JP4267356B2 - Chemical amplification type positive photoresist composition for thick film, thick film photoresist laminate, method for producing thick film resist pattern, and method for producing connection terminal - Google Patents
Chemical amplification type positive photoresist composition for thick film, thick film photoresist laminate, method for producing thick film resist pattern, and method for producing connection terminal Download PDFInfo
- Publication number
- JP4267356B2 JP4267356B2 JP2003102958A JP2003102958A JP4267356B2 JP 4267356 B2 JP4267356 B2 JP 4267356B2 JP 2003102958 A JP2003102958 A JP 2003102958A JP 2003102958 A JP2003102958 A JP 2003102958A JP 4267356 B2 JP4267356 B2 JP 4267356B2
- Authority
- JP
- Japan
- Prior art keywords
- thick film
- acid
- photoresist composition
- resin
- chemically amplified
- 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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- 229920002120 photoresistant polymer Polymers 0.000 title claims description 71
- 239000000203 mixture Substances 0.000 title claims description 53
- 239000000126 substance Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 230000003321 amplification Effects 0.000 title claims description 4
- 238000003199 nucleic acid amplification method Methods 0.000 title claims description 4
- 239000011347 resin Substances 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 238000011161 development Methods 0.000 claims description 13
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229920003986 novolac Polymers 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 83
- 238000007747 plating Methods 0.000 description 42
- -1 5-methyl-2-furyl Chemical group 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 18
- 238000000576 coating method Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 150000001491 aromatic compounds Chemical group 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- ABUIKOPEGIZINI-UHFFFAOYSA-N (1-ethylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(CC)CCCCC1 ABUIKOPEGIZINI-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012536 packaging technology Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- BFQFFNWLTHFJOZ-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=C3OCOC3=CC=2)=N1 BFQFFNWLTHFJOZ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YGBVAGIVGBLKFE-UHFFFAOYSA-N 2-phenylbut-1-en-1-ol Chemical compound CCC(=CO)C1=CC=CC=C1 YGBVAGIVGBLKFE-UHFFFAOYSA-N 0.000 description 2
- MKHXOKALQIHXPI-UHFFFAOYSA-N 2-phenylprop-1-en-1-ol Chemical compound OC=C(C)C1=CC=CC=C1 MKHXOKALQIHXPI-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- LOVKRNMQTUTWQJ-UHFFFAOYSA-N [[cyano-(4-methoxyphenyl)methylidene]amino] 2-chlorobenzenesulfonate Chemical compound C1=CC(OC)=CC=C1C(C#N)=NOS(=O)(=O)C1=CC=CC=C1Cl LOVKRNMQTUTWQJ-UHFFFAOYSA-N 0.000 description 1
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- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 229940106691 bisphenol a Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical class C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 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
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- 238000010894 electron beam technology Methods 0.000 description 1
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- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
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- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-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
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-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
- 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 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical group [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- IZJVVXCHJIQVOL-UHFFFAOYSA-N nitro(phenyl)methanesulfonic acid Chemical compound OS(=O)(=O)C([N+]([O-])=O)C1=CC=CC=C1 IZJVVXCHJIQVOL-UHFFFAOYSA-N 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- RQKYHDHLEMEVDR-UHFFFAOYSA-N oxo-bis(phenylmethoxy)phosphanium Chemical compound C=1C=CC=CC=1CO[P+](=O)OCC1=CC=CC=C1 RQKYHDHLEMEVDR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- VBOGDLCGFBSZKS-UHFFFAOYSA-N phenylsulfanylbenzene;trifluoromethanesulfonic acid Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[SH+]C1=CC=CC=C1 VBOGDLCGFBSZKS-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(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
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Description
【0001】
【発明の属する技術分野】
本発明は、厚膜用ポジ型化学増幅型ホトレジスト組成物、厚膜ホトレジスト積層体、厚膜レジストパターンの製造方法及び接続端子の製造方法に関するものである。さらに詳しくは、本発明は、回路基板の製造や、回路基板に実装するCSP(チップサイズパッケージ)等の電子部品の製造において、バンプやメタルポストなどの接続端子、配線パターン等の形成に好適に用いられる厚膜用化学増幅型ポジ型ホトレジスト組成物、厚膜ホトレジスト積層体、厚膜レジストパターンの製造方法及び接続端子の製造方法に関するものである。
【0002】
【従来の技術】
現在、精密微細加工技術の主流となっているホトファブリケーションとは、感光性樹脂組成物を加工物表面に塗布して塗膜を形成し、ホトリソグラフィー技術によって塗膜をパターニングし、これをマスクとして化学エッチング、電解エッチング及び/又は電気メッキを主体とするエレクトロフォーミングを行って、半導体パッケージ等の各種精密部品を製造する技術の総称である。
近年、電子機器のダウンサイジングに伴い、半導体パッケージの高密度実装技術が進み、パッケージの多ピン薄膜実装化、パッケージサイズの小型化、フリップチップ方式による2次元実装技術、3次元実装技術に基づいた実装密度の向上が図られている。このような高密度実装技術においては、接続端子として、例えば、パッケージ上に突出したバンプ等の突起電極(実装端子)や、ウエーハ上のペリフェラル端子から延びる再配線と実装端子とを接続するメタルポストなどが基板上に高精度に配置される。
【0003】
上記のようなホトファブリケーションに使用される材料として厚膜用ホトレジストがある。厚膜用ホトレジストは、厚膜ホトレジスト層を形成するものであり、例えば、メッキ工程によるバンプやメタルポストの形成などに用いられている。バンプやメタルポストは、例えば、支持体上に膜厚約20μmの厚膜ホトレジスト層を形成し、所定のマスクパターンを介して露光し、現像して、バンプやメタルポストを形成する部分が選択的に除去(剥離)されたレジストパターンを形成し、この除去された部分(非レジスト部)に銅などの導体をメッキによって埋め込んだ後、その周囲のレジストパターンを除去することにより形成することができる。
厚膜用ホトレジストとしては、パンプ形成用や配線形成用として用いられるキノンジアジド基含有化合物を有するポジ型感光性樹脂組成物が開示されている(例えば、特許文献1参照。)。
【0004】
一方、従来のキノンジアジド基含有化合物を有するポジ型感光性樹脂組成物よりも高感度な感光性樹脂組成物として、酸発生剤を含む化学増幅型ホトレジストが知られている。化学増幅型ホトレジストの特徴は、放射線照射(露光)により、酸発生剤から酸が発生し、露光後の加熱処理により酸の拡散が促進されて、樹脂組成物中のベース樹脂等に対し酸触媒反応を起こし、そのアルカリ溶解性を変化させることである。
化学増幅型レジストには、放射線照射により、アルカリ不溶であったものがアルカリ可溶化するポジ型と、アルカリ可溶であったものがアルカリ不溶化するネガ型とがある。
【0005】
上記のような厚膜用ホトレジスト組成物に対する要求項目としては、10μm以上の膜厚が形成できること、基板に対する密着性を有すること、バンプを形成するためのメッキを行う際に、耐メッキ液性およびメッキ液に対する良好な濡れ性を有していること、メッキによって得られる金属組成物がレジストパターンの形状に対応していること、メッキ処理後に剥離液により容易に剥離されること等である。また、メッキ技術の高度化により、複数回のメッキ工程や、より厳しい条件でのメッキ工程が必要になり、複数回のメッキ工程にも耐えられるような、メッキ工程そのものに対する耐性も求められている。
【0006】
厚膜用のホトレジスト組成物としては、例えば、ポジ型のメッキ用化学増幅型ホトレジスト組成物が開示されている(例えば、特許文献2参照。)。
また、良好な断面形状の良好なレジストパターンを得るために、露光前後のアルカリに対する溶解性変化(コントラスト)を大きくし、解像度及び焦点深度幅の向上を目的としたKrFエキシマレーザー用の化学増幅型ホトレジスト組成物が開示されている(例えば、特許文献3参照。)。
