CN116149140B - Positive photosensitive resin composition with high chemical resistance and preparation method and application thereof - Google Patents
Positive photosensitive resin composition with high chemical resistance and preparation method and application thereof Download PDFInfo
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- CN116149140B CN116149140B CN202310415913.9A CN202310415913A CN116149140B CN 116149140 B CN116149140 B CN 116149140B CN 202310415913 A CN202310415913 A CN 202310415913A CN 116149140 B CN116149140 B CN 116149140B
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- 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
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- 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
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
Abstract
The invention discloses a positive photosensitive resin composition with high chemical resistance, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The positive photosensitive resin composition of the present invention comprises the following components in parts by mass: 100 parts of alkali-soluble resin; 3-40 parts of a photosensitizer; 1-30 parts of aliphatic flexible compound containing unsaturated bonds; 1-30 parts of cross-linking agent and 100-1000 parts of organic solvent. The invention greatly improves the chemical resistance of the cured resin film by adding the aliphatic flexible compound containing unsaturated bonds and the cross-linking agent into the alkali-soluble resin, has excellent bonding performance with metals Cu and Au, has high resolution, low water absorption, excellent mechanical property, heat resistance and dielectric property and excellent comprehensive performance, and has good application prospect in the field of semiconductor manufacturing and packaging.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a positive photosensitive resin composition with high chemical resistance, a preparation method and application thereof.
Background
The photosensitive polyimide/polybenzoxazole resin solution has excellent photoetching manufacturability, and the cured resin has the advantages of high heat resistance, high electric insulation, high strength, high toughness and the like, and is widely applied to chip surface passivation in the semiconductor manufacturing process, interlayer insulation of a multilayer metal interconnection structure, multilayer wiring and bump/micro solder ball manufacturing processes of advanced electronic packaging (BGA, CSP, siP and the like) substrates, stress buffering inner coating protective layer films of plastic packaging circuits, multilayer wiring processes of photoelectric display devices and the like.
In order to satisfy the complicated process in the semiconductor manufacturing process, it is generally required that the photosensitive polyimide/polybenzoxazole cured resin film has excellent chemical resistance and excellent adhesion property to the substrate. Negative photosensitive polyimide has excellent chemical resistance and can resist corrosion of high-temperature resist stripping liquid, but organic solvents are used in the developing process, so that the negative photosensitive polyimide is not beneficial to environmental protection, and the photoetching resolution is poor, so that the requirements of high-resolution application scenes in the advanced packaging field cannot be met. Positive photosensitive resins, although having high resolution, have poor chemical resistance and limit their practical application. There are few reports of positive photosensitive resins with high chemical resistance.
Disclosure of Invention
The invention aims to provide a positive photosensitive resin composition with high chemical resistance, a preparation method and application thereof.
The invention firstly provides a positive photosensitive resin composition which comprises the following components in parts by mass:
100 parts of alkali-soluble resin; 3-40 parts of a photosensitizer; 1-30 parts of aliphatic flexible compound containing unsaturated bonds; 1-30 parts of cross-linking agent and 100-1000 parts of organic solvent.
The positive photosensitive resin composition comprises the following components in parts by mass: 100 parts of alkali-soluble resin; 8-15 parts of a photosensitizer; 10-15 parts of aliphatic flexible compound containing unsaturated bonds; 2-8 parts of cross-linking agent and 100-250 parts of organic solvent.
The positive photosensitive resin composition comprises the following components in parts by mass: 100 parts of alkali-soluble resin; 12 parts of a photosensitizer; 10-15 parts of aliphatic flexible compound containing unsaturated bonds; 5 parts of cross-linking agent and 180 parts of organic solvent.
In the positive photosensitive resin composition, the alkali-soluble resin is prepared by polymerizing a component 1 and a component 2 in an organic solvent under the action of a blocking agent; the GPC weight average molecular weight of the alkali-soluble resin is 10000-60000, preferably 10000-40000; when the weight average molecular weight of the resin is less than 10000, the mechanical properties and chemical resistance of the cured film are affected; above 60000, lithographic performance and processability are affected.
The component 1 is aromatic diacid chloride or a derivative thereof, and can be specifically selected from at least one of diphenyl ether diacid chloride, isophthaloyl dichloride, terephthaloyl dichloride, biphenyl diacid chloride, diphenyl sulfone diacid chloride, diphenylmethane diacid chloride and benzophenone diacid chloride; more specifically 4,4' -diphenyl ether dicarboxylic acid chloride;
the component 2 is aromatic diamine containing phenolic hydroxyl groups, or at least one of aliphatic diamine, aromatic diamine without phenolic hydroxyl groups and diamine containing silicon is added into the aromatic diamine containing phenolic hydroxyl groups to improve the mechanical property, thermal property, bonding property with a substrate and the like of the resin; wherein the molar ratio of the total amount of the aliphatic diamine, the aromatic diamine containing no phenolic hydroxyl groups and the siliceous diamine is not more than 20% of the total diamine, otherwise, the heat resistance of the cured film, the photosensitivity and the storage stability of the resin composition and the like are affected.
