CN116500859B - Chemical amplification type I-line photoresist and preparation and use methods thereof - Google Patents
Chemical amplification type I-line photoresist and preparation and use methods thereof Download PDFInfo
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- CN116500859B CN116500859B CN202211718689.2A CN202211718689A CN116500859B CN 116500859 B CN116500859 B CN 116500859B CN 202211718689 A CN202211718689 A CN 202211718689A CN 116500859 B CN116500859 B CN 116500859B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000003321 amplification Effects 0.000 title claims abstract description 13
- 238000003199 nucleic acid amplification method Methods 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002952 polymeric resin Substances 0.000 claims abstract description 35
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 35
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000011161 development Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- -1 hydroxystyrene compound Chemical class 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- QLNYTCSELYEEPV-UHFFFAOYSA-N 2,2-dimethylpropyl acetate Chemical compound CC(=O)OCC(C)(C)C QLNYTCSELYEEPV-UHFFFAOYSA-N 0.000 claims description 2
- BZUDVELGTZDOIG-UHFFFAOYSA-N 2-ethyl-n,n-bis(2-ethylhexyl)hexan-1-amine Chemical compound CCCCC(CC)CN(CC(CC)CCCC)CC(CC)CCCC BZUDVELGTZDOIG-UHFFFAOYSA-N 0.000 claims description 2
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 claims description 2
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-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
- 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 20
- 238000003860 storage Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 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 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- UAJRSHJHFRVGMG-UHFFFAOYSA-N p-Methoxystyrene Natural products COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention relates to a chemical amplification type I-line photoresist and a preparation and use method thereof, wherein the photoresist comprises the following components in percentage by mass: 10-20% of polymer resin and photoresist; 2-10% of photoacid and polymer resin; acid quenching agent, 8-30% of photoacid; 0.5 to 15 percent of stabilizer and polymer resin; 0.05 to 0.5 percent of flatting agent and photoresist; solvent, make up 100%; wherein the polymer resin is polyhydroxystyrene polymer resin. The preparation method comprises the following steps: the components of the chemically amplified I-line photoresist are mixed in proportion. The using method comprises the following steps: the chemical amplification type I-line photoresist is coated on a Si substrate, and the Si substrate is subjected to pre-baking, exposure, post-baking and development in sequence. The photoresist provided by the invention can effectively solve the problem of energy stability of the chemical amplification type I-line photoresist.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a chemical amplification type I-line photoresist and a preparation and use method thereof.
Background
The resist is an etching-resistant thin film material whose solubility is changed by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, or the like. A light-sensitive mixed liquid composed of a photosensitive resin, a sensitizer and a main component of the solvent 3. With the development of integrated circuits and devices, photoresist resolution in large-scale integrated circuits and very large-scale integrated circuits is increasing.
Photoresists are sensitive to light and have relatively short shelf lives, especially high-end photoresists, typically within six months. And because both light and heat energy can activate the photoresist, both storage and transport must be in a closed, low temperature, opaque environment. Once the memory or storage temperature range is exceeded, the positive glue experiences a delay in sensitization and the negative glue undergoes crosslinking.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a chemical amplification type I-line photoresist and a preparation and use method thereof, so as to solve the problem of energy stability of the chemical amplification type I-line photoresist.
In order to achieve the purpose of the invention, the following technical scheme is provided.
In a first aspect, the present application provides a chemically amplified I-line photoresist, the photoresist comprising the following components in mass percent:
wherein the polymer resin is polyhydroxystyrene polymer resin.
In one embodiment of the first aspect, the polyhydroxystyrene polymer resins include a first polyhydroxystyrene polymer resin and a second polyhydroxystyrene polymer resin;
the first polyhydroxystyrene polymer resin is a copolymer of hydroxystyrene compound, styrene compound and tert-butyl acrylate compound; the second polyhydroxystyrene polymer resin is a copolymer of hydroxystyrene compound, styrene compound and p-methoxystyrene compound.
In one embodiment of the first aspect, the first polyhydroxystyrene polymer resin has a mass of 8 to 17.5% of the photoresist, and the second polyhydroxystyrene polymer resin has a mass of 2 to 2.5% of the photoresist.
