TW201428426A - 正向感光材料 - Google Patents
正向感光材料 Download PDFInfo
- Publication number
- TW201428426A TW201428426A TW102144473A TW102144473A TW201428426A TW 201428426 A TW201428426 A TW 201428426A TW 102144473 A TW102144473 A TW 102144473A TW 102144473 A TW102144473 A TW 102144473A TW 201428426 A TW201428426 A TW 201428426A
- Authority
- TW
- Taiwan
- Prior art keywords
- thiol
- group
- meth
- acrylate
- unsubstituted
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 5
- -1 heterocyclic thiol compound Chemical class 0.000 claims abstract description 139
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 73
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- HWGBHCRJGXAGEU-UHFFFAOYSA-N Methylthiouracil Chemical compound CC1=CC(=O)NC(=S)N1 HWGBHCRJGXAGEU-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000004187 tetrahydropyran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 3
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 claims description 3
- KJTLQQUUPVSXIM-ZCFIWIBFSA-M (R)-mevalonate Chemical compound OCC[C@](O)(C)CC([O-])=O KJTLQQUUPVSXIM-ZCFIWIBFSA-M 0.000 claims description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 2
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004339 2,3-dimethylpent-3-yl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- NDMUQNOYNAWAAL-UHFFFAOYSA-N 3-diazo-1,4-dioxonaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C(=[N+]=[N-])C(S(=O)(=O)O)C(=O)C2=C1 NDMUQNOYNAWAAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 claims description 2
- CMKNYOJPKNSLHZ-UHFFFAOYSA-N 8-methylnonan-2-yl 2-methylprop-2-enoate Chemical compound CC(CCCCCC(C)C)OC(C(=C)C)=O CMKNYOJPKNSLHZ-UHFFFAOYSA-N 0.000 claims description 2
- VBYSNJGYQWXUEW-UHFFFAOYSA-N 9h-carbazole-1-thiol Chemical class N1C2=CC=CC=C2C2=C1C(S)=CC=C2 VBYSNJGYQWXUEW-UHFFFAOYSA-N 0.000 claims description 2
- KJTLQQUUPVSXIM-UHFFFAOYSA-N DL-mevalonic acid Natural products OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 claims description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical class C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 claims description 2
- OHRGSJZEJVGUTJ-UHFFFAOYSA-N O1CCOCC1.C=C Chemical class O1CCOCC1.C=C OHRGSJZEJVGUTJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000004141 diterpene derivatives Chemical class 0.000 claims description 2
- IZJVVXCHJIQVOL-UHFFFAOYSA-N nitro(phenyl)methanesulfonic acid Chemical compound OS(=O)(=O)C([N+]([O-])=O)C1=CC=CC=C1 IZJVVXCHJIQVOL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- GJWMYLFHBXEWNZ-UHFFFAOYSA-N tert-butyl (4-ethenylphenyl) carbonate Chemical compound CC(C)(C)OC(=O)OC1=CC=C(C=C)C=C1 GJWMYLFHBXEWNZ-UHFFFAOYSA-N 0.000 claims description 2
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- CXYVKXKWSPEULT-UHFFFAOYSA-N 1h-imidazol-1-ium-4-thiolate Chemical compound SC1=CNC=N1 CXYVKXKWSPEULT-UHFFFAOYSA-N 0.000 claims 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 claims 2
- QZQLBBPKPGSZBH-UHFFFAOYSA-N 1,2-dihydroindazole-3-thione Chemical compound C1=CC=C2C(S)=NNC2=C1 QZQLBBPKPGSZBH-UHFFFAOYSA-N 0.000 claims 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims 1
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 claims 1
- FVRSFOCASMKKEG-UHFFFAOYSA-N 3-azabicyclo[2.2.1]heptane-2-thione Chemical compound C1CC2C(=S)NC1C2 FVRSFOCASMKKEG-UHFFFAOYSA-N 0.000 claims 1