【0007】
【特許文献1】
特開2002−258479号公報
【特許文献2】
特開2001−281862号公報
【特許文献3】
特開2000−347405号公報
【0008】
【発明が解決しようとする課題】
しかしながら、特許文献2及び3に記載された従来の化学増幅型レジスト組成物を使用して厚膜レジスト層を作成した場合、ホトレジスト組成物のメッキに対する応力耐性が十分でないために、メッキ処理により得られる金属層が膨らみ、良好なメッキ生成物のパターンを得ることが困難であった。また、耐メッキ液性も十分でなく、メッキ工程中やメッキ処理後の洗浄中のレジストに欠けやクラックが生じ、複数回のメッキ工程を同じレジストパターンで行うのは困難であった(耐メッキ性に劣る。)。
また、特許文献1に記載された耐メッキ性に優れたナフトキノンジアジド基含有化合物を有する感光性樹脂組成物では、より高感度にすることが困難であった。
【0009】
本発明は、かかる従来技術の問題点に鑑みてなされたものであり、メッキによる生成物の形状が良好で、応力耐性、耐メッキ液性、及び耐メッキ性に優れ、かつ高感度であって、接続端子等の製造に適した厚膜用化学増幅型ポジ型ホトレジスト組成物、厚膜ホトレジスト積層体、これを用いた厚膜レジストパターンの製造方法及び接続端子の製造方法を提供することを課題とする。
【0010】
【課題を解決するための手段】
本発明者らは、上記の課題を解決すべく鋭意検討した結果、ポジ型の厚膜用化学増幅型ポジ型ホトレジスト組成物において、酸の作用によりアルカリに対する溶解性が増大する樹脂として、特定の構造の構成単位を有する樹脂を用いることによって、上記課題を解決することを見出し、本発明を完成するに至った。
【0011】
すなわち、本発明の第一の発明は、支持体上に、膜厚10〜150μmの厚膜ホトレジスト層を形成するために用いられる厚膜用化学増幅型ポジ型ホトレジスト組成物であって、(A)活性光線又は放射線照射により酸を発生する化合物と、(B)酸の作用によりアルカリに対する溶解性が増大する樹脂と、(C)アルカリ可溶性樹脂とを含有し、
前記(B)成分が、(b1)下記一般式(1):
【0012】
【化2】
【0013】
(式中、R1は水素原子又はメチル基、R2は炭素数1〜5の低級アルキル基を表す。)
で表される構成単位と、(b2)エーテル結合を有する重合性化合物から誘導された構成単位とを含み、かつ、質量平均分子量が10000〜500000の共重合体からなる樹脂を含有することを特徴とする厚膜用化学増幅型ポジ型ホトレジスト組成物である。
【0014】
本発明の第二の発明は、支持体と、前記厚膜用化学増幅型ポジ型ホトレジスト組成物からなる厚膜ホトレジスト層とが積層されていることを特徴とする厚膜ホトレジスト積層体である。
【0015】
本発明の第三の発明は、前記厚膜ホトレジスト積層体を得る積層工程と、該厚膜ホトレジスト積層体に選択的に活性光線又は放射線を照射する露光工程と、該露光工程後に現像して厚膜レジストパターンを得る現像工程とを含むことを特徴とする厚膜レジストパターンの製造方法である。
【0016】
本発明の第四の発明は、前記厚膜レジストパターン製造方法を用いて得られる厚膜レジストパターンの非レジスト部に、導体からなる接続端子を形成する工程を含むことを特徴とする接続端子の製造方法である。
【0017】
なお、「構成単位」とは、重合体を構成するモノマー単位を示す。また、(メタ)アクリル酸とは、メタクリル酸、アクリル酸の一方または両方を示す。
【0018】
【発明の実施の形態】
以下、本発明について詳細に説明する。
(A)活性光線又は放射線照射により酸を発生する化合物:
本発明に用いられる(A)活性光線又は放射線照射により酸を発生する化合物(以下、(A)成分という。)は、酸発生剤であり、光により直接若しくは間接的に酸を発生する化合物であれば特に限定されない。
具体的には、2,4−トリクロロメチル−6−ピペロニル−1,3,5−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(2−フリル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(5−メチル−2−フリル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(5−エチル−2−フリル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(5−プロピル−2−フリル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(3,5−ジメトキシフェニル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(3,5−ジエトキシフェニル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(3,5−ジプロポキシフェニル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(3−メトキシ−5−エトキシフェニル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(3−メトキシ−5−プロポキシフェニル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−[2−(3,4−メチレンジオキシフェニル)エテニル]−s−トリアジン、2,4−ビス(トリクロロメチル)−6−(3,4−メチレンジオキシフェニル)−s−トリアジン、2,4−ビス−トリクロロメチル−6−(3−ブロモ−4メトキシ)フェニル−s−トリアジン、2,4−ビス−トリクロロメチル−6−(2−ブロモ−4メトキシ)フェニル−s−トリアジン、2,4−ビス−トリクロロメチル−6−(2−ブロモ−4メトキシ)スチリルフェニル−s−トリアジン、2,4−ビス−トリクロロメチル−6−(3−ブロモ−4メトキシ)スチリルフェニル−s−トリアジン、2‐(4‐メトキシフェニル)‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、2‐(4‐メトキシナフチル)‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、2‐[2‐(2‐フリル)エテニル]‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、2‐[2‐(5‐メチル‐2‐フリル)エテニル]‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、2‐[2‐(3,5‐ジメトキシフェニル)エテニル]‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、2‐[2‐(3,4‐ジメトキシフェニル)エテニル]‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、2‐(3,4‐メチレンジオキシフェニル)‐4,6‐ビス(トリクロロメチル)‐1,3,5‐トリアジン、トリス(1,3‐ジブロモプロピル)‐1,3,5‐トリアジン、トリス(2,3‐ジブロモプロピル)‐1,3,5‐トリアジン等のハロゲン含有トリアジン化合物およびトリス(2,3‐ジブロモプロピル)イソシアヌレート等の下記の一般式(2)で表されるハロゲン含有トリアジン化合物;
【0019】
【化3】
【0020】
(式中、R3〜R5は、それぞれ同一であっても異なってもよく、ハロゲン化アルキル基を示す)
【0021】
α−(p−トルエンスルホニルオキシイミノ)−フェニルアセトニトリル、α−(ベンゼンスルホニルオキシイミノ)−2,4−ジクロロフェニルアセトニトリル、α−(ベンゼンスルホニルオキシイミノ)−2,6−ジクロロフェニルアセトニトリル、α−(2−クロロベンゼンスルホニルオキシイミノ)−4−メトキシフェニルアセトニトリル、α−(エチルスルホニルオキシイミノ)−1−シクロペンテニルアセトニトリル、下記一般式(3)で表される化合物;
【0022】
【化4】
【0023】
(式中、R6は、一価〜三価の有機基、R7は置換、未置換の飽和炭化水素基、不飽和炭化水素基または芳香族性化合物基を示し、nは1〜3の自然数を示す。ここで芳香族性化合物基とは、芳香族化合物に特有な物理的・化学的性質を示す化合物の基を指し、例えばフェニル基、ナフチル基などの芳香族炭化水素基や、フリル基、チエニル基などの複素環基が挙げられる。これらは環上に適当な置換基、例えばハロゲン原子、アルキル基、アルコキシ基、ニトロ基などを1個以上有していてもよい。また、R7は炭素数1〜4のアルキル基が特に好ましく、メチル基、エチル基、プロピル基、ブチル基が挙げられる。特にR6が芳香族性化合物基、R7が低級アルキル基の化合物が好ましい。上記一般式で表わされる酸発生剤としては、n=1の時、R6がフェニル基、メチルフェニル基、メトキシフェニル基のいずれかであって、R7がメチル基の化合物、具体的にはα−(メチルスルホニルオキシイミノ)−1−フェニルアセトニトリル、α−(メチルスルホニルオキシイミノ)−1−(p−メチルフェニル)アセトニトリル、α−(メチルスルホニルオキシイミノ)−1−(p−メトキシフェニル)アセトニトリルが挙げられる。n=2の時、上記一般式で表わされる酸発生剤としては、具体的には下記化学式で表される酸発生剤が挙げられる。)
【0024】
【化5】
【0025】
ビス(p‐トルエンスルホニル)ジアゾメタン、ビス(1,1‐ジメチルエチルスルホニル)ジアゾメタン、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(2,4‐ジメチルフェニルスルホニル)ジアゾメタン等のビススルホニルジアゾメタン類;p‐トルエンスルホン酸2‐ニトロベンジル、p‐トルエンスルホン酸2,6‐ジニトロベンジル、ニトロベンジルトシレート、ジニトロベンジルトシレート、ニトロベンジルスルホネート、ニトロベンジルカルボネート、ジニトロベンジルカルボネート等のニトロベンジル誘導体;ピロガロールトリメシレート、ピルガロールトリトシレート、ベンジルトシレート、ベンジルスルホネート、N−メチルスルホニルオキシスクシンイミド、N−トリクロロメチルスルホニルオキシスクシンイミド、N−フェニルスルホニルオキシマレイミド、N−メチルスルホニルオキシフタルイミド等のスルホン酸エステル;N−ヒドロキシフタルイミド、N−ヒドロキシナフタルイミド等のトリフルオロメタンスルホン酸エステル;ジフェニルヨードニウムヘキサフルオロフォスフェート、(4‐メトキシフェニル)フェニルヨードニウムトリフルオロメタンスルホネート、ビス(p‐tert‐ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムヘキサフルオロフォスフェート、(4‐メトキシフェニル)ジフェニルスルホニウムトリフルオロメタンスルホネート、(p‐tert‐ブチルフェニル)ジフェニルスルホニウムトリフルオロメタンスルホネート等のオニウム塩;ベンゾイントシレート、α‐メチルベンゾイントシレートなどのベンゾイントシレート類;その他のジフェニルヨードニウム塩、トリフェニルスルホニウム塩、フェニルジアゾニウム塩、ベンジルカルボネート等が挙げられる。
【0026】
前記の中でも、(A)成分として、一般式(4):
R−SO2O−N=C(CN)− (4)
(式中、Rは置換もしくは無置換の、例えば炭素数1〜8のアルキル基またはアリール基である)
で表されるオキシムスルホネート基を少なくとも2個有する化合物、とくに一般式(5):
R−SO2O−N=C(CN)−A−C(CN)=N−OSO2−R (5)(式中、Aは二価の、例えば置換または未置換の炭素数1〜8のアルキレン基または芳香族性化合物基であり、Rは置換もしくは無置換の、例えば炭素数1〜8のアルキル基またはアリール基である)
で表される化合物が好ましい。ここで芳香族性化合物基とは、芳香族化合物に特有な物理的・化学的性質を示す化合物の基を指し、例えばフェニル基、ナフチル基などの芳香族炭化水素基や、フリル基、チエニル基などの複素環基が挙げられる。これらは環上に適当な置換基、例えばハロゲン原子、アルキル基、アルコキシ基、ニトロ基などを1個以上有していてもよい。さらに前記一般式においてAがフェニレン基、Rが例えば炭素数1〜4の低級アルキル基であるのがさらに好ましい。
【0027】
この(A)成分は単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
また、(A)成分の配合量は、(B)成分100質量部に対し、0.1〜10質量部、好ましくは0.2〜5質量部とされる。0.1質量部以上とすることにより、十分な感度が得られる様になり、10質量部以下とすることにより溶剤に対する溶解性がよく、均一な溶液が得られ、保存安定性が向上する傾向がある。
【0028】
(B)酸の作用によりアルカリに対する溶解性が増大する樹脂:
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物に用いられる(B)酸の作用によりアルカリに対する溶解性が増大する樹脂(以下、(B)成分という。)は、(b1)下記一般式(1):
【0029】
【化6】
【0030】
(式中、R1は水素原子又はメチル基、R2は低級アルキル基を表す。)で表される構成単位(以下、(b1)単位という。)を含む共重合体からなる樹脂である。
【0031】
(b1)単位:
(b1)単位は、上記一般式(1)で表される構成単位である。
上記一般式(1)において、R1は水素原子又はメチル基である。
R2で示される低級アルキル基は、直鎖状及び枝分かれ状のいずれであってもよく、その例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、各種ペンチル基などが挙げられるが、これらの中で、高コントラストで、解像度、焦点深度幅などが良好な点から、炭素数2〜4の低級アルキル基が好適である。
【0032】
このような、上記一般式(1)で表される構成単位の好ましい具体例としては、下記のものを挙げることができる。
【0033】
【化7】
【0034】
【化8】
【0035】
【化9】
【0036】
(b1)単位としては、上記一般式(1)で表される構成単位のうち1種を用いてもよいが、構造の異なる2種以上の構成単位を用いてもよい。
【0037】