In one embodiment of the first aspect, the photoresist further includes at least one of the following technical features:
a1 The weight average molecular weight of the first polyhydroxystyrene polymer resin is 15000-26000;
a2 A molecular weight distribution coefficient of the first polyhydroxystyrene polymer resin is PDI <2.5;
a3 The first polyhydroxystyrene polymer resin is obtained by copolymerizing the following components in molar ratio:
50-70% of hydroxystyrene compound;
10-30% of a styrene compound;
the tert-butyl acrylate compound complements 100%;
a4 The weight average molecular weight of the second polyhydroxystyrene polymer resin is 8000-15000;
a5 A molecular weight distribution coefficient of the second polyhydroxystyrene polymer resin is PDI <2.5;
a6 The second polyhydroxystyrene polymer resin is obtained by copolymerizing the following components in molar ratio:
60-80% of hydroxystyrene compound;
5-15% of a styrene compound;
the p-methoxystyrene compound is 100 percent of the total.
In one embodiment of the first aspect, the photoresist further includes at least one of the following technical features:
b1 At least one of ionic or nonionic photoacid;
b2 The acid quencher is selected from at least one of triethanolamine, tetrabutylammonium hydroxide, tri (3, 6 dioxaheptyl) amine, trioctylamine, triisopropanolamine, triethylenediamine, 2-ethyl-N, N-bis (2-ethylhexyl) -1-hexylamine, 2-phenylbenzimidazole or diphenylamine;
b3 At least one stabilizer selected from antioxidants;
b4 At least one of 3M fluorocarbon surfactant FC-4430 or Troysol S366;
b5 The solvent is at least one selected from propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate, anisole, propylene glycol monoacetate, propylene glycol monoethyl ether, ethylene glycol methyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, butyl acetate, neopentyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol or gamma-butyrolactone.
In one embodiment of the first aspect, the ionic photoacid is selected from the following general formula:
in formula 1, R 1 Is C 1 -C 4 Alkyl of (a);
in formula 2, R 2 Is hydroxy or C 1 -C 4 Alkoxy, R 3 Is a hydrogen atom, a hydroxy group or C 1 -C 4 Alkoxy, R 4 And R is 5 Each independently is C 1 -C 4 Or R is an alkyl group of 4 And R is R 5 Can be bonded to form C 5 -C 8 R is a ring of 6 Is C 1 -C 4 Perfluoroalkyl of (2);
further, the ionic photoacid is selected from at least one of the following structures:
in one embodiment of the first aspect, the nonionic photoacid is selected from the following general formula:
in formula 3, R 3 Is hydrogen atom, phenoxy or C 1 -C 4 C containing sulfonate groups or alkyl groups 2 -C 10 Alkyl of R 4 Is thatR 5 Is C 1 -C 4 Perfluoroalkyl or perfluorophenyl;
in formula 4, R 6 Is C 1 -C 4 Alkyl or C of (2) 1 -C 6 Alkoxy, R 7 For connecting keys orR 8 Is C 1 -C 4 Alkyl, tolyl or trifluoromethylphenyl groups.
Further, the nonionic photoacid is selected from one of the following structures:
in one embodiment of the first aspect, the antioxidant is selected from the following general formula:
in formula 5, P 1 Is C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 4 -C 10 Or a group of formula 7, wherein P 11 、P 12 Each independently is C 1 -C 4 Alkyl of (a);
in formula 6, P 2 Is C 1 -C 4 N is a positive integer from 2 to 4.
Further, the antioxidant is selected from at least one of the following structures:
in a second aspect, the present application provides a method for preparing a chemically amplified I-line photoresist as described above, the method comprising the steps of: and mixing the polymer resin, the photoacid, the acid quencher, the stabilizer, the leveling agent and the solvent in proportion, and filtering to obtain the chemically amplified I-line photoresist.
In one embodiment of the second aspect, the filtration employs 1 μm+0.45 μm nylon membranes.
In a third aspect, the present application provides a method for using a chemically amplified I-line photoresist as described above, the method comprising the steps of: and coating the chemical amplification type I-line photoresist on a Si substrate, and sequentially performing pre-baking, exposure, post-baking and development to obtain a photoetching pattern.
In an embodiment of the third aspect, the usage method further includes one of the following technical features:
c1 The pre-baking temperature is 110-150 ℃, such as 130 ℃, and the pre-baking time is 40-100 s, such as 90s;
c2 The exposure energy is 105-235 ms;
c3 The post-baking temperature is 90-120 ℃, such as 120 ℃, and the post-baking time is 40-100 s, such as 90s;
c4 The developer used for the development included 2.38% tetramethylammonium hydroxide (TMAH).
Compared with the prior art, the invention has the beneficial effects that: the stabilizer is added in the photoresist formula, so that the problem of unstable energy of the chemical amplification type I-line photoresist can be effectively solved, and the problem of unstable long-term storage of the chemical amplification type I-line photoresist is greatly improved; the invention adopts the phenolic compound as the stabilizer, can effectively prevent the degradation and decomposition of the solvent, especially propylene glycol methyl ether acetate, and has excellent effect on the storage stability of the photoresist, and the price of the phenolic compound is low.
Drawings
FIG. 1a is a schematic diagram showing a photoresist pattern obtained from example 1 after storage in a room temperature storage environment and using different energies;
FIG. 1b shows a photoresist pattern obtained from example 1 after storage in a low temperature storage environment using different energies;
FIG. 1c is a graph showing the resulting lithographic pattern of the photoresist of example 1 after oven aging for one day using different energies;
FIG. 1d is a graph showing the resulting lithographic pattern of the photoresist of example 1 after three days of oven aging using different energies;
FIG. 1e is a graph showing the resulting lithographic pattern of the photoresist of example 1 after five days of oven aging using different energies;
FIG. 2a is a schematic diagram showing a photoresist pattern obtained from example 2 after storage in a room temperature storage environment and using different energies;
FIG. 2b is a graph showing the photoresist obtained from example 2 after being stored in a low temperature storage environment and using different energies;
FIG. 2c is a graph showing the resulting lithographic pattern of the photoresist of example 2 after oven aging for one day using different energies;
FIG. 2d is a graph showing the resulting lithographic pattern of the photoresist of example 2 after three days of oven aging using different energies;
FIG. 2e is a graph showing the resulting lithographic pattern of the photoresist of example 2 after five days of oven aging using different energies;
FIG. 3a is a graph showing a lithographic pattern obtained by using the photoresist obtained in comparative example 1 under different energies after being stored in a room temperature storage environment;
FIG. 3b is a graph showing the photoresist pattern obtained from comparative example 1 after storage in a low temperature storage environment and using different energies;
FIG. 3c is a graph showing the resulting lithographic pattern of the photoresist of comparative example 1 after oven aging for one day using different energies;
FIG. 3d is a graph showing the resulting lithographic pattern of the photoresist of comparative example 1 after three days of oven aging using different energies;
fig. 3e is a photo-resist pattern obtained in comparative example 1 using different energies after oven aging for five days.
Detailed Description
Unless otherwise indicated, implied from the context, or common denominator in the art, all parts and percentages in the present application are based on weight and the test and characterization methods used are synchronized with the filing date of the present application. Where applicable, the disclosure of any patent, patent application, or publication referred to in this application is incorporated by reference in its entirety, and the equivalent of such patent is incorporated by reference, particularly as regards the definitions of synthetic techniques, product and process designs, polymers, comonomers, initiators or catalysts, etc. in the art, as disclosed in such documents. If the definition of a particular term disclosed in the prior art does not conform to any definition provided in this application, the definition of that term provided in this application controls.
Numerical ranges in this application are approximations, so that it may include the numerical values outside of the range unless otherwise indicated. The numerical range includes all values from the lower value to the upper value that increase by 1 unit, provided that there is a spacing of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, melt index, etc.) is recited as being 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing values less than 1 or containing fractions greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is suitably considered to be 0.0001,0.001,0.01, or 0.1. For a range including units less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1 these are merely specific examples of what is intended to be expressed, and all possible combinations of values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. The numerical ranges within this application provide, inter alia, the calcium-containing filler content, the stirring temperature, and various features and properties of these components.
As used with respect to chemical compounds, the singular includes all isomeric forms and vice versa unless explicitly stated otherwise (e.g., "hexane" includes all isomers of hexane, either individually or collectively). In addition, unless explicitly stated otherwise, the use of the terms "a," "an," or "the" include plural referents.
