JP4519621B2 - Photoacid generator and photosensitive resin composition - Google Patents
Photoacid generator and photosensitive resin composition Download PDFInfo
- Publication number
- JP4519621B2 JP4519621B2 JP2004346723A JP2004346723A JP4519621B2 JP 4519621 B2 JP4519621 B2 JP 4519621B2 JP 2004346723 A JP2004346723 A JP 2004346723A JP 2004346723 A JP2004346723 A JP 2004346723A JP 4519621 B2 JP4519621 B2 JP 4519621B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- photoacid generator
- resin composition
- photosensitive resin
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011342 resin composition Substances 0.000 title claims description 21
- -1 polymethylene group Polymers 0.000 claims description 135
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000005110 aryl thio group Chemical group 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003459 sulfonic acid esters Chemical class 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000012658 bimolecular nucleophilic substitution Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- 125000005810 2,5-xylyl group Chemical group [H]C1=C([H])C(=C(*)C([H])=C1C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- ZWUWDFWEMWMTHX-UHFFFAOYSA-N 2-methoxybutyl acetate Chemical compound CCC(OC)COC(C)=O ZWUWDFWEMWMTHX-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical group CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 101000895926 Streptomyces plicatus Endo-beta-N-acetylglucosaminidase H Proteins 0.000 description 1
- QPMIVFWZGPTDPN-UHFFFAOYSA-N Tetrabromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C(C(Br)=C(Br)C(Br)=C2Br)=C2S(=O)(=O)O1 QPMIVFWZGPTDPN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CRJJYTRIBJBMLI-UHFFFAOYSA-H hexapotassium oxalate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O CRJJYTRIBJBMLI-UHFFFAOYSA-H 0.000 description 1
- MYMDYWSMEBELMC-UHFFFAOYSA-M hydroxymethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CO MYMDYWSMEBELMC-UHFFFAOYSA-M 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004718 n-hexylthio group Chemical group C(CCCCC)S* 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004712 n-pentylthio group Chemical group C(CCCC)S* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 1
- 125000005933 neopentyloxycarbonyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- RPMOERPGTQLCAT-UHFFFAOYSA-M triethyl(hydroxymethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CO RPMOERPGTQLCAT-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Description
本発明は、光照射によってスルホン酸を発生する新規な光酸発生剤および当該光酸発生剤を含む感光性樹脂組成物に関する。 The present invention relates to a novel photoacid generator that generates sulfonic acid by light irradiation and a photosensitive resin composition containing the photoacid generator.
近年、集積回路の集積度はますます高まる趨勢にある。高集積度を達成するためには、半導体基板の微細加工が必要である。
このような微細加工はフォトリソグラフィーによって行われている。加工時の解像度は露光光の波長に比例するので、加工の微細化を進めるためには必然的に露光光として用いる光の短波長化が必要となり、高圧水銀灯のｇ線（４３８ｎｍ）、ｉ線（３６５ｎｍ）からＫｒＦエキシマレーザー（２４８ｎｍ）、さらにＡｒＦエキシマレーザー（１９３ｎｍ）へと短波長化が進められてきた。
In recent years, the degree of integration of integrated circuits has been increasing. In order to achieve a high degree of integration, fine processing of the semiconductor substrate is necessary.
Such fine processing is performed by photolithography. Since the resolution at the time of processing is proportional to the wavelength of the exposure light, it is necessary to shorten the wavelength of the light used as the exposure light in order to advance the miniaturization of the processing. The g-line (438 nm) and i-line of the high-pressure mercury lamp The wavelength has been reduced from (365 nm) to KrF excimer laser (248 nm) and further to ArF excimer laser (193 nm).
フォトリソグラフィーのパターン形成には、光照射によりプロトン酸を発生する光酸発生剤を含む感光性樹脂組成物が用いられている。このような感光性樹脂組成物は化学増幅型レジストと呼ばれているものであり、光照射によって光酸発生剤から発生したプロトン酸と、構成樹脂とが、その後の加熱処理によって連鎖的に反応して現像液に対して可溶性となるものである。 For pattern formation of photolithography, a photosensitive resin composition containing a photoacid generator that generates protonic acid by light irradiation is used. Such a photosensitive resin composition is called a chemically amplified resist, and a proton acid generated from a photoacid generator by light irradiation and a constituent resin react in a chain reaction by a subsequent heat treatment. Thus, it becomes soluble in the developer.
このような用途に用いられる光酸発生剤としては、スルホニウム塩誘導体が汎用されており、たとえば、ＫｒＦエキシマレーザーに対応したもの（非特許文献１）およびＡｒＦエキシマレーザーに対応したもの（特許文献１、２）がある。しかしながら、これらの光酸発生剤の性能も十分ではなく、新たな光酸発生剤の開発が求められている。
本発明者らは、光酸発生剤の分子構造と反応メカニズムについて鋭意研究した結果、光酸発生剤に要求される諸性能を合わせ有する特定の化合物を見出し、本発明を完成させた。すなわち、本発明の目的は、新規な光酸発生剤を提供することである。 As a result of intensive studies on the molecular structure and reaction mechanism of the photoacid generator, the present inventors have found a specific compound having various performances required for the photoacid generator and completed the present invention. That is, an object of the present invention is to provide a novel photoacid generator.
本発明によれば、以下の光酸発生剤および感光性樹脂組成物が提供される。
［１］ 下記式（Ｉ）〜（ＩＩＩ）のいずれかで示される光酸発生剤：
式中、Ｒは、アルキル基、フッ素置換アルキル基、アリール基、フッ素置換アリール基、フルオロアルキル基で置換されたアリール基、フッ素原子、ニトロ基またはシアノ基である；
Ｘは、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、分子内もしくは分子間のＸ同士で連結したポリメチレン基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基であり、それぞれ同一または異なっていてもよいが、−ＯＳＯ2Ｒ基のβ位の炭素原子に結合しているＸのう
ち少なくとも１つは水素原子である；
ｐ、ｑ、ｒは２つの橋頭位炭素間を結ぶ炭素鎖の長さをそれぞれ独立に示し、ｐは１〜３、ｑは０〜３、ｒは１〜２の整数である。
According to the present invention, the following photoacid generator and photosensitive resin composition are provided.
