TWI465417B - 光酸產生劑及含該光酸產生劑之光阻劑 - Google Patents
光酸產生劑及含該光酸產生劑之光阻劑 Download PDFInfo
- Publication number
- TWI465417B TWI465417B TW100114602A TW100114602A TWI465417B TW I465417 B TWI465417 B TW I465417B TW 100114602 A TW100114602 A TW 100114602A TW 100114602 A TW100114602 A TW 100114602A TW I465417 B TWI465417 B TW I465417B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- photoresist
- optionally substituted
- photoacid generator
- photoacid
- Prior art date
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 55
- 239000000203 mixture Substances 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 28
- -1 iodonium cation Chemical class 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 4
- 125000002837 carbocyclic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000006413 ring segment Chemical group 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 238000010511 deprotection reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000007787 solid Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 9
- 229920003270 Cymel® Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000001624 naphthyl group Chemical group 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000004060 quinone imines Chemical class 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 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
- 125000005250 alkyl acrylate group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 4
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 3
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000254173 Coleoptera Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000004452 carbocyclyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- CGDXUTMWWHKMOE-UHFFFAOYSA-M difluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)F CGDXUTMWWHKMOE-UHFFFAOYSA-M 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000005415 substituted alkoxy group Chemical group 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 3
- OOIBFPKQHULHSQ-UHFFFAOYSA-N (3-hydroxy-1-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2(O)CC1(OC(=O)C(=C)C)C3 OOIBFPKQHULHSQ-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 241001446467 Mama Species 0.000 description 2
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- XVAIDCNLVLTVFM-UHFFFAOYSA-N methacetin Chemical compound COC1=CC=C(NC(C)=O)C=C1 XVAIDCNLVLTVFM-UHFFFAOYSA-N 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- XSQIGJCTPAJWQT-UHFFFAOYSA-M sodium;1,1-difluoro-2-hydroxy-2-oxoethanesulfonate Chemical compound [Na+].OS(=O)(=O)C(F)(F)C([O-])=O XSQIGJCTPAJWQT-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 239000012953 triphenylsulfonium Substances 0.000 description 2
- 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
- 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
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-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
- FEEJSMGPZFACMW-UHFFFAOYSA-N 1-methyladamantane;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.C1C(C2)CC3CC2CC1(C)C3 FEEJSMGPZFACMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 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
