WO2005109102A1 - Photoactive monomer, photosensitive polymer and chemically amplified photoresist composition including the same - Google Patents
Photoactive monomer, photosensitive polymer and chemically amplified photoresist composition including the same Download PDFInfo
- Publication number
- WO2005109102A1 WO2005109102A1 PCT/KR2005/001370 KR2005001370W WO2005109102A1 WO 2005109102 A1 WO2005109102 A1 WO 2005109102A1 KR 2005001370 W KR2005001370 W KR 2005001370W WO 2005109102 A1 WO2005109102 A1 WO 2005109102A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- methyl
- photosensitive polymer
- monomer
- photoresist composition
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 61
- 239000000178 monomer Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- -1 anion compound Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 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 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 claims description 2
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 claims description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 2
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 claims description 2
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 claims description 2
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 claims description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims description 2
- TVODIPKBEMSROH-UHFFFAOYSA-N ethyl 3-methoxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)COC TVODIPKBEMSROH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 229940117360 ethyl pyruvate Drugs 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 claims description 2
- LYLUAHKXJUQFDG-UHFFFAOYSA-N methyl 3-methoxy-2-methylpropanoate Chemical compound COCC(C)C(=O)OC LYLUAHKXJUQFDG-UHFFFAOYSA-N 0.000 claims description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims description 2
- 229940057867 methyl lactate Drugs 0.000 claims description 2
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 72
- 239000012530 fluid Substances 0.000 abstract description 6
- 238000007654 immersion Methods 0.000 abstract description 6
- 238000000671 immersion lithography Methods 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- 0 CC(*)C(Oc1ccc(C[S-](c2ccccc2)c2ccccc2)cc1)=O Chemical compound CC(*)C(Oc1ccc(C[S-](c2ccccc2)c2ccccc2)cc1)=O 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960004132 diethyl ether Drugs 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- JHIGBMVXTRJDTO-UHFFFAOYSA-N (4-hydroxyphenyl)-diphenylsulfanium;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.C1=CC(O)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 JHIGBMVXTRJDTO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 1
- QSUJHKWXLIQKEY-UHFFFAOYSA-N (2-oxooxolan-3-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCOC1=O QSUJHKWXLIQKEY-UHFFFAOYSA-N 0.000 description 1
- YAFVTOLUUZOHAS-UHFFFAOYSA-N (4-hydroxyphenyl)-diphenylsulfanium;chloride Chemical compound [Cl-].C1=CC(O)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 YAFVTOLUUZOHAS-UHFFFAOYSA-N 0.000 description 1
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 1
- FEVALTJSQBFLEU-UHFFFAOYSA-N 1-methyl-4-methylsulfinylbenzene Chemical compound CC1=CC=C(S(C)=O)C=C1 FEVALTJSQBFLEU-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- DYDWFNLGKFGCMS-UHFFFAOYSA-N 2-methylbutanoic acid;propane-1,2-diol Chemical compound CC(O)CO.CCC(C)C(O)=O DYDWFNLGKFGCMS-UHFFFAOYSA-N 0.000 description 1
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004187 tetrahydropyran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- 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
Abstract
Disclosed are a novel (meth)acrylic monomer having the function of a photoacid generator, a photosensitive polymer prepared with the monomer, and a chemically amplified photoresist composition including the polymer. The monomer have a merit in that the photoacid-generator does not elute from a photoresist during wet exposing process in immersion lithography. Thus, the contaminations of lens and immersion fluid used in wet exposing process can be prevented or reduced.
Description
Description PHOTOACTIVE MONOMER, PHOTOSENSITIVE POLYMER AND CHEMICALLY AMPLIFIED PHOTORESIST COMPOSITION INCLUDING THE SAME Technical Field
[1] This invention relates to a monomer having the function of a photoacid generator and a photosensitive polymer for forming photoresist pattern for a semiconductor. More specifically, this invention relates to a novel (meth)acrylic monomer having a chromophoric group which works as a photoacid generator, a photosensitive polymer prepared with the monomer, and a chemically amplified photoresist composition including the polymer. Background Art
[2] As the degree of integration of a semiconductor increases, dynamic random access memory (hereinafter "DRAM" having the memory capacity of more than one gigabit has been developed. To produce such a large capacity DRAM, it is required to form a fine photoresist pattern whose line width is less than lOOnm. Therefore, photo lithography processes using an exposure light source radiating light of a shorter wavelength than g-line(436nm) and i-line(365nm), has been developed. The light source radiating light of a shorter wavelength includes KrF excimer laser(248nm) and ArF excimer laser(193nm). On the other hands, active researches are carried out to prepare a chemically amplified photoresist composition having high resolution and high transparency in photolithography process using short wavelength exposing light (248nm, 193nm or less), excellent dry etching resistance, adhesiveness to a substrate, and developing property to the conventional developer composition such as 2.38 weight% tetramethyl ammoniumhydroxide (TMAH) aqueous solution. Generally, the chemically amplified photoresist composition includes a photoacid generator (PAG) which generates an acid when exposed to an exposing light, a photosensitive polymer having a protecting group which can be hydrolyzed by the acid, and a solvent. When the chemically amplified photoresist composition is exposed to an exposing light, the photoacid generator generates an acid, the generated acid consecutively decomposes the protecting groups on the photosensitive polymer, and thus the solubility of the photosensitive polymer is changed. Then, the photoresist is developed to form the pattern of high contrast.
