CN117826533A - MIL-53-acrylate compound, negative photoresist and preparation method - Google Patents
MIL-53-acrylate compound, negative photoresist and preparation method Download PDFInfo
- Publication number
- CN117826533A CN117826533A CN202410251271.8A CN202410251271A CN117826533A CN 117826533 A CN117826533 A CN 117826533A CN 202410251271 A CN202410251271 A CN 202410251271A CN 117826533 A CN117826533 A CN 117826533A
- Authority
- CN
- China
- Prior art keywords
- mil
- acrylate
- photoresist
- parts
- compound
- 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.)
- Granted
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000013206 MIL-53 Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 4-methylthiophenyl Chemical group 0.000 claims description 15
- 239000000975 dye Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical group COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 claims description 7
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 6
- QWWTXMUURQLKOT-UHFFFAOYSA-N 1-phenoxypropan-2-yl acetate Chemical compound CC(=O)OC(C)COC1=CC=CC=C1 QWWTXMUURQLKOT-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- IFDFMWBBLAUYIW-UHFFFAOYSA-N ethane-1,2-diol;ethyl acetate Chemical compound OCCO.CCOC(C)=O IFDFMWBBLAUYIW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001000 anthraquinone dye Substances 0.000 claims description 2
- 125000005410 aryl sulfonium group Chemical group 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000001007 phthalocyanine dye Substances 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004873 anchoring Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 238000001259 photo etching Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012898 sample dilution Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- GMEXDATVSHAMEP-UHFFFAOYSA-N dimethyl(phenyl)sulfanium Chemical class C[S+](C)C1=CC=CC=C1 GMEXDATVSHAMEP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000004383 yellowing 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention relates to the field of semiconductor chips and chemical industry, in particular to an MIL-53-acrylate compound, a negative photoresist and a preparation method thereof. The compound is prepared by the following method: mixing MIL-53 and acrylic monomers in a weight ratio of 1:1-10, adding into solvent under nitrogen protection, stirring at 200-1000rpm, sealing at high temperature for 36-48h, filtering, and vacuum drying. The negative photoresist composition comprises the following components: epoxy resin, MIL-53-acrylate compound, dye, photoinitiator, leveling agent and solvent; can improve the entanglement problem of the molecular chains of the resin, improve the verticality and the resolution of the edges, and have the potential of recognition, identification and bar code anchoring.
Description
Technical Field
The invention relates to the field of semiconductor chips and chemical industry, in particular to an MIL-53-acrylate compound, a negative photoresist and a preparation method thereof.
Background
According to the difference of removal or retention of an exposure area in the development process, the positive photoresist and the negative photoresist are divided into positive photoresist and negative photoresist, the positive photoresist has advantages, the positive photoresist transfers patterns to a photoresist coating under the irradiation of ultraviolet exposure, the photosensitive part after the irradiation is subjected to decomposition reaction, the positive photoresist is dissolved in a developing solution, the non-photosensitive part is insoluble in the developing solution, and the positive photoresist and the negative photoresist are retained on a substrate, so that the resolution is high and the positive photoresist is free from swelling; the negative photoresist is irradiated by ultraviolet exposure, the pattern is transferred onto the photoresist coating, the exposed part of the negative photoresist generates a crosslinking reaction under the action of the developing solution and is insoluble in the developing solution, the unexposed part is soluble in the developing solution, the negative photoresist has strong heat resistance, and the negative photoresist has irreplaceable effects in high-voltage power, high-energy-consumption devices and special devices and is suitable for more complex photoetching processes. But at the same time it is more difficult to remove and therefore is used in the final packaging stage of the chip, serving the function of insulating and protecting the chip.