- HDBQZGJWHMCXIL-UHFFFAOYSA-N 3,7-dihydropurine-2-thione Chemical compound SC1=NC=C2NC=NC2=N1 HDBQZGJWHMCXIL-UHFFFAOYSA-N 0.000 description 1
- NFGPNZVXBBBZNF-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(N)C=C1 NFGPNZVXBBBZNF-UHFFFAOYSA-N 0.000 description 1
- FUDDLSHBRSNCBV-UHFFFAOYSA-N 4-hydroxyoxolan-2-one Chemical compound OC1COC(=O)C1 FUDDLSHBRSNCBV-UHFFFAOYSA-N 0.000 description 1
- ZHBMGKRWRNEMOQ-UHFFFAOYSA-N 4-methylbenzenesulfonate;piperidin-1-ium Chemical compound C1CCNCC1.CC1=CC=C(S(O)(=O)=O)C=C1 ZHBMGKRWRNEMOQ-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003943 azolyl group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000994 contrast dye Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UMIJUNPUFYIHJW-UHFFFAOYSA-N dicyclohexylazanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1[NH2+]C1CCCCC1 UMIJUNPUFYIHJW-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-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
- 238000005530 etching Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- GQJCAQADCPTHKN-UHFFFAOYSA-N methyl 2,2-difluoro-2-fluorosulfonylacetate Chemical compound COC(=O)C(F)(F)S(F)(=O)=O GQJCAQADCPTHKN-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical group O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 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 1
- PWQLFIKTGRINFF-UHFFFAOYSA-N tert-butyl 4-hydroxypiperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(O)CC1 PWQLFIKTGRINFF-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
- C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- 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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本發明係關於新穎之光酸產生劑化合物(PAG)及包含此等PAG化合物之光阻劑組成物。具體地,本發明係關於包含結構-C(=O)N<之部份(如內醯胺、醯胺或醯亞胺)的離子性PAG。較佳之光酸產生劑係鹽類,其中,陰離子成份係包含結構C(=O)N<之部份(如內醯胺、醯胺或醯亞胺)。
光阻劑為用於將影像轉移至基板之光敏膜。他們形成負影像或正影像。將光阻劑塗佈於基板上後,該塗層係通過經圖案化之光罩曝光於活化能量源如紫外光,以在該光阻劑塗層中形成潛像。該光罩具有該活化輻射不可穿透之區域以及該活化輻射可穿透之區域,其定義待轉移至下方基板之所欲之影像。
已知之光阻劑可提供具有足以用於多數現存商業應用之解析度及尺寸的特徵。然而對於多數其他應用,對於能提供低於微米(submicron)之維度之高度解析影像的新光阻劑存在需要。
業經作出多種嘗試以改變光阻劑組成物之組成,以改善官能性質的表現。相較於其他事務,尤其是業經報導用於光阻劑組成物中之多種光活性(photoactive)化合物。參見美國專利第6,664,022號及第6,849,374號。
於一態樣中,本發明係提供新穎光酸產生劑化合物(PAG),其係包含結構-C(=O)N<之氮系官能成份(nitrogen-base functional component)。較佳地,此等部份(moiety)的功能係作為氫鍵受體。如本文所使用者,關於結構-C(=O)N<,該氮之價態(亦即<)係表示分離之鏈結,其可獨立鏈結至氫或非氫取代基。
於一較佳態樣中,本發明之光酸產生劑化合物係包含非環狀醯胺部份。
於另一較佳態樣中,本發明之光酸產生劑化合物係包含內醯胺部份。
於另一較佳態樣中,本發明之光酸產生劑化合物係包含醯亞胺(imide)部份。
於一特佳態樣中,光酸產生劑化合物係包含陰離子成分,該陰離子成分係包含結構-C(=O)N<,如內醯胺、醯胺或醯亞胺。例如,較佳之陰離子成分係包含磺酸(SO3 -
)基,該磺酸基可具有視需要經取代之烷基取代(亦即,經結構-C(=O)N<取代之氟烷基),該結構-C(=O)N<例如為內醯胺或非環狀醯胺或醯亞胺。
本發明之光酸產生劑化合物之較佳內醯胺部份係包括,如哌啶酮基(piperidinonyl)及吡咯啶酮基(pyrrolidinonyl)。
於另一態樣中,係提供光阻劑組成物,其係包含一種或多種本文所揭露之光酸產生劑化合物。較佳地,光阻劑組成物係包含一種或多種可與-C(=O)N<PAG結構氫鍵鍵合或錯合的成份。例如,較佳係包含具有丙烯酸單元之樹脂成份(該丙烯酸單元可自光酸誘導之去保護反應而得)的光阻劑組成物。此等酸性基可與-C(=O)N<PAG結構氫鍵鍵合。
非欲受縛於理論,咸信本發明之PAG可最小化非所欲之光酸擴散進入未經曝光之光阻劑區域。亦即,具有鹼性-C(=O)N<結構之光酸產生之酸可與阻劑之光酸不穩定成份之酸性基(如經去保護之羧酸基)錯合。該PAG之此錯合可有效地將經活化之PAG定位並限制於經曝光之阻劑區域,以及大大地阻止非所欲之光酸擴散進入未經經曝光之阻劑區域。
此外,仍非欲受縛於任何理論,存在於未經曝光區域內的未經活化之本發明之具有鹼性-C(=O)N<結構之光酸產生劑化合物可作為有效之粹滅劑分子,並限制光產生之酸向未經曝光之阻劑區域中的擴散性遷移。有差別地,於經曝光之光阻劑區域中,儘管具有鹼性-C(=O)N<部份,該光活化之PAG的酸性有效地活化該阻劑。
因此,作為若干獨立現象之結果,本發明之PAG可對經曝光與未經曝光之光阻劑組成物層區域之間賦予提升之對比度及解析度。