- CLEJZSNZYFJMKD-UHFFFAOYSA-N 3h-1,3-oxazole-2-thione Chemical class SC1=NC=CO1 CLEJZSNZYFJMKD-UHFFFAOYSA-N 0.000 claims 1
- CZCYNJKYXAWNLA-UHFFFAOYSA-N 4-azabicyclo[3.2.1]octane-3-thione Chemical compound N1C(=S)CC2CCC1C2 CZCYNJKYXAWNLA-UHFFFAOYSA-N 0.000 claims 1
- STUQITWXBMZUGY-UHFFFAOYSA-N 6-hydroxy-2-sulfanylidene-1h-pyrimidin-4-one Chemical compound OC1=CC(O)=NC(S)=N1 STUQITWXBMZUGY-UHFFFAOYSA-N 0.000 claims 1
- NKOPQOSBROLOFP-UHFFFAOYSA-N 6-methyl-3-sulfanylidene-2h-1,2,4-triazin-5-one Chemical compound CC1=NNC(=S)NC1=O NKOPQOSBROLOFP-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000012954 diazonium Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 125000005017 substituted alkenyl group Chemical group 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 125000004426 substituted alkynyl group Chemical group 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- 229920003986 novolac Polymers 0.000 description 22
- 235000012431 wafers Nutrition 0.000 description 22
- 238000009472 formulation Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 20
- 238000001459 lithography Methods 0.000 description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 18
- 229920002120 photoresistant polymer Polymers 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 11
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- RWHJHYXWZJKPAP-UHFFFAOYSA-L oxalate;tetrabutylazanium Chemical compound [O-]C(=O)C([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC RWHJHYXWZJKPAP-UHFFFAOYSA-L 0.000 description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 150000001454 anthracenes Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229960003742 phenol Drugs 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- XQKKKPPYAWEDHZ-UHFFFAOYSA-N (4-methylsulfonylphenyl)-diphenylphosphane Chemical compound C1=CC(S(=O)(=O)C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XQKKKPPYAWEDHZ-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- AHFWIRXJWWWORD-UHFFFAOYSA-N 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonic acid Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)O)CC1C2 AHFWIRXJWWWORD-UHFFFAOYSA-N 0.000 description 2
- OKOARRLHQZNSDP-RRKCRQDMSA-N 2-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-6-methyl-3-sulfanylidene-1,2,4-triazin-5-one Chemical compound S=C1NC(=O)C(C)=NN1[C@@H]1O[C@H](CO)[C@@H](O)C1 OKOARRLHQZNSDP-RRKCRQDMSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FBWSRAOCSJQZJA-UHFFFAOYSA-N 4-iminonaphthalen-1-one Chemical compound C1=CC=C2C(=N)C=CC(=O)C2=C1 FBWSRAOCSJQZJA-UHFFFAOYSA-N 0.000 description 2
- RYWBAUGTSAYDBR-UHFFFAOYSA-N 5-amino-6-phenyl-2-sulfanylidene-1h-pyrimidin-4-one Chemical compound N1C(=S)NC(=O)C(N)=C1C1=CC=CC=C1 RYWBAUGTSAYDBR-UHFFFAOYSA-N 0.000 description 2
- JYBWJPAOAQCXAX-UHFFFAOYSA-N 5-ethyl-2-sulfanylidene-1h-pyrimidin-4-one Chemical compound CCC1=CNC(=S)NC1=O JYBWJPAOAQCXAX-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- MJVVMJUZDATBOE-UHFFFAOYSA-N C1CCC(CC1)C2=CC=C(C=C2)P(C3=CC=CC=C3)C4=CC=CC=C4 Chemical compound C1CCC(CC1)C2=CC=C(C=C2)P(C3=CC=CC=C3)C4=CC=CC=C4 MJVVMJUZDATBOE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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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
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
本文揭示一種感光組合物,其包含雜環硫醇化合物或其互變異構形式;及其於基板上之使用方法,該基板可包括親硫基板。
Description