The negative photoresist is mainly prepared from macromolecular resin, which has low uniformity and poor stability due to uneven molecular weight distribution and component difference. However, single-molecule resin has high processing cost, needs multi-step organic synthesis to control purity and has high price, and the biggest problem is that small-molecule resin is difficult to prepare liquid with higher viscosity, easy to cause stripping and deletion of photoresist, difficult to realize preparation of thick film samples and also affects the quality of the whole chip. CN110256655a discloses a tannic acid multi-uterine epoxy resin as a negative photoresist component, and adopts the characteristic of phenolic hydroxyl group cross-linkable alkali-soluble property to cross-link tannic acid and epoxy resin, so as to obtain a negative photoresist product with environmental protection, simplicity and higher reactivity. CN112011031a discloses a negative photoresist resin, which is prepared by polymerizing a single molecule epoxy resin and acryloxypolymethylene carboxylic acid, etc., to obtain a modified single molecule epoxy resin, and to improve the resolution of the photoresist. However, the process needs to reform the resin product, and due to uncontrollable polymerization reaction in the reform process, partial byproducts and high polymer chain winding problem are caused, and after the epoxy resin is modified, the linked active groups such as phenolic hydroxyl groups or acryloxypolymethylene carboxylic acid have strong reactivity, and are extremely easy to crosslink under the illumination condition to cause deactivation of the photoresist, so that many challenges are brought to storage, in addition, uniformity of crosslinking degree under the photosensitive reaction condition is difficult to be ensured to cause reduction of edge uniformity, a certain defective rate is caused, and finally, the negative photoresist has higher adhesion requirement due to the requirement of multiple photoetching, and the modified small-molecule resin is difficult to realize.
Disclosure of Invention
The invention aims to provide a negative photoresist product for overcoming the problems in the prior art, which has the characteristics of neat edges and high resolution, has certain self-repairing property, has topology identification marking capability and high photoetching success rate, and simultaneously avoids photoetching process challenges caused by resin modification.
The invention provides an MIL-53-acrylate compound, which is prepared by the following method: mixing MIL-53 and acrylic monomers in a weight ratio of 1:1-10, adding into solvent under nitrogen protection, stirring at 200-1000rpm, performing high-temperature airtight reaction for 36-48h, filtering, and vacuum drying to obtain the final product; wherein the solvent is one or more of dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate and ethylene glycol ethyl acetate; the infrared spectrum of the complex shows the following characteristic peaks: (c=o) 1654cm -1 ,Cr-o 765 cm -1 , c-c 1370 cm -1 ,o-o 1567 cm -1 。
The technical scheme adopted by the invention for overcoming the difficulties in the prior art comprises the steps of providing a negative photoresist product, which comprises the following components:
20-40 parts of epoxy resin,
10-30 parts of MIL-53-acrylic ester compound,
1-5 parts of dye,
1-2 parts of a photoinitiator,
0.1 to 0.5 part of flatting agent,
20-50 parts of a solvent,
wherein the acrylate monomer and MIL-53 form a complex, and are added into the composition in the form of MIL-53-acrylate complex.
Specifically, the photoinitiator is one or more of benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2-isopropyl thioxanthone, alkyl sulfonium salt, alkyl iodonium salt, aryl iodonium salt and aryl sulfonium salt; the dye comprises naphthol dye, phthalocyanine dye, anthraquinone dye or benzimidazolone dye; the acrylic ester monomer is one or more of hydroxyethyl acrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate and methyl acrylate, and the solvent is one or more of dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate and ethylene glycol ethyl acetate.
Further, the acrylate monomer and MIL-53 form a complex (referred to as MIL-53-acrylate complex); the acrylate moiety in such composites is an acrylate-containing group, sources including, but not limited to, hydroxyethyl acrylate, tripropylene glycol diacrylate, trimethylol propane triacrylate, and/or methyl acrylate.
The specific preparation method comprises the following steps: 1) Placing acrylate monomer and MIL-53 in partial solvent, mixing at above 120deg.C for 24-72h, filtering, and vacuum drying to obtain compound; 2) And stirring and mixing the rest components and the compound uniformly.
Further, the leveling agent is selected from one or more of F-563 (DIC Co.), polymethylphenylsiloxane, polydimethylsiloxane, glide100, glide440, flow300, byk333, byk371, byk088, efk a2720, FC-4430 or Troysol S366.
Further, the epoxy resin of the present invention may be selected from the conventional types commercially available, and may also be selected from modified processed products including, but not limited to, bisphenol-based epoxy resins, phenolic epoxy resins, su-8 epoxy resins.
Further preferably, the photoresist of the present invention comprises the following components: 20-40 parts of epoxy resin, 15-30 parts of MIL-53-acrylate compound, 1-5 parts of dye, 0.1-0.5 part of flatting agent and 20-50 parts of solvent.
