TW201905589A - Chemically amplified positive photosensitive resin composition, photoresist pattern, method of forming same, and electronic device - Google Patents
Chemically amplified positive photosensitive resin composition, photoresist pattern, method of forming same, and electronic deviceInfo
- Publication number
- TW201905589A TW201905589A TW106120859A TW106120859A TW201905589A TW 201905589 A TW201905589 A TW 201905589A TW 106120859 A TW106120859 A TW 106120859A TW 106120859 A TW106120859 A TW 106120859A TW 201905589 A TW201905589 A TW 201905589A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- formula
- acid
- resin composition
- carbon atoms
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 61
- -1 polysiloxane Polymers 0.000 claims abstract description 125
- 239000000178 monomer Substances 0.000 claims abstract description 44
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910000077 silane Inorganic materials 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 125000006239 protecting group Chemical group 0.000 claims abstract description 35
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 87
- 125000000217 alkyl group Chemical group 0.000 claims description 85
- 239000002253 acid Substances 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 150000007514 bases Chemical class 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 11
- 125000004018 acid anhydride group Chemical group 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000758 substrate Substances 0.000 description 22
- 125000001424 substituent group Chemical group 0.000 description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 15
- 125000002947 alkylene group Chemical group 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 125000001624 naphthyl group Chemical group 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 125000001153 fluoro group Chemical group F* 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 229920005591 polysilicon Polymers 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 5
- GXDMUOPCQNLBCZ-UHFFFAOYSA-N 3-(3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CCCC1CC(=O)OC1=O GXDMUOPCQNLBCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- YRTGWRSQRUHPKX-UHFFFAOYSA-N 3-ethyloxolane-2,5-dione Chemical compound CCC1CC(=O)OC1=O YRTGWRSQRUHPKX-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- VXQYICLHHMETFH-UHFFFAOYSA-N 5-hydroxy-8-[5-(5-hydroxy-7-methoxy-4-oxochromen-2-yl)-2-methoxyphenyl]-7-methoxy-2-(4-methoxyphenyl)chromen-4-one Chemical compound C1=CC(OC)=CC=C1C1=CC(=O)C2=C(O)C=C(OC)C(C=3C(=CC=C(C=3)C=3OC4=CC(OC)=CC(O)=C4C(=O)C=3)OC)=C2O1 VXQYICLHHMETFH-UHFFFAOYSA-N 0.000 description 4
- 241000501754 Astronotus ocellatus Species 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical group CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000003759 ester based solvent Substances 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 3
- JIUWLLYCZJHZCZ-UHFFFAOYSA-N 3-propyloxolane-2,5-dione Chemical compound CCCC1CC(=O)OC1=O JIUWLLYCZJHZCZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-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
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940022663 acetate Drugs 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000008434 ginseng Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- ADXRZEBGDJHQDY-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxane-2,6-dione Chemical compound CO[Si](OC)(OC)CCCC1CCC(=O)OC1=O ADXRZEBGDJHQDY-UHFFFAOYSA-N 0.000 description 2
- ZADOWCXTUZWAKL-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxolane-2,5-dione Chemical compound CO[Si](OC)(OC)CCCC1CC(=O)OC1=O ZADOWCXTUZWAKL-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- JXVJCMCDVMQTCY-UHFFFAOYSA-N C(C1=CC=CC=C1)=C1CC=C(C=C1)SC1=CC=C(C=C1)C=1C(=C(C=2CC3=CC=CC=C3C2C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C1=CC=CC=C1)=C1CC=C(C=C1)SC1=CC=C(C=C1)C=1C(=C(C=2CC3=CC=CC=C3C2C1)C1=CC=CC=C1)C1=CC=CC=C1 JXVJCMCDVMQTCY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
Description
本發明是有關於一種化學增幅型正型感光性樹脂組成物、光阻圖案及其形成方法以及電子裝置,且特別是有關於一種能夠改善感度及耐熱性不佳問題的化學增幅型正型感光性樹脂組成物、由所述化學增幅型正型感光性樹脂組成物製得的光阻圖案及其形成方法、以及包括所述光阻圖案的電子裝置。The invention relates to a chemically amplified positive-type photosensitive resin composition, a photoresist pattern, a method for forming the same, and an electronic device, and more particularly to a chemically amplified positive-type photosensitive resin capable of improving the problem of poor sensitivity and heat resistance A photosensitive resin composition, a photoresist pattern made from the chemically amplified positive photosensitive resin composition, a method for forming the same, and an electronic device including the photoresist pattern.
目前為止,在使用玻璃基板製造液晶顯示元件的領域中,適合於g、h、i線曝光、價格較低廉、感度及解像性良好、可形成形狀優異的光阻圖案的光阻材料,大多採用以酚醛樹脂作為鹼可溶性樹脂,且使用含有醌二疊氮基化合物作為感光性成份的正型光阻組成物(專利文獻1~4)。Until now, in the field of manufacturing liquid crystal display elements using glass substrates, most photoresist materials are suitable for g, h, and i-line exposure, are relatively inexpensive, have good sensitivity and resolution, and can form photoresist patterns with excellent shapes. A positive photoresist composition using a phenolic resin as an alkali-soluble resin and containing a quinonediazide-based compound as a photosensitive component (Patent Documents 1 to 4) is used.
現在,作為次世代的LCD,在一枚玻璃基板上同時形成驅動器、數位模擬變換器(DAC)、圖像處理裝置、視頻控制器、RAM等積體電路部份與顯示部份,即所謂「系統LCD」的高功能LCD的技術開發非常的盛行。Now, as the next-generation LCD, integrated circuit parts and display parts such as drivers, digital analog converters (DACs), image processing devices, video controllers, and RAMs are formed on a glass substrate. "System LCD" technology development of high-performance LCD is very popular.
本說明書中,為方便起見,將在一個基板上形成積體電路與液晶顯示部份的基板稱為系統LCD。In this specification, for convenience, a substrate on which a integrated circuit and a liquid crystal display portion are formed on one substrate is referred to as a system LCD.
在系統LCD中,替代非晶質矽、且可在600℃以下的低溫製程形成的材料為低溫聚矽,相較於非晶質矽,低溫聚矽的電阻小、移動度高。因此,業者期望開發適合於製造使用低溫聚矽的系統LCD的光阻組成物。目前系統LCD所使用的光阻材料有各種的報告(專利文獻5~12)。In the system LCD, the material that can replace amorphous silicon and can be formed at a low temperature process below 600 ° C is low temperature polysilicon. Compared with amorphous silicon, low temperature polysilicon has lower resistance and higher mobility. Therefore, the industry expects to develop a photoresist composition suitable for manufacturing a system LCD using low-temperature polysilicon. There are various reports of photoresist materials used in current system LCDs (Patent Documents 5 to 12).
製造由低溫聚矽所成的TFT時,以低溫製程在玻璃基板上形成聚矽膜後,在該低溫聚矽膜上注入P(磷)、或B(硼)等,於所謂「注入步驟」中,需要注入非常高濃度的雜質。When manufacturing a TFT made of low-temperature polysilicon, a polysilicon film is formed on a glass substrate in a low-temperature process, and then P (phosphorus) or B (boron) is implanted on the low-temperature polysilicon film. Medium, it is necessary to implant a very high concentration of impurities.
此注入步驟,是在低溫聚矽玻璃基板上形成光阻圖案的狀態下,在高真空度的條件下進行。但此過程中,因藉由注入雜質時的發熱作用,將使基板上的光阻圖案加熱時引起光阻圖案的形狀改變,光阻圖案中的某些成份氣化,導致處理室內的真空度下降的問題點發生。This implantation step is performed under a condition of high vacuum in a state where a photoresist pattern is formed on a low-temperature polysilicon glass substrate. However, during this process, the shape of the photoresist pattern will change when the photoresist pattern on the substrate is heated due to the heating effect during the implantation of impurities, and some components in the photoresist pattern will vaporize, resulting in a vacuum in the processing chamber. The problem point of the drop occurred.
解決此問題的方法,以在注入步驟之前進行稱為「後烤」的加熱處理步驟,甚為有效。此處的「後烤」由於是在接近於注入時的加熱溫度的溫度條件下進行(例如200℃以上的高溫),故光阻材料需具備在該加熱處理中不使圖案形狀改變的高耐熱特性。The solution to this problem is to perform a heat treatment step called "post-baking" before the injection step, which is very effective. The "post-baking" here is performed under a temperature condition close to the heating temperature at the time of injection (for example, a high temperature of 200 ° C or higher), so the photoresist material must have high heat resistance that does not change the shape of the pattern during this heat treatment. characteristic.
因此,為使系統LCD的製造實現化,須謀求其使用的光阻組成物具有良好的耐熱性。Therefore, in order to realize the manufacture of the system LCD, it is necessary to make the photoresist composition used therein have good heat resistance.
此外,在系統LCD中,例如相對於顯示部份的圖案尺寸為2~10 μm,積體電路部份則以0.5~2.0 μm的精細尺寸形成。因此,製造系統LCD所使用的光阻組成物除要求可同時形成形狀良好的精細圖案與粗糙圖案的能力(線性)以外,更要求比以往製造LCD所使用的光阻材料具有更高的解析度、與良好的精細圖案的焦點深度寬(DOF)特性。In addition, in the system LCD, for example, the pattern size of the display portion is 2 to 10 μm, and the integrated circuit portion is formed with a fine size of 0.5 to 2.0 μm. Therefore, in addition to the photoresist composition used to manufacture system LCDs, the ability to form both fine patterns and rough patterns with good shapes (linearity) is required. It also requires a higher resolution than the photoresist materials used to manufacture LCDs in the past. , With a good fine pattern, the depth of focus (DOF) characteristics.
然而,在液晶顯示元件的製造領域中,光阻材料的感度低下的問題容易造成嚴重的生產力下降,故具有高感度之特性是業界所期望的。However, in the field of manufacturing liquid crystal display elements, the problem of low sensitivity of the photoresist material is likely to cause serious productivity degradation. Therefore, characteristics with high sensitivity are desirable in the industry.
[專利文獻] 專利文獻1:日本特開2000-131835號公報 專利文獻2:日本特開2001-075272號公報 專利文獻3:日本特開2000-181055號公報 專利文獻4:日本特開2000-112120號公報 專利文獻5:日本特開2004-233846號公報 專利文獻6:日本特開2004-191394號公報 專利文獻7:日本特開2004-145207號公報 專利文獻8:日本特開2004-144905號公報 專利文獻9:日本特開2004-077999號公報 專利文獻10:日本特開2004-045707號公報 專利文獻11:日本特開2004-045618號公報 專利文獻12:日本特開2003-233174號公報[Patent Literature] Patent Literature 1: Japanese Patent Laid-Open No. 2000-131835 Patent Literature 2: Japanese Patent Laid-Open No. 2001-075272 Patent Literature 3: Japanese Patent Laid-Open No. 2000-181055 Patent Literature 4: Japanese Patent Laid-Open No. 2000-112120 Patent Document 5: Japanese Patent Application Laid-Open No. 2004-233846 Patent Document 6: Japanese Patent Application Laid-Open No. 2004-191394 Patent Literature 7: Japanese Patent Application Laid-Open No. 2004-145207 Patent Literature 8: Japanese Patent Application Laid-Open No. 2004-144905 Patent Document 9: Japanese Patent Application Laid-Open No. 2004-077999 Patent Document 10: Japanese Patent Application Laid-Open No. 2004-045707 Patent Literature 11: Japanese Patent Application Laid-Open No. 2004-045618 Patent Literature 12: Japanese Patent Application Laid-Open No. 2003-233174
有鑑於此,本發明提供一種化學增幅型正型感光性樹脂組成物,使用所述化學增幅型正型感光性樹脂組成物能夠改善感度及耐熱性不佳的問題。In view of this, the present invention provides a chemically amplified positive photosensitive resin composition. The use of the chemically amplified positive photosensitive resin composition can improve the problems of poor sensitivity and heat resistance.
本發明提供一種化學增幅型正型感光性樹脂組成物,包括:含有酸解離性保護基的聚羥基苯乙烯樹脂(A)、聚矽氧烷(B)、光酸產生劑(C)、以及溶劑(D),其中,聚矽氧烷(B)至少是由式(B-1)表示的矽烷單體聚縮合而得: Si(Ra )w (ORb )4-w 式(B-1) 式(B-1)中,Ra 各自獨立表示氫原子、碳數為1至10的烷基、碳數為2至10的烯基、碳數為6至15的芳香基、含有酸酐基的碳數為1至10的烷基、含有環氧基的碳數為1至10的烷基或含有環氧基的碳數為1至10的烷氧基; Rb 各自獨立表示氫原子、碳數為1至6的烷基、碳數為1至6的醯基或碳數為6至15的芳香基; w表示1至3的整數; 且至少一個Ra 表示含有酸酐基的碳數為1至10的烷基、含有環氧基的碳數為1至10的烷基或含有環氧基的碳數為1至10的烷氧基。The present invention provides a chemically amplified positive photosensitive resin composition, comprising: a polyhydroxystyrene resin (A) containing an acid dissociative protective group, a polysiloxane (B), a photoacid generator (C), and Solvent (D), wherein polysiloxane (B) is obtained by polycondensation of at least a silane monomer represented by formula (B-1): Si (R a ) w (OR b ) 4-w formula (B- 1) In the formula (B-1), each of R a independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, and an acid anhydride The alkyl group has 1 to 10 carbon atoms, the epoxy group contains 1 to 10 carbon atoms or the epoxy group contains 1 to 10 alkoxy groups; R b each independently represents a hydrogen atom , An alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; w represents an integer of 1 to 3; and at least one R a represents a carbon containing an acid anhydride group An alkyl group having 1 to 10, an alkyl group having 1 to 10 carbons containing an epoxy group, or an alkoxy group having 1 to 10 carbons having an epoxy group.
在本發明的一實施例中,上述的化學增幅型正型感光性樹脂組成物更包括鹼性化合物(E)。According to an embodiment of the present invention, the chemically amplified positive photosensitive resin composition further includes a basic compound (E).
在本發明的一實施例中,上述的鹼性化合物(E)包括由式(E-1)所示的化合物: N(X)z (Y)3-z 式(E-1) 式(E-1)中,X各自獨立表示碳數為4以上的烷基、碳數為3以上的環烷基、苯基或芳烷基; Y各自獨立表示氫原子或碳數為3以下的烷基; z表示1至3的整數。In one embodiment of the present invention, the basic compound (E) includes a compound represented by formula (E-1): N (X) z (Y) 3-z formula (E-1) formula (E) In -1), X each independently represents an alkyl group having a carbon number of 4 or more, and a cycloalkyl group, a phenyl group, or an aralkyl group having a carbon number of 3 or more; each independently represents a hydrogen atom or an alkyl group having a carbon number of 3 or less ; Z represents an integer from 1 to 3.
在本發明的一實施例中,基於含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的總使用量為100重量份,聚矽氧烷(B)的含量為10重量份至100重量份,光酸產生劑(C)的含量為0.3重量份至3重量份,溶劑(D)的含量為150重量份至1200重量份。In one embodiment of the present invention, the total amount of the polyhydroxystyrene resin (A) containing the acid dissociable protective group is 100 parts by weight, and the content of the polysiloxane (B) is 10 to 100 parts by weight. The content of the photoacid generator (C) is 0.3 to 3 parts by weight, and the content of the solvent (D) is 150 to 1200 parts by weight.
在本發明的一實施例中,基於含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的總使用量為100重量份,鹼性化合物(E)的含量為0.03重量份至0.3重量份。In one embodiment of the present invention, the total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the basic compound (E) is 0.03 to 0.3 parts by weight. .
本發明也提供一種光阻圖案的形成方法,包括:將上述的化學增幅型正型感光性樹脂組成物以塗布、曝光、顯影處理的方式形成光阻圖案。The present invention also provides a method for forming a photoresist pattern, comprising: forming a photoresist pattern by coating, exposing, and developing the chemically amplified positive photosensitive resin composition described above.
本發明更提供一種光阻圖案,由上述的光阻圖案的形成方法所形成。The present invention further provides a photoresist pattern formed by the method for forming a photoresist pattern described above.
本發明又提供一種電子裝置,包括上述的光阻圖案。The present invention also provides an electronic device including the above-mentioned photoresist pattern.
基於上述,本發明的化學增幅型正型感光性樹脂組成物因含有含有酸解離性保護基的聚羥基苯乙烯樹脂(A)、以及聚矽氧烷(B),故能夠改善感度及耐熱性不佳的問題。Based on the above, since the chemically amplified positive photosensitive resin composition of the present invention contains a polyhydroxystyrene resin (A) and a polysiloxane (B) containing an acid dissociative protective group, the sensitivity and heat resistance can be improved. Poor question.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.
< 化學增幅型正型感光性樹脂組成物 > 本發明提供一種化學增幅型正型感光性樹脂組成物,包括:含有酸解離性保護基的聚羥基苯乙烯樹脂(A)、聚矽氧烷(B)、光酸產生劑(C)、以及溶劑(D),上述的聚矽氧烷(B)至少是由式(B-1)表示的矽烷單體聚縮合而得。此外,本發明的化學增幅型正型感光性樹脂組成物更可包含鹼性化合物(E)以及添加劑(F)。 < Chemically amplified positive photosensitive resin composition > The present invention provides a chemically amplified positive photosensitive resin composition, which includes a polyhydroxystyrene resin (A) containing an acid dissociable protective group, and a polysiloxane ( B), a photoacid generator (C), and a solvent (D). The polysiloxane (B) is obtained by at least a polycondensation of a silane monomer represented by the formula (B-1). In addition, the chemically amplified positive photosensitive resin composition of the present invention may further include a basic compound (E) and an additive (F).
