CN113773433B - Polymer resin and preparation method thereof, method for improving cracking of electron beam photoresist, electron beam photoresist and preparation and use thereof - Google Patents
Polymer resin and preparation method thereof, method for improving cracking of electron beam photoresist, electron beam photoresist and preparation and use thereof Download PDFInfo
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- CN113773433B CN113773433B CN202111032979.7A CN202111032979A CN113773433B CN 113773433 B CN113773433 B CN 113773433B CN 202111032979 A CN202111032979 A CN 202111032979A CN 113773433 B CN113773433 B CN 113773433B
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- electron beam
- alpha
- monomer
- beam photoresist
- polymer resin
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- 238000010894 electron beam technology Methods 0.000 title claims abstract description 77
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 33
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000005336 cracking Methods 0.000 title abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 150000002576 ketones Chemical class 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000011161 development Methods 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 229940072049 amyl acetate Drugs 0.000 claims description 10
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- VIXHMBLBLJSGIB-UHFFFAOYSA-N 1-fluoro-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(F)C=C1 VIXHMBLBLJSGIB-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- CVUNPKSKGHPMSY-UHFFFAOYSA-N ethyl 2-chloroprop-2-enoate Chemical compound CCOC(=O)C(Cl)=C CVUNPKSKGHPMSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001259 photo etching Methods 0.000 claims description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-M 2-chloroacrylate Chemical compound [O-]C(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-M 0.000 claims 2
- DJMOYRIAWTXGEY-UHFFFAOYSA-N ethyl 2-fluoroprop-2-enoate Chemical compound CCOC(=O)C(F)=C DJMOYRIAWTXGEY-UHFFFAOYSA-N 0.000 claims 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 238000000609 electron-beam lithography Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 6
- -1 alpha-fluoro ethyl Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001459 lithography Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- LWHOMMCIJIJIGV-UHFFFAOYSA-N (1,3-dioxobenzo[de]isoquinolin-2-yl) trifluoromethanesulfonate Chemical compound C1=CC(C(N(OS(=O)(=O)C(F)(F)F)C2=O)=O)=C3C2=CC=CC3=C1 LWHOMMCIJIJIGV-UHFFFAOYSA-N 0.000 description 1
- MMWJIPOJFXEFDQ-UHFFFAOYSA-N (4,7-dihydroxynaphthalen-1-yl)-dimethylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=C(O)C=C2C([S+](C)C)=CC=C(O)C2=C1 MMWJIPOJFXEFDQ-UHFFFAOYSA-N 0.000 description 1
- VSBGQWYZNVYIBG-UHFFFAOYSA-N (4,8-dihydroxynaphthalen-1-yl)-dimethylsulfanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C[S+](C)c1ccc(O)c2cccc(O)c12 VSBGQWYZNVYIBG-UHFFFAOYSA-N 0.000 description 1
- PXIVOQOPGZGSCE-UHFFFAOYSA-M (4-methoxynaphthalen-1-yl)-diphenylsulfanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PXIVOQOPGZGSCE-UHFFFAOYSA-M 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RFEJUZMOMHYSRO-UHFFFAOYSA-N 1-adamantyl 2-chloroprop-2-enoate Chemical compound ClC(=C)C(=O)OC12CC3CC(CC(C3)C1)C2 RFEJUZMOMHYSRO-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- QLNYTCSELYEEPV-UHFFFAOYSA-N 2,2-dimethylpropyl acetate Chemical compound CC(=O)OCC(C)(C)C QLNYTCSELYEEPV-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 1
- ANZONXRNCWFEIL-UHFFFAOYSA-N 2-[2-(2,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound COC1=CC(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ANZONXRNCWFEIL-UHFFFAOYSA-N 0.000 description 1
- WLCABOJDXMJKEB-UHFFFAOYSA-N 2-[4-(4-methoxyphenyl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=CC=C(C=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)C=C1 WLCABOJDXMJKEB-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- WEYUQUMMYNRIPP-UHFFFAOYSA-M diphenyl-(4-phenylsulfanylphenyl)sulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 WEYUQUMMYNRIPP-UHFFFAOYSA-M 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/16—Homopolymers or copolymers of alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2333/16—Homopolymers or copolymers of esters containing halogen atoms
Abstract
The invention relates to a polymer resin and a preparation method thereof, a method for improving cracking of electron beam photoresist, the electron beam photoresist and preparation and use thereof. The preparation method of the polymer resin comprises the following steps: 1) Polymerizing a monomer composition comprising an aromatic vinyl monomer and an alpha-halogenated acrylate monomer; 2) The resulting mixture is precipitated in a solution comprising a ketone solvent/or an alkyl solvent, filtered and dried. The polymer resin obtained by the preparation method for the electron beam photoresist improves the cracking of the electron beam photoresist. The preparation method of the electron beam photoresist comprises the following steps: the components of the electron beam resist are mixed. The using method comprises the following steps: and coating the electron beam photoresist on the silicon wafer, and sequentially performing pre-baking, exposure and development. The invention settles the mixture obtained by polymerizing the monomer composition in the solution containing ketone solvent/alkyl solvent, which can improve the cracking of the electron beam photoresist and the reliability of the electron beam photoresist exposure.
Description
Technical Field
The invention relates to the technical field of electron beam photoresist, in particular to polymer resin and a preparation method thereof, a method for improving cracking of electron beam photoresist, the electron beam photoresist and preparation and use thereof.
Background
Electron-beam Lithography (EBL) is considered as one of the most promising Lithography technologies below 22 nm node in terms of its high resolution and stable performance as a next generation Lithography technology, and the progress of the Lithography technology is often indispensible from the development of Lithography materials. In recent years, electron beams have placed higher demands on lithographic materials as nano-scale lithography techniques. The electron beam photoresist is a type of photoresist material coated on the surface of a substrate to realize pattern transfer through electron beam exposure, and can be classified into positive photoresist and negative photoresist according to whether cross-linking or chemical bond breakage occurs before and after polymer irradiation.
After electron beam exposure, the polymer of the photoresist is broken by chemical bonds, and broken polymer fragments are easy to dissolve in a developing solution, so that the photoresist is positive photoresist. On the contrary, when the photoresist is exposed, the small molecules are crosslinked and polymerized into macromolecules, and the exposed photoresist is difficult to dissolve in a developing solution, so that the photoresist is negative photoresist. Alpha-methyl chloroacrylate and alpha-methylstyrene copolymers and polymethyl methacrylate are two polymer resins commonly used in electron beam photoresists. The former photoresist has the characteristics of high resolution, high sensitivity and etching resistance, but the cracking problem often occurs. US5087551a solves the cracking problem of electron beam photoresists by optimizing the photoresist solvent, CN1815369a optimizing the coating process. The method solves the cracking problem of the electron beam photoresist from the polymer synthesis treatment process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polymer resin and a preparation method thereof, a method for improving cracking of an electron beam photoresist, the electron beam photoresist and preparation and use thereof.
The application also aims at providing the electron beam photoresist with high sensitivity, and the preparation method and the use method thereof.
In order to achieve the purpose of the invention, the following technical scheme is provided.
In a first aspect, the present application provides a method of preparing a polymer resin comprising the steps of:
1) Polymerizing a monomer composition comprising an aromatic vinyl monomer and an alpha-halogenated acrylate monomer;
2) And (2) settling, filtering and drying the mixture obtained in the step (1) in a solution comprising a ketone solvent and/or an alkyl solvent to obtain the polymer resin.
In a preferred manner of the first aspect, at least one of the following technical features is further included:
a1 The aromatic vinyl monomer is selected from at least one of alpha-methyl styrene monomer and 4-fluoro-alpha-methyl styrene monomer;
a2 The alpha-halogenated acrylate monomer is selected from alpha-methyl chloroacrylate monomer, alpha-ethyl chloroacrylate monomer, alpha-benzyl chloroacrylate monomer alpha-chloroacrylic acid-1-adamantyl ester monomer, alpha-chloroacrylic acid-2, 3-pentafluoropropyl ester monomer alpha-chloroacrylic acid-2, 3, 4-heptafluorobutyl ester monomer alpha-fluoro methyl acrylate monomer, alpha-fluoro ethyl acrylate monomer, alpha-fluoro benzyl acrylate monomer, alpha-fluoro 1-adamantyl acrylate monomer alpha-fluoro-acrylic acid-2, 3-pentafluoropropyl ester monomer and alpha-chloro at least one of 2,3, 4-heptafluorobutyl acrylate monomers;
a3 A molar ratio of the aromatic vinyl monomer to the alpha-halogenated acrylate monomer of 2:1 to 1:1, such as 2:1 to 5.2: 4. 5.2:4 to 1.1:1 or 1.1:1 to 1:1, a step of;
a4 The ketone solvent is selected from at least one of acetone, cyclohexanone and methyl isobutyl ketone; preferably acetone;
a5 The alkyl solvent is at least one selected from n-pentane, n-hexane, cyclohexane and n-heptane;
a6 The volume ratio of the mixture obtained in the step 1) to the solution comprising ketone solvents/or alkyl solvents is 1:5 to 1:2, such as 1:5 to 1:3 or 1: 3-1: 2;
a7 The volume ratio of the ketone solvent to the alkyl solvent is 6:1 to 1:2, such as 6:1 to 4: 1. 4:1 to 3:2 or 3: 2-1: 2;
a8 The drying temperature is 40-60 ℃, such as 40-50 ℃, 50-55 ℃ or 55-60 ℃.
In a second aspect, the present application provides a polymer resin obtained using the above-described preparation method.
In a preferred mode of the second aspect, at least one of the following technical features is further included:
b1 The weight average molecular weight of the polymer resin is 35000-70000, such as 35000-54100, 54100-57200, 57200-59500, 59500-61200 or 61200-70000;
b2 The molecular weight distribution coefficient of the polymer resin is less than 3, such as 1.62-1.74, 1.74-1.78, 1.78-1.81.
In a third aspect, the present application also provides a method of improving cracking of an electron beam resist to which the above polymer resin is added. Namely, the electron beam photoresist contains the polymer resin.
In a fourth aspect, the present application also provides an electron beam resist comprising the polymer resin described above.
In a preferred mode of the fourth aspect, the composition comprises the following components in percentage by mass:
3 to 15%, such as 3 to 10% or 10 to 15%, of the polymer resin;
85-97%, such as 85-90% or 90-97% of solvent.
In a preferred mode of the fourth aspect, at least one of the following technical features is further included:
c1 The solvent is at least one selected from anisole, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethylene glycol methyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, butyl acetate, neopentyl acetate, gamma-butyl lactone and ethyl lactate;
c2 The auxiliary agent is at least one selected from a photoacid generator, a viscosity control agent, a stabilizer and a leveling agent. The photoacid generator is selected from at least one of N-hydroxynaphthalimide triflate, (4, 8-dihydroxy-1-naphthyl) dimethyl sulfonium triflate, (4, 7-dihydroxy-1-naphthyl) dimethyl sulfonium triflate, (4-methoxynaphthyl) diphenyl sulfonium triflate, (4-phenylthiophenyl) diphenyl sulfonium triflate, 2- (benzo [ d ] [1,3] dioxolan-5-yl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (2, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 2- [4- (4-methoxyphenyl) phenyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, the viscosity controlling agent is selected from at least one of butanol, chloroform, ethanol, water, acetonitrile, hexane and isopropanol, and the stabilizer is selected from at least one of p-quinone, methyl hydroquinone, p-hydroxy anisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone. The leveling agent is one or more selected from acrylic leveling agent, silicon-containing leveling agent and fluorine-containing leveling agent, such as Dow Corning DC-7, MEGAFACE F-563 (purchased from DIC Co., ltd.), polymethylphenylsiloxane, polydimethylsiloxane, ETA-706, etc. Preferably, the electron beam photoresist comprises the following components in percentage by mass:
3 to 15%, such as 3 to 7% or 7 to 15%, of the polymer resin;
84.95 to 96.998 percent of solvent, such as 84.95 to 92.98 percent or 92.98 to 96.998 percent;
0.002-0.05% of auxiliary agent, such as 0.002-0.02% or 0.02-0.05%.
In a fifth aspect, the present invention also provides a method for preparing the electron beam photoresist as described above, comprising the steps of: and mixing the components of the electron beam photoresist to obtain the electron beam photoresist.
In a sixth aspect, the present invention also provides a method for using the electron beam photoresist as described above, comprising the steps of: and coating the electron beam photoresist on a silicon wafer, and sequentially performing pre-baking, exposure, development and fixation to obtain a photoetching pattern.