本專利申請案係屬於光阻劑成像領域。更具體言之,本專利申請案揭示並主張一種正向感光材料,其可(但不限於)在親硫或反射基板上使用。
在電子裝置製造領域中,必須使成像材料可在各種基板上工作。此項技術中已知,不同基板可帶來不同挑戰。例如,反射性高導電性基板可在可成像膜內施加光學條件,此會導致以下現象:諸如浮渣、底腳、駐波偽影(諸如「扇形褶皺」)等。另外,黏著力差可引起界面問題。黏著力差可導致底切或膜在顯影期間層離。另一方面,該膜可對某些類型的基板呈現強黏著力,此可導致底腳形成(foot formation)或浮渣。
已若干次試圖解決上述光學及界面現象。為提高黏著力,已描述基板處理。例如,在美國專利案第4,956,035號中,Sedlak揭示並主張「一種用於提高有機化合物對金屬表面之黏著力之組合物,其包含蝕刻溶液、有效量的四級銨陽離子界面活性劑及增溶量的第二界面活性劑或溶劑」。據稱,該組合物可用於提高光阻劑對銅包電路板之黏著力,及提高焊接遮罩對印刷電路之黏著力。然而,雖然該處理可對諸如銅包電路板之基板有效,但其對半導體基板之效用可能有問題,因為半導體基板之精確性要求高得多,尤其係在可能涉及到蝕刻化學
時。
作為另一實例,在美國專利申請案第2011/0214994號中,Utsumi等人揭示一種「與本發明有關的電鍍預處理劑,其特徵在於其包括一種水溶液,其含有:(A)至少一種抗吸附劑,其係選自三唑化合物、吡唑化合物、咪唑化合物、陽離子界面活性劑及兩性界面活性劑;及(B)作為基本成分之氯離子」。該預處理劑亦可包含非離子界面活性劑及至少一種選自水溶性醚、胺、醇、二醇醚、酮、酯及脂肪酸、酸及氧化劑之溶劑。雖然該調配物包含可起到抗吸附功能之成分,但其用途不可與半導體加工相容,因為其會增加額外步驟,並需要獨立的進料流。
因此,仍需要一種具有適合在反射及親硫基板上成像之組成之正向感光材料,其產生低缺陷、高解析度影像。顯而易知,本文所揭示之標的物可滿足上述需求。
如本文中所使用,除非上下文另有指示或要求,否則連接詞「或」無意為排他性。例如,片語「或,另外」意欲為排他性。關於另一實例,當描述某一具體位置上之化學取代時,「或」可係排他性。
如本文中所使用,術語「親硫元素(chalcophile)」為對硫族元素(硫、硒及碲)具有親和力之元素。除硫族元素本身以外,此等元素可包括銅、鋅、鎵、鍺、砷、銀、鎘、鑭、錫、銻、金、汞、鉈、鉛及鉍。無意限制地,此等元素可與該等硫族元素中之一或多者形成鍵結,其特徵主要為共價。親硫基板包含上述親硫元素中之一或多者。
如本文中所使用,應瞭解,聚合物中之重複單元可由其相應單
體提及。例如,丙烯酸酯單體(1)相當於其聚合物重複單元(2)。
如本文中所使用,名稱「(甲基)丙烯酸酯重複單元」可指代丙烯酸酯重複單元或甲基丙烯酸酯重複單元。因此,「丙烯酸」及「甲基丙烯酸」係統稱為「(甲基)丙烯酸」,「丙烯酸衍生物」及「甲基丙烯酸衍生物」係統稱為「(甲基)丙烯酸衍生物」,且「丙烯酸酯」及「甲基丙烯酸酯」係統稱為「(甲基)丙烯酸酯」。
本文揭示一種正向感光組合物,其包含:至少一種光酸產生劑;至少一種聚合物,其包含一或多種(甲基)丙烯酸酯重複單元,且另外包含一或多種具有至少一個酸可裂解基團之重複單元;至少一種雜環硫醇化合物,其包含選自下列通式之環結構:
或其互變異構體,其中該環結構為具有4-8個原子之單環結構或具有5-20個原子之多環結構,且其中該單環結構或該多環結構包括芳環、非芳環或雜芳環,且其中X係藉由單鍵偶聯於該環中且係選自CR1R2、O、S、Se、Te或NR3,或者X係藉由雙鍵偶聯於該環中且係選自CR1或N,且Y係選自CR1或N,且其中R1、R2及R3係相同或不同,且表示H、具有1-8個碳原子之經取代或未經取代的烷基、具有1-8個碳原子之經取代或未經取代的烯基、具有1-8個碳原子之經取代或未經取代的炔基,或具有1-20個碳原子之經取代或未經取代的芳族或雜芳族基團。
應瞭解,雜環硫醇3及4表示可能存在的若干種互變異構形式中之一者。例如(但無意限制),3可作為其質子移變互變異構體出現,無論呈平衡或非平衡形式。
例如(但無意限制),4可作為其質子移變互變異構體出現,無論呈平衡或非平衡形式。
此外,與表面(諸如親硫表面)或溶液中之其他組分之相互作用可影響環結構3及4及其各自互變異構體之相對濃度。因此,應瞭解,質子移變互變異構體(包括環狀互變異構體)及價鍵互變異構體可藉由命名其互變異構形式中之任一者互換地被提及。
另外,本文揭示一種形成正凸紋影像之方法,其包括:藉由將本文所述之正向感光組合物施加至基板上形成感光層;使該感光層成像曝露至光化輻射,以形成潛像;及使該潛像在顯影劑中顯影。視情況地,該成像曝露的感光層可經熱處理,端看去保護化學過程而定。
本文所揭示的感光組合物中之雜環硫醇可包括(但不限於)經取代或未經取代的三唑硫醇、經取代或未經取代的咪唑硫醇、經取代或未經取代的三嗪硫醇、經取代或未經取代的巰基嘧啶、經取代或未經取代的噻二唑-硫醇、經取代或未經取代的吲唑硫醇、其互變異構體或其組合。取代基可包括(但不限於)飽和或不飽和烴基、經取代或未經取代的芳族環、脂族醇、芳族醇或雜芳族醇、胺、醯胺、醯亞胺、羧酸、酯、醚、鹵化物等。此等取代基可與雜環硫醇配合使用,以提升
溶解度、調節與基板之相互作用、增強曝光或作為阻光染料。
此等雜環硫醇可包括(但不限於)以下呈未經取代或經取代形式的化合物:
硫尿嘧啶衍生物(諸如2-硫尿嘧啶)為其他實例。此等衍生物包括(但不限於)5-甲基-2-硫尿嘧啶、5,6-二甲基-2-硫尿嘧啶、6-乙基-5-甲基-2-硫尿嘧啶、6-甲基-5-正丙基-2-硫尿嘧啶、5-乙基-2-硫尿嘧啶、5-正丙基-2-硫尿嘧啶、5-正丁基-2-硫尿嘧啶、5-正己基-2-硫尿嘧啶、5-正丁基-6-乙基-2-硫尿嘧啶、5-羥基-2-硫尿嘧啶、5,6-二羥基-2-硫尿嘧啶、5-羥基-6-正丙基-2-硫尿嘧啶、5-甲氧基-2-硫尿嘧啶、5-正丁氧基-2-硫尿嘧啶、5-甲氧基-6-正丙基-2-硫尿嘧啶、5-溴-2-硫尿嘧啶、5-氯-2-硫尿嘧啶、5-氟-2-硫尿嘧啶、5-胺基-2-硫尿嘧啶、5-胺基-6-甲基-2-硫尿嘧啶、5-胺基-6-苯基-2-硫尿嘧啶、5,6-二胺基-2-硫
尿嘧啶、5-烯丙基-2-硫尿嘧啶、5-烯丙基-3-乙基-2-硫尿嘧啶、5-烯丙基-6-苯基-2-硫尿嘧啶、5-苄基-2-硫尿嘧啶、5-苄基-6-甲基-2-硫尿嘧啶、5-乙醯胺基-2-硫尿嘧啶、6-甲基-5-硝基-2-硫尿嘧啶、6-胺基-2-硫尿嘧啶、6-胺基-5-甲基-2-硫尿嘧啶、6-胺基-5-正丙基-2-硫尿嘧啶、6-溴-2-硫尿嘧啶、6-氯-2-硫尿嘧啶、6-氟-2-硫尿嘧啶、6-溴-5-甲基-2-硫尿嘧啶、6-羥基-2-硫尿嘧啶、6-乙醯胺基-2-硫尿嘧啶、6-正辛基-2-硫尿嘧啶、6-十二烷基-2-硫尿嘧啶、6-十四烷基-2-硫尿嘧啶、6-十六烷基-2-硫尿嘧啶、6-(2-羥乙基)-2-硫尿嘧啶、6-(3-異丙基辛基)-5-甲基-2-硫尿嘧啶、6-(間-硝基苯基)-2-硫尿嘧啶、6-(間-硝基苯基)-5-正丙基-2-硫尿嘧啶、6-α-萘基-2-硫尿嘧啶、6-α-萘基-5-第三丁基-2-硫尿嘧啶、6-(對-氯苯基)-2-硫尿嘧啶、6-(對-氯苯基)-2-乙基-2-硫尿嘧啶、5-乙基-6-二十烷基-2-硫尿嘧啶、6-乙醯胺基-5-乙基-2-硫尿嘧啶、6-二十烷基-5-烯丙基-2-硫尿嘧啶、5-胺基-6-苯基-2-硫尿嘧啶、5-胺基-6-(對-氯苯基)-2-硫尿嘧啶、5-甲氧基-6-苯基-2-硫尿嘧啶、5-乙基-6-(3,3-二甲基辛基)-2-硫尿嘧啶、6-(2-溴乙基)-2-硫尿嘧啶。
本文所揭示的感光組合物可包括各種光酸產生劑,諸如鎓鹽、二羧醯亞胺基磺酸酯、肟磺酸酯、重氮(磺醯基甲基)化合物、二磺醯基亞甲基肼化合物、磺酸硝基苄酯、聯咪唑化合物、重氮甲烷衍生物、乙二肟衍生物、β-酮碸衍生物、二碸衍生物、磺酸酯衍生物、亞胺基磺酸酯衍生物、鹵代三嗪化合物、重氮萘醌磺酸酯或其組合。