以下將詳細說明用於本發明的化學增幅型正型感光性樹脂組成物的各個成分。Hereinafter, each component of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail.
在此說明的是,以下是以(甲基)丙烯酸表示丙烯酸及/或甲基丙烯酸,並以(甲基)丙烯酸酯表示丙烯酸酯及/或甲基丙烯酸酯;同樣地,以(甲基)丙烯醯基表示丙烯醯基及/或甲基丙烯醯基。含有酸解離 性保護基的聚羥基苯乙烯樹脂( A ) In this description, acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylic acid ester; similarly, (meth) Acrylofluorenyl refers to acrylfluorenyl and / or methacrylfluorenyl. Polyhydroxystyrene resin containing acid-dissociable protective group ( A )
含有酸解離性保護基的聚羥基苯乙烯樹脂(A)中,所謂聚羥基苯乙烯樹脂(保護前)是包含由羥基苯乙烯所成的聚合物(羥基苯乙烯單獨聚合物)及其衍生物。如此的聚羥基苯乙烯例如:乙烯基苯酚的單獨聚合物,乙烯基苯酚、可與其共聚合的共聚用單體的共聚物等。於此,共聚用單體例如:(甲基)丙烯酸衍生物、(甲基)丙烯腈、苯乙烯、α-甲基苯乙烯、對-甲基苯乙烯、鄰-甲基苯乙烯、對-甲氧基苯乙烯、對-氯苯乙烯等苯乙烯衍生物等。聚羥基苯乙烯之中以羥基苯乙烯單獨聚合物、羥基苯乙烯-苯乙烯共聚物為佳。In the polyhydroxystyrene resin (A) containing an acid-dissociable protective group, the so-called polyhydroxystyrene resin (before protection) includes a polymer made of hydroxystyrene (hydroxystyrene alone polymer) and its derivative. . Such polyhydroxystyrene is, for example, a single polymer of vinylphenol, a copolymer of vinylphenol, a comonomer that can be copolymerized therewith, and the like. Here, the comonomers are, for example, (meth) acrylic acid derivatives, (meth) acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p- Styrene derivatives such as methoxystyrene and p-chlorostyrene. Among the polyhydroxystyrenes, a hydroxystyrene alone polymer and a hydroxystyrene-styrene copolymer are preferred.
含有酸解離性保護基的聚羥基苯乙烯樹脂(A)中,全酚性羥基的至少一部份的氫原子,以酸解離性保護基取代,顯示鹼難溶性或鹼不溶性,藉由所述酸解離性保護基自酚性羥基解離,成為鹼可溶性者即可。In the polyhydroxystyrene resin (A) containing an acid-dissociable protective group, at least a part of the hydrogen atoms of the all-phenolic hydroxyl group are substituted with the acid-dissociable protective group, which shows poor alkali solubility or alkali insolubility. The acid-dissociable protective group may be dissociated from the phenolic hydroxyl group and become alkali-soluble.
含有酸解離性保護基的聚羥基苯乙烯樹脂(A)可藉由使不具酸解離性保護基的聚羥基苯乙烯樹脂(保護前的聚羥基苯乙烯樹脂)、與相當於酸解離性保護基的化合物進行反應而得。The polyhydroxystyrene resin (A) containing an acid-dissociable protective group can be obtained by using a polyhydroxystyrene resin (a polyhydroxystyrene resin before protection) without an acid-dissociative protective group and an acid-dissociative protective group. The compound is obtained by reaction.
另外,所謂羥基苯乙烯也包含其衍生物。具體的羥基苯乙烯重複單元由下述式(A-1)所示:式(A-1) 式(A-1),R0 為氫原子或低級烷基;k表示1至3的整數。The term “hydroxystyrene” also includes derivatives thereof. The specific hydroxystyrene repeating unit is represented by the following formula (A-1): Formula (A-1) In formula (A-1), R 0 is a hydrogen atom or a lower alkyl group; k represents an integer of 1 to 3.
R0 為氫原子或低級烷基(例如碳數為1至5的直鏈或支鏈烷基、較佳為甲基),較佳為氫原子。羥基的位置,可為鄰位、間位、對位的任一種,從可輕易取得,且價格低廉而言,以對位為佳。R 0 is a hydrogen atom or a lower alkyl group (for example, a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a methyl group), and a hydrogen atom is preferred. The position of the hydroxyl group can be any of the ortho, meta, and para positions. From the viewpoint of easy availability and low price, the para position is preferred.
又,羥基苯乙烯-苯乙烯共聚物中,苯乙烯包含苯環不被烷基取代的苯乙烯、與苯環被碳數為1至5的低級烷基取代的化合物者。取代基的低級烷基的個數為1至3個。In the hydroxystyrene-styrene copolymer, styrene includes styrene in which the benzene ring is not substituted with an alkyl group, and compounds having a benzene ring substituted with a lower alkyl group having 1 to 5 carbon atoms. The number of the lower alkyl group of the substituent is 1-3.
含有酸解離性保護基的聚羥基苯乙烯樹脂(A)中的酸解離性保護基,只要是可以被後述的光酸產生劑(C)所產生的酸解離者即可,例如:1-乙氧基甲基、1-乙氧基乙基、1-丙氧基甲基、1-丙氧基乙基、1-正丁氧基甲基、1-異丁氧基甲基、1-第三丁氧基甲基等烷氧基烷基;第三丁氧基羰基、第三丁氧基碳基甲基、第三丁氧基羰基乙基等烷氧基羰基烷基;四氫呋喃基;四氫吡喃基;直鏈狀或支鏈狀的縮醛基;環狀縮醛基;三甲基甲矽烷基、三乙基甲矽烷基、三苯基甲矽烷基等三烷基甲矽烷基等。The acid-dissociable protective group in the polyhydroxystyrene resin (A) containing an acid-dissociable protective group may be any one that can be dissociated by an acid generated by a photoacid generator (C) described later, for example: 1-ethyl Oxymethyl, 1-ethoxyethyl, 1-propoxymethyl, 1-propoxyethyl, 1-n-butoxymethyl, 1-isobutoxymethyl, 1- Alkoxyalkyl groups such as tributoxymethyl; alkoxycarbonylalkyl groups such as third butoxycarbonyl, third butoxycarbonmethyl, and third butoxycarbonylethyl; tetrahydrofuranyl; Hydropyranyl; linear or branched acetal; cyclic acetal; trimethylsilyl, triethylsilyl, triphenylsilyl, etc. Wait.
上述保護前的聚羥基苯乙烯樹脂的質量平均分子量(Mw)的較佳範圍為1,000~200,000、更佳為2,000~50,000、最佳為3,000~30,000。The mass average molecular weight (Mw) of the polyhydroxystyrene resin before protection is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000, and most preferably 3,000 to 30,000.
當化學增幅型正型感光性樹脂組成物中不包含含有酸解離性保護基的聚羥基苯乙烯樹脂(A)時,化學增幅型正型感光性樹脂組成物的感度不佳。聚矽氧烷 ( B ) When the chemically amplified positive photosensitive resin composition does not include the polyhydroxystyrene resin (A) containing an acid dissociable protective group, the sensitivity of the chemically amplified positive photosensitive resin composition is not good. Polysiloxane ( B )
聚矽氧烷(B)的種類並沒有特別限制,只要可達到本發明的目的即可。聚矽氧烷(B)可使用矽烷單體(silane monomer)進行聚縮合(即水解(hydrolysis)及部分縮合)來合成,或是使用矽烷單體及其他可聚合之化合物進行聚縮合來合成。The type of the polysiloxane (B) is not particularly limited as long as the object of the present invention can be achieved. Polysiloxane (B) can be synthesized by polycondensation (ie, hydrolysis and partial condensation) using a silane monomer, or by polycondensation using a silane monomer and other polymerizable compounds.
矽烷單體包括由式(B-1)表示的矽烷單體(b1)及由式(B-2)表示的矽烷單體(b2);其他可聚合之化合物包含矽氧烷預聚物(b3)、二氧化矽粒子(b4),或其組合。以下,進一步說明各個成分以及聚縮合的反應步驟與條件。由式 (B-1) 表示的矽烷單體( b1 ) The silane monomer includes a silane monomer (b1) represented by the formula (B-1) and a silane monomer (b2) represented by the formula (B-2); other polymerizable compounds include a siloxane prepolymer (b3) ), Silica particles (b4), or a combination thereof. Hereinafter, the reaction steps and conditions of each component and the polycondensation will be further described. Silane monomer ( b1 ) represented by formula (B-1 )
矽烷單體(b1)為由式(B-1)表示的化合物。 Si(Ra )w (ORb )4-w 式(B-1) 式(B-1)中,Ra 各自獨立表示氫原子、碳數為1至10的烷基、碳數為2至10的烯基、碳數為6至15的芳香基、含有酸酐基的碳數為1至10的烷基、含有環氧基的碳數為1至10的烷基或含有環氧基的碳數為1至10的烷氧基。 Rb 各自獨立表示氫原子、碳數為1至6的烷基、碳數為1至6的醯基或碳數為6至15的芳香基。 w表示1至3的整數,且至少一個Ra 表示含有酸酐基的碳數為1至10的烷基、含有環氧基的碳數為1至10的烷基或含有環氧基的烷氧基。The silane monomer (b1) is a compound represented by the formula (B-1). Si (R a ) w (OR b ) 4-w Formula (B-1) In Formula (B-1), each of R a independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 2 to Alkenyl groups of 10, aromatic groups of 6 to 15 carbons, alkyl groups of 1 to 10 carbons containing acid anhydride groups, alkyl groups of 1 to 10 carbons containing epoxy groups, or carbons containing epoxy groups The number is 1 to 10 alkoxy groups. R b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms. w represents an integer of 1 to 3, and at least one R a represents an alkyl group having 1 to 10 carbon atoms containing an acid anhydride group, an alkyl group having 1 to 10 carbon atoms containing an epoxy group, or an alkoxy group containing epoxy groups base.
更詳細而言,當式(B-1)中的Ra 表示碳數為1至10的烷基時,具體而言,Ra 例如是甲基、乙基、正丙基、異丙基、正丁基、第三丁基、正己基或正癸基。又,Ra 也可以是烷基上具有其他取代基的烷基,具體而言,Ra 例如是三氟甲基、3,3,3-三氟丙基、3-胺丙基、3-巰丙基或3-異氰酸丙基。More specifically, when R a in the formula (B-1) represents an alkyl group having 1 to 10 carbon atoms, specifically, R a is, for example, methyl, ethyl, n-propyl, isopropyl, N-butyl, third butyl, n-hexyl or n-decyl. R a may be an alkyl group having another substituent on the alkyl group. Specifically, R a is, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.
當式(B-1)中的Ra 表示碳數為2至10的烯基時,具體而言,Ra 例如是乙烯基。又,Ra 也可以是烯基上具有其他取代基的烯基,具體而言,Ra 例如是3-丙烯醯氧基丙基或3-甲基丙烯醯氧基丙基。When R a in the formula (B-1) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R a is, for example, a vinyl group. R a may be an alkenyl group having another substituent on the alkenyl group. Specifically, R a is, for example, 3-propenyloxypropyl group or 3-methacryloxypropyl group.
當式(B-1)中的Ra 表示碳數為6至15的芳香基時,具體而言,Ra 例如是苯基、甲苯基(tolyl)或萘基(naphthyl)。又,Ra 也可以是芳香基上具有其他取代基的芳香基,具體而言,Ra 例如是對-羥基苯基(o-hydroxyphenyl)、1-(對-羥基苯基)乙基(1-(o-hydroxyphenyl)ethyl)、2-(對-羥基苯基)乙基(2-(o-hydroxyphenyl)ethyl)或4-羥基-5-(對-羥基苯基羰氧基)戊基(4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl)。When R a in the formula (B-1) represents an aromatic group having 6 to 15 carbon atoms, specifically, R a is, for example, a phenyl group, a tolyl group, or a naphthyl group. Moreover, R a may be an aromatic group having another substituent on the aromatic group. Specifically, R a is, for example, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl (1 -(O-hydroxyphenyl) ethyl), 2- (p-hydroxyphenyl) ethyl (2- (o-hydroxyphenyl) ethyl) or 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl ( 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl).
此外,式(B-1)中的Ra 表示含有酸酐基的烷基,其中烷基較佳為碳數為1至10的烷基。具體而言,所述含有酸酐基的烷基例如是式(B-1-1)所示的乙基丁二酸酐、式(B-1-2)所示的丙基丁二酸酐或式(B-1-3)所示的丙基戊二酸酐。值得一提的是,酸酐基是由二羧酸(dicarboxylic acid)經分子內脫水(intramolecular dehydration)所形成的基團,其中二羧酸例如是丁二酸或戊二酸。式(B-1-1)式(B-1-2)式(B-1-3)Further, R a in the formula (B-1) represents an alkyl group containing an acid anhydride group, and among these, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the acid-anhydride-containing alkyl group is, for example, ethylsuccinic anhydride represented by formula (B-1-1), propylsuccinic anhydride represented by formula (B-1-2), or formula ( B-1-3) shown by propylglutaric anhydride. It is worth mentioning that the acid anhydride group is a group formed by dicarboxylic acid by intramolecular dehydration. The dicarboxylic acid is, for example, succinic acid or glutaric acid. Formula (B-1-1) Formula (B-1-2) Formula (B-1-3)
再者,式(B-1)中的Ra 表示含有環氧基的烷基,其中烷基較佳為碳數為1至10的烷基。具體而言,所述含有環氧基的烷基例如是環氧丙烷基戊基(oxetanylpentyl)或2-(3,4-環氧環己基)乙基(2-(3,4-epoxycyclohexyl)ethyl)。值得一提的是,環氧基是由二元醇(diol)經分子內脫水所形成的基團,其中二元醇例如是丙二醇、丁二醇或戊二醇。In addition, R a in the formula (B-1) represents an alkyl group containing an epoxy group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the epoxy-containing alkyl group is, for example, oxetanylpentyl or 2- (3,4-epoxycyclohexyl) ethyl (2- (3,4-epoxycyclohexyl) ethyl ). It is worth mentioning that the epoxy group is a group formed by the intramolecular dehydration of a diol, such as propylene glycol, butanediol, or pentanediol.
式(B-1)中的Ra 表示含有環氧基的烷氧基,其中烷氧基較佳為碳數為1至10的烷氧基。具體而言,所述含有環氧基的烷氧基例如是環氧丙氧基丙基(glycidoxypropyl)或2-環氧丙烷基丁氧基(2-oxetanylbutoxy)。R a in the formula (B-1) represents an alkoxy group containing an epoxy group, and among these, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms. Specifically, the epoxy-group-containing alkoxy group is, for example, glycidoxypropyl or 2-oxetanylbutoxy.
另外,當式(B-1)的Rb 表示碳數為1至6的烷基時,具體而言,Rb 例如是甲基、乙基、正丙基、異丙基或正丁基。當式(B-1)中的Rb 表示碳數為1至6的醯基時,具體而言,Rb 例如是乙醯基。當式(B-1)中的Rb 表示碳數為6至15的芳香基時,具體而言,Rb 例如是苯基。In addition, when R b of the formula (B-1) represents an alkyl group having 1 to 6 carbon atoms, specifically, R b is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group. When R b in the formula (B-1) represents a fluorenyl group having 1 to 6 carbon atoms, specifically, R b is, for example, an ethenyl group. When R b in the formula (B-1) represents an aromatic group having 6 to 15 carbon atoms, specifically, R b is, for example, a phenyl group.
在式(B-1)中,w表示1至3的整數。當w表示2或3時,多個Ra 可為相同或不同;當w表示1或2時,多個Rb 可為相同或不同。In Formula (B-1), w represents an integer of 1 to 3. When w represents 2 or 3, multiple R a may be the same or different; when w represents 1 or 2, multiple R b may be the same or different.