本發明之PAG可適當地用於正作用或負作用化學增幅型光阻劑中,亦即,負作用阻劑組成物,其進行光酸促進之交聯反應以使得該阻劑塗層之經曝光區域於顯影劑中的溶解度小於未經曝光之區域;以及正作用阻劑組成物,其進行光酸促進之一種或多種組成物成份之酸不穩定基(acid-labile group)的去保護反應,以使得該阻劑塗層之經曝光之區域於水性顯影劑中的溶解度大於未經曝光之區域。含有共價鏈結至該酯之羧基氧之三級非環烷基碳或三級脂環碳的酯基通常係本發明之光阻劑中所採用樹脂之較佳光酸不穩定基。縮醛基亦係適當之光酸不穩定基。
本發明之光阻劑的較佳成像波長係包括低於300奈米(sub-300 nm)之波長,如248 nm,以及低於200 nm之波長,如193 nm及EUV。
本發明之特佳光阻劑係含有成像有效量之一種或多種本文所揭示之PAG以及選自下述所組成群組之樹脂:
1)含有能提供特別適用於在248 nm成像之化學增幅型正阻劑的酸不穩定基之酚系樹脂(phenolic resin)。特佳之此類樹脂係包括:i)含有乙烯基酚及丙烯酸烷基酯之聚合單元的聚合物,其中該經聚合之丙烯酸烷基酯單元能於光酸之存在下進行去封阻反應(deblocking reaction)。能進行光酸誘導之去封阻反應的例示性丙烯酸烷基酯係包括諸如丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸甲基金剛烷基酯、甲基丙烯酸甲基金剛烷基酯、以及其他能進行光酸誘導反應之丙烯酸非環狀烷基酯及丙烯酸脂環族酯,如藉由引用併入本文之美國專利案第6,042,997號及第5,492,793號中所揭示之聚合物;ii)含有下述聚合單元之聚合物:乙烯基酚、不含羥基或羧基環取代基之視需要經取代之乙烯基苯基(如苯乙烯)、以及丙烯酸烷基酯如上揭聚合物i)所揭示之該等去封阻基,如藉由引用併入本文之美國專利案第6,042,997號所揭示之聚合物;以及iii)含有下述重複單元之聚合物:包含將與光酸反應之縮醛或縮酮部分的重複單元、以及視需要之芳族重複單元如苯基或酚系基;
2)能提供特別適用於在低於200 nm之波長如193 nm成像之化學增幅型正阻劑的實質上或完全不含苯基或其他芳族基之樹脂。特佳之此類樹脂係包括:i)含有非芳族環狀烯烴(內環雙鍵)之聚合單元(如視需要經取代之降莰烯)的聚合物,如藉由引用併入本文之美國專利案第5,843,624號中所揭示之聚合物;ii)含有丙烯酸烷基酯單元如丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸甲基金剛烷基酯、甲基丙烯酸甲基金剛烷基酯、以及其他丙烯酸非環狀烷基酯及丙烯酸脂環族酯的聚合物;此等聚合物已經於美國專利案第6,057,083號中揭示之。
本發明之阻劑亦可包含區別(distinct)PAG的混合物,典型係2種或3種不同PAG之混合物,更典型由總計2種區別PAG所組成的混合物。
本發明亦提供形成本發明之光阻劑之浮雕影像的方法,包括用以形成低於0.25微米維度或更低,如低於0.2微米維度或低於0.1微米維度之高度解析圖案化光阻劑影像(如具有本質上豎直之側壁的經圖案化之線)的方法。
本發明進一步提供包含基板之製造件,如其上塗佈有本發明之光阻劑及浮雕影像之微電子晶圓或平板顯示器基板。本發明之其他態樣係揭露如下。
如上所述,本發明係提供光酸產生劑化合物(PAG),其係包含結構-C(=O)N<之氮系官能成份。
如上所述,如本文所使用者,關於結構-C(=O)N<,該氮之價態(亦即<)係表示分離之鏈結,其可獨立鏈結至氫或非氫取代基;以及該羰基價態(亦即-C(=O)N<)係鏈結至該PAG化合物之剩餘部份(balance)。因此,該結構-C(=O)N<可用-C(=O)N(R)(R1
)表示,其中,R及R1
係相同或不同,且可係氫或非氫取代基,如視需要經取代之烷基,包括視需要經取代之C1-30
烷基;視需要經取代之包括C3-30
環烷基;視需要經取代之烷氧基,包括視需要經取代之C1-30
烷氧基;視需要經取代之碳環基,包括C6-30
碳環基;視需要經取代之雜脂環基,包括含有1個、2個或3個N、O及/或S環原子之C3-30
雜脂環基;等。
本發明之特佳之PAG係包含:1)SO3 -
部份;2)結構-C(=O)N<;以及3)一個或多個氟化之碳(如,一個或多個-CF2
-、-CHF-)。於某些較佳態樣中,該氟化之碳中的一個或多個係直接或間接地經酯酮基(如-C(=O)OR,其中,R係氫或較佳為非氫取代基)及/或該結構-C(=O)N<取代。該氟化之碳係間接地經酯酮基(如-C(=O)OR)及/或-C(=O)N<取代,其中,未氟化之碳及/或雜原子係插置於該氟化之碳與該酯酮基之間;以及該氟化之碳係直接地經酯酮基(如-C(=O)OR)及/或該-C(=O)N<取代,其中,沒有未氟化之碳及/或雜原子插置於該氟化之碳與該酯酮基之間。於多數態樣中,較佳係氟化之碳係間接地經酯酮基及/或-C(=O)N<取代。
於特佳之態樣中,較佳係包含(1)酯酮基(如-C(=O)OR,其中,R係如上定義者)及(2)-C(=O)N<兩者之PAG。
於相關但分開之態樣中,較佳係包含一個或多個氟化之碳(包括二氟碳,如-CHF2
-、-CF2
-)之PAG,特別是其中-CF2
-係直接鍵結至SO3 -
部份(如-CF2
-SO3 -
)者。
本發明之特佳之光酸產生劑化合物係包含下式(I)之結構:
RO(C=O)(CXY)p
(CF2
)n
SO3 -
M+
(I)
其中,R係包含結構-C(=O)N(R1
)(R2
)之基的非氫取代基,其中,R1
及R2
係個別相同或不同,且可為氫或非氫取代基,如視需要經取代之烷基,包括視需要經取代之C1-30
烷基;視需要及取代之包括C3-30
環烷基;視需要經取代之烷氧基,包括視需要經取代之C1-30
烷氧基;視需要經取代之碳環基,包括C6-30
碳環基;視需要經取代之雜脂環基,包括含有1個、2個或3個N、O及/或S環原子之C3-30
雜脂環基;等,其中,較佳係R1
與R2
之一者或兩者為非氫者,或R1
及R2
可與該氮一起形成環,如內醯胺結構,如視需要經取代之哌啶酮基部份或視需要經取代之吡咯啶酮部份,或醯亞胺或醯胺結構;
X及Y係個別獨立為氫或非氫取代基,如鹵基(特別是氟基)、氰基、硝基,或如上文詳述之R之非氫取代基;
p為0或正整數,較佳p係1、2或3;
n為正整數,較佳係1、2或3,更佳係1或2;以及
M+
係相對離子,較佳係有機鎓鹽成份,如硫鎓(sulfonium)或碘鎓(iodonium)陽離子成份,特別是經三取代之硫鎓陽離子或經二取代之碘鎓陽離子。
於上式(I)中,適當地,一個或多個(如1個至10個)碳原子或雜原子係插置於該-C(=O)N(R1
)(R2
)基與O(C=O)(CXY)p
(CF2
)n
SO3 -
M+
之間,亦即,式(I)之R基可係-(CXY)1-10
C(=O)N(R1
)(R2
),其中,X及Y係個別獨立為氫或非氫取代基,如鹵基(特別是氟基)、氰基、硝基,或如上文詳述之式(I)之R之非氫取代基。
於某些態樣中,本發明之較佳陰離子性PAG之陰離子成份可包含下式(I)至(XV)之一結構:
其中,於式(I)至(XV)各者中,
m、n、o、p、q係獨立為0至10之整數;
R1
係選自下述(A)、(B)、(C)、(D)、(E)或(F)之一者:
其中,
R2
及R3
係獨立為分支鏈、非分支鏈或環狀脂肪族基,如視需要經取代之烷基,包括視需要經取代之C1-30
烷基;視需要經取代之包括C3-30
環烷基;視需要經取代之烷氧基,包括視需要經取代之C1-30
烷氧基;視需要經取代之碳環基,包括C6-30
碳環基;視需要經取代之雜脂環基,包括含有1個、2個或3個N、O及/或S環原子之C3-30
雜脂環基;
q及r係獨立為0至10之整數;以及