[1] A photoacid generator represented by any of the following formulas (I) to (III):
In the formula, R is an alkyl group, a fluorine-substituted alkyl group, an aryl group, a fluorine-substituted aryl group, an aryl group substituted with a fluoroalkyl group, a fluorine atom, a nitro group, or a cyano group;
X is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a polymethylene group, a carboxyl group, a hydroxyl group, a halogen atom, or a cyano group, which is connected by X within the molecule or between molecules. Each may be the same or different, but at least one of X bonded to the carbon atom at the β-position of the —OSO 2 R group is a hydrogen atom;
p, q, and r each independently represent the length of a carbon chain connecting two bridgehead carbons, p is 1 to 3, q is 0 to 3, and r is an integer of 1 to 2.
［２］ ［１］に記載の光酸発生剤を含む感光性樹脂組成物。 [2] A photosensitive resin composition comprising the photoacid generator according to [1].
本発明によれば、有機媒体との相溶性が高く、熱および求核剤に対して安定な新規光酸発生剤および当該光酸発生剤を含む感光性樹脂組成物が提供される。 According to the present invention, a novel photoacid generator that is highly compatible with an organic medium and is stable against heat and a nucleophile and a photosensitive resin composition containing the photoacid generator are provided.
以下、本発明について具体的に説明する。
本発明に係る光酸発生剤は、下記式（Ｉ）〜（ＩＩＩ）のいずれかで示されるものである。
Hereinafter, the present invention will be specifically described.
The photoacid generator according to the present invention is represented by any one of the following formulas (I) to (III).
式（Ｉ）〜（ＩＩＩ）において、Ｒは、アルキル基、フッ素置換アルキル基、アリール基、フッ素置換アリール基、フルオロアルキル基で置換されたアリール基、フッ素原子、ニトロ基またはシアノ基である。本発明に係る光酸発生剤は、後述するように光照射によってスルホン酸（ＨＯＳＯ2Ｒ）を発生する。Ｒは発生するスルホン酸の特性（酸性度な
ど）を決める要因となるものであり、光酸発生剤の用途に応じて適宜選択することができる。
In the formulas (I) to (III), R is an alkyl group, a fluorine-substituted alkyl group, an aryl group, a fluorine-substituted aryl group, an aryl group substituted with a fluoroalkyl group, a fluorine atom, a nitro group, or a cyano group. The photoacid generator according to the present invention generates sulfonic acid (HOSO 2 R) by light irradiation as described later. R is a factor that determines the characteristics (acidity and the like) of the generated sulfonic acid, and can be appropriately selected according to the use of the photoacid generator.
Ｒがアルキル基である場合のＲとしては、具体的には炭素数１〜２０の直鎖状、分岐状または環状のアルキル基などが挙げられる。さらに具体的には、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−エイコシル基、ベンジル基などの直鎖状アルキル基；ｉ−プロピル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基などの分岐状アルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、３−メチルシクロペンチル基、３−メトキシシクロペンチル基、３−カルボキシシクロペンチル基、３−メチルカルボニルシクロペンチル基、３−メトキシカルボニルシクロペンチル基、３−ジメチルアミノシクロペンチル基、シクロヘキシル基、４−メチルシクロヘキシル基、４−メトキシシクロヘキシル基、４−カルボキシシクロヘキシル基、４−ジメチルアミノシクロヘキシル基、シクロヘプチル基、シクロオクチル基などの環状アルキル基などが挙げられる。 Specific examples of R when R is an alkyl group include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. More specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl Linear alkyl group such as benzyl group; branched alkyl group such as i-propyl group, i-butyl group, s-butyl group, t-butyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, 3- Methylcyclopentyl group, 3-methoxycyclopentyl group, 3-carboxycyclopentyl group, 3-methylcarbonylcyclopentyl group, 3-methoxycarbonyl group Cyclic alkyl groups such as lopentyl, 3-dimethylaminocyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-methoxycyclohexyl, 4-carboxycyclohexyl, 4-dimethylaminocyclohexyl, cycloheptyl and cyclooctyl Etc.
Ｒがフッ素置換アルキル基である場合のＲとしては、具体的には炭素数１〜１２のフッ素置換アルキル基などが挙げられる。さらに具体的には、トリフルオロメチル基、フルオロメチル基、ジフルオロメチル基、ペンタフルオロエチル基、３−フルオロシクロペンチル基、３−トリフルオロメチルシクロペンチル基、４−フルオロシクロヘキシル基などが挙げられる。 Specific examples of R in the case where R is a fluorine-substituted alkyl group include a fluorine-substituted alkyl group having 1 to 12 carbon atoms. More specifically, trifluoromethyl group, fluoromethyl group, difluoromethyl group, pentafluoroethyl group, 3-fluorocyclopentyl group, 3-trifluoromethylcyclopentyl group, 4-fluorocyclohexyl group and the like can be mentioned.
Ｒがアリール基である場合のＲとしては、具体的には炭素数６〜１４のアリール基などが挙げられる。さらに具体的には、フェニル基、２，４−キシリル基、２，５−キシリル基、３，４−キシリル基、３，５−キシリル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリ
ル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、４−カルボキシフェニル基、４−メチルカルボニルフェニル基、４−メトキシカルボニルフェニル基、ジメチルアミノカルボニルフェニル基、１−ナフチル基、４−メチル−１−ナフチル基、４−メトキシ−１−ナフチル基、４−カルボキシル−１−ナフチル基、２−ナフチル基、１−アントラセニル基、９−アントラセニル基などが挙げられる。
Specific examples of R when R is an aryl group include aryl groups having 6 to 14 carbon atoms. More specifically, phenyl, 2,4-xylyl, 2,5-xylyl, 3,4-xylyl, 3,5-xylyl, o-tolyl, m-tolyl, p-tolyl Group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 4-methylcarbonylphenyl group, 4-methoxycarbonylphenyl group, dimethylaminocarbonylphenyl group, 1-naphthyl group 4-methyl-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-carboxyl-1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group, and the like.
Ｒがフッ素置換アリール基である場合のＲとしては、具体的には炭素数６〜１０のフッ素置換アリール基などが挙げられる。さらに具体的には、２−フルオロフェニル基、３−フルオロフェニル基、４−フルオロフェニル基、ペンタフルオロフェニル基、ヘプタフルオロナフチル基などが挙げられる。 Specific examples of R when R is a fluorine-substituted aryl group include fluorine-substituted aryl groups having 6 to 10 carbon atoms. More specific examples include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, pentafluorophenyl group, heptafluoronaphthyl group and the like.