鎓鹽光酸產生劑可包括(但不限於)烷基磺酸根陰離子、經取代及未經取代的芳基磺酸根陰離子、氟代烷基磺酸根陰離子、氟代芳烷基磺酸根陰離子、氟化芳烷基磺酸根陰離子、六氟磷酸根陰離子、六氟砷酸根陰離子、六氟銻酸根陰離子、四氟硼酸根陰離子、其等效物或其組合。
具體言之(但無意限制),適宜的光酸產生劑可包括三氟甲磺酸三苯基鋶、九氟正丁磺酸三苯基鋶、全氟正辛磺酸三苯基鋶及2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸三苯基鋶、三氟甲磺酸4-環己基苯基二苯基鋶、九氟正丁磺酸4-環己基苯基二苯基鋶、全氟正辛磺酸4-環己基苯基二苯基鋶、2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸4-環己基苯基二苯基鋶、三氟甲磺酸4-甲磺醯基苯基二苯基鋶、九氟正丁磺酸4-甲磺醯基苯基二苯基鋶、全氟正辛磺酸4-甲磺醯基苯基二苯基鋶及2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸4-甲磺醯基苯基二苯基鋶、三氟甲磺酸二苯基錪、九氟正丁磺酸二苯基錪、全氟正辛磺酸二苯基錪、2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸二苯基錪、三氟甲磺酸雙(4-第三丁基苯基)錪、九氟正丁磺酸雙(4-第三丁基苯基)錪、全氟正辛磺酸雙(4-第三丁基苯基)錪、2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸雙(4-第三丁基苯基)錪、三氟甲磺酸1-(4-正丁氧基-萘-1-基)四氫噻吩鎓、九氟正丁磺酸1-(4-正丁氧基-萘-1-基)四氫噻吩鎓、全氟正辛磺酸1-(4-正丁氧基-萘-1-基)四氫噻吩鎓、2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸1-(4-正丁氧基-萘-1-基)四氫噻吩鎓、三氟甲磺酸1-(6-正丁氧基-萘-2-基)四氫噻吩鎓、九氟正丁磺酸1-(6-正丁氧基-萘-2-基)四氫噻吩鎓、全氟正辛磺酸1-(6-正丁氧基-萘-2-基)四氫噻吩鎓、2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸1-(6-正丁氧基-萘-2-基)四氫噻吩鎓、三氟甲磺酸1-(3,5-二甲基-4-羥基苯基)四氫噻吩鎓、九氟正丁磺酸1-(3,5-二甲基-4-羥基苯基)四氫噻吩鎓、全氟正辛磺酸1-(3,5-二甲基-4-羥基苯基)四氫噻吩鎓、2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸1-(3,5-二甲基-4-羥基苯基)四氫噻吩鎓、N-(三氟甲磺醯基氧基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(九氟正丁磺醯基氧基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(全氟正辛磺醯基氧基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-[2-(雙環[2.2.1]庚-2-基)-1,1,2,2-
四氟乙磺醯基氧基]雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基三氟甲磺酸酯(萘二甲醯亞胺基三氟甲磺酸酯)、N-[2-(四環[4.4.0.12,5.17,10]十二烷-3-基)-1,1-二氟乙磺醯基氧基]雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、1,3-二側氧基異吲哚啉-2-基三氟甲磺酸酯、1,3-二側氧基異吲哚啉-2-基九氟正丁磺酸酯、1,3-二側氧基異吲哚啉-2-基全氟正辛磺酸酯、1,3-二側氧基異吲哚啉-2-基2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸酯、1,3-二側氧基異吲哚啉-2-基N-[2-(四環[4.4.0.12,5.17,10]十二烷-3-基)-1,1-二氟乙磺酸酯、1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基三氟甲磺酸酯、1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基九氟正丁磺酸酯、1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基全氟正辛磺酸酯、1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙磺酸酯或1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基N-[2-(四環[4.4.0.12,5.17,10]十二烷-3-基)-1,1-二氟乙磺酸酯、(E)-2-(4-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(甲氧基苯基)-4,6-雙-(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、其等效物或其組合。適宜的光酸產生劑亦可包括含上文未顯示的陰離子及陽離子之組合之鎓鹽。
本文所揭示的感光組合物亦可包含可擴展有效波長及/或能量範圍之光敏劑。此等光敏劑可為(但不限於)經取代及未經取代的蒽、經取代及未經取代的吩噻嗪、經取代及未經取代的苝、經取代及未經取代的芘及及芳族羰基化合物(諸如二苯甲酮及噻噸酮)、茀、咔唑、吲哚、苯并咔唑、吖啶酮、氯丙嗪、其等效物或以上任何化合物之組合。
根據本發明,該新穎組合物包含一或多種聚合物。該等聚合物
可包括一或多種重複單元。特定言之,聚合物可包括選自苯乙烯重複單元、(甲基)丙烯酸酯重複單元或其組合之重複單元。該組合物可另外包含兩種或更多種聚合物(諸如酚醛清漆聚合物及丙烯酸酯及/或苯乙烯共聚物)之組合。本發明範圍內之聚合物係揭示於2012年6月15日申請之美國申請案第13/524,790號中,且該案之全文係併入本文中。
更特定言之,苯乙烯重複單元可具有以下結構:
其中R4係選自H、Cl或CH3,且R5及R6可係相同或不同,且係選自H、OH、OCOOR7或OCOCOOR7,且R7為酸可裂解基團。本發明聚合物可僅包含(甲基)丙烯酸酯單元或(甲基)丙烯酸酯及苯乙烯單元之混合物。酸不穩定基團可存在於該聚合物中。該聚合物可包含酸可裂解基團,該基團可透過羧酸基團酯化為(甲基)丙烯酸酯重複單元,或酯化為碳酸酯或草酸酯基團;該碳酸酯或草酸酯基團進而酯化成酚或醇。例如,此項技術中已知的單體重複單元為碳酸第三丁基4-乙烯基苯酯,其中碳酸第三丁基酯係酯化為4-羥基苯乙烯。酸可裂解基團可包括(但不限於)第三丁基、四氫哌喃-2-基、四氫呋喃-2-基、4-甲氧基四氫哌喃-4-基、1-乙氧基乙基、1-丁氧基-乙基、1-丙氧基乙基、3-側氧基環己基、2-甲基-2-金剛烷基、2-乙基-2-金剛烷基、8-甲基-8-三環[5.2.1.0 2,6]癸基、1,2,7,7-四甲基-2-降莰基、2-乙醯氧基薄荷基、2-羥甲基、1-甲基-1-環己基乙基、4-甲基-2-側氧基四氫-2H-哌喃-4-
基、2,3-二甲基丁-2-基、2,3,3-三甲基丁-2-基、1-甲基環戊基、1-乙基環戊基、1-甲基環己基、1-乙基環己基、1,2,3,3-四甲基雙環[2.2.1]庚-2-基、2-乙基-1,3,3-三甲基雙環[2.2.1]庚-2-基、2,6,6-三甲基雙環[3.1.1]庚-2-基、2,3-二甲基戊-3-基或3-乙基-2-甲基戊-3-基。據稱,具有酸可裂解基團之單體重複單元係受保護。聚合物可完全經保護、部份經保護、部份去保護或完全去保護。例如,當存在光生酸時,去保護可在(例如)感光組合物曝露期間或之後出現。
