CN116909100B - Photosensitive polyimide precursor composition - Google Patents

Photosensitive polyimide precursor composition Download PDF

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CN116909100B
CN116909100B CN202310418545.3A CN202310418545A CN116909100B CN 116909100 B CN116909100 B CN 116909100B CN 202310418545 A CN202310418545 A CN 202310418545A CN 116909100 B CN116909100 B CN 116909100B
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photosensitive polyimide
polyimide precursor
parts
precursor composition
mass
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CN116909100A (en
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李�杰
单良
王宙东
周选智
孙蓉
张国平
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Shenzhen Institute of Advanced Electronic Materials
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Shenzhen Institute of Advanced Electronic Materials
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a photosensitive polyimide precursor composition, which comprises the following components: 100 parts by mass of a polyamic acid ester as a photosensitive polyimide precursor; 0.1-10 parts by mass of a multi-arm structure compound containing an azole structure; 1-20 parts by mass of a radical polymerization monomer; 0.5-10 parts by mass of a photoinitiator; 0.5-10 parts by mass of a silane coupling agent; 0.01-5 parts by mass of a polymerization inhibitor; 50-1500 parts by mass of an organic solvent. Wherein the multi-arm structure compound containing the azole structure is an azole structure Z 1 And multi-arm unit Z 2 A bonded compound. The photosensitive polyimide precursor composition provided by the invention has excellent mechanical property, good chemical resistance and excellent bonding force with a copper surface after being cured, and can meet the application requirements of advanced packaging processes such as high-density fan-out type wafer level packaging and the like.

Description

Photosensitive polyimide precursor composition
Technical Field
The invention belongs to the technical field of semiconductor devices, in particular to the technical field of polyimide, and particularly relates to a photosensitive polyimide precursor composition.
Background
Semiconductor devices are widely used in the fabrication of various electronic products such as computers, cell phones, digital cameras, and other electronic devices. With the trend of high integration, miniaturization, and portability of semiconductor chip packages, the density of package wiring is increasingly required, and in order to provide higher density wiring on the same package area, the line width and line spacing of the wiring need to be greatly reduced. In advanced packaging of semiconductor chips (e.g., wafer level packaging, fan-out packaging), the wiring layer is typically composed of a patterned polyimide dielectric layer and metal embedded therein, wherein the precision and density of the polyimide dielectric layer patterning determines the density of the wiring layer.
The photosensitive polyimide (PSPI) material has excellent heat resistance, chemical resistance, dielectric property and mechanical property of Polyimide (PI) on one hand, and can be used as a photoetching material, so that the photosensitive polyimide (PSPI) material is widely applied to surface passivation of integrated circuit chips and surface rewiring processes of wafer level packaging and panel level packaging, and is a key material in the advanced wafer level packaging process. The conventional PSPI material needs a curing temperature above 350 ℃ to obtain various excellent performances of the polyimide material, and at such high curing temperature, problems such as wafer warpage, stress cracking and the like easily occur in advanced packaging processes such as high-density fan-out type wafer level packaging and the like, so that the PSPI needs to meet the requirement of lower-temperature curing. However, the low-temperature cured PSPI material often encounters problems of poor mechanical properties, poor chemical corrosion resistance and the like due to insufficient imidization degree, and poor device reliability due to poor bonding force with other materials, particularly electroplated copper, in the packaging process or the like.
In order to solve the above problems, photo/thermal alkaline generators have been introduced to reduce the activation of imidization of polyimide precursor resins, so as to obtain polyimide resins with excellent properties in various aspects at low temperature processes, such as the technical solution in patent CN112639616A, CN112513219A, CN112639615A, CN111919172 a. Or controlling the molecular weight of the precursor resin so that the molecular chain obtains a sufficiently high mobility at the time of low temperature curing to increase the imidization rate, such as CN108475020a. Other solutions, such as introducing a polymer containing urethane and urea bond structures into CN112334833a and introducing a polymer containing sulfite structures into CN110741318A, CN113168093a, are to obtain a combination of low-temperature curing, high imidization rate, good chemical resistance, and excellent copper surface binding force. In addition, various small molecule copper side aids, such as CN102375336B, CN112799281a, are typically introduced to improve the adhesion of the rewiring layer to the copper.
The photo/thermal alkaline agent is introduced to obtain the effect of promoting low-temperature imidization of PSPI or the copper auxiliary agent is introduced to obtain excellent copper surface binding force, and small molecule free auxiliary agents are often introduced, so that when the using amount of the auxiliary agents is large, obvious adverse effects are brought to the photoetching performance of PSPI, and the residual of the small molecule auxiliary agents in a cured film is likely to cause exhaust problems in a later multilayer structure process or migration occurs in a long-term reliability test to bring adverse effects to reliability.
Disclosure of Invention
In view of the above technical problems, the present invention provides a photosensitive polyimide precursor composition, which can be cured at a low temperature (below 260 ℃), and has excellent mechanical properties, good chemical resistance and excellent bonding force with copper surfaces after curing, so as to meet the application requirements of advanced packaging processes such as high-density fan-out type wafer level packaging.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the present invention provides a photosensitive polyimide precursor composition comprising:
100 parts by mass of a polyamic acid ester as a photosensitive polyimide precursor;
0.1-10 parts by mass of a multi-arm structure compound containing an azole structure;
1-20 parts by mass of a radical polymerization monomer;
0.5-10 parts by mass of a photoinitiator;
0.5-10 parts by mass of a silane coupling agent;
0.01-5 parts by mass of a polymerization inhibitor;
50-1500 parts by mass of an organic solvent;
the multi-arm structure compound containing the azole structure is an azole structure Z 1 And multi-arm unit Z 2 A bonded compound;
the azole structure Z 1 Selected from any one or more of the following structures:
；
the multi-arm unit Z 2 Selected from any one of the structures shown belowOr several:
。
as a preferred embodiment, the polyamic acid ester has a structure as shown in formula (I):
（I）；
in the formula (I), X is a 4-valent aromatic group-containing organic group, Y is a 2-valent aromatic group-containing organic group, R 1 And R is 2 Each independently selected from 1-valent organic groups having a structure represented by formula (II), n is 2 to 150;
（II）；
in the formula (II), R 3 、R 4 And R is 5 Independently selected from hydrogen atoms and alkyl groups with 1-3 carbon atoms; m is 2 to 10.
