CN118307704A - Bridge-structure photoresist resin, krF photoresist composition and preparation method thereof - Google Patents
Bridge-structure photoresist resin, krF photoresist composition and preparation method thereof Download PDFInfo
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- CN118307704A CN118307704A CN202410511630.9A CN202410511630A CN118307704A CN 118307704 A CN118307704 A CN 118307704A CN 202410511630 A CN202410511630 A CN 202410511630A CN 118307704 A CN118307704 A CN 118307704A
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 121
- 239000011347 resin Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 14
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical group CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- -1 tertagine Chemical compound 0.000 claims description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 6
- 102100040409 Ameloblastin Human genes 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- VSYDNHCEDWYFBX-UHFFFAOYSA-N (1-methylcyclopentyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCC1 VSYDNHCEDWYFBX-UHFFFAOYSA-N 0.000 description 3
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 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 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 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 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LBHPSYROQDMVBS-UHFFFAOYSA-N (1-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1 LBHPSYROQDMVBS-UHFFFAOYSA-N 0.000 description 1
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 1
- ZCSHACFHMFHFKK-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;2,4,6-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)C1NC([N+]([O-])=O)NC([N+]([O-])=O)N1.CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZCSHACFHMFHFKK-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- OGOYZCQQQFAGRI-UHFFFAOYSA-N 9-ethenylanthracene Chemical compound C1=CC=C2C(C=C)=C(C=CC=C3)C3=CC2=C1 OGOYZCQQQFAGRI-UHFFFAOYSA-N 0.000 description 1
- KTPLMACSFXCPHL-UHFFFAOYSA-N 9-ethenylphenanthrene Chemical compound C1=CC=C2C(C=C)=CC3=CC=CC=C3C2=C1 KTPLMACSFXCPHL-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- UAWBWGUIUMQJIT-UHFFFAOYSA-N azanium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound N.OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAWBWGUIUMQJIT-UHFFFAOYSA-N 0.000 description 1
- DNFSNYQTQMVTOK-UHFFFAOYSA-N bis(4-tert-butylphenyl)iodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DNFSNYQTQMVTOK-UHFFFAOYSA-N 0.000 description 1
- VGZKCAUAQHHGDK-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 VGZKCAUAQHHGDK-UHFFFAOYSA-M 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 238000000233 ultraviolet lithography Methods 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
Abstract
The invention belongs to the technical field of photoresist, and particularly relates to a bridge-structure photoresist resin, a KrF photoresist composition and a preparation method thereof. The preparation method of the bridge structure photoresist resin comprises the following steps: s1, carrying out polymerization reaction on a first monomer, a second monomer, a third monomer and a fourth monomer in the presence of an initiator to obtain a copolymerization product, wherein the first monomer is 4-acetoxystyrene, the second monomer has a structure shown in a formula (1), the third monomer has a structure shown in a formula (2), and the fourth monomer has a structure shown in a formula (3); s2, carrying out hydrolysis reaction on the copolymerization product obtained in the step S1 in the presence of a catalyst to obtain a product of the photoresist resin with the bridge structure. The bridge photoresist resin and the KrF photoresist composition prepared by the method have high resolution, high sensitivity and good chemical stability.
Description
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to a bridge-structure photoresist resin, a KrF photoresist composition and a preparation method thereof.
Background
With the development of semiconductor technology, the density and complexity of integrated circuits have increased. In order to achieve smaller device sizes and higher integration, photolithography is one of the key processes for fabricating fine structures. Photoresist is an important component of the lithographic process and serves as a photomask during the lithographic process. However, as device sizes continue to shrink, the resolution and performance of ultraviolet lithography have reached a limit. To meet the higher demands, it is necessary to develop a photoresist of higher resolution. Compared to conventional ultraviolet rays, krF lasers have shorter wavelengths and higher energies, enabling higher resolution and smaller feature sizes, which makes it possible to fabricate higher performance microelectronic devices. However, conventional photoresist materials may have problems such as resolution limitations or photoresist exhaustion at high resolution. Therefore, based on the urgent need for higher resolution and higher performance microelectronic devices, it is important to find a photoresist resin and KrF photoresist composition having high resolution, high sensitivity and good chemical stability.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a bridge-structure photoresist resin with high resolution, high sensitivity and good chemical stability, aiming at the defect that the resolution, sensitivity and chemical stability of the photoresist resin in the prior art are insufficient.