除具有酸可裂解基團之單體重複單元以外,聚合物可另外包含可賦予抗蝕刻性,調節呈保護、部份保護、部份去保護或完全去保護形式之聚合物之溶解特性,調節光敏性,調節黏著力,提供結合型光酸產生劑或賦予其他有用特性之單體重複單元。單體重複單元可包括(但不限於)若干化學官能基,諸如內酯、酸酐、醇、羧酸、經取代及未經取代的苄基、醚、脂環族酯、酯醇、酯醚、脂族酯、芳族酯等。
單體可包括(但不限於)(甲基)丙烯酸、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥苄酯、甲基丙烯酸2-異莰酯、(甲基)丙烯酸3-異莰酯、(甲基)丙烯酸1-金剛烷酯、苯乙烯、4-羥基苯乙烯、碳酸第三丁基4-乙烯基苯酯、甲羥戊酸內酯甲基丙烯酸酯、2-側氧基四氫呋喃-3-基(甲基)丙烯酸酯、2-側氧基四氫-2H-哌喃-3-基(甲基)丙烯酸酯或2-側氧基氧雜環庚-3-基(甲基)丙烯酸酯。
丙烯酸酯聚合物可包括下式結構:
其中R8-R12獨立地為-H、F或-CH3,A為直鏈或分支鏈C1-C10伸烷基,B為C1-C12烷基或脂環基,D為鍵聯基團,其可為化學鍵、羧酸基團(其中羰基碳係連接至聚合物主鏈)或-COOCH2-基團(其中羰基碳係連接至聚合物主鏈),Ar為經取代或未經取代的芳族基團或雜芳族基團,E為直鏈或分支鏈C2-C10伸烷基,G為酸可裂解基團,v為0-10莫耳%,w為0莫耳%-20莫耳%,x為14莫耳%-80莫耳%,y為0莫耳%-40莫耳%,且z為20莫耳%-50莫耳%。經取代的Ar可包括經羥基取代的芳族基團。Ar可為苯基或羥基苯基。上述通式無意顯示聚合物之組成部份之確切定位,所以該等部份可隨機地一起存在,同樣地,兩個或更多個相同組成部份可以並列方式存在於該聚合物中。
根據上述實施例,就(5)而言,v之示例性莫耳百分比範圍可為0-10%。v之另一示例性莫耳百分比範圍可為3-8%。v之又一示例性莫耳百分比範圍可為4-6%。w之示例性莫耳百分比範圍可為0-20%。w之另一示例性莫耳百分比範圍可為7-15%。w之又一示例性莫耳百分比範圍可為9-12%。x之示例性莫耳百分比範圍可為14-80%。x之另一示例性莫耳百分比範圍可為15-30%。x之又一示例性莫耳百分比範圍可為16-20%。y之示例性莫耳百分比範圍可為0-40%。y之另一示例性莫耳百分比範圍可為25-35%。y之又一示例性莫耳百分比範圍可為28-33%。z之示例性莫耳百分比範圍可為20-50%。z之另一示例性莫耳百分比範圍可為25-40%。z之又一示例性莫耳百分比範圍可為29-36%。莫耳百分比並非獨立,而是其等必須總計為100%。
根據上述實施例,可使用所指示單體之一或多次進料來合成(5)。其中至少一些單體可在聚合反應開始時全部或部份引入。另外,可在反應期間以選定進料速率完成單體進給,以適應不同的單體共反應性,或控制其他聚合物性質(諸如分子量或溶解度)。可藉由自由基引發劑、陽離子聚合引發劑、陰離子聚合引發劑或螯合觸媒引發
聚合反應。
用於該新穎組合物中之酚醛清漆聚合物包括具有橋聯及酚類化合物之重複單元。適宜的酚類化合物包括(但不限於)苯酚、甲酚、經取代及未經取代的間苯二酚、二甲苯酚、經取代及未經取代的苯三酚及其組合。酚醛清漆聚合物通常係使用酸性觸媒藉由酚類化合物與醛類(諸如甲醛、乙醛或經取代或未經取代的苯甲醛)之縮聚作用或酚類化合物與經取代或未經取代的羥甲基化合物之縮合產物製得。上述橋聯可包括亞甲基或次甲基。酚醛清漆聚合物亦可作為酮類(諸如丙酮、甲基乙基酮、苯乙酮等)之縮合產物製得。觸媒可包括路易斯(Lewis)酸、貝氏(Brnstead)酸、二價金屬陽離子及三價金屬陽離子等。例如,可使用(但不限於)氯化鋁、氯化鈣、氯化錳、草酸、鹽酸、硫酸、甲磺酸、三氟甲磺酸或包含任何上述物質之組合。
適宜酚醛清漆聚合物之實例包括彼等藉由酚類化合物(諸如苯酚、鄰甲酚、間甲酚、對甲酚、2,5-二甲苯酚等)與醛類化合物(諸如甲醛)在酸或多價金屬離子觸媒之存在下進行縮合反應所得到者。鹼溶性酚醛清漆聚合物之示例性重量平均分子量可於1,000至30,000道耳頓之範圍內。另一示例性重量平均分子量可為1,000至20,000道耳頓。又一示例性重量平均分子量可為1,500至10,000道耳頓。酚醛清漆聚合物在2.38%氫氧化四甲基銨水溶液中之示例性體溶解速率為10Å/sec(埃單位/秒)至15,000Å/sec。其他示例性體溶解速率為100Å/sec至10,000Å/sec。其他示例性體溶解速率為200Å/sec至5,000Å/sec。可自單一酚醛清漆聚合物或酚醛清漆聚合物之摻合物(各包含間甲酚重複單元)獲得1,000Å/sec之又一示例性體溶解速率。
就甲酚莫耳百分比而言,示例性甲酚酚醛清漆聚合物可包含0%-60%對甲酚、0%-20%鄰甲酚及0%-80%間甲酚。其他示例性甲酚酚醛清漆聚合物可包含0%-50%對甲酚、0%-20%鄰甲酚及50%-100%間甲
酚。酚醛清漆聚合物中之重複單元係由該聚合物之組成決定,因此,例如,對甲酚可藉由與醛聚合引入或藉由二羥甲基-對甲酚引入。此外,甲酚酚醛清漆聚合物可含有其他酚類化合物,諸如苯酚、二甲苯酚、間苯二酚、苯三酚等。另外,酚醛清漆聚合物可為分支鏈或直鏈,且可經摻合以得到選定的重複單元莫耳百分比或溶解速率。可藉由以下步驟測量體溶解速率:(1)自溶液在矽晶圓上旋塗1-3μm(微米)酚醛清漆樹脂膜,並在接觸熱板上於110℃下軟烤120秒;(2)使用光學方法(諸如干涉術或橢圓測量術)或機械表面輪廓儀測量膜厚度;(3)將該經塗覆的晶圓浸沒於氫氧化四甲基銨(TMAH)顯影劑溶液中,並以肉眼方式或藉助光學干涉法(例如,溶解速率監視器)檢測完全溶解該酚醛清漆膜之時間(tc)。將膜厚度除以tc以計算出體溶解速率。
具有一般組成(5)之聚合物可包含(甲基)丙烯酸重複單元及經取代或未經取代的苯乙烯單元。因此,R8-R12可獨立地為-H或-CH3。
在上文之(5)中,A之示例性基團可為(但不限於)亞甲基、甲基亞甲基、伸乙基、1,2-伸丙基、2,1-伸丙基等。B之示例性基團可為(但不限於)甲基、乙基、丙基、異丙基、丁基、異丁基等。E之示例性基團可為(但不限於)亞甲基、甲基亞甲基、伸乙基、1,2-伸丙基、2,1-伸丙基等。D之示例性基團可為-COOCH2-(其中羰基碳係連接至聚合物主鏈)、化學鍵或-COO-基團(其中羰基碳係連接至聚合物主鏈)。-Ar之示例性基團可為(但不限於)苯基、2-甲基苯基、3-甲基苯基或4-甲基苯基、2-羥基苯基、3-羥基苯基或4-羥基苯基、1-萘基、2-萘基或3-萘基等。在上文(5)中,G之示例性酸可裂解基團可為(但不限於)第三丁基、四氫哌喃-2-基、四氫呋喃-2-基、4-甲氧基四氫哌喃-4-基、1-乙氧基乙基、1-丁氧基-乙基、1-丙氧基乙基、3-側氧基環己基、2-甲基-2-金剛烷基、2-乙基-2-金剛烷基、8-甲基-8-三環[5.2.1.0 2,6]癸基、1,2,7,7-四甲基-2-降莰基、2-乙醯氧基薄荷基、2-羥甲基、1-甲
基-1-環己基乙基、4-甲基-2-側氧基四氫-2H-哌喃-4-基、2,3-二甲基丁-2-基、2,3,3-三甲基丁-2-基、1-甲基環戊基、1-乙基環戊基、1-甲基環己基、1-乙基環己基、1,2,3,3-四甲基雙環[2.2.1]庚-2-基、2-乙基-1,3,3-三甲基雙環[2.2.1]庚-2-基、2,6,6-三甲基雙環[3.1.1]庚-2-基、2,3-二甲基戊-3-基或3-乙基-2-甲基戊-3-基。
結構(5)之示例性重量平均分子量可介於(但不限於)800道耳頓至30,000道耳頓之範圍內。結構(5)之其他示例性重量平均分子量可介於(但不限於)1,500道耳頓至20,000道耳頓之範圍內。結構(5)之其他示例性重量平均分子量可介於(但不限於)2,500道耳頓至20,000道耳頓之範圍內。