s係1至10之正整數。
此等式(I)至(XV)陰離子成份係適當地與相對陽離子(如對於上揭M+所討論者)錯合,亦即,與有機鎓鹽成份(如硫鎓或碘鎓陽離子成份,特別是經三取代之硫鎓陽離子或經二取代之碘鎓陽離子)錯合。
如本文上揭所稱者,本發明之PAG之各種取代基可視需要經取代。經取代之部份係適當地於一個或多個可用位置經諸如下列取代:鹵素如F、Cl、Br及/或I;硝基;氰基;磺醯基(sulfono);烷基,包括C1-16
烷基,且C1-8
烷基係較佳者;鹵烷基,如氟烷基(如三氟甲基)及全鹵烷基如全氟C1-4
烷基;烷氧基,包括具有一個或多個氧鏈結之C1-16
烷氧基,且C1-8
烷氧基係較佳者;烯基,包括C2-12
烯基,且C2-8
烯基係較佳者;烯基,包括C2-12
烯基,且C2-8
炔基係較佳者;芳基,如苯基或萘基;以及經取代之芳基,如經鹵基、烷氧基、烯基、炔基及/或烷基取代之芳基,較佳經取代之芳基的取代基係具有上揭用於相應基之碳原子數目者。較佳之經取代之芳基係包括經取代之苯基、蒽基及萘基。
如本文所使用者,本發明之PAG化合物的烷氧基係具有一個或多個氧鏈結,典型1個至約5或6個氧鏈結。如本文所使用者,碳環芳基係指代具有1個至3個分開或稠合之環以及6個至約18個碳環成員的非雜芳族基,且可包括,例如苯基、萘基、聯苯基、二氫苊基(acenaphthyl)、菲基等。苯基及萘基往往為較佳者。適當之雜芳族基或雜芳基將具有1個至3個環,每一環中具有3個至8個環成員,以及1個至約3個雜原子(N、O或S)。具體適當之雜芳族基或雜芳基係包括,例如香豆素基(courmarinyl)、喹啉基、吡啶基、吡基、嘧啶基、呋喃基、吡咯基、噻吩基、噻唑基、唑基、咪唑基、吲哚基、苯并呋喃基及苯并噻唑基。
本發明之光酸產生劑化合物可容易地製備。例示性合成係於後文之實施例中詳述。例如,可使用鹼處理包含酸部份(如磺酸部份)之化合物,隨後將之與包含結構-C(=O)N<之化合物(如內醯胺、醯胺或醯亞胺)偶合。隨後,包含酸及結構-C(=O)N<兩者之偶合化合物可為酸性,並與相對離子如硫鎓或碘鎓陽離子結合。本發明之特佳之PAG之合成係於下文之實施例1中詳述之。
如上所述,本發明之PAG可作為放射敏感性成份用於光阻劑組成物中,包括正作用及負作用化學增幅型阻劑組成物兩者。
本發明之光阻劑典型係包含樹脂黏合劑(binder)及上揭之本發明之光活性成份。較佳地,該樹脂黏合劑係具有官能基,該官能基能對該阻劑組成物賦予鹼性水性顯影劑之可顯影性。舉例而言,較佳係包含極性官能基如羥基或羧酸根基(carboxylate)的樹脂黏合劑。較佳地,該樹脂黏合劑係以足以使得該阻劑可用鹼性水溶液顯影的量用於阻劑組成物中。
較佳地,本發明之光酸產生劑化合物係用於化學增幅型正作用阻劑中。業經揭示大量之此種阻劑組成物,如於美國專利第4,968,581號;第4,883,740號;第4,810,613號及第4,491,628號中以及加拿大專利申請案第2,001,384中揭露者,上述專利全部藉由引用其之製作及使用化學增幅型正作用阻劑之教示而併入本文。根據本發明,彼等先前技術之阻劑組成物係藉由改以本發明之光活性成份替代作為輻射敏感性成份而予以修改。
本發明之PAG也較佳地與含有一個或多個光酸不穩定基以及實質上、本質上或完全不含苯基的聚合物組合使用。此等光阻劑組成物特別有用於以低於200 nm之輻射,如193 nm之輻射成像。
舉例而言,較佳之聚合物係含有低於約10或5莫耳%或重量%之芳族基,更佳低於約1或2莫耳%或重量%之芳族基,更佳低於約0.1、0.02、0.04及0.08莫耳%或重量%之芳族基,再更佳低於約0.01莫耳%或重量%之芳族基。特佳之聚合物係完全不含芳族基。芳族基可高度吸收低於200 nm之輻射,並因此對於在此種短波長輻射下成像之光阻劑中的用途係非所欲者。於某些較佳態樣中,該光阻劑聚合物可含有低於約10或5莫耳%之除了萘基之外(特別是除了羥基萘基之外)之芳族基,更佳低於約1或2莫耳%之除了萘基之外(特別是除了羥基萘基之外)之芳族基。於此等較佳之系統中,該光阻劑聚合物可包含顯著量之萘基(特別是羥基萘基),如,至少1、5、10、15、20、25、30、35、40、45或50莫耳%或重量%之該聚合物係由萘基(特別是羥基萘基)組成。
實質上或完全不含芳族基且可與本發明之PAG共同配製以提供用於在低於200 nm成像之光阻劑的適當聚合物,係於Shipley Company之歐洲申請案第EP930542A1號中揭露。
實質上或完全不含芳族基之適當聚合物係適當地含有丙烯酸酯單元,如光酸不穩定丙烯酸酯單元,如可藉由丙烯酸甲基金剛烷基酯、甲基丙烯酸甲基金剛烷基酯、丙烯酸乙基葑基酯、甲基丙烯酸乙基葑基酯等之聚合反應所提供;稠合之非芳族脂環族基,例如可藉由降莰烯化合物或其他具有內環碳-碳雙鍵之脂環族化合物的聚合反應所提供;酸酐,例如可藉由馬來酸酐之聚合反應所提供;等。
本發明之較佳之負作用組成物係包含在暴露於酸後將固化、交聯或硬化之材料的混合物,以及本發明之光活性成份。
特佳之負作用組成物係包含樹脂黏合劑如酚系樹脂,交聯劑成份以及本發明之光活性成份。此等組成物及其用途業已於Thackeray等人之歐洲專利申請案第0164248號及第0232972號以及美國專利案第5,128,232號中揭露。用作該樹脂黏合劑成份之較佳酚系樹脂係包括酚醛樹脂(novolak)及聚(乙烯基酚),如彼等上揭者。較佳之交聯劑係包括胺系材料,包括三聚氰胺、乙炔脲(glycoluril)、苯胍胺(benzoguanamine)系材料及脲系材料。三聚氰胺-甲醛樹脂通常為最佳者。此等交聯劑為市售可得者,例如:美國氰胺公司(American Cyanamid)販售之商品名為Cymel 300、Cymel 301及Cymel 303之三聚氰胺樹脂。美國氰胺公司販售之商品名為Cymel 1170、Cymel 1171、Cymel 1172之乙炔脲樹脂;以商品名Beetle 60、Beetle 65及Beetle 80販售之脲系樹脂;以及以商品名Cymel 1123及Cymel 1125販售之苯胍胺樹脂。
本發明之光阻劑亦可含有其他材料。舉例而言,其他視需要之添加劑包括光化及對比染料、抗條紋劑(anti-striation agent)、塑化劑、加速劑及敏化劑等。除了填料及染料可以相對大濃度(例如,為阻劑乾燥成份之總重量的5至30重量%)存在外,此等視需要之添加劑典型將以較小濃度存在於光阻劑組成物中。
本發明之阻劑之較佳之視需要添加劑係添加鹼(added base)。特別是氫氧化四丁基銨(TBAH),其可提升經顯影之阻劑浮雕影像的解析度。該添加鹼係適當地以相對小量使用,例如,相對於該PAG,約1至10重量%,更典型1至約5重量%。其他較佳之鹼性添加劑係包括磺酸銨鹽,如對甲苯磺酸哌啶鎓及對甲苯磺酸二環己基銨;烷基胺類如三丙胺及十二烷基胺;芳基胺類如二苯基胺、三苯基胺、胺基酚、2-(4-胺基苯基)-2-(4-羥基苯基)丙烷;等。
本發明之阻劑的樹脂黏合劑成份典型係以足以用例如鹼性水溶液將經曝光之該阻劑塗層顯影的量使用。更特定言之,樹脂黏合劑將適宜地包含該阻劑總固體之50至約90重量%。該光活性成份應以足以於該阻劑之塗層中產生潛像(latent image)之量存在。更具體而言,該光活性成份將適宜地以阻劑之總固體的約1至40重量%的量存在。典型地,較少量之該光活性成份將適用於化學增幅型阻劑。