矽烷單體(b1)的具體例包括:3-環氧丙氧基丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane,簡稱GPTMS)、3-環氧丙氧基丙基三乙氧基矽烷(3-glycidoxypropyl triethoxysilane)、2-(3,4-環氧環己基)乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane)、2-環氧丙烷基丁氧基丙基三苯氧基矽烷(2-oxetanylbutoxypropyltriphenoxysilane)、由東亞合成所製造的市售品:2-環氧丙烷基丁氧基丙基三甲氧基矽烷(2-oxetanylbutoxypropyltrimethoxysilane,商品名TMSOX-D)、2-環氧丙烷基丁氧基丙基三乙氧基矽烷(2-oxetanylbutoxy propyltriethoxysilane,商品名TESOX-D)、3-(三苯氧基矽基)丙基丁二酸酐、由信越化學所製造的市售品:3-(三甲氧基矽基)丙基丁二酸酐(商品名X-12-967)、由WACKER公司所製造的市售品:3-(三乙氧基矽基)丙基丁二酸酐(商品名GF-20)、3-(三甲氧基矽基)丙基戊二酸酐(簡稱TMSG)、3-(三乙氧基矽基)丙基戊二酸酐、3-(三苯氧基矽基)丙基戊二酸酐、二異丙氧基-二(2-環氧丙烷基丁氧基丙基)矽烷(diisopropoxy-di(2-oxetanylbutoxypropyl)silane,簡稱DIDOS)、二(3-環氧丙烷基戊基)二甲氧基矽烷(di(3-oxetanyl pentyl)dimethoxysilane)、(二正丁氧基矽基)二(丙基丁二酸酐)、(二甲氧基矽基)二(乙基丁二酸酐)、3-環氧丙氧基丙基二甲基甲氧基矽烷(3-glycidoxypropyldimethylmethoxysilane)、3-環氧丙氧基丙基二甲基乙氧基矽烷(3-glycidoxypropyldimethylethoxysilane)、二(2-環氧丙烷基丁氧基戊基)-2-環氧丙烷基戊基乙氧基矽烷(di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxysilane)、三(2-環氧丙烷基戊基)甲氧基矽烷(tri(2-oxetanylpentyl)methoxy silane)、(苯氧基矽基)三(丙基丁二酸酐)、(甲基甲氧基矽基)二(乙基丁二酸酐),或上述化合物的組合。Specific examples of the silane monomer (b1) include: 3-glycidoxypropyltrimethoxysilane (GPTMS) and 3-glycidoxypropyltrimethoxysilane (3- glycidoxypropyl triethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-epoxypropylalkylbutoxypropyltriphenoxy Siloxane (2-oxetanylbutoxypropyltriphenoxysilane), a commercially available product manufactured by Toa Synthesis: 2-oxetanylbutoxypropyltrimethoxysilane (trade name TMSOX-D), 2-epoxypropylalkyl 2-oxetanylbutoxy propyltriethoxysilane (trade name TESOX-D), 3- (triphenoxysilyl) propylsuccinic anhydride, commercially available product manufactured by Shin-Etsu Chemical Co., Ltd .: 3 -(Trimethoxysilyl) propylsuccinic anhydride (trade name X-12-967), a commercially available product manufactured by WACKER: 3- (triethoxysilyl) propylsuccinic anhydride (commodity Name GF-20), 3- (trimethoxysilyl) propylglutaric anhydride (TMSG), 3- (triethoxysilyl) propylglutaric acid , 3- (triphenoxysilyl) propylglutaric anhydride, diisopropoxy-di (2-oxetanylbutoxypropyl) silane (abbreviated for short) DIDOS), di (3-oxetanyl pentyl) dimethoxysilane, (di-n-butoxysilyl) bis (propylsuccinic anhydride), (di (Methoxysilyl) bis (ethylsuccinic anhydride), 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane 3-glycidoxypropyldimethylethoxysilane, di (2-glycidoxybutoxypentyl) -2-glycidylpentylethoxysilane (di (2-oxetanylbutoxypentyl) -2-oxetanylpentylethoxysilane), three (2-Epoxypropylalkylpentyl) methoxysilane (tri (2-oxetanylpentyl) methoxy silane), (phenoxysilyl) tris (propylsuccinic anhydride), (methylmethoxysilyl) Bis (ethylsuccinic anhydride), or a combination of the above.
矽烷單體(b1)可單獨使用或組合多種來使用。The silane monomer (b1) can be used alone or in combination.
矽烷單體(b1)的具體例較佳為包括3-(三乙氧基矽基)丙基丁二酸酐、3-(三甲氧基矽基)丙基丁二酸酐、3-環氧丙氧基丙基三甲氧基矽烷、3-(三甲氧基矽基)丙基戊二酸酐、(二甲氧基矽基)二(乙基丁二酸酐)、2-環氧丙烷基丁氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-環氧丙烷基丁氧基丙基三乙氧基矽烷或上述化合物的組合。Specific examples of the silane monomer (b1) preferably include 3- (triethoxysilyl) propylsuccinic anhydride, 3- (trimethoxysilyl) propylsuccinic anhydride, and 3-glycidoxy Propyltrimethoxysilane, 3- (trimethoxysilyl) propylglutaric anhydride, (dimethoxysilyl) bis (ethylsuccinic anhydride), 2-glycidylbutoxypropyl Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-glycidylbutoxypropyltriethoxysilane, or a combination thereof.
當化學增幅型正型感光性樹脂組成物中的聚矽氧烷(B)的合成單體不包括由式(B-1)表示的矽烷單體時,化學增幅型正型感光性樹脂組成物所形成的光阻圖案的耐熱性不佳。由式 (B-2) 表示的矽烷單體( b2 ) When the synthetic monomer of polysiloxane (B) in the chemically amplified positive photosensitive resin composition does not include the silane monomer represented by the formula (B-1), the chemically amplified positive photosensitive resin composition The formed photoresist pattern has poor heat resistance. Silane monomer ( b2 ) represented by formula (B-2 )
矽烷單體(b2)為由式(B-2)表示的化合物。 Si(Rc )u (ORd )4-u 式(B-2) 式(B-2)中,Rc 各自獨立表示氫原子、碳數為1至10的烷基、碳數為2至10的烯基或碳數為6至15的芳香基;Rd 各自獨立表示氫原子、碳數為1至6的烷基、碳數為1至6的醯基或碳數為6至15的芳香基;u表示0至3的整數。The silane monomer (b2) is a compound represented by the formula (B-2). Si (R c ) u (OR d ) 4-u Formula (B-2) In Formula (B-2), R c each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 2 to An alkenyl group of 10 or an aromatic group having 6 to 15 carbons; each of R d independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or 6 to 15 carbon atoms Aromatic group; u represents an integer of 0 to 3.
更詳細而言,當式(B-2)中的Rc 表示碳數為1至10的烷基時,具體而言,Rc 例如是甲基、乙基、正丙基、異丙基、正丁基、第三丁基、正己基或正癸基。又,Rc 也可以是烷基上具有其他取代基的烷基,具體而言,Rc 例如是三氟甲基、3,3,3-三氟丙基、3-胺丙基、3-巰丙基或3-異氰酸丙基。More specifically, when R c in the formula (B-2) represents an alkyl group having 1 to 10 carbon atoms, specifically, R c is, for example, methyl, ethyl, n-propyl, isopropyl, N-butyl, third butyl, n-hexyl or n-decyl. R c may be an alkyl group having another substituent on the alkyl group. Specifically, R c is, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.
當式(B-2)中的Rc 表示碳數為2至10的烯基時,具體而言,Rc 例如是乙烯基。又,Rc 也可以是烯基上具有其他取代基的烯基,具體而言,Rc 例如是3-丙烯醯氧基丙基或3-甲基丙烯醯氧基丙基。When R c in the formula (B-2) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R c is, for example, a vinyl group. R c may be an alkenyl group having another substituent on the alkenyl group. Specifically, R c is, for example, 3-propenyloxypropyl or 3-methacryloxypropyl.
當式(B-2)中的Rc 表示碳數為6至15的芳香基時,具體而言,Rc 例如是苯基、甲苯基(tolyl)或萘基(naphthyl)。又,Rc 也可以是芳香基上具有其他取代基的芳香基,具體而言,Rc 例如是對-羥基苯基(o-hydroxyphenyl)、1-(對-羥基苯基)乙基(1-(o-hydroxyphenyl)ethyl)、2-(對-羥基苯基)乙基(2-(o-hydroxy phenyl)ethyl)或4-羥基-5-(對-羥基苯基羰氧基)戊基(4-hydroxy-5- (p-hydroxyphenylcarbonyloxy)pentyl)。When R c in the formula (B-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, R c is, for example, a phenyl group, a tolyl group, or a naphthyl group. R c may be an aromatic group having another substituent on the aromatic group. Specifically, R c is, for example, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl (1 -(o-hydroxyphenyl) ethyl), 2- (p-hydroxyphenyl) ethyl, or 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl).
另外,當式(B-2)的Rd 表示碳數為1至6的烷基時,具體而言,Rd 例如是甲基、乙基、正丙基、異丙基或正丁基。當式(B-2)中的Rd 表示碳數為1至6的醯基時,具體而言,Rd 例如是乙醯基。當式(B-2)中的Rd 表示碳數為6至15的芳香基時,具體而言,Rd 例如是苯基。In addition, when Rd in Formula (B-2) represents an alkyl group having 1 to 6 carbon atoms, specifically, Rd is methyl, ethyl, n-propyl, isopropyl, or n-butyl, for example. When Rd in the formula (B-2) represents a fluorenyl group having 1 to 6 carbon atoms, specifically, R d is, for example, an ethylfluorenyl group. When Rd in Formula (B-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, Rd is, for example, a phenyl group.
在式(B-2)中,u為0至3的整數。當u表示2或3時,多個Rc 可為相同或不同;當u表示0、1或2時,多個Rd 可為相同或不同。In Formula (B-2), u is an integer of 0 to 3. When u represents 2 or 3, multiple R c may be the same or different; when u represents 0, 1 or 2, multiple R d may be the same or different.
在式(B-2)中,當u=0時,表示矽烷單體為四官能性矽烷單體(亦即具有四個可水解基團的矽烷單體);當u=1時,表示矽烷單體為三官能性矽烷單體(亦即具有三個可水解基團的矽烷單體);當u=2時,表示矽烷單體為二官能性矽烷單體(亦即具有二個可水解基團的矽烷單體);並且當u=3時,則表示矽烷單體為單官能性矽烷單體(亦即具有一個可水解基團的矽烷單體)。值得一提的是,所述可水解基團是指可以進行水解反應並且與矽鍵結的基團,舉例來說,可水解基團例如是烷氧基、醯氧基(acyloxy group)或苯氧基(phenoxy group)。In formula (B-2), when u = 0, it means that the silane monomer is a tetrafunctional silane monomer (that is, a silane monomer having four hydrolyzable groups); when u = 1, it means silane The monomer is a trifunctional silane monomer (that is, a silane monomer having three hydrolyzable groups); when u = 2, it means that the silane monomer is a difunctional silane monomer (that is, two hydrolyzable monomers) Silane monomer); and when u = 3, it means that the silane monomer is a monofunctional silane monomer (that is, a silane monomer having a hydrolyzable group). It is worth mentioning that the hydrolyzable group refers to a group that can undergo a hydrolysis reaction and is bonded to silicon. For example, the hydrolyzable group is, for example, an alkoxy group, an acyloxy group, or benzene Oxygen (phenoxy group).
由式(B-2)表示的矽烷單體的具體例包括但不限於: (1)四官能性矽烷單體:四甲氧基矽烷(tetramethoxy silane)、四乙氧基矽烷(tetraethoxysilane)、四乙醯氧基矽烷(tetraacetoxysilane)或四苯氧基矽烷等(tetraphenoxysilane); (2)三官能性矽烷單體:甲基三甲氧基矽烷(methyltrimethoxy silane,簡稱MTMS)、甲基三乙氧基矽烷(methyltriethoxysilane)、甲基三異丙氧基矽烷(methyltriisopropoxysilane)、甲基三正丁氧基矽烷(methyltri-n-butoxysilane)、乙基三甲氧基矽烷(ethyltrimethoxysilane)、乙基三乙氧基矽烷(ethyltriethoxysilane)、乙基三異丙氧基矽烷(ethyltriisopropoxysilane)、乙基三正丁氧基矽烷(ethyltri-n-butoxysilane)、正丙基三甲氧基矽烷(n-propyl trimethoxysilane)、正丙基三乙氧基矽烷(n-propyltriethoxysilane)、正丁基三甲氧基矽烷(n-butyltrimethoxysilane)、正丁基三乙氧基矽烷(n-butyltriethoxysilane)、正己基三甲氧基矽烷(n-hexyl trimethoxysilane)、正己基三乙氧基矽烷(n-hexyltriethoxysilane)、癸基三甲氧基矽烷(decyltrimethoxysilane)、乙烯基三甲氧基矽烷(vinyltrimethoxysilane)、乙烯基三乙氧基矽烷(vinyltriethoxy silane)、苯基三甲氧基矽烷(phenyltrimethoxysilane,簡稱PTMS)、苯基三乙氧基矽烷(phenyltriethoxysilane,簡稱PTES)、對-羥基苯基三甲氧基矽烷(p-hydroxyphenyltrimethoxysilane)、1-(對-羥基苯基)乙基三甲氧基矽烷(1-(p-hydroxyphenyl)ethyltrimethoxy silane)、2-(對-羥基苯基)乙基三甲氧基矽烷(2-(p-hydroxyphenyl) ethyltrimethoxysilane)、4-羥基-5-(對-羥基苯基羰氧基)戊基三甲氧基矽烷(4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl trimethoxysilane)、三氟甲基三甲氧基矽烷(trifluoromethyl trimethoxysilane)、三氟甲基三乙氧基矽烷(trifluoromethyl triethoxysilane)、3,3,3-三氟丙基三甲氧基矽烷(3,3,3-trifluoro propyltrimethoxysilane)、3-胺丙基三甲氧基矽烷(3-aminopropyl trimethoxysilane)、3-胺丙基三乙氧基矽烷(3-aminopropyl triethoxysilane)、3-巰丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷或3-甲基丙烯醯氧基丙基三乙氧基矽烷; (3)二官能性矽烷單體:二甲基二甲氧基矽烷(dimethyl dimethoxysilane,簡稱DMDMS)、二甲基二乙氧基矽烷(dimethyl diethoxysilane)、二甲基二乙醯氧基矽烷(dimethyldiacetyl oxysilane)、二正丁基二甲氧基矽烷(di-n-butyldimethoxysilane)或二苯基二甲氧基矽烷(diphenyldimethoxysilane);或 (4)單官能性矽烷單體:三甲基甲氧基矽烷(trimethyl methoxysilane)或三正丁基乙氧基矽烷(tri-n-butylethoxysilane)等。Specific examples of the silane monomer represented by the formula (B-2) include, but are not limited to: (1) tetrafunctional silane monomer: tetramethoxy silane, tetraethoxysilane, tetraethoxysilane, Tetraacetoxysilane or tetraphenoxysilane; (2) Trifunctional silane monomers: methyltrimethoxysilane (MTMS), methyltriethoxysilane (methyltriethoxysilane), methyltriisopropoxysilane (methyltriisopropoxysilane), methyltri-n-butoxysilane (methyltri-n-butoxysilane), ethyltrimethoxysilane (ethyltrimethoxysilane), ethyltriethoxysilane ( ethyltriethoxysilane), ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyl trimethoxysilane, n-propyltrimethoxysilane N-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyl trimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyl Trimethoxysilane (phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethane 1- (p-hydroxyphenyl) ethyltrimethoxy silane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- ( P-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl trimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethyl Trifluoromethyl triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyl trimethoxysilane oxysilane), 3-aminopropyl triethoxysilane, 3-aminopropyl triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propoxypropyltrimethoxysilane, 3-methacrylic acid Propyltrimethoxysilane or 3-methacryloxypropyltriethoxysilane; (3) difunctional silane monomer: dimethyl dimethoxysilane (DMDMS), Dimethyl diethoxysilane, dimethyldiacetyloxysilane, di-n-butyldimethoxysilane or diphenyldimethoxysilane Diphenyldimethoxysilane; or (4) monofunctional silane monomer: trimethyl methoxysilane (trimethyl methoxysilane) or tri-n-butylethoxysilane (tri-n-butylethoxysilane), etc.
所述的各種矽烷單體可單獨使用或組合多種來使用。矽氧烷預聚物 ( b3 ) The various silane monomers can be used alone or in combination. Siloxane prepolymer ( b3 )
矽氧烷預聚物(b3)是由式(B-3)表示的化合物。式(B-3) 式(B-3)中,Re 、Rf 、Rg 及Rh 各自獨立表示氫原子、碳數為1至10的烷基、碳數為2至6的烯基或碳數為6至15的芳香基,其中該烷基、烯基及芳香基中任一者可選擇地含有取代基;Ri 與Rj 各自獨立表示氫原子、碳數為1至6的烷基、碳數為1至6的醯基或碳數為6至15的芳香基,其中該烷基、醯基及芳香基中任一者可選擇地含有取代基;s表示1至1000的整數。The siloxane prepolymer (b3) is a compound represented by the formula (B-3). In the formula (B-3) of formula (B-3), R e , R f, R g , and R h each independently represents a hydrogen atom, alkyl having 1 to 10 carbons, alkenyl having 2 to 6 Or an aromatic group having 6 to 15 carbon atoms, wherein any one of the alkyl group, alkenyl group, and aromatic group optionally contains a substituent; R i and R j each independently represent a hydrogen atom, and having 1 to 6 carbon atoms Alkyl, fluorenyl having 1 to 6 carbons, or aromatic group having 6 to 15 carbons, wherein any one of the alkyl, fluorenyl, and aromatic groups optionally contains a substituent; s represents 1 to 1000 Integer.
更詳細而言,當式(B-3)中的Re 、Rf 、Rg 及Rh 各自獨立表示碳數為1至10的烷基時,具體而言,Re 、Rf 、Rg 及Rh 例如各自獨立為甲基、乙基或正丙基。當式(B-3)中的Re 、Rf 、Rg 及Rh 各自獨立表示碳數為2至10的烯基時,具體而言,Re 、Rf 、Rg 及Rh 例如各自獨立為乙烯基、丙烯醯氧基丙基或甲基丙烯醯氧基丙基。當式(B-3)中的Re 、Rf 、Rg 及Rh 各自獨立表示碳數為6至15的芳香基時,具體而言,Re 、Rf 、Rg 及Rh 例如各自獨立為苯基、甲苯基或萘基。又,所述烷基、烯基及芳香基中任一者可以具有其他取代基。More specifically when, in formula (B-3) R e, R f, R g , and R h each independently represent an alkyl group having a carbon number of 1 to 10, specifically, R e, R f, R g and R h are each independently methyl, ethyl or n-propyl. In the formula (B-3) R e, R f, R g , and R h each independently is a C 2-10 alkenyl group, specifically, R e, R f, R g and R h e.g. Each is independently a vinyl, acryloxypropyl or methacryloxypropyl. When in the formula (B-3) R e, R f, R g , and R h each independently represents an aromatic group having a carbon number of 6 to 15, specifically, R e, R f, R g and R h e.g. Each is independently phenyl, tolyl or naphthyl. In addition, any of the alkyl group, alkenyl group, and aromatic group may have another substituent.