[3]
[4] Recently, an immersion lithography process is also developed to produce photoresist pattern having the half -pitch of less than 65nm in DRAM manufacturing
process. However, the immersion lithography process has a drawback in that the photoacid generator elutes from the photoresist when an immersion fluid is applied to the photoresist. The eluted photoacid contaminates lens and the immersion fluid, which reduces the life span of the lens, changes the refractive index of the immersion fluid, and finally decreases the process yield. Disclosure of Invention Technical Problem
[5] It is an object of the present invention to provide a monomer having the function of a photoacid generator which can prevent the leakage of the photoacid generator in the immersion lithography process, a photosensitive polymer prepared with the monomer, and a chemically amplified photoresist composition including the polymer.
[6] It is other object of the present invention to provide a monomer which can prevent the contaminations of lens, immersion fluid, and so on in the immersion lithography process, a photosensitive polymer prepared with the monomer, and a chemically amplified photoresist composition including the polymer.
[7] It is another object of the present invention to provide a photosensitive polymer and a chemically amplified photoresist composition for providing high resolution, high process margin and low line edge roughness (LER).
[8] It is yet another object of the present invention to provide a photosensitive polymer and a chemically amplified photoresist composition which are suitable for the dry exposing process as well as the wet exposing process, and especially for the ArF wet exposing process. Technical Solution
[9] To achieve these and other objects, the present invention provides a monomer having the function of a photoacid generator of the following formula.
[10]
[11] In the formula, R is a hydrogen, methyl or CF , R and R are independently a homo or hetero, saturated or unsaturated hydrocarbyl group having 1 to 25 carbon atoms, An is an anion compound, for example, trifluoromethane sulfonate, nonaflu- orobutane sulfonate, heptadecafluorooctane sulfonate, camphosulfonate, bistrifluo- romethanesulfonyl amide or tristrifluoromethanesulfonyl methylate, and X and X are
both hydrogen or are connected together to form a benzene ring. [12] The present invention also provides a photosensitive polymer of the following formula.
[13]
[14] In the formula, R , R 1 , R 2 and An are the same as defined above, R 3 is a saturated hydrocarbyl group having 1 to 25 carbon atoms, R and R are independently a homo or hetero saturated hydrocarbyl group having 1 to 30 carbon atoms, a, b, c and d are mole ratio of each repeating unit, and a : b : c : d is 0.01-10 mol% : 5-85 mol% : 5-85 mol% : 5-85 mol%. [15] The present invention also provides a chemically amplified photoresist composition including the photosensitive polymer and a solvent. Brief Description of the Drawings [16] A more complete appreciation of the invention, and many of the attendant advantages thereof, will be better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings, wherein: [17] Figs. 1 and 2 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3a, respectively; [18] Figs. 3 and 4 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3b, respectively; [19] Figs. 5 and 6 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3c, respectively; [20] Figs. 7 and 8 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3d, respectively; [21] Figs. 9 and 10 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3e, respectively; [22] Figs. 11 and 12 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3f, respectively; and [23] Figs. 13 and 14 are photographs of the pattern formed by the dry exposing process and the wet exposing process according to Example 3g, respectively. Mode for the Invention [24] According to the present invention, a monomer having the function of a photoacid generator is provided, the monomer is polymerized to prepare a photosensitive
polymer, and the photosensitive polymer is used to prepare a chemically amplified photoresist composition having high resolution and broad process margin. The monomer according to the present invention is a novel (meth)acrylic monomer having a chromophoric group which generates an acid when exposed to light. The monomer includes 4-(anion dialkylsulfonium)phenol (meth)acrylate or 4-(anion dialkyl- sulfonium)naphtol (meth)acrylate, which can be represented by the following Formula 1.
[25] (Formula 1)
[26]
[27] In formula 1, R is a hydrogen, methyl or CF , R and R are independently a homo or hetero, saturated or unsaturated hydrocarbyl group having 1 to 25 carbon atoms, preferably 1 to 10 carbon atoms, An is an anion compound, for example, trifluo- romethane sulfonate(CF SO "), nonafluorobutane sulfonate(C F SO "), heptadecaflu- orooctane sulfonate(C F SO ), camphosulfonate, bistrifluoromethanesulfonyl amide(N"(SO CF ) ) or tristrifluoromethane sulfonyl methylate(C"(SO CF ) ), and X and X are both hydrogen or are connected together to form a benzene ring.
