CN117003698A - Polymerizable oxime sulfonate photoinduced acid generator, photoresist resin and preparation method thereof - Google Patents
Polymerizable oxime sulfonate photoinduced acid generator, photoresist resin and preparation method thereof Download PDFInfo
- Publication number
- CN117003698A CN117003698A CN202310988871.8A CN202310988871A CN117003698A CN 117003698 A CN117003698 A CN 117003698A CN 202310988871 A CN202310988871 A CN 202310988871A CN 117003698 A CN117003698 A CN 117003698A
- Authority
- CN
- China
- Prior art keywords
- photoacid generator
- solvent
- polymerizable
- acid
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 30
- -1 oxime sulfonate Chemical class 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000006467 substitution reaction Methods 0.000 claims abstract description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- QSUJHKWXLIQKEY-UHFFFAOYSA-N (2-oxooxolan-3-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCOC1=O QSUJHKWXLIQKEY-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Chemical group 0.000 claims description 4
- 229910052739 hydrogen Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 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 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- LVRCEUVOXCJYSV-UHFFFAOYSA-N CN(C)S(=O)=O Chemical compound CN(C)S(=O)=O LVRCEUVOXCJYSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- AOWTYVFGMCEIRN-UHFFFAOYSA-N ethoxycyclopentane Chemical compound CCOC1CCCC1 AOWTYVFGMCEIRN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 claims description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- DTUOTSLAFJCQHN-UHFFFAOYSA-N 4-bromo-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Br DTUOTSLAFJCQHN-UHFFFAOYSA-N 0.000 description 3
- VHEKFTULOYIMSU-UHFFFAOYSA-N 4-ethenylbenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=C(C=C)C=C1 VHEKFTULOYIMSU-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AYGAKGHUCUNBHE-UHFFFAOYSA-N benzenethiol;fluorobenzene Chemical compound FC1=CC=CC=C1.SC1=CC=CC=C1 AYGAKGHUCUNBHE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a polymerizable sulfoximine ester photoacid generator and a photoresist resin and a preparation method thereof, wherein the method comprises the following steps: dispersing bromide I and a first base in a first solvent, adding R 4 H is subjected to a first substitution reaction, hydroxylamine is added to carry out dehydration condensation reaction, acid is added to adjust pH, and the intermediate II is obtained by filtration; mixing intermediate II, second base and second solvent, cooling, adding the mixture containing R 1 ‑R 2 The sulfonyl chloride compound undergoes a second substitution reaction to obtain the photoacid generator monomer III. Compared with the prior art, the invention can effectively solve the problems of uneven distribution of the photoacid generator and acid migration in the post-baking process, and realizes that the photoacid generator is used in the following stepsAnd uniformly distributed in the photoresist film.
Description
Technical Field
The invention belongs to the technical field of photoresist, and relates to a polymerizable oxime sulfonate photoacid generator, a photoresist resin and a preparation method thereof.
Background
Photolithography is a key technology used to fabricate Integrated Circuits (ICs) and other micro-nano devices. The method forms tiny patterns and structures by irradiating a light source onto the surface of a semiconductor material by using a photosensitive material and a photoetching machine, and photoresist is a key material for realizing fine pattern processing to prepare an integrated circuit. Photoresists (also known as photoresists) are used in photolithography to transfer a pattern or structure onto a surface of a semiconductor material and are photosensitive and undergo a chemical or physical change upon exposure to a light source such as ultraviolet light, electron beam, or the like, thereby curing or dissolving to cause a significant change in solubility. Chemically amplified photoresists (Chemically Amplified Photoresist, CAR) were developed in the 80 s of the 20 th century, with the main components being film forming resins, photoacid generators (Photoacid Generator, PAG), dissolution inhibitors, alkaline quenchers and solvents, etc.
PAG is one of the key components of chemically amplified resists. During exposure (light, radiation, plasma, etc.), the PAG absorbs photon energy and releases a catalytic amount of acid. These acids can undergo deprotection reactions with acid-sensitive groups in the polymer resin to form leaving groups during post-exposure bake, altering the polarity of the polymer, providing a high solubility contrast between the exposed and unexposed areas. The acid production efficiency, acid production intensity, thermal stability and transparency after photolysis of the PAG have a great influence on the performance of the photoresist. PAGs are mainly divided into ionic and nonionic types, and because nonionic PAGs have better solubility in organic solvents and polymers than ionic PAGs, and have the characteristics of low acidogenesis toxicity, wide absorption spectrum, simple synthesis and the like, the PAGs are of great interest in the fields of ultraviolet curing and microelectronics.