In the technical scheme of the invention, the free radical polymerization monomer is preferably any one or more of (methyl) acrylic ester compounds, and is further preferably any one or more of difunctional (methyl) acrylic ester compounds and trifunctional (methyl) acrylic ester compounds; in the technical scheme of the invention, the (methyl) acrylic ester compound comprises acrylic ester compound and/or methacrylic ester compound;
Specifically, the free radical polymerization monomer is selected from at least one or more of tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1, 3-acryloyloxy-2-hydroxypropane, 1, 3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N-dimethylacrylamide and N-methylolacrylamide; preferably tetraethyleneglycol dimethacrylate.
As a preferred embodiment, the method for preparing the polyamic acid ester comprises the steps of:
reacting a tetracarboxylic dianhydride containing an X group, an alcohol having a free radical polymerizable unsaturated double bond and/or a saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid; it is then subjected to an amide polycondensation with a diamine containing Y groups.
The tetracarboxylic dianhydride containing an X group is not particularly limited, and specific examples thereof include pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3',4,4' -tetracarboxylic dianhydride, diphenyl sulfone-3, 3', 4' -tetracarboxylic dianhydride, diphenylmethane-3, 3',4,4' -tetracarboxylic dianhydride, 2-bis (3, 4-phthalic anhydride) propane, 2-bis (3, 4-phthalic anhydride) -1, 3-hexafluoropropane, and the like, preferably pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, more preferably pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, etc., which may be used alone or in any combination.
The diamine containing a Y group is not particularly limited, specific examples include p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone, and 3,4' -diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 4' -diaminobiphenyl, 3' -diaminobiphenyl, 4' -diaminobenzophenone, 3' -diaminobenzophenone, 4' -diaminodiphenylmethane, 4' -diaminodiphenyl methane, and 3,4' -diaminodiphenylmethane, 3' -diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 4-bis (4-aminophenoxy) biphenyl, 4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, bis [4- (3-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 9, 10-bis (4-aminophenyl) anthracene, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl) propane 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 1, 4-bis (3-aminopropyl dimethylsilyl) benzene, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfone, 9-bis (4-aminophenyl) fluorene and the like, the above may be used alone or in any combination.
As a preferred embodiment, the photoinitiator is selected from any one or more of oxime ester compounds, benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin and benzildimethyl ketal, and further preferably oxime ester compounds.
As a preferable embodiment, the organic solvent is selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides;
specifically, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, and alcohols having an alcoholic hydroxyl group in the molecule and having no olefinic double bond; the alcohol having an alcoholic hydroxyl group in the molecule and having no olefinic double bond is selected from any one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, 2-hydroxyisobutyrate, ethylene glycol and propylene glycol.
In the technical scheme of the invention, the silane coupling agent is not particularly limited, and is preferably any one or more of silane coupling agents containing urea bonds (-NH-CO-NH-);
specifically, the silane coupling agent is selected from any one or more of urea propyl triethoxysilane, gamma-aminopropyl dimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldimethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane, gamma-mercaptopropyl methyldimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidoxypropyl methylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl ] phthalimide, benzophenone-3, 3 '-bis (N- [ 3-triethoxysilyl ] propylamide) -4,4' -dicarboxylic acid, benzene-1, 4-bis (N- [ 3-triethoxysilyl ] propylamide) -2, 5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride and N-phenylaminopropyl trimethoxysilane; preferably ureidopropyltriethoxysilane.
In the technical scheme of the invention, the polymerization inhibitor is not particularly limited, and is preferably any one or more of phenolic radical polymerization inhibitors;
specifically, the polymerization inhibitor is selected from any one or more of hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt and N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, preferably 2-nitroso-1-naphthol.
As a preferred embodiment, 0.1 to 10 parts of a thermal alkaline agent is also included;
preferably, the thermal alkaline agent is an amine compound protected with a t-butoxycarbonyl group, and in the embodiment of the present invention, as the amine compound protected with a t-butoxycarbonyl group, there are no particular restrictions, and specific examples thereof include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1, 3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexane ethanol, 4- (2-aminoethyl) cyclohexanol, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, a-methylethanolamine, a-4-hydroxy-4-phenylpiperidine, piperidine, 3-hydroxy-4-phenylpiperidine, piperidine, and the like, any one or more of 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2- (4-piperidyl) -2-propanol, 1, 4-butanol bis (3-aminopropyl) ether, 1, 2-bis (2-aminoethoxy) ethane, 2' -oxydiethylamine, 1, 14-diamino-3, 6,9, 12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis (3-aminopropyl) ether, 1, 11-diamino-3, 6, 9-trioxaundecane and diethylene glycol bis (3-aminopropyl) ether; the t-butoxycarbonyl-protected amine compound is further preferably N-t-butoxycarbonyl-4-piperidinemethanol.