Ｒがフルオロアルキル基で置換されたアリール基である場合のＲとしては、具体的には炭素数７〜１１のフルオロアルキル基で置換されたアリール基などが挙げられる。さらに具体的には、２−トリフルオロメチルフェニル基、３−トリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基などが挙げられる。 Specific examples of R when R is an aryl group substituted with a fluoroalkyl group include an aryl group substituted with a fluoroalkyl group having 7 to 11 carbon atoms. More specifically, a 2-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, a pentafluoroethylphenyl group, and the like can be given.
上記した中でもＲとしては、フッ素置換アルキル基が好ましく、特にトリフルオロメチル基が好ましい。
Ｘは、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、分子内もしくは分子間のＸ同士で連結したポリメチレン基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基であり、それぞれ同一または異なっていてもよいが、−ＯＳＯ2Ｒ基のβ位の炭素原子に結合しているＸのう
ち少なくとも１つは水素原子である。
Among the above, R is preferably a fluorine-substituted alkyl group, particularly preferably a trifluoromethyl group.
X is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a polymethylene group, a carboxyl group, a hydroxyl group, a halogen atom, or a cyano group, which is connected by X within the molecule or between molecules. And each may be the same or different, but at least one of X bonded to the β-position carbon atom of the —OSO 2 R group is a hydrogen atom.
Ｘがアルキル基である場合のＸとしては、具体的には炭素数１〜２０の直鎖状、分岐状または環状のアルキル基などが挙げられる。さらに具体的には、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−エイコシル基、ベンジル基などの直鎖状アルキル基；ｉ−プロピル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基などの分岐状アルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、３−メチルシクロペンチル基、３−メトキシシクロペンチル基、３−カルボキシシクロペンチル基、３−メチルカルボニルシクロペンチル基、３−メトキシカルボニルシクロペンチル基、３−ジメチルアミノシクロペンチル基、シクロヘキシル基、４−メチルシクロヘキシル基、４−メトキシシクロヘキシル基、４−カルボキシシクロヘキシル基、４−ジメチルアミノシクロヘキシル基、シクロヘプチル基、シクロオクチル基などの環状アルキル基などが挙げられる。 Specific examples of X when X is an alkyl group include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. More specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl Linear alkyl group such as benzyl group; branched alkyl group such as i-propyl group, i-butyl group, s-butyl group, t-butyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, 3- Methylcyclopentyl group, 3-methoxycyclopentyl group, 3-carboxycyclopentyl group, 3-methylcarbonylcyclopentyl group, 3-methoxycarbonyl group Cyclic alkyl groups such as lopentyl, 3-dimethylaminocyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-methoxycyclohexyl, 4-carboxycyclohexyl, 4-dimethylaminocyclohexyl, cycloheptyl and cyclooctyl Etc.
Ｘがアルコキシ基である場合のＸとしては、具体的には炭素数１〜２０のアルコキシ基などが挙げられる。さらに具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｎ−ブチロキシ基、ｎ−ペンチロキシ基、ｎ−ヘキシロキシ基、ｎ−へプチロキシ基、ｎ−オクチロキシ基、ｉ−プロポキシ基、ｉ−ブチロキシ基、ｓ−ブチロキシ基、ｔ−ブチロキシ基などが挙げられる。 Specific examples of X in the case where X is an alkoxy group include an alkoxy group having 1 to 20 carbon atoms. More specifically, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, i-propoxy group, i- A butyroxy group, an s-butyroxy group, a t-butyroxy group and the like can be mentioned.
Ｘがアルコキシカルボニル基である場合のＸとしては、具体的には炭素数２〜１３のアルコキシカルボニル基などが挙げられる。さらに具体的には、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｎ−ブトキシカルボニル基、イソブトキシカルボニル基、ｓ−ブトキシカルボニル基、ｔ−ブトキシカルボニル基、ペントキシカルボニル基、ネオペントキシカルボニル基、アミロキシカルボニル基、ヘキトキシカルボ
ニル基、ヘプトキシカルボニル基、オクトキシカルボニル基、２−エチルヘキトキシカルボニル基、ヘプトキシカルボニル基、オクトキシカルボニル基などが挙げられる。
Specific examples of X when X is an alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 13 carbon atoms. More specifically, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentoxycarbonyl group, neopentoxycarbonyl Group, amyloxycarbonyl group, hexoxycarbonyl group, heptoxycarbonyl group, octoxycarbonyl group, 2-ethylhexoxycarbonyl group, heptoxycarbonyl group, octoxycarbonyl group and the like.
Ｘがアシル基である場合のＸとしては、具体的には炭素数２〜１０のアシル基などが挙げられる。さらに具体的には、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、ピバロイル基、ベンゾイル基などが挙げられる。 Specific examples of X when X is an acyl group include acyl groups having 2 to 10 carbon atoms. More specifically, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, and the like can be given.