The terms "comprises," "comprising," "including," and their derivatives do not exclude the presence of any other component, step or procedure, and are not related to whether or not such other component, step or procedure is disclosed in the present application. For the avoidance of any doubt, all use of the terms "comprising," "including," or "having" herein, unless expressly stated otherwise, may include any additional additive, adjuvant, or compound. Rather, the term "consisting essentially of … …" excludes any other component, step or process from the scope of any of the terms recited below, except as necessary for operability. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. The term "or" refers to the listed individual members or any combination thereof unless explicitly stated otherwise.
In the present invention, the equipment, materials, etc. used are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The first polyhydroxystyrene-based polymer resin R1 used in the following examples and comparative examples was obtained by the following synthesis method:
to a 500ml four-necked flask, 4-Acetoxystyrene (ASM) (97.2 g,0.6 mol), styrene (ST) (20.6 g,0.2 mol) and t-butyl acrylate (TBA) (25.4 g,0.2 mol) were sequentially added under nitrogen protection, then 3.8g of an initiator Azobisisobutyronitrile (AIBN) was added, tetrahydrofuran was used as a solvent, and then reacted at 65 to 70℃for 18 hours. Removing protecting group from reaction product to obtain 4-hydroxystyrene-styrene-butyl acrylateEster terpolymer having weight average molecular weight M w 25700, its molecular weight distribution coefficient M w /M n 2.3.
The second polyhydroxystyrene-based polymer resin R2 used in the following examples and comparative examples was obtained by the following synthesis method:
under the protection of nitrogen, sequentially adding 4-Acetoxystyrene (ASM) (104.9 g,0.647 mol), styrene (ST) (9.6 g,0.092 mol) and p-Methoxystyrene (MOST) (10.3 g,0.077 mol) into a 500ml four-neck flask, adding 14.3g of initiator azo-diisobutyronitrile (AIBN) and tetrahydrofuran as solvents, reacting at 65-70 ℃ for 18 hours to remove protective groups, and obtaining the 4-hydroxystyrene-styrene-p-methoxystyrene terpolymer with the weight average molecular weight M w 12300, its molecular weight distribution coefficient M w /M n 2.2.
Examples
The following will describe embodiments of the present invention in detail, and the embodiments and specific operation procedures are given by implementing the present invention on the premise of its technical solution, but the scope of protection of the present invention is not limited to the following embodiments.
Example 1
The chemically amplified I-line photoresist comprises the following components in parts by mass (total 100 parts):
the photoresist was prepared as follows: adding the components according to the formula, uniformly mixing and stirring, and filtering by using two nylon membranes with the thickness of 1 mu m plus 0.45 mu m to prepare the required photoresist; the photoresist was then divided into five portions and stored using five conditions to simulate a long-term storage environment, normal temperature (-C), low temperature (-L), oven aging at 45℃for one day (-H1), oven aging at 45℃for three days (-H3), and oven aging at 45℃for five days (-H5), respectively.
The prepared photoresist is used according to the following method:
coating photoresist 6000A on a Si substrate, pre-baking for 90s on a hot plate at 130 ℃, exposing by an I-line exposure machine I-9, post-baking for 90s on a hot plate at 120 ℃, developing for 40s by using 2.38% TMAH developer after the wafer is cooled to room temperature, and finally flushing for 30s by using deionized water to obtain the required photoetching pattern. The resulting lithographic pattern is shown in fig. 1 a-1 e, and then the energy required for 600nm CD is obtained from the energy versus corresponding CD curve, i.e., EOP, as shown in tables 1-6.
Example 2
The chemically amplified I-line photoresist comprises the following components in parts by mass (total 100 parts):
the photoresist was prepared in the same manner as in example 1, and the photoresist was used in the same manner as in example 1. The resulting photoresist pattern is shown in fig. 2a to 2e, and then the energy required for 600nmCD is obtained from the curve of the energy corresponding to the corresponding CD, i.e., EOP, as shown in tables 2 to 6.
Comparative example 1
The chemically amplified I-line photoresist comprises the following components in parts by mass (total 100 parts):
the photoresist was prepared in the same manner as in example 1, and the photoresist was used in the same manner as in example 1. The resulting photoresist pattern is shown in fig. 3a to 3e, and then the energy required for 600nmCD is obtained from the curve of the energy corresponding to the corresponding CD, i.e., EOP, as shown in tables 3 to 6.