[28]
[29] The preferable monomer according to the present invention includes the compounds of the following formulas la to lg.
[30] (Formula la)
[31]
[32] (Formula lb)
[33]
[34] (Formula lc) [35]
[36] (Formula Id) [37]
[40] (Formula If) [41]
[42] (Formula lg) [43]
[44] In above Formulas, R and An are the same as defined in Formula 1.
[45] The monomer of Formula 1 can be prepared by various organic synthetic methods. An example of the organic synthetic method is shown in the following Reaction 1. As shown in Reaction 1, phenol and dialkylsulfoxide are reacted in the presence of an alcoholic solvent such as methanol and an acid catalyst (HX: X is CI, SO or CH CO J 4 3 2 ), and then the obtained reaction product and An M+(An is an anion compound as defined in the above Formula 1, M is K, Na or NH ) are subjected to anion exchange reaction in the presence of an organic solvent such as acetone to obtain 4-(anion di- alkylsulfonium)phenol. Then the obtained 4- (anion dialkylsulfonium)phenol and (meth)acryloyl chloride are reacted in the presence of a base catalyst solution such as NaOH/MeOH to obtain the monomer of Formula 1 (wherein X and X are both hydrogen.).
[46] (Reaction 1)
[47]
[48] The monomer of Formula 1, in which X and X are connected together to form a benzene ring, can be prepared according to the following Reaction 2. As shown in Reaction 2, 1-naphtol and dialkylsulfoxide are reacted in the presence of an alcoholic solvent such as methanol and an acid catalyst (HX: X is CI, SO or CH CO ), and the J 4 3 2 obtained reaction product and An M+ (An is an anion compound as defined in the above Formula 1, M is K, Na or NH 4.) are subjected to anion exchange reaction in the presence of an organic solvent such as acetone to obtain 4-(anion dialkyl- sulfonium)naphtol. Then the obtained 4-(anion dialkylsulfonium)naphtol and (meth)acryloyl chloride are reacted in the presence of a base catalyst solution such as NaOH/MeOH to obtain the monomer of Formula 1, in which X 1 and X 2 are connected together to form a benzene ring. [49] (Reaction 2)
[50]
[51] In Reactions 1 and 2, R 1 and R 2 are the same as defined in Formula 1. [52] [53] The photosensitive polymer according to the present invention is the polymer including the repeating unit produced from the 4- (anion dialkylsulfonium)phenol (meth)acrylate monomer or 4-(anion dialkylsulfonium) naphtol (meth)acrylate monomer, and can be represented by the following Formula 2.
[54] (Formula 2) [55]
[56] In above Formulas, R , R 1 , R 2 and An are the same as defined in Formula 1, R 3 is a saturated hydrocarbyl group having 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms, R and R are independently a homo or hetero saturated hydrocarbyl group having 1 to 30 carbon atoms, a, b, c and d are mole ratio of each repeating unit, and a : b : c : d is 0.01-10 mol% : 5-85 mol% : 5-85 mol% : 5-85 mol%.
[57] The R , R and R can be a group to be deprotected by an acid (leaving group), a group for improving the adhesiveness of the polymer to the substrate, or a group for improving the developing property of the polymer with respect to a developing solution. The conventional substituents which are used in a conventional photosensitive polymer can be unlimitedly used as R , R or R . For example, R , R or R can be t-butyl, tetrahydropyran-2-yl, 2-methyl-tetrahydropyran-2-yl, tetrahydrofuran- 2-yl, 2-methyl tetrahydrofuran-2-yl, 1-methoxypropyl, 1-methoxy-l-methylethyl, 1-ethoxypropyl, 1-ethoxy-l-methylethyl, 1-methoxyethyl, 1-ethoxyethyl, t- butoxyethyl, 1-isobutoxyethyl, adamantyl, hydroxy adamantyl and so on. The molecular weight of the photosensitive polymer according to the present invention can be varied according to the lithography conditions. The preferable weight average molecular weight thereof is 3,000 to 100,000 and the preferable polydispersity is 1.0 to 5.0. If the weight average molecular weight is less than 3,000, etching resistance can
be deteriorated, and if the weight average molecular weight is more than 100,000, the solubility to a solvent and the resolution can be deteriorated.
[58] [59] Exemplary photosensitive polymer according to the present invention includes the polymer of the following Formula 2a to 2h.
[60] (Formula 2a) [61]
[62] (Formula 2b) [63]
[64] (Formula 2c) [65]
[70] (Formula 2f) [71]
[72] (Formula 2g) [73]
[74] (Formula 2h)
[75]
[76] In above Formulas, R , R 1 , R 2 , An", a, b, c and d are the same as defined in Formula 2.