Ｘがアルキルチオ基である場合のＸとしては、具体的には炭素数１〜２０のアルキルチオ基などが挙げられる。さらに具体的には、メチルチオ基、エチルチオ基、ｎ−プロピルチオ基、ｎ−ブチルチオ基、ｎ−ペンチルチオ基、ｎ−ヘキシルチオ基、ｎ−ヘプチルチオ基、ｎ−オクチルチオ基、ｎ−ノニルチオ基、ｎ−デシルチオ基、ｎ−ウンデシルチオ基、ｎ−ドデシルチオ基、ｎ−トリデシルチオ基、ｎ−テトラデシルチオ基、ｎ−ペンタデシルチオ基、ｎ−ヘキサデシルチオ基、ｎ−ヘプタデシルチオ基、ｎ−オクタデシルチオ基、ｎ−ノナデシルチオ基、ｎ−エイコシルチオ基、ベンジルチオ基などの直鎖状アルキルチオ基；ｉ−プロピルチオ基、ｉ−ブチルチオ基、ｓ−ブチルチオ基、ｔ−ブチルチオ基などの分岐状アルキルチオ基；シクロプロピルチオ基、シクロブチルチオ基、シクロペンチルチオ基、３−メチルシクロペンチルチオ基、３−メトキシシクロペンチルチオ基、３−カルボキシシクロペンチルチオ基、３−メチルカルボニルシクロペンチルチオ基、３−メトキシカルボニルシクロペンチルチオ基、３−ジメチルアミノシクロペンチルチオ基、シクロヘキシルチオ基、４−メチルシクロヘキシルチオ基、４−メトキシシクロヘキシルチオ基、４−カルボキシシクロヘキシルチオ基、４−ジメチルアミノシクロヘキシルチオ基、シクロヘプチルチオ基、シクロオクチルチオ基などの環状アルキルチオ基などが挙げられる。 Specific examples of X in the case where X is an alkylthio group include an alkylthio group having 1 to 20 carbon atoms. More specifically, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group. Group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group, n-nonadecylthio group Group, linear alkylthio group such as n-eicosylthio group, benzylthio group; branched alkylthio group such as i-propylthio group, i-butylthio group, s-butylthio group, t-butylthio group; cyclopropylthio group, cyclobutyl A thio group, a cyclopentylthio group, a 3-methylcyclopentylthio group, -Methoxycyclopentylthio group, 3-carboxycyclopentylthio group, 3-methylcarbonylcyclopentylthio group, 3-methoxycarbonylcyclopentylthio group, 3-dimethylaminocyclopentylthio group, cyclohexylthio group, 4-methylcyclohexylthio group, 4- Examples thereof include cyclic alkylthio groups such as methoxycyclohexylthio group, 4-carboxycyclohexylthio group, 4-dimethylaminocyclohexylthio group, cycloheptylthio group, and cyclooctylthio group.
Ｘがアリールチオ基である場合のＸとしては、具体的には炭素数６〜１４のアリールチオ基などが挙げられる。さらに具体的には、フェニルチオ基、２，４−キシリルチオ基、２，５−キシリルチオ基、３，４−キシリルチオ基、３，５−キシリルチオ基、ｏ−トリルチオ基、ｍ−トリルチオ基、ｐ−トリルチオ基、２−メトキシフェニルチオ基、３−メトキシフェニルチオ基、４−メトキシフェニルチオ基、４−カルボキシフェニルチオ基、４−メチルカルボニルフェニルチオ基、４−メトキシカルボニルフェニルチオ基、ジメチルアミノカルボニルフェニルチオ基、１−ナフチルチオ基、４−メチル−１−ナフチルチオ基、４−メトキシ−１−ナフチルチオ基、４−カルボキシル−１−ナフチルチオ基、２−ナフチルチオ基、１−アントラセニルチオ基、９−アントラセニルチオ基などが挙げられる。 Specific examples of X in the case where X is an arylthio group include an arylthio group having 6 to 14 carbon atoms. More specifically, phenylthio group, 2,4-xylylthio group, 2,5-xylylthio group, 3,4-xylylthio group, 3,5-xylylthio group, o-tolylthio group, m-tolylthio group, p-tolylthio group. Group, 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 4-carboxyphenylthio group, 4-methylcarbonylphenylthio group, 4-methoxycarbonylphenylthio group, dimethylaminocarbonylphenyl Thio group, 1-naphthylthio group, 4-methyl-1-naphthylthio group, 4-methoxy-1-naphthylthio group, 4-carboxyl-1-naphthylthio group, 2-naphthylthio group, 1-anthracenylthio group, 9-anthra Examples include a senylthio group.
Ｘが、分子内もしくは分子間のＸ同士で連結したポリメチレン基である場合のＸとしては、具体的には炭素数１〜３のポリメチレン基などが挙げられる。
Ｘがハロゲン原子である場合のＸとしては、具体的には、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
Specific examples of X in the case where X is a polymethylene group linked in the molecule or between the molecules include a polymethylene group having 1 to 3 carbon atoms.
Specific examples of X when X is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
上記した中でもＸとしては、水素原子またはアルキル基が好ましく、特に水素原子またはメチル基が好ましい。
式（Ｉ）〜（ＩＩＩ）において、ｐ、ｑ、ｒは２つの橋頭位炭素間を結ぶ炭素鎖の長さをそれぞれ独立に示し、ｐは１〜３、ｑは０〜３、ｒは１〜２の整数である。ｐ、ｑ、ｒの組み合わせは、それぞれが上記範囲内であれば特に限定されないが、式（Ｉ）（ＩＩ）においては、好ましくは（ｐ、ｑ、ｒ）＝（２、１、１）または（２、０、１）、特に好ましくは（ｐ、ｑ、ｒ）＝（２、１、１）であり、式（ＩＩＩ）においては、好ましくは（ｐ、ｑ）＝（２、１）または（２、０）であり、特に好ましくは（ｐ、ｑ）＝（２、１）である。
Among the above, X is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group.
In the formulas (I) to (III), p, q and r each independently represent the length of the carbon chain connecting the two bridgehead carbons, p is 1 to 3, q is 0 to 3, and r is 1 It is an integer of ~ 2. The combination of p, q and r is not particularly limited as long as each is within the above range. In the formulas (I) and (II), preferably (p, q, r) = (2, 1, 1) or (2, 0, 1), particularly preferably (p, q, r) = (2, 1, 1), and in formula (III), preferably (p, q) = (2, 1) or (2, 0), particularly preferably (p, q) = (2, 1).
本発明の光酸発生剤は、下記式ＸもしくはＹで示される方法で製造することができる。式Ｘ、Ｙにおいては、構造式（Ｉ）〜（ＩＩＩ）のスルホン酸エステルのアルコール残基部分をＡｌｃで示している。 The photoacid generator of the present invention can be produced by a method represented by the following formula X or Y. In the formulas X and Y, the alcohol residue part of the sulfonate esters of the structural formulas (I) to (III) is indicated by Alc.
式Ｘで示される方法は、目的とするスルホン酸エステルのアルコール残基部分に対応するアルコール（Ａｌｃ−ＯＨ）と１当量のスルホン酸無水物とを、塩基（ｂａｓｅ）の存在下で反応させる製造方法である。式Ｙで示される方法は、目的とするスルホン酸エステルのアルコール残基部分に対応するアルコール（Ａｌｃ−ＯＨ）と１当量のスルホン酸塩化物とを反応させる製造方法である。 In the method represented by the formula X, the alcohol (Alc-OH) corresponding to the alcohol residue part of the target sulfonic acid ester and 1 equivalent of sulfonic anhydride are reacted in the presence of a base. Is the method. The method represented by Formula Y is a production method in which an alcohol (Alc-OH) corresponding to an alcohol residue portion of a target sulfonic acid ester is reacted with 1 equivalent of a sulfonic acid chloride.
上記した本発明の光酸発生剤には、次に示す（ｉ）〜（ｉｖ）の特徴がある。
（ｉ）本発明の光酸発生剤は、イオン性ではなく中性の有機分子から構成されているので、有機媒体との相溶性が高い。したがって、たとえば感光性樹脂組成物の成分として用いる場合、樹脂などの有機媒体に対して任意の割合で、極めて均一に分散させることができる。そのような感光性樹脂組成物をフォトリソグラフィーに用いれば、形成パターンのエッジが粗くなることもなく、極めて高精度の微細加工が可能である。
The above-mentioned photoacid generator of the present invention has the following features (i) to (iv).
(I) Since the photoacid generator of the present invention is composed of neutral organic molecules rather than ionic, it is highly compatible with organic media. Therefore, for example, when used as a component of the photosensitive resin composition, it can be dispersed extremely uniformly in an arbitrary ratio with respect to an organic medium such as a resin. If such a photosensitive resin composition is used for photolithography, the edge of the formation pattern does not become rough, and extremely fine processing with high accuracy is possible.
（ｉｉ）式（Ｉ）および式（ＩＩ）の構造においては、−ＯＳＯ2Ｒのα位の炭素は、
カゴ型化合物の橋頭位であるため、２分子的求核置換反応（ＳN２）は全く起こらない。
また、カゴ型化合物の橋頭位では、分子歪みのため、カルボカチオンが不安定であり、１分子的求核置換反応（ＳN１）は全く起こらないか、もしくは、極めて起こりにくい。式
（ＩＩＩ）の構造では、−ＯＳＯ2Ｒのα位の炭素は、カルボニル基の隣接位であり、カ
ルボカチオンが不安定であり、また、当該ビシクロ骨格においては、−ＯＳＯ2Ｒのα位
の炭素への求核剤の接近はメチレン鎖との立体反発により困難である。したがって、２分子的求核置換反応（ＳN２）および１分子的求核置換反応（ＳN１）は、全く起こらないか、もしくは極めて起こりにくい。上記のような理由から、本発明の光酸発生剤をたとえば感光性樹脂組成物の成分として用いる場合、非共有電子対を持つ官能基を有する樹脂などの有機成分および水などの求核性物質と共存しても、保存時または使用時に求核置換反応が起きて分解してしまうことがない。
(Ii) In the structures of formula (I) and formula (II), the carbon at the α-position of —OSO 2 R is
Due to the bridgehead position of the cage compound, the bimolecular nucleophilic substitution reaction (S N 2) does not occur at all.
Further, at the bridgehead position of the cage-type compound, the carbocation is unstable due to molecular distortion, and the one-molecule nucleophilic substitution reaction (S N 1) does not occur at all or is extremely difficult to occur. In the structure of formula (III), the carbon at the α-position of —OSO 2 R is adjacent to the carbonyl group, the carbocation is unstable, and in the bicyclo skeleton, the α-position of —OSO 2 R The access of nucleophiles to the carbon is difficult due to steric repulsion with the methylene chain. Therefore, the bimolecular nucleophilic substitution reaction (S N 2) and the monomolecular nucleophilic substitution reaction (S N 1) do not occur at all or are extremely difficult to occur. For the above reasons, when the photoacid generator of the present invention is used as a component of a photosensitive resin composition, for example, an organic component such as a resin having a functional group having an unshared electron pair and a nucleophilic substance such as water. Even if it coexists with the nucleophilic substitution reaction, it does not decompose during storage or use.
（ｉｉｉ）下記式（ＩＶ）で一般的なスルホン酸エステルの脱離反応を示すが、スルホン酸が脱離した後の化合物は、ＣおよびＹが全て同一平面上に存在する平面構造となる。一方、本発明の光酸発生剤は、特定のビシクロ骨格を有しており、ブレッド則が成立するため、このような反応によって形成される平面構造をとることができない。したがって、このような脱離反応は抑制されているため、本発明の光酸発生剤は熱に対して安定である。 (Iii) A general elimination reaction of a sulfonic acid ester is shown by the following formula (IV). The compound after elimination of the sulfonic acid has a planar structure in which C and Y are all present on the same plane. On the other hand, since the photoacid generator of the present invention has a specific bicyclo skeleton and the Bread rule is established, it cannot take a planar structure formed by such a reaction. Therefore, since such elimination reaction is suppressed, the photoacid generator of the present invention is stable against heat.
（ｉｖ）上述したように、本発明の光酸発生剤は、非光照射時においては、熱および求核剤に対して安定であるが、光を照射することによってスルホン酸（ＨＯＳＯ2Ｒ）を発
生させることができる。その反応機構としては下記式（Ｖ）が推定される。なお、下記式（Ｖ）の光酸発生剤Ａは上記式（ＩＩ）において、Ｘが全て水素原子で（ｐ、ｑ、ｒ）＝（２、１、１）のものである。光酸発生剤Ａに対して光を照射すると、まずビラジカルＢが生成する。この光開裂反応はノリッシュＩ（Norrish I）タイプと呼ばれているもので
あり、カルボニル基と隣接炭素がラジカル的に開裂する光反応である。ビラジカルＢは分子内的に不均化して化合物Ｃを与えるが、Ｃにおいては上述したブレット則はもはや成立していないため−ＯＳＯ2Ｒ基とプロトンが脱離し、スルホン酸（ＨＯＳＯ2Ｒ）が生成する。
(Iv) As described above, the photoacid generator of the present invention is stable against heat and a nucleophile at the time of non-light irradiation, but by irradiation with light, sulfonic acid (HOSO 2 R) Can be generated. The following formula (V) is estimated as the reaction mechanism. In addition, the photoacid generator A of the following formula (V) is a compound in which X is a hydrogen atom and (p, q, r) = (2, 1, 1) in the above formula (II). When the photoacid generator A is irradiated with light, biradical B is first generated. This photocleavage reaction is called the Norrish I type, and is a photoreaction in which a carbonyl group and adjacent carbon are cleaved radically. Biradical B disproportionates intramolecularly to give compound C. However, in C, the above-mentioned Brett's rule is no longer established, so -OSO 2 R group and proton are eliminated, and sulfonic acid (HOSO 2 R) is Generate.
本発明の光酸発生剤にスルホン酸を発生させるために照射する光としては、３２０ｎｍより短波長の光であれば特に限定されないが、たとえば等圧水銀灯の３１３ｎｍ、２５４ｎｍの共鳴線、ＫｒＦエキシマレーザー光（２４８ｎｍ）およびＡｒＦエキシマレーザー光（１９３ｎｍ）を用いることができる。中でもＡｒＦエキシマレーザー光を好適に用いることができる。 The light irradiated to generate sulfonic acid in the photoacid generator of the present invention is not particularly limited as long as it is light having a wavelength shorter than 320 nm. For example, 313 nm, 254 nm resonance line of an isobaric mercury lamp, KrF excimer laser Light (248 nm) and ArF excimer laser light (193 nm) can be used. Among them, ArF excimer laser light can be preferably used.
本発明の感光性樹脂組成物は、本発明の光酸発生剤を含むことを特徴としている。光酸発生剤は単独でも用いられるが、２種以上を混合して用いても良い。本発明の感光性樹脂組成物における本発明の光酸発生剤の含有率は、感光性樹脂組成物の全固形分１００重量部に対して通常０．１〜４０重量部、好ましくは１〜２５重量部である。この含有率が０．１重量部未満では感度が著しく低下し、パターンの形成が困難である。また４０重量部を越えると、均一な塗布膜の形成が困難になり、さらに現像後には残さ（スカム）が発生
し易くなるなどの問題が生ずる。
The photosensitive resin composition of the present invention includes the photoacid generator of the present invention. Although a photo-acid generator is used individually, you may mix and use 2 or more types. The content of the photoacid generator of the present invention in the photosensitive resin composition of the present invention is usually 0.1 to 40 parts by weight, preferably 1 to 25 parts per 100 parts by weight of the total solid content of the photosensitive resin composition. Parts by weight. If the content is less than 0.1 parts by weight, the sensitivity is remarkably lowered and it is difficult to form a pattern. On the other hand, when the amount exceeds 40 parts by weight, it becomes difficult to form a uniform coating film, and a problem such that a residue (scum) easily occurs after development.
本発明の感光性樹脂組成物を構成する樹脂としては、使用する光に対して高透明性であり、かつ酸に対して不安定な基を有する樹脂を適宜選択して使用することができる。たとえば下記式（ＶＩ）により表される樹脂を用いることが出来る。 As the resin constituting the photosensitive resin composition of the present invention, a resin having high transparency to the light used and having a group unstable to an acid can be appropriately selected and used. For example, a resin represented by the following formula (VI) can be used.
［上式において、ｎは５〜１０００（より好ましくは１０〜２００）の正の整数、Ｒ4は
表１に示したような、トリシクロデカニル基、ジシクロペンテニル基、ジシクロペンテニルオキシエチル基、シクロヘキシル基、ノルボニル基あるいはアダマンチル基、Ｒ5はｔ
ｅｒｔ−ブチル基、メチル基、エチル基、プロピル基、テトラヒドロピラニル基あるいは３−オキソシクロヘキシル基、ｘは０．１〜１（より好ましくは０．２〜０．７）を表す。］
[In the above formula, n is a positive integer of 5 to 1000 (more preferably 10 to 200), R 4 is a tricyclodecanyl group, dicyclopentenyl group, dicyclopentenyloxyethyl as shown in Table 1. Group, cyclohexyl group, norbornyl group or adamantyl group, R 5 is t
ert-butyl group, methyl group, ethyl group, propyl group, tetrahydropyranyl group or 3-oxocyclohexyl group, x represents 0.1 to 1 (more preferably 0.2 to 0.7). ]
また本発明の感光性樹脂組成物には、必要に応じて界面活性剤、色素、安定剤、塗布性改良剤、染料、架橋剤などの他の成分を添加しても構わない。
本発明の感光性樹脂組成物を塗布する際に用いる溶剤として好ましいものは、本発明の感光性樹脂組成物を充分に溶解し、かつその溶液がスピンコート法で均一な塗布膜が形成可能な有機溶媒である。それらは単独でも２種類以上を混合して用いても良い。具体的には、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノエチルエーテルアセテート、乳酸メチル、乳酸エチル、酢酸２−メトキシブチル、酢酸２−エトキシエチル、ピルビン酸メチル、ピルビン酸エチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、Ｎ−メチル−２−ピロリジノン、シクロヘキサノン、シクロペンタノン、シクロヘキサノール、メチルエチルケトン、１、４−ジオキサン、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテル、エチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、などが挙げられるが、もちろんこれらだけに限定されるものではない。
Moreover, you may add other components, such as surfactant, a pigment | dye, a stabilizer, a coating property improving agent, dye, and a crosslinking agent, to the photosensitive resin composition of this invention as needed.
A preferable solvent used when the photosensitive resin composition of the present invention is applied is that the photosensitive resin composition of the present invention is sufficiently dissolved and a uniform coating film can be formed by spin coating. It is an organic solvent. They may be used alone or in combination of two or more. Specifically, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-methoxybutyl acetate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidinone, cyclohexanone, cyclopentanone, cyclohexanol, methyl ethyl ketone, 1, 4 -Dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl Pills ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like, but the present invention is of course not limited thereto.
