JP2004151605A - Positive photosensitive resin composition and semiconductor device - Google Patents
Positive photosensitive resin composition and semiconductor device Download PDFInfo
- Publication number
- JP2004151605A JP2004151605A JP2002319226A JP2002319226A JP2004151605A JP 2004151605 A JP2004151605 A JP 2004151605A JP 2002319226 A JP2002319226 A JP 2002319226A JP 2002319226 A JP2002319226 A JP 2002319226A JP 2004151605 A JP2004151605 A JP 2004151605A
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- Prior art keywords
- resin composition
- photosensitive resin
- group
- positive photosensitive
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims description 20
- 239000002253 acid Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 238000011161 development Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- -1 phenol compound Chemical class 0.000 claims description 30
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 5
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 5
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 4
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000003997 cyclic ketones Chemical class 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 0 CCCCc1c(*)c(*)c(C)cc1N Chemical compound CCCCc1c(*)c(*)c(C)cc1N 0.000 description 24
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000006239 protecting group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LWHOMMCIJIJIGV-UHFFFAOYSA-N (1,3-dioxobenzo[de]isoquinolin-2-yl) trifluoromethanesulfonate Chemical compound C1=CC(C(N(OS(=O)(=O)C(F)(F)F)C2=O)=O)=C3C2=CC=CC3=C1 LWHOMMCIJIJIGV-UHFFFAOYSA-N 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 150000001923 cyclic compounds Chemical group 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- PCXUSBICWPJFTN-UHFFFAOYSA-N [[cyano-(4-methoxyphenyl)methylidene]amino] 4-methylbenzenesulfonate Chemical compound C1=CC(OC)=CC=C1C(C#N)=NOS(=O)(=O)C1=CC=C(C)C=C1 PCXUSBICWPJFTN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005079 alkoxycarbonylmethyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 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
- 239000002966 varnish Substances 0.000 description 1
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
- Polyamides (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、高感度かつ高解像度の特性を有するポジ型感光性樹脂組成物及びそれを用いた半導体装置に関するものである。
【０００２】
【従来の技術】
従来、半導体素子の表面保護膜、層間絶縁膜には、耐熱性に優れ又卓越した電気特性、機械特性等を有するポリイミド樹脂が用いられているが、近年半導体素子の高集積化、大型化、半導体装置の薄型化、小型化、半田リフローによる表面実装への移行等により耐熱サイクル性、耐熱ショック性等の著しい向上の要求があり、更に高性能の樹脂が必要とされるようになってきた。
【０００３】
一方、ポリイミド樹脂自身に感光性を付与する技術が注目を集めてきており、例えば下記式（１０）に示されるネガ型感光性ポリイミド樹脂が挙げられる。
【化８】
これを用いるとパターン作成工程の一部が簡略化でき、工程短縮及び歩留まり向上の効果はあるが、現像の際にＮ−メチル−２−ピロリドン等の溶剤が必要となるため、安全性、取扱い性に問題がある。そこで、アルカリ水溶液で現像ができるポジ型感光性樹脂組成物が開発されている（例えば、特許文献１、特許文献２、特許文献３、特許文献４、特許文献５参照。）。これらには、ポリイミド樹脂の前駆体であるポリアミド酸と感光材であるジアゾキノン化合物より構成されるポジ型感光性樹脂組成物が開示されている。これらの感光材として用いられているジアゾキノン化合物は露光することにより化学変化を起こし、アルカリ水溶液に可溶となる。しかしその変化率は４０％程度であるだけでなく、それ自身の光に対する吸収が大きいために、厚膜に塗布した場合、膜の底面にまで十分な光が届かない。そのため露光部を開口させるために多くの露光量を必要とし、感度が低くなるという問題があった。
【０００５】
更に、ｇ線、ｉ線等の紫外線を光源として用いる半導体用レジストに代表されるポジ型感光性樹脂組成物は、ベース樹脂としてフェノールノボラック樹脂が用いられているが、これらに比べ、上述のポリアミド樹脂は単位分子量当たりの水酸基濃度が小さいために、ジアゾキノン化合物と相互作用することで発揮されるアルカリ水溶液に対する溶解阻止能が弱く、現像後における未露光部の膜減り量が大きい。従って露光部が現像液で十分に溶解除去される前に、未露光部が目的とする膜厚以下になるために、結果として感度が低下するだけでなく、パターンの壁面が削られることにより、開口部の寸法安定性が低下する。又カルボキシル基の場合には、ジアゾキノン化合物と相互作用することがなく、更にフェノール性水酸基よりもアルカリ水溶液に対する溶解性が非常に高いという理由により、未露光部の溶解阻止能が発揮されず、目的とする膜厚が得られないばかりかパターンの形成自体が困難になる問題がある。又適当な保護基でブロックされたカルボキシル基の場合、未露光部のアルカリ水溶液に対する耐性は十分あるが、露光部の溶解性が劣るために感度の低下、現像後に樹脂の残り（スカム）が見られるという問題がある。
【０００６】
そこで、光化学反応による触媒作用を取り入れた化学増幅型のポジ型感光性樹脂組成物が開発されている。この化学増幅型のポジ型感光性樹脂組成物は、一般的に水酸基又はカルボキシル基を適当な酸不安定基で保護されたベース樹脂と光の照射により酸を発生する光酸発生材から構成されている。この化学増幅型のポジ型感光性樹脂組成物の現像メカニズムは、以下のようになっている。未露光部において酸不安定基で保護されたベース樹脂は現像液であるアルカリ水溶液に耐性がある。一方露光部は、光酸発生材から発生した酸が露光後の熱処理により拡散して触媒として働き、ベース樹脂中の保護基を脱離し、水酸基又はカルボキシル基を再生させてアルカリ水溶液に可溶となる。この露光部と未露光部との溶解性の差を利用し、露光部を溶解除去することにより未露光部のみの塗膜パターンの形成が可能となるものである。更に、この触媒酸は脱離反応後も存在し、多くの反応を引き起こすため見かけの量子収率が高く、高感度化が容易となるだけでなく高い溶解コントラストが得られるために高解像度化も期待できる。半導体用レジストとしては、例えば第２８４７４１４号公報、第２８４８６１１号公報、特開平３−２４９６５４号公報、特開平９−２３０５８８号公報等が挙げられるが、これらに使用されているベース樹脂は主にポリヒドロキシスチレンであり、高い解像度は得られるが耐熱性に乏しく、半導体素子の表面保護膜、層間絶縁膜用途には適さない。