さらに、(B)成分は、前記(b1)構成単位、および(b2)エーテル結合を有する重合性化合物から誘導された構成単位を含む共重合体からなる樹脂であることが好ましい。(b2)成分を含むことによって、現像時の基板との密着性、耐メッキ液性が良好となる。
【0038】
(b2)単位:
(b2)単位は、エーテル結合を有する重合性化合物から誘導された構成単位である。
エーテル結合を有する重合性化合物としては、2−メトキシエチル(メタ)アクリレート、2−エトキシエチル(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、3−メトキシブチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、メトキシポリプロピレングリコール(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート等のエーテル結合およびエステル結合を有する(メタ)アクリル酸誘導体等のラジカル重合性化合物を例示することができ、好ましくは、2−メトキシエチル(メタ)アクリレート、2−エトキシエチル(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレートである。これらの化合物は単独もしくは2種以上組み合わせて使用できる。
【0039】
さらに、(B)成分には、物理的、化学的特性を適度にコントロールする目的で他の重合性化合物をモノマーとして含むことができる。ここで「他の重合性化合物」とは、前出の(b1)単位および(b2)単位以外の重合性化合物の意味である。この様な重合性化合物としては、公知のラジカル重合性化合物や、アニオン重合性化合物が挙げられる。例えば、アクリル酸、メタクリル酸、クロトン酸などのモノカルボン酸、マレイン酸、フマル酸、イタコン酸などのジカルボン酸、2−メタクリロイルオキシエチルコハク酸、2−メタクリロイルオキシエチルマレイン酸、2−メタクリロイルオキシエチルフタル酸、2−メタクリロイルオキシエチルヘキサヒドロフタル酸などのカルボキシル基およびエステル結合を有するメタクリル酸誘導体等のラジカル重合性化合物;メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレートなどの(メタ)アクリル酸アルキルエステル類;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレートなどの(メタ)アクリル酸ヒドロキシアルキルエステル類;フェニル(メタ)アクリレート、ベンジル(メタ)アクリレートなどの(メタ)アクリル酸アリールエステル類;マレイン酸ジエチル、フマル酸ジブチルなどのジカルボン酸ジエステル類;スチレン、α−メチルスチレン、クロロスチレン、クロロメチルスチレン、ビニルトルエン、ヒドロキシスチレン、α−メチルヒドロキシスチレン、α−エチルヒドロキシスチレンなどのビニル基含有芳香族化合物;酢酸ビニルなどのビニル基含有脂肪族化合物;ブタジエン、イソプレンなどの共役ジオレフィン類;アクリロニトリル、メタクリロニトリルなどのニトリル基含有重合性化合物;塩化ビニル、塩化ビニリデンなどの塩素含有重合性化合物;アクリルアミド、メタクリルアミドなどのアミド結合含有重合性化合物を挙げることができる。
【0040】
(B)成分中における(b1)単位の含有量は、10〜90質量%が好ましく、さらに好ましくは20〜80質量%がよい。90質量%を超えると、感度が低下する傾向があり、10質量%未満では残膜率が低下する傾向がある。
【0041】
(B)成分中における(b2)単位の含有量は、10〜90質量%が好ましく、さらに好ましくは20〜80質量%がよい。90質量%を超えると、残膜率が低下する傾向があり、10質量%未満では現像時の基板との密着性、耐メッキ液性が悪化する傾向がある。
【0042】
また、(B)成分のポリスチレン換算質量平均分子量(以下、質量平均分子量という。)は、好ましくは500,000以下、より好ましくは400,000以下である。質量平均分子量が500,000を超えると剥離性が低下する。また、前記(B)成分の質量平均分子量は、10,000以上であることが好ましく、より好ましくは30,000以上である。質量平均分子量が10,000より小さいとレジスト膜が十分な強度を得られず、メッキ時のプロファイルの膨れ、クラックの発生を引き起こすおそれがある。
(B)成分は、上記(b1)単位を有するため、露光前後のアルカリに対する溶解変化(コントラスト)が高い。
【0043】
(C)アルカリ可溶性樹脂:
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物には、物理的、化学的特性を適度にコントロールするために、さらに、(C)アルカリ可溶性樹脂(以下、(C)成分という。)を含有させることが好ましい。この(C)成分としては、従来化学増幅型レジストにおけるアルカリ可溶性樹脂として公知のものの中から任意のものを適宜選択して用いることができる。これらのうち、特に、(c1)ノボラック樹脂、(c2)ヒドロキシスチレン構成単位とスチレン構成単位とを有する共重合体、及び(c3)アクリル樹脂から選ばれる1種以上の樹脂を含有することが好ましく、さらに、(c1)ノボラック樹脂及び/または(c2)ヒドロキシスチレン構成単位とスチレン構成単位とを有する共重合体を含有することが好ましい。これは、塗布性、現像速度を制御することが容易であるからである。
【0044】
(c1)ノボラック樹脂:
(c1)成分であるノボラック樹脂は、例えばフェノール性水酸基を持つ芳香族化合物(以下、単に「フェノール類」という。)とアルデヒド類とを酸触媒下で付加縮合させることにより得られる。
この際、使用されるフェノール類としては、例えばフェノール、o−クレゾール、m−クレゾール、p−クレゾール、o−エチルフェノール、m−エチルフェノール、p−エチルフェノール、o−ブチルフェノール、m−ブチルフェノール、p−ブチルフェノール、2,3−キシレノール、2,4−キシレノール、2,5−キシレノール、2,6−キシレノール、3,4−キシレノール、3,5−キシレノール、2,3,5−トリメチルフェノール、3,4,5−トリメチルフェノール、p−フェニルフェノール、レゾルシノール、ヒドロキノン、ヒドロキノンモノメチルエーテル、ピロガロール、フロログリシノール、ヒドロキシジフェニル、ビスフェノールA、没食子酸、没食子酸エステル、α−ナフトール、β−ナフトール等が挙げられる。
またアルデヒド類としては、例えばホルムアルデヒド、フルフラール、ベンズアルデヒド、ニトロベンズアルデヒド、アセトアルデヒド等が挙げられる。
【0045】
付加縮合反応時の触媒は、特に限定されるものではないが、例えば酸触媒では、塩酸、硝酸、硫酸、蟻酸、蓚酸、酢酸等が使用される。
特に、フェノール類としてm−クレゾールのみを用いたノボラック樹脂は、現像プロファイルが特に良好であり好ましい。
【0046】
(c2)ヒドロキシスチレン構成単位とスチレン構成単位とを有する共重合体:本発明に用いられる(c2)成分は、少なくともヒドロキシスチレン構成単位とスチレン構成単位とを有する共重合体である。すなわち、ヒドロキシスチレン構成単位とスチレン構成単位とからなる共重合体や、ヒドロキシスチレン構成単位及びスチレン構成単位とそれら以外の構成単位とからなる共重合体である。
【0047】
ヒドロキシスチレン構成単位としては、例えば、p−ヒドロキシスチレン等のヒドロキシスチレン、α−メチルヒドロキシスチレン、α−エチルヒドロキシスチレン等のα−アルキルヒドロキシスチレン等のヒドロキシスチレン構成単位が挙げられる。
スチレン構成単位としては、例えば、スチレン、クロロスチレン、クロロメチルスチレン、ビニルトルエン、α−メチルスチレン等が挙げられる。
【0048】
(c3)アクリル樹脂:
(c3)成分であるアクリル樹脂は、アルカリ可溶性のアクリル樹脂であれば特に限定されないが、特に、エーテル結合を有する重合性化合物から誘導された構成単位、およびカルボキシル基を有する重合性化合物から誘導された構成単位を含有することが好ましい。
エーテル結合を有する重合性化合物としては、2−メトキシエチル(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、3−メトキシブチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、メトキシポリプロピレングリコール(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート等のエーテル結合及びエステル結合を有する(メタ)アクリル酸誘導体等を例示することができ、好ましくは、2−メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレートである。これらの化合物は単独もしくは2種以上組み合わせて使用できる。
【0049】
カルボキシル基を有する重合性化合物としては、アクリル酸、メタクリル酸、クロトン酸などのモノカルボン酸、マレイン酸、フマル酸、イタコン酸などのジカルボン酸、2−メタクリロイルオキシエチルコハク酸、2−メタクリロイルオキシエチルマレイン酸、2−メタクリロイルオキシエチルフタル酸、2−メタクリロイルオキシエチルヘキサヒドロフタル酸などのカルボキシル基及びエステル結合を有する化合物等を例示することができ、好ましくは、アクリル酸、メタクリル酸である。これらの化合物は単独もしくは2種以上組み合わせて使用できる。
【0050】
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物には、上記(A)〜(C)成分に加えて、(c4)ビニル樹脂を含有させてもよい。
(c4)ビニル樹脂:
(c4)成分であるビニル樹脂は、ポリ(ビニル低級アルキルエーテル)であり、下記一般式(6)で表されるビニル低級アルキルエーテルの単独または2種以上の混合物を重合することにより得られる(共)重合体からなる。
【0051】
【化10】
【0052】
(上記一般式(6)において、R8 は炭素数1〜5の直鎖状もしくは分岐状のアルキル基を示す。)
【0053】
一般式(6)において、炭素数1〜5の直鎖状もしくは分岐状のアルキル基としては、例えば、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、n−ペンチル基、i−ペンチル基等を挙げることができる。これらのアルキル基のうち、メチル基、エチル基、i−ブチル基が好ましく、特にメチル基が好ましい。本発明において、特に好ましいポリ(ビニル低級アルキルエーテル)は、ポリ(ビニルメチルエーテル)である。
【0054】
上記(C)成分の配合量は、(B)成分100質量部に対し、0〜300質量部、好ましくは0〜200質量部とされる。300質量部を超えると、パターンを形成するための露光部と未露光部とのコントラストが低下し、膜減りが生じる可能性があるため好ましくない。
【0055】
(D)酸拡散制御剤:
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物には、レジストパターン形状、引き置き安定性等の向上のために、さらに(D)酸拡散制御剤(以下、(D)成分という。)を含有させることが好ましい。
(D)成分としては、従来化学増幅型レジストにおける酸拡散制御剤として公知のものの中から任意のものを適宜選択して用いることができる。特に、(d1)含窒素化合物を含有させることが好ましく、さらに必要に応じて、(d2)有機カルボン酸又はリンのオキソ酸若しくはその誘導体を含有させることができる。
【0056】
(d1)含窒素化合物:
(d1)成分である含窒素化合物としては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ−n−プロピルアミン、トリ−n−プロピルアミン、トリベンジルアミン、ジエタノールアミン、トリエタノールアミン、n−ヘキシルアミン、n−ヘプチルアミン、n−オクチルアミン、n−ノニルアミン、エチレンジアミン、N,N,N’,N’−テトラメチルエチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノベンゾフェノン、4,4’−ジアミノジフェニルアミン、ホルムアミド、N−メチルホルムアミド、N,N−ジメチルホルムアミド、アセトアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、プロピオンアミド、ベンズアミド、ピロリドン、N−メチルピロリドン、メチルウレア、1,1−ジメチルウレア、1,3−ジメチルウレア、1,1,3,3−テトラメチルウレア、1,3−ジフェニルウレア、イミダゾール、ベンズイミダゾール、4−メチルイミダゾール、8−オキシキノリン、アクリジン、プリン、ピロリジン、ピペリジン、2,4,6−トリ(2−ピリジル)−S−トリアジン、モルホリン、4−メチルモルホリン、ピペラジン、1,4−ジメチルピペラジン、1,4−ジアザビシクロ[2.2.2]オクタン等を挙げることができる。
これらのうち、特にトリエタノールアミンのようなアルカノールアミンが好ましい。
これらは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
(d1)成分は(B)成分を100質量%とした場合、通常0〜5質量%の範囲で用いられ、特に0〜3質量%の範囲で用いられることが好ましい。
【0057】
(d2)有機カルボン酸又はリンのオキソ酸若しくはその誘導体:
有機カルボン酸としては、例えば、マロン酸、クエン酸、リンゴ酸、コハク酸、安息香酸、サリチル酸などが好適であり、特にサリチル酸が好ましい。
リンのオキソ酸若しくはその誘導体としては、リン酸、リン酸ジ‐n‐ブチルエステル、リン酸ジフェニルエステルなどのリン酸又はそれらのエステルのような誘導体、ホスホン酸、ホスホン酸ジメチルエステル、ホスホン酸‐ジ‐n‐ブチルエステル、フェニルホスホン酸、ホスホン酸ジフェニルエステル、ホスホン酸ジベンジルエステルなどのホスホン酸及びそれらのエステルのような誘導体、ホスフィン酸、フェニルホスフィン酸などのホスフィン酸及びそれらのエステルのような誘導体が挙げられ、これらの中で特にホスホン酸が好ましい。
これらは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
(d2)成分は、(B)成分を100質量%とした場合、通常0〜5質量%の範囲で用いられ、特に0〜3質量%の範囲で用いられることが好ましい。