また、本発明を用いて微細パターンの形成をおこなう場合の現像液としては、本発明で使用する感光性樹脂組成物の溶解性に応じて適当な有機溶媒、またはその混合溶媒、あるいは適度な濃度のアルカリ溶液あるいはアルカリ水溶液を選択すれば良い。使用される有機溶媒としてはアセトン、メチルエチルケトン、メチルアルコール、エチルアルコ−ル、イソプロピルアルコール、テトラヒドロフラン、ジオキサンなどが挙げられる。また、使用されるアルカリ溶液としては、たとえば、水酸化ナトリウム、水酸化カリウム、ケイ酸ナトリウム、アンモニアなどの無機アルカリ類や、エチルアミン、プロピルアミン、ジエチルアミン、ジプロピルアミン、トリメチルアミン、トリエチルアミン、などの有機アミン類、そしてテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、トリメチルヒドロキシメチルアンモニウムヒドロキシド、トリエチルヒドロキシメチルアンモニウムヒドロキシド、トリメチルヒドロキシエチルアンモニウムヒドロキシドなどの有機アンモニウム塩などを含む溶液あるいは水溶液が挙げられるが、これらだけに限定されるものではない。 Further, as a developer for forming a fine pattern using the present invention, an appropriate organic solvent or a mixed solvent thereof, or an appropriate concentration depending on the solubility of the photosensitive resin composition used in the present invention is used. An alkaline solution or an alkaline aqueous solution may be selected. Examples of the organic solvent used include acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, tetrahydrofuran and dioxane. Examples of the alkaline solution used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia, and organic substances such as ethylamine, propylamine, diethylamine, dipropylamine, trimethylamine, and triethylamine. Examples include solutions and aqueous solutions containing amines and organic ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide. However, it is not limited to these.
本発明の感光性樹脂組成物を用いたフォトリソグラフィーについて説明する。まず本発明の感光性樹脂組成物を塗布してレジスト膜を形成し、ＡｒＦエキシマレーザー等の照射光によって露光すると、レジスト膜の露光部に含まれる光酸発生剤がスルホン酸を発生する。 Photolithography using the photosensitive resin composition of the present invention will be described. First, the photosensitive resin composition of the present invention is applied to form a resist film, and when exposed to irradiation light such as an ArF excimer laser, the photoacid generator contained in the exposed portion of the resist film generates sulfonic acid.
たとえば式（ＶＩ）（Ｒ5はｔｅｒｔ−ブチル基）で示した樹脂を用いたとき、光照射
により発生したスルホン酸は下記式（ＶＩＩ）の反応式に従って樹脂のｔｅｒｔ−ブトキシ基に作用し、カルボキシル基および２−ブテンを生成し、その結果レジスト膜の溶解性の変化を誘起する。
For example, when a resin represented by the formula (VI) (R 5 is a tert-butyl group) is used, sulfonic acid generated by light irradiation acts on the tert-butoxy group of the resin according to the reaction formula of the following formula (VII): A carboxyl group and 2-butene are generated, and as a result, a change in the solubility of the resist film is induced.
露光に引き続く加熱処理（ポストエクスポージャベイク）を所定温度でおこなうと、この脱保護反応が触媒反応的に進行し、感度の増幅が起こる。この反応により官能基が水酸基に変化した樹脂はアルカリ可溶性となるため、アルカリ性の現像液を使用することにより樹脂が溶け出し、結果として露光部が溶けてポジ型のパターンを形成する。 When the heat treatment (post-exposure bake) subsequent to exposure is performed at a predetermined temperature, this deprotection reaction proceeds catalytically, and sensitivity is amplified. Since the resin in which the functional group is changed to a hydroxyl group by this reaction becomes alkali-soluble, the resin is dissolved by using an alkaline developer, and as a result, the exposed portion is melted to form a positive pattern.
＜実施例＞
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
<Example>
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
＜3,3-ジメチルビシクロ[2.2.1]ヘプタ-2-オン-1-トリフラート(２)の合成＞
文献（J. Org. Chem., 36, 1075-1079 (1971)）の方法に従って合成した。3,3-ジメチ
ルビシクロ[2.2.1]ヘプタ-2-オン-1-オール(１)の1g(6.48 mmol)をセプタムゴム栓、三方バルブ、磁気撹拌子を備えた二口フラスコに入れ、三方バルブのひとつの口に窒素風船を装着し、真空ポンプで内部を窒素置換した。ここへ、乾燥ピリジン20mLを注射器を用いて導入して溶解した。氷冷下、この溶液にトリフルオロメタンスルホン酸無水物3.7g(13 mmol)を注射器で加え、0℃で12時間放置した。反応混合物を50mLの氷水に注ぎ、100mLのジ
エチルエーテルで抽出し、有機層を希塩酸、炭酸ナトリウム水溶液、飽和食塩水の順で洗浄した後、硫酸ナトリウムで乾燥した。溶媒を留去すると、ほぼ純粋な3,3-ジメチルビシクロ[2.2.1]ヘプタ-2-オン-1-トリフラート(２)が1.5g(5.24 mmol)得られた（収率80.9％）。ジイソプロピルエーテルから再結晶した。mp.33℃: IR(KBr, cm-1); 2976, 2931, 1773, 1418, 1212, 1145: NMR(CDCl3, ppm); 1.13(s, 3H, CH3), 1.19(s, 3H, CH3), 1.92-1.99(m, 3H), 2.09-2.18(m, 2H), 2.26(br, 1H, bridge head), 2.61(d, 1H, endo-H at β-C)
<Synthesis of 3,3-dimethylbicyclo [2.2.1] hept-2-one-1-triflate (2)>
It was synthesized according to the method of literature (J. Org. Chem., 36, 1075-1079 (1971)). Place 1 g (6.48 mmol) of 3,3-dimethylbicyclo [2.2.1] hept-2-one-1-ol (1) into a two-necked flask equipped with a septum rubber stopper, a three-way valve, and a magnetic stirrer. A nitrogen balloon was attached to one of the mouths, and the inside was replaced with nitrogen by a vacuum pump. Here, 20 mL of dry pyridine was introduced and dissolved using a syringe. Under ice cooling, 3.7 g (13 mmol) of trifluoromethanesulfonic anhydride was added to the solution with a syringe and left at 0 ° C. for 12 hours. The reaction mixture was poured into 50 mL of ice water and extracted with 100 mL of diethyl ether. The organic layer was washed with diluted hydrochloric acid, aqueous sodium carbonate solution and saturated brine in that order, and then dried over sodium sulfate. When the solvent was distilled off, 1.5 g (5.24 mmol) of almost pure 3,3-dimethylbicyclo [2.2.1] hept-2-one-1-triflate (2) was obtained (yield 80.9%). Recrystallized from diisopropyl ether. mp.33 ° C: IR (KBr, cm -1 ); 2976, 2931, 1773, 1418, 1212, 1145: NMR (CDCl 3 , ppm); 1.13 (s, 3H, CH 3 ), 1.19 (s, 3H, CH 3 ), 1.92-1.99 (m, 3H), 2.09-2.18 (m, 2H), 2.26 (br, 1H, bridge head), 2.61 (d, 1H, endo-H at β-C)
＜3,3-ジメチルビシクロ[2.2.1]ヘプタ-2-オン-1-トリフラート(２)の熱安定性＞
3,3-ジメチルビシクロ[2.2.1]ヘプタ-2-オン-1-トリフラート(２)をガラス封管に封入
して、８０℃で５時間加熱し、変化をＮＭＲで観測したが、変化は認められなかった。
<Thermal stability of 3,3-dimethylbicyclo [2.2.1] hept-2-one-1-triflate (2)>
3,3-dimethylbicyclo [2.2.1] hept-2-one-1-triflate (2) was sealed in a glass sealed tube and heated at 80 ° C. for 5 hours, and the change was observed by NMR. I was not able to admit.