[77] [78] The photosensitive polymer of Formula 2 can be prepared by a conventional polymerization reaction. For example, the photosensitive polymer of Formula 2 can be
prepared according to the following polymerization Reactions 3 and 4. As shown in Reactions 3 and 4, the monomers for preparing the photosensitive polymer, such as (meth)acrylate compound of Formula 1 and other kinds of (meth)acrylate compounds, are mixed by necessary amounts in an organic solvent, and subjected to a polymerization reaction to obtain a reaction product. Exemplary organic solvent for the polymerization reaction includes tetrahydrofuran (THF), cyclohexanone, cy- clopentanone, dimethyl formamide, dimethyl sulfoxide, dioxane, methylethylketone, benzene, toluene, xylene and so on. The obtained reaction product can be crystallized in an organic solvent such as diethylether to produce the photosensitive polymer of the present invention. The polymerization reaction is preferably carried out in the presence of an initiator. Exemplary initiator includes benzoyl peroxide, 2,2- azobisisobuty- ronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butyl peracetate, t-butyl hy- droperoxide, di-t-butyl peroxide and so on.
[79] (Reaction 3) [80]
[81] (Reaction 4) [82]
[83] In Reactions 3 and 4, R*, R , R , R , R , R , An", a, b, c and d are the same as 1 2 3 4 5 defined in the Formula 2.
[84]
[85] The chemically amplified photoresist composition according to the present invention includes the photosensitive polymer of Formula 2 and a solvent, and, if necessary, may include various additives. The amount of the photosensitive polymer is 1 to 30 weight%, preferably 5 to 15 weight% with respect to the total amount of the chemically amplified photoresist composition, and the preferable amount of the solvent can be controlled so that the amount of solid material is 5 to 70 weight%, preferably 10 to 60 weight% with respect to the total amount of the photoresist composition. If the amount of the photosensitive polymer and the amount of the organic solvent are not in the above ranges, a photoresist layer may not be effectively formed. Conventional solvents for a photoresist composition can be used as the solvent of the photoresist composition according to the present invention. Exemplary solvent includes ethyleneglycol monomethylethyl, ethyleneglycol monoethylether, ethyleneglycol monomethylether, ethyleneglycol monoacetate, diethyleneglycol, diethyleneglycol monoethylether, propyleneglycol monomethyletheracetate, propyleneglycol, propy- leneglycol monoacetate, toluene, xylene, methyl ethyl ketone, methyl isoamil ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate, ethyl ethoxy propionate, N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone, 3-ethoxy ethyl propionate, 2-heptanone, gamma-butyrolactone, 2-hydroxypropion ethyl, 2-hydroxy-2-methyl propionic acid ethyl ester, ethoxy acetic acid ethyl ester, hydroxy acetic acid ethyl ester, 2-hydroxy-3-methyl butanoic acid methyl ester, 3-methoxy-2-methyl propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, 3-methoxy-2-methyl propionic acid ethyl ester, ethyl acetate, butyl acetate and the mixtures thereof. The photoresist
composition of the present invention can further include an organic base as an additive. If the organic base is used, the amount of the organic base is 0.01 to 2.00 weight% with respect to the total photoresist composition. Exemplary organic base includes triethyl amine, triisobutyl amine, triisooctyl amine, diethanolamine, triethanolamine and the mixtures thereof. The photoresist composition of the present invention can be prepared by mixing the photosensitive polymer, the organic solvent and the optional additives, and optionally by filtering the mixture with a filter, for example, with a filter having the filter size of 0.2D. The photoresist composition of the present invention is suitable for the dry exposing process as well as the wet exposing process, and especially for the ArF wet exposing process.
[86]
[87] Photoresist pattern can be formed on a substrate using the photoresist composition according to the following conventional photolithography process. First, the photoresist composition is spin coated on the substrate, such as silicon wafer or aluminium wafer, for example, with a spin coater to form a photoresist layer on the substrate. Then the photoresist layer is exposed, developed and baked to form photoresist pattern on the substrate. The developing solution (developer) for the developing process can be 0.1 to 10 weight% alkali aqueous solution containing alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethyl ammonium hydroxide(TM AH), and so on. If desired, a surfactant or water-soluble organic solvent such as methanol and ethanol can be added to the developing solution. In addition, the substrate can be washed with pure water after the developing process.
[88]
[89] Hereinafter, the preferable examples are provided for better understanding of the present invention. However, the present invention is not limited to the following examples.
[90]
[91] (Example la) Preparation of monomer
[92] 9.41g(0. lmol) of phenol and 20.2g(0. lmol) of phenyl sulfoxide are added into a 500mL round-bottom flask, 60g of methanol is added thereto, and a reaction carried out at room temperature for 2 hours and 30 minutes while bubbling 4.73g(0.13mol) of dry hydrogen chloride gas in the reaction solution and stirring the reaction solution. Then, the obtained diphenyl-4-hydroxyphenyl sulfonium chloride 26.8g(0.085mol) is dissolved with 80g of acetone, and a solution including 33.8g(0.1mol) of potassium nonafluorobutane sulfonate and 50g of acetone is added thereto to produce diphenyl- 4-hydroxyphenyl sulfonium nonafluorobutane sulfonate. Then, the obtained diphenyl- 4-hydroxyphenyl sulfonium nonafluorobutane sulfonate 46.3g(0.08mol) is treated with
6.8g(0.2mol, excess amount) of sodium hydroxide and 50g of methanol to obtain a sodium salt. Then the obtained sodium salt is added to 50g of acetonitrile at room temperature, and is reacted with 8.9g(0.85mol) of methacryloyl chloride for 1 hour under nitrogen atmosphere. After completion of reaction, a monomer of solid salt state is obtained, and the obtained monomer is recrystallized with methanol and stayed at room temperature to obtain nonafluorobutane sulfonate monomer of Formula la in 60% yield. [93]
[94] (Example lb) Preparation of monomer
[95] Nonafluorobutane sulfonate monomer of Formula lb is obtained in 75% yield by th e same method as Example la except for using 15.4g(0.1mol) of methyl-p-tolyl sulfoxide instead of 20.2g(0.1mol) of phenyl sulfoxide. [96]
[97] (Example lc) Preparation of monomer
[98] Nonafluorobutane sulfonate monomer of Formula lc is obtained in 70% yield by the same method as Example la except for using 16.2g(0.1mol) of n-butyl sulfoxide instead of 20.2g(0. lmol) of phenyl sulfoxide. [99]
[100] (Example Id) Preparation of monomer
[101] Nonafluorobutane sulfonate monomer of Formula Id is obtained in 53% yield by the same method as Example la except for using 14.4g(0.1mol) of 1-naphtol instead of 9.41g(0. lmol) of phenol. [102]
[103] (Example le) Preparation of monomer
[104] Nonafluorobutane sulfonate monomer of Formula le is obtained in 65% yield by the same method as Example lb except for using 14.4g(0.1mol) of 1-naphtol instead of 9.41g(0. lmol) of phenol. [105]
[106] (Example If) Preparation of monomer
[107] Nonafluorobutane sulfonate monomer of Formula If is obtained in 55% yield by the same method as Example lc except for using 14.4g(0.1mol) of 1-naphtol instead of 9.41g(0. lmol) of phenol. [108]
[109] (Example lg) Preparation of monomer
[110] Nonafluorobutane sulfonate monomer of Formula lg is obtained in 65% yield by the same method as Example la except for using 14.4g(0.1mol) of 1-naphtol and 7.8 lg(0. lmol) of dimethyl sulfoxide instead of 9.41g(0. lmol) of phenol and 20.2g(0.1mol) of phenyl sulfoxide.
[111]
[112] (Example 2a) Preparation of photosensitive polymer
[113] 12.9g(0.02mol) of methacrylate monomer(Formula la) obtained in Example la, 23.4g(0.1mol) of 2-methyl-2-methacryloyloxy adamantane, 15.8g(0.1mol) of methacryloyloxy butyrolactone, 23.6g(0.1mol) of l-methacryloyloxy-3-hydroxy adamantane and 10. lg of azobisisobutyronitrile(AIBN) are dissolved in 35g of anhydrous THF. Then, gas in the solution is removed using an ampoule by freezing method, and polymerization reaction is carried out at 68°C for 24 hours. After completion of reaction, excess amount of diethyl ether is slowly added to the reaction solution to precipitate the reaction product, and the precipitated reaction product is dissolved with THF, and again precipitated by using diethyl ether to obtain a photosensitive polymer of Formula 2a in 55% yield. The obtained polymer has the weight average molecular weight of 8,000 and the polydispersity of 1.65.
[114]
[115] (Example 2b) Preparation of photosensitive polymer
[116] The photosensitive polymer of Formula 2b is prepared in 60% yield by the same method as Example 2a except for using 12.0g(0.02mol) of methacrylate monomer (Formula lb) prepared in Example lb instead of 12.9g(0.02mol) of methacrylate monomer (Formula la) prepared in Example la. The prepared polymer has the weight average molecular weight of 9,500 and the polydispersity of 1.85.
[117]
[118] (Example 2c) Preparation of photosensitive polymer
[119] The photosensitive polymer of Formula 2c is prepared in 60% yield by the same method as Example 2a except for using 12.1g(0.02mol) of methacrylate monomer(Formula lc) prepared in Example lc instead of 12.9g(0.02mol) of methacrylate monomer(Formula la) prepared in Example la. The prepared polymer has the weight average molecular weight of 9,100 and the polydispersity of 1.65.
[120]
[121] (Example 2d) Preparation of photosensitive polymer
[122] The photosensitive polymer of Formula 2d is prepared in 55% yield by the same method as Example 2a except for using 14.0g(0.02mol) of methacrylate monomer(Formula Id) prepared in Example Id instead of 12.9g(0.02mol) of methacrylate monomer (Formula la) prepared in Example la. The prepared polymer has the weight average molecular weight of 9,800 and the polydispersity of 1.92.