また、(d2)成分は、(d1)成分に対して同量用いられることが好ましい。これは、(d2)成分と(d1)成分とが塩を形成して安定化するためである。
【0058】
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物には、本質的な特性を損なわない範囲で、さらに所望により混和性のある添加物、例えばレジスト膜の性能を改良するための付加的樹脂、可塑剤、接着助剤、安定剤、着色剤、界面活性剤などの慣用されているものを添加含有させることができる。
【0059】
さらに、本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物は、粘度調整のため有機溶剤を適宜配合することができる。前記有機溶剤としては具体的には、アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソアミルケトン、2−ヘプタノンなどのケトン類;エチレングリコール、エチレングリコールモノアセテート、ジエチレングリコール、ジエチレングリコールモノアセテート、プロピレングリコール、プロピレングリコールモノアセテート、ジプロピレングリコール又はジプロピレングリコールモノアセテートのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテル又はモノフェニルエーテルなどの多価アルコール類及びその誘導体;ジオキサンのような環式エーテル類;及び乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチルなどのエステル類を挙げることができる。これらは単独で用いてもよいし、2種以上を混合して用いてもよい。
【0060】
例えばスピンコート法を用いて、好ましくは10μm以上の膜厚を得るためには、これらの溶剤の使用量は、厚膜用化学増幅型ポジ型ホトレジスト組成物における固形分濃度が30質量%から65質量%になる範囲とすることが好ましい。固形分濃度が30質量%未満の場合は、接続端子の製造に好適な厚膜を得ることが困難であり、65質量%を超えると組成物の流動性が著しく悪化し、取り扱いが困難な上、スピンコート法では、均一なレジストフィルムが得られにくい。
【0061】
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物の調製は、例えば、上記各成分を通常の方法で混合、攪拌するだけでよく、必要に応じディゾルバー、ホモジナイザー、3本ロールミルなどの分散機を用い分散、混合させてもよい。また、混合した後で、さらにメッシュ、メンブレンフィルターなどを用いてろ過してもよい。
【0062】
本発明の厚膜用化学増幅型ポジ型ホトレジスト組成物は、支持体上に、10〜150μm、より好ましくは20〜120μm、さらに好ましくは20〜80μmの膜厚の厚膜ホトレジスト層を形成するのに適している。
【0063】
次に、本発明の厚膜ホトレジスト積層体は、支持体上に前記厚膜用化学増幅型ポジ型ホトレジスト組成物からなる厚膜ホトレジスト層が積層されているものである。
支持体としては、特に限定されず、従来公知のものを用いることができ、例えば、電子部品用の基板や、これに所定の配線パターンが形成されたものなどを例示することができる。該基板としては、例えば、シリコン、窒化シリコン、チタン、タンタル、パラジウム、チタンタングステン、銅、クロム、鉄、アルミニウムなどの金属製の基板やガラス基板などが挙げられる。配線パターンの材料としては、例えば銅、ハンダ、クロム、アルミニウム、ニッケル、金などが用いられる。
【0064】
上記のような厚膜ホトレジスト積層体は、例えば以下のようにして製造することができる。
すなわち、上述したように調製した厚膜用化学増幅型ポジ型ホトレジスト組成物の溶液を支持体上に塗布し、加熱により溶媒を除去することによって所望の塗膜を形成する。被処理支持体上への塗布方法としては、スピンコート法、スリットコート法、ロールコート法、スクリーン印刷法、アプリケーター法などの方法を採用することができる。本発明の組成物の塗膜のプレベーク条件は、組成物中の各成分の種類、配合割合、塗布膜厚などによって異なるが、通常は70〜150℃で、好ましくは80〜140℃で、2〜60分間程度である。
【0065】
本発明の厚膜ホトレジスト層の膜厚は、10〜150μm、好ましくは20〜120μm、より好ましくは20〜80μmの範囲であることが望ましい。
【0066】
そして、このようにして得られた厚膜ホトレジスト積層体を用いてレジストパターンを形成するには、得られた厚膜ホトレジスト層に、所定のパターンのマスクを介して、活性光線または放射線、例えば波長が300〜500nmの紫外線または可視光線を選択的に照射(露光)する。
ここで活性光線とは、酸を発生するために酸発生剤を活性化させる光線を意味する。放射線の線源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、アルゴンガスレーザーなどを用いることができる。ここで放射線とは、紫外線、可視光線、遠紫外線、X線、電子線、イオン線などを意味する。放射線照射量は、組成物中の各成分の種類、配合量、塗膜の膜厚などによって異なるが、例えば超高圧水銀灯使用の場合、100〜10,000mJ/cm2である。
【0067】
そして、露光後、公知の方法を用いて加熱することにより酸の拡散を促進させて、この露光部分の厚膜ホトレジスト層のアルカリ溶解性を変化させる。
ついで、例えば、所定のアルカリ性水溶液を現像液として用いて、不要な部分を溶解、除去して所定のレジストパターンを得る。現像液としては、例えば水酸化ナトリウム、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、エチルアミン、n−プロピルアミン、ジエチルアミン、ジ−n−プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、1,8−ジアザビシクロ[5,4,0]−7−ウンデセン、1,5−ジアザビシクロ[4,3,0]−5−ノナンなどのアルカリ類の水溶液を使用することができる。また前記アルカリ類の水溶液にメタノール、エタノールなど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現像液として使用することもできる。
現像時間は、組成物各成分の種類、配合割合、組成物の乾燥膜厚によって異なるが、通常1〜30分間であり、また現像の方法は液盛り法、ディッピング法、パドル法、スプレー現像法などのいずれでも良い。現像後は、流水洗浄を30〜90秒間行い、エアーガンや、オーブンなどを用いて乾燥させる。
【0068】
そして、このようにして得られたレジストパターンの非レジスト部(アルカリ現像液で除去された部分)に、例えばメッキなどによって金属などの導体を埋め込むことにより、メタルポストやバンプ等の接続端子を形成することができる。なお、メッキ処理方法はとくに制限されず、従来から公知の各種方法を採用することができる。メッキ液としては、とくにハンダメッキ、銅メッキ、金メッキ、ニッケルメッキ液が好適に用いられる。
残っているレジストパターンは、最後に、定法に従って、剥離液等を用いて除去する。
【0069】
【実施例】
以下本発明の実施例を説明するが、本発明の範囲はこれらの実施例に限定されるものではない。
[合成例1]
<(B)酸の作用によりアルカリに対する溶解性が増大する樹脂(B−1)〜(B−5)の合成>
攪拌装置、還流器、温度計、滴下槽のついたフラスコを窒素置換した後、溶媒としてプロピレングリコールメチルエーテルアセテートを仕込み、攪拌を始めた。その後、溶剤の温度を80℃まで上昇させた。滴下槽に重合触媒として2,2’−アゾビスイソブチロニトリル、(b1)として1−エチルシクロヘキシルメタクリレート構成単位50質量%、および(b2)として2−エトキシエチルアクリレート構成単位50質量%を仕込み、重合触媒が溶解するまで攪拌した後、この溶液をフラスコ内に3時間均一滴下し、引き続き80℃で5時間重合を行った。その後、室温まで冷却し、(B)成分となる樹脂を得た。
この樹脂に対して分別処理を施し、以下のように質量平均分子量の異なる6種類の樹脂(B−1)〜(B−5)を得た。
(B−1):質量平均分子量50,000
(B−2):質量平均分子量150,000
(B−3):質量平均分子量250,000
(B−4):質量平均分子量350,000
(B−5):質量平均分子量500,000
【0070】
[合成例2]
<(B−6)酸の作用によりアルカリに対する溶解性が増大する樹脂の合成>
(b1)として1−エチルシクロヘキシルメタクリレート構成単位20質量%、および(b2)として2−エトキシエチルアクリレート構成単位80質量%とを用いたほかは、合成例1と同様にして質量平均分子量350,000の樹脂(B−6)を得た。
[合成例3]
<(B−7)酸の作用によりアルカリに対する溶解性が増大する樹脂の合成>
(b1)として1−エチルシクロヘキシルメタクリレート構成単位80質量%、および(b2)として2−エトキシエチルアクリレート構成単位20質量%とを用いたほかは、合成例1と同様にして質量平均分子量350,000の樹脂(B−7)を得た。
【0071】
[合成例4]
<(c1)ノボラック樹脂の合成>
m−クレゾールとp−クレゾールとを質量比60:40の割合で混合し、これにホルマリンを加え、シュウ酸触媒を用いて常法により縮合してクレゾールノボラック樹脂を得た。この樹脂に対して分別処理を施し、低分子領域をカットして質量平均分子量15,000のノボラック樹脂を得た。この樹脂を(C−1)とする。
[合成例5]
<(c2)ヒドロキシスチレン構成単位とスチレン構成単位とを有する共重合体の合成>
構成単位として、ヒドロキシスチレン単位75質量%とスチレン単位25質量%とを用いたほかは、合成例1と同様にして、質量平均分子量3,000の樹脂(C−2)を得た。
【0072】
[合成例6]
<(c3)アクリル樹脂の合成>
構成単位として、2−メトキシエチルアクリレート130質量部、ベンジルメタクリレート50質量部、およびアクリル酸20質量部を用いたほかは、合成例1と同様にして、質量平均分子量250,000の樹脂(C−3)を得た。
[合成例7]
<(c4)ビニル樹脂の合成>
ポリ(ビニルメチルエーテル)(質量平均分子量50,000)のメタノール溶液(東京化成工業(株)製、濃度50質量%)をロータリーエバポレーターを用いてプロピレングリコールモノメチルエーテルアセテートに溶媒置換して、濃度50質量%の溶液として(C−4)を得た。
【0073】
[実施例1〜13]
<厚膜用化学増幅型ポジ型ホトレジスト組成物の調製>
表1に示す各成分をプロピレングリコールモノメチルエーテルアセテートに混合して均一溶液とした後、孔径1μmのメンブレンフィルターをとおして濾過し、厚膜用化学増幅型ポジ型ホトレジスト組成物を得た。ただし、実施例1、5は参考例である。
(A)成分である酸発生剤としては、以下の2種類を用いた。
(A−1):(5−プロピルスルホニルオキシイミノ−5H−チオフェン−2−イリデン)−(2−メチルフェニル)アセトニトリル
(A−2):下記[化11]で表される化合物
【0074】
【化11】
【0075】
また、表1において、(D−1)はサリチル酸を表し、(D−2)はトリエタノールアミンを表す。なお、表1中の数値は各成分の質量部を表わす。
【0076】
【表1】
【0077】
[比較例1]
<厚膜用化学増幅型ポジ型ホトレジスト組成物の調整>
(A)酸発生剤:上記[化11]で表される化合物 ;3質量部
(B)成分:ヒドロキシスチレン単位67モル%とスチレン単位22モル%と1−エチルシクロヘキシルメタクリレート単位11モル%とからなる質量平均分子量8,000の共重合体67質量部と、ヒドロキシスチレン単位67モル%とスチレン単位29モル%と、1−エチルシクロヘキシルメタクリレート4モル%とからなる共重合体33質量部との混合樹脂 ;100質量部
(d1)トリエタノールアミン ;0.1質量部
(d2)フェニルホスホン酸 ;0.1部
上記各成分を、乳酸エチル300質量部に溶解し、さらにフッ素系界面活性剤[商品名「Fluorad FC−171」(スリーエム社製)]を全量に対して1.0質量%添加したのち、孔径0.2μmのメンブレンフィルターをとおしてろ過し、ポジ型レジスト組成物を得た。
【0078】
[試験例1]
上記実施例で製造したポジ型の化学増幅型ホトレジスト組成物を用いて下記に示す特性評価を行った。
・相溶性
各組成物をそれぞれ室温にて12時間混合、攪拌し、攪拌直後および攪拌後12時間経過後の溶解状態を目視にて観察した。分散状態を下記の評価基準で判定した。
○:12時間攪拌後に組成物が、均一に分散することが目視で確認された。
△:12時間攪拌後に組成物が、均一に分散するが長時間静置により相分離した。
×:12時間攪拌後に組成物が、均一に分散していない。
【0079】
・塗布性
5インチの金スパッタリングウエーハ(金基板)上にスピンナーを用いて、各組成物を1000rpmにて25秒間塗布した後、110℃で6分間ホットプレート上で加熱した。形成された塗膜を目視で観察し、塗布性を下記の評価基準で判定した。
〇:得られた塗膜にムラがなく均一である。
△:得られた塗膜の平坦性が悪く、均一でない。
×:得られた塗膜にピンホールやはじき等のムラがある。
【0080】
・現像・解像性
5インチの金スパッタリングウェーハ上にスピンナーを用いて、各組成物を、膜厚約20μmとなるように、1800rpmにて25秒間塗布後、110℃で6分間ホットプレート上でプレベークして厚膜ホトレジスト積層体を形成した。膜厚約65μmの塗膜の場合、800rpmにて25秒間塗布後、110℃で1分間ホットプレート上でプレベークし、さらに800rpmにて25秒間塗布後、110℃で12分間プレベークして厚膜ホトレジスト積層体を形成した。
また、膜厚約120μmの塗膜の場合、800rpmにて25秒間塗布後、110℃で1分間ホットプレート上でプレベークし、さらに500rpmにて25秒間塗布後、110℃で1分間ホットプレート上でプレベークし、さらに500rpmにて25秒間塗布後、110℃で20分間プレベークして厚膜ホトレジスト積層体を形成した。
上記で得られた厚膜ホトレジスト積層体を、ステッパー(Nikon社製、NSR-2005i10D)を用いて解像度測定用のパターンマスクを介して、それぞれを100〜10,000mJ/cm2の範囲で段階的に紫外線露光を行った。露光後、70℃で5分間加熱し、これを、現像液(商品名PMERシリーズ、P−7G、東京応化工業社製)で現像した。
この後、流水洗浄し、窒素ブローしてパターン状硬化物を得た。これを顕微鏡で観察し、現像・解像性を下記の評価基準で判定した。
○:アスペクト比が2以上のパターンが前記いずれかの露光量で形成し、残渣が認められない場合。
×:アスペクト比が2未満のパターンが形成していない、または、残渣が認められた場合。
なお、アスペクト比は、(パターン上のレジスト高さ÷パターン上のレジスト幅)を示す。
【0081】
・耐メッキ液性
「現像・解像性評価」で得られたパターン状硬化物を有する基板を試験体として、酸素プラズマでアッシング処理後、亜硫酸金メッキ液に65℃で40分間浸漬し、流水洗浄し、被処理試験体を得た。光学顕微鏡または電子顕微鏡を用いて、被処理試験体上に形成されたバンプとパターン状硬化物の状態を観察し、パターン状硬化物のメッキ液に対する耐性、形成されたパンプの形状、パターン状硬化物のメッキ処理工程に対する耐性を下記の評価基準で判定した。
〇:形成されたバンプとパターン状硬化物の状態に特に変化が無く良好
×:パターン状硬化物にクラックや膨らみや欠けが生じる、またはパターン状硬化物の表面が荒れている。
【0082】
・バンプ形状
「耐メッキ性評価」と同様の操作で被処理試験体を得、形成されたバンプとパターン状硬化物の状態を光学顕微鏡または電子顕微鏡を用いて観察し、形成されたバンプの形状を下記の評価基準で判定した。また、バンプ形状が良好である場合には、基板とバンプの角度とマスク寸法に対する誤差比率を測定した。
○:バンプの形状がパターン状硬化物に依存(追随)し、良好。
×:パンプの形状がパターン状硬化物に依存せず、膨らみが生じている。
【0083】
・剥離性
「現像・解像性評価」で得られたパターン状硬化物を有する基板を試験体として、70℃にて攪拌中の剥離液(東京応化工業社製ストリッパー104)に10分間浸漬した後、アルコールでリンス液洗浄してパターン状硬化物を剥離し、目視観察あるいは光学顕微鏡で観察し下記の基準で評価した。
〇:パターン状硬化物の残渣が認められない。
×:パターン状硬化物の残渣が認められた。
【0084】
・感光性
5インチのシリコンウエーハ上、各種膜厚の塗膜を形成し、解像度測定用のパターンマスクを介して、ステッパー(Nikon社製、NSR-2005i10D)を用いて100〜10,000mJ/cm2の範囲で分割露光した。これを、現像液(商品名PMERシリーズ、P−7G、東京応化工業社製)で現像した。この後、流水洗浄し、窒素ブローしてパターン状硬化物を得た。これを顕微鏡で観察し、アスペクト比2以上のパターンを形成し、残渣が認められなくなる露光量、すなわちパターンを形成するのに必要な最低限の露光量を測定した。
【0085】
実施例1〜13、および比較例1で調製したポジ型ホトレジスト組成物について、上記の各試験を行い評価した。結果を表2に示す。
【0086】
【表2】
【0087】
【発明の効果】
以上説明したように、本発明によれば、メッキによる生成物の形状が良好で耐メッキ性に優れ、かつ高コントラストであって、接続端子等製造に好適な厚膜用化学増幅型ポジ型ホトレジスト組成物、厚膜ホトレジスト積層体、これを用いた厚膜レジストパターンの製造方法及び接続端子の製造方法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thick film positive chemically amplified photoresist composition, a thick film photoresist laminate, a method for producing a thick film resist pattern, and a method for producing a connection terminal. More specifically, the present invention is suitable for forming connection terminals such as bumps and metal posts, wiring patterns, etc. in the manufacture of circuit boards and electronic parts such as CSPs (chip size packages) mounted on the circuit boards. The present invention relates to a thick film chemically amplified positive photoresist composition, a thick film photoresist laminate, a thick film resist pattern manufacturing method, and a connection terminal manufacturing method.
[0002]
[Prior art]
Photofabrication, which is currently the mainstream of precision microfabrication technology, is the application of a photosensitive resin composition to the surface of a workpiece to form a coating film, which is then patterned by photolithography technology and masked. Is a general term for technologies for manufacturing various precision parts such as semiconductor packages by performing chemical forming, electrolytic etching and / or electroforming mainly composed of electroplating.
In recent years, with the downsizing of electronic equipment, high-density packaging technology for semiconductor packages has progressed. Based on multi-pin thin film packaging of packages, miniaturization of package size, flip-chip two-dimensional packaging technology, and three-dimensional packaging technology. The packaging density is improved. In such a high-density mounting technique, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts that connect the rewirings extending from the peripheral terminals on the wafer and the mounting terminals. Are arranged with high accuracy on the substrate.
[0003]
There is a thick film photoresist as a material used for the above photofabrication. The thick film photoresist forms a thick film photoresist layer, and is used, for example, for forming bumps and metal posts by a plating process. For bumps and metal posts, for example, a thick photoresist layer with a film thickness of about 20 μm is formed on a support, exposed through a predetermined mask pattern, developed, and a portion where bumps and metal posts are formed is selective. The resist pattern removed (peeled) is formed, and a conductor such as copper is embedded in the removed portion (non-resist portion) by plating, and then the resist pattern around the resist pattern is removed. .
As the photoresist for thick film, a positive photosensitive resin composition having a quinonediazide group-containing compound used for forming a pump or wiring is disclosed (for example, see Patent Document 1).
[0004]
On the other hand, a chemically amplified photoresist containing an acid generator is known as a photosensitive resin composition having higher sensitivity than a conventional positive photosensitive resin composition having a quinonediazide group-containing compound. The feature of chemically amplified photoresist is that acid is generated from the acid generator by radiation irradiation (exposure), and acid diffusion is promoted by heat treatment after exposure, and it is an acid catalyst for the base resin in the resin composition. It is to cause a reaction and change its alkali solubility.
The chemically amplified resist includes a positive type in which an alkali-insoluble one becomes alkali-soluble by irradiation and a negative type in which an alkali-soluble one becomes alkali-insoluble.
[0005]
The required items for the photoresist composition for thick film as described above include that a film thickness of 10 μm or more can be formed, adhesion to the substrate, and resistance to plating solution when performing plating for forming bumps. It has good wettability with respect to the plating solution, the metal composition obtained by plating corresponds to the shape of the resist pattern, and is easily peeled off by the peeling solution after the plating treatment. In addition, with the advancement of plating technology, multiple plating processes and plating processes under more severe conditions are required, and resistance to the plating process itself that can withstand multiple plating processes is also required. .
[0006]
As a photoresist composition for thick film, for example, a positive type chemically amplified photoresist composition for plating is disclosed (for example, refer to Patent Document 2).
In addition, in order to obtain a good resist pattern with a good cross-sectional shape, a chemical amplification type for KrF excimer laser aimed at improving resolution and depth of focus by increasing solubility change (contrast) in alkali before and after exposure. A photoresist composition is disclosed (for example, see Patent Document 3).
[0007]
[Patent Document 1]
JP 2002-258479 A
[Patent Document 2]
JP 2001-281862 A
[Patent Document 3]
JP 2000-347405 A
[0008]
[Problems to be solved by the invention]
However, when a thick film resist layer is formed using the conventional chemically amplified resist composition described in Patent Documents 2 and 3, the stress resistance to plating of the photoresist composition is not sufficient, so that it can be obtained by plating. The resulting metal layer swelled, and it was difficult to obtain a good plating product pattern. In addition, the plating solution resistance is not sufficient, and the resist during the plating process and during the cleaning process after the plating process is chipped and cracked, making it difficult to perform multiple plating processes with the same resist pattern (plating resistance Inferior.)
Moreover, in the photosensitive resin composition which has the naphthoquinone diazide group containing compound excellent in the plating resistance described in Patent Document 1, it was difficult to achieve higher sensitivity.
[0009]
The present invention has been made in view of the problems of the prior art, the product shape by plating is good, the stress resistance, the plating solution resistance, the plating resistance are excellent, and the sensitivity is high. PROBLEM TO BE SOLVED: To provide a chemically amplified positive photoresist composition for thick film suitable for manufacturing connection terminals, a thick film photoresist laminate, a method for manufacturing a thick film resist pattern using the same, and a method for manufacturing a connection terminal And
[0010]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have identified a specific resin as a resin whose solubility in an alkali is increased by the action of an acid in a chemically amplified positive photoresist composition for a positive thick film. The present inventors have found that the above problems can be solved by using a resin having a structural unit, and have completed the present invention.
[0011]
That is, the first invention of the present invention is a thick film chemically amplified positive photoresist composition used for forming a thick film photoresist layer having a film thickness of 10 to 150 μm on a support. ) Compounds that generate acid upon irradiation with actinic rays or radiationWhen,(B) Resin whose solubility in alkali is increased by the action of acidAnd (C) an alkali-soluble resinContaining
The component (B) is (b1) the following general formula (1):
[0012]
[Chemical formula 2]
[0013]
(Wherein R1Is a hydrogen atom or a methyl group, R2Is1 to 5 carbon atomsRepresents a lower alkyl group. )
The unit represented byAnd (b2) a structural unit derived from a polymerizable compound having an ether bondIncludingAnd having a mass average molecular weight of 10,000 to 500,000A thick film chemically amplified positive photoresist composition comprising a resin comprising a copolymer.
[0014]
According to a second aspect of the present invention, there is provided a thick film photoresist laminate comprising a support and a thick film photoresist layer made of the thick film chemically amplified positive photoresist composition.
[0015]
According to a third aspect of the present invention, there is provided a laminating step for obtaining the thick film photoresist laminate, an exposure step for selectively irradiating the thick film photoresist laminate with an actinic ray or radiation, and developing and thickening after the exposing step. And a developing step for obtaining a film resist pattern.
[0016]
According to a fourth aspect of the present invention, there is provided a connection terminal comprising a step of forming a connection terminal made of a conductor in a non-resist portion of a thick film resist pattern obtained by using the method for manufacturing a thick film resist pattern. It is a manufacturing method.
[0017]
The “structural unit” refers to a monomer unit constituting the polymer. Moreover, (meth) acrylic acid shows one or both of methacrylic acid and acrylic acid.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
(A) Compound that generates acid upon irradiation with actinic rays or radiation:
The compound (A) that generates acid upon irradiation with actinic rays or radiation used in the present invention (hereinafter referred to as component (A)) is an acid generator, and is a compound that generates acid directly or indirectly by light. If there is no particular limitation.
Specifically, 2,4-trichloromethyl-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl] -s-triazine 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5- Ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethenyl] -S-triazine, 2 4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5) -Ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s- Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4me Xyl) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo- 4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-Methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4,6- Screw( Trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3 , 4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3 Halogen-containing triazine compounds such as -dibromopropyl) -1,3,5-triazine and halogen-containing triazine compounds represented by the following general formula (2) such as tris (2,3-dibromopropyl) isocyanurate;
[0019]
[Chemical 3]
[0020]
(Wherein R3~ R5Each may be the same or different and represents a halogenated alkyl group)
[0021]
α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2 -Chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, a compound represented by the following general formula (3);
[0022]
[Formula 4]
[0023]
(Wherein R6Is a monovalent to trivalent organic group, R7Represents a substituted, unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic compound group, and n represents a natural number of 1 to 3. Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, a thienyl group. And heterocyclic groups such as These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. R7Is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Especially R6Is an aromatic compound group, R7Is preferably a compound having a lower alkyl group. As the acid generator represented by the above general formula, when n = 1, R6Is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R7Is a methyl group, specifically α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) ) -1- (p-methoxyphenyl) acetonitrile. When n = 2, the acid generator represented by the above general formula includes specifically an acid generator represented by the following chemical formula. )
[0024]
[Chemical formula 5]
[0025]
Bissulfonyldiazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfone Nitrobenzyl derivatives such as acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate; pyrogallol trimesylate , Pyrgallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinate Sulfonic acid esters such as imide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxy Phenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) Onium salts such as diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate, α -Benzoin tosylate such as methylbenzoin tosylate; and other diphenyl iodonium salts, triphenyl sulfonium salts, phenyl diazonium salts, benzyl carbonates and the like.
[0026]
Among these, as the component (A), the general formula (4):
R-SO2ON = C (CN)-(4)
(Wherein R is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an aryl group)
A compound having at least two oxime sulfonate groups represented by general formula (5):
R-SO2ON-C = CN (CN) -AC (CN) = N-OSO2-R (5) (wherein A is a divalent, for example, substituted or unsubstituted alkylene group having 1 to 8 carbon atoms or an aromatic compound group, and R is a substituted or unsubstituted, for example, 1 carbon atom) -8 alkyl group or aryl group)
The compound represented by these is preferable. Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, a thienyl group. And heterocyclic groups such as These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. Further, in the above general formula, it is more preferable that A is a phenylene group and R is a lower alkyl group having 1 to 4 carbon atoms, for example.
[0027]
This (A) component may be used independently and may be used in combination of 2 or more type.
Moreover, the compounding quantity of (A) component shall be 0.1-10 mass parts with respect to 100 mass parts of (B) component, Preferably it is 0.2-5 mass parts. By setting it to 0.1 parts by mass or more, sufficient sensitivity can be obtained, and by setting it to 10 parts by mass or less, the solubility in a solvent is good, a uniform solution is obtained, and the storage stability tends to be improved. There is.
[0028]
(B) Resin whose solubility in alkali is increased by the action of acid:
The resin (hereinafter referred to as “component (B)”) whose solubility in alkali is increased by the action of acid (B) used in the chemically amplified positive photoresist composition for thick film of the present invention is represented by the following general formula (b1): (1):
[0029]
[Chemical 6]
[0030]
(Wherein R1Is a hydrogen atom or a methyl group, R2Represents a lower alkyl group. ) (Hereinafter, referred to as a unit (b1)).
[0031]
(B1) Unit:
The unit (b1) is a structural unit represented by the general formula (1).
In the general formula (1), R1Is a hydrogen atom or a methyl group.
R2The lower alkyl group represented by may be either linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -Butyl group, tert-butyl group, various pentyl groups, etc., among these, lower alkyl groups having 2 to 4 carbon atoms are preferable from the viewpoint of high contrast, good resolution, depth of focus, etc. It is.
[0032]
Preferred examples of the structural unit represented by the general formula (1) include the following.
[0033]
[Chemical 7]
[0034]
[Chemical 8]
[0035]
[Chemical 9]
[0036]
As the unit (b1), one type of structural units represented by the general formula (1) may be used, but two or more types of structural units having different structures may be used.
[0037]
Furthermore, the component (B) is preferably a resin composed of a copolymer including the structural unit (b1) and a structural unit derived from the polymerizable compound (b2) having an ether bond. By including the component (b2), adhesion to the substrate during development and plating solution resistance are improved.
[0038]
(B2) Unit:
The unit (b2) is a structural unit derived from a polymerizable compound having an ether bond.
Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol ( Illustrative radical polymerizable compounds such as (meth) acrylic acid derivatives having ether bonds and ester bonds such as (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Preferably, it is 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These compounds can be used alone or in combination of two or more.
[0039]
Furthermore, the component (B) can contain other polymerizable compounds as monomers for the purpose of appropriately controlling physical and chemical properties. Here, the “other polymerizable compound” means a polymerizable compound other than the above-mentioned (b1) unit and (b2) unit. Examples of such polymerizable compounds include known radically polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid and 2-methacryloyloxyethyl Radical polymerizable compounds such as methacrylic acid derivatives having carboxyl groups and ester bonds such as phthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylic (Meth) acrylic acid aryl esters such as benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, Vinyl group-containing aromatic compounds such as hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile, methacrylonitrile, etc. And nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.
[0040]
The content of the unit (b1) in the component (B) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass. If it exceeds 90% by mass, the sensitivity tends to decrease, and if it is less than 10% by mass, the residual film ratio tends to decrease.
[0041]
(B) As for content of the (b2) unit in a component, 10-90 mass% is preferable, More preferably, 20-80 mass% is good. If it exceeds 90% by mass, the residual film ratio tends to decrease, and if it is less than 10% by mass, the adhesion to the substrate during development and the plating solution resistance tend to deteriorate.
[0042]
Moreover, the polystyrene conversion mass average molecular weight (hereinafter referred to as mass average molecular weight) of the component (B) is preferably 500,000 or less, more preferably 400,000 or less. When the mass average molecular weight exceeds 500,000, the peelability decreases. The mass average molecular weight of the component (B) is preferably 10,000 or more, and more preferably 30,000 or more. If the mass average molecular weight is less than 10,000, the resist film cannot obtain sufficient strength, and there is a possibility that profile swelling and cracking may occur during plating.
Since the component (B) has the unit (b1), the dissolution change (contrast) with respect to alkali before and after exposure is high.
[0043]
(C) Alkali-soluble resin:
In the chemically amplified positive photoresist composition for thick film of the present invention, (C) an alkali-soluble resin (hereinafter referred to as “component (C)”) is further added in order to appropriately control physical and chemical characteristics. It is preferable to contain. As the component (C), an arbitrary one can be appropriately selected from known alkali-soluble resins in conventional chemically amplified resists. Among these, in particular, (c1) a novolak resin, (c2) a copolymer having a hydroxystyrene structural unit and a styrene structural unit,as well as(C3) Acrylic resinFromIt is preferable to contain one or more selected resins, and it is further preferable to contain a copolymer having (c1) a novolak resin and / or (c2) a hydroxystyrene structural unit and a styrene structural unit. This is because it is easy to control the coating property and the development speed.
[0044]
(C1) Novolac resin:
The novolak resin as component (c1) can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst.
In this case, examples of phenols used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p -Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phlorogricinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. The
Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.
[0045]
The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.
In particular, a novolak resin using only m-cresol as a phenol is preferable because the development profile is particularly good.
[0046]
(C2) Copolymer having a hydroxystyrene structural unit and a styrene structural unit: The component (c2) used in the present invention is a copolymer having at least a hydroxystyrene structural unit and a styrene structural unit. That is, a copolymer comprising a hydroxystyrene constituent unit and a styrene constituent unit, or a copolymer comprising a hydroxystyrene constituent unit, a styrene constituent unit and other constituent units.
[0047]
Examples of the hydroxystyrene structural unit include hydroxystyrene structural units such as hydroxystyrene such as p-hydroxystyrene, and α-alkylhydroxystyrene such as α-methylhydroxystyrene and α-ethylhydroxystyrene.
Examples of the styrene structural unit include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, and the like.
[0048]
(C3) Acrylic resin:
The acrylic resin as the component (c3) is not particularly limited as long as it is an alkali-soluble acrylic resin. In particular, it is derived from a structural unit derived from a polymerizable compound having an ether bond and a polymerizable compound having a carboxyl group. It is preferable to contain the structural unit.
Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meta ), (Meth) acrylic acid derivatives having an ether bond and an ester bond such as methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc., preferably 2-methoxyethyl acrylate, Methoxytriethylene glycol acrylate. These compounds can be used alone or in combination of two or more.
[0049]
Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl. Examples include maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid and other compounds having a carboxyl group and an ester bond, and acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.
[0050]
The chemically amplified positive photoresist composition for thick film of the present invention may contain (c4) vinyl resin in addition to the components (A) to (C).
(C4) Vinyl resin:
The vinyl resin as the component (c4) is poly (vinyl lower alkyl ether), and can be obtained by polymerizing a vinyl lower alkyl ether represented by the following general formula (6) alone or a mixture of two or more kinds ( Co) polymer.
[0051]
[Chemical Formula 10]
[0052]
(In the above general formula (6), R8 Represents a linear or branched alkyl group having 1 to 5 carbon atoms. )
[0053]
In the general formula (6), examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- A butyl group, n-pentyl group, i-pentyl group, etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, and an i-butyl group are preferable, and a methyl group is particularly preferable. In the present invention, a particularly preferred poly (vinyl lower alkyl ether) is poly (vinyl methyl ether).
[0054]
The blending amount of the component (C) is 0 to 300 parts by mass, preferably 0 to 200 parts by mass with respect to 100 parts by mass of the component (B). If it exceeds 300 parts by mass, the contrast between the exposed part and the unexposed part for forming the pattern is lowered, and there is a possibility that the film may be reduced.
[0055]
(D) Acid diffusion controller:
In the chemically amplified positive photoresist composition for thick film of the present invention, (D) an acid diffusion control agent (hereinafter referred to as “component (D)”) is further added in order to improve the resist pattern shape, the stability of holding and the like. It is preferable to contain.
As the component (D), an arbitrary one can be appropriately selected from known ones as acid diffusion control agents in conventional chemically amplified resists. In particular, (d1) a nitrogen-containing compound is preferably contained, and (d2) an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be further contained as necessary.
[0056]
(D1) Nitrogen-containing compound:
Examples of the nitrogen-containing compound as component (d1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n -Heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-di Tylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, Imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholine, piperazine, 1 , 4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.
Of these, alkanolamines such as triethanolamine are particularly preferred.
These may be used alone or in combination of two or more.
When the component (B1) is 100% by mass, the component (d1) is usually used in the range of 0 to 5% by mass, and particularly preferably in the range of 0 to 3% by mass.
[0057]
(D2) Organic carboxylic acid or phosphorus oxo acid or derivative thereof:
As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable, and salicylic acid is particularly preferable.
Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid- Like phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof, phosphinic acids such as phosphinic acid, phenylphosphinic acid and their esters Among these, phosphonic acid is particularly preferable.
These may be used alone or in combination of two or more.
The component (d2) is usually used in the range of 0 to 5% by mass, particularly preferably in the range of 0 to 3% by mass, when the component (B) is 100% by mass.
The component (d2) is preferably used in the same amount as the component (d1). This is because the component (d2) and the component (d1) form a salt and stabilize.
[0058]
The thick-film chemically amplified positive photoresist composition of the present invention has an additive resin for improving the performance of the resist film as desired, as long as it does not impair the essential characteristics. Conventional materials such as a plasticizer, an adhesion assistant, a stabilizer, a colorant, and a surfactant can be added and contained.
[0059]
Furthermore, the chemically amplified positive photoresist composition for thick film of the present invention can be appropriately mixed with an organic solvent for viscosity adjustment. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, Polyhydric alcohols such as dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl lactate, Ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid Can be exemplified Le, esters such as ethyl ethoxypropionate. These may be used alone or in combination of two or more.
[0060]
For example, in order to obtain a film thickness of preferably 10 μm or more by using a spin coating method, the amount of these solvents used is such that the solid content concentration in the chemically amplified positive photoresist composition for thick film is from 30% by mass to 65%. It is preferable to be in the range of mass%. When the solid content concentration is less than 30% by mass, it is difficult to obtain a thick film suitable for the production of connection terminals. When the solid content concentration exceeds 65% by mass, the fluidity of the composition is remarkably deteriorated and the handling is difficult. In the spin coating method, it is difficult to obtain a uniform resist film.
[0061]
The chemical amplification type positive photoresist composition for thick film of the present invention can be prepared, for example, by mixing and stirring the above-mentioned components by ordinary methods, and if necessary, a disperser such as a dissolver, a homogenizer, a three roll mill, etc. May be dispersed and mixed. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.
[0062]
The chemically amplified positive photoresist composition for thick film of the present invention forms a thick photoresist layer having a thickness of 10 to 150 μm, more preferably 20 to 120 μm, still more preferably 20 to 80 μm on a support. Suitable for
[0063]
Next, the thick film photoresist laminate of the present invention is obtained by laminating a thick film photoresist layer made of the chemically amplified positive photoresist composition for thick films on a support.
The support is not particularly limited, and a conventionally known one can be used. Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. Examples of the substrate include substrates made of metal such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and glass substrates. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.
[0064]
The thick film photoresist laminate as described above can be manufactured, for example, as follows.
That is, a thick film chemically amplified positive photoresist composition solution prepared as described above is applied onto a support, and the solvent is removed by heating to form a desired coating film. As a coating method on a to-be-processed support body, methods, such as a spin coat method, a slit coat method, a roll coat method, a screen printing method, an applicator method, are employable. The pre-baking conditions for the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C. ~ About 60 minutes.
[0065]
The thickness of the thick photoresist layer of the present invention is desirably 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm.
[0066]
Then, in order to form a resist pattern using the thick film photoresist laminate obtained in this way, actinic rays or radiation, for example, wavelength, is applied to the obtained thick film photoresist layer through a mask having a predetermined pattern. Are selectively irradiated (exposed) with ultraviolet rays or visible rays of 300 to 500 nm.
Here, the actinic ray means a ray that activates the acid generator in order to generate an acid. As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. Here, the radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, ion rays, and the like. The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the film thickness of the coating film, and the like, for example, when using an ultrahigh pressure mercury lamp, 100 to 10,000 mJ / cm.2It is.
[0067]
After the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the thick film photoresist layer in the exposed portion.
Next, for example, using a predetermined alkaline aqueous solution as a developer, unnecessary portions are dissolved and removed to obtain a predetermined resist pattern. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethyl. Ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0 An aqueous solution of an alkali such as -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but it is usually 1 to 30 minutes, and the development method is a liquid piling method, dipping method, paddle method, spray development method. Any of these may be used. After the development, washing with running water is performed for 30 to 90 seconds and dried using an air gun or an oven.
[0068]
Then, a connection terminal such as a metal post or a bump is formed by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkaline developer) of the resist pattern thus obtained, for example, by plating or the like. can do. The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating, copper plating, gold plating, or nickel plating solution is particularly preferably used.
The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.
[0069]
【Example】
Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.
[Synthesis Example 1]
<(B) Synthesis of Resins (B-1) to (B-5) whose solubility in alkali is increased by the action of acid>
A flask equipped with a stirrer, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then propylene glycol methyl ether acetate was charged as a solvent and stirring was started. Thereafter, the temperature of the solvent was raised to 80 ° C. 2,2′-Azobisisobutyronitrile as a polymerization catalyst, 50 mass% of 1-ethylcyclohexyl methacrylate structural unit as (b1), and 50 mass% of 2-ethoxyethyl acrylate structural unit as (b2) are added to the dropping tank. After stirring until the polymerization catalyst was dissolved, this solution was uniformly dropped into the flask for 3 hours, followed by polymerization at 80 ° C. for 5 hours. Then, it cooled to room temperature and obtained resin used as (B) component.
The resin was subjected to a fractionation treatment to obtain six types of resins (B-1) to (B-5) having different mass average molecular weights as follows.
(B-1): Mass average molecular weight 50,000
(B-2): Mass average molecular weight 150,000
(B-3): Mass average molecular weight 250,000
(B-4): Mass average molecular weight 350,000
(B-5): Mass average molecular weight 500,000
[0070]
[Synthesis Example 2]
<(B-6) Synthesis of Resin with Increased Alkali Solubility by Action of Acid>
The mass average molecular weight 350,000 was the same as in Synthesis Example 1 except that 1-ethylcyclohexyl methacrylate structural unit 20% by mass as (b1) and 80% by mass of 2-ethoxyethyl acrylate structural unit as (b2) were used. Of resin (B-6) was obtained.
[Synthesis Example 3]
<(B-7) Synthesis of Resin with Increased Alkali Solubility by Action of Acid>
The mass average molecular weight 350,000 was the same as in Synthesis Example 1 except that 80% by mass of 1-ethylcyclohexyl methacrylate structural unit was used as (b1) and 20% by mass of 2-ethoxyethyl acrylate structural unit was used as (b2). Of resin (B-7) was obtained.
[0071]
[Synthesis Example 4]
<Synthesis of (c1) novolac resin>
m-cresol and p-cresol were mixed at a mass ratio of 60:40, formalin was added thereto, and condensed by an ordinary method using an oxalic acid catalyst to obtain a cresol novolak resin. The resin was subjected to a fractionation treatment, and the low molecular weight region was cut to obtain a novolak resin having a mass average molecular weight of 15,000. This resin is referred to as (C-1).
[Synthesis Example 5]
<Synthesis of (c2) copolymer having hydroxystyrene structural unit and styrene structural unit>
A resin (C-2) having a mass average molecular weight of 3,000 was obtained in the same manner as in Synthesis Example 1 except that 75% by mass of hydroxystyrene units and 25% by mass of styrene units were used as structural units.
