TWI753105B - 圖型形成方法 - Google Patents
圖型形成方法 Download PDFInfo
- Publication number
- TWI753105B TWI753105B TW107105115A TW107105115A TWI753105B TW I753105 B TWI753105 B TW I753105B TW 107105115 A TW107105115 A TW 107105115A TW 107105115 A TW107105115 A TW 107105115A TW I753105 B TWI753105 B TW I753105B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- bis
- group
- oxime
- film
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000007261 regionalization Effects 0.000 title description 2
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 16
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 238000001312 dry etching Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000011161 development Methods 0.000 abstract description 12
- 238000002444 silanisation Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- -1 tert-hexyl Chemical group 0.000 description 144
- 239000010408 film Substances 0.000 description 75
- 150000002923 oximes Chemical class 0.000 description 54
- 125000004432 carbon atom Chemical group C* 0.000 description 42
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 21
- 239000002585 base Substances 0.000 description 21
- 150000001412 amines Chemical class 0.000 description 19
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 125000001841 imino group Chemical group [H]N=* 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 230000018109 developmental process Effects 0.000 description 11
- 150000007514 bases Chemical class 0.000 description 10
- 125000006165 cyclic alkyl group Chemical group 0.000 description 10
- 125000005843 halogen group Chemical group 0.000 description 10
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 235000013772 propylene glycol Nutrition 0.000 description 8
- 229920001169 thermoplastic Polymers 0.000 description 8
- 239000004416 thermosoftening plastic Substances 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- NCJZVRPXSSYDBG-UHFFFAOYSA-N 2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone Chemical compound COC1=CC=C(C(=O)C(F)(F)F)C=C1 NCJZVRPXSSYDBG-UHFFFAOYSA-N 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- XGMDYIYCKWMWLY-UHFFFAOYSA-N 2,2,2-trifluoroethanesulfonic acid Chemical compound OS(=O)(=O)CC(F)(F)F XGMDYIYCKWMWLY-UHFFFAOYSA-N 0.000 description 4
- IKMBXKGUMLSBOT-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F IKMBXKGUMLSBOT-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- KYXIHKXHBSORRJ-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)-2,2,2-trifluoroethanone Chemical compound CC1=CC=C(C(=O)C(F)(F)F)C(C)=C1 KYXIHKXHBSORRJ-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- VINRTVDNUHIWCB-UHFFFAOYSA-N 2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanone Chemical compound CC1=CC(C)=C(C(=O)C(F)(F)F)C(C)=C1 VINRTVDNUHIWCB-UHFFFAOYSA-N 0.000 description 3
- DYILUJUELMWXAL-UHFFFAOYSA-N 2,2,2-trifluoro-1-(4-methylphenyl)ethanone Chemical compound CC1=CC=C(C(=O)C(F)(F)F)C=C1 DYILUJUELMWXAL-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- IKIZLVYCVDOMRH-UHFFFAOYSA-N 4-(4-methylphenyl)sulfonyloxybenzenesulfonic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=C(S(O)(=O)=O)C=C1 IKIZLVYCVDOMRH-UHFFFAOYSA-N 0.000 description 3
- RLTPXEAFDJVHSN-UHFFFAOYSA-N 4-(trifluoromethyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C(F)(F)F)C=C1 RLTPXEAFDJVHSN-UHFFFAOYSA-N 0.000 description 3
- WVSYONICNIDYBE-UHFFFAOYSA-N 4-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(F)C=C1 WVSYONICNIDYBE-UHFFFAOYSA-N 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
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