The phenolic hydroxyl group-containing aromatic diamine is selected from the group consisting of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, 3 '-diamino-4, 4' -dihydroxydiphenyl ether at least one of 4,4 '-diamino-3, 3' -dihydroxydiphenyl ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxybenzophenone, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, and 1, 3-diamino-4, 6-dihydroxybenzene;
The aliphatic diamine is a linear aliphatic diamine having 2 to 20 carbon atoms, a cycloalkane diamine, or a linear aliphatic diamine having 2 to 20 carbon atoms containing oxygen atoms in the structure; specifically, the catalyst is at least one selected from 1, 4-butanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, dodecanediamine, 1, 4-cyclohexanediamine, 1, 3-cyclobutanediamine, 1, 8-diamino-3, 6-dioxaoctane, 4,7, 10-trioxo-1, 13-tridecanediamine, 4, 9-dioxa-1, 12-dodecanediamine and ethylene glycol bis (3-aminopropyl) ether; specifically, hexamethylenediamine;
the phenolic hydroxyl-free aromatic diamine may be selected from the group consisting of 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3, 4-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -diethyl-4, 4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminobiphenyl, 3' -diethyl-4, 4' -diaminobiphenyl, 2', at least one of 3,3' -tetramethyl-4, 4' -diaminobiphenyl, 3', 4' -tetramethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl; specifically, the catalyst can be 4,4' -diaminodiphenyl ether;
The siliceous diamine may be selected from the group consisting of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (4-aminobutyl) -1, 3-tetramethyldisiloxane 1, 3-bis (2-aminoethyl) -1, 1-dimethyl-3, 3-diethyl-disiloxane 1, 5-bis (2-aminoethyl) -1,3, 5-hexamethyltrisiloxane, 1, 5-bis (3-aminopropyl) -1,3, 5-hexamethyltrisiloxane 1-aminopropyl-5-aminoethyl-1, 3, 5-hexamethyltrisiloxane 1, 7-bis (2-aminoethyl) -1,3, 5, 7-octamethyltetrasiloxane, 1, 3-bis (3-aminophenyl) -1, 3-tetramethyldisiloxane at least one of 1, 3-bis (4-aminophenyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (3-aminopropyl) -1, 3-dimethyl-1, 3-diphenyldisiloxane; specifically, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane is used.
The end-capping agent is at least one of maleic anhydride, norbornenedianhydride, methylnorbornenedianhydride, 4-ethynylphthalic anhydride, 4-phenylacetylenephthalic anhydride, 4-vinylaniline, norborneneamine, allylamine, 4-ethynylaniline, 3-phenylethynylaniline, 4- (4-aminophenylethynyl) phenylacetylene, 4- [ (trimethylsilyl) -ethynyl ] aniline, 4- (4-amino-phenyl) -2-methyl-but-3-yn-2-ol, (E) -3-aminocinnamic acid and propargylamine; specifically norbornene dianhydride or 4-ethynyl phthalic anhydride;
The organic solvent is at least one of N 'N-dimethylformamide, N' N-dimethylacetamide, N-methyl-epsilon-caprolactam, N-methylpyrrolidone, gamma-butyrolactone, ethyl lactate, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, methyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylpropyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate; specifically, N-methylpyrrolidone is used.
In the positive photosensitive resin composition described above, the photosensitizer is at least one of a diazonaphthoquinone compound, an iodonium salt compound, and a sulfonium salt compound;
the diazonaphthoquinone compound is any one of the following 1) to 3): 1) A compound generated by esterification reaction of diazonaphthoquinone sulfonic acid and polyhydroxy compound; 2) A compound produced by the sulfonylation reaction of diazonaphthoquinone sulfonic acid and a polyamine compound; 3) A compound generated by esterification and/or sulfonylation of diazonaphthoquinone sulfonic acid and polyhydroxy polyamine compound; wherein the ratio of substitution by the diazonaphthoquinone sulfonic acid in the polyhydroxy polyamine compound is 50% -100%;
The diazonaphthoquinone compound comprises a 1, 2-diazonaphthoquinone-5-sulfonyl compound and/or a 1, 2-diazonaphthoquinone-4-sulfonyl compound; the polyol includes Bis-Z, bisP-EZ, bisP-AP, tekP-4HBPA, trisP-HAP, trisP-PA, trisP-SA, trisOCR-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methylenetris-FR-CR, bisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34-X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, triML-P, triML-35XL, TML-BP, TML-HQ, TML-PP-BPF, TML-TPBP, HML-TPOM-BP, HML-TPBA (trade name: HMHAL-TPP, available from chemical industries, inc., of Benzhou), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name above, product of Asahi organic materials industries, inc.), 2, 6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-p-cresol, naphthol, 2,3, 4-trihydroxybenzophenone, 2,3, 4' -tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, pyrogallol acetone resin, any one of m-cresol formaldehyde resin, phenol formaldehyde resin and the like;
The iodonium salt compounds include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nitrate, [4- (trifluoromethyl) phenyl ] (2, 4, 6-trimethylphenyl) iodonium trifluoromethane sulfonate, [3- (trifluoromethyl) phenyl ] (2, 4, 6-trimethylphenyl) iodonium trifluoromethane sulfonate, [ (4-trifluoromethyl) phenyl ] (2, 4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, phenyl [3- (trifluoromethyl) phenyl ] iodonium trifluoromethane sulfonate, (4-nitrophenyl) (phenyl) iodonium trifluoromethane sulfonate, (4-methylphenyl) (2, 4, 6-trimethylphenyl) iodonium trifluoromethane sulfonate, (3-methylphenyl) (2, 4, 6-trimethylphenyl) iodonium trifluorom-sulfonate, [ 2,4, 6-trimethylphenyl ] (2, 4-trifluoromethylphenyl) iodonium ] hexafluorosulfonate, [ 2, 4-trifluoromethylphenyl ] iodonium p-toluenesulfonate, phenyl ] phenyl [3- (4-nitrophenyl) iodonium triflate, 4-trifluoromethane sulfonate, [ 4-trifluoromethylphenyl ] iodonium triflate (5-fluoro-2-nitrophenyl) (2, 4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsonate, (3, 5-dichlorophenyl) (2, 4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, (3-bromophenyl) (mesityl) iodonium trifluoromethanesulfonate, [4- (bromomethyl) phenyl ] (2, 4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, bis (2, 4, 6-trimethylpyridine) iodonium hexafluorophosphate, 4' -xylyliodonium hexafluorophosphate, and mixtures thereof in any combination thereof;
The sulfonium salt compound comprises a mixture of 1, 3-benzodithiopyrrole boron tetrafluoride, cyclopropyl diphenyl sulfonium tetrafluoroborate, dimethyl (methylthio) sulfonium tetrafluoroborate, diphenyl (methyl) sulfonium tetrafluoroborate, (difluoromethyl) bis (2, 5-dimethylphenyl) sulfonium tetrafluoroborate, 2- [4- (3-ethoxy-2-hydroxy propoxy) benzoyl ] ethyldimethyl sulfide p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium methanesulfonate, triphenyl sulfonium tetrafluoroborate, tris (4-tolyl) sulfonium hexafluorophosphate, tris (4-tolyl) sulfonium trifluoromethanesulfonate, triethyl sulfonium bis (trifluoromethanesulfonyl) imide and the like which are combined according to any proportion.