MILs-53-acrylate composites were prepared by the following method: mixing MIL-53 and acrylic monomers in a weight ratio of 1:1-10, adding into solvent under nitrogen protection, stirring at 200-1000rpm, sealing at high temperature (about 120 deg.C) for 36-48 hr, filtering, and vacuum drying. Samples were taken for infrared spectroscopy testing.
All reagents of the invention are commercially available. MIL-53 (CAS: 442912-79-0) is also referred to as CrMIL-53 or MIL-53 (Cr), namely MIL-53 with Cr metal, available from the Siam Aziyue organism and other suppliers, and epoxy resin can be available from such suppliers as Wenchang chips SU-8, EPON, microChem SU-8 and the like. FSU-8 (fluorine-containing SU-8 epoxy resin) was purchased from Shandong Luyuan chemical technology Co., ltd, polymerization degree was 4-8, refractive index (n 20 D ) 1.5154. Leveling agent TEGO cube and Glide series are purchased from Kaine chemical industry.
MIL-53 is not a MOF metal framework compound in the traditional sense, has great flexibility and a 'breathing' effect generated between two different configurations of a large hole (lp) and a narrow hole (np) in the adsorption process, so that the volume difference is as high as 40%, and the prepared compound has larger volume tolerance.
Unless otherwise indicated, all terms "comprising," "including," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising … …" does not exclude that an additional identical element is present in a commodity or system comprising the element. The room temperature in the present invention means 15-25 ℃, and all percentages by weight unless otherwise indicated are by weight, and the present solution is an aqueous solution. Numerical ranges in this application are approximations, by use of the particular examples only, and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
As used with respect to chemical compounds, unless explicitly stated otherwise, the singular includes all of the isomeric forms, as do the plural.
The invention has the beneficial effects that:
1) The epoxy resin is matched with components such as MIL-53-acrylate compound, and a metal framework compound with a topological structure is introduced, so that the problem of entanglement of a resin molecular chain is solved. And meanwhile, the method has the potential of identification, authentication and bar code anchoring. If biotin or a polypeptide is coupled, it may also have a biorecognition chip function.
2) The preparation process is simplified, the molecular weight and uniformity of the epoxy resin are not limited, the epoxy resin is not subjected to further polymerization modification and the like, and a series of problems caused by modification are avoided.
3) The storage stability is improved.
4) The application range of the epoxy resin in the negative photoresist is enlarged, and the resolution and the photoetching performance of the conventional photoresist resin are improved.
Drawings
FIG. 1 is a schematic diagram of photoresist improvement (A: without MIL-53-acrylate compound B: with MIL-53-acrylate compound)
Detailed Description
The present invention will be specifically described below with reference to the drawings and examples, but the present invention is not limited to these examples. The test analysis methods employed in the examples were as follows: fourier infrared spectroscopy FTIR: the test samples were prepared by a tabletting method using an infrared spectrometer (Nicolet 5700).
Example 1
20 parts of Su-8 epoxy resin,
10 parts of hydroxyethyl acrylate, which is used for preparing the adhesive,
MIL-53 parts by weight of the total of 1 part,
1 part of phthalocyanine, wherein the phthalocyanine is mixed with the organic solvent,
1 part of benzoin dimethyl ether,
0.1 part of polymethylphenylsiloxane,
40 parts of dipropylene glycol methyl ether acetate;
the preparation method comprises the following steps:
1) Adding 10 parts of hydroxyethyl acrylate and 1 part of MIL-53 into a closed flask containing 10 parts of dipropylene glycol methyl ether acetate under the protection of nitrogen, heating to above 120 ℃ in a fume hood, stirring and mixing at 700rpm for 48h, filtering, vacuum drying to obtain a compound, and infrared spectrumThe following characteristic peaks are shown: (c=o) 1654cm -1 ,Cr-o 765 cm -1 , c-c 1370 cm -1 ,o-o 1567 cm -1 ；
2) Adding the rest components and the rest solvent, mixing and dispersing for 1h to obtain the photoresist.
