CN100425630C - Filming copolymer resin containing silicon coupler and its organic antiflecting coating - Google Patents
Filming copolymer resin containing silicon coupler and its organic antiflecting coating Download PDFInfo
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- CN100425630C CN100425630C CNB200610039656XA CN200610039656A CN100425630C CN 100425630 C CN100425630 C CN 100425630C CN B200610039656X A CNB200610039656X A CN B200610039656XA CN 200610039656 A CN200610039656 A CN 200610039656A CN 100425630 C CN100425630 C CN 100425630C
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- alkyl
- methyl
- forming resin
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- ester
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- 239000011248 coating agent Substances 0.000 title abstract description 21
- 238000000576 coating method Methods 0.000 title abstract description 21
- 239000010703 silicon Substances 0.000 title abstract description 14
- 229910052710 silicon Inorganic materials 0.000 title abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 13
- 229920006026 co-polymeric resin Polymers 0.000 title 1
- -1 acrylic ester Chemical class 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 230000008033 biological extinction Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 24
- 229920001296 polysiloxane Polymers 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 13
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003667 anti-reflective effect Effects 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- 238000001259 photo etching Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 10
- 150000003254 radicals Chemical class 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004377 microelectronic Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract description 2
- 238000000206 photolithography Methods 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 32
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 125000003545 alkoxy group Chemical group 0.000 description 24
- 150000001721 carbon Chemical group 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- 125000005395 methacrylic acid group Chemical group 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229920002120 photoresistant polymer Polymers 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N alpha-methyl-naphthalene Natural products C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 4
- XGWFJBFNAQHLEF-UHFFFAOYSA-N 9-anthroic acid Chemical class C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=CC2=C1 XGWFJBFNAQHLEF-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000010748 Photoabsorption Effects 0.000 description 4
- 239000006117 anti-reflective coating Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWGSAMLIJGTMCH-UHFFFAOYSA-N C1(=CC=CC=C1)OCC.C=C Chemical compound C1(=CC=CC=C1)OCC.C=C RWGSAMLIJGTMCH-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- JCJNNHDZTLRSGN-UHFFFAOYSA-N anthracen-9-ylmethanol Chemical compound C1=CC=C2C(CO)=C(C=CC=C3)C3=CC2=C1 JCJNNHDZTLRSGN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- UBNWPQXLFRMMEI-GQCTYLIASA-N 5-[3-[(e)-3-(3-hydroxy-2-methoxycarbonylphenoxy)prop-1-enyl]phenyl]-1,2-oxazole-3-carboxylic acid Chemical compound COC(=O)C1=C(O)C=CC=C1OC\C=C\C1=CC=CC(C=2ON=C(C=2)C(O)=O)=C1 UBNWPQXLFRMMEI-GQCTYLIASA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N beta-methyl-naphthalene Natural products C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ACVMIWRKOQXFSK-UHFFFAOYSA-N 1-ethenyl-3,5-diethoxybenzene Chemical compound CCOC1=CC(OCC)=CC(C=C)=C1 ACVMIWRKOQXFSK-UHFFFAOYSA-N 0.000 description 1
- HAOCOEDZAZUQHN-UHFFFAOYSA-N 2-(2-ethenylphenoxy)ethanol Chemical compound OCCOC1=CC=CC=C1C=C HAOCOEDZAZUQHN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- WAJBVZLQQFZDIR-UHFFFAOYSA-N 9-ethylanthracen-1-ol Chemical class C(C)C=1C2=CC=CC=C2C=C2C=CC=C(C12)O WAJBVZLQQFZDIR-UHFFFAOYSA-N 0.000 description 1
- KEDPGTIWGQAXMW-UHFFFAOYSA-N 9-methylanthracen-1-ol Chemical class C1=CC(O)=C2C(C)=C(C=CC=C3)C3=CC2=C1 KEDPGTIWGQAXMW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOMBFBVBZZRKOR-UHFFFAOYSA-N CC(C(=O)O)(C)C.C(C)(C)(C)OO Chemical compound CC(C(=O)O)(C)C.C(C)(C)(C)OO ZOMBFBVBZZRKOR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FIXANHZJVHLQBJ-UHFFFAOYSA-N benzoic acid hydrogen peroxide Chemical compound C(C1=CC=CC=C1)(=O)O.OO FIXANHZJVHLQBJ-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000276 deep-ultraviolet lithography Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 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
- 239000000975 dye Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention relates to a couplant containing silicon copolymer film forming resin and an organic bottom antireflection coating film composition used for the microelectronics photoetching technology using KrF laser (248 nm), Arf laser (193 nm) or F2 laser (157 nm) as exposure light sources. The film forming resin is formed mainly by 1 to 40 shares by weight of acrylic ester class coupling agent monomers containing silicon and 20 to 80 shares by weight of acrylic ester class coupling agent monomers containing extinction base groups through copolymerization and corresponding postprocessing under the existing condition of free radical initiator, and the film forming resin is used for preparing antireflection coating film glue solution with stabilizing agent, flatting agent and other small quantity additive in solvent. The scheme prevents the influence on the quality of photoetching patterns brought by diffraction and reflection between a photoetching rubber bottom layer and a silicon wafer in the process of photolithography for obtaining good photoetching patterns by using the characteristics of acrylic ester coupling agent containing silicon which can take part in copolymerization of monomers with high extinction performance for forming copolymers with good antireflection performance, and can carry out crosslinking reaction under the condition of being heated.