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- 229920002223 polystyrene Polymers 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003216 pyrazines Chemical class 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- SCKJMHAZRHWHTP-UHFFFAOYSA-N 1-(4-benzylphenyl)-2,2,2-trifluoroethanone Chemical compound C1=CC(C(=O)C(F)(F)F)=CC=C1CC1=CC=CC=C1 SCKJMHAZRHWHTP-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
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- VQCWOGKZDGCRES-UHFFFAOYSA-N 2,2,2-trifluoro-1-naphthalen-1-ylethanone Chemical compound C1=CC=C2C(C(=O)C(F)(F)F)=CC=CC2=C1 VQCWOGKZDGCRES-UHFFFAOYSA-N 0.000 description 2
- JWQLBVFFLIHXHA-UHFFFAOYSA-N 2,2,2-trifluoro-1-naphthalen-2-ylethanone Chemical compound C1=CC=CC2=CC(C(=O)C(F)(F)F)=CC=C21 JWQLBVFFLIHXHA-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- FEWSKCAVEJNPBX-UHFFFAOYSA-N 2-(2-hydroxy-2-phenylacetyl)benzenesulfonic acid Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1S(O)(=O)=O FEWSKCAVEJNPBX-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical class C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Abstract
本發明之課題為提供使用化學增幅正型光阻組成物,不經矽烷化,即可藉由乾式顯影形成正型圖型之製程。 其解決手段為一種圖型形成方法,其包含(i)使用含有(A)含有具有經酸不安定基取代之酚性羥基,且藉由酸的作用,前述酸不安定基會脫離而成為鹼可溶性之聚合物的基底樹脂、(B)光酸產生劑、(C)有機溶劑,及(D)聚乙烯醇或聚乙烯烷基醚之化學增幅正型光阻組成物,於基板上形成化學增幅正型光阻膜之步驟、(ii)將前述化學增幅正型光阻膜曝光之步驟,及 (iii)使用含有氧之氣體,以乾式蝕刻進行顯影之步驟。
Description
本發明係關於圖型形成方法。
目前,半導體製造步驟之光阻顯影步驟中,係使用濕式製程。但是,以濕式製程進行之顯影中,必須考慮圖型之膨潤或錐形形狀之產生,進一步於有機溶劑顯影中,必須考慮對環境或人體之影響,但使用乾式蝕刻法之乾式顯影中,不會產生如此之問題。因此,從以前即進行用以將光阻顯影步驟乾式化之研究,但為了得到高解像之圖型,曝光後之製程較濕式顯影複雜,故尚未正式使用。
例如,作為乾式顯影製程對正型光阻之適用事例,有報告將苯乙烯系或酚醛清漆系之化學增幅正型光阻組成物塗佈於基板並曝光後,將光阻表面以蝕刻耐性高的矽系化合物矽烷化,使曝光部與未曝光部之顯影對比增大的方法(專利文獻1、2)。又,係有藉由控制乾式蝕刻時之基板溫度,使用正型光阻組成物,得到曝光部殘存之負型圖型的報告例(專利文獻3)。因此,使用正型光阻組成物,即使解像性低,亦可藉由乾式顯影而簡便地得到正型圖型,於圖型部分不殘留殘渣的組成物與製程係受到需求。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開平7-22304號公報 [專利文獻2]日本特開2004-103926號公報 [專利文獻3]日本特開平7-161607號公報
[發明所欲解決之課題]
本發明係有鑑於前述實情而為者,其目的為提供使用化學增幅正型光阻組成物,不經矽烷化,即可藉由乾式顯影形成正型圖型之製程。 [用以解決課題之手段]
本發明者等人為了達成前述目的而進行努力探討的結果,發現藉由使用含有(A)含有具有經酸不安定基取代之酚性羥基,且藉由酸的作用,前述酸不安定基會脫離而成為鹼可溶性之聚合物的基底樹脂、(B)光酸產生劑、(C)有機溶劑,及(D)聚乙烯醇或聚乙烯烷基醚之化學增幅正型光阻組成物,則不需要曝光後之矽烷化製程,而完成本發明。
因此,本發明提供下述圖型形成方法。 1.一種圖型形成方法,其包含(i)使用含有(A)含有具有經酸不安定基取代之酚性羥基,且藉由酸的作用,前述酸不安定基會脫離而成為鹼可溶性之聚合物的基底樹脂、(B)光酸產生劑、(C)有機溶劑,及(D)聚乙烯醇或聚乙烯烷基醚之化學增幅正型光阻組成物,於基板上形成化學增幅正型光阻膜之步驟; (ii)將前述化學增幅正型光阻膜曝光之步驟;及 (iii)使用含有氧之氣體,以乾式蝕刻進行顯影之步驟。 2.如1之圖型形成方法,其中於步驟(i)與步驟(ii)之間包含(i-2)加熱處理步驟。 3.如1或2之圖型形成方法,其中於步驟(ii)與步驟(iii)之間包含(ii-2)加熱處理步驟。 4.如1~3中任一項之圖型形成方法,其中前述化學增幅正型光阻組成物,為薄膜狀組成物。 5.如1~4中任一項之圖型形成方法,其中曝光係藉由波長300~500nm之光來進行。 [發明之效果]
依照本發明之圖型形成方法,可不將化學增幅正型光阻膜表面矽烷化,即以乾式顯影形成正型圖型,能夠以短時間之製程,形成未有SiO2
等所致之表面污染的圖型。
首先,說明本發明之圖型形成方法中所用的化學增幅正型光阻組成物。前述化學增幅正型光阻組成物,為含有(A)含有具有經酸不安定基取代之酚性羥基,且藉由酸的作用,前述酸不安定基會脫離而成為鹼可溶性之聚合物的基底樹脂、(B)光酸產生劑、(C)有機溶劑及(D)聚乙烯醇或聚乙烯烷基醚者。
[(A)基底樹脂] (A)成分之基底樹脂,含有(A)具有經酸不安定基取代之酚性羥基,且藉由酸的作用,前述酸不安定基會脫離而成為鹼可溶性之聚合物(以下稱為聚合物A)。聚合物A例如可列舉含有來自羥基苯乙烯及其衍生物之重複單位的聚合物,且係其酚性羥基之氫原子的一部分或全部經酸不安定基取代之聚合物。聚合物A,較佳為包含下述式(1-1)表示之重複單位及下述式(1-2)表示之重複單位者。
式(1-1)及(1-2)中,R1
及R2
係分別獨立地為氫原子、羥基、直鏈狀或分支狀之碳數1~6之烷基、鹵素原子或三氟甲基。R3
為鹵素原子,或直鏈狀、分支狀或環狀之碳數1~8之烷基,R3
存在複數個時,各R3
可互為相同亦可相異。R4
為羥基、鹵素原子,或直鏈狀、分支狀或環狀之碳數1~8之烷基,R4
存在複數個時,各R4
可互為相同亦可相異。m及n為滿足0≦m<1、0<n≦1,且0<m+n≦1之數,但較佳為0<m<1、0<n<1、更佳為0.3≦m≦0.9、0.1≦n≦0.7、又更佳為0.5≦m≦0.8、0.2≦n≦0.5。
式(1-1)及(1-2)中,w及x為滿足0≦w≦4、1≦x≦5,且1≦w+x≦5之整數,但較佳為0≦w≦2、1≦x≦2。y及z為滿足0≦y≦4、1≦z≦5,且1≦y+z≦5之整數,但較佳為0≦y≦2、1≦z≦2。
前述R3
及R4
之碳數1~8之烷基,可列舉甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、tert-戊基、n-己基、n-庚基等。此等之中較佳為甲基、乙基、n-丙基、異丙基等。又,前述烷基之氫原子的一部分或全部亦可被氟原子等之鹵素原子取代,如此之鹵素取代烷基,可列舉氟甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、五氟乙基等。
式(2-1)中,R11
~R13
係分別獨立地為直鏈狀、分支狀或環狀之碳數1~8之烷基。R11
與R12
、R11
與R13
或R12
與R13
,亦可互相鍵結並與此等所鍵結之碳原子一起形成環,形成環時,牽涉環的形成之R11
、R12
及R13
,係分別獨立地為直鏈狀或分支狀之碳數1~16之伸烷基。
式(2-2)中,R14
及R15
係分別獨立地為氫原子,或直鏈狀或分支狀之碳數1~8之烷基。R16
為直鏈狀、分支狀或環狀之碳數1~10之烷基。又,R14
與R15
、R14
與R16
或R15
與R16
亦可互相鍵結並與此等所鍵結之碳原子或碳原子與氧原子一起形成環,形成環時,牽涉環的形成之R14
、R15
及R16
係分別獨立地為直鏈狀或分支狀之碳數1~6之伸烷基。
式(2-3)中,R17
為碳數4~40之3級烷基。A為0~6之整數。
R11
~R15
表示之碳數1~8之烷基,可列舉與前述的相同者。前述碳數4~40之3級烷基,較佳為碳數4~12者、更佳為碳數4~8者、又更佳為碳數4~6者,具體而言,可列舉tert-丁基、tert-戊基、tert-己基等。
式(2-1)表示之基,可列舉tert-丁基、tert-戊基、1-甲基環己基等。
式(2-2)表示之基,可列舉1-甲氧基乙基、1-乙氧基乙基、1-n-丙氧基乙基、1-異丙氧基乙基、1-n-丁氧基乙基、1-異丁氧基乙基、1-sec-丁氧基乙基、1-tert-丁氧基乙基、1-tert-戊氧基乙基、1-甲氧基-1-丙基、1-乙氧基-1-丙基、2-甲氧基-2-丙基、2-乙氧基-2-丙基、1-環己氧基乙基、四氫吡喃基、四氫呋喃基等。此等之中,較佳為1-乙氧基乙基、1-乙氧基-1-丙基等。
式(2-3)表示之基,可列舉tert-丁氧基羰基、tert-丁氧基羰基甲基、tert-戊氧基羰基、1-甲基環戊氧基羰基、1-乙基環戊氧基羰基、1-乙基環己氧基羰基、tert-戊氧基羰基甲基等。
式中,R21
、R23
及R26
係分別獨立地為氫原子、羥基、直鏈狀或分支狀之碳數1~6之烷基、鹵素原子或三氟甲基。
式(3-1)中,R22
為鹵素原子,或直鏈狀、分支狀或環狀之碳數1~8之烷基,R22
存在複數個時,各R22
可互為相同亦可相異。a及b為滿足0≦a≦4、1≦b≦5,且1≦a+b≦5之整數,較佳為0≦a≦2、1≦b≦2。
式(3-2)中,R24
為羥基、鹵素原子,或直鏈狀、分支狀或環狀之碳數1~8之烷基,R24
存在複數個時,各R24
可互為相同亦可相異。R25
為酸不安定基。R25
表示之酸不安定基,可列舉與前述R表示之酸不安定基為相同者。此等之中,R25
特佳為式(2-1)表示之基、式(2-2)表示之基。c及d為滿足0≦c≦4、1≦d≦5,且1≦c+d≦5之整數,較佳為0≦c≦2、1≦d≦2。
式(3-3)中,R27
為可經氟原子取代之碳數1~12之烷基、可經氟原子取代之碳數1~12之1級或2級烷氧基、-C(CF3
)2
-OH基,或各烷基分別獨立地為碳數1~6之烷基的三烷基矽烷基。e為0~5之整數,較佳為0~4。
式(3-4)中,R28
為氫原子或甲基。R29
為氫原子、甲基、碳數2~6之烷氧基羰基、氰基、鹵素原子或三氟甲基。R30
為取代或非取代之直鏈狀、分支狀或環狀之碳數4~30之烷基。
前述烷基,可列舉與前述的相同者。前述鹵素原子,可列舉氟原子、氯原子、溴原子等。
前述碳數1~12之烷氧基,可列舉甲氧基、乙氧基、n-丙氧基、異丙氧基、n-丁氧基、異丁氧基、sec-丁氧基、n-戊氧基、環戊氧基、n-己氧基、環己氧基、環辛氧基、環壬氧基等。
式(4-1)中,R31
為甲基、乙基、異丙基、環己基、環戊基、乙烯基、乙醯基、苯基、苄基或氰基。f為0~3之整數。式(4-2)中,R32
為甲基、乙基、異丙基、環己基、環戊基、乙烯基、苯基、苄基或氰基。
式(4-1)表示之基,較佳為5員環或6員環者。其具體例子,可列舉1-甲基環戊基、1-乙基環戊基、1-異丙基環戊基、1-乙烯基環戊基、1-乙醯基環戊基、1-苯基環戊基、1-氰基環戊基、1-甲基環己基、1-乙基環己基、1-異丙基環己基、1-乙烯基環己基、1-乙醯基環己基、1-苯基環己基、1-氰基環己基等。
式(4-2)表示之基,可列舉tert-丁基、1-乙烯基二甲基甲基、1-苄基二甲基甲基、1-苯基二甲基甲基、1-氰基二甲基甲基等。
式(3-1)~(3-4)中,p、q、r及s,為滿足0≦p<1、0<q≦1、0≦r<1、0≦s<1,且p+q+r+s=1之數。p、q、r及s,較佳為滿足0.2≦p≦0.8、0.1≦q≦0.8、0≦r≦0.35、0≦s≦0.35,更佳為滿足0.25≦p≦0.75、0.1≦q≦0.45、0≦r≦0.35、0.05≦s≦0.3。藉由於前述範圍內適當選定p、q、r及s之值,可控制化學增幅正型光阻膜之溶解對比或溶解速度,可任意地進行圖型之尺寸控制、圖型之形狀控制。
含有式(3-1)~(3-4)表示之重複單位的聚合物,適宜使用下述2成分系聚合物((A-1))、3成分系聚合物((A-2)、(A-3)、(A-4))、4成分系聚合物((A-5))。再者,下述式中,R21
~R30
及a~e係與前述相同。
聚合物A之重量平均分子量(Mw),較佳為1,000~500,000、更佳為2,000~30,000。Mw若為前述範圍,則耐熱性優良、鹼溶解性亦充分,圖型形成後無產生拖尾現象之虞。再者,本發明中,Mw係以使用四氫呋喃(THF)作為溶劑之凝膠滲透層析(GPC)所得的聚苯乙烯換算測定值。
再者,式(1-1)或式(1-2)表示之重複單位、又,式(3-1)~(3-4)表示之重複單位,於分子中可各僅含1種、亦可含有複數種。
又,聚合物A可1種單獨或組合2種以上使用。
式中,R41
及R43
係分別獨立地為氫原子或甲基。R42
及R44
係分別獨立地為氫原子、甲基、碳數2~6之烷氧基羰基、氰基、鹵素原子或三氟甲基。R45
表示取代或非取代之直鏈狀或分支狀之碳數1~30之烷基、碳數4~30之環烷基、碳數4~30之含有內酯環之基,或包含氧原子、硫原子或氮原子之碳數1~24之1價有機基。j及k為滿足0≦j<1、0<k≦1,且j+k=1之數。
前述丙烯酸聚合物之含量,相對於聚合物A 100質量份而言,為0~100質量份,含有的情況時,較佳為5~50質量份。前述丙烯酸聚合物,可1種單獨或組合2種以上使用。
[(B)光酸產生劑] (B)成分之光酸產生劑,只要係藉由高能量線照射而產生酸之化合物,則無特殊限定。前述高能量線可列舉紫外線、遠紫外線、電子束(EB)等,具體而言,可列舉g線、h線、i線、KrF準分子雷射、ArF準分子雷射、EB、同步輻射光等。
適合的光酸產生劑,可列舉鋶鹽、錪鹽、磺醯基重氮甲烷、N-磺醯氧基醯亞胺型光酸產生劑、苯偶姻磺酸酯型光酸產生劑、鄰苯三酚三磺酸酯型光酸產生劑、硝基苄基磺酸酯型光酸產生劑、碸型光酸產生劑、O-芳基磺醯基肟化合物或O-烷基磺醯基肟化合物(肟磺酸酯)型光酸產生劑等。
前述鋶鹽,係鋶陽離子與磺酸陰離子之鹽。前述鋶陽離子,可列舉三苯基鋶、(4-tert-丁氧基苯基)二苯基鋶、雙(4-tert-丁氧基苯基)苯基鋶、參(4-tert-丁氧基苯基)鋶、(3-tert-丁氧基苯基)二苯基鋶、雙(3-tert-丁氧基苯基)苯基鋶、參(3-tert-丁氧基苯基)鋶、(3,4-二tert-丁氧基苯基)二苯基鋶、雙(3,4-二tert-丁氧基苯基)苯基鋶、參(3,4-二tert-丁氧基苯基)鋶、二苯基(4-硫代苯氧基苯基)鋶、(4-tert-丁氧基羰基甲氧基苯基)二苯基鋶、參(4-tert-丁氧基羰基甲氧基苯基)鋶、(4-tert-丁氧基苯基)雙(4-二甲基胺基苯基)鋶、參(4-二甲基胺基苯基)鋶、2-萘基二苯基鋶、二甲基2-萘基鋶、4-羥基苯基二甲基鋶、4-甲氧基苯基二甲基鋶、三甲基鋶、2-側氧基環己基環己基甲基鋶、三萘基鋶、三苄基鋶等。前述磺酸陰離子,可列舉三氟甲磺酸陰離子、九氟丁磺酸陰離子、十七氟辛磺酸陰離子、2,2,2-三氟乙磺酸陰離子、五氟苯磺酸陰離子、4-三氟甲基苯磺酸陰離子、4-氟苯磺酸陰離子、甲苯磺酸陰離子、苯磺酸陰離子、4-(4-甲苯磺醯氧基)苯磺酸陰離子、萘磺酸陰離子、樟腦磺酸陰離子、辛磺酸陰離子、十二烷基苯磺酸陰離子、丁磺酸陰離子、甲磺酸陰離子等。前述鋶鹽,較佳為由此等之組合所成者。
前述錪鹽,係錪陽離子與磺酸陰離子之鹽。前述錪陽離子,可列舉二苯基錪、雙(4-tert-丁基苯基)錪、4-tert-丁氧基苯基苯基錪、4-甲氧基苯基苯基錪等之芳基錪陽離子等。前述磺酸陰離子,可列舉三氟甲磺酸陰離子、九氟丁磺酸陰離子、十七氟辛磺酸陰離子、2,2,2-三氟乙磺酸陰離子、五氟苯磺酸陰離子、4-三氟甲基苯磺酸陰離子、4-氟苯磺酸陰離子、甲苯磺酸陰離子、苯磺酸陰離子、4-(4-甲苯磺醯氧基)苯磺酸陰離子、萘磺酸陰離子、樟腦磺酸陰離子、辛磺酸陰離子、十二烷基苯磺酸陰離子、丁磺酸陰離子、甲磺酸陰離子等。前述錪鹽,較佳為由此等之組合所成者。
前述磺醯基重氮甲烷,可列舉雙(乙基磺醯基)重氮甲烷、雙(1-甲基丙基磺醯基)重氮甲烷、雙(2-甲基丙基磺醯基)重氮甲烷、雙(1,1-二甲基乙基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷、雙(全氟異丙基磺醯基)重氮甲烷、雙(苯基磺醯基)重氮甲烷、雙(4-甲基苯基磺醯基)重氮甲烷、雙(2,4-二甲基苯基磺醯基)重氮甲烷、雙(2-萘基磺醯基)重氮甲烷、4-甲基苯基磺醯基苄醯基重氮甲烷、tert-丁基羰基-4-甲基苯基磺醯基重氮甲烷、2-萘基磺醯基苄醯基重氮甲烷、4-甲基苯基磺醯基-2-萘甲醯基重氮甲烷、甲基磺醯基苄醯基重氮甲烷、tert-丁氧基羰基-4-甲基苯基磺醯基重氮甲烷等之雙磺醯基重氮甲烷,或磺醯基羰基重氮甲烷。
前述N-磺醯氧基醯亞胺型光酸產生劑,可列舉琥珀醯亞胺、萘二羧酸醯亞胺、鄰苯二甲醯亞胺、環己基二羧酸醯亞胺、5-降莰烯-2,3-二羧酸醯亞胺、7-氧雜雙環[2.2.1]-5-庚烯-2,3-二羧酸醯亞胺等之醯亞胺的氮原子上所鍵結的氫原子,被三氟甲磺醯氧基、九氟丁磺醯氧基、十七氟辛磺醯氧基、2,2,2-三氟乙磺醯氧基、五氟苯磺醯氧基、4-三氟甲基苯磺醯氧基、4-氟苯磺醯氧基、甲苯磺醯氧基、苯磺醯氧基、萘磺醯氧基、樟腦磺醯氧基、辛磺醯氧基、十二烷基苯磺醯氧基、丁磺醯氧基、甲磺醯氧基等之磺醯氧基取代之化合物。
苯偶姻磺酸酯型光酸產生劑,可列舉苯偶姻甲苯磺酸酯、苯偶姻甲磺酸酯、苯偶姻丁磺酸酯等。
鄰苯三酚三磺酸酯型光酸產生劑,可列舉鄰苯三酚、氟甘胺酸、兒茶酚、間苯二酚或氫醌之羥基的全部,被三氟甲磺醯氧基、九氟丁磺醯氧基、十七氟辛磺醯氧基、2,2,2-三氟乙磺醯氧基、五氟苯磺醯氧基、4-三氟甲基苯磺醯氧基、4-氟苯磺醯氧基、甲苯磺醯氧基、苯磺醯氧基、萘磺醯氧基、樟腦磺醯氧基、辛磺醯氧基、十二烷基苯磺醯氧基、丁磺醯氧基、甲磺醯氧基等之磺醯氧基取代之化合物。
硝基苄基磺酸酯型光酸產生劑,可列舉磺酸2,4-二硝基苄酯、磺酸2-硝基苄酯、磺酸2,6-二硝基苄酯等之硝基苄醇與三氟甲磺酸、九氟丁磺酸、十七氟辛磺酸、2,2,2-三氟乙磺酸、五氟苯磺酸、4-三氟甲基苯磺酸、4-氟苯磺酸、甲苯磺酸、苯磺酸、萘磺酸、樟腦磺酸、辛磺酸、十二烷基苯磺酸、丁磺酸、甲磺酸等之磺酸之酯。再者,亦可同樣地使用將硝基以三氟甲基取代之化合物作為光酸產生劑。
碸型光酸產生劑,可列舉雙(苯基磺醯基)甲烷、雙(4-甲基苯基磺醯基)甲烷、雙(2-萘基磺醯基)甲烷、2,2-雙(苯基磺醯基)丙烷、2,2-雙(4-甲基苯基磺醯基)丙烷、2,2-雙(2-萘基磺醯基)丙烷、2-甲基-2-(p-甲苯磺醯基)丙醯苯、2-(環己基羰基)-2-(p-甲苯磺醯基)丙烷、2,4-二甲基-2-(p-甲苯磺醯基)戊烷-3-酮等。
O-芳基磺醯基肟化合物或O-烷基磺醯基肟化合物(肟磺酸酯)型光酸產生劑,可列舉乙二醛二肟衍生物型、介隔有噻吩或環己二烯之共軛系的長肟磺酸酯型、以如三氟甲基之電子吸引基增加化合物之安定性的肟磺酸酯型、使用苯基乙腈等之取代乙腈衍生物之肟磺酸酯型、雙肟磺酸酯型等者。
乙二醛二肟衍生物型光酸產生劑,可列舉雙-O-(p-甲苯磺醯基)-α-二甲基乙二醛二肟、雙-O-(p-甲苯磺醯基)-α-二苯基乙二醛二肟、雙-O-(p-甲苯磺醯基)-α-二環己基乙二醛二肟、雙-O-(p-甲苯磺醯基)-2,3-戊烷二酮=二肟、雙-O-(n-丁磺醯基)-α-二甲基乙二醛二肟、雙-O-(n-丁磺醯基)-α-二苯基乙二醛二肟、雙-O-(n-丁磺醯基)-α-二環己基乙二醛二肟、雙-O-(甲磺醯基)-α-二甲基乙二醛二肟、雙-O-(三氟甲磺醯基)-α-二甲基乙二醛二肟、雙-O-(2,2,2-三氟乙磺醯基)-α-二甲基乙二醛二肟、雙-O-(10-樟腦磺醯基)-α-二甲基乙二醛二肟、雙-O-(苯磺醯基)-α-二甲基乙二醛二肟、雙-O-(4-氟苯磺醯基)-α-二甲基乙二醛二肟、雙-O-(4-三氟甲基苯磺醯基)-α-二甲基乙二醛二肟、雙-O-(二甲苯磺醯基)-α-二甲基乙二醛二肟、雙-O-(三氟甲磺醯基)-尼肟、雙-O-(2,2,2-三氟乙磺醯基)-尼肟、雙-O-(10-樟腦磺醯基)-尼肟、雙-O-(苯磺醯基)-尼肟、雙-O-(4-氟苯磺醯基)-尼肟、雙-O-(4-(三氟甲基)苯磺醯基)-尼肟、雙-O-(二甲苯磺醯基)-尼肟等。
介隔有噻吩或環己二烯之共軛系的長肟磺酸酯型光酸產生劑,可列舉(5-(p-甲苯磺醯基)氧基亞胺基-5H-噻吩-2-亞基)苯基乙腈、(5-(10-樟腦磺醯基)氧基亞胺基-5H-噻吩-2-亞基)苯基乙腈、(5-n-辛磺醯氧基亞胺基-5H-噻吩-2-亞基)苯基乙腈、(5-(p-甲苯磺醯基)氧基亞胺基-5H-噻吩-2-亞基)(2-甲基苯基)乙腈、(5-(10-樟腦磺醯基)氧基亞胺基-5H-噻吩-2-亞基)(2-甲基苯基)乙腈、(5-n-辛磺醯氧基亞胺基-5H-噻吩-2-亞基)(2-甲基苯基)乙腈、(5-(4-(p-甲苯磺醯氧基)苯磺醯基)氧基亞胺基-5H-噻吩-2-亞基)苯基乙腈、(5-(2,5-雙(p-甲苯磺醯氧基)苯磺醯基)氧基亞胺基-5H-噻吩-2-亞基)苯基乙腈等。
以如三氟甲基之電子吸引基增加化合物之安定性的肟磺酸酯型光酸產生劑,可列舉2,2,2-三氟-1-苯基乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-苯基乙酮=O-(10-樟腦磺醯基)肟、2,2,2-三氟-1-苯基乙酮=O-(4-甲氧基苯磺醯基)肟、2,2,2-三氟-1-苯基乙酮=O-(1-萘基磺醯基)肟、2,2,2-三氟-1-苯基乙酮=O-(2-萘基磺醯基)肟、2,2,2-三氟-1-苯基乙酮=O-(2,4,6-三甲基苯基磺醯基)肟、2,2,2-三氟-1-(4-甲基苯基)乙酮=O-(10-樟腦磺醯基)肟、2,2,2-三氟-1-(4-甲基苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(2-甲基苯基)乙酮=O-(10-樟腦磺醯基)肟、2,2,2-三氟-1-(2,4-二甲基苯基)乙酮=O-(10-樟腦磺醯基)肟、2,2,2-三氟-1-(2,4-二甲基苯基)乙酮=O-(1-萘基磺醯基)肟、2,2,2-三氟-1-(2,4-二甲基苯基)乙酮=O-(2-萘基磺醯基)肟、2,2,2-三氟-1-(2,4,6-三甲基苯基)乙酮=O-(10-樟腦磺醯基)肟、2,2,2-三氟-1-(2,4,6-三甲基苯基)乙酮=O-(1-萘基磺醯基)肟、2,2,2-三氟-1-(2,4,6-三甲基苯基)乙酮=O-(2-萘基磺醯基)肟、2,2,2-三氟-1-(4-甲氧基苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(4-甲硫基苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(3,4-二甲氧基苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(4-甲氧基苯基)乙酮=O-(4-甲基苯基磺醯基)肟、2,2,2-三氟-1-(4-甲氧基苯基)乙酮=O-(4-甲氧基苯基磺醯基)肟、2,2,2-三氟-1-(4-甲氧基苯基)乙酮=O-(4-十二烷基苯基磺醯基)肟、2,2,2-三氟-1-(4-甲氧基苯基)乙酮=O-(辛基磺醯基)肟、2,2,2-三氟-1-(4-硫甲基苯基)乙酮=O-(4-甲氧基苯基磺醯基)肟、2,2,2-三氟-1-(4-硫甲基苯基)乙酮=O-(4-十二烷基苯基磺醯基)肟、2,2,2-三氟-1-(4-硫甲基苯基)乙酮=O-(辛基磺醯基)肟、2,2,2-三氟-1-(4-硫甲基苯基)乙酮=O-(2-萘基磺醯基)肟、2,2,2-三氟-1-(2-甲基苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(4-甲基苯基)乙酮=O-(苯基磺醯基)肟、2,2,2-三氟-1-(4-氯苯基)乙酮=O-(苯基磺醯基)肟、2,2,3,3,4,4,4-七氟-1-苯基丁酮=O-(10-樟腦磺醯基)肟、2,2,2-三氟-1-(1-萘基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(2-萘基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(4-苄基苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(4-(苯基-1,4-二氧雜-丁-1-基)苯基)乙酮=O-(甲基磺醯基)肟、2,2,2-三氟-1-(1-萘基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(2-萘基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-苄基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-甲基磺醯基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-甲基磺醯氧基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-甲基羰氧基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(6H,7H-5,8-二側氧基萘并-2-基