Specifically, the preparation method of the bridge structure photoresist resin provided by the invention comprises the following steps:
S1, carrying out polymerization reaction on a first monomer, a second monomer, a third monomer and a fourth monomer in the presence of an initiator to obtain a copolymerization product; the first monomer is 4-acetoxystyrene, the second monomer has a structure shown in a formula (1), the third monomer has a structure shown in a formula (2), and the fourth monomer has a structure shown in a formula (3);
S2, carrying out hydrolysis reaction on the copolymerization product obtained in the step S1 in the presence of a catalyst to obtain a product containing bridge-structure photoresist resin;
In the formula (1), R 2 is an acid-sensitive group, and R 3 is H or methyl;
in the formula (2), R4 is a high ultraviolet absorption group.
In a preferred embodiment, the molar ratio of the first monomer M1, the second monomer, the third monomer and the fourth monomer is (4-8): 1-2): 1.
In a preferred embodiment, in step S1, the polymerization conditions include a temperature of 70 to 100 ℃ for 20 to 28 hours.
In a preferred embodiment, in step S2, the hydrolysis reaction is carried out for a period of time ranging from 10 to 15 hours.
In a preferred embodiment, the acid-sensitive group has a structural formula selected from one of the structures shown below;
wherein the position represents a position bonded to an oxygen atom in formula (1).
In a preferred embodiment, the compound containing a high ultraviolet absorbing group is selected from one of the structures shown below;
In a preferred embodiment, the preparation method of the bridge photoresist resin further comprises adding a precipitant into the reaction solution obtained in the step S2 to perform precipitation reaction, and performing solid-liquid separation to obtain a solid product, namely the bridge photoresist resin.
The second object of the present invention is to provide a bridge photoresist resin prepared by the above method.
In a preferred embodiment, the bridge photoresist resin has a structural unit represented by formula (4), a structural unit represented by formula (5), a structural unit represented by formula (6), and a structural unit represented by formula (7);
In the formula (4), R 1 is OH;
In the formula (5), R 2 is an acid-sensitive group, and R 3 is H or methyl;
In formula (6), R 4 is a high ultraviolet absorbing group.
It is still another object of the present invention to provide a KrF photoresist composition comprising the above bridge photoresist resin, a surfactant, an acid quencher, a photoacid generator, and an organic solvent.
In a preferred embodiment, the bridge structure photoresist resin is present in an amount of 10 to 20wt%, the surfactant is present in an amount of 0.001 to 0.1wt%, the acid quencher is present in an amount of 0.001 to 0.1wt%, the photoacid generator is present in an amount of 0.05 to 6wt%, and the organic solvent is present in an amount of 74 to 88wt%, based on the total mass of the KrF photoresist composition.
In a preferred embodiment, the surfactant is a fluorosurfactant.
In a preferred embodiment, the acid quencher is selected from at least one of tetrabutylammonium hydroxide, triisopropanolamine, tertagine, and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
In a preferred embodiment, the photoacid generator is selected from sulfonium salts and/or iodonium salts.
In a preferred embodiment, the organic solvent is selected from at least one of an ether solvent, an ester solvent, a ketone solvent, and a hydroxyl group-containing solvent.
The fourth object of the present invention is to provide a method for preparing the above KrF photoresist composition, which comprises uniformly mixing a bridge structure photoresist resin, a surfactant, an acid quencher, a photoacid generator and an organic solvent to obtain the KrF photoresist composition.