More preferably, the photosensitizer is
Wherein R is 1, 2-naphthoquinone diazide sulfonyl and/or H.
In the positive photosensitive resin composition, the unsaturated bond-containing aliphatic flexible compound refers to an aliphatic compound having two or more unsaturated ethylenic groups in the molecule; specifically, any one of the following is possible:
。
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Are H or methyl; r is R 7 Is H, hydroxy, alkyl or alkoxy; n is n 1 Is an integer of 1 to 10; n is n 2 Is an integer of 0 to 10;
specifically, the alkyl or alkoxy is alkyl or alkoxy with 1-6 carbon atoms;
The invention can improve the residual stress of the cured film, improve the high-temperature corrosion of the resist stripping liquid and especially prevent the cracking phenomenon of rectangular patterns caused by the concentration of angular stress by adding the aliphatic flexible compound containing unsaturated bonds into the positive photosensitive resin composition.
The aliphatic flexible compound containing unsaturated bond is preferably ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, 1, 5-pentanediol diacrylate, 1, 5-pentanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 7-heptanediol diacrylate, 1, 7-heptanediol dimethacrylate, 1, 8-octanediol diacrylate, 1, 8-octanediol dimethacrylate, 1, 9-nonanediol diacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol diacrylate, 1, 10-decanediol dimethacrylate, diethylene glycol diacrylate diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol diacrylate, pentaethylene glycol dimethacrylate, hexaethylene glycol diacrylate, hexaethylene glycol dimethacrylate, polypropylene glycol dimethacrylate (with a degree of polymerization of 1 to 10), ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, at least one of dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, polydipentaerythritol hexaacrylate, polydipentaerythritol hexamethylacrylate, and tris (2-hydroxyethyl) isocyanurate triacrylate;
More preferably, the said unsaturated-containing componentThe bond aliphatic flexibilizing compound is selected from any one of the following:
。
in the positive photosensitive resin composition described above, the crosslinking agent refers to a compound that can undergo a crosslinking reaction under heating or by the action of a lewis acid, and includes a compound containing an epoxy group, a compound containing a hydroxymethyl group or an alkoxymethyl group, and the like;
the epoxy group-containing compound includes any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) and epoxy group-containing silicone; more preferably 3,3'- [ oxybis methylene ] bis [ 3-ethyl ] oxetane, 1, 4-butanediol diglycidyl ether, 2-bis (4-glycidoxyphenyl) propane, 9-bis (4-glycidoxy-3-tolyl) fluorene, 9-bis (4-glycidoxyphenyl) fluorene 1, 3-bis [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] -1, 3-tetramethyldisiloxane, diglycidyl 1, 2-cyclohexanedicarboxylate, diglycidyl 1,2,7, 8-diglycidyl octane, diglycidyl 4-cyclohexene-1, 2-dicarboxylate, triglycidyl isocyanurate, 4' -methylenebis (N, N-dicyclohexyl aniline), neopentyl glycol diglycidyl ether, 2'- (2, 3,4, 5-octafluorohexane-1, 6-diyl) bis (ethylene oxide), neopentyl glycol diglycidyl ether vinyl cyclohexene diglycidyl ether, polyethylene glycol diglycidyl ether (polymerization degree 1-15), polypropylene glycol diglycidyl ether (polymerization degree 1-15), and polydimethyl siloxane diglycidyl ether (polymerization degree of 1-15), butanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, 5-dimethyl-1, 3-di (oxiranylmethyl) imidazolidine-2, 4-dione, 2',2'' - [ methyne-tris (phenoxymethylene) ] tris (ethylene oxide), 1-tris (4-hydroxyphenyl) ethyl triglycidyl ether, bis (2, 3-epoxycyclopentyl) ether, 3, 4-epoxy-6-methylcyclohexylmethyl formate, vinylcyclohexene and epoxide compound, 3, 4-epoxycyclohexylmethyl formate-3 ',4' -epoxycyclohexylmethyl ester, diisoprenyl diepoxide compound, tetraphenylglycidyl ether ethane, triphenylglycidyl ether methane, triglycidyl-p-aminophenol, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylylenediamine or tetraglycidyl-1, 3-diaminomethyl cyclohexane; as the product having trade names, HP-850, HP-4032, HP-7200, HP-820, HP-4700, EXA-4710, HP-4770, EXA-859CRP, EXA-1514, EXA-48180, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA-4812, BEO-60E, BPO-20E, HBE-100, DME-100, NC-3000, NC-6000 (Japanese chemical Co., ltd.) and a mixture thereof in any ratio can be mentioned.