CARs have gained wide attention and application due to their high sensitivity and high resolution, but because PAGs are typically small molecular compounds, they have inherent incompatibility properties with polymers as film-forming resins, i.e., small molecular photoacid generators have limited compatibility with polymer resins, resulting in phase separation of components in the photoresist, uneven photoacid generator distribution, and acid migration of small molecules during post-bake, resulting in uneven acid-catalyzed photochemical reactions in the exposed areas, resulting in large line edge roughness (Line Width Roughness, LER) of the imaged pattern, and reduced photoresist resolution.
Patent CN112592304a discloses a polymerizable photo-acid generator containing a double onium salt structure, a preparation method and a photoresist, and the polymerizable photo-acid generator containing the double onium salt structure has the following structural general formula:
wherein n is an integer of 1 or more; r is R 1 -R 4 Is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen hetero atoms; anions M - Is a sulfonic acid anion.
Patent CN115594790a discloses a photoacid generator-containing photopolymer, which can be prepared as a photopolymer by including a photoacid generator, in which vinyl groups are introduced into an alicyclic ring, and a method of preparing the same.
Patent CN106527046a discloses a new photoresist with a photosensitizer bonded to an acid generator, the photoresist comprising a polymer and a photoacid generator; the photoacid generator comprises a sensitizer component, an acid generator component, and a bonding component that bonds the sensitizer component to the acid generator component; the bonding component may be a single bond or a conjugated bond; the lithographic process may be an EUV lithographic process or an electron beam lithographic process.
Patent CN111699206a discloses a polymer comprising a photoacid generator.
The above patents all have the problems of compatibility between the photoacid generator and the resin and acid diffusion of the photoacid generator in the post-exposure baking process, thereby reducing line edge roughness and photoresist resolution.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art and provide a polymerizable oxime sulfonate photoacid generator, a photoresist resin and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a polymerizable oxime sulfonate photoacid generator, which is a polymerizable monomer and has the structural formula:
wherein R is 1 Comprising vinyl or methyl methacrylate, R 2 Comprises benzene ring, R 3 Comprising benzene or naphthalene rings, R 4 Comprising hydrogen atoms, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 ring members, R 4 The carbon or hydrogen substituted group on the polymer comprises-O-; -S-, -CO-O-, -SO 2 -or-F.
The invention provides a preparation method of a polymerizable oxime sulfonate photoacid generator, which comprises the following steps:
wherein R is 1 Comprising vinyl or methyl methacrylate, R 2 Comprises benzene ring, R 3 Comprising benzene or naphthalene rings, R 4 Comprising hydrogen atoms, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 ring members, R 4 The carbon or hydrogen substituted group on the polymer comprises-O-; -S-, -CO-O-, -SO 2 -or-F;
the method comprises the following steps:
(1) Dispersing bromide I and a first base in a first solvent, adding R 4 H is subjected to a first substitution reaction, hydroxylamine is added to carry out dehydration condensation reaction, acid is added to adjust pH, after stirring is carried out for a while, precipitate is filtered and recovered, and then decompression drying is carried out to obtain the intermediateAn intermediate II;
(2) Mixing intermediate II, second base and second solvent, cooling, adding the mixture containing R 1 -R 2 The sulfonyl chloride compound undergoes a second substitution reaction, washing, recrystallization and drying to obtain the photoacid generator monomer III.
As a preferable technical scheme, the structural formula of the intermediate II in the step (1) comprises:
the structural formula of the photoacid generator monomer III in the step (2) comprises:
。
further, in the step (1), the mole ratio of the bromide I to the first base is 1 (0.8-1.5), the mole ratio of the bromide I to the first solvent is 1 (85-105), and the mole ratio of the bromide I to the R is 1 4 H molar ratio is 1 (1.5-3);
the first base comprises lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, lithium hydroxide, potassium hydroxide or sodium hydroxide, and the first solvent is selected from one or more of ethyl acetate, butyl acetate, diethyl malonate, acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N-dimethylformamide, diethyl ether, ethylcyclopentyl ether, tetrahydrofuran, dioxane, toluene, xylene, acetonitrile, propionitrile, dimethyl sulfoxide and dimethyl sulfonamide.
Further, the first substitution reaction temperature in the step (1) is 60-120 ℃ and the time is 6-20h.
Further, in the step (1), the molar ratio of bromide I to hydroxylamine is 1 (4.5-7.5);
the dehydration condensation reaction temperature is room temperature and the time is 2-6h;
the pH is adjusted to 5-6.5;
the acid includes hydrochloric acid, phosphoric acid, formic acid, acetic acid or glycine.
As a preferable technical scheme, after the dehydration condensation reaction in the step (1) is finished, adding a reaction solution into a fourth solvent, wherein the volume ratio of the reaction solution to the fourth solvent is (50-80): 500-800, and the fourth solvent is one or more selected from water, methanol and ethanol.
As a preferable technical scheme, the reduced pressure drying temperature in the step (1) is 60-80 ℃.
Further, in the step (2), the molar ratio of the intermediate II to the second base is 4 (18-25), the dosage ratio of the intermediate II to the second solvent is 4-5 mol) (16-30 mL), and the molar ratio of the intermediate II to the second solvent is R 1 -R 2 The molar ratio of the sulfonyl chloride compound is 40 (40-65);
the second base comprises methylamine, ethylamine, N-propylamine, isopropylamine, N-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, trimethylamine, triethylamine, methyldiethylamine or N-ethyldiisopropylamine, and the second solvent is one or more selected from methanol, dichloromethane, chloroform, ethyl acetate, ethanol, acetone, methyl ethyl ketone and tetrahydrofuran.
Further, the cooling temperature in the step (2) is 0-5 ℃, the second substitution reaction temperature is room temperature, and the time is 5-24 hours.
As a preferred embodiment, the recrystallization in step (2) uses a fifth solvent, which includes methanol or butanone.
As a preferable technical scheme, the drying temperature in the step (2) is 30-75 ℃.
One of the technical schemes of the invention is to provide a photoresist resin, which is structurally characterized in that the photoacid generator is grafted to a polymer resin main chain.
One of the technical schemes of the invention is to provide a preparation method of photoresist resin, which comprises the following steps:
adding tert-butyl acrylate, 2-oxo-tetrahydrofuran-3-yl methacrylate, a photoacid generator and an initiator, dissolving with a third solvent, introducing inert gas for protection, heating for reaction to obtain a polymer solution, allowing the system to be in a turbid state, precipitating, filtering, and vacuum drying to obtain the photoresist resin.
As a preferable technical scheme, the structural formula of the tert-butyl acrylate is as follows:
the structural formula of the 2-oxo-tetrahydrofuran-3-yl methacrylate is as follows:
further, the mass ratio of the tert-butyl acrylate to the 2-oxo-tetrahydrofuran-3-yl methacrylate and the photoacid generator to the initiator is (1.2-1.5), the mass ratio of the photoacid generator to the initiator is (2.5-3.2), the mass ratio of the tert-butyl acrylate to the second solvent is (0.2-0.4), and the mass ratio of the tert-butyl acrylate to the second solvent is (1.2-1.5 g), the mass ratio of the photoacid generator to the initiator is (20-55 mL);
the initiator comprises an azo initiator or a free radical initiator of peroxide, wherein the azo initiator is selected from one or two of azodiisobutyronitrile and azodiisoheptonitrile, the free radical initiator of peroxide is selected from one or more of tert-butyl pivalate peroxide, tert-butyloxy hydroperoxide, benzoic acid hydroperoxide and benzoyl peroxide, and the third solvent comprises tetrahydrofuran, methanol, acetone, dioxane or chloroform;
the protection time is 5-120min, the heating reaction temperature is 40-90 ℃ and the time is 3-24h;
the inert gas comprises nitrogen or argon.
According to the preferable technical scheme, after the heating reaction is finished, a sixth solvent is added into the polymer solution, the volume ratio of the polymer solution to the sixth solvent is (24-50): 240-500, and the sixth solvent is one or more selected from petroleum ether, n-hexane, water and methanol.