[0072]
[Synthesis Example 6]
<Synthesis of (c3) acrylic resin>
A resin having a mass average molecular weight of 250,000 (C--) was used in the same manner as in Synthesis Example 1, except that 130 parts by mass of 2-methoxyethyl acrylate, 50 parts by mass of benzyl methacrylate, and 20 parts by mass of acrylic acid were used as structural units. 3) was obtained.
[Synthesis Example 7]
<Synthesis of (c4) vinyl resin>
A methanol solution of poly (vinyl methyl ether) (mass average molecular weight 50,000) (manufactured by Tokyo Chemical Industry Co., Ltd., concentration 50 mass%) was solvent-substituted with propylene glycol monomethyl ether acetate using a rotary evaporator to obtain a concentration of 50 (C-4) was obtained as a mass% solution.
[0073]
[Examples 1 to 13]
<Preparation of chemically amplified positive photoresist composition for thick filmMade>
Each component shown in Table 1 was mixed with propylene glycol monomethyl ether acetate to form a uniform solution, and then filtered through a membrane filter having a pore size of 1 μm to obtain a chemically amplified positive photoresist composition for thick film.However, Examples 1 and 5 are reference examples.
As the acid generator as the component (A), the following two types were used.
(A-1): (5-Propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile
(A-2): Compound represented by the following [Chemical Formula 11]
[0074]
Embedded image
[0075]
In Table 1, (D-1) represents salicylic acid, and (D-2) represents triethanolamine. In addition, the numerical value in Table 1 represents the mass part of each component.
[0076]
[Table 1]
[0077]
[Comparative Example 1]
<Preparation of chemically amplified positive photoresist composition for thick film>
(A) Acid generator: Compound represented by the above [Chemical Formula 11]; 3 parts by mass
Component (B): 67 parts by mass of a copolymer having a mass average molecular weight of 8,000 consisting of 67 mol% of hydroxystyrene units, 22 mol% of styrene units and 11 mol% of 1-ethylcyclohexyl methacrylate units, and 67 mols of hydroxystyrene units. %, A styrene unit 29 mol%, and a 1-ethylcyclohexyl methacrylate 4 mol% copolymer 33 parts by mass;
(D1) Triethanolamine; 0.1 parts by mass
(D2) phenylphosphonic acid; 0.1 part
Each of the above components was dissolved in 300 parts by mass of ethyl lactate, and after adding 1.0% by mass of a fluorosurfactant [trade name “Fluorad FC-171” (manufactured by 3M)] to the total amount, Filtration through a 0.2 μm membrane filter gave a positive resist composition.
[0078]
[Test Example 1]
The following characteristics evaluation was performed using the positive chemically amplified photoresist composition produced in the above example.
・ Compatibility
Each composition was mixed and stirred for 12 hours at room temperature, and the dissolved state immediately after stirring and 12 hours after stirring was visually observed. The dispersion state was determined according to the following evaluation criteria.
○: It was visually confirmed that the composition was uniformly dispersed after stirring for 12 hours.
(Triangle | delta): The composition disperse | distributed uniformly after 12-hour stirring, but phase-separated by standing still for a long time.
X: The composition is not uniformly dispersed after stirring for 12 hours.
[0079]
・ Applicability
Each composition was applied on a 5-inch gold sputtering wafer (gold substrate) using a spinner at 1000 rpm for 25 seconds, and then heated on a hot plate at 110 ° C. for 6 minutes. The formed coating film was visually observed and applicability was determined according to the following evaluation criteria.
◯: The obtained coating film is uniform and uniform.
(Triangle | delta): The flatness of the obtained coating film is bad and is not uniform.
X: The obtained coating film has unevenness such as pinholes and repellency.
[0080]
・ Development and resolution
Using a spinner on a 5-inch gold sputtering wafer, each composition was applied at 1800 rpm for 25 seconds to a film thickness of about 20 μm, and then pre-baked on a hot plate at 110 ° C. for 6 minutes to form a thick film photoresist. A laminate was formed. In the case of a coating film having a film thickness of about 65 μm, it is applied at 800 rpm for 25 seconds, pre-baked on a hot plate at 110 ° C. for 1 minute, further applied at 800 rpm for 25 seconds, and then pre-baked at 110 ° C. for 12 minutes to form a thick film photoresist. A laminate was formed.
In the case of a coating film having a film thickness of about 120 μm, after being applied at 800 rpm for 25 seconds, pre-baked on a hot plate at 110 ° C. for 1 minute, and further applied at 500 rpm for 25 seconds and then at 110 ° C. for 1 minute on the hot plate. Pre-baking was further performed at 500 rpm for 25 seconds, followed by pre-baking at 110 ° C. for 20 minutes to form a thick film photoresist laminate.
Each of the thick film photoresist laminates obtained above was 100 to 10,000 mJ / cm through a pattern mask for resolution measurement using a stepper (Nikon, NSR-2005i10D).2UV exposure was carried out stepwise within the range. After the exposure, it was heated at 70 ° C. for 5 minutes, and developed with a developer (trade name PMER series, P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.).
Thereafter, it was washed with running water and blown with nitrogen to obtain a patterned cured product. This was observed with a microscope, and development / resolution was judged according to the following evaluation criteria.
A: A pattern having an aspect ratio of 2 or more is formed with any of the above exposure amounts, and no residue is observed.
X: A pattern having an aspect ratio of less than 2 is not formed or a residue is observed.
The aspect ratio indicates (resist height on the pattern / resist width on the pattern).
[0081]
・ Plating solution resistance
Using the substrate with the patterned cured product obtained in “Development / Resolution Evaluation” as a test specimen, after ashing with oxygen plasma, immersing in gold sulfite plating solution at 65 ° C. for 40 minutes, washing with running water, and test Got the body. Using an optical microscope or an electron microscope, observe the state of the bumps and patterned cured product formed on the specimen to be processed, and the resistance of the patterned cured product to the plating solution, the shape of the formed pump, and the patterned cured product The resistance of the object to the plating process was determined according to the following evaluation criteria.
◯: Good with no particular change in the state of the formed bump and pattern-like cured product
X: Cracks, bulges and chips are generated in the patterned cured product, or the surface of the patterned cured product is rough.
[0082]
・ Bump shape
Obtain a specimen to be processed by the same operation as the “Plating Resistance Evaluation”, observe the state of the formed bump and the patterned cured product using an optical microscope or an electron microscope, and determine the shape of the formed bump as follows. Judgment was made based on evaluation criteria. Further, when the bump shape was good, the error ratio with respect to the angle between the substrate and the bump and the mask dimension was measured.
○: The shape of the bump depends on (follows) the cured pattern and is good.
X: The shape of the pump does not depend on the pattern-like cured product, and swelling is generated.
[0083]
・ Peelability
The substrate having the pattern-like cured product obtained in “Development / Resolution Evaluation” was used as a test specimen and immersed in a stripping solution (Stripper 104 manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 10 minutes at 70 ° C. The pattern-like cured product was peeled off with a rinse solution, and visually observed or observed with an optical microscope and evaluated according to the following criteria.
◯: No residue of the patterned cured product is observed.
X: The residue of the pattern-like hardened | cured material was recognized.
[0084]
・ Photosensitivity
A film of various thicknesses is formed on a 5-inch silicon wafer, and 100 to 10,000 mJ / cm using a stepper (Nikon, NSR-2005i10D) through a pattern mask for resolution measurement.2The exposure was divided in the range of. This was developed with a developer (trade name PMER series, P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, it was washed with running water and blown with nitrogen to obtain a patterned cured product. This was observed with a microscope, a pattern having an aspect ratio of 2 or more was formed, and the exposure amount at which no residue was observed, that is, the minimum exposure amount necessary to form the pattern was measured.
[0085]
The positive photoresist compositions prepared in Examples 1 to 13 and Comparative Example 1 were evaluated by performing the above tests. The results are shown in Table 2.
[0086]
[Table 2]
[0087]
【The invention's effect】
As described above, according to the present invention, the chemically amplified positive photoresist for thick film suitable for the production of connection terminals, etc., having a good product shape by plating, excellent plating resistance and high contrast. Provided are a composition, a thick film photoresist laminate, a method for producing a thick film resist pattern using the same, and a method for producing a connection terminal.
Claims (8)
(A)活性光線又は放射線照射により酸を発生する化合物と、(B)酸の作用によりアルカリに対する溶解性が増大する樹脂と、(C)アルカリ可溶性樹脂とを含有し、
前記(B)成分が、(b1)下記一般式(1):
で表される構成単位と、(b2)エーテル結合を有する重合性化合物から誘導された構成単位とを含み、かつ、質量平均分子量が10000〜500000の共重合体からなる樹脂を含有することを特徴とする厚膜用化学増幅型ポジ型ホトレジスト組成物。A chemically amplified positive photoresist composition for thick film used for forming a thick photoresist layer having a thickness of 10 to 150 μm on a support,
A compound generating an acid by (A) an actinic ray or radiation, and a resin which exhibits increased solubility in an alkali by the action of (B) acid, and containing a (C) an alkali-soluble resin,
The component (B) is (b1) the following general formula (1):
And a structural unit represented by in, that it contains (b2) viewed contains a constitutional unit derived from a polymerizable compound having an ether bond, and a resin weight average molecular weight of a copolymer of 10,000 to 500,000 A chemically amplified positive photoresist composition for thick films.
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US7169532B2 (en) | 2004-12-29 | 2007-01-30 | Tokyo Ohka Kogyo Co., Ltd. | Chemically amplified positive photoresist composition for thick film, thick-film photoresist laminated product, manufacturing method for thick-film resist pattern, and manufacturing method for connection terminal |
US7927778B2 (en) | 2004-12-29 | 2011-04-19 | Tokyo Ohka Kogyo Co., Ltd. | Chemically amplified positive photoresist composition for thick film, thick-film photoresist laminated product, manufacturing method for thick-film resist pattern, and manufacturing method for connection terminal |
US7951522B2 (en) | 2004-12-29 | 2011-05-31 | Tokyo Ohka Kogyo Co., Ltd. | Chemically amplified positive photoresist composition for thick film, thick-film photoresist laminated product, manufacturing method for thick-film resist pattern, and manufacturing method for connection terminal |
JP4499591B2 (en) | 2005-03-23 | 2010-07-07 | 東京応化工業株式会社 | Chemically amplified positive photoresist composition for thick film formation |
JP2006330180A (en) * | 2005-05-24 | 2006-12-07 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition, thick film photoresist laminated body, method for manufacturing thick film resist pattern, and method for manufacturing connecting terminal |
JP4949790B2 (en) * | 2006-09-26 | 2012-06-13 | 株式会社テラミクロス | Manufacturing method of semiconductor device |
US9057951B2 (en) * | 2009-08-26 | 2015-06-16 | International Business Machines Corporation | Chemically amplified photoresist composition and process for its use |
WO2021094423A1 (en) | 2019-11-14 | 2021-05-20 | Merck Patent Gmbh | Dnq-type photoresist composition including alkali-soluble acrylic resins |
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