The key point of the invention is that 4-acetoxyl styrene (first monomer), acrylic ester containing acid sensitive group (second monomer), ethylene containing high ultraviolet absorbing group (third monomer) and 2, 5-norbornadiene (NBD, fourth monomer) with bridge structure are subjected to free radical polymerization reaction, thus the obtained bridge structure photoresist resin and KrF photoresist composition have high resolution, high sensitivity and good chemical stability. The possible reasons are: by utilizing the advantages of the bridge structure of NBD, a monomer containing a low activation energy deprotected acid group (acid sensitive group) is connected into a main chain of photoresist resin, so that the transmittance control of the photoresist can be solved, the pattern resolution and the photoetching performance in the traditional crosslinking state are improved, and the photoetching pattern with high resolution and good morphology is obtained; the high ultraviolet absorption group structure is introduced into the branched chain of the bridge-structure photoresist resin, so that the photosensitivity, selectivity and anti-interference performance of the photoresist can be enhanced, and the effect of a micro-lithography process is improved.
Drawings
FIG. 1 is a critical dimension scanning electron microscope (CD-SEM) image and a V-SEM image of the KrF photoresist composition obtained in example 1, wherein FIG. 1 is a CD-SEM image and FIGS. 2 and 3 are V-SEM images.
FIG. 2 is a critical dimension scanning electron microscope (CD-SEM) image and a V-SEM image of the KrF photoresist composition obtained in example 2, wherein FIG. 1 is a CD-SEM image and FIGS. 2 and 3 are V-SEM images.
FIG. 3 is a scanning electron microscope (CD-SEM) image and a V-SEM image of critical dimensions of a reference KrF photoresist composition obtained in comparative example 1, wherein FIG. 1 is a CD-SEM image and FIG. 2 is a V-SEM image.
FIG. 4 is a critical dimension scanning electron microscope (CD-SEM) image and a V-SEM image of a reference KrF photoresist composition obtained in comparative example 2, wherein FIG. 1 is a CD-SEM image and FIG. 2 is a V-SEM image.
Detailed Description
The preparation method of the bridge structure photoresist resin provided by the invention comprises the following steps:
s1, carrying out polymerization reaction on a first monomer, a second monomer, a third monomer and a fourth monomer in the presence of an initiator to obtain a copolymerization product, wherein the first monomer is 4-acetoxystyrene, the second monomer has a structure shown in a formula (1), the third monomer has a structure shown in a formula (2), and the fourth monomer has a structure shown in a formula (3);
S2, carrying out hydrolysis reaction on the copolymerization product obtained in the step S1 in the presence of a catalyst to obtain a product containing bridge-structure photoresist resin;
In the formula (1), R 2 is an acid-sensitive group, and R 3 is H or methyl;
in formula (2), R 4 is a high ultraviolet absorbing group.
In the invention, the molar ratio of the first monomer to the second monomer to the third monomer to the fourth monomer is preferably (4-8): 1-2): 1. The number of moles of the first monomer is preferably 4 to 8 moles, such as 4 moles, 5 moles, 6 moles, 7 moles, 8 moles or any value therebetween, based on 1 mole of the fourth monomer; the molar number of the second monomer is preferably 4 to 8mol, such as 4mol, 5mol, 6mol, 7mol, 8mol or any value therebetween; the number of moles of the third monomer is preferably 1 to 2 moles, such as 1 mole, 1.2 moles, 1.5 moles, 1.8 moles, 2 moles or any value therebetween.
In the present invention, in step S1, the conditions for the polymerization reaction include a temperature of preferably 70 to 100℃such as 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃,100℃or any value therebetween; the time is preferably 20 to 28h, such as 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h or any value therebetween.
In the present invention, in step S2, the time of the hydrolysis reaction is preferably 10 to 15 hours, such as 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any value therebetween.
In the invention, the preparation method of the bridge structure photoresist resin can also comprise the steps of adding a precipitator into the reaction liquid obtained in the step S2 for precipitation reaction, and carrying out solid-liquid separation, wherein the obtained solid product is the bridge structure photoresist resin. The precipitant is preferably at least one of deionized water, methanol, ethanol, diethyl ether and petroleum ether. The time of the precipitation reaction is 1-5 h, such as 1h, 2h, 3h, 4h, 5h or any value between them.