As a preferable technical scheme, the vacuum drying temperature is 35-45 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the preparation of the small molecular photoacid generator structure into the polymerizable monomer structure, and the polymerizable photoacid generator structure is copolymerized onto the polymer resin main chain through free radical polymerization, namely, the polymerizable photoacid generator monomer is grafted onto the polymer resin main chain, so that proton transfer is limited, the problems of uneven photoacid generator distribution and acid migration in the post-baking process can be effectively improved, the uniform distribution of the photoacid generator in the photoresist film is realized, the segregation of the photoacid generator in the photoresist formula can be eliminated, the outgassing causing film defects is reduced, and the swelling effect is reduced;
(2) The preparation method of the invention is simple and convenient, low in cost and high in yield.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The equipment used in the following examples is representative of conventional equipment in the art unless otherwise specified; unless otherwise indicated, all reagents used are commercially available or prepared by methods conventional in the art, and all of the following examples, not specifically described, are accomplished by means of conventional experimentation in the art.
Example 1:
a polymerizable sulfoximine ester photoacid generator monomer PMeO and a preparation method thereof are provided, wherein the equation is as follows:
the method comprises the following specific steps:
(1) 4-bromo-1, 8-naphthalic anhydride (2.8 g,0.01 mol) and potassium carbonate (1.51 g,0.01 mol) were dispersed in acetonitrile (51 mL,0.974 mol), and p-methoxyphenylthiol (2.832 g,0.02 mol) was charged and reacted at 75℃for 6 hours; next, 50% aqueous hydroxylamine (1.67 mL,0.054 mol) was added dropwise thereto and reacted at room temperature for 2 hours; after the reaction was completed, 60mL of the reaction solution was poured into 500mL of ion-exchanged water, and then 0.01mol/L hydrochloric acid was poured until the pH reached 5; after stirring for a short time, the precipitate was recovered by filtration and dried under reduced pressure at 70℃to give intermediate A1 (3.11 g,0.008mol, 88.6%);
(2) Intermediate A1 (1.4 g, 0.04 mol), triethylamine (TEA, 2.04g,0.02 mol) and dichloromethane (DCM, 16ml,0.25 mol) were put into a one-necked flask, cooled in an ice-water bath, and p-vinylbenzenesulfonyl chloride (0.284 g,0.0048 mol) was slowly put into the one-necked flask through a constant pressure funnel, followed by further reaction at room temperature for 5 hours; after the reaction was completed, the reaction mixture was washed with water, and then 1.93g of the reaction product was recrystallized from 21mL of butanone and dried in an oven at 40℃to obtain polymerizable oxime sulfonate photoacid generator monomer PMeO (1.89 g,0.0036mol, 91.5%).
A polymerizable sulfoximine ester photoacid generator copolymerized photoresist resin PM1 and a preparation method thereof are disclosed, wherein the equation is as follows:
the method comprises the following specific steps:
firstly, taking a clean 250mL double-mouth bottle, installing a stirring and condensing device, sequentially adding 1.28g of tert-butyl acrylate (TBA), 2.55g of 2-oxo-tetrahydrofuran-3-yl methacrylate, 0.5g of polymerizable oxime sulfonate photoinduced acid generator monomer PMeO and 0.205g of azo diisobutyronitrile, dissolving with 24mL of tetrahydrofuran, introducing nitrogen for protection for 5min, and heating and reacting for 24h under the oil bath condition at 65 ℃ to obtain 28mL of polymer solution, wherein the system is in a turbid state; after the reaction was completed, 500mL of petroleum ether was added to 28mL of the polymer solution, precipitated and filtered, and vacuum-dried at 40℃to obtain 1.62g of polymerizable oxime sulfonate photoacid generator-copolymerized type resist resin PM1.
The GPC apparatus measured the polymerizable oxime sulfonate photoacid generator-copolymerized photoresist resin PM1 prepared in this example, which had a molecular weight mn=7783, mw=12625, and pdi=1.622.
Example 2:
a polymerizable sulfoximine ester photoacid generator monomer PtBu and a preparation method thereof are disclosed, wherein the equation is as follows:
the method comprises the following specific steps:
(1) 4-bromo-1, 8-naphthalic anhydride (2.8 g,0.01 mol) and potassium carbonate (1.51 g,0.01 mol) were dispersed in acetonitrile (51 mL,0.974 mol), and p-tert-butylphenol (3.325 g,0.02 mol) was charged and reacted at 75℃for 6 hours; next, 50% aqueous hydroxylamine (1.67 mL,0.054 mol) was added dropwise thereto and reacted at room temperature for 2 hours; after the reaction was completed, 60mL of the reaction solution was poured into 500mL of ion-exchanged water, and then 0.01mol/L hydrochloric acid was poured until the pH reached 5; after stirring for a short time, the precipitate was recovered by filtration and dried under reduced pressure at 70℃to give intermediate A2 (3.25 g,0.008mol, 86.4%);
(2) Intermediate A2 (1.5 g, 0.04 mol), triethylamine (2.04 g,0.02 mol) and methylene chloride (16 mL,0.25 mol) were put into a one-necked flask, cooled in an ice-water bath, and p-vinylbenzenesulfonyl chloride (0.284 g,0.0048 mol) was slowly put into the one-necked flask through a constant pressure funnel, and then the reaction was continued at room temperature for 5 hours; after the reaction was completed, the reaction mixture was washed with water, and then 2.13g of the reaction product was recrystallized from 21mL of butanone and dried in an oven at 40℃to obtain a polymerizable oxime sulfonate photoacid generator monomer PtBu (1.92 g,0.0036mol, 88.2%).
Example 3:
a polymerizable sulfoximine ester photoacid generator monomer POF and a preparation method thereof are provided, wherein the equation is as follows:
the method comprises the following specific steps:
(1) 4-bromo-1, 8-naphthalic anhydride (2.8 g,0.01 mol) and potassium carbonate (1.51 g,0.01 mol) were dispersed in acetonitrile (51 mL,0.974 mol), and then 4-fluorobenzene thiophenol (2.56 g,0.02 mol) was charged and reacted at 75℃for 6 hours; next, 50% aqueous hydroxylamine (1.67 mL,0.054 mol) was added dropwise thereto and reacted at room temperature for 2 hours; after the reaction was completed, 60mL of the reaction solution was poured into 500mL of ion-exchanged water, and then 0.01mol/L hydrochloric acid was poured until the pH reached 5; after stirring for a moment, the precipitate was recovered by filtration and dried under reduced pressure at 70℃to give intermediate A3 (2.91 g,0.008mol, 85.7%);
(2) Intermediate A3 (1.356 g, 0.04 mol), triethylamine (2.04 g,0.02 mol) and methylene chloride (16 mL,0.25 mol) were put into a one-necked flask, cooled in an ice-water bath, and p-vinylbenzenesulfonyl chloride (0.284 g,0.0048 mol) was slowly put into the one-necked flask through a constant pressure funnel, followed by further reaction at room temperature for 5 hours; after the reaction was completed, the reaction mixture was washed with water, and then 1.95g of the reaction product was recrystallized from 21mL of butanone and dried in an oven at 40℃to obtain polymerizable oxime sulfonate photoacid generator monomer POF (1.88 g,0.0037mol, 92.7%).
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The polymerizable oxime sulfonate photoacid generator is characterized in that the photoacid generator is a polymerizable monomer and has the structural formula:
wherein R is 1 Comprising vinyl or methyl methacrylate, R 2 Comprises benzene ring, R 3 Comprising benzene or naphthalene rings, R 4 Comprising hydrogen atoms, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 ring members, R 4 The carbon or hydrogen substituted group on the polymer comprises-O-; -S-, -CO-O-, -SO 2 -or-F.
2. A method for preparing the polymerizable oxime sulfonate photoacid generator of claim 1, wherein the method comprises the following steps:
wherein R is 1 Comprising vinyl or methyl methacrylate, R 2 Comprises benzene ring, R 3 Comprising benzene or naphthalene rings, R 4 Comprising hydrogen atoms, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 ring members, R 4 The carbon or hydrogen substituted group on the polymer comprises-O-; -S-, -CO-O-, -SO 2 -or-F;
the method comprises the following steps:
(1) Dispersing bromide I and a first base in a first solvent, adding R 4 H is subjected to a first substitution reaction, hydroxylamine is added to carry out dehydration condensation reaction, acid is added to adjust pH, and the intermediate II is obtained by filtration;
(2) Intermediate II, second base and firstMixing the two solvents, cooling, and adding R-containing solvent 1 -R 2 The sulfonyl chloride compound undergoes a second substitution reaction to obtain the photoacid generator monomer III.