另外,當式(B-3)的Ri 與Rj 各自獨立表示碳數為1至6的烷基時,具體而言,Ri 與Rj 例如各自獨立為甲基、乙基、正丙基、異丙基或正丁基。當式(B-3)的Ri 與Rj 各自獨立表示碳數為1至6的醯基時,具體而言,Ri 與Rj 例如是乙醯基。當式(B-3)中的Ri 與Rj 各自獨立表示碳數為6至15的芳香基時,具體而言,Ri 與Rj 例如是苯基。其中,上述烷基、醯基及芳香基中任一者可選擇地具有取代基。In addition, when R i and R j in the formula (B-3) each independently represent an alkyl group having 1 to 6 carbon atoms, specifically, R i and R j are each independently a methyl group, an ethyl group, or an n-propyl group. Base, isopropyl or n-butyl. When R i and R j in the formula (B-3) each independently represent a fluorenyl group having 1 to 6 carbon atoms, specifically, R i and R j are, for example, an ethenyl group. When R i and R j in the formula (B-3) each independently represent an aromatic group having 6 to 15 carbon atoms, specifically, R i and R j are, for example, a phenyl group. Among them, any of the alkyl group, fluorenyl group, and aromatic group may optionally have a substituent.
式(B-3)中,s可為1至1000的整數,較佳為3至300的整數,更佳為5至200的整數。當s為2至1000的整數時,Re 各自為相同或不同的基團,且Rf 各自為相同或不同的基團。In the formula (B-3), s may be an integer of 1 to 1,000, preferably an integer of 3 to 300, and more preferably an integer of 5 to 200. When s is an integer from 2 to 1000, R e is each the same or different group, and R f is each the same or different group.
矽氧烷預聚物(b3)的具體例包括但不限於:1,1,3,3-四甲基-1,3-二甲氧基二矽氧烷、1,1,3,3-四甲基-1,3-二乙氧基二矽氧烷、1,1,3,3-四乙基-1,3-二乙氧基二矽氧烷或者由吉來斯特(Gelest)公司製造的末端為矽烷醇的聚矽氧烷(Silanol terminated polydimethylsiloxane)的市售品(商品名如DMS-S12(分子量400至700)、DMS-S15(分子量1500至2000)、DMS-S21(分子量4200)、DMS-S27(分子量18000)、DMS-S31(分子量26000)、DMS-S32(分子量36000)、DMS-S33(分子量43500)、DMS-S35(分子量49000)、DMS-S38(分子量58000)、DMS-S42(分子量77000)或PDS-9931(分子量1000至1400))。Specific examples of the siloxane prepolymer (b3) include, but are not limited to: 1,1,3,3-tetramethyl-1,3-dimethoxydisilaxane, 1,1,3,3- Tetramethyl-1,3-diethoxydisilaxane, 1,1,3,3-tetraethyl-1,3-diethoxydisilaxane or Gelest Manufactured commercially available products of silanol terminated polydimethylsiloxane (termed as DMS-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (molecular weight 4200) ), DMS-S27 (molecular weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular weight 49000), DMS-S38 (molecular weight 58000), DMS-S42 (molecular weight 77000) or PDS-9931 (molecular weight 1000 to 1400)).
矽氧烷預聚物(b3)可單獨使用或組合多種來使用。二氧化矽粒子( b4 ) The siloxane prepolymer (b3) can be used alone or in combination. Silicon dioxide particles ( b4 )
二氧化矽粒子(b4)的平均粒徑並無特別的限制。平均粒徑的範圍為2 nm至250 nm,較佳為5 nm至200 nm,且更佳為10 nm至100 nm。The average particle diameter of the silicon dioxide particles (b4) is not particularly limited. The average particle diameter ranges from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more preferably from 10 nm to 100 nm.
二氧化矽粒子的具體例包括但不限於:由觸媒化成公司所製造的市售品,商品名如OSCAR 1132(粒徑12nm;分散劑為甲醇)、OSCAR 1332(粒徑12nm;分散劑為正丙醇)、OSCAR 105(粒徑60nm;分散劑為γ-丁內酯)、OSCAR 106(粒徑120nm;分散劑為二丙酮醇)等、由扶桑化學公司所製造的市售品,商品名如Quartron PL-1-IPA(粒徑13nm;分散劑為異丙酮)、Quartron PL-1-TOL(粒徑13nm;分散劑為甲苯)、Quartron PL-2L-PGME(粒徑18nm;分散劑為丙二醇單甲醚)或Quartron PL-2L-MEK(粒徑18nm;分散劑為甲乙酮)等、或由日產化學公司所製造的市售品,商品名如IPA-ST(粒徑12nm;分散劑為異丙醇)、EG-ST(粒徑12nm;分散劑為乙二醇)、IPA-ST-L(粒徑45nm;分散劑為異丙醇)或IPA-ST-ZL(粒徑100nm;分散劑為異丙醇)。二氧化矽粒子可單獨使用或組合多種來使用。聚矽氧烷 ( B )的合成方法 Specific examples of silicon dioxide particles include, but are not limited to, commercially available products manufactured by Catalytic Chemicals, such as OSCAR 1132 (particle diameter 12nm; dispersant is methanol), OSCAR 1332 (particle diameter 12nm; dispersant is N-propanol), OSCAR 105 (particle diameter 60nm; dispersant is γ-butyrolactone), OSCAR 106 (particle diameter 120nm; dispersant is diacetone alcohol), etc., commercially available products manufactured by Fuso Chemical Company, products Names such as Quartron PL-1-IPA (particle diameter 13nm; dispersant is isoacetone), Quartron PL-1-TOL (particle diameter 13nm; dispersant is toluene), Quartron PL-2L-PGME (particle diameter 18nm; dispersant Propylene glycol monomethyl ether) or Quartron PL-2L-MEK (particle diameter 18nm; dispersant is methyl ethyl ketone), etc., or a commercially available product manufactured by Nissan Chemical Company under the trade name IPA-ST (particle diameter 12nm; dispersant Isopropanol), EG-ST (particle diameter 12nm; dispersant is ethylene glycol), IPA-ST-L (particle diameter 45nm; dispersant is isopropanol) or IPA-ST-ZL (particle diameter 100nm; The dispersant is isopropanol). The silica particles can be used alone or in combination. Method for synthesizing polysiloxane ( B )
聚矽氧烷(B)可使用矽烷單體進行聚縮合來合成,或是使用矽烷單體及其他可聚合用之化合物進行聚縮合來合成。一般而言,上述聚縮合反應是以下列步驟來進行:在矽烷單體中添加溶劑、水,或可選擇性地添加觸媒(catalyst);以及於50°C至150°C下加熱攪拌0.5小時至120小時,且可進一步藉由蒸餾(distillation)除去副產物(醇類、水等)。Polysiloxane (B) can be synthesized by polycondensation using a silane monomer, or by polycondensation using a silane monomer and other polymerizable compounds. Generally speaking, the above-mentioned polycondensation reaction is performed by the following steps: adding a solvent, water, or optionally a catalyst to the silane monomer; and heating and stirring at 50 ° C to 150 ° C for 0.5 Hours to 120 hours, and by-products (alcohols, water, etc.) can be further removed by distillation.
聚縮合反應所使用的溶劑並沒有特別限制,且所述溶劑可與本發明的化學增幅型正型感光性樹脂組成物所包括的溶劑(D)相同或不同。基於矽烷單體的總量為1莫耳,溶劑的使用量較佳為20克至1000克;更佳為30克至800克;進而更佳為50克至600克。The solvent used for the polycondensation reaction is not particularly limited, and the solvent may be the same as or different from the solvent (D) included in the chemically amplified positive photosensitive resin composition of the present invention. Based on the total amount of the silane monomer being 1 mole, the amount of the solvent used is preferably from 20 g to 1,000 g; more preferably from 30 g to 800 g; even more preferably from 50 to 600 g.
基於矽烷單體的可水解基團為1莫耳,聚縮合反應所使用的水(亦即用於水解的水)較佳為10克至500克;更佳為15克至400克;進而更佳為20克至300克。The hydrolyzable group based on the silane monomer is 1 mole, and the water used for the polycondensation reaction (that is, water used for hydrolysis) is preferably 10 to 500 g; more preferably 15 to 400 g; further more Preferably it is 20 grams to 300 grams.
聚縮合反應所使用的觸媒沒有特別的限制,且較佳為選自酸觸媒或鹼觸媒。酸觸媒的具體例包括但不限於鹽酸、硝酸、硫酸、氫氟酸(hydrofluoric acid)、草酸、磷酸、醋酸、三氟醋酸、蟻酸、多元羧酸或其酸酐或離子交換樹脂等。鹼觸媒的具體例包括但不限於二乙胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺、二乙醇胺、三乙醇胺、氫氧化鈉、氫氧化鉀、含有胺基的具有烷氧基的矽烷或離子交換樹脂等。The catalyst used for the polycondensation reaction is not particularly limited, and is preferably selected from an acid catalyst or an alkali catalyst. Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, or ion exchange resins. Specific examples of the base catalyst include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide , Potassium hydroxide, amine-containing alkoxy-containing silane or ion exchange resin, and the like.
基於矽烷單體的總量為1莫耳,觸媒的使用量較佳為0.05克至5克;更佳為0.07克至4克;進而更佳為0.1克至3克。Based on the total amount of the silane monomer being 1 mole, the amount of the catalyst used is preferably 0.05 g to 5 g; more preferably 0.07 g to 4 g; even more preferably 0.1 g to 3 g.
基於安定性(stability)的觀點,聚矽氧烷(B)較佳為不含副產物(如醇類或水)及觸媒。因此,可選擇性地將聚縮合反應後的反應混合物進行純化(purification)來獲得聚矽氧烷(B)。純化的方法無特別限制,較佳為可使用疏水性溶劑(hydrophobic solvent)稀釋反應混合物。接著,將疏水性溶劑與反應混合物轉移至分液漏斗(separation funnel)。然後,以水洗滌有機層數回,再以旋轉蒸發器(rotary evaporator)濃縮有機層,以除去醇類或水。另外,可使用離子交換樹脂除去觸媒。From the viewpoint of stability, the polysiloxane (B) is preferably free of by-products (such as alcohols or water) and catalysts. Therefore, the reaction mixture after the polycondensation reaction can be selectively purified to obtain polysiloxane (B). The purification method is not particularly limited, and it is preferred that the reaction mixture can be diluted with a hydrophobic solvent. Next, the hydrophobic solvent and the reaction mixture were transferred to a separation funnel. Then, the organic layer was washed several times with water, and then the organic layer was concentrated with a rotary evaporator to remove alcohol or water. In addition, the catalyst can be removed using an ion exchange resin.
聚矽氧烷(B)的重量平均分子量為3000至50000,較佳為3500至40000,更佳為4000至30000。The weight average molecular weight of the polysiloxane (B) is 3,000 to 50,000, preferably 3500 to 40,000, and more preferably 4,000 to 30,000.
基於含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的總使用量為100重量份,聚矽氧烷(B)的含量為10重量份至100重量份,較佳為12重量份至90重量份,更佳為15重量份至80重量份。The total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the polysiloxane (B) is 10 to 100 parts by weight, preferably 12 to parts by weight. 90 parts by weight, more preferably 15 to 80 parts by weight.
當化學增幅型正型感光性樹脂組成物中不包含聚矽氧烷(B)時,化學增幅型正型感光性樹脂組成物所形成的光阻圖案的耐熱性不佳。光酸產生 劑( C ) When the polysiloxane (B) is not included in the chemically amplified positive photosensitive resin composition, the heat resistance of the photoresist pattern formed by the chemically amplified positive photosensitive resin composition is not good. Photoacid generator ( C )
光酸產生劑(C)係藉由光化射線或放射線的照射而產生酸的化合物,只要為可藉由光直接或間接地產生酸的化合物即可,無特別限制。作為光酸產生劑(C),較佳為以下所說明的第一~第五形態的酸產生劑。以下,對感光性樹脂組成物中適合使用的光酸產生劑(C)當中的較佳者,以第一至第五形態加以說明。The photoacid generator (C) is a compound that generates an acid by irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound that can generate an acid directly or indirectly by light. As the photoacid generator (C), the acid generators of the first to fifth aspects described below are preferred. Hereinafter, preferred ones of the photoacid generators (C) suitably used in the photosensitive resin composition will be described in the first to fifth aspects.
作為光酸產生劑(C)之第一形態,可舉出下述式(C-1)所示之化合物:式(C-1) 式(C-1)中,X1 表示g價的硫原子或碘原子,g為1或2。h表示括弧內之結構的重複單元數。W1 為與X1 鍵結的有機基,表示碳原子數為6至30的芳基、碳原子數為4至30的雜環基、碳原子數為1至30的烷基、碳原子數為2至30的烯基、或碳原子數為2至30的炔基,W1 可經由烷基、羥基、烷氧基、烷羰基、芳羰基、烷氧羰基、芳氧羰基、芳硫羰基、醯氧基、芳硫基、烷硫基、芳基、雜環、芳氧基、烷亞磺醯基、芳亞磺醯基、烷磺醯基、芳磺醯基、伸烷氧基、胺基、氰基、硝基、及鹵素所成之群中選出的至少1種取代。W1 的個數為g+h(g-1)+1,W1 可分別彼此相同或相異。又,2個以上的W1 可彼此直接鍵結、或經由-O-、-S-、-SO-、-SO2 -、-NH-、-NW2 -、-CO-、-COO-、-CONH-、碳原子數為1至3的伸烷基、或者伸苯基鍵結而形成包含X1 的環結構。W2 為碳原子數為1至5的烷基或碳原子數為6至10的芳基。Examples of the first form of the photoacid generator (C) include compounds represented by the following formula (C-1): Formula (C-1) In formula (C-1), X 1 represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. W 1 is an organic group bonded to X 1 , and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and a carbon atom. An alkenyl group of 2 to 30, or an alkynyl group of 2 to 30 carbon atoms, W 1 may pass through an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group , Fluorenyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkanesulfinyl, arylenesulfonyl, alkanesulfonyl, arylsulfonyl, alkyleneoxy, At least one selected from the group consisting of amine, cyano, nitro, and halogen. The number of W 1 is g + h (g-1) +1, and W 1 may be the same as or different from each other. In addition, two or more W 1 may be directly bonded to each other or via -O-, -S-, -SO-, -SO 2- , -NH-, -NW 2- , -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group is bonded to form a ring structure including X 1 . W 2 is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
X2 為下述式(C-1a)所示之結構:式(C-1a) 式(C-1a)中,X4 表示碳原子數為1至8的伸烷基、碳原子數為6至20的伸芳基、或碳原子數為8至20的2價雜基,X4 可經由碳原子數為1至8的烷基、碳原子數為1至8的烷氧基、碳原子數為6至10的芳基、羥基、氰基、硝基、及鹵素所成之群中選出的至少1種取代。X5 表示-O-、-S-、-SO-、-SO2 -、-NH-、-NW2 -、-CO-、-COO-、-CONH-、碳原子數為1至3的伸烷基、或伸苯基。h表示括弧內之結構的重複單元數。h+1個X4 及h個X5 可分別相同或相異。W2 係與前述定義相同。X 2 is a structure represented by the following formula (C-1a): Formula (C-1a) In formula (C-1a), X 4 represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylene group having 8 to 20 carbon atoms. Divalent hetero group, X 4 can pass through an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, and a nitro group And at least one selected from the group consisting of halogens. X 5 represents -O-, -S-, -SO-, -SO 2- , -NH-, -NW 2- , -CO-, -COO-, -CONH-, carbon atoms having a number of 1 to 3 Alkyl, or phenylene. h represents the number of repeating units of the structure in parentheses. The h + 1 X 4 and h X 5 may be the same or different, respectively. W 2 is the same as defined above.
(X3 )- 為鎓之對離子(counter ion),可舉出下述式(C-1b)所示之氟烷基氟磷酸陰離子或下述式(C-1c)所示之硼酸根陰離子: [(W3 )j PF6-j ]- 式(C-1b) 式(C-1b)中,W3 表示80%以上的氫原子經氟原子取代的烷基。j表示其個數,為1至5的整數。j個W3 可分別相同或相異。式(C-1c) 式(C-1c)中,W4 ~W7 分別獨立表示氟原子或苯基,該苯基中的氫原子的一部分或全部可經由氟原子及三氟甲基所成之群中選出的至少1種取代。(X 3) - the onium ion (counter ion), may be exemplified by the following formula (C-1b) of FIG fluoroborate fluoroalkyl phosphate anions or the following formula (C-1c) shown in the anion : [(W 3) j PF 6-j] - in formula (C-1b) of formula (C-1b), W 3 represents more than 80% of the hydrogen atoms of the alkyl group substituted with a fluorine atom. j represents the number, and is an integer from 1 to 5. The j W 3s may be the same or different. In formula (C-1c), in formula (C-1c), W 4 to W 7 each independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms in the phenyl group may be formed through a fluorine atom and a trifluoromethyl group. At least one substitution selected from the group.