In yet another aspect, the present invention provides a photosensitive polyimide composition obtained by thermal imidization of the above photosensitive polyimide precursor composition; the temperature of the thermal imidization is preferably 150-400 ℃.
The technical scheme has the following advantages or beneficial effects:
according to the invention, the multi-arm structure compound with a specific azole structure is introduced into the negative photosensitive polyamide acid ester composition, and a polyimide cured film with good photoetching resolution, excellent mechanical property, good chemical resistance and excellent binding force of an electroplated copper surface can be obtained after low-temperature curing, so that the application requirements of advanced packaging processes such as high-density fan-out type wafer level packaging and the like can be met.
Compared with the prior technical scheme of introducing a small-molecule copper surface auxiliary agent into the polyamide acid ester composition to strengthen the binding force, the multi-arm structural compound with a specific azole structure is introduced, the molecular weight of the auxiliary agent is increased, so that the migration or exhaust problems possibly caused by small molecule residues are favorably inhibited, the performance of the azole compound serving as the copper surface auxiliary agent can be further enhanced due to the intramolecular pulling effect, the copper surface binding force better than that of the small-molecule copper surface auxiliary agent can be obtained, the generation of copper surface pores is effectively inhibited, and the excellent reliability is further ensured.
Drawings
FIGS. 1 to 7 show chemical structures of CA-1 to 6 in production example 2 of the present invention and CA-7 to 10 used in comparative example.
FIG. 8 is a table showing the components and contents of the polyamic acid ester compositions prepared in the examples of the present invention and comparative examples, and the curing process.
FIG. 9 is a table of data relating to performance tests of the polyamic acid ester compositions prepared in the examples of the present invention and the comparative examples.
Detailed Description
The following examples are only some, but not all, of the examples of the invention. Accordingly, the detailed description of the embodiments of the invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the present invention, all the equipment, raw materials and the like are commercially available or commonly used in the industry unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
The technical scheme of the invention is to design a photosensitive polyimide precursor composition, which comprises the following components:
(1) Polyamic acid esters as photosensitive polyimide precursors; (2) a multi-arm structure compound containing an azole structure; (3) free radically polymerizing monomers; (4) a photoinitiator.
Component (1): polyamic acid esters
In the technical scheme of the invention, the polyamic acid ester is converted into polyimide through thermal imidization, and the polyimide precursor as photosensitive polyimide precursor in the invention has a structure shown as a formula (I):
（I）；
(in the formula (I), X is a 4-valent aromatic group-containing organic group, Y is a 2-valent aromatic group-containing organic group, R 1 And R is 2 Each independently selected from 1-valent organic groups having a structure represented by formula (II), n is 2 to 150);
（II）；
(in the formula (II), R 3 、R 4 And R is 5 Independently selected from hydrogen atoms and alkyl groups with 1-3 carbon atoms; m is 2 to 10).
The tetracarboxylic dianhydride containing an X group is not particularly limited, and specific examples thereof include pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3',4,4' -tetracarboxylic dianhydride, diphenyl sulfone-3, 3', 4' -tetracarboxylic dianhydride, diphenylmethane-3, 3',4,4' -tetracarboxylic dianhydride, 2-bis (3, 4-phthalic anhydride) propane, 2-bis (3, 4-phthalic anhydride) -1, 3-hexafluoropropane, and the like, preferably pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, more preferably pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, etc., which may be used alone or in any combination.
The diamine containing a Y group is not particularly limited, specific examples include p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone, and 3,4' -diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 4' -diaminobiphenyl, 3' -diaminobiphenyl, 4' -diaminobenzophenone, 3' -diaminobenzophenone, 4' -diaminodiphenylmethane, 4' -diaminodiphenyl methane, and 3,4' -diaminodiphenylmethane, 3' -diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 4-bis (4-aminophenoxy) biphenyl, 4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, bis [4- (3-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 9, 10-bis (4-aminophenyl) anthracene, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl) propane 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 1, 4-bis (3-aminopropyl dimethylsilyl) benzene, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfone, 9-bis (4-aminophenyl) fluorene and the like, the above may be used alone or in any combination.
The alcohol having a radically polymerizable unsaturated double bond is not particularly limited, and specific examples thereof include 2-acryloyloxy ethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxy ethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like, and these may be used singly or in any combination thereof.
The saturated aliphatic alcohols having 1 to 4 carbon atoms are not particularly limited, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol, and the above may be used alone or in any combination.
Preparation of polyamic acid esters
In the technical scheme of the invention, the preparation of the polyamic acid ester with the structure shown above can be carried out by adopting the following method:
reacting a tetracarboxylic dianhydride containing an X group, an alcohol having a free radical polymerizable unsaturated double bond and/or a saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid; it is then subjected to an amide polycondensation with a diamine containing Y groups.
The tetracarboxylic dianhydride and the alcohol are preferably reacted in the presence of a basic catalyst such as pyridine in a suitable reaction solvent at 20 to 50 ℃ with stirring for 4 to 10 hours, thereby obtaining the partially esterified tetracarboxylic acid.
The solvent used in the above reaction is preferably a solvent which can completely dissolve the reaction raw material and/or the product, and more preferably a solvent which can completely dissolve the photosensitive polyimide precursor. Specific examples of such solvents include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and the like, and the above may be used alone or in any combination.
The solution containing the partially esterified tetracarboxylic acid obtained in the above reaction is preferably subjected to an ice-cooling condition, and a dehydration condensing agent is added thereto to obtain a polyanhydride, and then the diamine containing the Y group or a solution thereof is added thereto to obtain the objective polyamic acid ester by an amide polycondensation.