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-甲氧基羰基甲氧基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-(甲氧基羰基)-(4-胺基-1-氧雜-戊-1-基)苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(3,5-二甲基-4-乙氧基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-苄氧基苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(2-硫苯基)乙酮=O-(丙基磺酸酯)肟、及2,2,2-三氟-1-(1-二氧雜噻吩-2-基)乙酮=O-(丙基磺酸酯)肟、2,2,2-三氟-1-(4-(3-(4-(2,2,2-三氟-1-(三氟甲磺醯氧基亞胺基)乙基)苯氧基)丙氧基)苯基)乙酮=O-(三氟甲磺醯基)肟、2,2,2-三氟-1-(4-(3-(4-(2,2,2-三氟-1-(1-丙磺醯氧基亞胺基)乙基)苯氧基)丙氧基)苯基)乙酮=O-(丙基磺醯基)肟、2,2,2-三氟-1-(4-(3-(4-(2,2,2-三氟-1-(1-丁磺醯氧基亞胺基)乙基)苯氧基)丙氧基)苯基)乙酮=O-(丁基磺醯基)肟、2,2,2-三氟-1-(4-(3-(4-(2,2,2-三氟-1-(4-(4-甲基苯基磺醯氧基)苯基磺醯氧基亞胺基)乙基)苯氧基)丙氧基)苯基)乙酮=O-(4-(4-甲基苯基磺醯氧基)苯基磺醯基)肟、2,2,2-三氟-1-(4-(3-(4-(2,2,2-三氟-1-((2,5-雙(4-甲基苯基磺醯氧基)苯磺醯氧基)苯基磺醯氧基亞胺基)乙基)苯氧基)丙氧基)苯基)乙酮=O-((2,5-雙(4-甲基苯基磺醯氧基)苯磺醯氧基)苯基磺醯基)肟等。
使用取代乙腈衍生物之肟磺酸酯型光酸產生劑,可列舉4-甲基苯基磺醯氧基亞胺基-α-(4-甲氧基苯基)乙腈、α-(p-甲苯磺醯氧基亞胺基)-苯基乙腈、α-(p-氯苯磺醯氧基亞胺基)-苯基乙腈、α-(4-硝基苯磺醯氧基亞胺基)-苯基乙腈、α-(4-硝基-2-三氟甲基苯磺醯氧基亞胺基)-苯基乙腈、α-(苯磺醯氧基亞胺基)-4-氯苯基乙腈、α-(苯磺醯氧基亞胺基)-2,4-二氯苯基乙腈、α-(苯磺醯氧基亞胺基)-2,6-二氯苯基乙腈、α-(苯磺醯氧基亞胺基)-4-甲氧基苯基乙腈、α-(2-氯苯磺醯氧基亞胺基)-4-甲氧基苯基乙腈、α-(苯磺醯氧基亞胺基)-2-噻吩基乙腈、α-(4-十二烷基苯磺醯氧基亞胺基)-苯基乙腈、α-((4-甲苯磺醯氧基亞胺基)-4-甲氧基苯基)乙腈、α-((十二烷基苯磺醯氧基亞胺基)-4-甲氧基苯基)乙腈、α-(甲苯磺醯氧基亞胺基)-3-噻吩基乙腈、α-(甲基磺醯氧基亞胺基)-1-環戊烯基乙腈、α-(乙基磺醯氧基亞胺基)-1-環戊烯基乙腈、α-(異丙基磺醯氧基亞胺基)-1-環戊烯基乙腈、α-(n-丁基磺醯氧基亞胺基)-1-環戊烯基乙腈、α-(乙基磺醯氧基亞胺基)-1-環己烯基乙腈、α-(異丙基磺醯氧基亞胺基)-1-環己烯基乙腈、α-(n-丁基磺醯氧基亞胺基)-1-環己烯基乙腈等。
又,雙肟磺酸酯型光酸產生劑,可列舉雙(α-(p-甲苯磺醯氧基)亞胺基)-p-苯二乙腈、雙(α-(苯磺醯氧基)亞胺基)-p-苯二乙腈、雙(α-(甲磺醯氧基)亞胺基)-p-苯二乙腈雙(α-(丁磺醯氧基)亞胺基)-p-苯二乙腈、雙(α-(10-樟腦磺醯氧基)亞胺基)-p-苯二乙腈、雙(α-(三氟甲磺醯氧基)亞胺基)-p-苯二乙腈、雙(α-(4-甲氧基苯磺醯氧基)亞胺基)-p-苯二乙腈、雙(α-(p-甲苯磺醯氧基)亞胺基)-m-苯二乙腈、雙(α-(苯磺醯氧基)亞胺基)-m-苯二乙腈、雙(α-(甲磺醯氧基)亞胺基)-m-苯二乙腈、雙(α-(丁磺醯氧基)亞胺基)-m-苯二乙腈、雙(α-(10-樟腦磺醯氧基)亞胺基)-m-苯二乙腈、雙(α-(三氟甲磺醯氧基)亞胺基)-m-苯二乙腈、雙(α-(4-甲氧基苯磺醯氧基)亞胺基)-m-苯二乙腈等。
式中,R101
表示取代或非取代之碳數1~10之鹵代烷基磺醯基或鹵代苯磺醯基。R102
表示碳數1~11之鹵代烷基。R103
表示取代或非取代之芳基或雜芳基。
式(Ox-1)表示之肟磺酸酯,可列舉2-(2,2,3,3,4,4,5,5-八氟-1-(九氟丁基磺醯氧基亞胺基)戊基)茀、2-(2,2,3,3,4,4-五氟-1-(九氟丁基磺醯氧基亞胺基)丁基)茀、2-(2,2,3,3,4,4,5,5,6,6-十氟-1-(九氟丁基磺醯氧基亞胺基)己基)茀、2-(2,2,3,3,4,4,5,5-八氟-1-(九氟丁基磺醯氧基亞胺基)戊基)-4-聯苯、2-(2,2,3,3,4,4-五氟-1-(九氟丁基磺醯氧基亞胺基)丁基)-4-聯苯、2-(2,2,3,3,4,4,5,5,6,6-十氟-1-(九氟丁基磺醯氧基亞胺基)己基)-4-聯苯等。
其中尤佳可使用之光酸產生劑,係鋶鹽、雙磺醯基重氮甲烷、N-磺醯氧基醯亞胺、磺醯基肟化合物類。
最適合之所產生之酸的陰離子雖依聚合物所用之酸不安定基的切斷容易性等而異,但一般而言係選擇無揮發性者、極端地擴散性不高者。此時,適合的陰離子,係苯磺酸陰離子、甲苯磺酸陰離子、4-(4-甲苯磺醯氧基)苯磺酸陰離子、五氟苯磺酸陰離子、2,2,2-三氟乙磺酸陰離子、九氟丁磺酸陰離子、十七氟辛磺酸陰離子、樟腦磺酸陰離子。
前述光阻組成物中,(B)光酸產生劑之含量,相對於(A)成分之基底樹脂100質量份而言,較佳為0.2~20質量份、更佳為0.3~10質量份。含量若為前述範圍,則可得到實用上無問題之感度與圖型形狀。(B)光酸產生劑,可1種單獨或組合2種以上使用。進一步地,亦可使用於曝光波長之透過率低的光酸產生劑,以其添加量來控制光阻膜中之光透過率。
[(C)有機溶劑] 作為(C)成分之有機溶劑,只要係對其他成分具有充分之溶解性,且具有良好之塗膜性,則無特殊限定。如此之有機溶劑,可列舉甲基賽珞蘇、乙基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯等之賽珞蘇系溶劑;丙二醇、二丙二醇等之丙二醇系溶劑;丙二醇單甲基醚、丙二醇單丁基醚等之丙二醇烷基醚系溶劑;丙二醇單甲基醚乙酸酯、丙二醇二甲基醚、丙二醇單乙基醚乙酸酯等之丙二醇烷基醚乙酸酯系溶劑;乙酸丁酯、乙酸戊酯、乳酸甲酯、乳酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯等之酯系溶劑;甲醇、乙醇、異丙醇、丁醇、己醇、二丙酮醇等之醇系溶劑;丙酮、環己酮、環戊酮、甲基乙基酮、甲基戊基酮、甲基異丁基酮等之酮系溶劑;甲基苯基醚、二乙二醇二甲基醚等之醚系溶劑;N,N-二甲基甲醯胺、N-甲基吡咯啶酮、二甲基亞碸等之高極性溶劑;及此等之混合溶劑。
特佳之有機溶劑,係丙二醇烷基醚乙酸酯系溶劑、乳酸烷酯、烷基酮。此等溶劑可1種單獨或混合2種以上使用。前述丙二醇烷基醚乙酸酯之烷基,可列舉碳數1~4者,例如甲基、乙基、丙基等,較宜為甲基及乙基。又,丙二醇烷基醚乙酸酯係有1,2取代體與1,3取代體,且係有依取代位置之組合所致的3種異構物,此等亦可為混合物。又,乳酸烷酯之烷基,可列舉碳數1~4者,例如甲基、乙基、丙基等,較宜為甲基及乙基。烷基酮之烷基,可列舉碳數1~10者,例如甲基、乙基、丙基、異丁基、環戊基、環己基等,特佳為異丁基、環戊基、環己基。
前述光阻組成物中,(C)有機溶劑之含量,相對於(A)成分之基底樹脂100質量份而言,較佳為20~1,000質量份、更佳為30~800質量份。
[(D)聚乙烯醇或聚乙烯烷基醚] (D)成分,係聚乙烯醇或羥基成為烷基醚基之聚乙烯烷基醚。聚乙烯烷基醚的情況時,烷基醚基之長度,較佳為碳數1~10,烷基部可列舉直鏈狀、分支狀或環狀者,特佳為甲基醚基、乙基醚基、丙基醚基、丁基醚基等之碳數1~4者。
又,聚乙烯醇,可使用將聚乙酸乙烯酯皂化者,較佳為使用皂化度60~99.5mol%、更佳為使用70~99mol%者即可。
聚乙烯醇或聚乙烯烷基醚之Mw,較佳為1,000~500,000、更佳為1,500~50,000。Mw若為前述範圍,則對有機溶劑之溶解性良好。
前述光阻組成物中,(D)聚乙烯醇或聚乙烯烷基醚之含量,相對於(A)成分之基底樹脂100質量份而言,較佳為1~100質量份、更佳為5~50質量份。(D)成分可1種單獨或組合2種以上使用。含量若為前述範圍,則無損及對基板之塗佈性之虞,於乾式蝕刻之曝光部與未曝光部的蝕刻速率產生充分差距,可得到高的對比。
[(E)鹼性化合物] 前述光阻組成物,亦可依需要含有(E)鹼性化合物。(E)鹼性化合物,係以可抑制由光酸產生劑所產生之酸擴散於光阻膜中時之擴散速度的化合物為適宜,藉由含有如此之鹼性化合物,於光阻膜中之酸的擴散速度被抑制,解像度提高,可抑制曝光後之感度變化、使基板或環境依存性減少、或提高曝光裕度或圖型輪廓等。