[123]
[124] (Example 2e) Preparation of photosensitive polymer
[125] The photosensitive polymer of Formula 2e is prepared in 65% yield by the same method as Example 2a except for using 13.0g(0.02mol) of methacrylate monomer
(Formula le) prepared in Example le instead of 12.9g(0.02mol) of methacrylate monomer(Formula la) prepared in Example la. The prepared polymer has the weight average molecular weight of 9,200 and the polydispersity of 1.75.
[126]
[ 127 ] (Example 2f) Preparation of photosensitive polymer
[128] The photosensitive polymer of Formula 2f is prepared in 60% yield by the same method as Example 2a except for using 13.2g(0.02mol) of methacrylate monomer(Formula If) prepared in Example If instead of 12.9g(0.02mol) of methacrylate monomer(Formula la) prepared in Example la. The prepared polymer has weight average molecular weight of 8,700 and the polydispersity of 1.65.
[129]
[130] (Example 2g _ Preparation of photosensitive polymer
[131] The photosensitive polymer of Formula 2g is prepared in 80% yield by the same method as Example 2a except for using 11.4g(0.02mol) of methacrylate monomer(Formula lg) prepared in Example lg instead of 12.9g(0.02mol) of methacrylate monomer(Formula la) prepared in Example la. The prepared polymer has the weight average molecular weight of 8,900 and the polydispersity of 1.75.
[132]
[133] (Examples 3a-3g) Preparation of photoresist composition
[134] 2g of photosensitive polymer prepared in Examples 2a to 2g is dissolved in 20g of propyleneglycol methylethylacetate, and filtered with a filter of 0.20μm filter size to prepare photoresist compositions 3a to 3g, respectively.
[135]
[136] (Example 4) Formation of photoresist pattern by dry exposing process and wet exposing process
[137] The photoresist composition prepared in Examples 3a to 3g is spin coated on a silicon substrate to be etched to form a photoresist layer. Then the photoresist layer is subjected to soft bake process at 90°C for 90 seconds in oven or on hot plate, and then subjected to dry exposing process or wet exposing process with ArF excimer laser, and again subjected to bake process at 90°C for 90 seconds. Then the baked wafer is developed by immersing the baked wafer in 2.38 weight% TMAH aqueous solution for 40 seconds to form photoresist L/S pattern of 0.07 μm. The CD(critical dimension) and cross-sectional profile of the obtained photoresist pattern are measured by Critical Dimension Scanning Electron Microscopes(CD-SEM) and Field Emission Scanning Electron Microscope(FE-SEM) to obtain minimum resolution, depth of focus, line edge roughness and processing margin of energy of each photoresist composition, and the results are set forth in Table 1. Also, photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of
Example 3a are represented by Figs. 1 and 2, respectively. Photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of Example 3b are represented by Figs. 3 and 4, respectively. Photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of Example 3c are represented by Figs. 5 and 6, respectively. Photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of Example 3d are represented by Figs. 7 and 8, respectively. Photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of Example 3e are represented by Figs. 9 and 10, respectively. Photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of Example 3f are represented by Figs. 11 and 12, respectively. Photographs of the pattern formed by the dry exposing process and the wet exposing process with the photoresist composition of Example 3g are represented by Figs. 13 and 14, respectively.
[138] [139] As inferred from Table 1 and Figs. 1 to 14, the photoresist composition of the present invention can form the photoresist pattern which has excellent resolution, excellent depth of focus, low line edge roughness and excellent processing margin of energy because the leakage or elution of the photoacid-generator does not occur.
[140] Table 1
[141] As described above, the monomer having the function of a photoacid generator, the photosensitive polymer and the chemically amplified photoresist composition of the present invention have a merit in that the photoacid-generator does not elute from a photoresist during wet exposing process in immersion lithography. Thus, the contaminations of lens and immersion fluid used in wet exposing process can be reduced. Also the chemically amplified photoresist of the present invention has merits in that it can decrease line edge roughness(LER), and has high resolution, high processing
margin of energy, excellent depth of focus margin, and is suitable for the dry exposing process as well as the wet exposing process, and especially for the ArF wet exposing process.
Claims
[1] A monomer having the function of a photoacid generator of the following Formula 1, (Formula 1)
[2] The monomer having the function of a photoacid generator of claim 1, wherein the monomer is selected from the group consisting of the compounds of the following Formulas la to lg, (Formula la)
(Formula Id)
[3] The monomer having the function of a photoacid generator of claim 1, wherein
the anion compound is selected from the group consisting of trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, campho- sulfonate, bistrifluoromethanesulfonyl amide and tristrifluoromethanesulfonyl methylate.