The dehydration condensing agent is not particularly limited, and specific examples thereof include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, and N, N' -disuccinimidyl carbonate, and the above may be used alone or in any combination thereof.
Component (2): multi-arm structure compound containing azole structure
In the technical scheme of the invention, the multi-arm structural compound containing the azole structure is added into the photosensitive polyimide precursor composition, the molecular weight of the azole copper surface auxiliary agent is increased so as to be beneficial to inhibiting migration or exhaust problems possibly caused by small molecule residues, and meanwhile, the performance of the azole compound serving as the copper surface auxiliary agent can be further enhanced due to the intramolecular pulling effect, so that the copper surface binding force better than that of the small molecule copper surface auxiliary agent can be obtained, the generation of copper surface pores is effectively inhibited, and the more excellent reliability is ensured, wherein the copper surface binding force is better than that of the small molecule copper surface auxiliary agent Z1 And multi-arm unit Z 2 A bonded compound, wherein:
azole structure Z 1 Selected from any one or more of the following structures:
；
multi-arm unit Z 2 Selected from any one or more of the following structures:
。
In the technical scheme of the invention, the addition amount of the multi-arm structure compound containing the azole structure is 0.1-10 parts by mass based on 100 parts of polyamic acid ester from the viewpoint of improving the binding force of a copper surface, the addition amount is less than 0.1 part by mass, the effect of enhancing the binding force of the copper surface is limited, and the addition amount is more than 10 parts, so that the mechanical property of a cured film is reduced and the photoetching performance is damaged.
Component (3): free radical polymerized monomers
The invention further compounds a free radical polymerization monomer containing unsaturated bond in the photosensitive polyimide precursor composition, which can generate free radical polymerization reaction with the free radical polymerization substituent on the side chain of the polyamic acid ester.
The radical polymerizable monomer is preferably any one or more of (meth) acrylic acid ester compounds capable of undergoing radical polymerization by a photoinitiator. In the technical scheme of the invention, the (methyl) acrylic ester compound comprises acrylic ester compound and/or methacrylic ester compound: mono (meth) acrylates or di (meth) acrylates including, but not limited to, ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate; mono (meth) acrylate or di (meth) acrylate of propylene glycol or polypropylene glycol; mono-, di-or tri (meth) acrylates of glycerol; cyclohexane di (meth) acrylate; diacrylates and dimethacrylates of 1, 4-butane diol, and di (meth) acrylates of 1, 6-hexane diol; di (meth) acrylate of neopentyl glycol; mono (meth) acrylate or di (meth) acrylate of bisphenol a; phenyl trimethacrylate; isobornyl (meth) acrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane tri (meth) acrylate; di (meth) acrylate or tri (meth) acrylate of glycerol; di (meth) acrylate, tri (meth) acrylate, or tetra (meth) acrylate of pentaerythritol; and an ethylene oxide or propylene oxide adduct of these compounds, more preferably any one or more of a difunctional (meth) acrylate compound and a trifunctional (meth) acrylate compound.
Specific examples of the above-mentioned radical polymerizable monomers include tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1, 3-acryloyloxy-2-hydroxypropane, 1, 3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N-dimethylacrylamide, N-methylolacrylamide, and the like, and any of these monomers may be used, and the above-mentioned monomers may be preferably used as the respective monomers, and the monomers may be used as well as the preferred glycol dimethacrylate.
In the technical scheme of the invention, from the viewpoint of improving the photoetching resolution, the addition amount of the free radical polymerization monomer is 1-20 parts by mass based on 100 parts of the polyamic acid ester, if the amount of the free radical polymerization monomer is too low, the high photoetching resolution is not easy to obtain, and if the amount of the free radical polymerization monomer is too high, the chemical corrosion resistance of the cured film is reduced.
Component (4): photoinitiator
The photoinitiator to be used in the present invention is not particularly limited, and examples thereof include oxime ester compounds, benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin and benzildimethyl ketal, and the above may be used alone or in any mixture, and further, oxime ester compounds are preferable.
In the technical scheme of the invention, the addition amount of the photoinitiator is 0.1-10 parts by mass based on 100 parts of the polyamic acid ester from the viewpoints of improving the photoetching resolution and widening the photoetching window, the development residual film rate is greatly reduced when the parts are too low, and the photoetching overexposure is easily caused when the parts are too high, so that the photoetching window is obviously smaller.
Other components:
the photosensitive polyimide precursor composition of the present invention may further comprise components other than the above-described components.
The photosensitive polyimide precursor composition of the present invention can be prepared by dissolving the above-mentioned components and optional components added as needed in a solvent to form a liquid resin composition. Thus, as the other component, a solvent may be exemplified. As other components, resins other than the above components, silane coupling agents, polymerization inhibitors, thermal alkaline agents, and the like can be cited.
Component (5): organic solvents
In the technical scheme of the invention, the applicable solvent is not particularly limited, and can be specifically selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides.
Polar solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, and N-cyclohexyl-2-pyrrolidone are preferable from the viewpoint of solubility of polyimide precursors, and these may be used alone or in any combination.
Alcohols having an alcoholic hydroxyl group in the molecule and having no olefinic double bond are preferable from the viewpoint of stability of the photosensitive polyimide precursor composition; specific examples include: alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol; lactic acid esters such as ethyl lactate; propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, and propylene glycol-2- (n-propyl) ether; monohydric alcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether and ethylene glycol n-propyl ether; 2-hydroxyisobutyric acid esters; any one or more of glycols such as ethylene glycol and propylene glycol are preferable, and any one or more of lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrates and ethanol are more preferable, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-1- (n-propyl) ether and the like are used alone or in combination.
In the technical scheme of the invention, the addition amount of the solvent used as above can be determined according to the requirements of the viscosity and the coating thickness of the photosensitive polyimide precursor composition, for example, 50-1500 parts by mass based on 100 parts of polyamic acid ester.
Component (6): silane coupling agent
In the technical scheme of the invention, the silane coupling agent is added to the photosensitive polyimide precursor composition, so that the bonding strength of the photosensitive polyimide precursor composition and a substrate can be added.
The silane coupling agent used in the present invention is not particularly limited, and specific examples thereof include ureidopropyltriethoxysilane, γ -aminopropyldimethoxysilane, N- (. Beta. -aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl ] phthalamic acid, benzophenone-3, 3 '-bis (N- [ 3-triethoxysilyl ] propionamide) -4,4' -dicarboxylic acid, benzene-1, 4-bis (N- [ 3-triethoxysilyl ] propionamide) -2, 5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic anhydride and N-phenylaminopropyltrimethoxysilane, and the like may be used singly or in any combination thereof, and preferably used as a triethoxysilane.
Preferably, the silane coupling agent is selected from any one or more of silane coupling agents containing urea bonds (-NH-CO-NH-).
In the technical scheme of the invention, the addition amount of the silane coupling agent is 0.5-10 parts by mass based on 100 parts of the polyamic acid ester from the viewpoint of improving the adhesion and coating uniformity of the silicon surface, and when the addition amount is too low, the adhesion performance of the silicon surface is poor, and when the addition amount is too high, the coating uniformity is obviously damaged.
Component (7): polymerization inhibitor
In the technical scheme of the invention, in order to improve the viscosity and stability during storage in the case of the photosensitive polyimide precursor composition, particularly in the case of containing a solvent, a polymerization inhibitor can be optionally mixed. The polymerization inhibitor is not particularly limited, and any one or more of the phenolic radical polymerization inhibitors are preferable. Examples of the polymerization inhibitor suitable for the present invention include hydroquinone, N-nitrosodiphenylamine, p-t-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt and N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, and the above may be used alone or in any mixture, and preferably 2-nitroso-1-naphthol.
In the technical scheme of the invention, the addition amount of the polymerization inhibitor is 0.005-12 parts by mass based on 100 parts of the polyamic acid ester from the viewpoint of improving the storage stability of the glue solution, and when the addition amount is too low, the storage stability of the glue solution is damaged, and when the addition amount is too high, the photoetching performance of the glue solution is damaged.
Component (8): thermal alkaline producing agent
In the technical scheme of the invention, the photosensitive polyimide precursor composition can further comprise a thermal alkaline agent, and the thermal alkaline agent can generate alkali by heating and can promote imidization of the photosensitive polyimide precursor composition.
The thermal alkaline agent to which the present invention is applicable is not particularly limited, and is preferably a t-butoxycarbonyl-protected amine compound;
the amine compound protected with t-butoxycarbonyl group is not particularly limited, specific examples thereof include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1, 3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexane ethanol, and 4- (2-aminoethyl) cyclohexanol, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, alpha- [2- (methylamino) ethyl ] benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinmethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4- (3-hydroxyphenyl) piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2- (4-piperidinyl) -2-propanol, 1, 4-butanol bis (3-aminopropyl) ether, 1, 2-bis (2-aminoethoxy) ethane, 2' -oxydiethylamine, 1, 14-diamino-3, 6,9, 12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis (3-aminopropyl) ether, 1, 11-diamino-3, 6, 9-trioxaundecane, diethylene glycol bis (3-aminopropyl) ether, and the like; and compounds in which the amino group of the amino acid or its derivative is protected by t-butoxycarbonyl group, etc., which may be used alone or in any combination.
The thermal alkaline generator in the present invention is more preferably N-t-butoxycarbonyl-4-piperidinemethanol.
In the technical scheme of the invention, from the viewpoint of improving the thermal imidization degree of polyimide precursor resin, the addition amount of the thermal alkaline agent is 0.1-10 parts by mass based on 100 parts of polyamic acid ester, the thermal imidization degree of polyimide precursor resin is not improved when the amount is too low, and the storage stability of the glue solution is obviously shortened when the amount is too high.
Production example 1:
polyamic acid ester A
103 g of 4,4' -oxydiphthalic anhydride (ODPA) was dispersed in the solvent gamma-butyrolactone (GBL), and 87 g hydroxyethyl methacrylate (HEMA) was added to the reaction system at once, followed by dropwise addition of 3 g pyridine, and reaction at room temperature was 16 h. 137 g Dicyclohexylcarbodiimide (DCC) was dissolved in GBL, and the mixture was slowly added dropwise to the reaction system, followed by stirring for 2 hours. 67g of 4,4' -diaminodiphenyl ether (ODA) is dissolved in GBL in nitrogen atmosphere, slowly added into the reaction system in a dropwise manner, and after the dropwise addition, 9 h (the reaction system can be diluted by adding a solvent if stirring is difficult during the whole reaction) is stirred, and 2 g ethanol is added for reaction, and 2h is reacted to finish the reaction.
And (3) carrying out filter pressing on the quenched reaction liquid, immediately adding the filtrate into methanol to separate out massive solids, refrigerating 12-h, then dropwise adding the obtained product into water after redissolving, and carrying out filtration and drying to obtain the corresponding polyamic acid ester A.
The molecular weight of the polymer obtained by testing by using an ultra-high performance polymer chromatographic Analyzer (APC) is as follows: m is M w 24000 and PDI of 1.85.
Polyamic acid ester B
The polyamide acid ester B was obtained by substituting 103 g of ODPA in the production example of polyamide acid ester A with 82.4 g of ODPA and 14.5. 14.5 g g of pyromellitic dianhydride (PMDA) and the remainder were identical.
The polymer molecular weight obtained using the APC test was: m is M w 23500 and PDI of 1.91.
Polyamic acid ester C
62 g of ODPA and 29 g of PMDA were used in place of 103 g of ODPA component in the production example of the polyamic acid ester A, and the rest was identical to the same, thereby obtaining a polyamic acid ester C.
The polymer molecular weight obtained using the APC test was: m is M w 24200 and pdi of 1.89.
Polyamic acid ester D
41.3 g of ODPA and 43.6 g of PMDA were used in place of 103 g of ODPA component in the production example of polyamic acid ester A, and the rest was identical to the same, to obtain polyamic acid ester D.
The polymer molecular weight obtained using the APC test was: m is M w 23800 and a PDI of 1.95.
Polyamic acid esters E
The polyamide acid ester E was obtained by replacing 103 g of the ODPA component in the production example of the polyamide acid ester A with 72.7 g of PMDA and the remainder being identical.
The polymer molecular weight obtained using the APC test was: m is M w 24500 and a PDI of 1.85.
Polyamic acid esters F
36 g para-phenylenediamine (PPDA) was used in place of 67 g of the ODA component in the example of production of polyamic acid ester A, the remainder being identical thereto, to thereby obtain polyamic acid ester F.
The polymer molecular weight obtained using the APC test was: m is M w 23000 and a PDI of 1.88.
Production example 2:
multi-arm compound CA-1
39.7 g of 1,2, 3-benzotriazole is dispersed in N-methylpyrrolidone (NMP), 40.7 g of 4, 4-triphenylmethane triisocyanate is dissolved in NMP and slowly added into a reaction system in a water bath at room temperature, after the dripping is finished, the mixture is slowly heated to 50 ℃ to react in the water bath for 12 h, thus obtaining NMP solution (30% of mass concentration) of CA-1, the NMP solution is stored at a low temperature for standby, and the product purity is 95.7% by using a High Performance Liquid Chromatograph (HPLC) test.
Multi-arm compound CA-2
The preparation of the multi-arm compound CA-1 was carried out by substituting 26.4 g of 1,2, 3-benzotriazole and 24.7. 24.7 g of isophorone diisocyanate for 39.7 g of 1,2, 3-benzotriazole and 40.7 g of 4, 4-triphenylmethane triisocyanate, respectively, and the remainder was consistent with them, and testing by HPLC gave a product of 98.5% purity.
Multi-arm compound CA-3
The multi-arm compound CA-1 was prepared by substituting 26.4 g of 1,2, 3-benzotriazole and 18.7. 18.7 g hexamethylene diisocyanate for 39.7 g of 1,2, 3-benzotriazole and 40.7 g of 4, 4-triphenylmethane triisocyanate, respectively, and the remainder were identical, and the purity of the product was 98.7% by HPLC test.
Multi-arm compound CA-4
15.6 g of 1H-tetrazole and 18.7. 18.7 g of hexamethylene diisocyanate were used in place of 39.7 g of 1,2, 3-benzotriazole and 40.7 g of 4, 4-triphenylmethane triisocyanate, respectively, in the preparation of the multi-arm compound CA-1, and the remainder were identical to each other, and the purity of the product was 97.5% by HPLC test.
Multi-arm compound CA-5
The multi-arm compound CA-1 was prepared by substituting 26.7 g of 7H-purine and 18.7. 18.7 g of hexamethylene diisocyanate for 39.7 g of 1,2, 3-benzotriazole and 40.7 g of 4, 4-triphenylmethane triisocyanate, respectively, and the remainder were identical, and the purity of the product was 96.5% by HPLC test.
Multi-arm compound CA-6
26.7 g of 1H-imidazo [4,5-b ] pyrazine and 18.7. 18.7 g hexamethylene diisocyanate were used in place of 39.7 g of 1,2, 3-benzotriazole and 40.7 g of 4, 4-triphenylmethane triisocyanate, respectively, in the preparation of the multi-arm compound CA-1, and the remainder were identical, and the purity of the product was 95.8% by HPLC test.
The structural formula of the multi-arm compound CA-1-6 in the preparation example is shown in figures 1-6.
Example 1
20. 20 g of polyamic acid ester A,34 g of NMP solvent, 2.0. 2.0 g of free radical polymerization monomer tetraethyleneglycol dimethacrylate (PC-1), 0.5. 0.5 g of NMP solution of the self-synthesized CA-3, 0.8 g of photoinitiator BASF IRGACURE OXE-01,0.4 g of silane coupling agent ureidopropyltriethoxysilane, and 0.04 g of polymerization inhibitor 2-nitroso-1-naphthol are sequentially added to a 100 mL brown flask under constant temperature and humidity (24 ℃ C., 50% RH), and after shaking and dissolving 24 h on a shaking table, an appropriate amount of NMP is further added, and the viscosity of the obtained solution is adjusted to about 30 poise, thereby preparing a negative photosensitive resin composition.
Example 2
The remaining components and operational procedures remain the same as in example 1, except that the 20 g polyamic acid ester A in example 1 is replaced with 20 g polyamic acid ester B.
Example 3
The remaining components and operational procedures remain the same as in example 1, except that the 20 g polyamic acid ester A in example 1 is replaced with 20 g polyamic acid ester C.
Example 4
The remaining components and operational procedures remain the same as in example 1, except that the 20 g polyamic acid ester A in example 1 is replaced with 20 g polyamic acid ester D.
Example 5
The remaining components and operational procedures remain the same as in example 1, except that the 20 g polyamic acid ester A in example 1 is replaced with 20 g polyamic acid ester E.
Example 6
The remaining components and operational procedures remain the same as in example 1, substituting the 20 g polyamic acid ester a of example 1 with the 10 g polyamic acid ester E and the 10 g polyamic acid ester F.
Example 7
The NMP solution of 0.5 g CA-3 in example 6 was replaced with the NMP solution of 0.5 g CA-1, and the remaining components and operational procedure were identical to those of example 6.
Example 8
The remaining components and operational procedure were identical to example 6 except that the NMP solution of example 6 was replaced with a NMP solution of 0.5 g CA-3 and 0.5 g CA-2.
Example 9
The NMP solution of 0.5 g CA-3 in example 6 was replaced with the NMP solution of 0.5 g CA-4, and the remaining components and operational procedure were identical to those of example 6.
Example 10
The NMP solution of 0.5g CA-3 in example 6 was replaced with the NMP solution of 0.5g CA-5, and the remaining components and operational procedure were identical to those of example 6.
Example 11
The NMP solution of 0.5g CA-3 in example 6 was replaced with the NMP solution of 0.5g CA-6, and the remaining components and operational procedure were identical to those of example 6.
Example 12
The NMP solution of 0.5g CA-3 in example 6 was replaced with the NMP solution of 0.2 g CA-3, and the remaining components and operational procedure were identical to those of example 6.
Example 13
The remaining components and operational procedures were identical to those of example 6 except that 0.5g of the above-described NMP solution of self-synthesized CA-3 in example 6 was replaced with 1.0g of the above-described NMP solution of self-synthesized CA-3.
Example 14
Based on the preparation process of the example 6, 0.4. 0.4 g hot alkaline agent N-tert-butoxycarbonyl-4-piperidinemethanol was added, and the rest components and operation procedures were kept the same as in the example 6.
Comparative example 1
The NMP solution of 0.5g CA-3 in example 6 was replaced with 0.1 g CA-7 (see FIG. 7 for chemical formula), and the remaining components and operational procedure were identical to those of example 6.
Comparative example 2
The NMP solution of 0.5g CA-3 in example 6 was replaced with 0.1 g CA-8 (see FIG. 7 for chemical formula), and the remaining components and operational procedure were identical to those of example 6.
Comparative example 3
The NMP solution of 0.5 g CA-3 in example 6 was replaced with 0.1g CA-9 (see FIG. 7 for chemical formula), and the remaining components and operational procedure were identical to those of example 6.
Comparative example 4
The NMP solution of 0.5 g CA-3 in example 6 was replaced with 0.1g CA-10 (see FIG. 7 for chemical formula), and the remaining components and operational procedure were identical to those of example 6.
Effect examples:
1. weight average molecular weight test:
the weight average molecular weight of the polyamic acid ester in the above production example was obtained by the test with an ultra-high performance polymer chromatography analyzer (ACQUITY APC), and the relevant test conditions were as follows: the chromatographic column model was ACQUITY APC XT 45.7 um/ACQUITY APC XT 200.5 μm/ACQUITY APC XT 450.5 μm, the column oven and detector temperatures were 40℃and the mobile phase was Tetrahydrofuran (THF) with a flow rate of 0.5 mL/min.
2. The preparation and evaluation method of the photoetching pattern comprises the following steps:
the photosensitive polyamic acid ester composition prepared in the above example was spin-coated on an 8-inch silicon wafer by a spin coater (WS-650 Mz-8NPPB, MYCRO) and prebaked at 100℃for 240 seconds with a hot plate to form a coating film about 10. Mu.m. On the coating film, a mask with a test pattern is usedi-line stepper (Shanghai microelectronics) irradiation 400 mJ/cm 2 Is a function of the energy of the (c). Next, this coating film was subjected to spray development with a developing machine (MST-EF 1-DV, shenzhen keldi) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate, to thereby obtain a lithographic pattern. A cured lithographic pattern of the composition was obtained by heating for 2 hours at the curing temperature shown in Table 1 under a nitrogen atmosphere using a temperature-programmed curing oven (HCM-500D, shanghai Siwang electron) to a thickness of about 10. Mu.m.
The cured lithographic pattern obtained above was subjected to a slice analysis by a focused ion beam electron microscope (FIB, helios G4, thermo Fisher), and its lithographic accuracy and cross-sectional profile were evaluated, and further, the negative photosensitive resin composition was subjected to a lithographic performance evaluation: the photoetching line precision is smaller than 10 mu m and is rated as 'excellent', the photoetching line precision is rated as 'good' at 10-20 mu m, the photoetching line precision is rated as 'fair' at 20-50 mu m, and the photoetching line precision is larger than 50 mu m and is rated as 'poor'.
3. Mechanical and thermal properties testing of cured films:
the cured exposure film prepared by the mask with the specific pattern and the curing method in the method is peeled off from a silicon wafer after being soaked in 1% hydrofluoric acid aqueous solution for 10 min to obtain a 5 mm multiplied by 10 cm film sample strip, the film sample strip is subjected to mechanical tensile test by a universal stretcher (Shenzhen three Si and X S technology) after being dried in an oven at 150 ℃, and the mechanical properties of the film sample strip are evaluated according to the elongation at break: elongation at break greater than 50% is rated "good", elongation at break between 40% and 50% is rated "good", elongation at break between 20% and 40% is rated "fair", and elongation at break less than 20% is rated "poor".
The membrane bars prepared above were tested using a dynamic thermo-mechanical analyzer (DMA, TA Instruments) to obtain a modulus-temperature curve and glass transition temperature, and their thermal properties were evaluated.
4. Chemical resistance test of cured films:
the cured exposure film prepared by the mask with the specific pattern and the curing method in the method is peeled off from the silicon wafer after being soaked in 1% hydrofluoric acid aqueous solution for 10 min to obtain a complete cured film, the complete cured film is soaked in a dimethyl sulfoxide solution of tetramethyl ammonium hydroxide with the mass concentration of 2.38% for 60 min under the condition of maintaining 50 ℃ after being dried in an oven at 150 ℃, and then the complete cured film is washed by deionized water, and then the moisture is dried in the oven at 150 ℃ and the chemical resistance of the complete cured film is evaluated according to the weight loss condition of the cured film before and after the chemical resistance treatment: weight loss less than 5% is rated as "good", weight loss between 5% and 15% is rated as "good", weight loss between 15% and 25% is rated as "fair", weight loss greater than 25% is rated as "poor".
5. Binding force test of cured film on copper surface:
preparing a cured exposure film on a copper substrate by using a mask with a specific pattern and the method 3, placing the cured exposure film in a high-temperature high-humidity accelerated aging test chamber (EHS-222 MD, ESPEC) under the test conditions of 130 ℃ and 85% RH of 264 h, and evaluating the bonding force of the cured film on a copper surface by using a hundred-gram method after the test: the failure of the lattice to fall off by 100% was rated as "excellent", the falling rate of the lattice was rated as "good" within 5%, the falling rate of the lattice was rated as "fair" within 5% -15%, and the falling rate of the lattice was rated as "poor" greater than 15%.
The components and contents of the polyamic acid ester compositions prepared in the above examples and comparative examples, the curing process are shown in Table 1 of FIG. 8, and the related property test data are shown in Table 2 of FIG. 9. As can be seen from tables 1 and 2, the related examples in which the azole structure-containing multi-arm compound synthesized according to the present invention was added are superior in chemical resistance and copper surface binding force as a whole, as compared to the comparative examples in which the azole compound of small molecule was added.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (13)

1. A photosensitive polyimide precursor composition comprising:
100 parts by mass of a polyamic acid ester as a photosensitive polyimide precursor;
0.1-10 parts by mass of a multi-arm structure compound containing an azole structure;
1-20 parts by mass of a radical polymerization monomer;
0.5-10 parts by mass of a photoinitiator;
0.5-10 parts by mass of a silane coupling agent;
0.01-5 parts by mass of a polymerization inhibitor;
50-1500 parts by mass of an organic solvent;
The multi-arm structure compound containing the azole structure is an azole structure Z 1 And multi-arm unit Z 2 A bonded compound; the azole structure Z 1 Selected from any one or more of the following structures:
the multi-arm unit Z 2 Selected from any one or more of the following structures:
2. the photosensitive polyimide precursor composition according to claim 1, wherein the polyamic acid ester has a structure as shown in formula (I):
in the formula (I), X is a 4-valent aromatic group-containing organic group, Y is a 2-valent aromatic group-containing organic group, R 1 And R is 2 Each independently selected from 1-valent organic groups having a structure represented by formula (II), n is 2 to 150;
in the formula (II), R 3 、R 4 And R is 5 Independently selected from hydrogen atoms and alkyl groups having 1 to 3 carbon atoms; m is 2-10.
3. The photosensitive polyimide precursor composition according to claim 1, wherein the radical-polymerizable monomer is selected from any one or more of (meth) acrylic acid ester compounds.
4. The photosensitive polyimide precursor composition according to claim 3, wherein the radical-polymerizable monomer is any one or more of a difunctional (meth) acrylate compound and a trifunctional (meth) acrylate compound.
5. The photosensitive polyimide precursor composition according to claim 1, wherein the photoinitiator is selected from any one or more of oxime ester compounds, benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin and benzildimethyl ketal.
6. The photosensitive polyimide precursor composition according to claim 5, wherein the photoinitiator is an oxime ester compound.
7. The photosensitive polyimide precursor composition according to claim 1, wherein the solvent is selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides.
8. The photosensitive polyimide precursor composition according to claim 1, wherein the silane coupling agent is selected from any one or more of silane coupling agents having urea bond (-NH-CO-NH-).
9. The photosensitive polyimide precursor composition according to claim 1, wherein the polymerization inhibitor is selected from any one or more of phenolic radical polymerization inhibitors.
10. The photosensitive polyimide precursor composition of claim 1, further comprising 0.1 to 10 parts of a thermal alkaline generator.
11. The photosensitive polyimide precursor composition of claim 10, wherein said photoinitiator said thermal alkaline generator is a t-butoxycarbonyl protected amine compound.
12. A photosensitive polyimide composition obtained by thermal imidization of the photosensitive polyimide precursor composition according to any one of claims 1 to 11.
13. The photosensitive polyimide composition of claim 12, wherein the thermal imidization temperature is 150 to 400 ℃.
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JP2020173431A (en) * 2019-04-09 2020-10-22 旭化成株式会社 Negative type photosensitive resin composition, method for producing polyimide, and method for producing cured relief pattern
JP2021120698A (en) * 2020-01-30 2021-08-19 旭化成株式会社 Negative photosensitive resin composition, and polyimide and cured relief pattern production method based on the same
JP2023023169A (en) * 2021-08-04 2023-02-16 旭化成株式会社 Photosensitive resin composition, method for producing polyimide, method for producing cured relief pattern, and semiconductor device

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Publication number Priority date Publication date Assignee Title
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JP2015151536A (en) * 2014-02-19 2015-08-24 日立化成株式会社 Adhesive composition and connection structure
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