(E)鹼性化合物,可列舉1級、2級或3級之脂肪族胺類、混成胺類、芳香族胺類、雜環胺類、具有羧基之含氮化合物、具有磺醯基之含氮化合物、具有羥基之含氮化合物、具有羥基苯基之含氮化合物、醇性含氮化合物、醯胺衍生物、醯亞胺衍生物等。
具體而言,1級脂肪族胺類,可列舉氨、甲胺、乙胺、n-丙胺、異丙胺、n-丁胺、異丁胺、sec-丁胺、tert-丁胺、戊胺、tert-戊胺、環戊胺、己胺、環己胺、庚胺、辛胺、壬胺、癸胺、十二烷基胺、鯨蠟胺、亞甲二胺、乙二胺、四乙五胺等。
2級脂肪族胺類,可列舉二甲胺、二乙胺、二-n-丙胺、二異丙胺、二-n-丁胺、二異丁胺、二-sec-丁胺、二戊胺、二環戊胺、二己胺、二環己胺、二庚胺、二辛胺、二壬胺、二癸胺、二-十二烷基胺、二鯨蠟胺、N,N-二甲基亞甲二胺、N,N-二甲基乙二胺、N,N-二甲基四乙五胺等。
3級脂肪族胺類,可列舉三甲胺、三乙胺、三-n-丙胺、三異丙胺、三-n-丁胺、三異丁胺、三-sec-丁胺、三戊胺、三環戊胺、三己胺、三環己胺、三庚胺、三辛胺、三壬胺、十三烷基胺、三-十二烷基胺、三鯨蠟胺、N,N,N',N'-四甲基亞甲二胺、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基四乙五胺等。
混成胺類,可列舉二甲基乙胺、甲基乙基丙胺、苄胺、苯乙胺、苄基二甲胺等。
芳香族胺類及雜環胺類,可列舉苯胺衍生物(例如苯胺、N-甲基苯胺、N-乙基苯胺、N-丙基苯胺、N,N-二甲基苯胺、2-甲基苯胺、3-甲基苯胺、4-甲基苯胺、乙基苯胺、丙基苯胺、三甲基苯胺、2-硝基苯胺、3-硝基苯胺、4-硝基苯胺、2,4-二硝基苯胺、2,6-二硝基苯胺、3,5-二硝基苯胺、N,N-二甲基甲苯胺等)、二苯基(p-甲苯基)胺、甲基二苯胺、三苯胺、苯二胺、萘胺、二胺基萘、吡咯衍生物(例如吡咯、2H-吡咯、1-甲基吡咯、2,4-二甲基吡咯、2,5-二甲基吡咯、N-甲基吡咯等)、噁唑衍生物(例如噁唑、異噁唑等)、噻唑衍生物(例如噻唑、異噻唑等)、吡唑衍生物、呋咱衍生物、二氫吡咯衍生物(例如二氫吡咯、2-甲基-1-二氫吡咯等)、吡咯啶衍生物(例如吡咯啶、N-甲基吡咯啶、吡咯烷酮(pyrrolidinone)、N-甲基吡咯啶酮等)、咪唑啉衍生物、咪唑啶衍生物、吡啶衍生物(例如吡啶、甲基吡啶、乙基吡啶、丙基吡啶、丁基吡啶、4-(1-丁基戊基)吡啶、二甲基吡啶、三甲基吡啶、三乙基吡啶、苯基吡啶、3-甲基-2-苯基吡啶、4-tert-丁基吡啶、二苯基吡啶、苄基吡啶、甲氧基吡啶、丁氧基吡啶、二甲氧基吡啶、1-甲基-2-吡啶、4-吡咯啶基吡啶、1-甲基-4-苯基吡啶、2-(1-乙基丙基)吡啶、胺基吡啶、二甲基胺基吡啶等)、嗒嗪衍生物、嘧啶衍生物、吡嗪衍生物、吡唑啉衍生物、吡唑啶衍生物、哌啶衍生物、哌嗪衍生物、嗎啉衍生物、吲哚衍生物、異吲哚衍生物、1H-吲唑衍生物、吲哚啉衍生物、喹啉衍生物(例如喹啉、3-喹啉碳腈等)、異喹啉衍生物、辛啉衍生物、喹唑啉衍生物、喹噁啉衍生物、酞嗪衍生物、嘌呤衍生物、喋啶衍生物、咔唑衍生物、啡啶衍生物、吖啶衍生物、啡嗪衍生物、1,10-啡啉衍生物、腺嘌呤衍生物、腺苷衍生物、鳥嘌呤衍生物、鳥苷衍生物、尿嘧啶衍生物、尿苷衍生物等。
具有羧基之含氮化合物,例如可列舉胺基安息香酸、吲哚羧酸、胺基酸衍生物(例如菸鹼酸、丙胺酸、精胺酸、天門冬胺酸、麩胺酸、甘胺酸、組胺酸、異白胺酸、甘胺醯基白胺酸、白胺酸、甲硫胺酸、苯基丙胺酸、蘇胺酸、離胺酸、3-胺基吡嗪-2-羧酸、甲氧基丙胺酸等)等。
具有磺醯基之含氮化合物,可列舉3-吡啶磺酸、p-甲苯磺酸吡啶鎓等。
具有羥基之含氮化合物、具有羥基苯基之含氮化合物及醇性含氮化合物,可列舉2-羥基吡啶、胺基甲酚、2,4-喹啉二醇、3-吲哚甲醇水合物、單乙醇胺、二乙醇胺、三乙醇胺、N-乙基二乙醇胺、N,N-二乙基乙醇胺、三異丙醇胺、2,2'-亞胺基二乙醇、2-胺基乙醇、3-胺基-1-丙醇、4-胺基-1-丁醇、4-(2-羥基乙基)嗎啉、2-(2-羥基乙基)吡啶、1-(2-羥基乙基)哌嗪、1-[2-(2-羥基乙氧基)乙基]哌嗪、哌啶乙醇、1-(2-羥基乙基)吡咯啶、1-(2-羥基乙基)-2-吡咯烷酮、3-哌啶基-1,2-丙二醇、3-吡咯啶基-1,2-丙二醇、8-羥基久咯啶、3-奎寧醇(3-quinuclidinol)、3-托品醇、1-甲基-2-吡咯啶乙醇、1-氮丙啶乙醇、N-(2-羥基乙基)鄰苯二甲醯亞胺、N-(2-羥基乙基)異菸鹼醯胺等。
醯胺衍生物,可列舉甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、丙醯胺、苄醯胺等。醯亞胺衍生物,可列舉鄰苯二甲醯亞胺、琥珀醯亞胺、馬來醯亞胺等。
式中,g為1、2或3。X1
係分別獨立地為氫原子,或直鏈狀、分支狀或環狀之碳數1~20之烷基,亦可含有醚基或羥基。X2
係分別獨立地為下述式(E-2)~(E-4)表示之基。又,X2
彼此亦可鍵結,並與此等所鍵結之氮原子一起形成環。
式中,R201
、R203
及R206
係分別獨立地為直鏈狀或分支狀之碳數1~4之伸烷基。R202
及R205
係分別獨立地為氫原子,或直鏈狀、分支狀或環狀之碳數1~20之烷基,亦可含有1個或2個以上之羥基、醚基、酯基或內酯環。R204
為單鍵或直鏈狀或分支狀之碳數1~4之伸烷基。R207
為直鏈狀、分支狀或環狀之碳數1~20之烷基,亦可含有1個或2個以上之羥基、醚基、酯基或內酯環。
式(E-1)表示之鹼性化合物,可列舉參(2-甲氧基甲氧基乙基)胺、參{2-(2-甲氧基乙氧基)乙基}胺、參{2-(2-甲氧基乙氧基甲氧基)乙基}胺、參{2-(1-甲氧基乙氧基)乙基}胺、參{2-(1-乙氧基乙氧基)乙基}胺、參{2-(1-乙氧基丙氧基)乙基}胺、參[2-{2-(2-羥基乙氧基)乙氧基}乙基]胺、4,7,13,16,21,24-六氧雜-1,10-二氮雜雙環[8.8.8]二十六烷、4,7,13,18-四氧雜-1,10-二氮雜雙環[8.5.5]二十烷、1,4,10,13-四氧雜-7,16-二氮雜雙環十八烷、1-氮雜-12-冠-4、1-氮雜-15-冠-5、1-氮雜-18-冠-6、參(2-甲醯氧基乙基)胺、參(2-乙醯氧基乙基)胺、參(2-丙醯氧基乙基)胺、參(2-丁醯氧基乙基)胺、參(2-異丁醯氧基乙基)胺、參(2-戊醯氧基乙基)胺、參(2-三甲基乙醯氧基乙基)胺、N,N-雙(2-乙醯氧基乙基)2-(乙醯氧基乙醯氧基)乙胺、參(2-甲氧基羰氧基乙基)胺、參(2-tert-丁氧基羰氧基乙基)胺、參[2-(2-側氧基丙氧基)乙基]胺、參[2-(甲氧基羰基甲基)氧基乙基]胺、參[2-(tert-丁氧基羰基甲氧基)乙基]胺、參[2-(環己氧基羰基甲氧基)乙基]胺、參(2-甲氧基羰基乙基)胺、參(2-乙氧基羰基乙基)胺、N,N-雙(2-羥基乙基)2-(甲氧基羰基)乙胺、N,N-雙(2-乙醯氧基乙基)2-(甲氧基羰基)乙胺、N,N-雙(2-羥基乙基)2-(乙氧基羰基)乙胺、N,N-雙(2-乙醯氧基乙基)2-(乙氧基羰基)乙胺、N,N-雙(2-羥基乙基)2-(2-甲氧基乙氧基羰基)乙胺、N,N-雙(2-乙醯氧基乙基)2-(2-甲氧基乙氧基羰基)乙胺、N,N-雙(2-羥基乙基)2-(2-羥基乙氧基羰基)乙胺、N,N-雙(2-乙醯氧基乙基)2-(2-乙醯氧基乙氧基羰基)乙胺、N,N-雙(2-羥基乙基)2-[(甲氧基羰基)甲氧基羰基]乙胺、N,N-雙(2-乙醯氧基乙基)2-[(甲氧基羰基)甲氧基羰基]乙胺、N,N-雙(2-羥基乙基)2-(2-側氧基丙氧基羰基)乙胺、N,N-雙(2-乙醯氧基乙基)2-(2-側氧基丙氧基羰基)乙胺、N,N-雙(2-羥基乙基)2-(四氫呋喃甲基氧基羰基)乙胺、N,N-雙(2-乙醯氧基乙基)2-(四氫呋喃甲基氧基羰基)乙胺、N,N-雙(2-羥基乙基)2-[(2-側氧基四氫呋喃-3-基)氧基羰基]乙胺、N,N-雙(2-乙醯氧基乙基)2-[(2-側氧基四氫呋喃-3-基)氧基羰基]乙胺、N,N-雙(2-羥基乙基)2-(4-羥基丁氧基羰基)乙胺、N,N-雙(2-甲醯氧基乙基)2-(4-甲醯氧基丁氧基羰基)乙胺、N,N-雙(2-甲醯氧基乙基)2-(2-甲醯氧基乙氧基羰基)乙胺、N,N-雙(2-甲氧基乙基)2-(甲氧基羰基)乙胺、N-(2-羥基乙基)雙[2-(甲氧基羰基)乙基]胺、N-(2-乙醯氧基乙基)雙[2-(甲氧基羰基)乙基]胺、N-(2-羥基乙基)雙[2-(乙氧基羰基)乙基]胺、N-(2-乙醯氧基乙基)雙[2-(乙氧基羰基)乙基]胺、N-(3-羥基-1-丙基)雙[2-(甲氧基羰基)乙基]胺、N-(3-乙醯氧基-1-丙基)雙[2-(甲氧基羰基)乙基]胺、N-(2-甲氧基乙基)雙[2-(甲氧基羰基)乙基]胺、N-丁基雙[2-(甲氧基羰基)乙基]胺、N-丁基雙[2-(2-甲氧基乙氧基羰基)乙基]胺、N-甲基雙(2-乙醯氧基乙基)胺、N-乙基雙(2-乙醯氧基乙基)胺、N-甲基雙(2-三甲基乙醯氧基乙基)胺、N-乙基雙[2-(甲氧基羰氧基)乙基]胺、N-乙基雙[2-(tert-丁氧基羰氧基)乙基]胺、參(甲氧基羰基甲基)胺、參(乙氧基羰基甲基)胺、N-丁基雙(甲氧基羰基甲基)胺、N-己基雙(甲氧基羰基甲基)胺、β-(二乙基胺基)-δ-戊內酯等。
前述光阻組成物中,(E)鹼性化合物之含量,相對於(A)成分之基底樹脂100質量份而言,為0~5質量份,含有的情況時,較適宜為0.01~2質量份。含量若為前述範圍,則無感度降低之虞。(E)鹼性化合物,可1種單獨或組合2種以上使用。
[(F)界面活性劑] 前述光阻組成物,亦可依需要含有(F)界面活性劑。(F)界面活性劑,可列舉聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯油基醚等之聚氧乙烯烷基醚類、聚氧乙烯辛基酚醚、聚氧乙烯壬基酚醚等之聚氧乙烯烷基烯丙基醚類、聚氧乙烯聚氧丙烯嵌段共聚物類、山梨醇酐單月桂酸酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯等之山梨醇酐脂肪酸酯類、聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單棕櫚酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚醚聚矽氧、聚氧乙烯山梨醇酐三油酸酯、聚氧乙烯山梨醇酐三硬脂酸酯等之聚氧乙烯山梨醇酐脂肪酸酯之非離子系界面活性劑、Eftop EF301、EF303、EF352((股)Tokem Products製)、Megafac F171、F172、F173(DIC(股)製)、Fluorad FC-4430、FC-430、FC-431(住友3M(股)製)、Sufynol E1004(日信化學工業(股)製)、Asahiguard AG710、Surflon S-381、S-382、SC101、SC102、SC103、SC104、SC105、SC106、KH-10、KH-20、KH-30、KH-40(AGC SEIMI CHEMICAL(股)製)等之氟系界面活性劑、有機矽氧烷聚合物KP-341、X-70-092、X-70-093(信越化學工業(股)製)、丙烯酸系或甲基丙烯酸系Polyflow No.75、No.95(共榮社化學(股)製)等。其中尤以FC-4430、KP-341、X-70-093較適宜。此等可1種單獨或組合2種以上使用。
前述光阻組成物中,(F)界面活性劑之含量,相對於(A)成分之基底樹脂100質量份而言,係0~5質量份,含有的情況時,較佳為0.01~2質量份。
[(G)聚酯樹脂] 前述光阻組成物,亦可依需要含有(G)聚酯樹脂。(G)成分之聚酯樹脂,為於主鏈具有酯鍵者,較佳為多元羧酸與多元醇之縮合物(所謂的聚酯)。又,(G)成分之聚合物,亦可為多元羧酸酐與多元醇之縮合物。
前述多元羧酸,較佳為具有2~6個羧基者,具體而言,可列舉草酸、琥珀酸、丙二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、甲基丙二酸、檸康酸、富馬酸、馬來酸、甲基馬來酸、中康酸、戊烯二酸、依康酸、烯丙基丙二酸、托康酸、黏康酸、丁炔二酸、烏頭酸、蘋果酸、酒石酸、消旋酒石酸、檸檬酸、側氧基丙二酸、側氧基琥珀酸、硫代蘋果酸、麩胺酸、乙二胺四乙酸、1,2-環丙烷二羧酸、吐昔酸、樟腦酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯基琥珀酸、2-(3-羧基苯基)-2-側氧基乙酸、罌粟酸、環丁烷二羧酸等。進而可使用此等之酸酐。此等之中,較佳為2元羧酸。前述多元羧酸,可1種單獨或組合2種以上使用。
又,多元醇可列舉1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,4-丁二醇、1,4-環己烷甲二醇、1,2-戊二醇、1,3-戊二醇、1,5-戊二醇、1,6-己二醇、2-甲基-2,4-戊二醇、3-甲基-1,5-戊二醇、乙二醇、丙二醇、新戊二醇、甘油、五甘油等。此等之中,較佳為2元醇。前述多元醇,可1種單獨或組合2種以上使用。
只要基於前述原料,遵照公知方法進行縮合聚合即可。原料之使用量,只要依所得之聚合物的分子量來適當調整即可,通常相對於多元羧酸1莫耳而言,多元醇為0.5~3莫耳左右。
又,酯化可為公知之方法,只要使用硫酸等之酸性觸媒、鈦化合物、錫化合物、鋅化合物、鍺化合物、銻化合物等之金屬,依需要加熱150~300℃左右進行縮合反應即可。
(G)成分之聚合物之Mw,較佳為700~50,000、更佳為1,500~45,000。
前述光阻組成物中,(G)成分之含量,相對於(A)成分之基底樹脂100質量份而言,較佳為0~100質量份、更佳為10~60質量份、又更佳為15~50質量份。含量若為前述範圍,則因可充分得到薄膜的柔軟性,故可抑制於階差基板上之孔隙缺陷的產生。(G)成分之聚合物,可1種單獨或組合2種以上使用。
[(H)羧酸] 前述光阻組成物,亦可依需要含有(H)羧酸。(H)羧酸可列舉飽和或不飽和脂肪族羧酸、脂環式羧酸、羥基羧酸、烷氧基羧酸、酮基羧酸、芳香族羧酸等。
前述飽和脂肪族羧酸,可列舉甲酸、乙酸、丙酸、丁酸、異丁酸、戊酸、己酸、庚酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸等之1元或多元羧酸。前述不飽和脂肪族羧酸,可列舉丙烯酸、巴豆酸、異巴豆酸、3-丁烯酸、甲基丙烯酸、4-戊烯酸、丙酸、2-丁炔酸、馬來酸、富馬酸等。前述羥基羧酸,可列舉羥基乙酸等。前述烷氧基羧酸,可列舉甲氧基乙酸等。前述酮基羧酸,可列舉丙酮酸等。前述芳香族羧酸,可列舉安息香酸、p-羥基安息香酸、o-羥基安息香酸、鄰苯二甲酸、對苯二甲酸、間苯二甲酸等。此等之中,較佳為二羧酸、特佳為飽和脂肪族二羧酸。
前述光阻組成物中,(H)羧酸之含量,相對於(A)成分之基底樹脂100質量份而言,為0~1質量份,含有的情況時,較佳為0.0001~0.5質量份。含量若為前述範圍,則無密合性降低之虞。(H)羧酸,可1種單獨或組合2種以上使用。
[其他成分] 前述光阻組成物,於前述成分以外,亦可依需要含有苯并三唑化合物、咪唑化合物、用以使鹼顯影速度加快的溶解促進劑、用以減少來自基板之漫反射的染料等之吸光性材料、分子中具有1,2-萘醌二疊氮磺醯基之化合物、增感劑、交聯劑、光鹼產生劑、酸增殖劑等。再者,任意成分之含量,於不妨礙本發明之效果的範圍內可為一般量。
前述吸光性材料,可列舉2-苯偶氮-4-甲基酚、4-羥基-4'-二甲基胺基偶氮苯等之偶氮化合物或薑黃素等。
前述化學增幅正型光阻組成物,可藉由將前述之(A)基底樹脂、(B)光酸產生劑及(D)聚乙烯醇或聚乙烯烷基醚以及依需要之(E)~(H)成分或其他成分,同時或以任意順序溶解於(C)有機溶劑,成為均勻溶液來調製。又,亦可依需要對所得到之均勻溶液使用濾器來進行過濾。
[圖型形成方法] 本發明之圖型形成方法,為包含下述步驟(i)~(iii)者。
[步驟(i)] 步驟(i),係使用前述化學增幅正型光阻組成物,於基板上形成化學增幅正型光阻膜之步驟。
作為形成化學增幅正型光阻膜之方法之一例,可列舉將前述化學增幅正型光阻組成物直接塗佈於作為目標的基板上,形成光阻膜之方法。
此時,塗佈方法可為以往公知之方法。具體而言,可於Si、SiO2
、SiN、SiON、TiN、WSi、BPSG、SOG等之基板、Au、Ti、W、Cu、Ni-Fe、Ta、Zn、Co、Pb等之金屬基板、有機抗反射膜等之基板、玻璃基板、有機基板上,藉由旋轉塗佈、輥塗佈、流動塗佈、浸漬塗佈、噴霧塗佈、刮刀塗佈等之適當的塗佈方法,塗佈為所期望之膜厚。
作為形成化學增幅正型光阻膜之方法之其他例子,可列舉使用前述化學增幅正型光阻組成物,一時於有機薄膜上形成光阻膜來製作光阻薄膜層合體,之後將該光阻膜轉印於作為目標的基板之方法。
此時,首先,將化學增幅正型光阻組成物,於潔淨度1,000以下之潔淨室(clean room)中,使用設置於較佳為於溫度5~45℃、更佳為於15~35℃,且較佳為於濕度5~90%、更佳為於10~70%管理的區域之正向輥塗佈器、逆向輥塗佈器、缺角輪塗佈器、模具塗佈器、唇口塗佈器、凹版塗佈器、浸漬塗佈器、氣刀塗佈器、毛細管塗佈器、提起&上昇(R&R)塗佈器、刮刀塗佈器、棒塗佈器、塗抹器、擠出成形機等,塗佈於熱可塑性薄膜(脫模基材)之上。此時,塗佈速度較佳為0.05~1,000m/min、更佳為0.1~500m/min。然後,將塗佈有化學增幅正型光阻組成物之熱可塑性薄膜,於線內乾燥器(in-line dryer)(熱風循環烘箱)中,40~130℃、1~40分鐘;更佳為50~120℃、2~30分鐘,將有機溶劑及揮發成分去除,乾燥而形成化學增幅正型光阻薄膜層合體。再者,亦可利用以紅外線照射等之溶劑去除、同時使用線內乾燥器與紅外線照射之方法等複數種乾燥手法,以取代線內乾燥器,來進行溶劑去除,而形成化學增幅正型光阻薄膜層合體。又,亦可依需要,使用輥疊合機將保護薄膜(脫模基材)壓接於前述化學增幅正型光阻薄膜層合體上來進行層合。