The hydroxymethyl or alkoxymethyl group-containing compound includes 46DMOC, 46DMOEP (trade name above, manufactured by Asahi organic materials Co., ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34-X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DMLMBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisoc-P, DMOM-PC, DMOMPTBP, DMOM-MBPC, triML-P, triML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TMOM-BP, TMOM-BPE, TMOM-BPAF, TMOM-BPAP, HML-TPBA, HMOM-TPP (trade name above, HMOM-TPP), available from the present state chemical industry Co., ltd.), "NIKALAC" MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (Sanand chemical Co., ltd.) and mixtures thereof in any ratio.
More preferably, the crosslinking agent is any one of the following:
in the positive photosensitive resin composition, the organic solvent is at least one of N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethylsulfoxide, gamma-butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate;
Specifically, the solvent consists of gamma-butyrolactone (GBL) and propylene glycol methyl ether acetate (PGEMA); more specifically, the mass ratio of GBL to PGEMA is 9:1.
The positive photosensitive resin composition comprises, in addition to the components, 0.1 to 20 parts by mass of other components including at least one of an adhesion promoter and a development inhibitor;
preferably, the other components are adhesion promoters and development inhibitors.
In the positive photosensitive resin composition, the adhesion promoter may be selected from gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyldimethoxy silane, 3-mercaptomethyl trimethoxysilane, 3-mercaptomethyl dimethoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, 3-mercaptopropyl tributoxy silane, 3-ureido propyl trimethoxysilane, 3-ureido propyl triethoxy silane, gamma-glycidoxy propyl trimethoxysilane, gamma-glycidoxy propyl triethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane, epoxybutyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, p-aminophenyl trimethoxysilane, 3- (m-aminophenoxy) trimethoxysilane, 3-methacryloxypropyl dimethoxy methylsilane, 3-methacryloxypropyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, gamma-glycidoxy propyl trimethoxy silane, 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, epoxybutyl trimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, p-aminophenoxy trimethoxy silane, 3- (m-aminophenoxy) trimethoxy) 3-acryloxy propyl trimethoxy silane, 3-methacryloxy propyl triethoxy silane, vinyloxy silane, 3-glycidoxy propyl ethoxysilane, triethoxy silane, at least one of 2-hydroxyethyl trimethoxysilane, 2-hydroxyethyl triethoxysilane, 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 4-hydroxybutyl trimethoxysilane, 4-hydroxybutyl triethoxysilane, 3- [ bis (2-hydroxyethyl) amino ] propane-trimethoxysilane, propyl trimethoxysilane isocyanate, propyl triethoxysilane, 3-isothiocyanato propyl trimethoxysilane, 3-isothiocyanato propyl triethoxysilane, 2-cyanoethyl trimethoxysilane, 2-cyanoethyl triethoxysilane, and 3-piperazinylpropyl methyldimethoxy silane;
More preferably, the adhesion promoter is any one of the following:
。
the mass ratio of the adhesion promoter to the alkali-soluble resin is 1-20:100; specifically, the ratio of the raw materials can be 3:100;
the development inhibitor is a compound which can prevent the dissolution of the positive photosensitive resin in an alkaline aqueous solution after exposure and is helpful for adjusting the film retention rate and the development time. The development inhibitor is selected from at least one of diphenyl iodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyl iodonium bromide, diphenyl iodonium chloride and diphenyl iodonium iodide; diphenyliodonium nitrate is preferred.
The mass ratio of the development inhibitor to the alkali-soluble resin is 0.1-20:100; specifically, the ratio of the raw materials can be 2-3:100;
the positive photosensitive resin composition comprises the following components in parts by mass: 100 parts of alkali-soluble resin; 3-40 parts of a photosensitizer; 1-30 parts of aliphatic flexible compound containing unsaturated bonds; 1-20 parts of adhesion promoter; 0.1-20 parts of a development inhibitor; 1-30 parts of cross-linking agent and 100-1000 parts of organic solvent.
The invention also provides a preparation method of the positive photosensitive resin composition, which comprises the following steps:
(1) Mixing the alkali-soluble resin with the organic solvent, and stirring under the protection of a yellow light area and nitrogen to form a homogeneous solution;
(2) Adding the photosensitizer, the aliphatic flexible compound containing unsaturated bonds, the cross-linking agent and/or the other components into the homogeneous solution in the step (1) and mixing to form a homogeneous solution; and adding the organic solvent to adjust the solution viscosity, and filtering to obtain the positive photosensitive resin composition.
The invention further provides a patterned polybenzoxazole resin film which is obtained by coating, exposing, developing and curing the positive photosensitive resin composition.
Specifically, the preparation method of the patterned polybenzoxazole resin film comprises the following steps:
1) Coating the positive photosensitive resin composition on a wafer substrate to obtain a liquid adhesive film;
2) Baking at 80-130 ℃ for 1-30 min to obtain a solid adhesive film;
3) Covering the mask plate, and exposing by using ultraviolet i-line or (i-line and g-line) exposure equipment;
4) Developing with developer to dissolve and eliminate the exposed area;
5) Washing with a rinsing liquid to obtain an uncured patterned resin film;
6) The uncured patterned resin film is heat cured to convert into a patterned polybenzoxazole resin film.
In the method, the developer and the rinsing liquid are all conventional assistants in the prior art. Among them, the developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, choline hydroxide, diethanolamine, diethylaminoethanol triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and 1, 6-hexamethylenediamine. The rinsing liquid is preferably rinsed with water or an aqueous solution containing an alcohol such as methanol, ethanol, or isopropanol, an ester such as ethyl lactate, or propylene glycol monomethyl ether acetate.
The patterned polybenzoxazole resin film is excellent in resistance to chemicals such as a strong polar organic reagent, a resist stripping solution and the like; meanwhile, the adhesive has excellent adhesive property with metal Cu and Au, and also has high resolution, low water absorption, excellent mechanical property, heat resistance and dielectric property, the main performances are shown in table 1, and the preparation method can be used for surface protection films, passivation films, stress buffer layers for bump manufacture and the like of chips in the semiconductor manufacturing process, and has good application prospects.
Drawings
FIG. 1 is a graphic representation of a FIB pattern obtained by immersing a stereolithography pattern obtained by photolithographic development and curing of a positive photosensitive resin composition solution provided in Experimental group 1 in a DMSO/MEA (3/7) solution at 85℃for 60 minutes.
FIG. 2 is a graphic representation of the FIB pattern obtained by immersing a stereolithography pattern obtained by photolithographic development and curing of the positive photosensitive resin composition solution provided in control group 1 in a DMSO/MEA (3/7) solution at 85℃for 60 min.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The test or evaluation methods for each performance index in the following examples are as follows:
(1) Molecular weight test
The weight average molecular weight was measured by GPC with PS as standard. Using a catalyst containing LiBr (0.03 mol/L) and H 3 PO 4 (0.06 mol/L) NMP solution as eluent, polymer concentration being1mg/mL。
(2) Evaluation of lithographic Performance
A. Film retention rate
Spin-coating a positive photosensitive resin composition solution on a 6 inch Si wafer; pre-baking at 80-130 ℃ for 1-30 min to obtain an 8-10 mu m solid adhesive film; placing a mask plate on the surface of the substrate, and exposing by adopting ultraviolet i-line exposure equipment; then, development was performed with a 2.38wt% aqueous tetramethylammonium hydroxide developer, and after rinsing with deionized water, an uncured patterned resin film was obtained. The film thickness of the unexposed portion after development was measured by an optical interferometer, and the film thickness was compared with the film thickness before development, namely, the film retention rate.
B. Resolution and sensitivity
The developed pattern was observed with an optical microscope with L/s=10μm/10μm, the development time at which the edge of the pattern was smooth and free of scum was set as a reference, the minimum pattern size that could be observed under the reference was set as resolution L/S (μm), and the minimum exposure energy required for the resolution was sensitivity (mJ/mm) 2 ）。
(3) Evaluation of chemical resistance
Spin-coating a positive photosensitive resin composition solution on a 6-inch silicon wafer; heating at 80-130 ℃ for 1-30 min to form a solid adhesive film; placing a mask plate on the surface of the substrate, and exposing by adopting ultraviolet i-line exposure equipment; then developed with a 2.38wt% aqueous tetramethylammonium hydroxide developer and rinsed with deionized water to provide an uncured positive resin pattern. The silicon wafer with the resin pattern was placed in a nitrogen-protected air-blown oven (oxygen concentration 100ppm or less) and cured at 150 ℃ for 30min, followed by heating to 350 ℃ and curing for 1h, to obtain a stereolithography pattern 10 μm thick. The patterned silicon wafer was immersed in an aqueous solution of organic reagents of acetone, N-methylpyrrolidone (NMP) and 2.38% tetramethylammonium hydroxide (TMAH) for 30min, in a solution of resist stripping solution of dimethyl sulfoxide (DMSO)/Monoethanolamine (MEA) (mass ratio of 3/7) at 85℃for 60min, in a solution of dimethyl sulfoxide (DMSO)/Monoethanolamine (MEA) (mass ratio of 9/1) at 90℃for 30min, and NMP/DMSO (mass ratio of 1/1) at 90℃for 30min, and after washing with water and drying by air blast, the film thickness change of the patterned silicon wafer was measured by a film thickness meter, and square holes of 50 μm were observed by an optical microscope to evaluate the chemical resistance.
The chemical resistance before and after the immersion was evaluated as a, the chemical resistance before and after the immersion was evaluated as B, the chemical resistance before and after the immersion was evaluated as more than ±5%, and the chemical resistance after less than ±10%, and the chemical resistance after the film surface was cracked, pattern corner cracked, pattern edge chemical permeated, or the cured film was peeled off from the substrate was evaluated as C.
Evaluation of adhesion
Spin-coating positive photosensitive resin composition solution on 6 inch wafers sputtered with Cu and Au layers with the thickness of 100nm (hereinafter referred to as Cu substrate and Au substrate), curing for 30min at 150 ℃ in a nitrogen-protected blast oven, and then heating to 350 ℃ for curing for 1h to obtain a cured film; the cured film was then placed in an aging oven and aged with Uhast96 (130 ℃/85RH%/96 h). Referring to the method of the national standard 'GB/T9286-1998 cross-cut test of paint films and varnish films', 10 rows of cross-cuts are cut on the cured film before and after aging by using a cross-cut machine, then a special 3M adhesive tape is adopted for peeling test, and the peeling test is recorded according to an 'X/100' format, wherein 'X' represents the total peeling number. The number of the square checks peeled off on any substrate is not more than 5, and the adhesion performance is evaluated as good; the number of squares peeled off from any one of the substrates was 5 or more, and the adhesion performance was evaluated as poor.
Example 1
36.63g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 146.5g of NMP were successively added to a 1L three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to dissolve to form a homogeneous transparent diamine solution; cooling to below 5 ℃ by using an ice bath, and dropwise adding a mixed solution of 4,4' -diphenyl ether diformyl chloride (25.97 g) and NMP (103.9 g) into the diamine solution under stirring for 0.5h; then, reacting for 3 hours at room temperature; 3.94g of norbornene dianhydride is added and stirring is continued for 1h; the reaction solution was poured into 5L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polybenzoxazole precursor resin A1 having a weight average molecular weight mw=17800 and a molecular weight distribution of 1.60 by GPC test.
Example 2
In a 1L three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 32.96g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1.16g of hexamethylenediamine and 136g of NMP were sequentially added and stirred to dissolve to form a homogeneous transparent diamine solution; cooling to below 5 ℃ by using an ice bath, and dropwise adding a mixed solution of 4,4' -diphenyl ether diformyl chloride (25.97 g) and NMP (103.9 g) into the diamine solution under stirring for 0.5h; then, reacting for 3 hours at room temperature; 3.94g of norbornene dianhydride is added and stirring is continued for 1h; the reaction solution was poured into 5L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polybenzoxazole precursor resin A2 having a weight average molecular weight mw=18800 and a molecular weight distribution of 1.78 by GPC test.
Example 3
29.30g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1.74g of hexamethylenediamine, 1.24g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane and 139g of NMP were successively introduced into a 1L three-neck round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to dissolve them to form a homogeneous transparent diamine solution; cooling to below 5 ℃ by using an ice bath, and dropwise adding a mixed solution of 4,4' -diphenyl ether diformyl chloride (25.97 g) and NMP (103.9 g) into the diamine solution under stirring for 0.5h; then, reacting for 3 hours at room temperature; 4.13g of 4-ethynyl phthalic anhydride is added and stirring is continued for 1h; the reaction solution was poured into 5L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polybenzoxazole precursor resin A3 having a weight average molecular weight mw=18300 and a molecular weight distribution of 1.84 by GPC test.
Example 4
Into a 1L three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device were successively added 32.96g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1.00g of 4,4' -diaminodiphenyl ether, 1.24g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane and 141g of NMP, and stirred to dissolve to form a homogeneous transparent diamine solution; cooling to below 5 ℃ by using an ice bath, and dropwise adding a mixed solution of 4,4' -diphenyl ether diformyl chloride (25.97 g) and NMP (103.9 g) into the diamine solution under stirring for 0.5h; then, reacting for 3 hours at room temperature; 4.13g of 4-ethynyl phthalic anhydride is added and stirring is continued for 1h; the reaction solution was poured into 5L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polybenzoxazole precursor resin A4 having a weight average molecular weight mw=17500 and a molecular weight distribution of 1.70 by GPC test.
Example 5
Mixing a polybenzoxazole precursor resin with a solvent G (solvent G is formed by mixing gamma-butyrolactone (GBL) and Propylene Glycol Methyl Ether Acetate (PGMEA) according to a mass ratio of 9/1) according to the addition amount in the following table 2, and stirring under the protection of a yellow light region and nitrogen gas to form a homogeneous solution; then adding aliphatic flexible compound (short for flexible component), photosensitizer, cross-linking agent and other components (adhesion promoter and development inhibitor) into the above-mentioned solution, mixing them to form homogeneous solution, then adding solvent G to regulate solution viscosity, and press-filtering by means of 0.5 micrometer pore-size filter so as to obtain the invented positive photosensitive resin composition solution.
Aliphatic flexible compound containing unsaturated bond:
wherein, the viscosity of B7 is 900-1300 cps, and the average Mn of B8 is 640.
Photosensitizer C:
crosslinking agent:
adhesion promoter:
the development inhibitor F is diphenyl iodonium nitrate.
Remarks: in table 2, () the amount of benzoxazole precursor resin added (parts by mass) relative to 100 parts by weight is shown.
The test groups 1 to 12 and the control groups 1 to 6 were evaluated according to the chemical resistance evaluation method, and the evaluation results are shown in table 3.
As can be seen from the chemical resistance evaluation results of the experimental groups 1-12 and the control groups 1-6, the patterned resin film prepared from the positive photosensitive resin composition can resist room-temperature etching of a strong-polarity organic reagent, and also can resist high-temperature etching of a resist stripping solution, and has outstanding chemical resistance. The high-temperature etching performance of the resist stripping liquid of the control groups 1-2 and 5-6 is poor, and the room-temperature etching performance and the high-temperature etching performance of the resist stripping liquid of the control groups 3-4 are poor, which shows that the chemical resistance of the cured film can be greatly improved only by the combination of the aliphatic flexible compound containing unsaturated bonds and the cross-linking agent.
FIG. 1 is a graphic representation of a FIB pattern obtained by immersing a stereolithography pattern obtained by photolithographic development and curing of a positive photosensitive resin composition solution provided in Experimental group 1 in a DMSO/MEA (3/7) solution at 85℃for 60 minutes.
FIG. 2 is a graphic representation of the FIB pattern obtained by immersing a stereolithography pattern obtained by photolithographic development and curing of the positive photosensitive resin composition solution provided in control group 1 in a DMSO/MEA (3/7) solution at 85℃for 60 min. As can be seen from fig. 1 and 2, the addition of the unsaturated bond-containing aliphatic flexible compound to the polybenzoxazole precursor resin composition can greatly improve the chemical resistance of the patterned resin film.
The test groups 1 to 12 and the control groups 1 to 6 were evaluated according to the adhesion property evaluation method, and the evaluation results are shown in Table 4.
As can be seen from Table 4, the positive photosensitive resin compositions of the present invention (experimental groups 1 to 12) have good adhesion to the metals Cu and Au, and the comparative examples 2,5 and 6 have poor adhesion to Au, indicating that the aliphatic flexible compound having an unsaturated bond can enhance adhesion to Au.
In summary, the most outstanding characteristics of the positive photosensitive resin composition of the invention are that the resin film formed after exposure, development and thermal curing has excellent resistance to chemicals such as strong polar organic reagents, resist stripping liquid and the like, and has excellent adhesion performance with metals Cu and Au, and in addition, the positive photosensitive resin composition has high resolution, low water absorption, excellent mechanical property, heat resistance and dielectric property, and excellent comprehensive performance, and can meet the use requirements in the fields of semiconductor manufacturing and packaging.
Claims (12)
1. A positive photosensitive resin composition characterized in that: the positive photosensitive resin composition comprises the following components in parts by mass: 100 parts of alkali-soluble resin; 3-40 parts of a photosensitizer; 1-30 parts of an unsaturated compound; 1-30 parts of a cross-linking agent and 100-1000 parts of an organic solvent A;
the alkali-soluble resin is prepared by polymerizing a component 1 and a component 2 in an organic solvent B under the action of a blocking agent;
the component 1 is aromatic diacid chloride or a derivative thereof;
the component 2 is aromatic diamine containing phenolic hydroxyl, or at least one of aliphatic diamine, aromatic diamine without phenolic hydroxyl and diamine containing silicon is added into the aromatic diamine containing phenolic hydroxyl;
the unsaturated compound is selected from any one of the following structures:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Are H or methyl; r is R 7 Is H, hydroxy, alkyl or alkoxy; n is n 1 Is an integer of 1 to 10; n is n 2 Is an integer of 0 to 10;
the cross-linking agent is a compound which can undergo a cross-linking reaction under the heating condition or the action of Lewis acid, and is a compound containing hydroxymethyl or alkoxymethyl.
2. The positive photosensitive resin composition according to claim 1, wherein: the GPC weight average molecular weight of the alkali-soluble resin is 10000-60000.
3. The positive photosensitive resin composition according to claim 2, characterized in that: the component 1 is at least one selected from diphenyl ether diformyl chloride, isophthaloyl chloride, terephthaloyl chloride, biphenyl diformyl chloride, diphenyl sulfone diformyl chloride, diphenyl methane diformyl chloride and benzophenone diformyl chloride;
the molar ratio of the aliphatic diamine to the total amount of the aromatic diamine without phenolic hydroxyl groups to the siliceous diamine is not higher than 20%;
the phenolic hydroxyl group-containing aromatic diamine is selected from the group consisting of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, 3 '-diamino-4, 4' -dihydroxydiphenyl ether at least one of 4,4 '-diamino-3, 3' -dihydroxydiphenyl ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxybenzophenone, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, and 1, 3-diamino-4, 6-dihydroxybenzene;
the aliphatic diamine is a linear aliphatic diamine having 2 to 20 carbon atoms, a cycloalkane diamine, or a linear aliphatic diamine having 2 to 20 carbon atoms containing oxygen atoms in the structure;
The phenolic hydroxyl-free aromatic diamine is selected from the group consisting of 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3, 4-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -diethyl-4, 4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminobiphenyl, 3' -diethyl-4, 4' -diaminobiphenyl, 2', at least one of 3,3' -tetramethyl-4, 4' -diaminobiphenyl, 3', 4' -tetramethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl;
the silicon-containing diamine is selected from 1, 3-di (3-aminopropyl) -1, 3-tetramethyl disiloxane, 1, 3-di (4-aminobutyl) -1, 3-tetramethyl disiloxane 1, 3-bis (2-aminoethyl) -1, 1-dimethyl-3, 3-diethyl-disiloxane 1, 5-bis (2-aminoethyl) -1,3, 5-hexamethyltrisiloxane, 1, 5-bis (3-aminopropyl) -1,3, 5-hexamethyltrisiloxane 1-aminopropyl-5-aminoethyl-1, 3, 5-hexamethyltrisiloxane 1, 7-bis (2-aminoethyl) -1,3, 5, 7-octamethyltetrasiloxane, 1, 3-bis (3-aminophenyl) -1, 3-tetramethyldisiloxane at least one of 1, 3-bis (4-aminophenyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (3-aminopropyl) -1, 3-dimethyl-1, 3-diphenyldisiloxane;
The end-capping agent is at least one of maleic anhydride, norbornenedianhydride, methylnorbornenedianhydride, 4-ethynylphthalic anhydride, 4-phenylacetylene phthalic anhydride, 4-vinylaniline, norborneneamine, allylamine, 4-ethynylaniline, 3-ethynylaniline, 4-phenylethynylaniline, 4- (4-aminophenylethynyl) phenylacetylene, 4- [ (trimethylsilyl) -ethynyl ] aniline, 4- (4-amino-phenyl) -2-methyl-but-3-yn-2-ol, (E) -3-aminocinnamic acid and propargylamine;
the organic solvent B is at least one selected from N 'N-dimethylformamide, N' N-dimethylacetamide, N-methyl-epsilon-caprolactam, N-methylpyrrolidone, gamma-butyrolactone, ethyl lactate, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, methyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylpropyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether.
4. The positive photosensitive resin composition according to claim 1, wherein: the photosensitizer is at least one of diazonaphthoquinone compounds, iodonium salt compounds and sulfonium salt compounds;
the organic solvent A is at least one selected from N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate.