In a preferred mode of the sixth aspect, at least one of the following technical features is further included:
d1 The pre-baking temperature is 160-180 ℃, such as 160-170 ℃ or 170-180 ℃;
d2 The pre-baking time is 160-200 s, such as 160-180 s or 180-200 s;
d3 Exposure energy of 1-10C/m 2 Such as 1-2C/m 2 、2～3C/m 2 、3～4C/m 2 Or 4 to 10C/m 2 ；
d4 The developing solution used for developing is amyl acetate or a mixed solution comprising amyl acetate and isopropanol; preferably amyl acetate;
d5 The development time is 50 to 70s, such as 50 to 60s or 60 to 70s;
d6 A fixing liquid used for fixing is isopropanol;
c7 The fixing time is 30 to 50s, such as 30 to 40s or 40 to 50s.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing the mixture by polymerizing the monomer composition containing the aromatic vinyl monomer and the alpha-halogenated acrylate monomer, which is characterized in that the mixture is settled in a solution containing ketone solvents/alkyl solvents, so that the cracking of the electron beam photoresist can be improved, the reliability of the exposure of the electron beam photoresist can be improved, and the operation is simple, convenient and reliable.
Drawings
Fig. 1 is a scanning electron microscope image obtained by the electron beam resist of example 1.
Fig. 2 is a scanning electron microscope image obtained by the electron beam resist of example 2.
Fig. 3 is a scanning electron microscope image obtained by the electron beam resist of example 3.
Fig. 4 is a scanning electron microscope image obtained by the electron beam resist of example 4.
Fig. 5 is a scanning electron microscope image obtained by the electron beam resist of comparative example 1.
Detailed Description
Unless otherwise indicated, implied from the context, or common denominator in the art, all parts and percentages in the present application are based on weight and the test and characterization methods used are synchronized with the filing date of the present application. Where applicable, the disclosure of any patent, patent application, or publication referred to in this application is incorporated by reference in its entirety, and the equivalent of such patent is incorporated by reference, particularly as regards the definitions of synthetic techniques, product and process designs, polymers, comonomers, initiators or catalysts, etc. in the art, as disclosed in such documents. If the definition of a particular term disclosed in the prior art does not conform to any definition provided in this application, the definition of that term provided in this application controls.
Numerical ranges in this application are approximations, so that it may include the numerical values outside of the range unless otherwise indicated. The numerical range includes all values from the lower value to the upper value that increase by 1 unit, provided that there is a spacing of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, melt index, etc.) is recited as being 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing values less than 1 or containing fractions greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is suitably considered to be 0.0001,0.001,0.01, or 0.1. For a range including units less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1 these are merely specific examples of what is intended to be expressed, and all possible combinations of values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. The numerical ranges within this application provide, inter alia, the calcium-containing filler content, the stirring temperature, and various features and properties of these components.
As used with respect to chemical compounds, the singular includes all isomeric forms and vice versa unless explicitly stated otherwise (e.g., "hexane" includes all isomers of hexane, either individually or collectively). In addition, unless explicitly stated otherwise, the use of the terms "a," "an," or "the" include plural referents.
The terms "comprises," "comprising," "including," and their derivatives do not exclude the presence of any other component, step or procedure, and are not related to whether or not such other component, step or procedure is disclosed in the present application. For the avoidance of any doubt, all use of the terms "comprising," "including," or "having" herein, unless expressly stated otherwise, may include any additional additive, adjuvant, or compound. Rather, the term "consisting essentially of … …" excludes any other component, step or process from the scope of any of the terms recited below, except as necessary for operability. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. The term "or" refers to the listed individual members or any combination thereof unless explicitly stated otherwise.
Examples
The following will describe embodiments of the present invention in detail, and the embodiments and specific operation procedures are given by implementing the present invention on the premise of its technical solution, but the scope of protection of the present invention is not limited to the following embodiments.
Example 1
A method for preparing a polymer resin, comprising the steps of:
1) 482.1g (4.0 mol) of alpha-methyl chloroacrylate and 614.51g (5.2 mol) of alpha-methylstyrene are dissolved in 1253.5g of dioxane and the temperature is raised to 85 ℃. Then a dioxane solution containing 0.50g of azobisisobutyronitrile was added. After the reaction was continued for 18 hours, it was cooled to room temperature. The methylene chloride was diluted to twice the original volume.
2) Settling the system into 5 times of mixed solution comprising acetone and n-heptane, filtering and drying, wherein the volume ratio of the acetone to the n-heptane is 4:1, the drying temperature was 60 ℃. GPC test data: the weight average molecular weight Mw was 59.5K and the molecular weight distribution coefficient D was 1.74.
An electron beam photoresist comprises the following components in percentage by mass:
7% of a polymer resin obtained by the above-mentioned production method;
92.98% of anisole solvent;
0.02% of auxiliary agent isopropanol.
The preparation method of the electron beam photoresist comprises the following steps: adding the components according to the formula, and stirring to completely dissolve.
The electron beam photoresist prepared is used according to the following method:
spin-coating the electron beam photoresist on a 4-inch silicon wafer, wherein the spin-coating rotating speed is 3000rpm, and the coating thickness of the electron beam photoresist is 1200A; pre-baking at 180 ℃ for 180s; exposing in electron beam lithography machine with electron beam lithography voltage of 100KeV, current of 500pA and exposure energy of 2C/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing in a developing solution of amyl acetate for 60s, fixing with isopropanol for 40s, and observing the pattern morphology by a scanning electron microscope, wherein the pattern of the square single-end line combination groove has no crack as shown in figure 1.
Example 2
A method for preparing a polymer resin, comprising the steps of:
1) 482.1g (4.0 mol) of alpha-methyl chloroacrylate and 614.51g (5.2 mol) of alpha-methylstyrene are dissolved in 1253.5g of dioxane and the temperature is raised to 85 ℃. Then a dioxane solution containing 0.50g of azobisisobutyronitrile was added. After the reaction was continued for 18 hours, it was cooled to room temperature. The methylene chloride was diluted to twice the original volume.
2) The system was precipitated into 5 volumes of acetone solution, filtered and dried at 40 ℃. GPC test data: the weight average molecular weight Mw was 57.2K and the molecular weight distribution coefficient D was 1.78.
An electron beam photoresist comprises the following components in percentage by mass:
10% of a polymer resin obtained by the above-mentioned production method;
90% of propylene glycol methyl ether acetate solvent.
The preparation method of the electron beam photoresist comprises the following steps: adding the components according to the formula, and stirring to completely dissolve.
The electron beam photoresist prepared is used according to the following method:
spin-coating the electron beam photoresist on a 4-inch silicon wafer, wherein the spin-coating rotating speed is 3000rpm, and the coating thickness of the electron beam photoresist is 1200A; pre-baking at 180 ℃ for 180s; exposing in electron beam lithography machine with electron beam lithography voltage of 100KeV, current of 500pA and exposure energy of 3C/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The development is carried out in the developer solution,the developing solution is amyl acetate, the developing time is 60s, the isopropanol is used for fixing for 40s, the pattern morphology is observed by a scanning electron microscope, and the pattern of the square single-end line combination groove has no crack as shown in figure 2.
Example 3
A method for preparing a polymer resin, comprising the steps of:
1) 241.1g (2.0 mol) of alpha-methyl chloroacrylate and 472.7g (4.0 mol) of alpha-methylstyrene were dissolved in 620g of dioxane and the temperature was raised to 80 ℃. Then a dioxane solution containing 0.28g of azobisisobutyronitrile was added. After the reaction was continued for 20 hours, it was cooled to room temperature. The methylene chloride was diluted to twice the original volume.
2) Settling the system into a mixed solution which is 2 times of volume and comprises acetone and n-heptane, filtering and drying, wherein the volume ratio of the acetone to the n-heptane is 6:1, the drying temperature was 50 ℃. GPC test data: the weight average molecular weight Mw was 61.2K and the molecular weight distribution coefficient D was 1.81.
An electron beam photoresist comprises the following components in percentage by mass:
15% of a polymer resin obtained by the above-mentioned production method;
84.95% of propylene glycol monomethyl ether as a solvent;
the auxiliary agent is Dow Corning DC-7.05%.
The preparation method of the electron beam photoresist comprises the following steps: adding the components according to the formula, and stirring to completely dissolve.
The electron beam photoresist prepared is used according to the following method:
spin-coating the electron beam photoresist on a 4-inch silicon wafer, wherein the spin-coating rotating speed is 3000rpm, and the coating thickness of the electron beam photoresist is 1200A; pre-baking at 160 ℃ for 200s; exposing in electron beam lithography machine with electron beam lithography voltage of 100KeV, current of 500pA and exposure energy of 4C/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing in a developing solution of amyl acetate for 70s, fixing with isopropanol for 50s, and observing the pattern morphology by a scanning electron microscope, wherein the pattern of the combined grooves at the two ends of the square is free from cracking, as shown in fig. 3.
Example 4
A method for preparing a polymer resin, comprising the steps of:
1) 238.54g (1 mol) of alpha-chloropropionate 2, 3-pentafluoropropyl ester and 149.79g (1.1 mol) of 4-fluoro-alpha-methylstyrene are dissolved in 350g of dioxane and the temperature is raised to 85 ℃. Then a dioxane solution containing 0.15g of azobisisobutyronitrile was added. After the reaction was continued for 16 hours, it was cooled to room temperature. The methylene dichloride is diluted to 3 times of the original volume.
2) Settling the system into 3 times of mixed solution comprising cyclohexanone and cyclohexane, filtering and drying, wherein the volume ratio of the cyclohexanone to the cyclohexane is 1:2, the drying temperature was 55 ℃. GPC test data: the weight average molecular weight Mw was 54.1K and the molecular weight distribution coefficient D was 1.62.
An electron beam photoresist comprises the following components in percentage by mass:
3% of a polymer resin obtained by the above-mentioned production method;
96.998% of anisole solvent;
0.002% of auxiliary agent p-hydroxyanisole.
The preparation method of the electron beam photoresist comprises the following steps: adding the components according to the formula, and stirring to completely dissolve.
The electron beam photoresist prepared is used according to the following method:
spin-coating the electron beam photoresist on a 4-inch silicon wafer, wherein the spin-coating rotating speed is 3000rpm, and the coating thickness of the electron beam photoresist is 1200A; pre-baking at 170 ℃ for 160s; exposing in electron beam lithography machine with electron beam lithography voltage of 100KeV, current of 500pA and exposure energy of 4C/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing in a developing solution of amyl acetate for 50s, fixing with isopropanol for 30s, and observing the pattern morphology by a scanning electron microscope, wherein the pattern of the combined grooves at the two ends of the square is free from cracking, as shown in fig. 4.
Comparative example 1
A method for preparing a polymer resin, comprising the steps of:
1) 482.1g (4.0 mol) of alpha-methyl chloroacrylate and 614.51g (5.2 mol) of alpha-methylstyrene are dissolved in 1253.5g of dioxane and the temperature is raised to 85 ℃. Then a dioxane solution containing 0.50g of azobisisobutyronitrile was added. After the reaction was continued for 18 hours, it was cooled to room temperature. The methylene chloride was diluted to twice the original volume.
2) The system was precipitated into 5 volumes of n-heptane, filtered and dried at 60 ℃. GPC test data: the weight average molecular weight Mw was 39.3K and the molecular weight distribution coefficient D was 1.81.
An electron beam photoresist comprises the following components in percentage by mass:
10% of a polymer resin obtained by the above-mentioned production method;
89.98% of anisole solvent;
0.02% of auxiliary agent isopropanol.
The preparation method of the electron beam photoresist comprises the following steps: adding the components according to the formula, and stirring to completely dissolve.
The electron beam photoresist prepared is used according to the following method:
spin-coating the electron beam photoresist on a 4-inch silicon wafer, wherein the spin-coating rotating speed is 3000rpm, and the coating thickness of the electron beam photoresist is 1200A; pre-baking at 180 ℃ for 180s; exposing in electron beam lithography machine with electron beam lithography voltage of 100KeV, current of 500pA and exposure energy of 2C/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing in a developing solution of amyl acetate for 60s, fixing with isopropanol for 40s, and observing the pattern morphology by a scanning electron microscope, wherein in FIG. 5, the corners of the square single-end line combined groove pattern are provided with cracking patterns.
Therefore, the mixture obtained by polymerizing the monomer composition containing the aromatic vinyl monomer and the alpha-halogenated acrylate monomer is settled in the solution containing the ketone solvent/the alkyl solvent, so that the cracking of the electron beam photoresist can be improved, the reliability of the exposure of the electron beam photoresist can be improved, and the operation is simple, convenient and reliable.
The embodiments are described above in order to facilitate the understanding and application of the present application by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Accordingly, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications without departing from the scope and spirit of the present application.
Claims (6)
1. The electron beam photoresist is characterized by comprising 3-15% of polymer resin and 85-97% of solvent, wherein the solvent is at least one of anisole, propylene glycol methyl ether acetate and propylene glycol monomethyl ether; the polymer resin is prepared by the following steps:
1) Polymerizing a monomer composition comprising an aromatic vinyl monomer and an alpha-halogenated acrylate monomer; wherein the aromatic vinyl monomer is selected from at least one of alpha-methyl styrene monomer and 4-fluoro-alpha-methyl styrene monomer, the alpha-halogenated acrylate monomer is selected from alpha-methyl chloroacrylate monomer, alpha-ethyl chloroacrylate monomer, alpha-benzyl chloroacrylate monomer, alpha-1-adamantyl chloroacrylate monomer, alpha-2, 3-pentafluoropropyl chloroacrylate monomer, alpha-methyl fluoroacrylate monomer at least one of an alpha-ethyl fluoroacrylate monomer, an alpha-benzyl fluoroacrylate monomer, an alpha-1-adamantyl fluoroacrylate monomer, an alpha-2, 3-pentafluoropropyl fluoroacrylate monomer and an alpha-2, 3, 4-heptafluorobutyl chloroacrylate monomer, the molar ratio of the aromatic vinyl monomer to the alpha-halogenated acrylate monomer is 2: 1-1: 1, a step of;
2) Settling, filtering and drying the mixture obtained in the step 1) in a ketone solvent or a solution consisting of the ketone solvent and an alkyl solvent to obtain the polymer resin, wherein the ketone solvent is at least one selected from acetone and cyclohexanone; the alkyl solvent is at least one selected from cyclohexane and n-heptane; the volume ratio of the mixture obtained in the step 1) to the ketone solvent or the solution consisting of the ketone solvent and the alkyl solvent is 1: 5-1: 2; the volume ratio of the ketone solvent to the alkyl solvent is 6: 1-1: 2; the drying temperature is 40-60 ℃.
2. The electron beam resist of claim 1, further comprising at least one of the following technical features:
b1 The weight average molecular weight of the polymer resin is 35000-70000;
b2 A molecular weight distribution coefficient of the polymer resin is < 3.
3. The electron beam resist of claim 1, further comprising an auxiliary agent selected from at least one of a photoacid generator, a viscosity control agent, a stabilizer, and a leveling agent.
4. A method for preparing an electron beam resist according to any one of claims 1 to 3, comprising the steps of: and mixing the components of the electron beam photoresist to obtain the electron beam photoresist.
5. A method of using the electron beam resist as claimed in any one of claims 1 to 3, comprising the steps of: and coating the electron beam photoresist on a silicon wafer, and sequentially performing pre-baking, exposure, development and fixation to obtain a photoetching pattern.
6. The method of claim 5, further comprising at least one of the following features:
d1 The pre-baking temperature is 160-180 ℃;
d2 The pre-baking time is 160-200 s;
d3 Exposure energy of 1-10C/m 2 ；
d4 The developing solution used for developing is amyl acetate or a mixed solution comprising amyl acetate and isopropanol;
d5 Developing time is 50-70 s;
d6 A fixing liquid used for fixing is isopropanol;
d7 Fixing time is 30-50 s.
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| WO2000016160A1 (en) * | 1998-09-10 | 2000-03-23 | Toray Industries, Inc. | Positive radiation-sensitive composition |
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| WO2019150966A1 (en) * | 2018-02-05 | 2019-08-08 | 日本ゼオン株式会社 | Resist composition and resist film |
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| JPH03132760A (en) * | 1989-10-19 | 1991-06-06 | Fujitsu Ltd | Resist pattern forming method |
| WO2000016160A1 (en) * | 1998-09-10 | 2000-03-23 | Toray Industries, Inc. | Positive radiation-sensitive composition |
| CN103339568A (en) * | 2011-01-25 | 2013-10-02 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for manufacturing printed wiring board |
| CN105393171A (en) * | 2013-07-23 | 2016-03-09 | 日立化成株式会社 | Photosensitive resin composition for projection exposure, photosensitive element, method for forming resist pattern, process for producing printed wiring board and process for producing lead frame |
| WO2019150966A1 (en) * | 2018-02-05 | 2019-08-08 | 日本ゼオン株式会社 | Resist composition and resist film |
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