＜3,3-ジメチルビシクロ[2.2.1]ヘプタ-2-オン-1-トリフラート(２)の光酸発生機能＞
3,3-ジメチルビシクロ[2.2.1]ヘプタ-2-オン-1-トリフラート(２)のアセトニトリル溶
液を濃度０．０５mol/Lに調製し、光路長１ｃｍの石英光学セルに入れ、キセノンランプ
から分光した光（２９０nm）を照射し、酸発生のアクチノメトリーを行った。酸発生量は、テトラブロモフェノールブルーの６１０ｎｍにおける吸収で観察した。トリオキサラト鉄酸カリウムで光量を測定して、量子収率を求めたところ、０．２であり、高い酸発生機能を示した。
<Photoacid generation function of 3,3-dimethylbicyclo [2.2.1] hept-2-one-1-triflate (2)>
An acetonitrile solution of 3,3-dimethylbicyclo [2.2.1] hept-2-one-1-triflate (2) was prepared to a concentration of 0.05 mol / L and placed in a quartz optical cell with an optical path length of 1 cm. The actinometry of the acid generation was performed by irradiating with the separated light (290 nm). The amount of acid generated was observed by the absorption of tetrabromophenol blue at 610 nm. When the amount of light was measured with potassium trioxalate ferrate and the quantum yield was determined, it was 0.2, indicating a high acid generation function.
Claims (2)
式中、Ｒは、アルキル基、フッ素置換アルキル基、アリール基、フッ素置換アリール基、フルオロアルキル基で置換されたアリール基、フッ素原子、ニトロ基またはシアノ基である；
Ｘは、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、分子内もしくは分子間のＸ同士で連結したポリメチレン基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基であり、それぞれ同一または異なっていてもよいが、−ＯＳＯ2Ｒ基のβ位の炭素原子に結合しているＸのうち
少なくとも１つは水素原子である；
ｐ、ｑ、ｒは２つの橋頭位炭素間を結ぶ炭素鎖の長さをそれぞれ独立に示し、ｐは１〜３、ｑは０〜３、ｒは１〜２の整数である。
In the formula, R is an alkyl group, a fluorine-substituted alkyl group, an aryl group, a fluorine-substituted aryl group, an aryl group substituted with a fluoroalkyl group, a fluorine atom, a nitro group, or a cyano group;
X is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a polymethylene group, a carboxyl group, a hydroxyl group, a halogen atom, or a cyano group, which is connected by X within the molecule or between molecules. Each may be the same or different, but at least one of X bonded to the carbon atom at the β-position of the —OSO 2 R group is a hydrogen atom;
p, q, and r each independently represent the length of a carbon chain connecting two bridgehead carbons, p is 1 to 3, q is 0 to 3, and r is an integer of 1 to 2.
A photosensitive resin composition comprising the photoacid generator according to claim 1.
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|---|---|---|---|---|
| JPH09301948A (en) * | 1996-05-08 | 1997-11-25 | Sumitomo Chem Co Ltd | Glyoxime-based ester, production method and use thereof |
| JP2000035665A (en) * | 1998-05-11 | 2000-02-02 | Kunihiro Ichimura | Acid multiplication agent and photosensitive composition |
| JP2000034272A (en) * | 1998-05-11 | 2000-02-02 | Kunihiro Ichimura | Cross-linked cyclic carbon compound having hydroxyl group and sulfonate group |
| JP2000511932A (en) * | 1996-12-23 | 2000-09-12 | エラン ファーマシューティカルズ，インコーポレイテッド | Cycloalkyls, lactams, lactones and related compounds and pharmaceutical compositions thereof, and methods for inhibiting β-amyloid peptide release and / or synthesis using the compounds |
| JP2004002411A (en) * | 2002-05-02 | 2004-01-08 | Kumho Petrochemical Co Ltd | New acid-generating agent and thin film composition containing the same |
| JP2004026804A (en) * | 2002-03-29 | 2004-01-29 | Jsr Corp | Compound having sulfonyl structure, radiation-sensitive acid-generating agent using the same, positive radiation-sensitive resin composition, and negative radiation-sensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09301948A (en) * | 1996-05-08 | 1997-11-25 | Sumitomo Chem Co Ltd | Glyoxime-based ester, production method and use thereof |
| JP2000511932A (en) * | 1996-12-23 | 2000-09-12 | エラン ファーマシューティカルズ，インコーポレイテッド | Cycloalkyls, lactams, lactones and related compounds and pharmaceutical compositions thereof, and methods for inhibiting β-amyloid peptide release and / or synthesis using the compounds |
| JP2000035665A (en) * | 1998-05-11 | 2000-02-02 | Kunihiro Ichimura | Acid multiplication agent and photosensitive composition |
| JP2000034272A (en) * | 1998-05-11 | 2000-02-02 | Kunihiro Ichimura | Cross-linked cyclic carbon compound having hydroxyl group and sulfonate group |
| JP2004026804A (en) * | 2002-03-29 | 2004-01-29 | Jsr Corp | Compound having sulfonyl structure, radiation-sensitive acid-generating agent using the same, positive radiation-sensitive resin composition, and negative radiation-sensitive resin composition |
| JP2004002411A (en) * | 2002-05-02 | 2004-01-08 | Kumho Petrochemical Co Ltd | New acid-generating agent and thin film composition containing the same |
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