5. The positive photosensitive resin composition according to claim 1, wherein: the positive photosensitive resin composition also comprises 0.1-20 parts by mass of other components;
the other components include at least one of an adhesion promoter and a development inhibitor;
The mass ratio of the adhesion promoter to the alkali-soluble resin is 1-20:100;
the mass ratio of the development inhibitor to the alkali-soluble resin is 0.1-20:100.
6. The positive photosensitive resin composition according to claim 5, wherein: the adhesion promoter is selected from gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptomethyl trimethoxysilane, 3-mercaptomethyl dimethoxysilane, 3-mercaptopropyl ethoxydimethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-mercaptopropyl tributoxysilane, 3-ureido propyl trimethoxysilane, 3-ureido propyl triethoxysilane, gamma-glycidoxy propyl trimethoxysilane, gamma-glycidoxy propyl triethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane, epoxybutyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, p-aminophenyl trimethoxysilane, 3- (m-aminophenoxy) trimethoxysilane, 3-methacryloxypropyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-glycidoxy propyl trimethoxysilane, 2-epoxypropyl trimethoxy silane, 2-ethoxymethyl vinylsilane, at least one of 2-hydroxyethyl triethoxysilane, 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 4-hydroxybutyl trimethoxysilane, 4-hydroxybutyl triethoxysilane, 3- [ bis (2-hydroxyethyl) amino ] propane-trimethoxysilane, propyl trimethoxysilane isocyanate, propyl triethoxysilane isocyanate, 3-isocyanopyl trimethoxysilane, 3-isothiocyanato propyl triethoxysilane, 2-cyanoethyl trimethoxysilane, 2-cyanoethyl triethoxysilane, and 3-piperazinylpropyl methyldimethoxy silane;
The development inhibitor is a compound which can prevent the dissolution of the positive photosensitive resin in an alkaline aqueous solution after exposure and is helpful for adjusting the film retention rate and the development time, and is at least one selected from diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride and diphenyliodonium iodide.
7. The positive photosensitive resin composition according to claim 6, wherein:
the adhesion promoter is any one of the following:
；
the development inhibitor is diphenyl iodonium nitrate.
8. The positive photosensitive resin composition according to claim 1, wherein: the unsaturated compound is selected from any one of the following structures:
the cross-linking agent is any one of the following:
the photosensitizer is
Wherein R is 1, 2-naphthoquinone diazide sulfonyl and/or H;
the organic solvent A consists of gamma-butyrolactone and propylene glycol methyl ether acetate.
9. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 8, characterized in that: the method comprises the following steps: (1) Mixing the alkali-soluble resin with the organic solvent A, and stirring under the protection of a yellow light area and nitrogen to form a homogeneous solution; (2) Adding the rest components into the homogeneous solution in the step (1) and mixing to form a homogeneous solution; and adding the organic solvent A to adjust the solution viscosity, and filtering to obtain the positive photosensitive resin composition.
10. A patterned polybenzoxazole resin film characterized by: the patterned polybenzoxazole resin film is obtained by coating, exposing, developing and curing the positive photosensitive resin composition according to any of claims 1 to 8.
11. The patterned polybenzoxazole resin film according to claim 10 wherein: the preparation method of the patterned polybenzoxazole resin film comprises the following steps:
1) Coating the positive photosensitive resin composition according to any one of claims 1 to 8 on a wafer substrate to obtain a liquid adhesive film;
2) Baking at 80-130 ℃ for 1-30 min to obtain a solid adhesive film;
3) Covering the mask plate, and exposing by using ultraviolet i-line or i-line and g-line exposure equipment;
4) Developing with developer to dissolve and eliminate the exposed area;
5) Washing with a rinsing liquid to obtain an uncured patterned resin film;
6) The uncured patterned resin film is heat cured to convert into a patterned polybenzoxazole resin film.
12. Use of the positive photosensitive resin composition according to any one of claims 1 to 8 in semiconductor manufacturing and/or packaging.
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| CN101477309B (en) * | 2009-01-21 | 2014-05-07 | 北京波米科技有限公司 | Positive light-sensitive polyamic ester resin composition and its preparation and use |
| KR101333704B1 (en) * | 2009-12-29 | 2013-11-27 | 제일모직주식회사 | Positive type photosensitive resin composition |
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| WO2017073481A1 (en) * | 2015-10-28 | 2017-05-04 | 東レ株式会社 | Positive photosensitive resin composition, photosensitive sheet, cured film, interlayer insulating film, semiconductor protective film, method for manufacturing semiconductor device, semiconductor electronic component and semiconductor device |
| CN105859587B (en) * | 2016-04-15 | 2018-06-15 | 江苏利田科技股份有限公司 | A kind of 4 degree of functionality urethane acrylates based on pentaerythrite and its preparation method and application |
| CN109270792A (en) * | 2018-10-30 | 2019-01-25 | 浙江福斯特新材料研究院有限公司 | A kind of high tenacity, high heat resistance, can weak base water development polyimides/photosensitive epoxy acrylic resin composition |
| CN113801291B (en) * | 2021-04-27 | 2023-05-12 | 杭州福斯特电子材料有限公司 | Photosensitive resin composition, photosensitive dry film resist and manufacturing method of PCB |
| CN114874441B (en) * | 2022-07-12 | 2022-11-01 | 明士(北京)新材料开发有限公司 | Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof |
| CN115220305A (en) * | 2022-08-01 | 2022-10-21 | 明士(北京)新材料开发有限公司 | Positive photosensitive resin composition and preparation method and application thereof |
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