【０００７】
半導体素子の表面保護膜、層間絶縁膜用途として、ベース樹脂にポリイミド樹脂又はポリアミド樹脂を用いた化学増幅型感光性樹脂組成物が開示されている（例えば、特許文献６、特許文献７、特許文献８、特許文献９参照。）。しかし開示されているベース樹脂は、熱で硬化させた後も水酸基が残ってしまうために耐湿信頼性が低下したり、十分な溶解コントラストが得られないために解像度の低下や、結果的に高感度でも未露光部の膜減り量の増加によって目的とする膜厚が得られなかったり、サイドエッチが大きくプロファイル性が悪い等の問題があった。
【０００８】
【特許文献１】
特開平３−２４７６５５号公報、
【特許文献２】
特開平５−２０４１５６号公報、
【特許文献３】
特開平６−２５８８３６号公報、
【特許文献４】
特開平１０−１８６６５８号公報、
【特許文献５】
特開平１０−３０７３９４号公報
【特許文献６】
特開平３−７６３号公報
【特許文献７】
特開平４−１２０１７１号公報
【特許文献８】
特開平１１−２０２４８９号公報
【特許文献９】
特開２００１−１９４７９１号公報
【０００９】
【発明が解決しようとする課題】
本発明は、高感度かつ高解像度で、現像後の未露光部の膜減り量が少ない特性を有するポジ型感光性樹脂組成物及びそれを用いた半導体装置を提供するものである。
【００１０】
【課題を解決するための手段】
本発明は、
［１］ 一般式（１）で示されるポリアミド樹脂（Ａ）、光により酸を発生する化合物（Ｂ）、一般式（２）で示されるフェノール化合物の水酸基を、酸の存在下で分解する酸不安定基で保護された化合物（Ｃ）及び溶剤（Ｄ）を含むことを特徴とするポジ型感光性樹脂組成物、
【００１１】
【化９】
【化１０】
［２］ 一般式（１）で示されるポリアミド樹脂中のＸが、式（３）の群より選ばれてなる第［１］項記載のポジ型感光性樹脂組成物、
【００１４】
【化１１】
［３］ 一般式（１）で示されるポリアミド樹脂中のＹが、式（４）の群より選ばれてなる第［１］項又は［２］項記載のポジ型感光性樹脂組成物、
【００１６】
【化１２】
［４］ 一般式（２）で示されるフェノール化合物の水酸基を、酸の存在下で分解する酸不安定基で保護された化合物（Ｃ）が、テトラヒドロピラニル基、又はテトラヒドロフラニル基から選ばれた置換基で保護された化合物である第［１］〜［３］項記載のポジ型感光性樹脂組成物、
［５］ 溶剤（Ｄ）が炭素数３〜１０の環状ケトン、炭素数３〜１０の環状ラクトン、ジメチルスルホキシド、プロピレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテルアセテート、ジプロピレングリコールモノアルキルエーテル、乳酸メチル、乳酸エチル、乳酸ブチルより選ばれてなる第［１］〜［４］項記載のポジ型感光性樹脂組成物、
［６］ 第［１］項〜［５］項のいずれかに記載のポジ型感光性樹脂組成物が、更にフェノール化合物（Ｅ）を含むポジ型感光性樹脂組成物、
［７］ フェノール化合物（Ｅ）が、一般式（５）、（６）、（７）、（８）、（９）の群より選ばれてなる第［６］項記載のポジ型感光性樹脂組成物、
【００１８】
【化１３】
【化１４】
【化１５】
［８］ 第［１］〜［７］項のいずれかに記載のポジ型感光性樹脂組成物を半導体素子上に塗布し、プリベーク、露光、露光後加熱、現像、加熱して得られることを特徴とする半導体装置、
［９］ ポジ型感光性樹脂組成物を加熱脱水閉環後の膜厚が、０．１〜３０μｍになるように半導体素子上に塗布し、プリベーク、露光、露光後加熱、現像、加熱して得られる第［８］項記載の半導体装置、
である。
【００２２】
一般式（１）のポリアミド樹脂は、Ｘの構造を有するビス（アミノフェノール）、必要により配合されるＺの構造を有するシリコーンジアミンとＹの構造を有するジカルボン酸或いはジカルボン酸ジクロリド、ジカルボン酸誘導体とを反応した後、酸不安定基となる保護基をポリアミド樹脂中のフェノール性水酸基に置換させて得られるものである。なお、ジカルボン酸の場合には反応収率等を高めるため、１−ヒドロキシ−１，２，３−ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。酸不安定基となる保護基は、炭素数２〜２０のアルコキシカルボニル基、炭素数２〜２０のアルコキシアルキル基、炭素数１〜１０のアルキル置換シリル基、テトラヒドロピラニル基、テトラヒドロフラニル基が挙げられる。又現像後の未露光部の膜減り量が少なく、露光部と未露光部の溶解コントラストが大きい樹脂を得るために、ポリアミド樹脂中の全水酸基の５〜８０％を酸不安定基となる保護基で置換されていることが必要である。５％未満のときは、未露光部が十分な溶解阻止能を発揮できないので膜減り量が大きくなり、８０％を越えると露光部の溶解性も極端に遅くなり感度が低下するだけでなく、現像後に樹脂の残り（スカム）が発生しやすくなる。現像後、このポリアミド樹脂を約３００〜４００℃で加熱すると脱水閉環し、ポリベンゾオキサゾールという形で耐熱性樹脂が得られる。
【００２３】
本発明の一般式（１）のポリアミド樹脂のＸは、例えば、
【化１６】
【００２４】
又一般式（１）のポリアミド樹脂のＹは、例えば、
【化１７】
【００２５】
又本発明のポジ型感光性樹脂組成物は、保存性という観点から、Ｘの構造を有するビス（アミノフェノール）とＹの構造を有するジカルボン酸或いはジカルボン酸ジクロリド又はジカルボン酸誘導体とを反応させてポリアミド樹脂を合成した後、アルケニル基又はアルキニル基を少なくとも１個有する脂肪族基又は環式化合物基を含む酸無水物を用いて末端のアミノ基をキャップすることが重要である。アルケニル基又はアルキニル基を少なくとも１個有する脂肪族基又は環式化合物基を含む酸無水物に起因する基として、例えば、
【００２６】
【化１８】
【００２７】
これらの中で特に好ましいものとしては、
【化１９】
【００２８】
更に、必要によって用いる一般式（１）のポリアミド樹脂のＺは、例えば
【化２０】
等であるがこれらに限定されるものではなく、又２種以上用いても良い。
一般式（１）のＺは、例えば、シリコンウェハーのような基板に対して、特に優れた密着性が必要な場合に用いるが、その使用割合ｂは最大４０モル％までである。４０モル％を越えると現像液に対する樹脂の溶解性が極めて低下し、現像残り（スカム）が発生し、パターン加工ができなくなる。なお、これらＸ、Ｙ、Ｚの使用にあたっては、それぞれ１種類であっても２種類以上の混合物であっても構わない。一般式（１）のｎは、２〜３００であるが、３００を越えると現像後にスカムが発生する恐れがあるので好ましくない。
【００３０】
本発明のポジ型感光性樹脂組成物に用いられる、光により酸を発生する化合物（Ｂ）は、
Ｐｈｏｔｏｇｒａｐｈ．Ｓｃｉ．Ｅｎｇ．，１８，ｐ３８７（１９７４）、ＣＨＥＭＴＥＣＨ，Ｏｃｔ．ｐ６２４（１９８０）、Ｐｏｌｙｍ．Ｍａｔｅｒ．Ｓｃｉ．Ｅｎｇ．，７２，ｐ４０６（１９９５）、Ｍａｃｒｏｍｏｌ．Ｃｈｅｍ．Ｒａｐｉｄ Ｃｏｍｍｕｎ．１４，ｐ２０３（１９９３）、Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，６，ｐ６７（１９９３）記載のオニウム塩類、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２１，ｐ２００１（１９８８）、Ｃｈｅｍ．Ｍａｔｅｒ．３，ｐ４６２（１９９１）、Ｐｒｏｃ．ＳＰＩＥ，１０８６，２（１９８９）記載の２−ニトロベンジルエステル類、Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，２，ｐ４２９（１９８９）、Ｐｒｏｃ．ＳＰＩＥ，１２６２，ｐ５７５（１９９０）記載のＮ−イミノスルホネート類、Ｐｏｌｙｍ．Ｍａｔ．Ｓｃｉ．Ｅｎｇ．，６１，２６９（１９８９）記載のナフトキノンジアジド−４−スルホン酸エステル類、Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，４，ｐ３８９（１９９１）、Ｐｒｏｃ．ＳＰＩＥ，２１９５，ｐ１７３（１９９４）記載のハロゲン系化合物類等が挙げられる。これらは単独でも２種以上用いても良い。
【００３１】
本発明のポジ型感光性樹脂組成物は、更に露光部と未露光部の溶解コントラストを向上させるために、一般式（２）で示されるフェノール化合物の水酸基を、酸の存在下で分解する酸不安定基で保護された化合物（Ｃ）を配合することが重要である。これにより、未露光部においてはアルカリ水溶液に対する耐性が向上し、露光部では光酸発生材から発生した触媒酸の作用により酸不安定基が脱離することによって水酸基が再生し、溶解促進作用を促す。