Uniformly dispersing and coating the glue on the processed flat silicon wafer by using a2 mu m pull rod, baking 10 parts, exposing to ultraviolet light, developing by using a 0.2% sodium carbonate developer, cleaning by using pure water, and stripping the glue by using sodium hydroxide to obtain the photoetching pattern.
Example 2
30 parts of FSU-8 epoxy resin,
20 parts of trimethylolpropane triacrylate,
MIL-53 (10 parts by weight),
5 parts of benzimidazolone, which is used for preparing the medicine,
2 parts of photoinitiator (2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one and 2-isopropylthioxanthone in a weight ratio of 1:1),
0.5 part of Glide440, and the like,
50 parts of ethylene glycol ethyl ether acetate.
The preparation method comprises the following steps:
1) Adding 20 parts of trimethylolpropane triacrylate and 10 parts of MIL-53 into a closed flask containing 20 parts of ethylene glycol diethyl ether acetate under the protection of nitrogen, stirring and mixing for 38 hours at 600rpm above 120 ℃, filtering, and vacuum drying to obtain a compound, wherein the infrared spectrum shows the following characteristic peaks: (c=o) 1654cm -1 ,Cr-o 765 cm -1 , c-c 1370 cm -1 ,o-o 1567 cm -1 。
2) Adding the rest components and the rest solvent, mixing and dispersing for 1h to obtain the photoresist.
Uniformly dispersing and coating the glue on the processed flat silicon wafer by using a2 mu m pull rod, baking 10 parts, exposing to ultraviolet light, developing by using a 0.2% sodium carbonate developer, cleaning by using pure water, and stripping the glue by using sodium hydroxide to obtain the photoetching pattern.
Example 3
40 parts of SU-8 epoxy resin,
20 parts of tripropylene glycol diacrylate (TPGDA),
MIL-53 (10 parts by weight),
5 parts of dye, namely a dye, wherein the dye comprises,
1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one and 1 part of 2-isopropylthioxanthone,
0.5 part of polydimethylsiloxane,
50 parts of propylene glycol phenyl ether acetate.
The preparation method comprises the following steps: 1) Adding 20 parts of tripropylene glycol diacrylate and 10 parts of MIL-53 into a closed flask containing 20 parts of propylene glycol phenyl ether acetate solvent under the protection of nitrogen, heating to 120 ℃ in a fume hood, stirring and mixing at 600rpm for 45h, filtering, and vacuum drying to obtain a compound, wherein an infrared spectrum shows the following characteristic peaks: (c=o) 1654cm -1 ,Cr-o 765 cm -1 , c-c 1370 cm -1 . 2) Adding the rest components and the rest solvent, mixing and dispersing for 1h to obtain the photoresist.
Uniformly dispersing and coating the glue on the processed flat silicon wafer by using a2 mu m pull rod, baking 10 parts, exposing to ultraviolet light, developing by using a 0.2% sodium carbonate developer, cleaning by using pure water, and stripping the glue by using sodium hydroxide to obtain the photoetching pattern.
Comparative example 1:
MIL 100 (Cr) was used instead of MIL-53 (Cr), and the rest was the same as in example 1.
The structural differences are as follows:
MIL 100(Cr)
MIL-53 (Cr)
comparative example 2
MIL-53 was not contained, and the other components were the same as in example 2.
Comparative example 3
Polymethyl methacrylate was used instead of epoxy resin, and dimethylphenyl sulfonium salt was used as a photoinitiator, except that the same as in example 3 was used.
Comparative example 4
The photoresist is prepared by directly mixing the components without adopting the step 1) in the preparation method. I.e., without the step of mixing MILs-53 with acrylate monomers to prepare a composite, the two are mixed together with the remaining ingredients.
Comparative example commercial photoresist negative photoresist product containing SU-8 resin.
And (3) testing:
1) Resolution detection criteria reference GB/T29556-2013, optical mirrors detect photoresist edges (+more representative of higher edge smoothness perpendicularity).