在一實施例中,本文所揭示並主張的調配物包含酚醛清漆聚合物及(甲基)丙烯酸酯聚合物(諸如具有通式(5))兩者。作為一實例但不構成限制地,酚醛清漆聚合物可佔總聚合物負載量之20%至80%(重量/重量)。作為另一實例但不構成限制地,酚醛清漆聚合物可佔總聚合物負載量之30%至75%(重量/重量)。作為又一實例但不構成限制地,酚醛清漆聚合物可佔總聚合物負載量之40%至65%(重量/重量)。該新穎組合物可具有30-65重量%之總固體含量,且可用於形成5-200微米之塗層。
本文所揭示的感光組合物可溶解於有機溶劑中。適宜有機溶劑之實例包括(但不限於)乙酸丁酯、乙酸戊酯、乙酸環己酯、乙酸3-甲氧基丁酯、甲基乙基酮、甲基戊基酮、環己酮、環戊酮、乙基-3-乙氧基丙酸酯、甲基-3-乙氧基丙酸酯、甲基-3-甲氧基丙酸酯、乙醯乙酸甲酯、乙醯乙酸乙酯、二丙酮醇、特戊酸甲酯、特戊酸乙酯、丙二醇單甲醚、丙二醇單乙醚、丙二醇單甲醚丙酸酯、丙二醇單乙醚丙酸酯、乙二醇單甲醚、乙二醇單乙醚、二乙二醇單甲醚、二乙二醇單乙醚、3-甲基-3-甲氧基丁醇、N-甲基吡咯啶酮、二甲基亞碸、γ-丁內
酯、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丙醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、環丁碸、丙二醇二甲醚、二丙二醇二甲醚、乙二醇二甲醚或二乙二醇二甲醚、γ-丁內酯。此等溶劑可單獨使用或以兩者或更多者之混合物使用。
與本文所揭示並主張的組合物相容且可根據需要添加至該組合物中之其他可選添加劑包括用於改善抗蝕劑層性質之輔助樹脂、增塑劑、表面整平劑及穩定劑、用於增加藉由顯影所形成的圖案化抗蝕劑層之可見度之著色劑、阻光染料、四烷基銨鹽(諸如草酸四丁基銨)等。
表面整平劑可包括界面活性劑。界面活性劑並無特定限制,且其實例包括聚氧伸乙基烷基醚,諸如聚氧伸乙基十二烷基醚、聚氧伸乙基十八烷基醚、聚氧伸乙基十六烷基醚及聚氧伸乙基油精醚;聚氧伸乙基烷芳基醚,諸如聚氧伸乙基辛基酚醚及聚氧伸乙基壬基酚醚;聚氧乙烯聚氧丙烯嵌段共聚物;山梨糖醇酐脂肪酸酯,諸如山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯及山梨糖醇酐單硬脂酸酯;聚氧乙烯山梨糖醇酐脂肪酸酯之非離子界面活性劑,諸如聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐單棕櫚酸酯、聚氧乙烯山梨糖醇酐單硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯及聚氧乙烯山梨糖醇酐三硬脂酸酯;氟化界面活性劑,諸如F-Top EF301、EF303及EF352(Jemco Inc.製造)、Megafac F171、F172、F173、R08、R30、R90及R94(Dainippon Ink & Chemicals,Inc.製造)、Florad FC-430、FC-431、FC-4430及FC-4432(Sumitomo 3M Ltd.製造)、Asahi Guard AG710、Surflon S-381、S-382、S-386、SC101、SC102、SC103、SC104、SC105、SC106、Surfinol E1004、KH-10、KH-20、KH-30及KH-40(Asahi Glass Co.,Ltd.製造);有機矽氧烷聚合物,諸如KP-341、X-70-092及X-70-093(Shin-Etsu Chemical Co.,Ltd.製造);及丙
烯酸或甲基丙烯酸聚合物,諸如Polyflow No.75及No.95(Kyoeisha Yushikagaku Kogyo K.K.製造)。
藉由使用本文所揭示的感光組合物製備圖案化光阻劑層之步驟可係習知。例如,藉由使用適宜塗覆機(諸如旋塗機),以呈溶液形式的感光組合物均勻塗覆基板(諸如半導體矽晶圓)或具有前述金屬塗層之基板,隨後在對流烘箱中或熱板上烘烤以形成光阻劑層,然後在曝光裝置上透過具有所需圖案之光罩或反射罩圖案式曝露至光化輻射(諸如自低壓、高壓及超高壓汞燈、弧光燈、氙氣燈、ArF、KrF及F2準分子雷射器、電子束、x-射線、遠UV源等發射之深紫外光、近紫外光或可見光),並根據所需圖案進行電子束掃描,以在抗蝕劑層中建立該圖案的潛像。該光化輻射可介於250nm至436nm之範圍內。此後,可視情況於對流烘箱中或熱板上烘烤該光阻劑層中之潛像,使用鹼性顯影劑溶液(諸如氫氧化四(C1-C4烷基)銨、氫氧化膽鹼、氫氧化鋰、氫氧化鈉或氫氧化鉀之水溶液,例如,濃度為1至10%(重量/重量)之氫氧化四甲基銨)顯影,以得到對光罩圖案具有良好保真度之圖案化光阻劑層。
厚度可介於20nm至100微米之範圍內。為達到該等厚度,可採用不同旋轉速度與總固體濃度之組合。端看基板之尺寸,可使用500rpm至10,000rpm之旋轉速度。濃度可以總固體在該感光組合物中之重量百分比表示。不構成限制地,示例性總固體重量百分比為0.05%至65%。不構成限制地,另一示例性總固體重量百分比為20%至60%。不構成限制地,另一示例性總固體重量百分比為40%至55%。
該感光組合物包含一或多種聚合物、一或多種光酸產生劑、一或多種溶劑及一或多種上文所示之雜環硫醇添加劑。如上所述,該感光組合物可另外包含溶劑。例如,以總固體之重量百分比計,聚合物可以總固體之30%至80%存在,光酸產生劑可以總固體之20%至70%
存在,雜環硫醇添加劑可以總固體之0.01%至1%存在。或者,聚合物可以總固體之40%至60%存在,光酸產生劑可以總固體之30%至60%存在,雜環硫醇添加劑可以總固體之0.01%至1%存在。
出於所有目的,上文所引用的各文獻之全文係以引用的方式併入本文中。以下具體實例將提供製造及使用本發明組合物之方法之詳細說明。然而,該等實例無意以任何方式限制或約束本發明範圍,且不應被視為提供為實踐本發明所必須唯一使用的條件、參數或數值。
單體重複單元百分比係以莫耳百分比表示。在該實例中,將6.46g甲基丙烯酸、35.24g甲基丙烯酸苄酯、43.25g甲基丙烯酸羥丙酯、54.47g丙烯酸第三丁酯混合於209.1g PGME溶劑中。在2.3g AIBN存在下,在90℃下,於氮氣下進行聚合反應達18小時。冷卻至室溫後,使反應混合物在DI水中沈澱。清洗聚合物固體,並在45℃真空下加以乾燥,產量為137.1g(98%產率),且重量平均分子量為15,072道耳頓。
單體重複單元百分比係以莫耳百分比表示。在該實例中,將4.32g丙烯酸、24.67g甲基丙烯酸苄酯、34.60g甲基丙烯酸羥丙酯、46.14g丙烯酸第三丁酯混合於207.1g PGME溶劑中。在1.84g AIBN存在下,在90℃下,於氮氣下進行聚合反應達18小時。冷卻至室溫後,使反應混合物在DI水中沈澱。清洗聚合物固體,並在45℃真空下加以乾燥,產量為107.3g(98%產率),且重量平均分子量為16,138道耳頓。
將2.7g丙烯酸、6.5g丙烯酸甲氧基乙酯、15.4g甲基丙烯酸苄酯、21.6g甲基丙烯酸羥丙酯、24.9g甲基丙烯酸第三丁酯混合於135.2g PGME溶劑中。在1.6g AIBN存在下,在90℃下,於氮氣下進行聚合反應達18小時。冷卻至室溫後,使反應混合物在DI水中沈澱。清洗白色聚合物固體,並在45℃真空下加以乾燥,產量為70.3g(99%產率),且重量平均分子量為17,153道耳頓。
單體重複單元百分比係以莫耳百分比表示。在該實例中,將7.16g丙烯酸甲氧基乙酯、15.86g甲基丙烯酸苄酯、25.23g甲基丙烯酸羥
丙酯、32.78g甲基丙烯酸1-乙基環戊酯混合於152.6g PGME溶劑中。在1.2g AIBN存在下,在90℃下,於氮氣下進行聚合反應達18小時。冷卻至室溫後,使反應混合物在DI水中沈澱。清洗聚合物固體,並在45℃真空下加以乾燥,產量為79.3g(98%產率),且重量平均分子量為17,888道耳頓。
酚醛清漆聚合物:針對以下調配物實例,使用三種酚醛清漆聚合物。Novolak-1係由間甲酚及甲醛合成,且在2.38% TMAH顯影劑水溶液中具有700Å/sec之體溶解速率。Novolak-2係由間甲酚及甲醛合成,且在2.38% TMAH顯影劑水溶液中具有1,600Å/sec之體溶解速率。Novolak-3為Novolak-1與Novolak-2之1/1摻合物,其在2.38% TMAH顯影劑水溶液中之體溶解速率為1,000Å/sec。
聚合物(GIJ):可自DuPont購得,其係60%羥基苯乙烯、20%苯乙烯及20%丙烯酸第三丁酯之三元聚合物。
PAG:1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基三氟甲磺酸酯。其亦稱為萘二甲醯亞胺基三氟甲磺酸酯。
Lutonal M40:增塑劑,可自BASF購得。
Polyglykol B01/40:增塑劑,可自Clariant Corporation購得。
塗覆:在8"直徑Si及Cu晶圓上測試所有調配物。對Si晶圓進行脫水烘烤,並用六甲基二矽氮烷(HMDS)進行蒸氣底塗。Cu晶圓為塗覆有5,000埃二氧化矽、250埃氮化鉭及3,500埃Cu之矽晶圓(PVD沉積)。
藉由在呈接觸模式的標準晶圓追蹤熱板(standard wafer track hot plate)上旋塗光阻劑樣品並在130℃下施加軟烤300秒來製備光阻劑塗層。調節旋轉速度,以得到40微米厚光阻劑膜。所有薄膜厚度測量均係在Si晶圓上使用光學測量進行。
成像:於SUSS MA200 CC光罩對準機上使該等晶圓曝光。在
100℃下後曝光烘烤該光阻劑100秒,並在23℃下於AZ 300 MIF(0.26N氫氧化四甲基銨(=TMAH)水溶液)中進行浸置式顯影240秒。使用Hitachi S4700或AMRAY 4200L電子顯微鏡檢查顯影光阻劑影像。
調配物實例1:將10.0g合成實例1之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 1,3,5-三嗪-2,4,6-三硫醇溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有整齊垂直壁且不具有底腳之良好輪廓。
調配物實例2:將10.0g合成實例2之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 1,3,5-三嗪-2,4,6-三硫醇溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有整齊垂直壁且不具有底腳之良好輪廓。
調配物實例3:將10.0g合成實例3之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 1,3,5-三嗪-2,4,6-三硫醇溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有整齊垂直壁且不具有底腳之良好輪廓。
調配物實例4:將10.0g合成實例4之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 1,3,5-三嗪-2,4,6-三硫醇溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有整齊垂直壁且不具有底腳之良好輪廓。
調配物實例5:將10.0g合成實例3之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 1,3,4-噻二唑-2,5-二硫醇
溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有整齊垂直壁且不具有底腳之良好輪廓。
調配物實例6:將10.0g合成實例4之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 1H-1,2,4-三唑-3-硫醇溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有整齊垂直壁且不具有底腳之良好輪廓。
調配物實例7:將10.0g合成實例3之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 6-甲基-2-硫尿嘧啶溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有略微傾斜壁,在基板上具有少量底腳且無浮渣之輪廓。該等輪廓係可接受。
調配物實例8:將10.0g合成實例3之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 6-氮雜-2-硫胸腺嘧啶溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行如上所述之微影測試。微影結果顯示具有略微凹陷壁且無底腳及浮渣之輪廓。該等輪廓係可接受。
調配物實例9:將10.0g合成實例3之聚合物、15.0g Novolak-3、0.18g PAG、0.043g草酸四丁基銨及0.025g 2-硫巴比妥酸溶解於27.4g PGMEA溶劑中,以製得溶液。將該溶液塗覆於銅晶圓上,以進行微影測試。微影結果顯示具有略微凹陷壁,在基板上具有少量底腳且無浮渣之輪廓。該等輪廓係可接受。
調配物實例10:將38.919gm Novolak-3、58.3(GIJ)聚合物、2.033gm Lutonal M-40、0.7885gm PAG、0.0711gm 1H-1,2,4-三唑-3-硫醇及0.0755gm界面活性劑溶解於121.7gm PGMEA溶劑中,以得到
含有45%固體之光阻劑溶液。將該溶液塗覆於銅晶圓上,以產生16微米膜,並在110℃下乾燥180秒。處理該光阻劑以產生圖案化影像,在90℃下進行後曝光烘烤60秒,並顯影120秒。所得抗蝕劑圖案輪廓係垂直,但在基板上具有少量底腳,且無浮渣。該等輪廓係可接受。
調配物實例11(比較實例):將38.919gm Novolak-3、58.126gm(GIJ)聚合物、2.0027gm Lutonal M-40、0.7874gm PAG、0.0859 2,6-二異丙基苯胺及0.0786gm界面活性劑溶解於122.22gm PGMEA中,以產生含有45%固體之抗蝕劑溶液。將該溶液塗覆於銅晶圓上,以產生16μm膜,並在110℃下乾燥180秒。處理該抗蝕劑以產生圖案化影像,在90℃下進行後曝光烘烤60秒,並顯影120秒。所得抗蝕劑圖案輪廓係高度傾斜,且在基板上具有嚴重底腳。使用該實例與實例10作比較,結果顯示1H-1,2,4-三唑-3-硫醇添加劑對銅基板上之光阻劑輪廓及底腳減少有顯著影響。該等輪廓係不可接受。
調配物實例12:將34.97gm Novolak-3、48.26(GIJ)聚合物、15.89gm合成實例4之聚合物、0.742gm PAG、0.0744gm 1H-1,2,4-三唑-3-硫醇及0.0528gm界面活性劑溶解於111.4gm PGMEA溶劑中,以得到含有47.3%固體之光阻劑溶液。將該溶液塗覆於銅晶圓上,以產生40μm膜,並在130℃下乾燥300秒。處理該光阻劑以產生圖案化影像,在100℃下進行後曝光烘烤100秒,並顯影240秒。所得抗蝕劑圖案輪廓係垂直,在基板上具有極少量底腳,且無浮渣。該等輪廓係可接受。
調配物實例13(比較實例):將27.25gm Novolak-3、59.8(GIJ)聚合物、0.74gm PAG、0.16gm草酸第三丁基銨、5.0gm Lutonal M-40、7.0gm Polygykol B01/40及0.05gm界面活性劑溶解於112.7gm PGMEA溶劑中,以得到含有47%固體之抗蝕劑溶液。將該溶液塗覆於銅晶圓上,以產生40μm膜,並在126℃下乾燥540秒。處理該抗蝕
劑以產生圖案化影像,在105℃下進行後曝光烘烤100秒,並顯影120秒。所得抗蝕劑圖案輪廓係凹陷,且在基板上具有少量底腳。該抗蝕劑圖案之輪廓可與由實例12之調配物(其含有本發明所主張之化合物所涵蓋之添加劑)所產生之垂直輪廓進行定性比較。該等輪廓係不可接受。
與不含添加劑的調配物相比,一些添加劑(諸如1,3,5-三嗪-2,4,6-三硫醇、1,3,4-噻二唑-2,5-二硫醇、1H-1,2,4-三唑-3-硫醇)對輪廓具有顯著影響,其產生整齊垂直壁且無底腳。一些添加劑(諸如6-甲基-2-硫尿嘧啶、6-氮雜-2-硫胸腺嘧啶、2-硫巴比妥酸)對輪廓具有較少影響。
雖然已依據特定實例顯示並描述本發明,但對熟悉本發明所屬技術領域者顯而易見之各種改變及修飾應被視為在隨附申請專利範圍中所闡述之標的物之精神、範圍及意圖內。
Claims (10)
- 一種正向感光組合物,其包含:a.至少一種光酸產生劑;b.至少一種聚合物,其包含一或多種(甲基)丙烯酸酯重複單元,且另外包含一或多種具有至少一個酸可裂解基團之重複單元;c.至少一種雜環硫醇化合物,其包含選自以下通式之環結構:
- 如請求項1之正向感光組合物,其中該雜環硫醇係選自由下列組成之群:未經取代的三唑硫醇、經取代的三唑硫醇、未經取代的咪唑硫醇、經取代的咪唑硫醇、經取代的三嗪硫醇、未經取代的三嗪硫醇、經取代的巰基嘧啶、未經取代的巰基嘧啶、經 取代的噻二唑-硫醇、未經取代的噻二唑-硫醇、經取代的吲唑硫醇、未經取代的吲唑硫醇、其互變異構體及其組合。
- 如請求項1之正向感光組合物,其中該雜環硫醇係選自由下列組成之群:1,3,5-三嗪-2,4,6-三硫醇、2-巰基-6-甲基嘧啶-4-醇、3-巰基-6-甲基-1,2,4-三嗪-5-醇、2-巰基嘧啶-4,6-二醇、1H-1,2,4-三唑-3-硫醇、1H-1,2,4-三唑-5-硫醇、1H-咪唑-2-硫醇、1H-咪唑-5-硫醇、1H-咪唑-4-硫醇、2-氮雜雙環[3.2.1]辛-2-烯-3-硫醇、2-氮雜雙環[2.2.1]庚-2-烯-3-硫醇、1H-苯并[d]咪唑-2-硫醇、2-巰基-6-甲基嘧啶-4-醇、2-巰基嘧啶-4-醇、1-甲基-1H-咪唑-2-硫醇、1,3,4-噻二唑-2,5-二硫醇、1H-吲唑-3-硫醇、其互變異構體及其組合。
- 如請求項1之正向感光材料,其中該至少一種光酸產生劑係選自由下列組成之群:鎓鹽、二羧醯亞胺基磺酸酯、肟磺酸酯、重氮(磺醯基甲基)化合物、二磺醯基亞甲基肼化合物、磺酸硝基苄酯、聯咪唑化合物、重氮甲烷衍生物、乙二肟衍生物、β-酮碸衍生物、二碸衍生物、磺酸酯衍生物、亞胺基磺酸酯衍生物、鹵代三嗪化合物、重氮萘醌磺酸酯及其組合。
- 如請求項1之正向感光組合物,其中該酸可裂解基團係經酯化成(甲基)丙烯酸酯重複單元,且該酸可裂解基團係選自由下列組成之群:第三丁基、四氫哌喃-2-基、四氫呋喃-2-基、4-甲氧基四氫哌喃-4-基、1-乙氧基乙基、1-丁氧基-乙基、1-丙氧基乙基、3-側氧基環己基、2-甲基-2-金剛烷基、2-乙基-2-金剛烷基、8-甲基-8-三環[5.2.1.0 2,6]癸基、1,2,7,7-四甲基-2-降莰基、2-乙醯氧基薄荷基、2-羥甲基、1-甲基-1-環己基乙基、4-甲基-2-側氧基四氫-2H-哌喃-4-基、2,3-二甲基丁-2-基、2,3,3-三甲基丁-2-基、1-甲基環戊基、1-乙基環戊基、1-甲基環己基、1-乙基環己基、 1,2,3,3-四甲基雙環[2.2.1]庚-2-基、2-乙基-1,3,3-三甲基雙環[2.2.1]庚-2-基、2,6,6-三甲基雙環[3.1.1]庚-2-基、2,3-二甲基戊-3-基或3-乙基-2-甲基戊-3-基。
- 如請求項1之正向感光組合物,其中該聚合物另外包含一或多種選自由下列組成之群之重複單元:(甲基)丙烯酸、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥苄酯、甲基丙烯酸2-異莰酯、(甲基)丙烯酸3-異莰酯、(甲基)丙烯酸1-金剛烷酯、苯乙烯、4-羥基苯乙烯、碳酸第三丁基4-乙烯基苯酯、甲羥戊酸內酯甲基丙烯酸酯、2-側氧基四氫呋喃-3-基(甲基)丙烯酸酯、2-側氧基四氫-2H-哌喃-3-基(甲基)丙烯酸酯及2-側氧基氧雜環庚-3-基(甲基)丙烯酸酯。
- 如請求項1之正向感光組合物,其中該聚合物包含一或多種具有以下結構之苯乙烯重複單元:
- 一種形成正凸紋影像之方法,其包括:a.藉由將如請求項1之正向感光組合物施加至基板上來形成感光層;b.使該感光層成像曝露至光化輻射,以形成潛像; c.使該潛像在顯影劑中顯影;d.其中使該成像曝露的感光層視情況經熱處理。
- 如請求項8之方法,其中該基板包含親硫元素。
- 如請求項8之方法,其中該基板為銅。
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- 2013-12-04 EP EP13852369.1A patent/EP2929397B1/en active Active
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Cited By (5)
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TWI667275B (zh) * | 2013-09-24 | 2019-08-01 | 住友化學股份有限公司 | 光阻組成物 |
US10969685B2 (en) | 2013-09-24 | 2021-04-06 | Sumitomo Chemical Company, Limited | Photoresist composition |
TWI717543B (zh) * | 2016-08-09 | 2021-02-01 | 德商馬克專利公司 | 光阻組合物及其用途 |
US11385543B2 (en) | 2016-08-09 | 2022-07-12 | Merck Patent Gmbh | Enviromentally stable, thick film, chemically amplified resist |
TWI814788B (zh) * | 2018-03-12 | 2023-09-11 | 日商東京應化工業股份有限公司 | 化學增幅型正型感光性樹脂組成物、附有鑄模之基板的製造方法及鍍敷造形物的製造方法 |
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US8841062B2 (en) | 2014-09-23 |
WO2014086846A3 (en) | 2014-12-18 |
WO2014086846A2 (en) | 2014-06-12 |
KR20150092164A (ko) | 2015-08-12 |
SG11201502265VA (en) | 2015-04-29 |
CN104781731B (zh) | 2019-12-03 |
PH12015501057A1 (en) | 2015-07-27 |
MY169240A (en) | 2019-03-19 |
EP2929397A2 (en) | 2015-10-14 |
KR101828137B1 (ko) | 2018-02-09 |
EP2929397B1 (en) | 2020-03-18 |
JP6248121B2 (ja) | 2017-12-13 |
TWI591440B (zh) | 2017-07-11 |
JP2016502142A (ja) | 2016-01-21 |
CN104781731A (zh) | 2015-07-15 |
PH12015501057B1 (en) | 2015-07-27 |
US20140154624A1 (en) | 2014-06-05 |
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