【００３２】
酸の存在下で分解する酸不安定基としては、炭素数２〜２０のアルコキシカルボニル基、炭素数２〜２０のアルコキシカルボニルメチル基、炭素数２〜２０のアルコキシアルキル基、炭素数１〜１０のアルキル置換シリル基、テトラヒドロピラニル基、テトラヒドロフラニル基等が挙げられるが、特に好ましいものは、テトラヒドロピラニル基、テトラヒドロフラニル基である。具体的には下記のものを挙げることができるが、これらに限定されない。又これらは単独でも２種以上用いても良い。
【００３３】
【化２１】
【化２２】
本発明のポジ型感光性樹脂組成物は、これらの成分を溶剤（Ｄ）に溶解し、ワニス状にして使用する。溶剤（Ｄ）としては、光酸発生材から発生した触媒酸が失活するのを防ぐために窒素原子を含有していない溶媒を選択することが重要である。具体的な例としては、炭素数３〜１０の環状ケトン、炭素数３〜１０の環状ラクトン、ジメチルスルホキシド、ジエチレングリコールジアルキルエーテル、プロピレングリコールモノアルキルエーテル、ジプロピレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテルアセテート、３−メチル−３−メトキシブタノール、乳酸メチル、乳酸エチル、乳酸ブチル、メチル−１，３−ブチレングリコールアセテート、１，３−ブチレングリコール−３−モノアルキルエーテル、トリアルキルベンゼン、ピルビン酸メチル、ピルビン酸エチル、メチル−３−メトキシプロピオネート等が挙げられ、特に好ましいものとしては、γ−ブチロラクトン、シクロペンタノン、ジメチルスルホキシド、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、乳酸メチル、乳酸エチル、乳酸ブチルが挙げられ、これらは単独でも混合して用いてもよい。
【００３６】
又本発明のポジ型感光性樹脂組成物には、露光部と未露光部の溶解コントラストを高めるという目的で、光酸発生材から発生した触媒酸の拡散を促進するために、更にフェノール化合物（Ｅ）を配合することが好ましい。触媒酸の拡散は系中の親水性水酸基を経由する（Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．，ｖｏｌ．３５，Ｐｔ．１，Ｎｏ．１２Ｂ，ｐ６５０１（１９９６））挙動を示すことに基づくもので、適当なフェノール化合物（Ｅ）を配合することにより、保護基の脱離反応を促進させるものである。又これらのフェノール化合物（Ｅ）はアルカリ水溶液に可溶なため、露光部の溶解性が増加し、感度を高める働きもある。フェノール化合物（Ｅ）の配合量は、一般式（１）で示されるポリアミド樹脂（Ａ）１００重量部に対して１〜３０重量部が好ましい。１重量部未満だと触媒酸の拡散効果が認められなくなり、３０重量部を越えると現像時に著しい残膜率の低下が生じたり、冷凍保存中において析出が起こり実用性に欠けるおそれがあるので好ましくない。
【００３７】
フェノール化合物（Ｅ）としては下記のものを挙げることができるがこれらに限定されない。又これらは単独でも２種以上用いても良い。
【化２３】
【化２４】
【化２５】
本発明におけるポジ型感光性樹脂組成物には、必要によりレベリング剤、シランカップリング剤等の添加剤を配合することができる。
【００４１】
本発明のポジ型感光性樹脂組成物は、まず該樹脂組成物を適当な支持体、例えばシリコンウェハー、セラミック基板、アルミ基板等に塗布する。塗布量は、半導体装置の場合、硬化後の最終膜厚が０．１〜３０μｍになるように塗布する。膜厚が０．１μｍ未満だと半導体素子の保護表面膜としての機能を十分に発揮することが困難となり、３０μｍを越えると、微細な加工パターンを得ることが困難となる。塗布方法としては、スピンナーを用いた回転塗布、スプレーコーターを用いた噴霧塗布、浸漬、印刷、ロールコーティング等がある。次に、６０〜１３０℃でプリベークして塗膜を乾燥後、所望のパターン形状に化学線を照射する。化学線としては、Ｘ線、電子線、紫外線、可視光線等が使用できるが、２００〜５００ｎｍの波長のものが好ましい。露光後、オーブンやホットプレートを用い、６０〜１５０℃で熱処理を行う。露光後ベークによって光酸発生材から発生した酸が拡散し、触媒反応により保護基を脱離する。
【００４２】
次に照射部を現像液で溶解除去することによりレリーフパターンを得る。現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の第１アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の第２アミン類、トリエチルアミン、メチルジエチルアミン等の第３アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、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等の第４級アンモニウム塩等のアルカリ類の水溶液及びこれにメタノール、エタノールのごときアルコール類等の水溶性有機溶媒や界面活性剤を適当量添加した水溶液を好適に使用することができる。現像方法としては、スプレー、パドル、浸漬、超音波等の方式が可能である。
【００４３】
次に、現像によって形成したレリーフパターンをリンスする。リンス液としては、蒸留水を使用する。次に加熱処理を行い、オキサゾール環を形成して耐熱性に富む最終パターンを得る。
本発明によるポジ型感光性樹脂組成物は、半導体用途のみならず、多層回路の層間絶縁やフレキシブル銅張板のカバーコート、ソルダーレジスト膜や液晶配向膜等としても有用である。
【００４４】
【実施例】
以下、実施例により本発明を具体的に説明する。
＜実施例１＞
ポリアミド樹脂の合成
テレフタル酸０．９モルとイソフタル酸０．１モルと１−ヒドロキシ−１，２，３−ベンゾトリアゾール２モルとを反応させて得られたジカルボン酸誘導体（活性エステル）３５２．４ｇ（０．８８モル）とヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン３６６．３ｇ（１モル）とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた４つ口のセパラブルフラスコに入れ、γ−ブチロラクトン３０００ｇを加えて溶解させた。その後オイルバスを用いて７５℃にて１２時間反応させた。
【００４５】
次にγ−ブチロラクトン５００ｇに溶解させた５−ノルボルネン−２，３−ジカルボン酸無水物３２．８ｇ（０．２モル）を加え、更に１２時間攪拌して反応を終了した。反応混合物を濾過した後、反応混合物を水／メタノール＝３／１（体積比）の溶液に投入、沈殿物を濾集し水で充分洗浄した後、真空下で乾燥した。
【００４６】
乾燥後のポリアミド樹脂４９．６ｇを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた４つ口のセパラブルフラスコに入れ、γ−ブチロラクトン２５０ｇを加えて溶解させた。その後二炭酸ジ−ｔｅｒｔ−ブチル４．４ｇ（０．０２モル）をγ−ブチロラクトン２５ｇと共に滴下した。その後ピリジン１．６ｇ（０．０２モル）をγ−ブチロラクトン１０ｇと共に滴下し、室温で５時間反応させた。反応混合物を濾過した後、反応混合物を水／メタノール＝３／１（体積比）の溶液に投入、沈殿物を濾集し水で充分洗浄した後、真空下で乾燥し、一般式（１）で示され、Ｘが下記式Ｘ−１、Ｙが下記式Ｙ−１及びＹ−２の混合物で、ａ＝１００、ｂ＝０、ｎ＝４１からなり、核磁気共鳴法［装置：ＪＮＭ−ＧＳＸ４００型ＦＴ−ＮＭＲ装置（日本電子（株）製）、共鳴周波数：１００ＭＨｚ（プロトン）、溶媒：ジメチルスルホキシド］により全水酸基の１０％がｔｅｒｔ−ブトキシカルボニル基で保護された目的のポリアミド樹脂（Ａ−１）を合成した。
【００４７】
ポジ型感光性樹脂組成物の作製
合成したポリアミド樹脂（Ａ−１）１０ｇ、Ｎ−ヒドロキシナフタルイミドトリフルオロメタンスルホネート０．５ｇ、２−（ｐ−トルエンスルホニルオキシイミノ）−２−（４−メトキシフェニル）アセトニトリル０．５ｇ、下記式（Ｃ−１）の構造を有する酸不安定基で保護された化合物２．２ｇ、下記式（Ｅ−１）の構造を有するフェノール化合物０．５ｇをγ−ブチロラクトン２５ｇに溶解した後、０．２μｍのフッ素系樹脂フィルターで濾過しポジ型感光性樹脂組成物を得た。
【００４８】
特性評価
このポジ型感光性樹脂組成物をシリコンウェハー上にスピンコーターを用いて塗布した後、ホットプレートにて９０℃で３分プリベークし、膜厚７．０μｍの塗膜を得た。この塗膜に凸版印刷（株）製・マスク（テストチャートＮｏ．１：幅０．８８〜５０μｍの残しパターン及び抜きパターンが描かれている）を通して、ｉ線ステッパー（（株）ニコン製・４４２５ｉ）を用いて、露光量を変化させて照射した。その後ホットプレートにて１１０℃で５分露光後ベークを行った。次に２．３８％のテトラメチルアンモニウムヒドロキシド水溶液に２０秒間２回浸漬することによって露光部を溶解除去した後、純水で１０秒間リンスした。その結果、露光量１７０ｍＪ／ｃｍ２で照射した部分よりパターンが成形されていることが確認できた。（感度は１７０ｍＪ／ｃｍ２）。膜減り量は０．２μｍと低い値を示し、解像度は３μｍと非常に高い値を示した。又パターンのプロファイルも良好な形状を示した。
＜実施例２＞
実施例１における、酸不安定基で保護された化合物（Ｃ−１）を（Ｃ−２）に代え、その配合量を変えた他は、実施例１と同様の評価を行った。
【００４９】
＜実施例３＞
実施例１において、保護基導入前の乾燥後のポリアミド樹脂３０ｇを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた４つ口のセパラブルフラスコに入れ、酢酸エチル３００ｇを加えて溶解させた。１．０ｍｏｌ／Ｌの塩酸／ジエチルエーテル溶液３８．２ｍｌ（０．０４モル）を滴下した後、４０℃に加熱し、エチルビニルエーテル２．２ｇ（０．０３モル）を発熱に注意しながら滴下し、４０℃で４時間反応させた。その後、１０℃以下まで冷却し、トリエチルアミン２．０ｇ（０．０２モル）を滴下し、３０分攪拌した。反応混合物を濾過した後、反応混合物をヘキサン／酢酸エチル＝４／１（体積比）の溶液に投入、沈殿物を濾集し冷水で充分洗浄した後、真空下で乾燥し、一般式（１）で示され、Ｘが下記式Ｘ−１、Ｙが下記式Ｙ−１及びＹ−２の混合物で、ａ＝１００、ｂ＝０、ｎ＝４１からなり、前記した核磁気共鳴法により全水酸基の３０％がエトキシエチル基で保護された目的のポリアミド樹脂（Ａ−２）を合成した。
合成したポリアミド樹脂（Ａ−２）１０ｇ、Ｎ−ヒドロキシナフタルイミドトリフルオロメタンスルホネート０．５ｇ、２−（ｐ−トルエンスルホニルオキシイミノ）−２−（４−メトキシフェニル）アセトニトリル０．５ｇ、下記式（Ｃ−３）の構造を有する酸不安定基で保護された化合物２．０ｇ、下記式（Ｅ−２）の構造を有するフェノール化合物０．５ｇをγ−ブチロラクトン２５ｇに溶解した後、０．２μｍのフッ素系樹脂フィルターで濾過しポジ型感光性樹脂組成物を得た他は、実施例１と同様の評価を行った。
【００５０】
＜実施例４＞
実施例３における、酸不安定基で保護された化合物（Ｃ−３）を（Ｃ−４）に代えた他は、実施例１と同様の評価を行った。
＜実施例５＞
実施例３における、酸不安定基で保護された化合物（Ｃ−３）を（Ｃ−５）と（Ｃ−６）に代え、それぞれの配合量を変えた他は、実施例１と同様の評価を行った。
【００５１】
＜比較例１＞
テレフタル酸０．９モルとイソフタル酸０．１モルと１−ヒドロキシ−１，２，３−ベンゾトリアゾール２モルとを反応させて得られたジカルボン酸誘導体（活性エステル）３５２．４ｇ（０．８８モル）とヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン３６６．３ｇ（１モル）とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた４つ口のセパラブルフラスコに入れ、Ｎ−メチル−２−ピロリドン３０００ｇを加えて溶解させた。その後オイルバスを用いて７５℃にて１２時間反応させた。
次にＮ−メチル−２−ピロリドン５００ｇに溶解させた５−ノルボルネン−２，３−ジカルボン酸無水物３２．８ｇ（０．２モル）を加え、更に１２時間攪拌して反応を終了した。その他は実施例１と同様に反応し、一般式（１）で示され、Ｘが下記式Ｘ−１、Ｙが下記式Ｙ−１及びＹ−２の混合物で、ａ＝１００、ｂ＝０、ｎ＝４３からなり、水酸基に対する酸不安定基の置換率が０のポリアミド樹脂（Ａ−３）を合成した。合成したポリアミド樹脂（Ａ−３）１０ｇ、下記式（Ｑ−１）の構造を有する感光性ジアゾキノン化合物２ｇ、下記式（Ｅ−１）の構造を有するフェノール化合物０．６ｇをγ−ブチロラクトン２５ｇに溶解した後、０．２μｍのフッ素系樹脂フィルターで濾過しポジ型感光性樹脂組成物を得た他は実施例１と同様の評価を行った。
＜比較例２＞
実施例１における、酸不安定基で保護された化合物（Ｃ−１）を（Ｃ−７）に代えた他は実施例１と同様の評価を行った。
＜比較例３＞
実施例１における、酸不安定基で保護された化合物（Ｃ−１）を（Ｃ−８）に代え、その配合量を変えた他は、実施例１と同様の評価を行った。
＜比較例４＞
実施例３における、酸不安定基で保護された化合物（Ｃ−３）を（Ｃ−９）に代えた他は、実施例１と同様の評価を行った。
＜比較例５＞
実施例３における、酸不安定基で保護された化合物（Ｃ−３）を（Ｃ−１０）に代えた他は、実施例１と同様の評価を行った。
＜比較例６＞
実施例３における、酸不安定基で保護された化合物（Ｃ−３）を（Ｃ−１１）に代え、その配合量を変えた他は、実施例１と同様の評価を行った。
なお実施例１に対応するのは比較例２、実施例２に対応するのは比較例３、実施例３に対応するのは比較例４、実施例４に対応するのは比較例５、実施例５に対応するのは比較例６である。
以下に、実施例及び比較例のＸ−１、Ｙ−１、Ｙ−２、Ｃ−１〜Ｃ−１１、Ｅ−１、Ｅ−２、Ｑ−１の構造を示す。
以上の評価結果を表１、表２に示す。
【００５２】
【化２６】
【化２７】
【化２８】
【化２９】
【化３０】
【化３１】
【表１】
【表２】
【発明の効果】
本発明のポジ型感光性樹脂組成物は、高感度かつ高解像度であり、現像後の未露光部の膜減り量が少なく、形成されたプロファイル性も良好である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a positive photosensitive resin composition having high sensitivity and high resolution characteristics, and a semiconductor device using the same.
[0002]
[Prior art]
Conventionally, a polyimide resin having excellent heat resistance and excellent electrical properties and mechanical properties has been used for a surface protection film and an interlayer insulating film of a semiconductor element. There is a demand for remarkable improvements in heat cycle resistance and heat shock resistance due to the shift to surface mounting due to the thinning and miniaturization of semiconductor devices and solder reflow, and further high-performance resins are required. .
[0003]
On the other hand, a technique of imparting photosensitivity to the polyimide resin itself has attracted attention, and examples thereof include a negative photosensitive polyimide resin represented by the following formula (10).
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When this is used, a part of the pattern forming process can be simplified, and there is an effect of shortening the process and improving the yield. However, since a solvent such as N-methyl-2-pyrrolidone is required for development, safety and handling are improved. There is a problem with sex. Therefore, a positive photosensitive resin composition that can be developed with an aqueous alkali solution has been developed (for example, see Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, and Patent Literature 5). These disclose a positive photosensitive resin composition comprising a polyamic acid as a precursor of a polyimide resin and a diazoquinone compound as a photosensitive material. The diazoquinone compound used as such a photosensitive material undergoes a chemical change upon exposure to light and becomes soluble in an aqueous alkaline solution. However, the rate of change is not only about 40%, but also because of its large light absorption, when applied to a thick film, sufficient light does not reach the bottom of the film. Therefore, there is a problem that a large amount of exposure is required to open the exposed portion, and the sensitivity is lowered.
[0005]
Further, a positive-type photosensitive resin composition represented by a resist for semiconductors using ultraviolet rays such as g-rays and i-rays as a light source uses a phenol novolak resin as a base resin. Since the resin has a low hydroxyl group concentration per unit molecular weight, the resin has a weak dissolution inhibiting ability with respect to an aqueous alkaline solution exhibited by interacting with a diazoquinone compound, and has a large film loss amount in an unexposed portion after development. Therefore, before the exposed portion is sufficiently dissolved and removed with the developing solution, the unexposed portion has a thickness equal to or less than the target film thickness, so that not only the sensitivity is reduced as a result, but also the wall surface of the pattern is scraped, The dimensional stability of the opening decreases. In the case of a carboxyl group, it does not interact with the diazoquinone compound, and furthermore, the solubility in an aqueous alkali solution is much higher than that of a phenolic hydroxyl group. In addition, there is a problem that not only is it impossible to obtain a desired film thickness, but also it becomes difficult to form the pattern itself. In the case of a carboxyl group blocked with an appropriate protecting group, the unexposed portion has a sufficient resistance to an aqueous alkali solution, but the solubility of the exposed portion is poor, so that the sensitivity is lowered and the resin residue (scum) is observed after development. Problem.
[0006]
Therefore, a chemically amplified positive photosensitive resin composition incorporating a catalytic action by a photochemical reaction has been developed. This chemically amplified positive photosensitive resin composition is generally composed of a base resin in which a hydroxyl group or a carboxyl group is protected by a suitable acid labile group, and a photoacid generator which generates an acid upon irradiation with light. ing. The development mechanism of the chemically amplified positive photosensitive resin composition is as follows. The base resin protected by an acid labile group in the unexposed area is resistant to an aqueous alkali solution as a developing solution. On the other hand, in the exposed area, the acid generated from the photoacid generator is diffused by the heat treatment after exposure and acts as a catalyst, and removes the protective group in the base resin, regenerates the hydroxyl group or carboxyl group, and becomes soluble in the aqueous alkali solution. Become. By utilizing the difference in solubility between the exposed part and the unexposed part and dissolving and removing the exposed part, it is possible to form a coating pattern only on the unexposed part. Furthermore, this catalytic acid exists even after the elimination reaction, and causes many reactions, resulting in a high apparent quantum yield. Can be expected. Examples of the resist for semiconductor include, for example, Japanese Patent Nos. 2847414, 2848611, JP-A-3-249654, and JP-A-9-230588. The base resin used for these is mainly Hydroxystyrene, which can provide high resolution but has poor heat resistance, and is not suitable for use as a surface protective film or an interlayer insulating film of a semiconductor device.
[0007]
A chemically amplified photosensitive resin composition using a polyimide resin or a polyamide resin as a base resin has been disclosed as a surface protective film for semiconductor devices and an interlayer insulating film (for example, Patent Document 6, Patent Document 7, Patent Document 7). 8, see Patent Document 9.). However, in the disclosed base resin, the hydroxyl group remains even after being cured by heat, so that the moisture resistance reliability is lowered, or the resolution is lowered because a sufficient dissolution contrast is not obtained. Even with sensitivity, there were problems such as that a desired film thickness could not be obtained due to an increase in the amount of film reduction in an unexposed portion, and that side etching was large and profile properties were poor.
[0008]
[Patent Document 1]
JP-A-3-247655,
[Patent Document 2]
JP-A-5-204156,
[Patent Document 3]
JP-A-6-258836,
[Patent Document 4]
JP-A-10-186658,
[Patent Document 5]
JP 10-307394 A [Patent Document 6]
JP-A-3-763 [Patent Document 7]
JP-A-4-120171 [Patent Document 8]
JP-A-11-202489 [Patent Document 9]
JP 2001-194791 A
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION The present invention provides a positive photosensitive resin composition having high sensitivity and high resolution and having a small amount of film loss in an unexposed portion after development, and a semiconductor device using the same.
[0010]
[Means for Solving the Problems]
The present invention
[1] An acid that decomposes the hydroxyl group of the polyamide resin (A) represented by the general formula (1), the compound (B) that generates an acid by light, and the phenol compound represented by the general formula (2) in the presence of an acid A positive photosensitive resin composition comprising a compound (C) protected by an unstable group and a solvent (D);
[0011]
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[2] The positive photosensitive resin composition according to [1], wherein X in the polyamide resin represented by the general formula (1) is selected from the group of the formula (3):
[0014]
Embedded image
[3] The positive photosensitive resin composition according to item [1] or [2], wherein Y in the polyamide resin represented by the general formula (1) is selected from the group of the formula (4):
[0016]
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[4] The compound (C) in which the hydroxyl group of the phenol compound represented by the general formula (2) is protected by an acid labile group that decomposes in the presence of an acid, is selected from a tetrahydropyranyl group and a tetrahydrofuranyl group. Positive photosensitive resin composition according to any one of [1] to [3], which is a compound protected with a substituted group,
[5] The solvent (D) is a cyclic ketone having 3 to 10 carbon atoms, a cyclic lactone having 3 to 10 carbon atoms, dimethyl sulfoxide, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether, lactic acid The positive photosensitive resin composition according to any one of [1] to [4], which is selected from methyl, ethyl lactate, and butyl lactate,
[6] The positive photosensitive resin composition according to any one of [1] to [5], further comprising a phenolic compound (E);
[7] The positive photosensitive resin according to the item [6], wherein the phenol compound (E) is selected from the group consisting of the general formulas (5), (6), (7), (8) and (9). Composition,
[0018]
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[8] What is obtained by applying the positive photosensitive resin composition according to any of the items [1] to [7] on a semiconductor element, prebaking, exposing, heating after exposure, developing, and heating. Semiconductor device,
[9] A positive photosensitive resin composition is obtained by applying on a semiconductor element such that the film thickness after heat dehydration ring closure is 0.1 to 30 μm, prebaking, exposure, post-exposure heating, development, and heating. The semiconductor device according to item [8],
It is.
[0022]
The polyamide resin represented by the general formula (1) includes bis (aminophenol) having the structure of X, silicone diamine having the structure of Z optionally blended, dicarboxylic acid or dicarboxylic acid dichloride having the structure of Y, and a dicarboxylic acid derivative. After the reaction, the protecting group which becomes an acid labile group is replaced with a phenolic hydroxyl group in the polyamide resin. In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield and the like. The protecting group to be an acid labile group includes an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group. No. Also, in order to obtain a resin having a small amount of film loss in the unexposed area after development and a large dissolution contrast between the exposed area and the unexposed area, protection of 5-80% of all hydroxyl groups in the polyamide resin to an acid labile group. It must be substituted with a group. When it is less than 5%, the unexposed part cannot exert sufficient dissolution inhibiting ability, so that the amount of film loss increases. When it exceeds 80%, not only the solubility of the exposed part becomes extremely slow, but also the sensitivity decreases, Residual resin (scum) is likely to be generated after development. After the development, when the polyamide resin is heated at about 300 to 400 ° C., the ring is dehydrated and closed to form a heat-resistant resin in the form of polybenzoxazole.
[0023]
X of the polyamide resin of the general formula (1) of the present invention is, for example,
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[0024]
Further, Y of the polyamide resin of the general formula (1) is, for example,
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[0025]
Further, the positive photosensitive resin composition of the present invention is obtained by reacting bis (aminophenol) having the structure of X with dicarboxylic acid or dicarboxylic acid dichloride or dicarboxylic acid derivative having the structure of Y from the viewpoint of storage stability. After synthesizing the polyamide resin, it is important to cap the terminal amino group with an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. As a group derived from an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group, for example,
[0026]
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[0027]
Particularly preferred among these are:
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[0028]
Further, Z of the polyamide resin of the general formula (1) used as required may be, for example,
However, the present invention is not limited to these, and two or more kinds may be used.
Z in the general formula (1) is used, for example, when particularly excellent adhesion to a substrate such as a silicon wafer is required, and the use ratio b is up to 40 mol%. If it exceeds 40 mol%, the solubility of the resin in the developing solution is extremely reduced, and undeveloped portions (scum) are generated, so that pattern processing cannot be performed. When using X, Y, and Z, one type or a mixture of two or more types may be used. N in the general formula (1) is from 2 to 300, but if it exceeds 300, scum may be generated after development, which is not preferable.
[0030]
The compound (B) that generates an acid by light used in the positive photosensitive resin composition of the present invention includes:
Photograph. Sci. Eng. , 18, p387 (1974), CHEMTECH, Oct. p624 (1980), Polym. Mater. Sci. Eng. , 72, p406 (1995), Macromol. Chem. Rapid Commun. 14, p203 (1993); Photopolym. Sci. Technol. , 6, p67 (1993), Macromolecules, 21, p2001 (1988), Chem. Mater. 3, p462 (1991), Proc. 2-nitrobenzyl esters described in SPIE, 1086, 2 (1989); Photopolym. Sci. Technol. , 2, p429 (1989), Proc. SPIE, 1262, p575 (1990), N-iminosulfonates, Polym. Mat. Sci. Eng. Naphthoquinonediazide-4-sulfonic acid esters described in J. Am. Photopolym. Sci. Technol. , 4, p389 (1991), Proc. And halogen compounds described in SPIE, 2195, p173 (1994). These may be used alone or in combination of two or more.
[0031]
The positive photosensitive resin composition of the present invention further comprises an acid capable of decomposing a hydroxyl group of a phenol compound represented by the general formula (2) in the presence of an acid in order to further improve the dissolution contrast between an exposed portion and an unexposed portion. It is important to incorporate a compound (C) protected by a labile group. As a result, the resistance to an aqueous alkali solution is improved in the unexposed area, and in the exposed area, the acid labile group is eliminated by the action of the catalytic acid generated from the photoacid generator, thereby regenerating the hydroxyl group and promoting the dissolution promoting action. Prompt.
[0032]
Examples of the acid labile group that decomposes in the presence of an acid include an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxycarbonylmethyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and an alkoxyalkyl group having 1 to 10 carbon atoms. And alkyl-substituted silyl group, tetrahydropyranyl group, tetrahydrofuranyl group and the like. Particularly preferred are tetrahydropyranyl group and tetrahydrofuranyl group. Specific examples include, but are not limited to, the following. These may be used alone or in combination of two or more.
[0033]
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The positive photosensitive resin composition of the present invention is used by dissolving these components in a solvent (D) and forming a varnish. As the solvent (D), it is important to select a solvent that does not contain a nitrogen atom in order to prevent the catalytic acid generated from the photoacid generator from being deactivated. Specific examples include a cyclic ketone having 3 to 10 carbon atoms, a cyclic lactone having 3 to 10 carbon atoms, dimethyl sulfoxide, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. Acetate, 3-methyl-3-methoxybutanol, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monoalkyl ether, trialkylbenzene, methyl pyruvate, Ethyl pyruvate, methyl-3-methoxypropionate and the like are mentioned, and particularly preferable ones are γ-butyrolactone, cyclopentanone, dimethyl sulfoxide, propylene glycol monoamine. Chirueteru, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl lactate, ethyl lactate, include butyl lactate, and these may be used individually or as a mixture.
[0036]
The positive photosensitive resin composition of the present invention further comprises a phenol compound (P) to promote the diffusion of the catalytic acid generated from the photoacid generator for the purpose of increasing the dissolution contrast between the exposed and unexposed areas. It is preferred to blend E). The diffusion of the catalytic acid is based on the behavior via hydrophilic hydroxyl groups in the system (Jpn. J. Appl. Phys., Vol. 35, Pt. 1, No. 12B, p6501 (1996)). The addition of an appropriate phenol compound (E) promotes the elimination reaction of the protecting group. Further, since these phenol compounds (E) are soluble in an aqueous alkaline solution, the solubility of the exposed area is increased, and the phenol compound (E) also has a function of increasing the sensitivity. The amount of the phenol compound (E) is preferably 1 to 30 parts by weight based on 100 parts by weight of the polyamide resin (A) represented by the general formula (1). When the amount is less than 1 part by weight, the effect of diffusing the catalytic acid is not recognized. When the amount is more than 30 parts by weight, a remarkable reduction in the residual film ratio occurs during development, or precipitation during frozen storage may cause lack of practicality. Absent.
[0037]
Examples of the phenol compound (E) include, but are not limited to, the following. These may be used alone or in combination of two or more.
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If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition of the present invention.
[0041]
The positive photosensitive resin composition of the present invention is first applied to a suitable support, for example, a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. In the case of a semiconductor device, the application amount is such that the final film thickness after curing is 0.1 to 30 μm. If the thickness is less than 0.1 μm, it will be difficult to sufficiently exert the function as a protective surface film of the semiconductor element, and if it exceeds 30 μm, it will be difficult to obtain a fine processed pattern. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after pre-baking at 60 to 130 ° C. to dry the coating film, the desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. After exposure, heat treatment is performed at 60 to 150 ° C. using an oven or a hot plate. The acid generated from the photoacid generator is diffused by the post-exposure bake, and the protective group is eliminated by a catalytic reaction.
[0042]
Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developing solution. Examples of the developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and quaternary ammoniums such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a salt and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant thereto can be suitably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used.
[0043]
Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing liquid. Next, heat treatment is performed to form an oxazole ring, thereby obtaining a final pattern having high heat resistance.
The positive photosensitive resin composition according to the present invention is useful not only for semiconductor applications, but also as interlayer insulation for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like.
[0044]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
<Example 1>
Synthesis of polyamide resin 352.4 g of dicarboxylic acid derivative (active ester) obtained by reacting 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole (0.88 mol) and 366.3 g (1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were charged with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. The mixture was placed in a four-necked separable flask provided, and 3000 g of γ-butyrolactone was added and dissolved. Thereafter, the reaction was carried out at 75 ° C. for 12 hours using an oil bath.
[0045]
Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of γ-butyrolactone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), and the precipitate was collected by filtration, sufficiently washed with water, and then dried under vacuum.
[0046]
49.6 g of the dried polyamide resin was placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 250 g of γ-butyrolactone was added to dissolve the polyamide resin. Thereafter, 4.4 g (0.02 mol) of di-tert-butyl dicarbonate was added dropwise together with 25 g of γ-butyrolactone. Thereafter, 1.6 g (0.02 mol) of pyridine was added dropwise together with 10 g of γ-butyrolactone, and the mixture was reacted at room temperature for 5 hours. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), and the precipitate was collected by filtration, washed sufficiently with water, and dried under vacuum to obtain a compound represented by the general formula (1). Wherein X is a mixture of the following formulas X-1 and Y is a mixture of the following formulas Y-1 and Y-2, wherein a = 100, b = 0, and n = 41, and a nuclear magnetic resonance method [apparatus: JNM- GSX400 type FT-NMR apparatus (manufactured by JEOL Ltd.), resonance frequency: 100 MHz (proton), solvent: dimethyl sulfoxide], the target polyamide resin (A) in which 10% of all hydroxyl groups are protected by a tert-butoxycarbonyl group. -1) was synthesized.
[0047]
Preparation of Positive Photosensitive Resin Composition 10 g of synthesized polyamide resin (A-1), 0.5 g of N-hydroxynaphthalimide trifluoromethanesulfonate, 2- (p-toluenesulfonyloxyimino) -2- (4-methoxyphenyl) ) 0.5 g of acetonitrile, 2.2 g of a compound protected by an acid labile group having the structure of the following formula (C-1), and 0.5 g of a phenol compound having a structure of the following formula (E-1) were converted to γ-butyrolactone. After dissolving in 25 g, the solution was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.
[0048]
Characteristic evaluation After applying this positive photosensitive resin composition to a silicon wafer using a spin coater, it was prebaked on a hot plate at 90 ° C. for 3 minutes to obtain a coating film having a thickness of 7.0 μm. An i-line stepper (manufactured by Nikon Corporation, 4425i) is passed through a mask (test chart No. 1: a pattern with a width of 0.88 to 50 μm left and a blank pattern) manufactured by Toppan Printing Co., Ltd. ) Was used to change the exposure amount. Thereafter, baking was performed after exposure at 110 ° C. for 5 minutes on a hot plate. Next, the exposed portion was dissolved and removed by immersing it twice in a 2.38% tetramethylammonium hydroxide aqueous solution for 20 seconds, followed by rinsing with pure water for 10 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated at an exposure amount of 170 mJ / cm 2 . (The sensitivity is 170 mJ / cm 2 ). The amount of film reduction showed a low value of 0.2 μm, and the resolution showed a very high value of 3 μm. The profile of the pattern also showed a good shape.
<Example 2>
The same evaluation as in Example 1 was performed, except that the compound (C-1) protected by the acid labile group in Example 1 was changed to (C-2) and the amount was changed.
[0049]
<Example 3>
In Example 1, 30 g of the dried polyamide resin before the introduction of the protecting group was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a material inlet, and a dry nitrogen gas inlet tube, and 300 g of ethyl acetate was added. Dissolved. After dropping 38.2 ml (0.04 mol) of a 1.0 mol / L hydrochloric acid / diethyl ether solution, the mixture was heated to 40 ° C., and 2.2 g (0.03 mol) of ethyl vinyl ether was dropped while paying attention to heat generation. At 40 ° C. for 4 hours. Thereafter, the mixture was cooled to 10 ° C. or lower, 2.0 g (0.02 mol) of triethylamine was added dropwise, and the mixture was stirred for 30 minutes. After the reaction mixture was filtered, the reaction mixture was poured into a solution of hexane / ethyl acetate = 4/1 (volume ratio), and the precipitate was collected by filtration, washed sufficiently with cold water, dried under vacuum, and then dried under the general formula (1). Wherein X is a mixture of the following formulas X-1 and Y is a mixture of the following formulas Y-1 and Y-2, wherein a = 100, b = 0, and n = 41. An intended polyamide resin (A-2) in which 30% of the hydroxyl groups were protected by an ethoxyethyl group was synthesized.
10 g of the synthesized polyamide resin (A-2), 0.5 g of N-hydroxynaphthalimide trifluoromethanesulfonate, 0.5 g of 2- (p-toluenesulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, the following formula ( After dissolving 2.0 g of a compound protected by an acid labile group having the structure of C-3) and 0.5 g of a phenol compound having a structure of the following formula (E-2) in 25 g of γ-butyrolactone, The same evaluation as in Example 1 was performed, except that a positive photosensitive resin composition was obtained by filtration with a fluorine-based resin filter.
[0050]
<Example 4>
The same evaluation as in Example 1 was performed, except that the compound (C-3) protected with an acid labile group in Example 3 was changed to (C-4).
<Example 5>
Example 3 is the same as Example 1 except that the compound (C-3) protected by the acid labile group in Example 3 was changed to (C-5) and (C-6), and the amount of each compound was changed. An evaluation was performed.
[0051]
<Comparative Example 1>
352.4 g (0.88) of a dicarboxylic acid derivative (active ester) obtained by reacting 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole. Mol) and 366.3 g (1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were mixed with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. The mixture was placed in a separable flask having a mouth, and 3000 g of N-methyl-2-pyrrolidone was added to dissolve the mixture. Thereafter, the reaction was carried out at 75 ° C. for 12 hours using an oil bath.
Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. Others react in the same manner as in Example 1 and are represented by the general formula (1), where X is a mixture of the following formulas X-1, Y is a mixture of the following formulas Y-1 and Y-2, and a = 100 and b = 0 , N = 43, and a polyamide resin (A-3) having a substitution ratio of an acid labile group to a hydroxyl group of 0 was synthesized. 10 g of the synthesized polyamide resin (A-3), 2 g of a photosensitive diazoquinone compound having a structure of the following formula (Q-1), and 0.6 g of a phenol compound having a structure of the following formula (E-1) are converted to 25 g of γ-butyrolactone. After dissolving, the same evaluation as in Example 1 was performed except that a positive photosensitive resin composition was obtained by filtering through a fluorine resin filter of 0.2 μm.
<Comparative Example 2>
The same evaluation as in Example 1 was performed, except that the compound (C-1) protected with an acid labile group in Example 1 was replaced with (C-7).
<Comparative Example 3>
The same evaluation as in Example 1 was performed, except that the compound (C-1) protected by the acid labile group in Example 1 was changed to (C-8), and the amount was changed.
<Comparative Example 4>
The same evaluation as in Example 1 was performed, except that the compound (C-3) protected with an acid labile group in Example 3 was replaced with (C-9).
<Comparative Example 5>
The same evaluation as in Example 1 was performed, except that the compound (C-3) protected with an acid labile group in Example 3 was replaced with (C-10).
<Comparative Example 6>
The same evaluation as in Example 1 was performed, except that the compound (C-3) protected by the acid labile group in Example 3 was changed to (C-11) and the amount was changed.
Comparative Example 2 corresponds to Example 1; Comparative Example 3 corresponds to Example 2; Comparative Example 4 corresponds to Example 3; Comparative Example 5 corresponds to Example 4; Comparative Example 6 corresponds to Example 5.
The structures of X-1, Y-1, Y-2, C-1 to C-11, E-1, E-2, and Q-1 of Examples and Comparative Examples are shown below.
Tables 1 and 2 show the above evaluation results.
[0052]
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[Table 1]
[Table 2]
【The invention's effect】
The positive photosensitive resin composition of the present invention has high sensitivity and high resolution, has a small amount of film loss in an unexposed part after development, and has good formed profile.
Claims (9)
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| JP2007304125A (en) * | 2006-05-08 | 2007-11-22 | Tokyo Institute Of Technology | Positive photosensitive resin composition |
| JP2009276795A (en) * | 2003-02-17 | 2009-11-26 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method for manufacturing pattern and electronic part |
| US7851129B2 (en) | 2004-10-29 | 2010-12-14 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, resist pattern forming method and compound |
| US7862981B2 (en) | 2005-06-17 | 2011-01-04 | Tokyo Ohka Kogyo Co., Ltd. | Compound, positive resist composition and method of forming resist pattern |
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| JP2009276795A (en) * | 2003-02-17 | 2009-11-26 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method for manufacturing pattern and electronic part |
| US7923192B2 (en) | 2004-02-20 | 2011-04-12 | Tokyo Ohka Kogyo Co., Ltd. | Base material for pattern-forming material, positive resist composition and method of resist pattern formation |
| US7897319B2 (en) | 2004-07-28 | 2011-03-01 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US7901865B2 (en) | 2004-09-08 | 2011-03-08 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and process for formation of resist patterns |
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| US7981588B2 (en) | 2005-02-02 | 2011-07-19 | Tokyo Ohka Kogyo Co., Ltd. | Negative resist composition and method of forming resist pattern |
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| WO2015087830A1 (en) * | 2013-12-11 | 2015-06-18 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device |
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