2) The product after developing and showering the photoresist is subjected to parallel test by adopting a projection chrome plate method, and the pinhole density (p/cm) is detected 2 ) The higher density indicates lower quality, and although pinholes may not affect performance, subsequent chemical or mechanical damage is easily initiated, which may create a potential hazard to product quality. After 2min and 1h, the test time is 2min to determine whether the test device has a self-repairing function. The results are shown in Table 1:
3) Accelerated shelf life test
10g of each product of the above examples was weighed and diluted, and the diluent was diluted with the solvent in the photoresist formulation of each example, with a dilution of 100ml. For example, the product of example 1 is diluted by adding dipropylene glycol methyl ether acetate, the product of example 2 is diluted by adding ethylene glycol ethyl ether acetate, and so on.
The diluted samples are placed in the same light-shielding bottle, and a light incubator (35 ℃) in a laboratory is placed for 3-7 days, and compared with refrigerated sample dilutions, the clarity and color difference change of the sample dilutions are recorded. The results are shown in Table 2 below:
the appearance of the samples of examples 1-3 and comparative example 3 were unchanged. Comparative examples 1 and 4 were observed to have problems of yellowing in color and reduced clarity immediately after day 3; a significant decrease in clarity was observed after day 7 for comparative example 2 and the control.
From the above detection, it can be seen that examples 1-3 have high relative resolution and high sensitivity, and fig. 1 shows that the photoresist composition product (corresponding to B in fig. 1) of the present invention has a regular topological sequence, regular molecular arrangement, clear edges, and high verticality, and is suitable for thick glue processing, and can also be used to add tag substances, such as bar codes or bio-peptide sequences, to expand the bio-identifiable function, relative to a negative glue product containing resin without MILs-53.
The storage test shows that the stability of the photoresist negative photoresist product added with the MIL-53-acrylate compound is obviously increased, the photoresist negative photoresist product is easier to store, and the photoresist negative photoresist product added with other MIL is more unfavorable to store, which is related to the variable structure specificity of MIL-53; while it is seen that comparative example 4 (a photoresist composition that does not form a complex but is simply mixed) has a shortened shelf life and is less stable, this may be related to the metal oxide being more prone to light absorption and scattering resulting in increased photosensitivity during colloid storage. While inventive examples 1-3 contained the photoinitiator stably and strongly under normal storage conditions. The photosensitive substance and the initiator can be released by the change of volume when the water-based paint is used.
The pinhole density detection shows that the product has a small amount of self-repairing property, maintains colloid stability, is beneficial to the subsequent photoetching process, has unexpected technical effects on the quality improvement and wear resistance of the photoresist photoetching product, and has wide research value and application prospect.
Claims (6)
1. An MILs-53-acrylate composite, wherein the MILs-53-acrylate composite is prepared by the process comprising: mixing MIL-53 and acrylic monomers in a weight ratio of 1:1-10, adding into solvent under nitrogen protection, stirring at 200-1000rpm, performing high-temperature airtight reaction for 36-48h, filtering, and vacuum drying to obtain the final product; wherein the solvent is dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate, or ethylene glycol ethyl ether acetateOne or more of; the infrared spectrum of the complex shows the following characteristic peaks: (c=o) 1654cm -1 ,Cr-o 765 cm -1 , c-c 1370 cm -1 ,o-o 1567 cm -1 。
2. The negative photoresist is characterized by comprising the following components in percentage by weight:
20-40 parts of epoxy resin,
10-30 parts of MIL-53-acrylic ester compound,
1-5 parts of dye,
1-2 parts of a photoinitiator,
0.1 to 0.5 part of flatting agent,
20-50 parts of a solvent;
the MIL-53-acrylate compound adopts the MIL-53-acrylate compound as claimed in claim 1.
3. The photoresist of claim 2 wherein the photoinitiator is one or more of benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, 2-isopropylthioxanthone, alkyl sulfonium salt, alkyl iodonium salt, aryl sulfonium salt; the dye comprises naphthol dye, phthalocyanine dye, anthraquinone dye or benzimidazolone dye.
4. The photoresist of claim 2, wherein the MIL-53-acrylate compound is prepared by compounding MIL-53 with acrylate monomers, wherein the acrylate monomers are one or more of hydroxyethyl acrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate and methyl acrylate, and the solvent is one or more of dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate and ethylene glycol ethyl acetate.