作為式(C-1)所示之化合物中的鎓離子,可舉出三苯基鋶、三-對甲苯基鋶、4-(苯硫基)苯基二苯基鋶、雙[4-(二苯基鋶基)苯基]硫醚、雙[4-{雙[4-(2-羥乙氧基)苯基]鋶基}苯基]硫醚、雙{4-[雙(4-氟苯基)鋶基]苯基}硫醚、4-(4-苯甲醯基-2-氯苯硫基)苯基雙(4-氟苯基)鋶、7-異丙基-9-氧基-10-硫雜-9,10-二氫蒽-2-基二-對甲苯基鋶、7-異丙基-9-氧基-10-硫雜-9,10-二氫蒽-2-基二苯基鋶、2-[(二苯基)鋶基]硫雜蒽酮、4-[4-(4-三級丁基苯甲醯基)苯硫基]苯基二-對甲苯基鋶、4-(4-苯甲醯基苯硫基)苯基二苯基鋶、二苯基苯乙醯基鋶、4-羥苯基甲基苯甲基鋶、2-萘基甲基(1-乙氧羰基)乙基鋶、4-羥苯基甲基苯乙醯基鋶、苯基[4-(4-聯苯硫基)苯基]4-聯苯鋶、苯基[4-(4-聯苯硫基)苯基]3-聯苯鋶、[4-(4-乙醯苯硫基)苯基]二苯基鋶、十八基甲基苯乙醯基鋶、二苯基錪、二-對甲苯基錪、雙(4-十二基苯基)錪、雙(4-甲氧基苯基)錪、(4-辛氧基苯基)苯基錪、雙(4-十二氧基)苯基錪、4-(2-羥基十四氧基)苯基苯基錪、4-異丙苯基(對甲苯基)錪、或4-異丁苯基(對甲苯基)錪等。Examples of the onium ion in the compound represented by the formula (C-1) include triphenylphosphonium, tri-p-tolylphosphonium, 4- (phenylthio) phenyldiphenylphosphonium, and bis [4- ( Diphenylfluorenyl) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] fluorenyl} phenyl] sulfide, bis {4- [bis (4- Fluorophenyl) fluorenyl] phenyl} sulfide, 4- (4-benzylidene-2-chlorophenylthio) phenylbis (4-fluorophenyl) fluorene, 7-isopropyl-9- Oxy-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylfluorene, 7-isopropyl-9-oxy-10-thia-9,10-dihydroanthracene- 2-yldiphenylfluorene, 2-[(diphenyl) fluorenyl] thiaxanthone, 4- [4- (4-tert-butylbenzylfluorenyl) phenylthio] phenyldi-p- Tolylfluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, diphenylphenethylfluorene, 4-hydroxyphenylmethylbenzylfluorene, 2-naphthylmethyl (1-ethoxycarbonyl) ethylfluorene, 4-hydroxyphenylmethylphenethylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylfluorene, phenyl [ 4- (4-biphenylthio) phenyl] 3-biphenylfluorene, [4- (4-ethylfluorenylphenylthio) phenyl] diphenylfluorene, stearylmethylphenethylfluorenylfluorene, Diphenylfluorene, di-p-tolylfluorene, bis (4-dodecylphenyl) fluorene, (4-methoxyphenyl) fluorene, (4-octyloxyphenyl) phenylfluorene, bis (4-dodecyl) phenylfluorene, 4- (2-hydroxytetradecyloxy) phenyl Phenylhydrazone, 4-isopropylphenyl (p-tolyl) fluorene, 4-isobutylphenyl (p-tolyl) fluorene, and the like.
上述式(C-1)所示之化合物中的鎓離子當中,作為較佳之鎓離子可舉出下述式(C-1d)所示之鋶離子:式(C-1d) 式(C-1d)中,W8 分別獨立表示由氫原子、烷基、羥基、烷氧基、烷羰基、烷羰氧基、烷氧羰基、鹵素原子、可具取代基之芳基、芳羰基所成之群中選出的基。X2 表示與上述式(C-1)中的X2 相同之意義。Among the onium ions in the compound represented by the formula (C-1), preferred onium ions include a sulfonium ion represented by the following formula (C-1d): In formula (C-1d), in formula (C-1d), W 8 each independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, and may be substituted. Selected from the group consisting of aryl and arylcarbonyl. X 2 has the same meaning as X 2 in the formula (C-1).
作為上述式(C-1d)所示之鋶離子的具體實例,可舉出4-(苯硫基)苯基二苯基鋶、4-(4-苯甲醯基-2-氯苯硫基)苯基雙(4-氟苯基)鋶、4-(4-苯甲醯基苯硫基)苯基二苯基鋶、苯基[4-(4-聯苯硫基)苯基]4-聯苯鋶、苯基[4-(4-聯苯硫基)苯基]3-聯苯鋶、[4-(4-乙醯苯硫基)苯基]二苯基鋶、二苯基[4-(對三苯硫基)苯基]二苯基鋶。Specific examples of the europium ion represented by the above formula (C-1d) include 4- (phenylthio) phenyldiphenylsulfonium and 4- (4-benzylfluorenyl-2-chlorophenylthio). ) Phenylbis (4-fluorophenyl) fluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4 -Biphenylphosphonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylphosphonium, [4- (4-ethylphenylphenyl) phenyl] diphenylphosphonium, diphenyl [4- (p-triphenylthio) phenyl] diphenylphosphonium.
上述式(C-1b)所示之氟烷基氟磷酸陰離子中,W3 表示經氟原子取代的烷基,較佳之碳原子數為1~8,更佳之碳原子數為1~4。作為烷基的具體實例,可舉出甲基、乙基、丙基、丁基、戊基、辛基等直鏈烷基;異丙基、異丁基、二級丁基、三級丁基等分支烷基;甚而環丙基、環丁基、環戊基、環己基等環烷基等,烷基之氫原子經取代為氟原子的比例通常為80%以上,較佳為90%以上,更佳為100%。氟原子的取代率若未達80%時,上述式(C-1)所示之鎓氟烷基氟磷酸鹽的酸強度會降低。In the fluoroalkyl fluorophosphate anion represented by the above formula (C-1b), W 3 represents an alkyl group substituted with a fluorine atom. The preferred number of carbon atoms is 1 to 8, and the more preferred number of carbon atoms is 1 to 4. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; isopropyl, isobutyl, secondary butyl, and tertiary butyl And other branched alkyl groups; even cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., the proportion of hydrogen atoms of alkyl groups substituted with fluorine atoms is usually 80% or more, preferably 90% or more , More preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the formula (C-1) will decrease.
特佳之W3 為碳原子數為1~4,且氟原子的取代率為100%的直鏈狀或分支狀的全氟烷基,作為具體實例,可舉出CF3 、CF3 CF2 、(CF3 )2 CF、CF3 CF2 CF2 、CF3 CF2 CF2 CF2 、(CF3 )2 CFCF2 、CF3 CF2 (CF3 )CF、(CF3 )3 C。W3 的個數j為1~5之整數,較佳為2~4,特佳為2或3。Particularly preferred W 3 is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF 3 , CF 3 CF 2 , (CF 3 ) 2 CF, CF 3 CF 2 CF 2 , CF 3 CF 2 CF 2 CF 2 , (CF 3 ) 2 CFCF 2 , CF 3 CF 2 (CF 3 ) CF, (CF 3 ) 3 C. The number j of W 3 is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.
作為較佳之氟烷基氟磷酸陰離子的具體實例,可舉出[(CF3 CF2 )2 PF4 ]- 、[(CF3 CF2 )3 PF3 ]- 、[((CF3 )2 CF)2 PF4 ]- 、[((CF3 )2 CF)3 PF3 ]- 、[(CF3 CF2 CF2 )2 PF4 ]- 、[(CF3 CF2 CF2 )3 PF3 ]- 、[((CF3 )2 CFCF2 )2 PF4 ]- 、[((CF3 )2 CFCF2 )3 PF3 ]- 、[(CF3 CF2 CF2 CF2 )2 PF4 ]- 、或[(CF3 CF2 CF2 )3 PF3 ]- ,此等當中,特佳為[(CF3 CF2 )3 PF3 ]- 、[(CF3 CF2 CF2 )3 PF3 ]- 、[((CF3 )2 CF)3 PF3 ]- 、[((CF3 )2 CF)2 PF4 ]- 、[((CF3 )2 CFCF2 )3 PF3 ]- 、或[((CF3 )2 CFCF2 )2 PF4 ]- 。Specific examples of the preferred fluoroalkylfluorophosphate anion include [(CF 3 CF 2 ) 2 PF 4 ] - , [(CF 3 CF 2 ) 3 PF 3 ] - , [((CF 3 ) 2 CF ) 2 PF 4 ] - , [((CF 3 ) 2 CF) 3 PF 3 ] - , [(CF 3 CF 2 CF 2 ) 2 PF 4 ] - , [(CF 3 CF 2 CF 2 ) 3 PF 3 ] - , [((CF 3 ) 2 CFCF 2 ) 2 PF 4 ] - , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] - , [(CF 3 CF 2 CF 2 CF 2 ) 2 PF 4 ] - , Or [(CF 3 CF 2 CF 2 ) 3 PF 3 ] - , among these, particularly preferred is [(CF 3 CF 2 ) 3 PF 3 ] - , [(CF 3 CF 2 CF 2 ) 3 PF 3 ] - , [((CF 3 ) 2 CF) 3 PF 3 ] - , [((CF 3 ) 2 CF) 2 PF 4 ] - , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] - , or [ ((CF 3 ) 2 CFCF 2 ) 2 PF 4 ] - .
作為上述式(C-1c)所示之硼酸根陰離子的較佳具體實例,可舉出肆(五氟苯基)硼酸根([B(C6 F5 )4 ]- )、肆[(三氟甲基)苯基]硼酸根([B(C6 H4 CF3 )4 ]- )、二氟雙(五氟苯基)硼酸根([(C6 F5 )2 BF2 ]- )、三氟(五氟苯基)硼酸根([(C6 F5 )BF3 ]- )、肆(二氟苯基)硼酸根([B(C6 H3 F2 )4 ]- )等。此等當中,特佳為肆(五氟苯基)硼酸根([B(C6 F5 )4 ]- )。As preferable specific examples of the borate anion represented by the above formula (C-1c), there may be mentioned (pentafluorophenyl) borate ([B (C 6 F 5 ) 4 ] - ), [[Three Fluoromethyl) phenyl] borate ([B (C 6 H 4 CF 3 ) 4 ] - ), difluorobis (pentafluorophenyl) borate ([(C 6 F 5 ) 2 BF 2 ] - ) , Trifluoro (pentafluorophenyl) borate ([(C 6 F 5 ) BF 3 ] - ), (difluorophenyl) borate ([B (C 6 H 3 F 2 ) 4 ] - ), etc. . Among these, particularly preferred is penta (pentafluorophenyl) borate ([B (C 6 F 5 ) 4 ] - ).
作為光酸產生劑(C)之第二形態,可舉出2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(2-呋喃基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基-2-呋喃基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(5-乙基-2-呋喃基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(5-丙基-2-呋喃基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(3,5-二甲氧基苯基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(3,5-二乙氧基苯基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(3,5-二丙氧基苯基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(3-甲氧基-5-乙氧基苯基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(3-甲氧基-5-丙氧基苯基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-亞甲二氧基苯基)乙烯基]對稱三嗪、2,4-雙(三氯甲基)-6-(3,4-亞甲二氧基苯基)對稱三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基對稱三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基對稱三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基對稱三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基對稱三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(2-呋喃基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(5-甲基-2-呋喃基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(3,5-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(3,4-亞甲二氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、參(1,3-二溴丙基)-1,3,5-三嗪、參(2,3-二溴丙基)-1,3,5-三嗪等含鹵素之三嗪化合物、以及參(2,3-二溴丙基)三聚異氰酸酯等下述式(C-2)所示之含鹵素之三嗪化合物。式(C-2) 式(C-2)中,W9 ~W11 分別獨立表示為鹵烷基。Examples of the second form of the photoacid generator (C) include 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-triazine and 2,4-bis (trichloro) (Methyl) -6- [2- (2-furanyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furanyl) Vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furanyl) vinyl] symmetrical triazine, 2,4-bis (trichloro (Methyl) -6- [2- (5-propyl-2-furanyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-bis Methoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) vinyl] symmetric triazine, 2 , 4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [ 2- (3-methoxy-5-ethoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5- Propoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) symmetric triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4 -Methoxy) phenylsymmetric triazine, 2,4-bis -Trichloromethyl-6- (2-bromo-4-methoxy) phenylsymmetric triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) benzene Vinylphenyl symmetric triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl symmetric triazine, 2- (4-methoxybenzene ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- [2- (2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5 -Methyl-2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ) Vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, ginseng (1,3-dibromopropyl) -1,3,5-triazine, ginseng (2,3-dibromopropyl) -1,3,5-triazine, etc. A triazine compound and a halogen-containing triazine compound represented by the following formula (C-2) such as ginseng (2,3-dibromopropyl) trimeric isocyanate. Formula (C-2) In formula (C-2), W 9 to W 11 are each independently represented as a haloalkyl group.
又,作為光酸產生劑(C)之第三形態,可舉出α-(對甲苯磺醯氧基亞胺基)-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-(2-氯苯磺醯氧基亞胺基)-4-甲氧基苯基乙腈、α-(乙基磺醯氧基亞胺基)-1-氯戊烯基乙腈、以及含有磺酸肟基的下述式(C-3)所示之化合物。式(C-3) 式(C-3)中,W12 表示1價、2價、或3價有機基,W13 表示經取代或者未取代之飽和烴基、不飽和烴基、或芳香族性化合物基,n表示括弧內之結構的重複單元數。Further, as a third embodiment of the photoacid generator (C), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2 , 4-Dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4- A methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-chloropentenylacetonitrile, and a compound represented by the following formula (C-3) containing a sulfonic acid oxime group. Formula (C-3) In formula (C-3), W 12 represents a monovalent, divalent, or trivalent organic group, and W 13 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound. Base, n represents the number of repeating units of the structure within the parentheses.
上述式(C-3)中,芳香族性化合物基表示使芳香族化合物顯示特有的物理、化學性質的化合物之基,可舉出例如苯基、萘基等芳基、或呋喃基、噻吩基等雜芳基。此等亦可在環上具有1個以上的適當的取代基,例如鹵素原子、烷基、烷氧基、硝基等。又,W13 特佳為碳原子數為1至6的烷基,可舉出甲基、乙基、丙基、丁基。尤以W12 為芳香族性化合物基,W13 為碳原子數為1至4的烷基的化合物為較佳。In the formula (C-3), the aromatic compound group represents a group of a compound that makes the aromatic compound exhibit unique physical and chemical properties, and examples thereof include aryl groups such as phenyl and naphthyl, or furanyl and thienyl And so on heteroaryl. These may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, and the like. Further, W 13 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, and butyl. A compound in which W 12 is an aromatic compound group and W 13 is an alkyl group having 1 to 4 carbon atoms is particularly preferred.
作為上述式(C-3)所示之酸產生劑,當n=1時,可舉出W12 為苯基、甲基苯基、甲氧基苯基任一種,W13 為甲基的化合物,具體而言可舉出α-(甲磺醯氧基亞胺基)-1-苯基乙腈、α-(甲磺醯氧基亞胺基)-1-(對甲基苯基)乙腈、α-(甲磺醯氧基亞胺基)-1-(p-甲氧基苯基)乙腈、[2-(丙磺醯氧基亞胺基)-2,3-二羥基噻吩-3-亞基](鄰甲苯基)乙腈等。當n=2時,作為上述式(C-3)所示之酸產生劑,具體而言可舉出下述式(C-3-1)~式(C-3-8)所示之酸產生劑:式(C-3-1)式(C-3-2)式(C-3-3)式(C-3-4)式(C-3-5)式(C-3-6)式(C-3-7)式(C-3-8)As the acid generator represented by the formula (C-3), when n = 1, compounds in which W 12 is any of phenyl, methylphenyl, and methoxyphenyl, and W 13 is methyl Specific examples include α- (methanesulfonyloxyimino) -1-phenylacetonitrile, α- (methanesulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methanesulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, [2- (propanesulfonyloxyimino) -2,3-dihydroxythiophene-3- Subunit] (o-tolyl) acetonitrile and the like. When n = 2, examples of the acid generator represented by the formula (C-3) include acids represented by the following formulae (C-3-1) to (C-3-8) Generating agent: Formula (C-3-1) Formula (C-3-2) Formula (C-3-3) Formula (C-3-4) Formula (C-3-5) Formula (C-3-6) Formula (C-3-7) Formula (C-3-8)
另外,作為光酸產生劑(C)之第四形態,可舉出陽離子部分具有萘環的鎓鹽。該「具有萘環」係指具有萘所衍生的結構,意指至少2個環之結構,且可維持彼等之芳香性之意。該萘環亦可具有碳原子數為1至6的直鏈狀或分支狀的烷基、氫氧基、碳原子數為1至6的直鏈狀或分支狀的烷氧基等的取代基。萘環所衍生的結構可為1價基(游離原子價為1),亦可為2價基(游離原子價為2)以上,較理想為1價基(惟,此時,係扣除與上述取代基鍵結合的部分來計算游離原子價)。萘環數較佳為1~3。Moreover, as a 4th aspect of a photoacid generator (C), the onium salt which has a naphthalene ring in a cationic part is mentioned. The "having a naphthalene ring" means having a structure derived from naphthalene, meaning a structure of at least two rings, and maintaining their aromaticity. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and the like. . The structure derived from the naphthalene ring can be a monovalent radical (free atomic valence is 1), or a divalent radical (free atomic valence is 2) or more. It is more preferably a monovalent radical (however, in this case, it is deducted from the above) (To calculate the free atomic valence of the bonded part of the substituent). The number of naphthalene rings is preferably 1 to 3.