In a specific embodiment, the preparation method of the bridge structure photoresist resin may include the steps of:
S1', under the protection of normal temperature nitrogen, dissolving a first monomer, a second monomer, a third monomer and a fourth monomer in a first organic solvent to form a monomer mixed solution to be polymerized, weighing an initiator to dissolve and the first organic solvent to form an initiator solution, dripping the initiator solution into the monomer mixed solution to be polymerized, and heating to 70-100 ℃ to perform polymerization reaction for 20-28 h to obtain a copolymerization product;
S2 ', adding a catalyst into the copolymerization product obtained in the step S1', continuously stirring under the protection of normal-temperature nitrogen, and carrying out hydrolysis reaction for 10-15 h to obtain a reaction solution;
S3 ', mixing the reaction solution obtained in the step S3' with a precipitant, fully stirring and reacting for 1-5 h, filtering and washing the obtained precipitate, and vacuum drying at 60-80 ℃ to obtain the bridge-structure photoresist resin.
In the present invention, the high ultraviolet absorbing group preferably has a polycyclic aromatic hydrocarbon structure such as at least one of naphthalene, anthracene, and film. Specifically, the structural formula of the high ultraviolet absorbing group is preferably one of the structures shown below;
in the present invention, the initiator is preferably at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, cumene peroxide and t-butyl peroxide. The amount of the initiator used in the present invention is not particularly limited as long as it can initiate polymerization of each monomer to be polymerized.
In the present invention, the first organic solvent is preferably at least one selected from Propylene Glycol Methyl Ether Acetate (PGMEA), tetrahydrofuran, cyclopentanone, cyclohexanone, ethyl lactate, butyl acetate, 2-ethoxyethanol, ethyl 3-ethoxypropionate, ethyl acetate, ethylene glycol monomethyl ether and dipropylene glycol monomethyl ether.
In the present invention, the catalyst is preferably at least one selected from the group consisting of ethanolamine, triethylamine, ammonium acetate, trimethylamine, and dimethylaminopyridine.
In the present invention, the bridge structure photoresist resin preferably has a structural unit represented by formula (4), a structural unit represented by formula (5), a structural unit represented by formula (6), and a structural unit represented by formula (7);
In the formula (4), R 1 is OH;
In formula (5), R 2 is an acid-sensitive group, and R 3 is H or methyl.
In formula (6), R 4 is a high ultraviolet absorbing group.
In a specific embodiment, the bridge photoresist resin may have a structure as shown in formula (8);
In the formula (8), R 1 is OH, R 2 is an acid-sensitive group, R 3 is H or methyl, R 4 is a high ultraviolet absorbing group, x1, x2, x3, x4 represent the proportion of the first monomer in the bridge photoresist resin, y1, y2, y3, y4 represent the proportion of the second monomer in the bridge photoresist resin, z1, z2, z3, z4 represent the proportion of the third monomer in the bridge photoresist resin, v represents the proportion of the fourth monomer in the bridge photoresist resin, wherein x1+x2+x3=x4=x, y1+y2+y3+y4=y, z1+z2+z3+z4=z, and x+y+z+v=1. The bridge photoresist resin represented by the formula (8) is used only to indicate the monomer structural units contained and the content of each monomer structural unit, but is not used to indicate the connection relationship between each monomer structural unit, and these four monomer structural units may be present in the form of a random copolymer, an alternating copolymer or a block copolymer, and preferably may be present in the form of a random copolymer.
In the present invention, the KrF photoresist composition preferably contains a bridge structure photoresist resin, a surfactant, an acid quencher, a photoacid generator, and an organic solvent. Wherein the bridge photoresist resin is preferably present in an amount of 10 to 20wt%, such as 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, or any value therebetween, based on the total mass of the KrF photoresist composition. The surfactant is preferably present in an amount of 0.001 to 0.1wt%, such as 0.001wt%, 0.005wt%, 0.01wt%, 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt% or any value therebetween. The acid quencher is present in an amount of 0.001 to 0.1wt%, such as 0.001wt%, 0.005wt%, 0.01wt%, 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt% or any value therebetween. The photoacid generator is present in an amount of 0.05 to 6wt%, such as 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt% or any value therebetween. The organic solvent is present in an amount of 74 to 88wt%, such as 74wt%, 76wt%, 78wt%, 80wt%, 82wt%, 84wt%, 86wt%, 88wt% or any value therebetween.
In the present invention, the surfactant is preferably a fluorine-containing surfactant, which helps to improve the planarization degree of the film, improve the adhesion between the photoresist compound and the substrate, and reduce the residual film after development, and specific examples thereof include, but are not limited to: at least one of perfluorooctyl sodium sulfate (PFOS), ammonium perfluorooctane sulfonate (PFAS), perfluorooctyl polyether (PFPE), and perfluorooctane glycolate (PFOA).
Specific examples of the acid quencher in the present invention include, but are not limited to: at least one of tetrabutylammonium hydroxide (TBAH), triisopropanolamine, tertagine, and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).
In the present invention, the photoacid generator is preferably selected from sulfonium salts and/or iodonium salts, wherein the sulfonium salts are preferably selected from at least one of compounds having the structures shown below. The iodonium salt is preferably at least one selected from the group consisting of diphenyltriflic acid iodonium, bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonic acid, bis (4-tert-butylphenyl) iodonium triflate and diphenyliodonium hexafluorophosphate.
In the present invention, the organic solvent is preferably at least one selected from the group consisting of ether solvents, ester solvents, ketone solvents and hydroxyl group-containing solvents, and specific examples thereof include, but are not limited to: propylene Glycol Methyl Ether Acetate (PGMEA), tetrahydrofuran, cyclopentanone, cyclohexanone, ethyl lactate, butyl acetate, 2 ethoxyethanol, ethyl 3 ethoxypropionate, ethyl acetate, ethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.
The present invention will be described in detail by way of specific examples.
Preparation example 1 preparation of bridge Photoresist resin
S1, under the protection of normal temperature nitrogen, 43.3g of 4-acetoxystyrene (first monomer), 41.3g of 1-methylcyclopentyl methacrylate (second monomer), 12.1g of 1-vinylnaphthalene (third monomer), 4.13g of 2, 5-norbornadiene (NBD, fourth monomer) and 500g of PGMEA are weighed into a 1L flask, 0.433g of Azobisisovaleronitrile (AMBN) is weighed and dissolved in 50mL of PGMEA, then the AMBN/PGMEA solution is slowly dripped into the flask, and reflux reaction is carried out for 24 hours at 85 ℃ after the dripping is finished;
s2, stopping heating, weighing 14g of ethanolamine, adding the ethanolamine into a flask, and stirring and reacting for 12 hours under the protection of normal-temperature nitrogen;
S3, pouring the reaction solution into a methanol solution after the reaction is finished, fully stirring for 3 hours, filtering the obtained precipitate, washing with a large amount of methanol, vacuum drying at 65 ℃ to obtain 61g of white solid resin sample, namely bridge-structure photoresist resin (Mw=13000 g/mol), and preparing the solution A-1 with the solid content of 50wt% with PGMEA for later use.
Preparation example 2 preparation of bridge-structured Photoresist resin
S1, under the protection of normal temperature nitrogen, 43.3g of 4-acetoxystyrene (first monomer), 41.3g of 1-methylcyclopentyl methacrylate (second monomer), 9.2g of 9-vinyl anthracene (third monomer), 4.13g of 2, 5-norbornadiene (NBD, fourth monomer) and 500g of PGMEA are weighed into a 1L flask, 100mL of tetrahydrofuran is added for dissolution, nitrogen is stirred and introduced for deoxidization for 1h, 0.362g of dimethyl Azoisobutyrate (AIBME) is weighed and dissolved in 50mL of PGMEA, AIBME/PGMEA solution is slowly dripped into the flask, and reflux reaction is carried out for 24h at 85 ℃ after the dripping is finished;
S2, stopping heating, weighing 25g of ammonium acetate and 5mL of deionized water, mixing, dripping the ammonium acetate/water mixed solution into the reaction solution, and stirring for reaction for 12 hours under the protection of nitrogen at normal temperature;
S3, pouring the reaction solution into a methanol solution after the reaction is finished, fully stirring for 3 hours, filtering the obtained precipitate, washing with a large amount of methanol, vacuum drying at 65 ℃ to obtain 60g of white solid resin sample, namely bridge-structure photoresist resin (Mw=15000 g/mol), and preparing the solution A-2 with the solid content of 50wt% with PGMEA for later use.
Preparation example 3 preparation of bridge Photoresist resin
S1, under the protection of normal temperature nitrogen, weighing 32.7g of 4-acetoxystyrene (first monomer), 36.2g of 1-methylcyclohexyl methacrylate (second monomer), 12.1g of 1-vinylnaphthalene (third monomer), 4.13g of 2, 5-norbornadiene (NBD, fourth monomer) and 500g of PGMEA, adding into a 1L flask, weighing 0.433g of Azobisisovaleronitrile (AMBN) to dissolve in 50mL of PGMEA, slowly dropwise adding the AMBN/PGMEA solution into the flask, and carrying out reflux reaction at 70 ℃ for 28h after dropwise adding;
S2, stopping heating, weighing 14g of ethanolamine, adding the ethanolamine into a flask, and stirring and reacting for 10 hours under the protection of normal-temperature nitrogen;
s3, pouring the reaction solution into a methanol solution after the reaction is finished, fully stirring for 3 hours, filtering the obtained precipitate, washing with a large amount of methanol, vacuum drying at 65 ℃ to obtain 61g of white solid resin sample, namely bridge-structure photoresist resin (Mw=13400 g/mol), and preparing the solution A-3 with the solid content of 50wt% with PGMEA for later use.
Preparation example 4 preparation of bridge Photoresist resin
S1, under the protection of normal temperature nitrogen, weighing 54.6g of 4-acetoxystyrene (first monomer), 77.8g of 2-methyl-2-adamantyl methacrylate (second monomer), 13.7g of 9-vinylphenanthrene (third monomer), 4.13g of 2, 5-norbornadiene (NBD, fourth monomer) and 500g of PGMEA, adding into a 1L flask, adding 100mL of tetrahydrofuran for dissolution, stirring and introducing nitrogen for deoxidization for 1h, weighing 0.362g of azoisobutyric acid dimethyl ester (AIBME) for dissolution in 50mL of PGMEA, slowly dripping AIBME/PGMEA solution into the flask, and carrying out reflux reaction for 20h at 100 ℃ after the dripping is finished;
s2, stopping heating, weighing 25g of ammonium acetate and 5mL of deionized water, mixing, dripping the ammonium acetate/water mixed solution into the reaction solution, and stirring for reaction for 15 hours under the protection of nitrogen at normal temperature;
S3, pouring the reaction solution into a methanol solution after the reaction is finished, fully stirring for 3 hours, filtering the obtained precipitate, washing with a large amount of methanol, vacuum drying at 65 ℃ to obtain 60g of white solid resin sample, namely bridge-structure photoresist resin (Mw=16800 g/mol), and preparing the solution A-4 with the solid content of 50wt% with PGMEA for later use.
EXAMPLE 1 preparation of KrF Photoresist composition
The solution A-1 obtained in example 1 was mixed with 3wt% of triphenylsulfonium perfluorobutylsulfonate, 0.03wt% of triisopropanolamine, 0.003wt% of a fluorosurfactant, and a 3:7 ratio of PGMEA and ethyl lactate solution to prepare 300g of a KrF photoresist composition having a bridge structure and a solid content of 13.5wt% of photoresist resin, which was designated as B-1.
EXAMPLE 2 preparation of KrF Photoresist composition
A KrF photoresist composition was prepared as in example 1, except that solution A-1 was replaced with the same mass of solution A-2, with the remaining conditions being the same, to give KrF photoresist composition B-2.