Description
Technical field
The present invention relates to a kind of multipolymer film-forming resin that contains silicone couplet (also claiming " membrane-forming agent ") and utilize formulated being used for of this film-forming resin with KrF laser (248nm), ArF laser (193nm) or F
2Laser (157nm) is (BARC) composition of the organic bottom anti-reflection coating (filming) in the microelectronics photoetching process of exposure light source.
Background technology
The making of large-scale integrated circuit need realize by photoetching process.In high-resolution photoetching process, because the thickness of photoresist material is more and more thinner, diffraction and the reflection case quality that more and more influence litho pattern of light between photoresist material bottom and silicon chip in the exposure process, cause photoetching lines non-vertical or unfairness, so that can't moulding, have a strong impact on the carrying out of photoetching process.In order to address this problem, in photoetching process, introduced the technological process of anti-reflection coating, promptly before photoetching, earlier at silicon chip or need to be coated with on the matrix of photoetching one deck can light-absorbing coating, then thereon again resist coating carry out photoetching, absorbed by anti-reflection coating when exposure light arrives the photoresist material bottom like this, avoided light to the reflection of photoresist material or the generation of diffraction, thereby guaranteed the quality of litho pattern.People claim this coating that is applied between photoresist material and silicon chip or the base material be bottom anti-reflective coating (filming) (BARC).
The material that the light to exposure wavelength that general BARC coating (filming) is some organic (or inorganic) has high optical density.In g line or I linear light carving technology, generally use inorganic anti-reflection coating, as TiN, decolorizing carbon etc., and SiON generally is applied in the reflectance coating as a kind of interference of light material, and it also can be applicable in the KrF photoetching process.For organic BARC, generally be applied in deep ultraviolet (DUV) photoetching process, it comprises a kind of the have polymer materials of film forming properties and the dyestuff that can absorb particular light ray.These dyestuffs can be sneaked in the polymkeric substance and also can chamical binding be connected on the polymer molecular chain.In order to increase the intensity of coating, the solvability of minimizing in solvent, to prevent that photoresist layer comes off in the photoetching process, BARC filmed and will introduce linking agent and small amount of acid or alkali as crosslinking catalyst in polymkeric substance in the past, these linking agents can be the ready-made linking agents that adds in the process for preparation, also can be group with crosslinked function or the components on the polymer molecular chain.The deficiency that existing BARC films is: have small-molecule substance smooth finish and the planarization of filming that exert an influence itself when 1, crosslinked; 2, because the existence of acid or alkali, acid or alkali may be moved to and be gone in the photoresist coating and influence the quality of litho pattern in the photoetching process.Move in the positivity chemical amplification type photoresist material as tartaric acid or alkali, can cause the distortion of litho pattern, acid can cause etching excessively (undercut), and alkali can cause etching deficiency (footing).
Summary of the invention
The purpose of this invention is to provide a kind of multipolymer film-forming resin and organic anti-reflective thereof that has high photo absorption performance and cross-linking properties concurrently films, to avoid the influence that the diffraction between the photoresist material bottom and silicon chip and reflection are brought the litho pattern quality in photoetching process, to obtain better litho pattern.