5. The photoresist of claim 2 wherein the acrylate monomer and MILs-53 form a complex.
6. The method for preparing the photoresist according to claim 2, comprising:
1) Mixing MIL-53 and acrylic monomers in a weight ratio of 1:1-10, adding the mixture into a solvent under the protection of nitrogen, stirring at 200-1000rpm, performing high-temperature airtight reaction for 36-48h, filtering, and performing vacuum drying to obtain a compound of MIF-53 and an acrylic ester monomer;
2) And stirring and mixing the rest components and the compound uniformly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410251271.8A CN117826533B (en) | 2024-03-06 | 2024-03-06 | MIL-53-acrylate compound, negative photoresist and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410251271.8A CN117826533B (en) | 2024-03-06 | 2024-03-06 | MIL-53-acrylate compound, negative photoresist and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117826533A true CN117826533A (en) | 2024-04-05 |
| CN117826533B CN117826533B (en) | 2024-05-28 |
Family
ID=90524490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410251271.8A Active CN117826533B (en) | 2024-03-06 | 2024-03-06 | MIL-53-acrylate compound, negative photoresist and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117826533B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109921041A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation and application of base metal N doping carbon nanotubes elctro-catalyst |
| WO2021076049A1 (en) * | 2019-10-17 | 2021-04-22 | National University Of Singapore | Composite materials for water capture and release |
| WO2022016232A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Macrocycle-metal organic frameworks |
| WO2024026510A1 (en) * | 2022-07-29 | 2024-02-01 | Cornell University | Methods of purification of recycled monomers, and recycled monomers and uses thereof |
-
2024
- 2024-03-06 CN CN202410251271.8A patent/CN117826533B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109921041A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation and application of base metal N doping carbon nanotubes elctro-catalyst |
| WO2021076049A1 (en) * | 2019-10-17 | 2021-04-22 | National University Of Singapore | Composite materials for water capture and release |
| WO2022016232A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Macrocycle-metal organic frameworks |
| WO2024026510A1 (en) * | 2022-07-29 | 2024-02-01 | Cornell University | Methods of purification of recycled monomers, and recycled monomers and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117826533B (en) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101840055B1 (en) | Colored photosensitive resin composition for touch panel, touch panel and display device | |
| TWI806434B (en) | Photosensitive resin composition, and method for producing same, color filter, and method for producing same, and image display element | |
| JP6368240B2 (en) | Metal oxide dispersion, polymerizable composition containing metal oxide dispersion, and polymer thereof | |
| TW200426503A (en) | Photoresist compositions and processes for preparing the same | |
| CN101891845A (en) | Application of carbazole oxime ester compound serving as photoinitiator in photopolymerisable acrylate composition | |
| KR20130016045A (en) | Polymer compounds comprising dye and curable resin composition comprising the same | |
| KR101367572B1 (en) | Polymer compounds comprising dye and curable resin composition comprising the same | |
| CN101482699B (en) | Coloring light-sensitive resin composition | |
| JP5035930B2 (en) | Anti-reflective coating composition for photoresist containing solvent mixture | |
| CN111032720B (en) | Resin, photosensitive resin composition, resin cured film, and image display device | |
| CN117826533B (en) | MIL-53-acrylate compound, negative photoresist and preparation method | |
| JP2003277437A (en) | Functionalized polymer | |
| TW202323331A (en) | Photosensitive resin composition, color filter, image display element, and method for producing a color filter | |
| EP2000852B1 (en) | Halogenated anti-reflective coatings | |
| JP4570786B2 (en) | High-purity 1,3-propanediol derivative solvent, method for producing the same, and use | |
| EP1629046B1 (en) | Curable polymer compound | |
| CN106886128B (en) | Negative photoresist | |
| CN110382627A (en) | Colorant compound and coloured composition comprising it | |
| CN118151491A (en) | Enhanced negative photoresist and preparation method thereof | |
| JP2000258603A (en) | Coating agent for optical film and emulsion mask using same | |
| CN103443708A (en) | Negative photosensitive resin composition | |
| KR101492679B1 (en) | Polymer and photo-sensitive resin composition comprising the same | |
| JPH01198615A (en) | Photosensitive resin composition | |
| EP3037454B1 (en) | Polyether compound, preparation method and photoresist composition thereof | |
| KR20150085295A (en) | A photocurable composition comprising multifunctional acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |