the present invention onto a substrate to obtain a resist film, an exposure step of selectively exposing the resist film to an active ray and exposing the resist film, And a developing step of obtaining a resist pattern.
[도포 공정][Application step]
본 발명의 포지티브형 레지스트 조성물은 예를 들면 구리로 이루어지는 기판의 에칭시나 도금시에서의 보호막이나 반도체 제조용 레지스트막을 형성할 때에 사용할 수 있는 것이다. 레지스트 패턴의 형성 방법에서의 도포 공정에 있어서는 이러한 기판 상에 스피너 등을 이용하여 본 발명의 포지티브형 레지스트 조성물을 3㎛에서 30㎛의 막 두께로 도포하고, 도포막 두께나 사용 용도에 따라 80℃에서 150℃의 온도 조건하, 프리베이크(포스트 어플라이 베이크(PAB))를 40초 내지 600초간, 바람직하게는 60초 내지 360초간 실시하여 레지스트막을 형성한다.The positive resist composition of the present invention can be used, for example, when forming a resist film for a protective film or a semiconductor for etching a substrate made of copper or plating. In the coating step in the method of forming a resist pattern, a positive resist composition of the present invention is coated on such a substrate by a spinner or the like at a film thickness of 3 to 30 mu m, (Post-application baking (PAB)) is performed for 40 seconds to 600 seconds, preferably 60 seconds to 360 seconds, at a temperature of 150 占 폚 under a temperature condition to form a resist film.
[노광 공정][Exposure step]
이 레지스트막에 예를 들면 파장 365 nm(i선), 405 nm(h선), 435 nm(g선) 부근의 빛을 발광하는 광원인 저압 수은등, 고압 수은등 및 초고압 수은등을 이용하여 원하는 마스크 패턴을 통하여 선택적으로 조사한 후, 필요에 따라서 80℃에서 150℃의 온도 조건하, 노광 후 가열(PEB)을 40초간에서 600초간, 바람직하게는 60초간에서 360초간 실시한다. 또한, 노광에 이용하는 활성선으로는 상기 저압 수은등, 고압 수은등, 초고압 수은등에 의한 g선, h선 및 i선 외에도, ArF 엑시머 레이 저, KrF 엑시머 레이저, F2 엑시머 레이저, 극자외선(EUV), 진공 자외선(VUV), 전자선(EB), X선, 연(軟)X선 등의 방사선을 이용하여 실시할 수도 있다.A low-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high-pressure mercury lamp, which are light sources for emitting light near wavelengths of 365 nm (i line), 405 nm (h line), and 435 nm (PEB) is conducted for 40 seconds to 600 seconds, preferably 60 seconds to 360 seconds, at a temperature of 80 DEG C to 150 DEG C as occasion demands. Examples of active lines used for exposure include ArF excimer lasers, KrF excimer lasers, F 2 excimer lasers, extreme ultraviolet (EUV), and ultraviolet (EUV) radiation as well as g-line, h line and i line by the low pressure mercury lamp, high pressure mercury lamp, But may also be performed using radiation such as vacuum ultraviolet (VUV), electron beam (EB), X-ray, soft X-ray or the like.
[현상 공정][Development process]
그 다음에 노광 후의 레지스트막을 알칼리 현상액, 예를 들면 0.1 중량% 이상 10 중량%의 테트라메틸 암모늄 수산화물 수용액을 이용하여 20℃ 이상 30℃ 이하의 온도로 현상 처리하고, 순수를 이용하여 물 린스를 실시하고 건조를 실시한다. 또, 경우에 따라서는 상기 현상 처리 후에 베이크 처리(포스트 베이크)를 실시해도 된다. 이와 같이 하여 마스크 패턴에 충실한 레지스트 패턴을 얻을 수 있다.Then, the exposed resist film is developed with an alkali developing solution, for example, 0.1 wt% or more and 10 wt% of tetramethylammonium hydroxide aqueous solution at a temperature of 20 ° C or higher and 30 ° C or lower, and rinsed with pure water And drying is carried out. In some cases, a baking process (post-baking) may be performed after the above developing process. In this manner, a resist pattern faithful to the mask pattern can be obtained.
본 발명의 포지티브형 레지스트 조성물 및 이것을 이용한 레지스트 패턴의 형성 방법에 의하면, 포지티브형 레지스트 조성물이 소정의 벤조트리아졸계 화합물을 함유하므로, 레지스트막과 기판의 밀착성이 양호하게 유지되어 미세한 레지스트 패턴을 형성 가능함과 동시에 레지스트막의 현상 후에 있어서도 잔사의 발생을 적게 억제할 수 있다.According to the positive resist composition of the present invention and the method of forming a resist pattern using the same, since the positive resist composition contains a predetermined benzotriazole-based compound, the adhesion between the resist film and the substrate is maintained satisfactorily so that a fine resist pattern can be formed The generation of the residue can be suppressed even after development of the resist film.
실시예Example
＜조제예 1; 알칼리 가용성 노볼락 수지 A의 합성＞ <Preparation example 1> Synthesis of alkali-soluble novolac resin A >
m-크레졸과 p-크레졸을 m-크레졸/p-크레졸=60/40(중량비)으로 혼합하고, 포르말린을 더하고, 옥살산 촉매를 이용하여 상법(常法)에 의해 부가 축합하여 크레졸 노볼락 수지를 얻었다. 이 수지에 대해서 분별 처리를 실시하고, 저분자 영역 을 컷트하여 중량 평균 분자량 20000의 알칼리 가용성 노볼락 수지 A를 얻었다.m-cresol and p-cresol were mixed at an m-cresol / p-cresol ratio of 60/40 (weight ratio), formalin was added, and an additional condensation was carried out by a conventional method using a catalyst of oxalic acid to prepare a cresol novolak resin . This resin was subjected to fractionation treatment and a low molecular weight region was cut out to obtain an alkali-soluble novolac resin A having a weight average molecular weight of 20,000.
＜실시예 1＞≪ Example 1 >
알칼리 가용성 노볼락 수지 A 69 중량부, 감광제로서 1-[1-(4-히드록시 페닐)이소프로필]-4-[1,1-비스(4-히드록시 페닐)에틸]벤젠의 전(全)수산기의 2 몰%의 수소 원자가 1,2-나프토퀴논 디아지드-5-술포닐기로 치환된 화합물 20 중량부, 증감제로서 1,1-비스(4-히드록시 페닐) 시클로 헥산 20 중량부, 밀착 향상제인 벤조트리아졸계 화합물로서 하기 화학식 (C-1)로 표시되는 화합물 1 중량부를, 프로필렌 글리콜 모노에틸 에테르 아세테이트에 용해하여, 고형분 농도가 43 중량%가 되도록 조정하여 포지티브형 레지스트 조성물을 조제하였다.69 parts by weight of an alkali-soluble novolak resin A and 1 part by weight of a total of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] ) 20 parts by weight of a compound in which 2 mol% of the hydrogen atoms of the hydroxyl group are substituted with 1,2-naphthoquinonediazide-5-sulfonyl groups, 20 parts by weight of 1,1-bis (4-hydroxyphenyl) cyclohexane 1 part by weight of a compound represented by the following formula (C-1) as a benzotriazole-based compound as a adhesion promoter was dissolved in propylene glycol monoethyl ether acetate to adjust the solid concentration to 43% by weight to prepare a positive resist composition Lt; / RTI >
＜실시예 2＞≪ Example 2 >
벤조트리아졸계 화합물로서 상기 화학식 (C-1)로 표시되는 화합물로 대체하고, 하기 화학식 (C-2)로 표시되는 화합물을 이용한 점 이외에는 실시예 1과 같은 방법에 의해 포지티브형 레지스트 조성물을 조제하였다.A positive resist composition was prepared in the same manner as in Example 1 except that the compound represented by the formula (C-1) was replaced with the compound represented by the formula (C-1) as the benzotriazole-based compound .
＜비교예 1＞≪ Comparative Example 1 &
벤조트리아졸계 화합물로서 상기 화학식 (C-1)로 표시되는 화합물로 대체하고, 카르복시벤조트리아졸를 이용한 점 이외에는 실시예 1과 같은 방법에 의해 포지티브형 레지스트 조성물을 조제하였다.A positive resist composition was prepared in the same manner as in Example 1 except that the compound represented by the above formula (C-1) was used as the benzotriazole compound and carboxybenzotriazole was used.
＜비교예 2＞≪ Comparative Example 2 &
밀착 향상제로서 벤조트리아졸계 화합물인 상기 화학식 (C-1)로 표시되는 화합물로 대체하고, 피리딘 에탄올을 이용한 점 이외에는 실시예 1과 같은 방법에 의해 포지티브형 레지스트 조성물을 조제하였다.A positive resist composition was prepared in the same manner as in Example 1 except that the compound represented by the above formula (C-1) as a benzotriazole-based compound was used as an adhesion improver and pyridine ethanol was used.
＜비교예 3＞≪ Comparative Example 3 &
벤조트리아졸계 화합물인 상기 화학식 (C-1)로 표시되는 화합물을 첨가하지 않았던 점 이외에는 실시예 1과 같은 방법에 의해 포지티브형 레지스트 조성물을 조제하였다.A positive resist composition was prepared in the same manner as in Example 1, except that the compound represented by the above formula (C-1) as the benzotriazole-based compound was not added.
＜성능 평가＞<Performance evaluation>
[잔사 발생의 유무][Whether or not residue is generated]
실리콘 웨이퍼 상에 구리를 500 nm의 두께로 스패터링한 기판에 실시예 1,2 및 비교예 1 내지 3의 포지티브형 레지스트 조성물을 도포하고, 핫 플레이트 상, 110℃에서 240초간 건조하여 막 두께 10㎛의 레지스트막을 얻었다.The positive resist compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were applied to a substrate sputtered with copper to a thickness of 500 nm on a silicon wafer and dried on a hot plate at 110 DEG C for 240 seconds to obtain a film thickness of 10 Mu m of resist film was obtained.
그 다음에 이 막에 소정의 차광 패턴이 그려진 마스크를 통해 축소 투영 노광 장치 「NSR-2005i10D」(상품명, 주식회사 니콘제, NA=0.50)을 이용하여 현상 가능한 최저 노광량(ETH)의 1.2배까지 노광을 실시하였다.Then, exposure was performed to 1.2 times the minimum developable exposure dose (ETH) using a reduced projection exposure apparatus "NSR-2005i10D" (trade name, manufactured by Nikon Corporation, NA = 0.50) through a mask on which a predetermined shielding pattern was drawn. Respectively.
현상 조작으로서 이 레지스트막에 23℃의 2.38 중량% 테트라메틸 암모늄 수 산화물(TMAH) 수용액을 현상액으로서 적용하여 60초간 유지한 후, 스피너의 회전에 의해 현상액의 떨어냄을 실시하였다. 이 현상 조작을 3회 반복한 후, 30초간 수세하여 건조시켰다.As a developing operation, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 DEG C was applied to this resist film as a developer for 60 seconds, and then the developing solution was removed by spinning. This developing operation was repeated three times, followed by washing with water for 30 seconds.
그 후 얻어진 20㎛의 스페이스 패턴의 레지스트-기재 계면을 주사형 전자현미경(SEM)으로 관찰하여, 레지스트 용해 잔사(스컴)가 패턴 주위에 확인되는 것을 X, 확인되지 않는 것을 ○으로 하였다.Subsequently, the resist-based interface of the 20 탆 space pattern obtained was observed with a scanning electron microscope (SEM) to find that the resist dissolved residue (scum) was confirmed around the pattern, and X, which was not identified, was evaluated as & cir &
[밀착성 평가 1(현상시 밀착성)][Evaluation of adhesion 1 (adhesion at the time of development)]
실리콘 웨이퍼 상에 구리를 500 nm의 두께로 스패터링한 기판 상에 실시예 1, 2 및 비교예 1 내지 3의 포지티브형 레지스트 조성물을 도포하고, 핫 플레이트상, 110℃에서 240초간 건조하여 막 두께 10㎛의 레지스트막을 얻었다.The positive resist compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a substrate sputtered with copper to a thickness of 500 nm on a silicon wafer and dried on a hot plate at 110 DEG C for 240 seconds to measure the film thickness A resist film having a thickness of 10 mu m was obtained.
그 다음에 이 막에 소정의 차광 패턴이 그려진 마스크를 통해, 축소 투영 노광 장치 「NSR-2005i10D」(상품명, 주식회사 니콘제, NA=0.50)을 이용하여 현상 가능한 최저 노광량(ETH)의 1.0배 내지 1.4배까지 노광을 실시하였다.Then, using a reduction projection exposure apparatus "NSR-2005i10D" (trade name, manufactured by Nikon Corporation, NA = 0.50) through a mask on which a predetermined shielding pattern is drawn, Exposure was performed up to 1.4 times.
현상 조작으로서 이 레지스트막에 2.38 중량% 테트라메틸 암모늄 수산화물(TMAH) 수용액을 현상액으로서 적용하여 60초간 유지한 후, 스피너의 회전에 의해 현상액의 떨어냄을 실시하였다. 이 현상 조작을 3회 반복한 후, 30초간 수세하여 건조시켰다.As a developing operation, 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution was applied to the resist film as a developing solution for 60 seconds, and then the developing solution was removed by spinning. This developing operation was repeated three times, followed by washing with water for 30 seconds.
그 후 광학 현미경으로 레지스트 패턴을 관찰하고, 10㎛의 라인 앤드 스페이스, 닷의 양쪽 모두의 반복 패턴이 ETH의 1.0배만 밀착하고 있는 것을 X, 1.2배까지 밀착하고 있는 것을 △, 1.4배까지 밀착하고 있는 것을 ○으로 하였다.Thereafter, the resist pattern was observed with an optical microscope, and it was found that the repeating pattern of both the line-and-space and the dot of 10 mu m adhered only 1.0 times as much as the ETH, ○.
[밀착성 평가 2(사이드 에칭량의 측정)][Evaluation of adhesion 2 (measurement of side etching amount)]
실리콘 웨이퍼 상에 구리를 500 nm의 두께로 스패터링한 기판 상에[밀착성 평가 1]과 동일하게 포지티브형 레지스트 조성물의 도포, 레지스트막의 노광 및 현상을 실시한 후, 23℃의 「염화 제2철 용액 45° 보메」(상품명, 쥰세이 화학사제)에 5초간 침지한 후, 주사형 전자현미경(SEM)을 이용하여 레지스트 저부의 구리의 침식 길이를 측정하였다. 침식 길이가 5㎛ 이상을 X, 3㎛ 이상 5㎛ 미만을 △, 3㎛ 미만을 ○으로 하였다.A positive resist composition was applied, a resist film was exposed and developed in the same manner as in [Adhesion Evaluation 1] on a substrate sputtered with copper to a thickness of 500 nm on a silicon wafer, and then a ferric chloride solution (Trade name, manufactured by Junsei Chemical Co., Ltd.) for 5 seconds and then the length of erosion of copper at the bottom of the resist was measured using a scanning electron microscope (SEM). An erosion length of 5 mu m or more was defined as X, a value of 3 mu m or more and less than 5 mu m as DELTA, and a value of less than 3 mu m as O.
[용해성 시험][Solubility test]
300 ml의 비커에 실시예 1,2 및 비교예 1 및 2의 조성물 중, 알칼리 가용성 노볼락 수지 A를 65 중량부와 밀착 향상제를 5 중량부를 더하고, 고형분 농도가 43 중량%가 되도록 프로필렌 글리콜 모노에틸 에테르 아세테이트를 더하고, 교반기로 1시간 교반하였다. 육안으로 보아 완전하게 용해하고 있는 것을 ○, 용해 찌꺼기가 있는 것을 X로 하였다.65 parts by weight of the alkali-soluble novolak resin A and 5 parts by weight of the adhesion-improving agent in the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were added to a 300-ml beaker, and propylene glycol mono Ethyl ether acetate was added, and the mixture was stirred for 1 hour with a stirrer. A sample was completely dissolved when viewed from the naked eye, and a sample was found to have X-ray residue.
이상의 결과를 표 1에 나타낸다.Table 1 shows the above results.
[표 1][Table 1]
표 1으로부터 분명한 바와 같이, 본 발명에 관련되는 벤조트리아졸계 화합물 을 이용한 실시예 1 및 2에서는 상기 일반식 (1)로 표시되는 벤조트리아졸계 화합물에 포함되지 않는 카르복시벤조트리아졸을 이용한 비교예 1에 비해, 잔사의 발생이 적게 억제되어 있는 것을 알 수 있다. 또, 실시예 1 및 2에서는 벤조트리아졸계 화합물을 이용하고 있지 않은 비교예 2 및 3에 비해, 레지스트막과 기판 사이에서의 밀착성이 양호한 것으로 되고, 잔사의 발생도 적게 되어 있다.As is evident from Table 1, in Examples 1 and 2 using the benzotriazole-based compounds according to the present invention, Comparative Example 1 using carboxybenzotriazole not included in the benzotriazole-based compound represented by the general formula (1) It can be seen that the occurrence of the residue is suppressed to a lesser extent. Further, in Examples 1 and 2, the adhesiveness between the resist film and the substrate was better than that of Comparative Examples 2 and 3 in which the benzotriazole-based compound was not used, and the residue was less generated.
이상으로부터 본 발명의 포지티브형 레지스트 조성물은 레지스트막과 기판의 밀착성을 양호하게 유지하면서도 잔사의 발생을 적게 억제할 수 있음을 알 수 있다.From the above, it can be seen that the positive resist composition of the present invention can suppress the occurrence of residues to a small extent while maintaining good adhesion between the resist film and the substrate.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009020514A JP5190000B2 (en) | 2009-01-30 | 2009-01-30 | Positive resist composition and method for forming resist pattern using the same |
| JPJP-P-2009-020514 | 2009-01-30 |
Publications (2)
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| JP6208959B2 (en) * | 2013-03-14 | 2017-10-04 | 旭化成株式会社 | Photosensitive resin composition, method for producing cured relief pattern, semiconductor device and display device |
| KR101707155B1 (en) * | 2014-08-20 | 2017-02-27 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
| JP2021026229A (en) | 2019-08-06 | 2021-02-22 | 東京応化工業株式会社 | Positive type photosensitive resin composition, forming method of patterned resist film, and patterned resist film |
| JP2021182041A (en) | 2020-05-18 | 2021-11-25 | 東京応化工業株式会社 | Positive photosensitive resin composition, method for forming patterned resist film, and patterned resist film |
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| JP2000171968A (en) | 1998-12-04 | 2000-06-23 | Nagase Denshi Kagaku Kk | Positive photoresist composition |
| JP2004347951A (en) | 2003-05-23 | 2004-12-09 | Tokyo Ohka Kogyo Co Ltd | Chemically amplifying photoresist composition, photoresist layered body, method for manufacturing photoresist composition, method for manufacturing photoresist pattern and method for manufacturing connecting terminal |
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| US4268610A (en) * | 1979-11-05 | 1981-05-19 | Hercules Incorporated | Photoresist formulations |
| JP2753921B2 (en) * | 1992-06-04 | 1998-05-20 | 富士写真フイルム株式会社 | Positive photoresist composition |
| JP3230925B2 (en) * | 1994-04-12 | 2001-11-19 | 富士写真フイルム株式会社 | Positive photoresist composition |
| JP2004347617A (en) * | 2003-04-11 | 2004-12-09 | Clariant Internatl Ltd | Adhesion improving agent for substrate for photosensitive resin composition and photosensitive resin composition containing same |
| WO2006059392A1 (en) * | 2004-12-03 | 2006-06-08 | Tokyo Ohka Kogyo Co., Ltd. | Chemical amplification photoresist composition, photoresist layer laminate, method for producing photoresist composition, method for producing photoresist pattern and method for producing connecting terminal |
| JP2006251458A (en) * | 2005-03-11 | 2006-09-21 | Asahi Kasei Electronics Co Ltd | Long-sized laminated board with photosensitive resin |
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| JP2000171968A (en) | 1998-12-04 | 2000-06-23 | Nagase Denshi Kagaku Kk | Positive photoresist composition |
| JP2004347951A (en) | 2003-05-23 | 2004-12-09 | Tokyo Ohka Kogyo Co Ltd | Chemically amplifying photoresist composition, photoresist layered body, method for manufacturing photoresist composition, method for manufacturing photoresist pattern and method for manufacturing connecting terminal |
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| TWI483077B (en) | 2015-05-01 |
| JP2010176012A (en) | 2010-08-12 |
| JP5190000B2 (en) | 2013-04-24 |
| KR20100088525A (en) | 2010-08-09 |
| TW201028795A (en) | 2010-08-01 |
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