再者,可於熱可塑性薄膜上連續地形成光阻薄膜,成為長形光阻薄膜層,以操作容易之薄膜捲筒的形態捲起,又,於光阻薄膜層合體上形成保護薄膜的情況亦相同。
作為前述保護薄膜,與熱可塑性薄膜同樣地,只要係可在不損及化學增幅正型光阻薄膜之形態之下,由化學增幅正型光阻薄膜剝離者,則無特殊限定,可使用層合有單一或複數之聚合物薄膜的多層薄膜。具體而言,可列舉耐綸薄膜、聚乙烯(PE)薄膜、聚對苯二甲酸乙二酯(PET)薄膜、聚萘二甲酸乙二酯薄膜、聚苯硫醚(PPS)薄膜、聚丙烯(PP)薄膜、聚苯乙烯薄膜、聚甲基戊烯(TPX)薄膜、聚碳酸酯、含氟薄膜、特殊聚乙烯醇(PVA)薄膜、實施過脫模處理之聚酯薄膜等之塑膠薄膜等。
此等之中,作為保護薄膜,較佳為具有適度之可撓性的PET薄膜或PE薄膜。此等可使用市售品,PET薄膜可列舉前述者,PE薄膜例如可列舉GF-8(Tamapoly(股)製)、PE薄膜0型(Nippa(股)製)、Toretec 7332、Toretec 7111、Toretec 7721(以上,東麗薄膜加工(股)製)等。
前述熱可塑性薄膜及保護薄膜之厚度,由製造之安定性及防止對捲芯之捲繞不良即所謂捲曲的觀點而言,較佳均為10~150μm、更佳為25~100μm。
保護薄膜對於前述步驟中製造之化學增幅正型光阻薄膜的剝離力,通常為0.1~500gf/24mm之範圍,以下記述其測定方法。試驗方法,係根據JIS Z 0237記載之「將剝離襯墊對膠帶黏著面撕離的黏著力試驗方法」來進行。試驗環境為標準狀態(溫度為23±1℃、相對濕度為50±5%)。試驗所用之薄膜寬度為24mm,因薄膜寬度變動時,剝離力會變化,故不佳。製作特定尺寸之薄膜後,使用試驗機測定時,保護薄膜之撕離角度為180°,剝離速度為5.0±0.2mm/秒。再者,測定值,係除外最初25mm之測定值,使用之後50mm之平均值作為試驗值。
由光阻薄膜層合體轉印光阻膜時,藉由將光阻薄膜層合體貼附於基板,將熱可塑性薄膜剝離,使用真空疊合機等進行轉印,可將光阻膜轉印於作為目標之基板上。
光阻膜之厚度並無特殊限定,較佳為1~100μm、更佳為5~50μm。
光阻膜形成後,亦可(i-2)依需要,於加熱板上或烘箱內,較佳為60~150℃、0.5~30分鐘;更佳為80~120℃、1~10分鐘進行加熱處理(預烘烤)。
[步驟(ii)] 步驟(ii)為將前述光阻膜曝光之步驟。對於前述光阻膜,使用由紫外線、遠紫外線、電子束等中選出之光源,較佳為300nm以上、特別是300~500nm波長之光,依需要通過遮罩將作為目標之圖型曝光。曝光量較佳為10~3,000mJ/cm2
左右、更佳為20~2,000mJ/cm2
左右。
曝光後,亦可(ii-2)依需要,於加熱板上或烘箱內,較佳為60~150℃、1~30分鐘;更佳為80~120℃、1~10分鐘進行加熱處理(曝光後烘烤(PEB))。
[步驟(iii)] 步驟(iii),為使用含有氧之氣體,以乾式蝕刻進行顯影之步驟。乾式蝕刻可使用一般的乾式蝕刻裝置,進行使用含有氧氣之電漿的反應性離子蝕刻(RIE)等。一例可為藉由首先將腔室內之氣體排氣,使腔室內之壓力成為5~500mmTorr左右,以0.05~600W、較佳為50~500W供給高頻電力,並且以5~1,000sccm、較佳為10~500sccm左右導入氧,進行5~60分鐘,但不限定於此條件。又,為了控制蝕刻速率,亦可依需要混合Ar、He、N2
等之安定性高的氣體,或含有氟、氯、溴等之鹵素之蝕刻性氣體(以流量計係60%以下)。藉由使用如此之氧電漿的RIE,經曝光之部分之蝕刻速率快、未曝光部之蝕刻速率變慢,具有充分的蝕刻對比,因此最終可得到於未曝光部具有殘膜之正型圖型。
進一步地亦可對所得之圖型實施以鍍敷、濺鍍、蒸鍍等所為的電路形成步驟,來得到半導體基板。 [實施例]
以下敘明調製例、實施例及比較例,以更具體說明本發明,但本發明不限定於此等實施例。
[調製例] 將作為(A)成分之基底樹脂之聚合物1~聚合物3,及(B)~(H)成分,以下述表1所示之組成溶解,將所得之溶液以1.0μm之膜濾器過濾,調製化學增幅正型光阻組成物。
聚合物1~聚合物3之構造及表1中之(B)~(H)成分,係如以下所述。再者,聚合物(A)之重量平均分子量(Mw)及數平均分子量(Mn),係以使用THF作為溶劑的GPC所得的聚苯乙烯換算測定值。
(B)光酸產生劑 PAG-1:綠化學(股)製PAI-101(4-甲基苯基磺醯氧基亞胺基-α-(4-甲氧基苯基)乙腈) PAG-2:San-Apro(股)製HT-1CS (C)有機溶劑 EL:乳酸乙酯 CP:環戊酮 PMA:丙二醇單甲基醚乙酸酯 (D)聚乙烯醇或聚乙烯烷基醚 PVA1:聚乙烯醇(皂化度99mol%、Mw=20,000)、 PVA2:聚乙烯醇(皂化度88mol%、Mw=35,000) M40:BASF公司製Lutonal M40(聚乙烯基甲基醚(Mw=51,000)、70%乙醇溶液) A25:BASF公司製Lutonal A25(聚乙烯基乙基醚(Mw=3,700)) (E)鹼性化合物 TEA:三乙醇胺(關東化學(股)製) (F)界面活性劑 S-1:X-70-093(信越化學工業(股)製) (G)聚酯樹脂 PE1:己二酸系聚酯(Polycizer W-2050(DIC(股)製)) PE2:己二酸系聚酯(D645((股)J-PLUS製)) (H)羧酸 OA:草酸(關東化學(股)製) BA:安息香酸(關東化學(股)製)
[實施例1~10、比較例1~4] 對於表1之組成物1~7及9~12,係將各光阻組成物旋轉塗佈於8吋矽晶圓上,於加熱板上進行100℃、120秒之預烘烤,形成厚度10μm之光阻膜。接著,使用(股)Nikon製NSR-2205i11(波長365nm)進行曝光後,進行110℃、90秒之PEB。 又,對於組成物8、13及14,係使用模具塗佈器作為薄膜塗佈器、使用PET薄膜(厚度38μm)作為熱可塑性薄膜,將各光阻組成物塗佈於PET薄膜上,以熱風循環烘箱於100℃之烘箱溫度乾燥5分鐘,於潔淨度1,000、濕度40~45%、溫度22~26℃之潔淨室中,製作化學增幅正型光阻薄膜層合體。之後,於製作之光阻膜表面,以壓力1MPa貼合作為保護薄膜之PE薄膜(厚度50μm)。對於該所製作之化學增幅正型光阻薄膜層合體,首先,將保護薄膜剝離,使用真空疊合機TEAM-100M((股)Takatori製),將真空腔室內設定為真空度80Pa,轉印於8吋矽晶圓上。此時之溫度條件為60℃。回到常壓後,將前述基板由真空疊合機取出,剝離熱可塑性薄膜,確認厚度10μm之光阻膜被轉印,以(股)Nikon製NSR-2205i11進行曝光。
接著,使用乾式蝕刻裝置(日電Anelva(股)製DEM-451),於減壓下(0.01Pa),以RF功率200W、O2
流量60sccm,進行10分鐘蝕刻。
關於所得之線與間隙(line and space)的圖型,使用掃描型電子顯微鏡(SEM、(股)日立High-Technologies製S-4700),進行感度與解像性之確認。感度係設為100μm之線與間隙的重複成為1:1之曝光量,將以該曝光量所解像的最小圖型尺寸,判斷為最大解像性。結果示於表2。又,實施例中,以SEM觀察顯影後之基板表面後,確認到於去除之部分並無(類粒子之)殘渣。
Claims (5)
- 一種圖型形成方法,其包含(i)使用含有(A)含有具有經酸不安定基取代之酚性羥基,且藉由酸的作用,前述酸不安定基會脫離而成為鹼可溶性之聚合物的基底樹脂、(B)光酸產生劑、(C)有機溶劑,及(D)聚乙烯醇或聚乙烯烷基醚之化學增幅正型光阻組成物,於基板上形成化學增幅正型光阻膜之步驟、(ii)將前述化學增幅正型光阻膜曝光之步驟,及(iii)使用含有氧之氣體,以乾式蝕刻進行顯影之步驟。
- 如請求項1之圖型形成方法,其中於步驟(i)與步驟(ii)之間包含(i-2)加熱處理步驟。
- 如請求項1或2之圖型形成方法,其中於步驟(ii)與步驟(iii)之間包含(ii-2)加熱處理步驟。
- 如請求項1或2之圖型形成方法,其中前述化學增幅正型光阻組成物,為薄膜狀組成物。
- 如請求項1或2之圖型形成方法,其中曝光係藉由波長300~500nm之光來進行。
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