For achieving the above object, the technical scheme that the present invention contains the multipolymer film-forming resin employing of silicone couplet is: a kind of multipolymer film-forming resin that contains silicone couplet, by comonomer under the condition that radical initiator exists, by carrying out copolymerization and corresponding aftertreatment is prepared from solvent, comonomer is made up of following three class monomers:
(1), acrylate containing silicone class coupling agent 1-40 part weight;
Its chemical general formula:
In the formula:
N=1-8; R
1=H, CH
3Or CF
3R
2=C
1-C
20Alkyl; R
3=C
1-C
20Alkyl; R
4=OH, C
1-C
20Alkyl or C
1-C
20Alkoxyl group;
For example:
Methacrylic acid propyl trialkoxy silane ester (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid propyl trialkoxy silane ester (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid propyl group dialkoxy silicane ester (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid propyl group dialkoxy silicane ester (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid ethyl trialkoxy silane ester (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid ethyl trialkoxy silane ester (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid ethyl dialkoxy silicane ester (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid ethyl dialkoxy silicane ester (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methyl trialkoxy silane ester (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methyl trialkoxysilane ester (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methyl dialkoxy silicane ester (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methyl dialkoxy silicane ester (wherein alkoxyl group contains 1-20 carbon atom);
Perhaps
In the formula: m=1-8; R
5=H, CH
3Or CF
3R
6=C
1-C
20Alkyl; R
6 '=C
1-C
20Alkyl; R
7=C
1-C
20Alkyl; R
7 '=C
1-C
20Alkyl; R
8=OH, C
1-C
20Alkyl or C
1-C
20Alkoxyl group; R
8 '=OH, C
1-C
20Alkyl or C
1-C
20Alkoxyl group;
For example:
Methacrylic acid methylene radical two (propyl trialkoxy silane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methylene radical two (propyl trialkoxy silane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methylene radical two (propyl group dialkoxy silicane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methylene radical two (propyl group dialkoxy silicane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methylene radical two (ethyl trialkoxy silane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methylene radical two (ethyl trialkoxy silane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methylene radical two (ethyl dialkoxy silicane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methylene radical two (ethyl dialkoxy silicane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methylene radical two (methyl trialkoxysilane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methylene radical two (methyl trialkoxysilane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Methacrylic acid methylene radical two (methyl dialkoxy silicane ester) (wherein alkoxyl group contains 1-20 carbon atom);
Vinylformic acid methylene radical two (methyl dialkoxy silicane ester) (wherein alkoxyl group contains 1-20 carbon atom);
(2), contain extinction group acrylic ester monomer 20-80 part weight;
The described extinction group acrylic ester monomer that contains is selected a kind of monomer or two kinds of monomers in following two class material scopes:
1., contain the anthryl acrylic ester monomer
Chemical general formula:
In the formula: n=1-2; R
9=H or methyl; R
10=H or methyl; R
11=H or methyl;
For example:
Methacrylic acid-9-anthracene methyl ester;
Vinylformic acid-9-anthracene methyl ester;
Methacrylic acid-9-anthracene ethyl ester;
Vinylformic acid-9-anthracene ethyl ester;
Methacrylic acid [2-hydroxyl-3-(9-methyl anthracene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(9-methyl anthracene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(9-ethyl anthracene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(9-ethyl anthracene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(9-carboxyl anthracene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(9-carboxyl anthracene)] propyl diester;
2., the acrylic ester monomer that contains 1-naphthyl or 2-naphthyl extinction group
Its chemical general formula:
In the formula: n=1-2; R
12=H or methyl; R
13=H or methyl; R
14=H or methyl;
For example:
Methacrylic acid-1-menaphthyl ester;
Methacrylic acid-2-menaphthyl ester;
Vinylformic acid-1-menaphthyl ester;
Vinylformic acid-2-menaphthyl ester;
Methacrylic acid-1-naphthalene ethyl ester;
Methacrylic acid-2-naphthalene ethyl ester;
Vinylformic acid-1-naphthalene ethyl ester;
Vinylformic acid-2-naphthalene ethyl ester;
Methacrylic acid [2-hydroxyl-3-(1-methylnaphthalene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(2-methylnaphthalene)] propyl diester
Vinylformic acid [2-hydroxyl-3-(1-methylnaphthalene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(2-methylnaphthalene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(1-ethylnaphthalene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(2-ethylnaphthalene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(1-ethylnaphthalene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(2-ethylnaphthalene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(1-carboxyl naphthalene)] propyl diester;
Methacrylic acid [2-hydroxyl-3-(2-carboxyl naphthalene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(1-carboxyl naphthalene)] propyl diester;
Vinylformic acid [2-hydroxyl-3-(2-carboxyl naphthalene)] propyl diester;
(3), in following two class material scopes, select a kind of monomer or 1～70 part of weight of two kinds of monomers:
1., styrene monomer
Its chemical general formula:
In the formula: R
15=H, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl or C
6-C
20Aryloxy;
For example:
Vinylbenzene;
To t-butyl styrene;
To tert.-amylbenzene ethene;
To phenetole ethene;
3, the 5-dimethoxy styrene;
3,5-diethoxy vinylbenzene;
To phenoxy group vinylbenzene;
To 2-hydroxy ethoxy vinylbenzene;
2., acrylic ester monomer
Its chemical general formula:
In the formula: R
16=H or methyl; R
17=H, C
1-C
20Alkyl or C
1-C
20Alkoxyl group;
For example:
Hydroxyethyl methylacrylate;
Hydroxyethyl acrylate;
Glyceral methacrylate;
Vinylformic acid hydroxyl glyceryl ester;
Methacrylic acid ethoxy hydroxyethyl ester;
Vinylformic acid ethoxy hydroxyethyl ester;
The molecular weight of described multipolymer film-forming resin is 2000-100000, and molecular weight distribution is 1.4-2.8.
Related content in the technique scheme is explained as follows:
1, about polyreaction
(1), above-mentioned have copolymerization to carry out separately or in their mixture at all kinds of SOLVENTS, these solvents comprise methyl alcohol, ethanol, dioxane, acetone, pimelinketone, tetrahydrofuran (THF), 1-Methoxy-2-propyl acetate (PGMEA), propylene glycol monomethyl ether (PGME) toluene, benzene, dimethylbenzene, methylene dichloride, chloroform, trichloromethane, ethylene dichloride, trichloroethane etc.
(2), these copolymerizations can carry out in the presence of various radical initiators, comprise that azo two isobutyls are fine, azo initiator such as two different heptan of azo are fine, and the radical initiator of various superoxide, as tert-butyl hydroperoxide pivalate, tertbutyl peroxide, phenylformic acid hydrogen peroxide, benzoyl peroxides etc., initiator amount are the 0.3%-15% of total monomer weight.
(3), the adding of radical initiator can be adopted dual mode: first kind is after each comonomer is dissolved in solvent, is heated to polymerization temperature earlier, adds initiator then and carries out polyreaction.Second kind is after each comonomer is dissolved in solvent, adds earlier initiator, and then is warmed to polymerization temperature and carries out polyreaction.Described initiator can disposablely add in this dual mode, also can gradation add.The temperature of polyreaction: the temperature of polyreaction is controlled at 40～150 ℃ of scopes according to the solvent that uses is different with initiator.Polymerization reaction time is also according to be controlled at 16～28 hour different with initiator of solvent of using.
(4)、
Some multipolymer also can be obtained through suitable chemical reaction by the polymkeric substance of specific composition except can directly being formed by their corresponding monomer copolymerizable.Be shown below:
The following formula explanation, the multipolymer that contains the extinction group can be obtained by following two kinds of approach:
1., the first step, under the effect of AIBN initiator, polymerization obtains intermediate polymer by GMA monomer and KH-570 silicon-containing monomer; In second step, this intermediate polymer is carried out chemical reaction with the extinction group again under the BTEA catalyst action, the final multipolymer that obtains to contain the extinction group.
2., the first step, under the BTEA catalyst action, carry out chemical reaction by GMA monomer and extinction group, obtain to contain the monomer of extinction group; Second step, the polymerization under the effect of AIBN initiator with this monomer and KH-570 silicon-containing monomer, the final multipolymer that obtains to contain the extinction group.
Use the sort of method in the actually operating, should decide according to processing requirement and pricing.
3, the aftertreatment of polyreaction:
(1), purification process
After polyreaction was finished, unreacted residual monomer and part organic impurity thereof can be removed after extracting with heptane, hexane, hexanaphthene, pentane, sherwood oil, ether equal solvent.
(2), separate solid multipolymer
The synthetic copolymer solution can directly be used, if desired, multipolymer also can be in methyl alcohol, ethanol, Virahol, heptane, hexane, hexanaphthene, pentane, sherwood oil, ether equal solvent precipitate and separate, the yield of vacuum-drying rear copolymer is 50%-90%.
For achieving the above object, the organic anti-reflective of the present invention technical scheme that adopts of filming is: a kind of organic anti-reflective is filmed, and is mainly mixed by following component and content thereof and forms:
2～30 parts of weight of film-forming resin;
70～98 parts of weight of solvent;
0.1～1 part of weight of flow agent;
Wherein:
Described film-forming resin adopts the described multipolymer film-forming resin that contains silicone couplet of such scheme;
Described solvent is selected from one of following material:
1-Methoxy-2-propyl acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate, pimelinketone, methyl iso-butyl ketone (MIBK).
Other additives of anti-reflection coating solution, can also comprise linking agent (can), catalyzer (can), a small amount of component such as stablizer.
Design of the present invention and characteristics: general anti-reflection coating all needs to have the heat cross-linking ability, make it in the post-heating generation crosslinking reaction of filming, making films has the good resistance etching performance, simultaneously to be coated in photoresist coating above the reflecting layer have good adhesion again can be because of chemical substance takes place, as acid, the transfer of alkali or solvent produces detrimentally affect.Therefore, some BARC reaches this purpose with the method that adds linking agent and catalyzer.As (Cytec Industries Inc.) waits linking agent, and PTSA an acidic catalysts such as (tosic acid) to add Cymel 303 or Powderlink 1174.The invention provides a kind of multipolymer that has high photo absorption performance and cross-linking properties concurrently, it has under heating state or the self-crosslinking effect that takes place in the presence of minimum water gaging or acid, reaches the ability of carrying out crosslinking reaction with other hydroxy-containing compounds.This silicone couplet that contains carries out a kind of multipolymer film-forming resin with high light absorptive of crosslinked ability of copolymerization acquisition with the another kind of monomer that contains high extinction group, this film-forming resin and stablizer, leveling agent and small amount of additive is mixed with bottom anti-reflective coating glue in suitable solvent, be applied in the deep-UV lithography process.The monomeric copolymerization that this programme utilizes the acrylate containing silicone coupling agent both can participate in having high light absorptive forms the multipolymer with good antireflection property, also can under heating state, carry out the characteristic of crosslinking reaction, overcome and add acid, alkaline catalysts influence photoetching process.
Because the utilization of such scheme, the present invention compared with prior art has the following advantages:
1, the present invention can play crosslinked action owing to self have cross-linking properties under heating condition, do not need to add linking agent and corresponding acid or alkaline catalysts again, has therefore overcome anti reflection coating in the past and has contained linking agent and acid or defective that alkaline catalysts brought.
2, the present invention is to contain silicone couplet owing to what adopt, therefore silicon matrix is had good adhesivity, is not easy to come off.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
(1). synthesizing of methacrylic acid-9-anthracene methyl ester:
In a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add 104 gram 9-methyl anthranols, 40.0 gram pyridines, 300 gram tetrahydrofuran (THF)s.Slowly add methacrylic isoxazolecarboxylic acid 54.5 grams.Be heated to 60-65 ℃, continue to stir after 6 hours solids removed by filtration.Add 300 gram ethyl acetate, wash three final vacuums concentrated product methacrylic acid-9-anthracene methyl ester, yield 82%.
(2). a kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from.The chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
Methacrylic acid-9-anthracene methyl ester 48.3 grams;
2-hydroxyethyl methacrylate 28.5 grams;
Methacrylic acid propyl trimethoxy silicane ester (KH570) 18.6 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-9-anthracene methyl ester 48.3 grams, 2-hydroxyethyl methacrylate 28.5 grams, methacrylic acid propyl trimethoxy silicane ester (KH570) 18.6 grams, tetrahydrofuran (THF) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 5.0 grams in 20 gram tetrahydrofuran (THF)s, continue the reaction backflow after 16-24 hour, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in methyl alcohol, gets polymer solids, yield 85% after the vacuum-drying.
Embodiment two:
(1). synthesizing of methacrylic acid-9-anthracene ethyl ester:
In a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add 111.0 gram 9-ethyl anthranols, 40.0 gram pyridines, 300 gram tetrahydrofuran (THF)s.Slowly add methacrylic isoxazolecarboxylic acid 54.5 grams.Be heated to 60-65 ℃, continue to stir after 6 hours solids removed by filtration.Add 300 gram ethyl acetate, wash three final vacuums concentrated product methacrylic acid-9-anthracene ethyl ester, yield 81%.
(2). a kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
Methacrylic acid-9-anthracene ethyl ester 50.7 grams;
Methacrylic acid-2-methoxy ethyl ester 36.0 grams;
Methacrylic acid propyl-triethoxysilicane ester 18.9 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-9-anthracene ethyl ester 50.7 grams, methacrylic acid-2-methoxy ethyl ester 36.0 grams, methacrylic acid propyl-triethoxysilicane ester (KH570) 18.9 grams, tetrahydrofuran (THF) 450 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 5.5 grams in 20 gram tetrahydrofuran (THF)s, continue the reaction backflow after 6-24 hour, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in methyl alcohol, gets polymer solids, yield 86% after the vacuum-drying.
Embodiment three:
(1). synthesizing of methacrylic acid [2-hydroxyl-3-(9-anthracene methyl)] propyl diester:
In a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add 104 gram 9-anthracene methylols, 40.0 gram tetramethyl amido ammonium hydroxide (TMAH), 300 gram propylene glycol monomethyl ethers (PGME).Slowly add glytidyl methacrylate 72.5 grams, be heated to 120-125 ℃, continue to stir 24 hours.Add 300 gram ethyl acetate, wash three final vacuums concentrated product methacrylic acid [2-hydroxyl-3-(9-methyl anthracene)] propyl diester, yield 82%.
(2). a kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
To phenetole ethene 20.0 grams;
Methacrylic acid [2-hydroxyl-3-(9-methyl anthracene)] propyl diester 46.7 grams;
Methacrylic acid ethyl trimethoxy silane ester 16.5 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to phenetole ethene 20.0 grams, methacrylic acid [2-hydroxyl-3-(9-methyl anthracene)] propyl diester 46.7 grams, methacrylic acid ethyl trimethoxy silane ester 16.5 grams, tetrahydrofuran (THF) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 4.7 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 1-24 hour, add 80 gram A-21 (Rohm﹠amp; Haas, Amberlyst 21) ion exchange resin and 200 gram tetrahydrofuran (THF)s, back flow reaction 8 hours, and steam about 100 milliliters and steam thing, be cooled to room temperature then.Cross Lu deionizing exchange resin.Extract three times with heptane, polymers soln precipitates in methyl alcohol, gets polymer solids, yield 80% after the vacuum-drying.
Embodiment four:
(1). synthesizing of methacrylic acid [2-hydroxyl-3-(1-methylnaphthalene)] propyl diester:
In a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add 78.0 gram 1-methylnaphthalene alcohol, 40.0 gram tetramethyl amido ammonium hydroxide (TMAH), 300 gram propylene glycol monomethyl ethers (PGME).Slowly add glytidyl methacrylate 72.5 grams, be heated to 120-125 ℃, continue to stir 24 hours.Add 300 gram ethyl acetate, wash three final vacuums concentrated product methacrylic acid [2-hydroxyl-3-(1-methylnaphthalene)] propyl diester, yield 86%.
(2). a kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
Methacrylic acid-2-hydroxy-propyl ester 24.4 grams;
Methacrylic acid [2-hydroxyl-3-(1-methylnaphthalene)] propyl diester 40.7 grams;
Methacrylic acid methylene-bis ethyl trimethoxy silane ester 18.7 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-2-hydroxy-propyl ester 24.4 grams, methacrylic acid [2-hydroxyl-3-(1-methylnaphthalene)] propyl diester 40.7 grams, methacrylic acid methylene-bis ethyl trimethoxy silane ester 18.7 grams, tetrahydrofuran (THF) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 4.8 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 18-28 hour, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in methyl alcohol, gets polymer solids, yield 82% after the vacuum-drying.
Embodiment five:
(1). synthesizing of methacrylic acid [2-hydroxyl-3-(9-carboxyl anthracene)] propyl diester:
In a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add 111.0 gram 9-anthroic acids, 113.8 gram benzyltriethylammoinium chlorides (BTAC), 300 gram tetrahydrofuran (THF)s.Slowly add glytidyl methacrylate 73.0 grams, be heated to 60-70 ℃, continue to stir 16 hours.Add 300 gram ethyl acetate, wash three final vacuums concentrated product methacrylic acid [2-hydroxyl-3-(9-carboxyl anthracene)] propyl diester, yield 84%.
(2). a kind of multipolymer film-forming resin that contains silicone couplet, by following comonomer and content thereof, under the condition that radical initiator exists, carry out copolyreaction by heating and be prepared from, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
Methacrylic acid-2-hydroxy-propyl ester 23.8 grams;
Methacrylic acid [2-hydroxyl-3-(9-carboxyl anthracene)] propyl diester 40.8 grams;
Methacrylic acid methyl Trimethoxy silane ester 11.1 grams.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-2-hydroxy-propyl ester 23.8 grams, methacrylic acid [2-hydroxyl-3-(9-carboxyl anthracene)] propyl diester 40.8 grams, methacrylic acid methyl Trimethoxy silane ester 11.1 grams, tetrahydrofuran (THF) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 4.9 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 8-18 hour, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in Virahol, gets polymer solids, yield 82% after the vacuum-drying.
Embodiment six:
(1). synthesizing of prepolymer (I):
Methacrylic acid-2-hydroxyethyl ester 65.0 grams;
Methacrylic acid epoxypropyl ester 49.7 grams;
Methacrylic acid propyl trimethoxy silicane ester 37.2 grams.
Electric mixer is equipped with at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-2-hydroxy methacrylate 65.0 grams, glytidyl methacrylate 49.7 grams, methacrylic acid propyl trimethoxy silicane ester 37.2 grams, propylene glycol monomethyl ether (PGME) 300 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of azo two isobutyls fine (AIBN) 7.5 grams in 50 gram tetrahydrofuran (THF)s, continue the reaction backflow after 16-24 hour, be cooled to room temperature then, get prepolymer (I) 502 grams (solid content about 30.2%).
(2). a kind of multipolymer film-forming resin that contains silicone couplet,, under the condition that catalyzer exists, be prepared from by above synthetic prepolymer (I) and 9-anthroic acid by reacting by heating, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
9-anthroic acid 111.0 grams;
Benzyltriethylammoinium chloride (BTAC) 113.6 grams;
Prepolymer (I) 250.0 grams.
The preparation method is: in a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add prepolymer (I) 250 grams, 9-anthroic acid 111.0 grams, benzyltriethylammoinium chloride (BTAC) 114 grams, 1-Methoxy-2-propyl acetate (PGMEA) 250 grams, under agitation logical nitrogen 10 minutes is heated to 120-125 ℃ then, continue the reaction backflow after 24 hours, be cooled to room temperature then.Extract three times with heptane, get polymers soln (solid content about 25.4%), stand-by.
Embodiment seven:
A kind of multipolymer film-forming resin that contains silicone couplet, by synthetic prepolymer (I) among the above embodiment six and 9-anthryl carbinol under the condition that catalyzer exists, be prepared from by reacting by heating, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
9-anthryl carbinol 104.0 grams;
Tetramethylammonium hydroxide (TMAH) 41.5 grams;
Prepolymer (I) 250.0 grams.
The preparation method is: in a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet; add prepolymer (I) 250.0 grams; 9-anthryl carbinol 104.0 grams; Tetramethylammonium hydroxide (TMAH) 41.5 grams; 1-Methoxy-2-propyl acetate (PGMEA) 300 grams; under nitrogen protection, be heated to 120-125 ℃, continue the reaction backflow after 24 hours, be cooled to room temperature then.Extract three times with heptane, get polymers soln (solid content about 25.2%), stand-by.
Embodiment eight:
A kind of multipolymer film-forming resin that contains silicone couplet, by synthetic prepolymer (I) among the above embodiment six and 1-naphthalene methyl alcohol under the condition that catalyzer exists, be prepared from by reacting by heating, the chemical formula of multipolymer film-forming resin (not representing sequential structure) is as follows:
1-naphthalene methyl alcohol 79.0 grams;
Tetramethylammonium hydroxide (TMAH) 41.5 grams;
Prepolymer (I) 250.0 grams.
The preparation method is: in a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet; add prepolymer (I) 250.0 grams; 1-naphthalene methyl alcohol 79.0 grams; Tetramethylammonium hydroxide (TMAH) 41.5 grams; 1-Methoxy-2-propyl acetate (PGMEA) 300 grams; under nitrogen protection, be heated to 120-125 ℃, continue the reaction backflow after 24 hours, be cooled to room temperature then.Extract three times with heptane, get polymers soln (solid content about 25.2%), stand-by.
Embodiment nine:
A kind of compound method of anti reflection coating: in clean 250 new ml polypropylene Plastic Bottles, the multipolymer that adds preparation among the 5.8 gram embodiment one, 100 gram electronic grade propylene glycol monomethyl ether acetic ester (PGMEA) solvents, and 0.12 gram 9-anthracene ethyl ketone, 0.15 gram tensio-active agent.This mixture is fixed on the mechnical oscillator, at room temperature shakes 10-24 hour, and it is fully dissolved.Strainer with 0.5 micron pore size filters one time, and the strainer with 0.1 micron pore size filters one time then.
Lithography experiments method and result: the anti reflection coating of above-mentioned preparation is 6 "-8 " on the silicon chip with 2000-6000 rev/min speed rotation film forming, baking 90-180 second on 175 ℃ of hot plates, thickness 100-1000
, have good photo absorption performance, be suitable for KrF laser (248nm) ArF laser (193nm) or F
2Laser (157nm) is the bottom organic anti-reflective coating in the microelectronics photoetching process of exposure light source.
Embodiment ten:
A kind of compound method of anti-reflection coating: in clean 250 new ml polypropylene Plastic Bottles, the multipolymer that adds preparation among the 20.0. gram embodiment seven, 80.0 gram electronic grade propylene glycol monomethyl ether acetic ester (PGMEA) solvent, and 0.12 gram tensio-active agent.This mixture is fixed on the mechnical oscillator, at room temperature shakes 10-24 hour, and it is fully dissolved.Strainer with 0.5 micron pore size filters one time, and the strainer with 0.1 micron pore size filters one time then.
Lithography experiments method and result: the photoresist material of above-mentioned preparation is 6 "-8 " on the silicon chip with 2000-6000 rev/min speed rotation film forming, baking 90-180 second on 175 ℃ of hot plates, thickness 100-1000
, have good photo absorption performance, be suitable for KrF laser (248nm) ArF laser (193nm) or F
2Laser (157nm) is the bottom organic anti-reflective coating in the microelectronics photoetching process of exposure light source.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (2)
1, a kind of multipolymer film-forming resin that contains silicone couplet, by comonomer under the condition that radical initiator exists, by carrying out copolymerization and corresponding aftertreatment is prepared from solvent, it is characterized in that: comonomer is made up of following three class monomers:
(1), acrylate containing silicone class coupling agent 1-40 part weight;
Its chemical general formula:
Perhaps
In the formula:
N=1-8; R
1=H, CH
3Or CF
3R
2=C
1-C
20Alkyl; R
3=C
1-C
20Alkyl; R
4=OH, C
1-C
20Alkyl or C
1-C
20Alkoxyl group;
M=1-8; R
5=H, CH
3Or CF
3R
6=C
1-C
20Alkyl; R
6 '=C
1-C
20Alkyl; R
7=C
1-C
20Alkyl; R
7 '=C
1-C
20Alkyl; R
8=OH, C
1-C
20Alkyl or C
1-C
20Alkoxyl group; R
8 '=OH, C
1-C
20Alkyl or C
1-C
20Alkoxyl group;
(2), contain extinction group acrylic ester monomer 20-80 part weight;
The described extinction group acrylic ester monomer that contains is selected a kind of monomer or two kinds of monomers in following two class material scopes:
1., contain the anthryl acrylic ester monomer
Chemical general formula:
In the formula: n=1-2; R
9=H or methyl; R
10=H or methyl; R
11=H or methyl;
2., the acrylic ester monomer that contains 1-naphthyl or 2-naphthyl extinction group
Its chemical general formula:
In the formula: n=1-2; R
12=H or methyl; R
13=H or methyl; R
14=H or methyl;
(3), in following two class material scopes, select a kind of monomer or 1～70 part of weight of two kinds of monomers:
1., styrene monomer
Its chemical general formula:
In the formula: R
15=H, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl or C
6-C
20Aryloxy;
2., acrylic ester monomer
Its chemical general formula:
In the formula: R
16=H or methyl; R
17=H, C
1-C
20Alkyl or C
1-C
20Alkoxyl group;
The molecular weight of described multipolymer film-forming resin is 2000-100000, and molecular weight distribution is 1.4-2.8.
2, a kind of organic anti-reflective is filmed, and it is characterized in that: mainly mixed by following component and content thereof and form:
2～30 parts of weight of film-forming resin;
70～98 parts of weight of solvent;
0.1～1 part of weight of flow agent;
Wherein:
Described film-forming resin adopts the described multipolymer film-forming resin that contains silicone couplet of claim 1;
Described solvent is selected from one of following material:
1-Methoxy-2-propyl acetate, propylene glycol monomethyl ether, ethyl lactate, pimelinketone, methyl iso-butyl ketone (MIBK).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610039656XA CN100425630C (en) | 2006-04-19 | 2006-04-19 | Filming copolymer resin containing silicon coupler and its organic antiflecting coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610039656XA CN100425630C (en) | 2006-04-19 | 2006-04-19 | Filming copolymer resin containing silicon coupler and its organic antiflecting coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1847274A CN1847274A (en) | 2006-10-18 |
| CN100425630C true CN100425630C (en) | 2008-10-15 |
Family
ID=37077039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610039656XA Expired - Fee Related CN100425630C (en) | 2006-04-19 | 2006-04-19 | Filming copolymer resin containing silicon coupler and its organic antiflecting coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100425630C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4727567B2 (en) * | 2006-12-27 | 2011-07-20 | Ａｚエレクトロニックマテリアルズ株式会社 | Antireflection film forming composition and pattern forming method using the same |
| KR101766796B1 (en) * | 2008-11-27 | 2017-08-09 | 닛산 가가쿠 고교 가부시키 가이샤 | Composition for forming resist underlayer film with reduced outgassing |
| US8486609B2 (en) | 2009-12-23 | 2013-07-16 | Az Electronic Materials Usa Corp. | Antireflective coating composition and process thereof |
| CN101974121A (en) * | 2010-09-28 | 2011-02-16 | 昆山西迪光电材料有限公司 | Chemical amplified high-resolution silicon-containing I-ray ultraviolet photoresist and forming resin thereof |
| CN117417476B (en) * | 2023-12-19 | 2024-03-26 | 广东粤港澳大湾区黄埔材料研究院 | Modified polyacrylic resin, preparation method thereof and photoresist |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226978A (en) * | 1997-05-27 | 1999-08-25 | 克拉瑞特国际有限公司 | Composition for antireflection or light absorption film and compounds for use in the same |
| GB2364314A (en) * | 2000-06-30 | 2002-01-23 | Hynix Semiconductor Inc | Organic anti-reflective coating polymer |
| US20030078354A1 (en) * | 2001-02-23 | 2003-04-24 | Arch Specialty Chemicals, Inc. | Novel beta-oxo compounds and their use in photoresist |
| US6576681B2 (en) * | 2000-10-10 | 2003-06-10 | Shipley Company, L.L.C. | Antireflective porogens |
-
2006
- 2006-04-19 CN CNB200610039656XA patent/CN100425630C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226978A (en) * | 1997-05-27 | 1999-08-25 | 克拉瑞特国际有限公司 | Composition for antireflection or light absorption film and compounds for use in the same |
| GB2364314A (en) * | 2000-06-30 | 2002-01-23 | Hynix Semiconductor Inc | Organic anti-reflective coating polymer |
| US6576681B2 (en) * | 2000-10-10 | 2003-06-10 | Shipley Company, L.L.C. | Antireflective porogens |
| US20030078354A1 (en) * | 2001-02-23 | 2003-04-24 | Arch Specialty Chemicals, Inc. | Novel beta-oxo compounds and their use in photoresist |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1847274A (en) | 2006-10-18 |
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