EXAMPLE 3 preparation of KrF Photoresist composition
A KrF photoresist composition was prepared as in example 1, except that solution A-1 was replaced with the same mass of solution A-3, with the remaining conditions being the same, to give KrF photoresist composition B-3.
EXAMPLE 4 preparation of KrF Photoresist composition
A KrF photoresist composition was prepared as in example 1, except that solution A-1 was replaced with the same mass of solution A-4, with the remaining conditions being the same, to give KrF photoresist composition B-4.
Comparative example 1 preparation of reference photoresist resin and KrF photoresist composition
(1) Preparation of reference photoresist resin
43.3G of 4-acetoxystyrene, 3.11g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 41.3g of 1-methylcyclopentyl methacrylate, 12.1g of 1-vinylnaphthalene and 500g of PGMEA are weighed under the protection of normal temperature nitrogen, 0.433g of Azodiisovaleronitrile (AMBN) is weighed and dissolved in 50mL of PGMEA, the solution of AMBN/PGMEA is slowly dripped into the flask, and reflux reaction is carried out for 24 hours at 85 ℃ after the dripping is finished; stopping heating, weighing 14g of ethanolamine, adding into a beaker, and stirring under the protection of nitrogen at normal temperature for reaction for 12 hours; after the reaction, the reaction solution was poured into a methanol solution, stirred sufficiently for 3 hours, the obtained precipitate was filtered and rinsed with a large amount of methanol, and a 63g white solid resin sample was obtained after vacuum drying at 65 ℃ to obtain a reference photoresist resin (mw=13000 g/mol), which was formulated with PGMEA into a solution DA-1 having a solid content of 50wt% for use.
(2) Preparation of reference KrF Photoresist composition
A reference KrF photoresist composition was prepared as in example 1, except that solution A-1 was replaced with the same quality of solution DA-1, with the remaining conditions being the same, to give reference KrF photoresist composition DB-1.
Comparative example 2 preparation of reference photoresist resin and KrF photoresist composition
(1) Preparation of reference photoresist resin
A reference photoresist resin was prepared according to the method of example 1, except that 2, 5-norbornadiene (NBD, fourth monomer) was replaced with the same molar amount of 5-norbornene-2 alcohol, and the remaining conditions were the same, to obtain a reference photoresist resin solution DA-2.
(2) Preparation of reference KrF Photoresist composition
A reference KrF photoresist composition was prepared as in example 1, except that solution A-1 was replaced with the same mass of solution DA-2, with the remaining conditions being the same, to give reference KrF photoresist composition DB-2.
Test case
The KrF photoresist compositions of the above examples and comparative examples were coated on an 8 inch silicon wafer (spin-on rotation speed 1500rpm, spin-on thickness) Baking at 130deg.C for 60s to remove solvent, exposing with an exposure machine (exposure wavelength 248 nm), baking the exposed silicon wafer at the temperature shown in column "PEB" of Table 1 (90deg.C) for 60s, and developing in 2.38wt% tetramethylammonium hydroxide (TMAH) developer to obtain the lithography pattern. The sensitivity, film thickness change before and after development, and development resolution pattern were measured at the same resolution, and the results are shown in table 1, and the photolithography performance was observed by comparing the CD-SEM image with the V-SEM image after the sample was sliced.
