JP6271116B2 - フォトレジストおよびその使用方法 - Google Patents
フォトレジストおよびその使用方法 Download PDFInfo
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- JP6271116B2 JP6271116B2 JP2012000219A JP2012000219A JP6271116B2 JP 6271116 B2 JP6271116 B2 JP 6271116B2 JP 2012000219 A JP2012000219 A JP 2012000219A JP 2012000219 A JP2012000219 A JP 2012000219A JP 6271116 B2 JP6271116 B2 JP 6271116B2
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- resin
- keto
- photoresist
- photoresist composition
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- Prior art date
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- 229920002120 photoresistant polymer Polymers 0.000 title claims description 79
- 238000000034 method Methods 0.000 title claims description 24
- 239000000203 mixture Substances 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 40
- 239000010410 layer Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 239000000306 component Substances 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- -1 alicyclic acrylates Chemical class 0.000 description 16
- 235000012431 wafers Nutrition 0.000 description 15
- 125000000468 ketone group Chemical group 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910001092 metal group alloy Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000003384 imaging method Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 229930194542 Keto Natural products 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000005468 ion implantation Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical group OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GQRTVVANIGOXRF-UHFFFAOYSA-N (2-methyl-1-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)C2(OC(=O)C=C)C3 GQRTVVANIGOXRF-UHFFFAOYSA-N 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 2
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- GCIYMCNGLUNWNR-UHFFFAOYSA-N (2,4-dinitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O GCIYMCNGLUNWNR-UHFFFAOYSA-N 0.000 description 1
- MCJPJAJHPRCILL-UHFFFAOYSA-N (2,6-dinitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O MCJPJAJHPRCILL-UHFFFAOYSA-N 0.000 description 1
- AATKCDPVYREEEG-UHFFFAOYSA-N (2-methyl-1-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)C2(OC(=O)C(C)=C)C3 AATKCDPVYREEEG-UHFFFAOYSA-N 0.000 description 1
- MCVVDMSWCQUKEV-UHFFFAOYSA-N (2-nitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1[N+]([O-])=O MCVVDMSWCQUKEV-UHFFFAOYSA-N 0.000 description 1
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical class O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical group C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- GYQQFWWMZYBCIB-UHFFFAOYSA-N 1-[diazo-(4-methylphenyl)sulfonylmethyl]sulfonyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=C(C)C=C1 GYQQFWWMZYBCIB-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- FVNIIPIYHHEXQA-UHFFFAOYSA-N 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 FVNIIPIYHHEXQA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ASVIUQJICUIMEC-UHFFFAOYSA-L 2-hydroxypropanoate tetramethylazanium hydroxide Chemical group C(C(O)C)(=O)[O-].[OH-].C[N+](C)(C)C.C[N+](C)(C)C ASVIUQJICUIMEC-UHFFFAOYSA-L 0.000 description 1