除了使用本發明之PAG替代先前技術之光阻劑配方中的光活性化合物之外,本發明之光阻劑通常係藉由下列已知方法製備。舉例而言,本發明之阻劑可藉由將光阻劑之成份溶解於適宜溶劑中而製備為塗佈組成物,該溶劑為諸如二醇醚如2-甲氧基乙基醚(二甘二甲醚)、乙二醇單甲醚、丙二醇單甲醚;乳酸酯如乳酸乙酯或乳酸甲酯,其中乳酸乙酯為較佳者;丙酸酯,尤其是丙酸甲酯及丙酸乙酯;賽路蘇酯(Cellosolve ester)如乙酸甲賽路蘇酯;芳族烴如甲苯或二甲苯;或酮如甲基乙基酮、環己酮及2-庚酮。該光阻劑之固體含量典型係於該光阻劑組成物之總重量的5至35重量%間變化。
可根據已知過程使用本發明之光阻劑。儘管本發明之光阻劑可作為乾燥膜施加,他們較佳係作為液體塗佈組成物而施加於基板上,藉由加熱乾燥以移除溶劑,較佳直至該塗層無黏性,透過光罩曝光於活化輻射,視需要進行曝光後烘烤以創製或提升該阻劑塗層之經曝光區域與未經曝光區域之間的溶解度差異,隨後,較佳以水性鹼性顯影劑顯影以形成浮雕影像。其上施加有本發明之阻劑並經適當加工的基板可為用於涉及光阻劑之製程中的任何基板,如微電子晶圓。舉例而言,該基板可係矽、二氧化矽或鋁-氧化鋁微電子晶圓。也可使用砷化鎵、陶瓷、石英或銅基板。亦可適當地採用液晶顯示器及其他平板顯示器用之基板,如玻璃基板、塗覆有氧化銦錫之基板等。藉由任何標準手段如旋塗、浸塗或輥塗將液體塗佈阻劑組成物施加至基板上。曝光能量應足以有效地活化該輻射敏感性系統之光活性成份,以於該阻劑塗層中產生經圖案化之影像。適當之曝光能量典型係約1至300毫焦耳(mJ)/平方公分(cm2
)。如上所述,較佳之曝光波長係包括低於200 nm者,如193 nm。適當之曝光後烘烤溫度係約50℃或更高,更具體為約50℃至140℃。對於酸硬化負作用阻劑,若必要,可於約100℃至150℃之溫度進行幾分鐘或更長時間之顯影後烘烤,以進一步固化於顯影後所形成之浮雕影像。顯影及任何顯影後固化之後,隨後可選擇性地加工藉由顯影而裸露之基板表面,舉例而言,根據該技術領域中已知之過程化學刻蝕或鍍覆不覆蓋光阻劑之基板區域。適當之刻蝕劑係包括氫氟酸刻蝕溶液及電漿氣體刻蝕劑如氧電漿刻蝕劑。
下述非限制性實施例係例示性說明本發明。
方案1
標題化合物(1-N-吡咯啶酮基甲氧基羰基)二氟甲磺酸三苯基硫鎓鹽係如上揭方案1及下文中揭示者製備之:將氫氧化鈉(6.400公克(g),160毫莫耳(mmol))置於配備冷凝器之100毫升(mL)圓底燒瓶中,加入30 mL水。將該懸浮液磁力攪拌30分鐘之後,以冰浴冷卻至0℃。於15分鐘內滴加2,2-二氟-2-(氟磺醯基)乙酸甲酯(9.605 g,50 mmol)。完成該加入之後,將該混合物於回流下攪拌18小時。過了這時間之後,將該混合物冷卻至室溫,於布氏漏斗上過濾以移除鹽,以HCl水溶液將濾液酸化至pH=2。隨後於55℃減壓下移除水,以給出羧基二氟甲磺酸鈉之無色油。假設轉化率為100%實施下一步驟。13
C NMR(125 MHz,D2
O)δ113.69(t),165.53;19
F NMR(282 MHz,D2
O)δ-108.83。
將自前一步驟獲得之羧基二氟甲磺酸鈉、1-(2-羥基乙基)吡咯啶-2-酮(9.687 g,75 mmol)、對甲苯磺酸單水合物(19.020 g,100 mmoO)及氯化鈉(8.766 g,150 mmol)置於配備冷凝器及磁力攪拌器之250 mL三頸圓底燒瓶中。加入甲苯(200 mL)及水(12.5 mL),於強回流下將該懸浮液快速攪拌2小時。隨後,將迪恩-斯托普收集器(Dean-Starck trap)置於該燒瓶與冷凝器之間,並將該懸浮液於強回流下攪拌過夜。過了這時間之後,使該懸浮液來到室溫,於布氏漏斗上濾除固體,以甲苯洗滌並通風乾燥。將該固體懸浮於乙腈(100 mL)中,於室溫攪拌30分鐘,於布氏漏斗上濾除不溶物,並以乙腈洗滌。於減壓下將溶劑自該濾液中移除,以給出白色至橙色固體。所獲得之粗中間體產物的19
F NMR表明,這階段之轉化率為79.9%。隨後,將該固體置於250 mL圓底燒瓶中,加入溴化三苯基硫鎓(13.710 g,39.95 mmol)、二氯甲烷(120 mL)及水(120 mL)。將該懸浮液於室溫磁力攪拌過夜。隨後,將該懸浮液置於分液漏斗中,以水(5×100 mL)洗滌有機相。將活性炭(5 g)加入該有機相中,攪拌10分鐘之後濾除固體。以硫酸鎂乾燥該有機相,減壓移除溶劑以給出無色油。以丙酮(20 mL)稀釋該油,並緩慢加入乙酸乙酯(250 mL)。於冰箱中放置3天後,於布氏漏斗上收集白色結晶固體,以冷乙酸乙酯洗滌,通風乾燥,最終於40℃真空乾燥24小時。產率為4.32 g(總產率16%)。1
H NMR(500 MHz,丙酮-d6
):δ7.95(d,6H),7.90(t,3H),7.83(t,6H),4.30(t,2H),3.50(m,4H),2.16(t,2H),1.91(m,2H);13
C NMR(125 MHz,丙酮-d6
):δ172.5,161.8,161.5,135.5,132.4,132.3,126.0,65.3,48.6,41.8,31.0,18.9;19
F NMR(282 MHz,丙酮-d6
):δ-110.3。
如下述者製備標題聚合物,該聚合物係本發明之正作用化學增幅型光阻劑之有用之樹脂成份。
將16.25 g之MAMA、11.80 g之α-GBLMA、11.07 g之ODOTMA及10.92 g之HAMA溶解於48 g之THF中。藉由以氮氣鼓泡20分鐘對該混合物脫氣。將18 g之THF充填入配備冷凝器、氮氣入口及機械攪拌器之500 mL燒瓶中,使該溶液來到67℃。將4.87 g之V601(2,2-偶氮二異丁酸二甲酯,相對於單體,9.15 mol%)溶解於5 g之THF中,並充填入該燒瓶中。將單體溶液以28.57 mL/小時(h)之速率饋入該反應器中。單體之饋入係耗時3小時30分鐘。完成單體之饋入後,將聚合反應混合物於67℃再另外攪拌30分鐘。總計4小時之聚合反應時間(3小時30分鐘饋料,以及30分鐘攪拌)之後,將5 g之THF加入該反應器中,並將該聚合反應混合物冷卻至室溫。於1.5 L之異丙醇中施行沈澱。過濾之後,乾燥所得聚合物,並將其再溶解於96 g之THF’中,於1.9 L之異丙醇中再次沈澱,過濾,於真空烘箱中於45℃乾燥48小時,以給出42.5 g聚合物(Mw=9,255,且Mw/Mn=1.67)。
將2.780 g之上揭實施例2中所形成之聚合物溶解於24.225 g之丙二醇單甲醚乙酸酯(PGMEA)、24.225 g之環己酮以及48.450 g之2-羥基異丁酸甲酯中。將0.281 g之1-((3-羥基金剛烷基)甲氧基羰基)二氟甲磺酸三苯基硫鎓鹽(如可適當於上述實施例1中製備者)、0.035 g之1-(第三丁氧基羰基)-4-羥基哌啶以及0.005 g之PF-656界面活性劑(Omnova Solutions Inc.)加入該混合物中。將所得混合物於輥上滾動6小時,隨後透過具有0.2微米孔徑之鐵氟龍(Teflon)過濾器過濾,從而形成正作用光阻劑組成物。
將2.724 g之上揭實施例3中所形成之聚合物溶解於24.225 g之丙二醇單甲醚乙酸酯(PGMEA)、24.225 g之環己酮以及48.450 g之2-羥基異丁酸甲酯中。將0.281 g之1-((3-羥基金剛烷基)甲氧基羰基)二氟甲磺酸三苯基硫鎓鹽(如可適當於上述實施例1中製備者)、0.056 g之如上述實施例2中製備之(1-吡咯啶酮乙氧基羰基)-二氟甲磺酸三苯基硫鎓鹽(總固體重量之1.806%)、0.035 g之1-(第三丁氧基羰基)-4-羥基哌啶以及0.005 g之PF-656界面活性劑(Omnova Solutions Inc.)加入該混合物中。將所得混合物於輥上滾蹭6小時,隨後透過具有0.2微米孔尺寸之鐵氟龍過濾器過濾,從而形成正作用光阻劑組成物。