3. The process for preparing a polymerizable oxime sulfonate photoacid generator according to claim 2, wherein in the step (1), the molar ratio of bromide I to the first base is 1 (0.8-1.5), the molar ratio of bromide I to the first solvent is 1 (85-105), and the molar ratio of bromide I to R 4 H molar ratio is 1 (1.5-3);
the first base comprises lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, lithium hydroxide, potassium hydroxide or sodium hydroxide, and the first solvent is selected from one or more of ethyl acetate, butyl acetate, diethyl malonate, acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N-dimethylformamide, diethyl ether, ethylcyclopentyl ether, tetrahydrofuran, dioxane, toluene, xylene, acetonitrile, propionitrile, dimethyl sulfoxide and dimethyl sulfonamide.
4. The method for preparing a polymerizable oxime sulfonate photoacid generator according to claim 2, wherein the first substitution reaction temperature in the step (1) is 60-120 ℃ for 6-20 hours.
5. The method for preparing the polymerizable oxime sulfonate photoacid generator according to claim 2, wherein the molar ratio of bromide I to hydroxylamine in the step (1) is 1 (4.5-7.5);
the dehydration condensation reaction temperature is room temperature and the time is 2-6h;
the pH is adjusted to 5-6.5;
the acid includes hydrochloric acid, phosphoric acid, formic acid, acetic acid or glycine.
6. The process for producing a polymerizable oxime sulfonate photoacid generator as claimed in claim 2, wherein the molar ratio of the intermediate II to the second base in the step (2) is 4 (18)25 The dosage ratio of the intermediate II to the second solvent is (4-5 mol) (16-30 mL), the intermediate II and the solvent containing R 1 -R 2 The molar ratio of the sulfonyl chloride compound is 40 (40-65);
the second base comprises methylamine, ethylamine, N-propylamine, isopropylamine, N-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, trimethylamine, triethylamine, methyldiethylamine or N-ethyldiisopropylamine, and the second solvent is one or more selected from methanol, dichloromethane, chloroform, ethyl acetate, ethanol, acetone, methyl ethyl ketone and tetrahydrofuran.
7. The method for preparing a polymerizable oxime sulfonate photoacid generator according to claim 2, wherein the cooling temperature in step (2) is 0-5 ℃, the second substitution reaction temperature is room temperature, and the time is 5-24 hours.
8. A photoresist resin having a structure in which the photoacid generator of claim 1 is grafted onto a polymer resin backbone.
9. A method of preparing the photoresist resin according to claim 8, comprising the steps of:
adding tert-butyl acrylate, 2-oxo-tetrahydrofuran-3-yl methacrylate, a photoacid generator and an initiator, dissolving with a third solvent, introducing inert gas for protection, heating for reaction to obtain a polymer solution, and filtering after the reaction is finished to obtain the photoresist resin.
10. The method for preparing a photoresist resin according to claim 9, wherein the mass ratio of the tert-butyl acrylate to the 2-oxo-tetrahydrofuran-3-yl methacrylate and the photoacid generator to the initiator is (1.2-1.5): (2.5-3.2): (0.5-1): (0.2-0.4), and the ratio of the tert-butyl acrylate to the second solvent is (1.2-1.5 g): (20-55 mL);
the initiator comprises an azo initiator or a free radical initiator of peroxide, wherein the azo initiator is selected from one or two of azodiisobutyronitrile and azodiisoheptonitrile, the free radical initiator of peroxide is selected from one or more of tert-butyl pivalate peroxide, tert-butyloxy hydroperoxide, benzoic acid hydroperoxide and benzoyl peroxide, and the third solvent comprises tetrahydrofuran, methanol, acetone, dioxane or chloroform;
the protection time is 5-120min, the heating reaction temperature is 40-90 ℃ and the time is 3-24h;
the inert gas comprises nitrogen or argon.
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Inventor after: Zhang Jianhua Inventor after: Chen Jiao Inventor after: Xin Hanshen Inventor after: Xue Jie Inventor after: Li Haoyuan Inventor before: Xin Hanshen Inventor before: Chen Jiao Inventor before: Zhang Jianhua Inventor before: Xue Jie Inventor before: Li Haoyuan |