The photoresist of the five storage environments in example 1 gave the following lithographic patterns:
table 1-1 (Normal temperature)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 545.1 | 571.4 | 604.8 | 631.8 | 645.5 |
Tables 1-2 (Low temperature)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 543.1 | 571.8 | 606.4 | 618 | 641 |
Tables 1-3 (45 ℃ oven aging for one day)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 514.5 | 553.9 | 586.6 | 619.8 | 649.7 |
Tables 1-4 (oven aging at 45 ℃ for three days)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 541.9 | 573.7 | 596.2 | 619.8 | 640.3 |
Tables 1-5 (oven aging at 45 ℃ for five days)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 542.5 | 575.3 | 605.8 | 633.9 | 670 |
Tables 1 to 6 (energy required for CD 600 nm)
The photoresist of the five storage environments in example 2 gave the following lithographic patterns:
table 2-1 (Normal temperature)
| Energy/ms | 135 | 150 | 165 | 180 | 195 |
| CD/nm | 523 | 561.7 | 597.5 | 641.5 | 666.4 |
Table 2-2 (Low temperature)
| Energy/ms | 135 | 150 | 165 | 180 | 195 |
| CD/nm | 512.5 | 553.4 | 597.9 | 634.7 | 673.2 |
Tables 2-3 (45 ℃ oven aging for one day)
| Energy/ms | 135 | 150 | 165 | 180 | 195 |
| CD/nm | 502.1 | 557.7 | 598.3 | 646.8 | 678.8 |
Tables 2-4 (oven aging at 45 ℃ for three days)
| Energy/ms | 135 | 150 | 165 | 180 | 195 |
| CD/nm | 497.6 | 552.5 | 610.4 | 649.9 | 684.4 |
Tables 2-5 (45 ℃ oven aged five days)
| Energy/ms | 135 | 150 | 165 | 180 | 195 |
| CD/nm | 494.4 | 543.9 | 591.4 | 633.2 | 675.7 |
Tables 2 to 6 (energy required for CD 600 nm)
The photoresist of the five storage environments in comparative example 1 gave the following lithographic patterns:
table 3-1 (Normal temperature)
Table 3-2 (Low temperature)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 509.3 | 554.1 | 587.9 | 609.1 | 624.3 |
Table 3-3 (45 ℃ oven aging for one day)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 551.3 | 591.6 | 620.3 | 647.2 | 661.9 |
Tables 3-4 (oven aging at 45 ℃ for three days)
| Energy/ms | 140 | 150 | 160 | 170 | 180 |
| CD/nm | 530.3 | 599.6 | 638.1 | 664.4 | 695 |
Tables 3-5 (oven aging at 45 ℃ for five days)
| Energy/ms | 150 | 160 | 170 | 180 | 190 |
| CD/nm | 574.8 | 599 | 626.8 | 651.5 | 663 |
Tables 3 to 6 (energy required for CD 600 nm)
The results of forming photoresist patterns in example 1, example 2 and comparative example 1 are shown in Table 4
TABLE 4 Table 4
According to the above examples 1-2 and comparative example 1, the energy stability of examples 1-2 with the addition of the stabilizer is greatly improved in terms of the stability of the energy EOP required for the target CD (600 nm); however, in comparison with the two examples, the addition of too much stabilizer in example 2 resulted in the pattern having a partial black spot residual, so that the energy stability and the lithographic pattern of example 1 were superior to those of example 2.
The result shows that the problem of unstable energy of the chemical amplification type I-line photoresist can be effectively solved by adding a proper amount of stabilizer into the photoresist formula, and the photoresist with stable energy and better photoetching pattern can be obtained by adjusting the using amount of the stabilizer.
The embodiments are described above in order to facilitate the understanding and application of the present application by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Accordingly, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications without departing from the scope and spirit of the present application.
Claims (8)
1. The chemically amplified I-line photoresist is characterized by comprising the following components in percentage by mass:
wherein the polymer resin comprises a first polyhydroxystyrene polymer resin and a second polyhydroxystyrene polymer resin, the weight average molecular weight of the first polyhydroxystyrene polymer resin is 15000-26000, the mass of the first polyhydroxystyrene polymer resin is 8-17.5% of that of the photoresist,
the first polyhydroxystyrene polymer resin is obtained by copolymerizing the following components in percentage by mole:
50-70% of hydroxystyrene compound;
10-30% of a styrene compound;
the tert-butyl acrylate compound complements 100%;
the weight average molecular weight of the second polyhydroxystyrene polymer resin is 8000-15000, and the mass of the second polyhydroxystyrene polymer resin is 2-2.5% of that of the photoresist;
the second polyhydroxystyrene polymer resin is obtained by copolymerizing the following components in percentage by mole:
60-80% of hydroxystyrene compound;
5-15% of a styrene compound;
the p-methoxyl styrene compound is 100 percent;
the stabilizer is at least one selected from antioxidants selected from the following general formulas:
in formula 5, P 1 Is C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 4 -C 10 Or a group of formula 7, wherein P 11 、P 12 Each independently is C 1 -C 4 Alkyl of (a);
in formula 6, P 2 Is C 1 -C 4 N is a positive integer from 2 to 4,
2. the chemically amplified I-line resist of claim 1, further comprising at least one of the following features:
a2 A molecular weight distribution coefficient of the first polyhydroxystyrene polymer resin is PDI <2.5;
a5 The molecular weight distribution coefficient of the second polyhydroxystyrene polymer resin is PDI <2.5.
3. The chemically amplified I-line photoresist of claim 1, further comprising at least one of the following technical features:
b1 At least one of ionic or nonionic photoacid;
b2 The acid quencher is selected from at least one of triethanolamine, tetrabutylammonium hydroxide, tri (3, 6 dioxaheptyl) amine, trioctylamine, triisopropanolamine, triethylenediamine, 2-ethyl-N, N-bis (2-ethylhexyl) -1-hexylamine, 2-phenylbenzimidazole or diphenylamine;
b4 At least one of 3M fluorocarbon surfactant FC-4430 or Troysol S366;
b5 The solvent is at least one selected from propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate, anisole, propylene glycol monoacetate, propylene glycol monoethyl ether, ethylene glycol methyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, butyl acetate, neopentyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol or gamma-butyrolactone.
4. The chemically amplified I-line photoresist of claim 3, wherein the photoresist further comprises at least one of the following features:
c1 The ionic photoacid is selected from the following general formula:
in formula 1, R 1 Is C 1 -C 4 Alkyl of (a);
in formula 2, R 2 Is hydroxy or C 1 -C 4 Alkoxy, R 3 Is a hydrogen atom, a hydroxy group or C 1 -C 4 Alkoxy, R 4 And R is 5 Each independently is C 1 -C 4 Or R is an alkyl group of 4 And R is R 5 Can be bonded to form C 5 -C 8 R is a ring of 6 Is C 1 -C 4 Perfluoroalkyl of (2);
c2 The nonionic photoacid is selected from the following general formula:
in formula 3, R 3 Is hydrogen atom, phenoxy or C 1 -C 4 C containing sulfonate groups or alkyl groups 2 -C 10 Alkyl of R 4 Is thatR 5 Is C 1 -C 4 Perfluoroalkyl or perfluorophenyl;
in formula 4, R 6 Is C 1 -C 4 Alkyl or C of (2) 1 -C 6 Alkoxy, R 7 For connecting keys orR 8 Is C 1 -C 4 Alkyl, tolyl or trifluoromethylphenyl groups.
5. The chemically amplified I-line photoresist of claim 4, further comprising at least one of the following features:
d1 The ionic photoacid is selected from at least one of the following structures:
d2 The nonionic photoacid is selected from one of the following structures:
d3 The antioxidant is selected from at least one of the following structures:
6. a method for preparing a chemically amplified I-line photoresist according to any one of claims 1 to 5, comprising the steps of: and mixing the polymer resin, the photoacid, the acid quencher, the stabilizer, the leveling agent and the solvent in proportion, and filtering to obtain the chemically amplified I-line photoresist.
7. The method of preparing a chemically amplified I-line photoresist according to claim 6, wherein the filtration is performed using two nylon membranes of 1 μm+0.45 μm.
8. A method of using a chemically amplified I-line photoresist according to any one of claims 1 to 5, comprising the steps of: and coating the chemical amplification type I-line photoresist on a Si substrate, and sequentially performing pre-baking, exposure, post-baking and development to obtain a photoetching pattern.
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