於TEL CLEAN TRACKTM
LITHIUSTM
i+塗佈器/顯影器上旋塗有機抗反射塗層於300毫米(mm)矽晶圓上,以形成第一底部抗反射塗層(BARC)。於215℃烘烤該晶圓60秒,得到厚度為75 nm之第一BARC膜。接著,將第二BARC層塗佈於該第一BARC上,於205℃烘烤經塗佈之晶圓60秒,以產生23 nm頂部BARC層。
將上述實施例3及4之光阻劑組成物分開旋塗於雙層BARC之頂部上,於120℃軟烘烤60秒,得到厚度為900埃()之阻劑膜。塗佈有機頂塗層於該阻劑層上,並使用具有1.35數值孔徑及具有X-偏光之二極-35Y照明(0.96外σ/0.76內σ)之ASML TWINSCANTM
XT:1900i浸潤掃描儀透過網線(reticle)曝光於19至59 mJ/cm2
的多種劑量,該網線係具有於80 nm節距(pitch)為40 nm線及空間(lines and spaces,L/S)以及於84 nm節距為42 nm線及空間(L/S)的臨界維度。隨後,於125℃對該晶圓施行曝光後烘烤(PEB)60秒,並使用商購之0.26 N水性鹼性顯影劑顯影12秒。使用Hitachi CG 4000 SEM測量該臨界維度(CD)。
藉由混合下述成份製備本發明之光阻劑,其量係以基於該阻劑組成物之總重的重量百分比表示之:
該樹脂黏合劑係三元聚合物(甲基丙烯酸2-甲基-2-金剛烷基酯/β-羥基-γ-丁內酯甲基丙烯酸酯/甲基丙烯酸氰基降莰基酯)。該光酸產生劑係上述實施例1中之化合物TPS DHC-TFBS。彼等樹脂及PAG成份係混合於該乳酸乙酯溶劑中。
將所配製之阻劑組成物旋塗於HMDS蒸汽打底(vapor primed)之4吋矽晶圓上,通過真空熱板於90℃軟烘烤60秒。透過光罩將該阻劑塗層於193 nm曝光,隨後,於110℃對經曝光之塗層進行曝光後烘烤。隨後,以0.26N氫氧化四丁基銨水溶液處理經塗佈之晶圓,以將成像之阻劑層顯影。
Claims (6)
- 一種光酸產生劑化合物,其係包含下式之結構:RO(C=O)(CXY)p (CF2 )n SO3 - M+ 其中,R係包含結構-C(=O)N(R1 )(R2 )之基的非氫取代基,其中,R1 及R2 係個別相同或不同,且可為氫或非氫取代基;或R1 及R2 可與該氮一起形成環;X及Y係個別獨立為氫或非氫取代基;p為0或正整數;n為正整數;以及M+ 係相對離子。
- 如申請專利範圍第1項所述之光酸產生劑化合物,其中,該光酸產生劑化合物係包含具下式(I)、(II)、(IV)、(V)、(VII)、(VIII)、(X)、(XI)、(XIII)及(XIV)任一者之陰離子成分:
- 如申請專利範圍第2項所述之光酸產生劑化合物,其中,該陽離子成份係與硫鎓或碘鎓陽離子成份錯合。
- 一種光阻劑組成物,係包含樹脂成份及如申請專利範圍第1至3項中任一項所述之光酸產生劑化合物。
- 如申請專利範圍第4項所述之光阻劑組成物,其中,該光阻劑係包含具有在進行光酸誘導之去保護之後會產生羧酸基之光酸不穩定酯基的樹脂。
- 一種形成光阻劑浮雕影像之方法,係包含: a)將如申請專利範圍第4或5項所述之光阻劑組成物之塗層施加至基板上;以及b)將該光阻劑塗層曝光於經圖案化之活化輻射,以及將經曝光之光阻劑層顯影,以提供浮雕影像。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32860810P | 2010-04-27 | 2010-04-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201210998A TW201210998A (en) | 2012-03-16 |
TWI465417B true TWI465417B (zh) | 2014-12-21 |
Family
ID=44454765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW100114602A TWI465417B (zh) | 2010-04-27 | 2011-04-27 | 光酸產生劑及含該光酸產生劑之光阻劑 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8609891B2 (zh) |
EP (1) | EP2383611A3 (zh) |
JP (1) | JP5756672B2 (zh) |
KR (1) | KR101844307B1 (zh) |
CN (1) | CN102344400B (zh) |
TW (1) | TWI465417B (zh) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5969171B2 (ja) * | 2010-03-31 | 2016-08-17 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 光酸発生剤およびこれを含むフォトレジスト |
JP6034025B2 (ja) * | 2011-02-25 | 2016-11-30 | 住友化学株式会社 | レジスト組成物及びレジストパターンの製造方法 |
JP5977560B2 (ja) * | 2011-04-07 | 2016-08-24 | 住友化学株式会社 | レジスト組成物及びレジストパターンの製造方法 |
JP6013218B2 (ja) * | 2012-02-28 | 2016-10-25 | 信越化学工業株式会社 | 酸発生剤、化学増幅型レジスト材料、及びパターン形成方法 |
JP6052283B2 (ja) * | 2012-03-19 | 2016-12-27 | Jsr株式会社 | フォトレジスト組成物 |
TWI527792B (zh) * | 2012-06-26 | 2016-04-01 | 羅門哈斯電子材料有限公司 | 光酸產生劑、含該光酸產生劑之光阻劑及含該光阻劑之經塗覆物件 |
JP6306852B2 (ja) * | 2012-11-09 | 2018-04-04 | 住友化学株式会社 | レジスト組成物及びレジストパターンの製造方法 |
US9383644B2 (en) | 2014-09-18 | 2016-07-05 | Heraeus Precious Metals North America Daychem LLC | Sulfonic acid derivative compounds as photoacid generators in resist applications |
US9477150B2 (en) | 2015-03-13 | 2016-10-25 | Heraeus Precious Metals North America Daychem LLC | Sulfonic acid derivative compounds as photoacid generators in resist applications |
TWI662364B (zh) | 2015-12-31 | 2019-06-11 | Rohm And Haas Electronic Materials Llc | 光致抗蝕劑組合物、包含光致抗蝕劑組合物的經塗佈基板及形成電子裝置的方法 |