作為此類陽離子部分具有萘環的鎓鹽的陽離子部分,較佳為下述式(C-4)所示之結構:式(C-4) 式(C-4)中,W14 ~W16 中至少1者表示下述式(C-4a)所示之基,其餘表示碳原子數為1至6的直鏈狀或者分支狀的烷基、可具取代基之苯基、氫氧基、或碳原子數為1至6的直鏈狀或者分支狀的烷氧基。或者,W14 ~W16 中的一者為下述式(C-4a)所示之基,其餘兩者分別獨立為碳原子數W14 ~W16 直鏈狀或分支狀的伸烷基,此等之末端可鍵結而呈環狀。式(C-4a) 式(C-4a)中,W17 、W18 分別獨立表示氫氧基、碳原子數為1至6的直鏈狀或者分支狀的烷氧基、或碳原子數為1至6的直鏈狀或者分支狀的烷基,W18 表示單鍵或可具取代基之碳原子數為1至6的直鏈狀或者分支狀的伸烷基。l及m分別獨立表示0~2之整數,l+m為3以下。當W17 存在複數個時,彼等可彼此相同或相異。當W18 存在複數個時,彼等可彼此相同或相異。As the cation part of such an onium salt having a naphthalene ring in the cation part, a structure represented by the following formula (C-4) is preferred: Formula (C-4) In formula (C-4), at least one of W 14 to W 16 represents a group represented by the following formula (C-4a), and the rest represents a straight chain having 1 to 6 carbon atoms. Alternatively, it may be a branched alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of W 14 to W 16 is a group represented by the following formula (C-4a), and the other two are each independently a linear or branched alkylene group having carbon number W 14 to W 16 , These ends can be bonded to form a ring. Formula (C-4a) In formula (C-4a), W 17 and W 18 each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a carbon number of A linear or branched alkyl group of 1 to 6, W 18 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer from 0 to 2, and l + m is 3 or less. When there is a plurality of W 17 , they may be the same or different from each other. When plural W 18 are present, they may be the same as or different from each other.
上述W14 ~W16 當中上述式(C-4a)所示之基的數目,基於化合物的穩定性觀點較佳為1個,其餘為碳原子數為1至6的直鏈狀或分支狀的伸烷基,此等之末端可鍵結而呈環狀。此時,上述2個伸烷基可包含硫原子而構成3~9員環。構成環的原子(含硫原子)的數目較佳為5~6。The number of the groups represented by the above formula (C-4a) among the above W 14 to W 16 is preferably one from the viewpoint of the stability of the compound, and the rest are linear or branched having 1 to 6 carbon atoms. Alkyl groups, these ends may be bonded to form a ring. In this case, the two alkylene groups may include a sulfur atom to form a 3- to 9-membered ring. The number of atoms (sulfur-containing atoms) constituting the ring is preferably 5 to 6.
又,作為上述伸烷基可具有的取代基,可舉出氧原子(此時,與構成伸烷基的碳原子共同形成羰基)、氫氧基等。Examples of the substituent which the above-mentioned alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.
又,作為苯基可具有的取代基,可舉出氫氧基、碳原子數1~6之直鏈狀或分支狀的烷氧基、碳原子數1~6之直鏈狀或分支狀的烷基等。Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched group having 1 to 6 carbon atoms. Alkyl, etc.
屬適合作為此等陽離子部分者,可舉出下述式(C-4b)、(C-4c)所示者,尤以下述式(C-4c)所示之結構為佳。式(C-4b)式(C-4c)Those suitable as such cationic moieties include those represented by the following formulae (C-4b) and (C-4c), and a structure represented by the following formula (C-4c) is particularly preferred. Formula (C-4b) Formula (C-4c)
作為此類陽離子部分,可為錪鹽或鋶鹽;基於酸產生效率等觀點較理想為鋶鹽。As such a cationic moiety, a sulfonium salt or a sulfonium salt may be used; a sulfonium salt is preferred from the viewpoint of acid production efficiency and the like.
從而,對於適合作為陽離子部分具有萘環的鎓鹽的陰離子部分者,較理想為可形成鋶鹽的陰離子。Therefore, an anion part which is suitable as an anion part of an onium salt which has a naphthalene ring in a cationic part is desirable as an anion which can form a sulfonium salt.
作為此類酸產生劑的陰離子部分,係氫原子的一部分或全部經氟化的氟烷基磺酸離子或芳基磺酸離子。As an anion part of such an acid generator, a part or all of hydrogen atoms are fluorinated fluoroalkylsulfonic acid ions or arylsulfonic acid ions.
氟烷基磺酸離子中的烷基可為碳原子數為1至20的直鏈狀、分支狀或環狀,基於產生之酸的體積大小及其擴散距離,較佳為碳原子數為1至10。尤為呈分支狀或環狀者因擴散距離短而較佳。又,由可廉價地合成而言,可舉出甲基、乙基、丙基、丁基、辛基等作為較佳者。The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched, or cyclic with 1 to 20 carbon atoms. Based on the volume of the generated acid and its diffusion distance, the number of carbon atoms is preferably 1 To 10. It is particularly preferable to have a branched or ring shape because the diffusion distance is short. In addition, from the viewpoint of inexpensive synthesis, methyl, ethyl, propyl, butyl, and octyl are preferred.
芳基磺酸離子中的芳基為碳原子數為6至20的芳基,可舉出可經烷基、鹵素原子取代之苯基、萘基。特別是,由可廉價地合成而言,較佳為碳原子數為6至10的芳基。作為較佳者的具體實例,可舉出苯基、甲苯磺醯基、乙基苯基、萘基、甲基萘基等。The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted with an alkyl group or a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferred because it can be synthesized inexpensively. Specific preferred examples include phenyl, tosyl, ethylphenyl, naphthyl, and methylnaphthyl.
上述氟烷基磺酸離子或芳基磺酸離子中,氫原子的一部分或全部經氟化時的氟化率較佳為10~100%,更佳為50~100%,尤為以氟原子取代全部氫原子而成者,因酸的強度增強而較佳。屬此類者,具體而言可舉出三氟甲磺酸酯、全氟丁磺酸酯、全氟辛磺酸酯、全氟苯磺酸酯等。Among the above fluoroalkylsulfonic acid ions or arylsulfonic acid ions, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, and especially substituted with fluorine atoms. All hydrogen atoms are preferred because the strength of the acid is increased. Those belonging to this category include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.
此等當中,作為較佳之陰離子部分,可舉出下述式(C-4d)所示者: W20 SO3 - 式(C-4d) 式(C-4d)中,W20 為下述式(C-4e)、(C-4f)、及(C-4g)所示之基。 -Cx F2x+1 式(C-4e)式(C-4f)式(C-4g) 式(C-4e)中,x表示1~4之整數。式(C-4f)中,W21 表示氫原子、氫氧基、碳原子為1至6的直鏈狀或者分支狀的烷基、或碳原子數為1至6的直鏈狀或者分支狀的烷氧基,y表示1~3之整數。此等當中,基於安全性觀點較佳為三氟甲磺酸酯、全氟丁磺酸酯。Among these, as a preferable anion part, the following formula (C-4d) can be mentioned: W 20 SO 3 - Formula (C-4d) In formula (C-4d), W 20 is the following formula (C-4e), (C-4f), and (C-4g). -C x F 2x + 1 (C-4e) Formula (C-4f) Formula (C-4g) In formula (C-4e), x represents an integer of 1 to 4. In the formula (C-4f), W 21 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. Alkoxy, y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.
又,作為陰離子部分,亦可使用下述式(C-4h)、式(C-4i)所示之含氮者。式(C-4h)式(C-4i) 式(C-4h)、式(C-4i)中,Xa 表示至少1個氫原子經氟原子取代的直鏈狀或分支狀的伸烷基,該伸烷基的碳原子數為2~6,較佳為3~5,最佳為碳原子數為3。又,Ya 、Za 分別獨立表示至少1個氫原子經氟原子取代的直鏈狀或分支狀的烷基,該烷基的碳原子數為1~10,較佳為1~7,更佳為1~3。In addition, as the anion part, a nitrogen-containing one represented by the following formula (C-4h) or (C-4i) may be used. Formula (C-4h) Formula (C-4i) In formula (C-4h) and formula (C-4i), X a represents a linear or branched alkylene group having at least one hydrogen atom substituted with a fluorine atom. The number of carbon atoms is 2 to 6, preferably 3 to 5, and most preferably 3 carbon atoms. In addition, Y a and Z a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 7, and more It is preferably 1 ~ 3.
Xa 之伸烷基的碳原子數、或Ya 、Za 之烷基的碳原子數愈小則對有機溶劑的溶解性愈良好,因此較佳。X a number of carbon atoms of the alkylene group, or Y a, Z a group of the smaller number of carbon atoms is more excellent solubility in an organic solvent, and therefore preferred.
又,Xa 之伸烷基或Ya 、Za 之烷基中,經氟原子取代之氫原子的數目愈多,酸的強度愈強,因此較佳。該伸烷基或烷基中之氟原子的比例,亦即氟化率較佳為70~100%,更佳為90~100%,最佳為所有氫原子經氟原子取代的全氟伸烷基或全氟烷基。And, X a or an alkylene group of Y a, Z a in the alkyl group, the number of substituted hydrogen atoms in the more fluorine atoms, the stronger acid strength, and therefore preferred. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably perfluoroalkylene in which all hydrogen atoms are replaced by fluorine atoms. Or perfluoroalkyl.
屬適合作為此類陽離子部分具有萘環的鎓鹽者,可舉出下述式(C-4j)、式(C-4k)所示之化合物:式(C-4j)式(C-4k)Those which are suitable as such an onium salt having a naphthalene ring in the cationic moiety include compounds represented by the following formulae (C-4j) and (C-4k): Formula (C-4j) Formula (C-4k)
再者,作為光酸產生劑(C)之第五形態,可舉出雙(對甲苯磺醯基)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(2,4-二甲基苯基磺醯基)重氮甲烷等雙磺醯基重氮甲烷類;對甲苯磺酸2-硝基苯甲酯、對甲苯磺酸2,6-二硝基苯甲酯、甲苯磺酸硝基苯甲酯、甲苯磺酸二硝基苯甲酯、磺酸硝基苯甲酯、碳酸硝基苯甲酯、碳酸二硝基苯甲酯等硝基苯甲基衍生物;連苯三酚三氟甲磺酸酯、連苯三酚三甲苯磺酸酯、甲苯磺酸苯甲酯、磺酸苯甲酯、N-甲磺醯氧基琥珀醯亞胺、N-三氯甲基磺醯氧基琥珀醯亞胺、N-苯基磺醯氧基馬來醯亞胺、N-甲磺醯氧基鄰苯二甲醯亞胺等磺酸酯類;N-羥基鄰苯二甲醯亞胺、N-羥基萘醯亞胺等三氟甲磺酸酯類;二苯基錪六氟磷酸鹽、(4-甲氧基苯基)苯基錪三氟甲磺酸鹽、雙(對三級丁基苯基)錪三氟甲磺酸鹽、三苯基鋶六氟磷酸鹽、(4-甲氧基苯基)二苯基鋶三氟甲磺酸鹽、(對三級丁基苯基)二苯基鋶三氟甲磺酸鹽等鎓鹽類;安息香甲苯磺酸酯、α-甲基安息香甲苯磺酸酯等安息香甲苯磺酸酯類;其他的二苯基錪鹽、三苯基鋶鹽、苯基重氮鎓鹽、碳酸苯甲酯等。Furthermore, as a fifth embodiment of the photoacid generator (C), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and other bissulfonyldiazomethanes; p-toluenesulfonic acid 2-nitrobenzyl Esters, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate , Nitrobenzyl derivatives such as dinitrobenzyl carbonate, pyrogallol trifluoromethanesulfonate, pyrogallol tritoluenesulfonate, benzyltoluenesulfonate, benzylsulfonate , N-methanesulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methanesulfonyloxyimine Sulfonates such as xylylenediamine; trifluoromethanesulfonates such as N-hydroxyphthalimide and N-hydroxynaphthalene imine; diphenylsulfonium hexafluorophosphate, (4 -Methoxyphenyl) phenylsulfonium triflate, bis (p-tert-butylphenyl) sulfonium triflate, tris Onium salts such as sulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tributylphenyl) diphenylsulfonium trifluoromethanesulfonate ; Benzoin tosylate such as benzoin tosylate, α-methyl benzoin tosylate; other diphenylphosphonium salts, triphenylphosphonium salts, phenyldiazonium salts, benzyl carbonate, etc. .
光酸產生劑(C)可單獨使用,亦可組合2種以上使用。又,基於含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的總使用量為100重量份,光酸產生劑(C)的含量為0.3重量份至3重量份,較佳為0.4重量份至2.8重量份,更佳為0.5重量份至2.5重量份。溶劑( D ) The photoacid generator (C) may be used alone or in combination of two or more kinds. In addition, the total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the photoacid generator (C) is 0.3 to 3 parts by weight, preferably 0.4 weight. Parts to 2.8 parts by weight, more preferably 0.5 parts to 2.5 parts by weight. Solvent ( D )
溶劑(D)只要為化學增幅型正型感光性樹脂組成物所使用者,沒有特別的限制,均可使用。例如酯系溶劑、非酯系溶劑等。The solvent (D) is not particularly limited as long as it is used by the chemically amplified positive photosensitive resin composition, and it can be used. Examples thereof include an ester-based solvent and a non-ester-based solvent.
酯系溶劑有,丙二醇單烷基醚乙酸酯[例如丙二醇單甲醚乙酸酯(PGMEA)等]、3-乙氧基丙酸乙酯、乳酸酯(例如乳酸乙酯等)等。Examples of the ester-based solvent include propylene glycol monoalkyl ether acetate [for example, propylene glycol monomethyl ether acetate (PGMEA), etc.], ethyl 3-ethoxypropionate, and lactate (for example, ethyl lactate).
非酯系溶劑中,有酮類、多價醇類及其衍生物、環式醚類等。Non-ester solvents include ketones, polyvalent alcohols and their derivatives, and cyclic ethers.
酮類有,丙酮、甲乙酮、環己酮、甲異戊酮、2-庚酮等。多價醇類及其衍生物有,乙二醇、丙二醇、二乙二醇、或此等之單甲醚、單乙醚、單丙醚、單丁醚、二甲醚或單苯基醚等。環式醚類,有二噁烷等。Ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl isopentanone, and 2-heptanone. Polyvalent alcohols and derivatives thereof include ethylene glycol, propylene glycol, diethylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, dimethyl ether, or monophenyl ether. Cyclic ethers include dioxane and the like.
溶劑可一種或兩種以上混合使用。The solvent may be used singly or in combination of two or more.
本發明之化學增幅型正型感光性樹脂組成物,為提升儲存穩定性及確保塗膜性之穩定,有機溶劑以含有選自丙二醇單烷基醚乙酸酯及2-庚酮之至少一種為佳。In the chemically amplified positive photosensitive resin composition of the present invention, in order to improve the storage stability and ensure the stability of the coating film, the organic solvent contains at least one selected from the group consisting of propylene glycol monoalkyl ether acetate and 2-heptanone. good.
基於含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的總使用量為100重量份,溶劑(D)的含量為150重量份至1200重量份,較佳為200重量份至1100重量份,更佳為250重量份至1000重量份。鹼性化合物( E ) The total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the solvent (D) is 150 to 1200 parts by weight, preferably 200 to 1100 parts by weight , More preferably 250 parts by weight to 1000 parts by weight. Basic compounds ( E )
鹼性化合物(E)只要為對化學增幅型正型感光性樹脂組成物有相容性者,沒有特別的限制,有例如特開平9-006001號公報記載之化合物等。The basic compound (E) is not particularly limited as long as it is compatible with the chemically amplified positive-type photosensitive resin composition, and includes, for example, compounds described in Japanese Patent Application Laid-Open No. 9-006001.
鹼性化合物(E)較佳為包括由式(E-1)所示的化合物: N(X)z (Y)3-z 式(E-1) 式(E-1)中,X各自獨立表示碳數為4以上的烷基、碳數為3以上的環烷基、苯基或芳烷基; Y各自獨立表示氫原子或碳數為3以下的烷基; z表示1至3的整數。The basic compound (E) preferably includes a compound represented by the formula (E-1): N (X) z (Y) 3-z Formula (E-1) In the formula (E-1), each X is independent Represents an alkyl group having 4 or more carbon atoms, a cycloalkyl group, phenyl, or aralkyl group having 3 or more carbon atoms; Y each independently represents a hydrogen atom or an alkyl group having 3 or less carbon atoms; z represents an integer of 1 to 3 .
由式(E-1)所示的化合物較佳為z為2或3,且由X所表示的基團各自相同的化合物。The compound represented by formula (E-1) is preferably a compound in which z is 2 or 3, and the groups represented by X are each the same.
做為基團X的烷基,若碳數未達4時,難以提升光阻的經時穩定性。碳數進而為5以上,尤其為8以上更佳。上限值沒有特別的限制,從確認經時穩定效果、或商業上取得之點而言,為20以下,尤其以15以下更佳。還有,超過20時,鹼性強度減弱,使儲存穩定性之效果降低。As the alkyl group of the group X, if the carbon number is less than 4, it is difficult to improve the stability of the photoresist over time. The carbon number is further 5 or more, and more preferably 8 or more. The upper limit value is not particularly limited, and it is more preferably 20 or less, and more preferably 15 or less, from the viewpoint of confirming the effect of stabilization over time or commercially obtained. In addition, when it exceeds 20, the alkali strength decreases, and the effect of storage stability decreases.
烷基為直鏈狀、支鏈狀均可。具體而言,例如以正癸基、正辛基、正戊基等為佳。The alkyl group may be linear or branched. Specifically, for example, n-decyl, n-octyl, and n-pentyl are preferred.
做為基團X的環烷基中,尤其碳數4至8的環烷基可由商業上取得,且提升經時穩定性之效果優越,較為適合。碳數為6的環己基更佳。Among the cycloalkyl groups as the group X, especially cycloalkyl groups having 4 to 8 carbon atoms are commercially available, and the effect of improving stability over time is superior, which is more suitable. A cyclohexyl group having 6 carbon atoms is more preferred.
做為基團X的芳烷基,可列舉由式(E-1a)所示的基團: -R'-P 式(E-1a) 式(E-1a)中,R'表示伸烷基;P表示芳香族烴基。Examples of the aralkyl group of the group X include a group represented by the formula (E-1a): -R'-P Formula (E-1a) In the formula (E-1a), R 'represents an alkylene group ; P represents an aromatic hydrocarbon group.
做為基團P,可列舉苯基、萘基等,以苯基為佳。做為基團R'的伸烷基,碳數為1以上即可,較佳為1至3。Examples of the group P include a phenyl group and a naphthyl group, and a phenyl group is preferred. As the alkylene group of the group R ′, the carbon number may be 1 or more, and preferably 1 to 3.
做為基團X的芳烷基,以例如苄基、苯基乙基等為佳。As the aralkyl group of the group X, for example, benzyl, phenylethyl and the like are preferred.
做為基團Y的烷基,可為直鏈或支鏈者。尤其以甲基、乙基為佳。As the alkyl group of the group Y, it may be a straight chain or a branched chain. Especially preferred are methyl and ethyl.
由式(E-1)所示的化合物較佳為三級胺化合物。即,若由式(E-1)所示的化合物中具有基團Y時,基團Y較佳為烷基。The compound represented by the formula (E-1) is preferably a tertiary amine compound. That is, if the compound represented by the formula (E-1) has a group Y, the group Y is preferably an alkyl group.
由式(E-1)所示的化合物,具體而言,有例如三正癸胺、甲基二正辛胺、三正戊胺、N,N-二環己基甲基胺、三苄基胺等。Specific examples of the compound represented by the formula (E-1) include tri-n-decylamine, methyl-di-n-octylamine, tri-n-pentylamine, N, N-dicyclohexylmethylamine, and tribenzylamine. Wait.
鹼性化合物(E)可使用一種或兩種以上混合使用。基於含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的總使用量為100重量份,鹼性化合物(E)的含量為0.03重量份至0.3重量份,較佳為0.04重量份至0.28重量份,更佳為0.05重量份至0.25重量份。The basic compound (E) may be used alone or as a mixture of two or more thereof. The total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the basic compound (E) is 0.03 to 0.3 parts by weight, preferably 0.04 to 0.28 parts by weight. It is more preferably from 0.05 to 0.25 parts by weight.
當化學增幅型正型感光性樹脂組成物中更包含鹼性化合物(E)時,可進一步改善化學增幅型正型感光性樹脂組成物的耐熱性。添加劑( F ) When the chemically amplified positive photosensitive resin composition further contains a basic compound (E), the heat resistance of the chemically amplified positive photosensitive resin composition can be further improved. Additives ( F )
化學增幅型正型感光性樹脂組成物中,只要不影響本發明的效果,更可進一步包含添加劑(F),添加劑(F)可單獨使用一種或混用多種,端看實際需要而定。以下說明添加劑(F)的具體內容。In the chemically amplified positive photosensitive resin composition, as long as the effect of the present invention is not affected, additives (F) may be further included, and the additives (F) may be used singly or in combination of a plurality of types, depending on actual needs. The specific content of the additive (F) is described below.
化學增幅型正型感光性樹脂組成物中,為提升可塑性,亦可進一步含有聚乙烯樹脂作為添加劑(F)。作為聚乙烯樹脂的具體實例,可舉出聚氯乙烯、聚苯乙烯、聚羥基苯乙烯、聚乙酸乙烯酯、聚乙烯苯甲酸、聚乙烯甲醚、聚乙烯乙醚、聚乙烯醇、聚乙烯吡咯啶酮、聚乙烯酚、及此等之共聚物等。聚乙烯樹脂,基於玻璃轉移點較低而言,較佳為聚乙烯甲醚。The chemically amplified positive photosensitive resin composition may further contain a polyethylene resin as an additive (F) in order to improve the plasticity. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinyl methyl ether, polyvinyl ether, polyvinyl alcohol, and polyvinylpyrrole. Pyridone, polyvinylphenol, and copolymers thereof. Polyethylene resin is preferably polyethylene methyl ether because of its low glass transition point.
又,化學增幅型正型感光性樹脂組成物中,為提升使用感光性樹脂組成物所形成之模板與金屬基板的接著性,亦可進一步含有接著助劑作為添加劑(F)。In addition, the chemically amplified positive photosensitive resin composition may further include a bonding aid as an additive (F) in order to improve the adhesion between the template and the metal substrate formed using the photosensitive resin composition.
再者,化學增幅型正型感光性樹脂組成物中,為提升塗佈性、消泡性、均平性等,亦可進一步含有界面活性劑作為添加劑(F)。作為界面活性劑的具體實例,可舉出BM-1000、BM-1100(均為BM Chmie公司製)、MEGAFACE F142D、MEGAFACE F172、MEGAFACE F173、MEGAFACE F183(均為DIC公司製)、FLUORAD FC-135、FLUORAD FC-170C、FLUORAD FC-430、FLUORAD FC-431(均為住友3M公司製)、SURFLON S-112、SURFLON S-113、SURFLON S-131、SURFLON S-141、SURFLON S-145(均為旭硝子公司製)、SH-28PA、SH-190、SH-193、SZ-6032、SF-8428(均為Toray Silicone公司製)等市售之氟系界面活性劑,惟非限定於此等。Furthermore, the chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (F) in order to improve coating properties, defoaming properties, leveling properties, and the like. Specific examples of the surfactant include BM-1000, BM-1100 (all manufactured by BM Chmie), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all manufactured by DIC Corporation), FLUORAD FC-135 , FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (all made by Sumitomo 3M), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (all It is a commercially available fluorine-based surfactant such as manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone), but is not limited thereto.
此外,化學增幅型正型感光性樹脂組成物中,為進行對顯影液之溶解性的微調,亦可進一步含有酸、酸酐、或高沸點溶媒作為添加劑(F)。In addition, the chemically amplified positive-type photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling point solvent as an additive (F) in order to finely adjust the solubility of the developer.
作為酸及酸酐的具體實例,可舉出乙酸、丙酸、正丁酸、異丁酸、正戊酸、異戊酸、苯甲酸、桂皮酸等單羧酸類;乳酸、2-羥基丁酸、3-羥基丁酸、水楊酸、間羥基苯甲酸、對羥基苯甲酸、2-羥基桂皮酸、3-羥基桂皮酸、4-羥基桂皮酸、5-羥基間苯二甲酸、丁香酸等羥基單羧酸類;草酸、琥珀酸、戊二酸、己二酸、馬來酸、衣康酸、六氫鄰苯二甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2-環己烷二羧酸、1,2,4-環己烷三羧酸、丁烷四羧酸、偏苯三甲酸、苯均四酸、環戊烷四羧酸、丁烷四羧酸、1,2,5,8-萘四羧酸等多元羧酸類;衣康酸酐、琥珀酸酐、檸康酸酐、十二烯琥珀酸酐、丙烷三羧酸酐、馬來酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、腐植酸酐、1,2,3,4-丁烷四羧酸酐、環戊烷四羧酸二酐、鄰苯二甲酸酐、苯均四酸酐、偏苯三甲酸酐、二苯甲酮四羧酸酐、乙二醇雙偏苯三甲酸酐、丙三醇參偏苯三甲酸酐等酸酐;等。Specific examples of acids and anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc. Monocarboxylic acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2 -Cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, Polycarboxylic acids such as 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, propanetricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimylene Tricarboxylic anhydride, diphenyl Benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitic anhydride, glycerol, trimellitic anhydride reference anhydride; and the like.
又,作為高沸點溶媒的具體實例,可舉出N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、二甲基亞碸、苯甲基乙醚、二己醚、乙醯基丙酮、異佛酮、己酸、辛酸、1-辛醇、1-壬醇、苯甲醇、乙酸苯甲酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、苯基賽路蘇乙酸酯等。Further, as specific examples of the high-boiling-point solvent, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamidamine, N-methylpyrrolidone, dimethyl sulfene, benzyl ether, dihexyl ether, acetoacetone, isophorone, hexanoic acid, caprylic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, vinyl carbonate, propylene carbonate, phenylcellulose Acetate, etc.
又,化學增幅型正型感光性樹脂組成物中,為提升感度,亦可進一步含有敏化劑作為添加劑(F)。< 化學增幅型正型感光性樹脂組成物的製造方法 > The chemically amplified positive-type photosensitive resin composition may further contain a sensitizer as an additive (F) in order to increase sensitivity. < Method for producing chemically amplified positive photosensitive resin composition >
化學增幅型正型感光性樹脂組成物的製造方法並無特別限制,可以將上述的各成分以常用方法混合、攪拌而製得。作為將上述的各成分混合、攪拌時可使用的裝置,可舉出溶解機、均質機、三輥磨機等。將上述的各成分均勻混合後,亦可將所得混合物進一步利用篩網、膜濾器等加以過濾。< 光阻圖案的形成方法 > The method for producing the chemically amplified positive-type photosensitive resin composition is not particularly limited, and the aforementioned components can be obtained by mixing and stirring the components in a usual manner. Examples of a device that can be used when mixing and stirring the above-mentioned components include a dissolver, a homogenizer, and a three-roll mill. After the above components are uniformly mixed, the obtained mixture may be further filtered with a screen, a membrane filter, or the like. < Method of Forming Photoresist Pattern >
本發明更提供一種光阻圖案的形成方法,以下對本發明的光阻圖案的形成方法進行說明。The present invention further provides a method for forming a photoresist pattern. The method for forming the photoresist pattern of the present invention is described below.
首先,以旋轉器等將本發明之化學增幅型正型感光性樹脂組成物塗佈於基板,形成塗膜。First, the chemically amplified positive photosensitive resin composition of the present invention is applied to a substrate with a spinner or the like to form a coating film.
基板,以設置矽膜之玻璃基板為佳。矽膜之形成,通常使用非晶質矽,在系統LCD之領域,以低溫聚矽等為佳。又,可使用300 mm×400 mm以上之大型基板,尤其550 mm×650 mm以上之大型基板。The substrate is preferably a glass substrate provided with a silicon film. For the formation of silicon film, amorphous silicon is usually used. In the field of system LCD, low temperature polysilicon is preferred. In addition, a large substrate of 300 mm × 400 mm or more, especially a large substrate of 550 mm × 650 mm or more can be used.
接著,使形成此塗膜之基板在例如90~140℃下進行加熱處理(預烤),去除餘留溶劑,形成光阻被膜。加熱處理(預烤)的方法,以加熱板與基板之間具有間隙的鄰近烘烤(Proximity Bake)加熱方式為佳。Next, the substrate on which the coating film is formed is subjected to a heat treatment (pre-baking) at, for example, 90 to 140 ° C., and the remaining solvent is removed to form a photoresist film. The heat treatment (pre-baking) method is preferably a proximity baking (Proximity Bake) heating method with a gap between the heating plate and the substrate.
接著,使用描繪積體電路用之光罩圖案與液晶顯示部份用的光罩圖案之雙方的光罩對上述光阻被膜進行選擇性曝光。Next, the photoresist film is selectively exposed using a photomask that depicts both a photomask pattern for a integrated circuit and a photomask pattern for a liquid crystal display portion.
為形成精細的圖案,此處所使用之光源以使用i線(365 nm)為佳。又,在此曝光採用之曝光製程以NA為0.3以下,較佳為0.2以下,更佳為0.15以下之低NA條件的曝光製程。藉由採用在低NA條件下之曝光製程,可擴大一次之曝光面積,能提高生產能力。In order to form a fine pattern, the light source used here is preferably an i-line (365 nm). In addition, the exposure process used in this exposure is an exposure process with a NA of 0.3 or lower, preferably 0.2 or lower, and more preferably 0.15 or lower. By using the exposure process under low NA conditions, the exposure area can be enlarged at one time, and the production capacity can be improved.
接著,對選擇性曝光後之光阻被膜進行加熱處理(曝後烤)。曝後烤的方法有:在加熱板與基板之間具有間隙的鄰近烘烤(Proximity Bake)、與不具間隙的直接烘烤(Direct Bake)等方法。其中,為了不造成基板的翹曲而獲得曝後烤的擴散效果,較佳為進行鄰近烘烤後再進行直接烘烤的方法。此處,加熱溫度為90~150℃,以100~140℃更佳。Next, the photoresist film after selective exposure is heat-treated (post-exposure baking). Post-exposure bake methods include methods such as proximity baking with a gap between the heating plate and the substrate, and direct bake with no gap. Among them, in order to obtain the diffusion effect of post-exposure baking without causing warpage of the substrate, a method of performing direct baking after performing adjacent baking is preferred. Here, the heating temperature is 90 to 150 ° C, and more preferably 100 to 140 ° C.
接著,使用顯影液,例如1~10質量%氫氧化四甲基銨水溶液之鹼水溶液,對上述曝後烤後之光阻被膜進行顯影處理,溶解去除曝光部份,同時在基板上形成積體電路用的光阻圖案、與液晶顯示部份用的光阻圖案。Next, using a developing solution, for example, an alkali aqueous solution of 1 to 10% by mass of a tetramethylammonium hydroxide aqueous solution, the photoresist film after the above-mentioned baking is subjected to a development treatment to dissolve and remove the exposed portion, and at the same time form a bulk on the substrate. Photoresist pattern for circuit and photoresist pattern for liquid crystal display.
接著,藉由以純水等沖洗液將餘留於光阻圖案表面的顯影液洗淨,可形成光阻圖案。Next, the developing solution remaining on the surface of the photoresist pattern is washed with a washing liquid such as pure water to form a photoresist pattern.
在進行上述選擇性曝光的步驟中,以使用描繪2.0 μm以下之形成光阻圖案用光罩圖案、與超過2.0 μm之形成光阻圖案用光罩圖案的雙方之光罩做為上述光罩較為適合。In the step of performing the selective exposure described above, it is preferable to use a photomask that forms both a photoresist pattern-forming photomask pattern and a photoresist pattern-forming photomask pattern that exceeds 2.0 μm in size. Suitable for.
本發明的化學增幅型正型感光性樹脂組成物因其線性優異,故可獲得忠實重現光罩圖案之粗糙圖案與精細圖案的光阻圖案。因此,可同時在基板上形成圖案尺寸2.0 μm以下之積體電路用光阻圖案、與超過2.0 μm之液晶顯示部份用光阻圖案。< 實施例 > 含有酸解離 性保護基的聚羥基苯乙烯樹脂( A )的合成例 Since the chemically amplified positive photosensitive resin composition of the present invention is excellent in linearity, it is possible to obtain a photoresist pattern that faithfully reproduces a rough pattern and a fine pattern of a photomask pattern. Therefore, a photoresist pattern for an integrated circuit having a pattern size of 2.0 μm or less and a photoresist pattern for a liquid crystal display portion exceeding 2.0 μm can be simultaneously formed on a substrate. < Example > Synthesis example of polyhydroxystyrene resin ( A ) containing an acid dissociable protective group
以下說明含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的合成例A-1至A-6以及比較合成例A’-1:The following describes Synthesis Examples A-1 to A-6 and Comparative Synthesis Example A'-1 of the polyhydroxystyrene resin (A) containing an acid-dissociable protective group:
合成例A-1 將120重量份的重量平均分子量為13,000的聚羥基苯乙烯樹脂加入680重量份的N,N-二甲基乙醯胺中溶解之後,將42.3重量份的1-氯-乙氧基乙烷加入四頸錐瓶中,緩慢攪拌上述混合溶液至完全溶解。接著,以在30分鐘左右的時間內滴加完畢的速度,透過加液漏斗滴加78.8重量份的三乙基胺,並進行反應3小時。反應結束後,加入相對於上述混合溶液的總量為20倍量的純水,使含有1-乙氧基乙基做為酸解離性保護基的聚羥基苯乙烯樹脂析出,將上述的析出物以純水洗淨、脫水、乾燥後,即獲得酚性羥基的氫原子取代率為39 mol%的含有1-乙氧基乙基做為酸解離性保護基的聚羥基苯乙烯樹脂(A-1)。Synthesis Example A-1 After 120 parts by weight of a polyhydroxystyrene resin having a weight average molecular weight of 13,000 was added to 680 parts by weight of N, N-dimethylacetamide, 42.3 parts by weight of 1-chloro-ethyl Ethoxyethane was added to a four-necked conical flask, and the mixed solution was slowly stirred until completely dissolved. Next, 78.8 parts by weight of triethylamine was added dropwise through the addition funnel at a rate of completion of the dropwise addition within about 30 minutes, and the reaction was performed for 3 hours. After the reaction is completed, 20 times the amount of pure water relative to the total amount of the mixed solution is added to precipitate a polyhydroxystyrene resin containing 1-ethoxyethyl group as an acid dissociative protective group, and the above-mentioned precipitates are separated. After washing with pure water, dehydration, and drying, a polyhydroxystyrene resin containing 1-ethoxyethyl group as an acid-dissociable protective group (A- 1).
合成例A-2至A-3 合成例A-2至A-3是以與合成例A-1相同的步驟來製備,並且其不同處在於:改變所使用的聚羥基苯乙烯樹脂的重量平均分子量及其酚性羥基的氫原子取代率(如表1所示)。Synthesis Examples A-2 to A-3 Synthesis Examples A-2 to A-3 were prepared in the same procedure as Synthesis Example A-1, except that the weight average of the polyhydroxystyrene resin used was changed Molecular weight and hydrogen atom substitution rate of its phenolic hydroxyl group (as shown in Table 1).
合成例A-4 將120重量份的重量平均分子量為13,000的聚羥基苯乙烯樹脂加入680重量份的N,N-二甲基乙醯胺中溶解之後,將85重量份的二碳酸二第三丁酯加入四頸錐瓶中,緩慢攪拌上述混合溶液至完全溶解。接著,以在15分鐘左右的時間內滴加完畢的速度,透過加液漏斗滴加59重量份的三乙基胺,並進行反應3小時。反應結束後,加入相對於上述混合溶液的總量為20倍量的純水,使含有第三丁氧基羰基做為酸解離性保護基的聚羥基苯乙烯樹脂析出,將上述的析出物以純水洗淨、脫水、乾燥後,即獲得酚性羥基的氫原子取代率為39 mol%的含有第三丁氧基羰基做為酸解離性保護基的聚羥基苯乙烯樹脂(A-4)。Synthesis Example A-4 After 120 parts by weight of a polyhydroxystyrene resin having a weight average molecular weight of 13,000 was added to 680 parts by weight of N, N-dimethylacetamide, 85 parts by weight of dicarbonate was added. Butyl ester was added to a four-necked conical flask, and the mixed solution was slowly stirred until completely dissolved. Next, 59 parts by weight of triethylamine was added dropwise through the addition funnel at a rate at which the addition was completed in about 15 minutes, and the reaction was performed for 3 hours. After the reaction, 20 times the amount of pure water was added to the total amount of the mixed solution to precipitate a polyhydroxystyrene resin containing a third butoxycarbonyl group as an acid-dissociable protective group. After washing with pure water, dehydration, and drying, a polyhydroxystyrene resin (A-4) containing a third butoxycarbonyl group as an acid-dissociable protective group with a hydrogen atom substitution rate of 39 mol% was obtained. .
合成例A-5至A-6 合成例A-5至A-6是以與合成例A-1相同的步驟來製備,並且其不同處在於:改變所使用的聚羥基苯乙烯樹脂的重量平均分子量及其酚性羥基的氫原子取代率(如表1所示)。Synthesis Examples A-5 to A-6 Synthesis Examples A-5 to A-6 were prepared in the same procedure as Synthesis Example A-1, except that the weight average of the polyhydroxystyrene resin used was changed Molecular weight and hydrogen atom substitution rate of its phenolic hydroxyl group (as shown in Table 1).
比較合成例A’-1 在備有冷卻管的容積1000毫升的三頸錐瓶中,將120重量份的4-羥基苯乙烯加入480重量份的四氫呋喃中溶解之後,緩慢攪拌上述混合溶液至溶解。接著,將2,2’-偶氮雙-2-異丙基丁腈(AIBN)加入三頸錐瓶中以進行聚合反應,整個聚合過程的反應溫度維持在75℃。聚合完成後,將聚合產物自四頸錐瓶中取出,並把溶劑脫去,便可得不具酸解離性保護基的聚羥基苯乙烯樹脂(A’-1),其重量平均分子量為13,000。Comparative Synthesis Example A'-1 In a three-necked conical flask of 1,000 ml in volume equipped with a cooling tube, 120 parts by weight of 4-hydroxystyrene was added to 480 parts by weight of tetrahydrofuran to dissolve, and the mixed solution was slowly stirred until dissolved. . Next, 2,2'-azobis-2-isopropylbutyronitrile (AIBN) was added to a three-necked conical flask to perform a polymerization reaction, and the reaction temperature was maintained at 75 ° C throughout the polymerization process. After the polymerization was completed, the polymerization product was taken out of the four-necked conical flask and the solvent was removed to obtain a polyhydroxystyrene resin (A'-1) having no acid-dissociable protective group, and its weight average molecular weight was 13,000.
[表1]
以下說明聚矽氧烷(B)的合成例B-1至B-7以及比較合成例B’-1至B’-2:The following describes Synthesis Examples B-1 to B-7 and Comparative Synthesis Examples B'-1 to B'-2 of polysiloxane (B):
合成例B-1 在容積500毫升的三頸燒瓶上設置攪拌器、冷凝管及溫度計。然後,在三頸燒瓶中,加入0.03莫耳的3-(三乙氧基矽基)丙基丁二酸酐(以下簡稱為GF-20)、0.60莫耳的甲基三甲氧基矽烷(以下簡稱MTMS)、0.35莫耳的二甲基二甲氧基矽烷(以下簡稱為DMDMS)、0.02莫耳的四甲氧基矽烷(以下簡稱為TMOS)以及135克的4-羥基-4-甲基-2-戊酮(以下簡稱為DAA),並於室溫下一邊攪拌一邊於30分鐘內添加磷酸水溶液(0.25克磷酸/45克水)。接著,將三頸燒瓶浸漬於30℃的油浴中並攪拌30分鐘,然後於30分鐘內將油浴升溫至120℃,待溶液的內溫達到105℃時,持續加熱攪拌進行聚縮合6小時。待反應結束後,利用蒸餾方式將溶劑移除,即可獲得聚矽氧烷(B-1)。Synthesis Example B-1 A three-necked flask with a volume of 500 ml was provided with a stirrer, a condenser, and a thermometer. Then, in a three-necked flask, 0.03 mole of 3- (triethoxysilyl) propylsuccinic anhydride (hereinafter referred to as GF-20) and 0.60 mole of methyltrimethoxysilane (hereinafter referred to as MTMS), 0.35 moles of dimethyldimethoxysilane (hereinafter referred to as DMDMS), 0.02 moles of tetramethoxysilane (hereinafter referred to as TMOS), and 135 grams of 4-hydroxy-4-methyl- 2-pentanone (hereinafter referred to as DAA), and an aqueous phosphoric acid solution (0.25 g phosphoric acid / 45 g water) was added within 30 minutes while stirring at room temperature. Next, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 30 minutes, and then the oil bath was heated to 120 ° C. within 30 minutes. When the internal temperature of the solution reached 105 ° C., the mixture was continuously heated and stirred for 6 hours. . After the reaction is completed, the solvent is removed by distillation to obtain polysiloxane (B-1).
合成例B-2至B-7以及比較合成例B’-1至B’-2 合成例B-2至B-7以及比較合成例B’-1至B’-2的聚矽氧烷(B-2)至(B-7)以及(B’-1)至(B’-2)是以與合成例B-1相同的步驟來製備,並且其不同處在於:改變矽烷單體的成分種類及其使用量、反應溫度及聚縮合時間(如表2所示)。Synthesis Examples B-2 to B-7 and Comparative Synthesis Examples B'-1 to B'-2 Synthesis Examples B-2 to B-7 and Comparative Synthesis Examples B'-1 to B'-2 B-2) to (B-7) and (B'-1) to (B'-2) were prepared in the same steps as in Synthesis Example B-1, and the difference was that the composition of the silane monomer was changed Kind and its usage amount, reaction temperature and polycondensation time (as shown in Table 2).
表2中簡稱所對應的化合物如下所示。
[表2]
以下說明化學增幅型正型感光性樹脂組成物的實施例1至10、以及比較例1至4:Examples 1 to 10 and Comparative Examples 1 to 4 of the chemically amplified positive photosensitive resin composition are described below:
實施例1 將前述合成例A-1所得的100重量份的含有酸解離性保護基的聚羥基苯乙烯樹脂(A-1)、合成例B-1所得的10重量份的聚矽氧烷(B-1)以及1.0重量份的光酸產生劑C-1加入450重量份的丙二醇單甲醚乙酸酯(以下簡稱D-1)後,以搖動式攪拌器,加以溶解混合,即可調製而得化學增幅型正型感光性樹脂組成物,所述化學增幅型正型感光性樹脂組成物以下述之各測定評價方式進行評價,所得結果如表3所示。Example 1 100 parts by weight of the polyhydroxystyrene resin (A-1) containing an acid-dissociable protective group obtained in the aforementioned Synthesis Example A-1, and 10 parts by weight of the polysiloxane ( B-1) and 1.0 parts by weight of the photoacid generator C-1 are added to 450 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as D-1), and the mixture is dissolved and mixed with a shaking mixer to prepare A chemically amplified positive photosensitive resin composition was obtained. The chemically amplified positive photosensitive resin composition was evaluated by each of the following measurement and evaluation methods, and the results are shown in Table 3.
實施例2至實施例10 實施例2至實施例10是使用與實施例1的化學增幅型正型感光性樹脂組成物製作方法相同的操作方法,不同之處在於實施例2至實施例10是改變化學增幅型正型感光性樹脂組成物中原料的種類及使用量,其配方及下列的評價結果如表3及表4所示。Examples 2 to 10 Examples 2 to 10 use the same operation method as the method for manufacturing the chemically amplified positive-type photosensitive resin composition of Example 1, except that Examples 2 to 10 are Table 3 and Table 4 change the types and amounts of raw materials in the chemically amplified positive-type photosensitive resin composition, and their formulations and the following evaluation results.
比較例1至比較例4 比較例1至比較例4是使用與實施例1的化學增幅型正型感光性樹脂組成物製作方法相同之操作方法,不同之處在於比較例1至比較例4是改變化學增幅型正型感光性樹脂組成物中原料的種類及使用量,其配方及下列之評價結果如表4所示。Comparative Examples 1 to 4 Comparative Examples 1 to 4 use the same operation method as the method for producing the chemically amplified positive-type photosensitive resin composition of Example 1, except that Comparative Examples 1 to 4 are Table 4 shows the formula and the following evaluation results by changing the type and amount of raw materials in the chemically amplified positive photosensitive resin composition.
表3及表4中標號所對應的化合物如下所示
[表3]
[表4]
a.感度 使用光阻塗佈裝置(裝置名稱:TR36000,東京應化工業股份有限公司製),將實施例及比較例的化學增幅型正型感光性樹脂組成物塗佈於ITO基板(100 mm×100 mm)上之後,以110℃、90秒鐘的加熱條件,藉由間隙約1 mm的接近加熱,進行預熱,形成膜厚1.5 μm的光阻被膜。接著,使用i線曝光裝置(裝置名稱:FX-702J,尼康公司製,NA=0.14),使用能同時描繪2.0 μm L&S(線與空間)的光阻圖案與3.0 μm L&S的光阻圖案的試驗圖表光罩(標度線),進行選擇性曝光。接著,以110℃,90秒鐘的條件,藉由0.5 mm間隙的接近加熱,進行曝後烤(PEB)。接著,使用23℃,2.38質量%四甲基氫氧化銨(TMAH)水溶液,進行40秒鐘的顯影處理後,以純水進行15秒鐘的沖洗,並進行旋轉乾燥。以可忠實重現2.0 μm L&S的光阻圖案的曝光量(Eop,單位:mJ)做為感度評估的指標,評價標準如下: ◎:曝光量<60 mJ ○:60 mJ≦曝光量<150 mJ △:150 mJ≦曝光量<300 mJ ╳:曝光量≧300 mJa. Using a photoresist coating device (device name: TR36000, manufactured by Tokyo Chemical Industry Co., Ltd.), the chemically amplified positive photosensitive resin composition of the examples and comparative examples was coated on an ITO substrate (100 mm × 100 mm), and then preheated under a heating condition of 110 ° C and 90 seconds with a gap of approximately 1 mm to form a photoresist film having a thickness of 1.5 μm. Next, an i-line exposure device (device name: FX-702J, manufactured by Nikon Corporation, NA = 0.14) was used, and a photoresist pattern capable of simultaneously drawing 2.0 μm L & S (line and space) and a photoresist pattern of 3.0 μm L & S was tested. Graphic mask (scale line) for selective exposure. Then, at a temperature of 110 ° C. for 90 seconds, a close exposure heating with a gap of 0.5 mm was performed to perform post-exposure baking (PEB). Next, development was performed for 40 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C, followed by rinsing with pure water for 15 seconds, and spin drying. The exposure amount (Eop, unit: mJ) that faithfully reproduces a 2.0 μm L & S photoresist pattern is used as an index for sensitivity evaluation. The evaluation criteria are as follows: ◎: exposure amount <60 mJ ○: 60 mJ ≦ exposure amount <150 mJ △: 150 mJ ≦ exposure amount <300 mJ ╳: exposure amount ≧ 300 mJ
耐熱性 請參照圖1,圖1為量測光阻圖案的耐熱性的示意圖。如同上述感度評價的試驗,但在耐熱性評價試驗中,改為在基板1上描繪5.0 μm L&S的光阻圖案2,並靜置於設定在130℃的加熱板上150秒鐘後,觀測光阻圖案2的剖面形狀。以光阻圖案2的錐度角θ的變化量的絕對值(即|∆θ|)做為耐熱性評估的指標,評價標準如下: ◎:|∆θ|≦3° ○:3°<|∆θ|≦5° △:5°<|∆θ|≦10° ╳:10°<|∆θ|評價結果 Heat resistance Please refer to FIG. 1, which is a schematic diagram for measuring the heat resistance of a photoresist pattern. As in the sensitivity evaluation test described above, in the heat resistance evaluation test, a 5.0 μm L & S photoresist pattern 2 was drawn on the substrate 1 and placed on a hot plate set at 130 ° C. for 150 seconds, and the light was observed. The cross-sectional shape of the resist pattern 2. The absolute value of the change in the taper angle θ of the photoresist pattern 2 (that is, | Δθ |) is used as an index for evaluating heat resistance. The evaluation criteria are as follows: ◎: | Δθ | ≦ 3 ° ○: 3 ° <| ∆ θ | ≦ 5 ° △: 5 ° <| Δθ | ≦ 10 ° ╳: 10 ° <| Δθ | Evaluation result
由表3、表4得知,與包括含有酸解離性保護基的聚羥基苯乙烯樹脂(A)以及聚矽氧烷(B)的化學增幅型正型感光性樹脂組成物(實施例1-10)所製得的光阻圖案相比,未包括含有酸解離性保護基的聚羥基苯乙烯樹脂(A)的化學增幅型正型感光性樹脂組成物(比較例1-2),無法忠實重現2.0 μm或5.0 μm L&S的光阻圖案,故無法進行評價;而未包括具特定結構的聚矽氧烷(B)的化學增幅型正型感光性樹脂組成物(比較例3-4)所製得的光阻圖案的耐熱性不佳。As shown in Tables 3 and 4, chemically amplified positive-type photosensitive resin compositions containing polyhydroxystyrene resin (A) and polysiloxane (B) containing an acid-dissociable protective group (Example 1- 10) Compared with the obtained photoresist pattern, the chemically amplified positive photosensitive resin composition (Comparative Example 1-2) which does not include the polyhydroxystyrene resin (A) containing an acid dissociative protective group cannot be faithful A photoresist pattern of 2.0 μm or 5.0 μm L & S was reproduced, so evaluation could not be performed. A chemically amplified positive-type photosensitive resin composition containing polysiloxane (B) with a specific structure was not included (Comparative Example 3-4) The heat resistance of the obtained photoresist pattern is not good.
同時,當化學增幅型正型感光性樹脂組成物中,更包括鹼性化合物(E)(實施例5-10)時,其所製得的光阻圖案的耐熱性表現更佳。At the same time, when the chemically amplified positive photosensitive resin composition further includes a basic compound (E) (Examples 5-10), the heat resistance of the photoresist pattern obtained therefrom is better.
綜上所述,本發明的化學增幅型正型感光性樹脂組成物因包括含有酸解離性保護基的聚羥基苯乙烯樹脂(A)、以及聚矽氧烷(B),故能夠改善感度及耐熱性不佳的問題。In summary, since the chemically amplified positive photosensitive resin composition of the present invention includes a polyhydroxystyrene resin (A) and a polysiloxane (B) containing an acid dissociative protective group, it is possible to improve the sensitivity and The problem of poor heat resistance.
另一方面,若本發明的化學增幅型正型感光性樹脂組成物中更含有鹼性化合物(E)時,所製得的光阻圖案將能夠進一步獲得更佳的耐熱性。On the other hand, if the chemically amplified positive-type photosensitive resin composition of the present invention further contains a basic compound (E), the obtained photoresist pattern can further obtain better heat resistance.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.
1:基板 2:光阻圖案 θ:錐度角1: substrate 2: photoresist pattern θ: taper angle
圖1為量測光阻圖案的耐熱性的示意圖。FIG. 1 is a schematic diagram for measuring the heat resistance of a photoresist pattern.
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