- UUNHRGSUOBTBKW-UHFFFAOYSA-M 2-hydroxypropanoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CC(O)C([O-])=O UUNHRGSUOBTBKW-UHFFFAOYSA-M 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- YXZXRYDYTRYFAF-UHFFFAOYSA-M 4-methylbenzenesulfonate;triphenylsulfanium Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 YXZXRYDYTRYFAF-UHFFFAOYSA-M 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical class C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YPPVLYIFEAESGO-UHFFFAOYSA-N [2,3-bis(methylsulfonyloxy)phenyl] methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC(OS(C)(=O)=O)=C1OS(C)(=O)=O YPPVLYIFEAESGO-UHFFFAOYSA-N 0.000 description 1
- OIHCCWXZFYNOJS-UHFFFAOYSA-N [2,3-bis-(4-methylphenyl)sulfonyloxyphenyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC(OS(=O)(=O)C=2C=CC(C)=CC=2)=C1OS(=O)(=O)C1=CC=C(C)C=C1 OIHCCWXZFYNOJS-UHFFFAOYSA-N 0.000 description 1
- HKKMPPDCCCBZHM-UHFFFAOYSA-M [4-[(2-methylpropan-2-yl)oxy]phenyl]-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 HKKMPPDCCCBZHM-UHFFFAOYSA-M 0.000 description 1
- ZWFRZGJUJSOHGL-UHFFFAOYSA-N [Bi].[Cu].[Sn] Chemical compound [Bi].[Cu].[Sn] ZWFRZGJUJSOHGL-UHFFFAOYSA-N 0.000 description 1
- QFKJMDYQKVPGNM-UHFFFAOYSA-N [benzenesulfonyl(diazo)methyl]sulfonylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=CC=C1 QFKJMDYQKVPGNM-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 150000003998 acyclic ketones Chemical group 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- CYFLXLSBHQBMFT-UHFFFAOYSA-N sulfamoxole Chemical group O1C(C)=C(C)N=C1NS(=O)(=O)C1=CC=C(N)C=C1 CYFLXLSBHQBMFT-UHFFFAOYSA-N 0.000 description 1
- LYPVBFXTKUJYDL-UHFFFAOYSA-N sulfanium;trifluoromethanesulfonate Chemical compound [SH3+].[O-]S(=O)(=O)C(F)(F)F LYPVBFXTKUJYDL-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
- H01L21/266—Bombardment with radiation with high-energy radiation producing ion implantation using masks
-
- 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
-
- 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
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- High Energy & Nuclear Physics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Description
1)248nmでの像形成に特に好適な、化学増幅ポジ型レジストを提供できる酸不安定基を含むフェノール系樹脂。この種類の特に好ましい樹脂には以下のものが挙げられる:i)ビニルフェノールおよびアクリル酸アルキルの重合単位を含むポリマー、このポリマーにおいては、重合されたアクリル酸アルキル単位は光酸の存在下でデブロッキング(deblocking)反応を受けうる。典型的には、光酸誘起デブロッキング反応を受けうるアクリル酸アルキルには、例えば、アクリル酸t−ブチル、メタクリル酸t−ブチル、アクリル酸メチルアダマンチル、メタクリル酸メチルアダマンチル、および光酸誘起反応を受けうる他の非環式アルキルおよび脂環式アクリラートが挙げられ、例えば、米国特許第6,042,997号および第5,492,793号(参照により本明細書に組み込まれる)におけるポリマーが挙げられる;ii)ビニルフェノール、場合によって置換された(ただし、ヒドロキシまたはカルボキシ環置換基を含まない)ビニルフェニル(例えば、スチレン)、および上記ポリマーi)について記載されるデブロッキング基のもののようなアクリル酸アルキルの重合単位を含むポリマー、例えば、米国特許第6,042,997号(参照により本明細書に組み込まれる)に記載されているポリマー;並びに、iii)光酸と反応しうるアセタールまたはケタール部分を含む繰り返し単位を含み、および場合によって芳香族繰り返し単位、例えば、フェニルもしくはフェノール性基などを含むポリマー;
2)実質的にまたは完全にフェニルまたは他の芳香族基を含まない樹脂、これは193nmのようなサブ200nm波長での像形成に特に好適な化学増幅ポジ型レジストを提供できる。特に好ましいこの種類の樹脂には以下のものが挙げられる;i)場合によって置換されたノルボルネンのような、非芳香族環式オレフィン(環内二重結合)の重合単位を含むポリマー、例えば、米国特許第5,843,624号(参照により本明細書に組み込まれる)に記載されているポリマー;ii)アクリル酸アルキル単位、例えば、アクリル酸t−ブチル、メタクリル酸t−ブチル、アクリル酸メチルアダマンチル、メタクリル酸メチルアダマンチル、および他の非環式アルキルおよび脂環式アクリラートを含むポリマー;例えば、米国特許第6,057,083号に記載されているポリマー。
上述のように、ここで、本発明者は、1)光酸不安定基を適切に含むことができる樹脂成分;2)1種以上の光酸発生剤化合物;および3)上述のような隣り合うケト基を含む樹脂のような、多ケト成分;を適切に含む新規のフォトレジストを提供する。好ましくは、これら成分1)、2)および3)は別個であり、すなわち共有結合されておらず、かつそれぞれ異なる物質である。本発明の好ましいフォトレジストはポジ型レジストであり、特に化学増幅型レジストである。本発明は、ネガ型フォトレジストも含み、この場合、このレジストは、本明細書において開示されるように、樹脂、架橋機能およびフェノール系成分を含むことができる。
1.樹脂
フォトレジストの樹脂は上に示され(上の構造において「樹脂1」として指定される)、上で示された化学式においては、ターポリマーの各繰り返し単位の下の数字は、そのターポリマーにおけるその単位の重量割合(この樹脂合成の際に添加されるモノマーに基づく)を表す。この樹脂は流体フォトレジストの全重量の12.0重量パーセントの量で存在する。
2.光酸発生剤化合物(PAG)
PAGは、流体フォトレジストの全重量の2.5重量パーセントで存在するt−ブチルフェニルテトラメチレンスルホニウムペルフルオロブタンスルホナートである。
3.塩基性添加剤
塩基性添加剤は、フォトレジスト組成物の全重量を基準にして0.017重量%の量のN−アルキルカプロラクタムである。
4.多ケトン樹脂
このフォトレジストの多ケト樹脂は上に示され、示された化学式において、このターポリマーの各繰り返し単位の下の数字は、このターポリマーにおけるその単位の重量割合(この樹脂合成の際に添加されるモノマーに基づく)を表す。この多ケト樹脂は流体フォトレジストの全重量の8重量パーセントの量で存在する。
5.溶媒
溶媒は乳酸エチルであり、レジストの残部を提供する。
実施例1の配合されたレジスト組成物はSiONウェハ表面上にスピンコートされ、90℃で60秒間、真空ホットプレートでソフトベークされる。レジスト塗膜層は、フォトマスクを通して193nmで露光され、次いで、露光された塗膜層は110℃で露光後ベークされる。コーティングされたウェハは、次いで0.26Nのテトラブチルアンモニウムヒドロキシド水溶液で処理されて、像形成されたレジスト層を現像する。
フォトレジストレリーフ像の形成後、基体(レジストマスクを有する)は高エネルギー(>20eV、減圧環境)リンイオン注入処理にかけられる。
Claims (8)
- 前記1)樹脂が光酸不安定基を含む請求項1に記載の方法。
- 放射線が193nmの波長を有する、請求項4に記載の方法。
- フォトレジスト組成物が無機表面上に適用される、請求項4または5に記載の方法。
- 前記1)樹脂が光酸不安定基を含む請求項7に記載のフォトレジスト組成物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US201061428777P | 2010-12-30 | 2010-12-30 | |
US61/428,777 | 2010-12-30 |
Publications (2)
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JP2012141613A JP2012141613A (ja) | 2012-07-26 |
JP6271116B2 true JP6271116B2 (ja) | 2018-01-31 |
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JP2012000219A Active JP6271116B2 (ja) | 2010-12-30 | 2012-01-04 | フォトレジストおよびその使用方法 |
Country Status (6)
Country | Link |
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US (1) | US9508553B2 (ja) |
EP (1) | EP2472327A1 (ja) |
JP (1) | JP6271116B2 (ja) |
KR (1) | KR101897483B1 (ja) |
CN (1) | CN102592978B (ja) |
TW (1) | TWI486713B (ja) |
Families Citing this family (1)
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WO2015088478A1 (en) * | 2013-12-09 | 2015-06-18 | Empire Technology Development Llc | Graphene etching methods, systems, and composites |
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- 2011-12-30 KR KR1020110147462A patent/KR101897483B1/ko active IP Right Grant
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US9508553B2 (en) | 2016-11-29 |
US20120199957A1 (en) | 2012-08-09 |
TW201239540A (en) | 2012-10-01 |
KR101897483B1 (ko) | 2018-09-12 |
JP2012141613A (ja) | 2012-07-26 |
CN102592978A (zh) | 2012-07-18 |
KR20120078657A (ko) | 2012-07-10 |
TWI486713B (zh) | 2015-06-01 |
CN102592978B (zh) | 2015-09-09 |
EP2472327A1 (en) | 2012-07-04 |
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