TWI656111B (zh) * | 2015-12-31 | 2019-04-11 | Rohm And Haas Electronic Materials Llc | 光酸產生劑 |
JP7028136B2 (ja) * | 2018-10-24 | 2022-03-02 | 信越化学工業株式会社 | 新規オニウム塩、化学増幅レジスト組成物、及びパターン形成方法 |
CN114380722B (zh) * | 2021-12-30 | 2023-06-30 | 宁波南大光电材料有限公司 | 一种磺酰氟烷烃酯的快速水解方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007293332A (ja) * | 2006-04-11 | 2007-11-08 | Rohm & Haas Electronic Materials Llc | フォトリソグラフィ用コーティング組成物 |
WO2009057769A1 (ja) * | 2007-11-01 | 2009-05-07 | Central Glass Company, Limited | 新規スルホン酸塩及びその誘導体、光酸発生剤並びにこれを用いたレジスト材料及びパターン形成方法 |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4491628A (en) | 1982-08-23 | 1985-01-01 | International Business Machines Corporation | Positive- and negative-working resist compositions with acid generating photoinitiator and polymer with acid labile groups pendant from polymer backbone |
JPS604165A (ja) * | 1983-06-21 | 1985-01-10 | Taiho Yakuhin Kogyo Kk | スルホニウム誘導体 |
MX170270B (es) | 1984-06-01 | 1993-08-11 | Rohm & Haas | Imagenes sobre una superficie y un metodo para formar imagenes positivas y negativas termicamente estables sobre una superficie |
CA1307695C (en) | 1986-01-13 | 1992-09-22 | Wayne Edmund Feely | Photosensitive compounds and thermally stable and aqueous developablenegative images |
US4968581A (en) | 1986-02-24 | 1990-11-06 | Hoechst Celanese Corporation | High resolution photoresist of imide containing polymers |
US4885158A (en) * | 1988-04-29 | 1989-12-05 | Gaf Corporation | Heat stable quaternized lactams having oxylated sulfur anions |
US4810613A (en) | 1987-05-22 | 1989-03-07 | Hoechst Celanese Corporation | Blocked monomer and polymers therefrom for use as photoresists |
DE3721741A1 (de) | 1987-07-01 | 1989-01-12 | Basf Ag | Strahlungsempfindliches gemisch fuer lichtempfindliche beschichtungsmaterialien |
DE68926019T2 (de) | 1988-10-28 | 1996-10-02 | Ibm | Positiv arbeitende hochempfindliche Photolack-Zusammensetzung |
US5128232A (en) | 1989-05-22 | 1992-07-07 | Shiply Company Inc. | Photoresist composition with copolymer binder having a major proportion of phenolic units and a minor proportion of non-aromatic cyclic alcoholic units |
DE69322946T2 (de) | 1992-11-03 | 1999-08-12 | Ibm | Photolackzusammensetzung |
US5843624A (en) | 1996-03-08 | 1998-12-01 | Lucent Technologies Inc. | Energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
US5861231A (en) | 1996-06-11 | 1999-01-19 | Shipley Company, L.L.C. | Copolymers and photoresist compositions comprising copolymer resin binder component |
US6057083A (en) | 1997-11-04 | 2000-05-02 | Shipley Company, L.L.C. | Polymers and photoresist compositions |
US6165674A (en) | 1998-01-15 | 2000-12-26 | Shipley Company, L.L.C. | Polymers and photoresist compositions for short wavelength imaging |
JP3587743B2 (ja) | 1998-08-26 | 2004-11-10 | 株式会社ハイニックスセミコンダクター | フォトレジスト単量体とその製造方法、フォトレジスト共重合体とその製造方法、フォトレジスト組成物、フォトレジストパターン形成方法、および、半導体素子。 |
KR100546105B1 (ko) * | 1999-11-03 | 2006-01-24 | 주식회사 하이닉스반도체 | 신규의 포토레지스트용 중합체 및 이를 함유하는포토레지스트 조성물 |
US6692897B2 (en) * | 2000-07-12 | 2004-02-17 | Fuji Photo Film Co., Ltd. | Positive resist composition |
US6664022B1 (en) | 2000-08-25 | 2003-12-16 | Shipley Company, L.L.C. | Photoacid generators and photoresists comprising same |
US6749987B2 (en) * | 2000-10-20 | 2004-06-15 | Fuji Photo Film Co., Ltd. | Positive photosensitive composition |
AU2002239563A1 (en) | 2000-11-03 | 2002-06-03 | Shipley Company, L.L.C. | Photoacid generators and photoresists comprising same |
US6841333B2 (en) * | 2002-11-01 | 2005-01-11 | 3M Innovative Properties Company | Ionic photoacid generators with segmented hydrocarbon-fluorocarbon sulfonate anions |
JP4644457B2 (ja) * | 2003-09-10 | 2011-03-02 | 富士フイルム株式会社 | 感光性組成物及びそれを用いたパターン形成方法 |
TW200604740A (en) * | 2004-03-08 | 2006-02-01 | Rohm & Haas Elect Mat | Cyanoadamantyl compounds and polymers and photoresists comprising same |
JP4452632B2 (ja) * | 2005-01-24 | 2010-04-21 | 富士フイルム株式会社 | 感光性組成物、該感光性組成物に用いる化合物及び該感光性組成物を用いたパターン形成方法 |
US7838199B2 (en) * | 2007-02-28 | 2010-11-23 | Rohm And Haas Electronic Materials Llc | Polymers and photoresist compositions |
JP5449675B2 (ja) * | 2007-09-21 | 2014-03-19 | 富士フイルム株式会社 | 感光性組成物、該感光性組成物を用いたパターン形成方法及び該感光性組成物に用いられる化合物 |
JP5460230B2 (ja) * | 2008-10-31 | 2014-04-02 | 富士フイルム株式会社 | ポジ型感光性組成物 |
JP5292078B2 (ja) * | 2008-12-05 | 2013-09-18 | 富士フイルム株式会社 | 感活性光線または感放射線性樹脂組成物及び該組成物を用いたパターン形成方法 |
JP5703662B2 (ja) * | 2009-11-06 | 2015-04-22 | 住友化学株式会社 | 酸発生剤用の塩及びレジスト組成物 |
US8460851B2 (en) * | 2010-01-14 | 2013-06-11 | Sumitomo Chemical Company, Limited | Salt and photoresist composition containing the same |
EP2539316B1 (en) * | 2010-02-24 | 2019-10-23 | Basf Se | Latent acids and their use |
JP5624906B2 (ja) * | 2010-03-23 | 2014-11-12 | 富士フイルム株式会社 | パターン形成方法、化学増幅型レジスト組成物、及び、レジスト膜 |
-
2011
- 2011-04-26 EP EP11163651A patent/EP2383611A3/en not_active Withdrawn
- 2011-04-26 JP JP2011098236A patent/JP5756672B2/ja active Active
- 2011-04-27 CN CN201110187346.3A patent/CN102344400B/zh active Active
- 2011-04-27 KR KR1020110039308A patent/KR101844307B1/ko active IP Right Grant
- 2011-04-27 TW TW100114602A patent/TWI465417B/zh active
- 2011-04-27 US US13/095,533 patent/US8609891B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007293332A (ja) * | 2006-04-11 | 2007-11-08 | Rohm & Haas Electronic Materials Llc | フォトリソグラフィ用コーティング組成物 |
WO2009057769A1 (ja) * | 2007-11-01 | 2009-05-07 | Central Glass Company, Limited | 新規スルホン酸塩及びその誘導体、光酸発生剤並びにこれを用いたレジスト材料及びパターン形成方法 |
Also Published As
Publication number | Publication date |
---|---|
US20110287361A1 (en) | 2011-11-24 |
KR101844307B1 (ko) | 2018-04-02 |
US8609891B2 (en) | 2013-12-17 |
JP2012031134A (ja) | 2012-02-16 |
JP5756672B2 (ja) | 2015-07-29 |
CN102344400A (zh) | 2012-02-08 |
EP2383611A3 (en) | 2012-01-25 |
KR20110119582A (ko) | 2011-11-02 |
TW201210998A (en) | 2012-03-16 |
EP2383611A2 (en) | 2011-11-02 |
CN102344400B (zh) | 2015-07-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI465417B (zh) | 光酸產生劑及含該光酸產生劑之光阻劑 | |
TWI568779B (zh) | 光酸產生劑及含該光酸產生劑之光阻 | |
JP6646633B2 (ja) | 光酸発生剤およびこれを含むフォトレジスト | |
US10809616B2 (en) | Cholate photoacid generators and photoresists comprising same | |
TWI464141B (zh) | 磺醯基光酸產生劑及含該光酸產生劑之光阻 | |
TWI507462B (zh) | 包含有含氮化合物之光阻 | |
TWI422973B (zh) | 正型阻劑組成物 | |
KR101839640B1 (ko) | 감방사선성 수지 조성물 및 감방사선성 산 발생제 | |
KR20140056098A (ko) | 이온성 화합물을 포함하는 포토레지스트 | |
JP3975790B2 (ja) | 感放射線性樹脂組成物 | |
KR101845113B1 (ko) | 감방사선성 수지 조성물 및 감방사선성 산발생제 |