[4] A photosensitive polymer of the following Formula 2, (Formula 2)
[5] The photosensitive polymer of claim 4, wherein the photosensitive polymer has the weight average molecular weight of 3,000 to 100,000 and the polydispersity of 1.0 to 5.0.
[6] The photosensitive polymer of claim 4, wherein the photosensitive polymer is selected from the group consisting of the compounds of the following Formulas 2a to 2h, (Formula 2a)
(Formula 2c)
(Formula 2d)
(Formula 2f)
[7] A chemically amplified photoresist composition comprising: the photosensitive polymer of Formula 2; and a solvent.
[8] The chemically amplified photoresist composition of claim 7, wherein the amount of the photosensitive polymer of Formula 2 is 1 to 30 weight% with respect to the total chemically amplified photoresist composition.
[9] The chemically amplified photoresist composition of claim 7, wherein the solvent is selected from the group consisting of ethyleneglycol monomethylethyl, ethyleneglycol monoethylether, ethyleneglycol monomethylether, ethyleneglycol monoacetate, diethyleneglycol, diethyleneglycol monoethylether, propyleneglycol monomethyletheracetate, propyleneglycol, propyleneglycol monoacetate, toluene, xylene, methyl ethyl ketone, methyl isoamil ketone, cy- clohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate, ethyl ethoxy propionate, N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone, 3-ethoxy ethyl propionate, 2-heptanone, gamma-butyrolactone, 2-hydroxypropion ethyl, 2-hydroxy-2-methyl propionic acid ethyl ester, ethoxy acetic acid ethyl ester, hydroxy acetic acid ethyl ester, 2-hydroxy-3-methyl butanoic acid methyl ester, 3-methoxy-2-methyl propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, 3-methoxy-2-methyl propionic acid ethyl ester, ethyl acetate, butyl acetate and the mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2004-0033620 | 2004-05-12 | ||
| KR1020040033620A KR20050108277A (en) | 2004-05-12 | 2004-05-12 | Photoactive monomer, photosensitive polymer and chemically amplified photoresist composition including the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005109102A1 true WO2005109102A1 (en) | 2005-11-17 |
Family
ID=35320361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2005/001370 WO2005109102A1 (en) | 2004-05-12 | 2005-05-11 | Photoactive monomer, photosensitive polymer and chemically amplified photoresist composition including the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20050108277A (en) |
| TW (1) | TWI356053B (en) |
| WO (1) | WO2005109102A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1830227A1 (en) * | 2004-12-20 | 2007-09-05 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition for liquid immersion exposure and method for resist pattern formation |
| US7629106B2 (en) * | 2005-11-16 | 2009-12-08 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process using the same |
| US7776505B2 (en) * | 2001-11-05 | 2010-08-17 | The University Of North Carolina At Charlotte | High resolution resists for next generation lithographies |
| EP2584409A1 (en) * | 2010-06-15 | 2013-04-24 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, resist pattern formation method, polymeric compound, and compound |
| US8685616B2 (en) | 2008-06-10 | 2014-04-01 | University Of North Carolina At Charlotte | Photoacid generators and lithographic resists comprising the same |
| JP2017146521A (en) * | 2016-02-19 | 2017-08-24 | 信越化学工業株式会社 | Positive resist material, and pattern forming method |
| JP2018043976A (en) * | 2016-09-07 | 2018-03-22 | 住友化学株式会社 | Salt, acid generator, resin, resist composition, and method for producing resist pattern |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101308695B1 (en) * | 2006-07-10 | 2013-09-13 | 주식회사 동진쎄미켐 | Acid amplifier and photosensitive polymer including the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482567B1 (en) * | 2000-08-25 | 2002-11-19 | Shipley Company, L.L.C. | Oxime sulfonate and N-oxyimidosulfonate photoacid generators and photoresists comprising same |
| US6664022B1 (en) * | 2000-08-25 | 2003-12-16 | Shipley Company, L.L.C. | Photoacid generators and photoresists comprising same |
| US6692893B2 (en) * | 2000-10-23 | 2004-02-17 | Shin-Etsu Chemical Co., Ltd. | Onium salts, photoacid generators, resist compositions, and patterning process |
| US6713612B2 (en) * | 2002-05-01 | 2004-03-30 | Shin-Etsu Chemical Co., Ltd. | Sulfonyldiazomethanes, photoacid generators, resist compositions, and patterning process |
-
2004
- 2004-05-12 KR KR1020040033620A patent/KR20050108277A/en not_active Application Discontinuation
-
2005
- 2005-05-11 TW TW094115277A patent/TWI356053B/en not_active IP Right Cessation
- 2005-05-11 WO PCT/KR2005/001370 patent/WO2005109102A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482567B1 (en) * | 2000-08-25 | 2002-11-19 | Shipley Company, L.L.C. | Oxime sulfonate and N-oxyimidosulfonate photoacid generators and photoresists comprising same |
| US6664022B1 (en) * | 2000-08-25 | 2003-12-16 | Shipley Company, L.L.C. | Photoacid generators and photoresists comprising same |
| US6692893B2 (en) * | 2000-10-23 | 2004-02-17 | Shin-Etsu Chemical Co., Ltd. | Onium salts, photoacid generators, resist compositions, and patterning process |
| US6713612B2 (en) * | 2002-05-01 | 2004-03-30 | Shin-Etsu Chemical Co., Ltd. | Sulfonyldiazomethanes, photoacid generators, resist compositions, and patterning process |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776505B2 (en) * | 2001-11-05 | 2010-08-17 | The University Of North Carolina At Charlotte | High resolution resists for next generation lithographies |
| EP1830227A1 (en) * | 2004-12-20 | 2007-09-05 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition for liquid immersion exposure and method for resist pattern formation |
| EP1830227A4 (en) * | 2004-12-20 | 2008-12-31 | Tokyo Ohka Kogyo Co Ltd | Resist composition for liquid immersion exposure and method for resist pattern formation |
| US7629106B2 (en) * | 2005-11-16 | 2009-12-08 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process using the same |
| US8685616B2 (en) | 2008-06-10 | 2014-04-01 | University Of North Carolina At Charlotte | Photoacid generators and lithographic resists comprising the same |
| US10310375B2 (en) | 2008-06-10 | 2019-06-04 | University Of North Carolina At Charlotte | Photoacid generators and lithographic resists comprising the same |
| EP2584409A1 (en) * | 2010-06-15 | 2013-04-24 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, resist pattern formation method, polymeric compound, and compound |
| EP2584409A4 (en) * | 2010-06-15 | 2014-03-12 | Tokyo Ohka Kogyo Co Ltd | Resist composition, resist pattern formation method, polymeric compound, and compound |
| US9023581B2 (en) | 2010-06-15 | 2015-05-05 | Tokyo Ohka Kogyo Co., Ltd | Resist composition, method of forming resist pattern, polymeric compound, and compound |
| JP2017146521A (en) * | 2016-02-19 | 2017-08-24 | 信越化学工業株式会社 | Positive resist material, and pattern forming method |
| JP2018043976A (en) * | 2016-09-07 | 2018-03-22 | 住友化学株式会社 | Salt, acid generator, resin, resist composition, and method for producing resist pattern |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI356053B (en) | 2012-01-11 |
| KR20050108277A (en) | 2005-11-16 |
| TW200536825A (en) | 2005-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3749674B2 (en) | Resist composition comprising photosensitive polymer containing lactone in backbone | |
| JP4205078B2 (en) | Positive resist composition and resist pattern forming method | |
| WO2005109102A1 (en) | Photoactive monomer, photosensitive polymer and chemically amplified photoresist composition including the same | |
| KR20010062537A (en) | Chemically amplified positive resist composition | |
| US6517990B1 (en) | Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same | |
| KR100413756B1 (en) | Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition comprising the same | |
| KR101378765B1 (en) | Monomer for photoresist having photoacid generator, polymer thereof and photoresist composition including the same | |
| KR100881304B1 (en) | Positive resist composition and method for forming resist pattern | |
| JP3990150B2 (en) | Photosensitive polymer and resist composition in which phenyl ring and lactone group coexist | |
| KR20040039731A (en) | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same | |
| KR20030017947A (en) | Photosensitive Polymer and Photoresist Composition Containing the Same | |
| KR101207446B1 (en) | Polymer for photoresist and photoresist composition including the same | |
| KR100944727B1 (en) | Photoacid-labile polymers and photoresists comprising same | |
| KR20030087190A (en) | Photosensitive polymer and resist composition comprising the same | |
| US20040157151A1 (en) | Photosensitive polymer including fluorine, resist composition containing the same and patterning method using the resist composition | |
| KR100557553B1 (en) | Photoresist monomer, polymer thereof and photoresist composition containing it | |
| KR101207444B1 (en) | Photoresist monomer, polymer thereof and photoresist composition including the same | |
| JP4611813B2 (en) | Positive resist composition and resist pattern forming method | |
| KR101439951B1 (en) | Monomer for photoresist including sulfonyl group, polymer thereof and photoresist composition including the same | |
| US20030224289A1 (en) | Photosensitive polymers and resist compositions containing the same | |
| KR20060083581A (en) | Polymer for chemically amplified photoresist and chemically amplified photoresist composition including the same | |
| KR100505635B1 (en) | Polymer having butadiene sulfone repeating unit and resist composition comprising the same | |
| KR20040039118A (en) | Chemically amplified polymer having pendant group with cyclododecyl and resist composition comprising the same | |
| KR20050094723A (en) | Photoresist polymer and photoresist composition containing it | |
| KR20040039732A (en) | Chemically amplified polymer having pendant group with camphoryl and resist composition comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
| 122 | Ep: pct application non-entry in european phase |