TABLE 1
As can be seen from table 1, the bridge photoresist resin and KrF photoresist composition prepared in the examples of the present invention have higher sensitivity at the same resolution and small film thickness variation before and after development, compared with the comparative examples, indicating high resolution, high sensitivity and good chemical stability. As can be seen from the CD-SEM images and the V-SEM images of the patterns obtained in the comparative examples and comparative examples, the patterns obtained in the examples have better morphological effects. Specifically, as can be seen from fig. 1 and fig. 2, the patterns obtained in example 1 and example 2 have better edge flatness and straight morphology under the same resolution, which illustrates that the bridge-type structured photoresist grafted with the NBD type monomer has an improvement effect on the pattern morphology. As can be seen from fig. 3 and fig. 4, the patterns obtained in comparative examples 1 and 2 have poor edge flatness, are not developed and opened, and have poor pattern morphology under the same resolution, which indicates that the structural resin has poor photoetching performance and cannot meet the requirement of a process window. In summary, the bridge photoresist resin and the KrF photoresist composition provided by the invention have high resolution, high sensitivity and good chemical stability.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (10)
1. The preparation method of the bridge-structure photoresist resin is characterized by comprising the following steps of:
S1, carrying out polymerization reaction on a first monomer, a second monomer, a third monomer and a fourth monomer in the presence of an initiator to obtain a copolymerization product; the first monomer is 4-acetoxystyrene, the second monomer has a structure shown in a formula (1), the third monomer has a structure shown in a formula (2), and the fourth monomer has a structure shown in a formula (3);
S2, carrying out hydrolysis reaction on the copolymerization product obtained in the step S1 in the presence of a catalyst to obtain a product containing bridge-structure photoresist resin;
In the formula (1), R 2 is an acid-sensitive group, and R 3 is H or methyl;
in formula (2), R 4 is a high ultraviolet absorbing group.
2. The method for preparing a bridge photoresist resin according to claim 1, wherein the mole ratio of the first monomer to the second monomer to the third monomer to the fourth monomer is (4-8): (1-2): 1;
preferably, in the step S1, the conditions of the polymerization reaction comprise a temperature of 70-100 ℃ and a time of 20-28 h;
preferably, in step S2, the hydrolysis reaction time is 10 to 15 hours.
3. The method for producing a bridge photoresist resin according to claim 1, wherein the structural formula of the acid-sensitive group is selected from one of the following structures;
wherein the position represents a position bonded to an oxygen atom in formula (1).
4. The method for producing a bridge photoresist resin according to claim 1, wherein the structural formula of the high ultraviolet absorbing group is selected from one of the following structures;
5. The method according to any one of claims 1 to 4, wherein the method further comprises adding a precipitant into the reaction solution obtained in step S2 to perform precipitation reaction, and performing solid-liquid separation to obtain a solid product, namely the bridge-structured photoresist resin.
6. The bridge photoresist resin of any one of claims 1 to 5, wherein the bridge photoresist resin has a structural unit represented by formula (4), a structural unit represented by formula (5), a structural unit represented by formula (6) and/or a structural unit represented by formula (7);
In the formula (4), R 1 is OH;
In the formula (5), R 2 is an acid-sensitive group, and R 3 is H or methyl;
In formula (6), R 4 is a high ultraviolet absorbing group.
7. A KrF photoresist composition comprising the bridge photoresist resin of claim 6, a surfactant, an acid quencher, a photoacid generator, and an organic solvent.
8. The KrF photoresist composition according to claim 7, wherein the bridge structure photoresist resin is present in an amount of 10 to 20wt%, the surfactant is present in an amount of 0.001 to 0.1wt%, the acid quencher is present in an amount of 0.001 to 0.1wt%, the photoacid generator is present in an amount of 0.05 to 6wt%, and the organic solvent is present in an amount of 74 to 88wt%, based on the total mass of the KrF photoresist composition.
9. The KrF photoresist composition according to claim 7, wherein the surfactant is a fluorosurfactant;
Preferably, the acid quencher is selected from at least one of tetrabutylammonium hydroxide, triisopropanolamine, tertagine, and 1,8 diazabicyclo [5.4.0] undec-7-ene;
preferably, the photoacid generator is selected from sulfonium salts and/or iodonium salts;
Preferably, the organic solvent is selected from at least one of an ether solvent, an ester solvent, a ketone solvent, and a hydroxyl group-containing solvent.
10. The method for preparing the KrF photoresist composition according to any one of claims 7 to 9, wherein the method comprises uniformly mixing a bridge structure photoresist resin, a surfactant, an acid quencher, a photoacid generator and an organic solvent to obtain the KrF photoresist composition.
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