CN115951559A - Photosensitive resin composition, preparation method thereof, cured film and application thereof - Google Patents
Photosensitive resin composition, preparation method thereof, cured film and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of semiconductor element coatings, and discloses a photosensitive resin composition, a preparation method thereof, a cured film and application thereof. The photosensitive resin composition comprises phenolic resin with a structure shown in a formula (1), a photoacid generator and a cross-linking agent. The photosensitive resin composition can be completely cured at a lower temperature, and the obtained cured film has good elasticity, tensile property and thermal stability, can be applied to semiconductor elements with poor heat resistance, has good alkali solubility, can be used as a raw material to prepare high-precision relief patterns, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductor element coatings, and particularly relates to a photosensitive resin composition, a preparation method thereof, a cured film and application thereof.
Background
In a protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and a planarization film for a TFT substrate, polyimide resins, polybenzoxazole resins, polyamideimide resins, and the like, which have excellent heat resistance and mechanical properties, are mainly used as raw materials.
Polyimide resins are widely used for coating semiconductor devices because cured films obtained from the resins have better heat resistance and elasticity than other resins. The polyimide resin generally refers to a solution (so-called varnish) of a polyimide precursor (polyamic acid) obtained by reacting a tetracarboxylic dianhydride with a diamine, and when used, the solution is made into a thin film by a method such as spin coating, and the polyimide precursor is heated to dehydrate and ring-close the polyimide precursor, thereby curing the polyimide precursor to form a cured film. The heat curing temperature of the polyimide resin is usually 300 ℃ or higher.
With the continuous development of technology in recent years, more and more materials with poor heat resistance are applied in the semiconductor field, and therefore, resins are required to have a lower curing temperature. However, the heat curing temperature of the polyimide resin is usually 300 ℃ or higher, and when the polyimide resin is cured at a low temperature, imidization is incomplete, and thus a cured film formed becomes brittle, and the physical properties thereof are deteriorated, resulting in poor performance.
Disclosure of Invention
The invention aims to solve the defects of high brittleness, low elasticity and poor thermal stability of the conventional cured film, and provides a photosensitive resin composition with good toughness, high elasticity and good thermal stability, a preparation method thereof, a cured film and application thereof.
The invention aims to provide a photosensitive resin composition, which comprises a phenolic resin with a structure shown as a formula (1), a photoacid generator and a cross-linking agent;
in the formula (1), R 1 ～R 4 Each independently selected from hydrogen atom, C 1 ～C 10 And C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 Is equal toOne of aliphatic groups, and n 1 Not less than 2; x is selected from hydrogen atom, C 2 ～C 10 Alkoxycarbonyl group of (A), C 2 ～C 10 Alkoxycarbonylalkyl of (C) 2 ～C 10 Of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 5 Is selected from C 1 ～C 10 A hydrocarbon group of (C) 1 ～C 10 And n is one of alkoxy, nitro and cyano of 2 ≥2，m 1 =1, 2 or 3,m 2 =0, 1 or 2,2 ≦ (m) 1 +m 2 ) Less than or equal to 4; y is a divalent organic group with a structure shown as a formula (3) or a formula (4):
in the formula (3), R 6 And R 7 Each independently selected from hydrogen atom, C 1 ～C 11 And one of a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;
in the formula (4), R 8 ～R 11 Each independently selected from hydrogen atom, C 1 ～C 10 A monovalent aliphatic group of (A), C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of monovalent aliphatic groups of (a); r 12 One or more selected from halogen atom, hydroxyl group, carboxyl group, sulfonic group and monovalent organic group, m 3 =1, 2, 3 or 4.
In some embodiments, Y in the phenolic resin structure is a divalent organic group having the structure of formula (5):
in the formula (5), R 13 Is C 1 ～C 5 And/or C 1 ～C 5 Alkoxy of (a), m 4 =1, 2 or 3,m 5 =0, 1,2 or 3, and 1 ≦ (m) 4 +m 5 )≤4。
In some specific embodiments, Y in the phenolic resin structure is a divalent organic group having a structure represented by formula (6);
in the formula (6), R 13 Is C 1 ～C 5 And/or C 1 ～C 5 Alkoxy of (a), m 5 =0, 1,2 or 3.
In some embodiments, n in the phenolic resin 1 /(n 1 +n 2 )＝0.15～0.50。
In some embodiments, the weight average molecular weight of the phenolic resin is 2000 to 200000Da.
In some embodiments, the photoacid generator is a quinone diazide compound.
In some specific embodiments, the photoacid generator is a compound having a diazo-1,2-benzoquinone structure and/or a compound having a diazo-1,2-naphthoquinone structure.
In some specific embodiments, the crosslinking agent is selected from one or more of epoxy compounds, oxetane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, compounds containing unsaturated bonds, melamine and derivatives thereof, methylol compounds, alkoxymethyl compounds, N-methylol compounds, and N-alkoxymethyl compounds.
In some specific embodiments, the photosensitive resin composition comprises the following raw materials in parts by weight:
95-120 parts of phenolic resin;
1-30 parts of a photoacid generator;
1-30 parts of a cross-linking agent.
In some embodiments, the photosensitive resin composition further comprises one or more of a thermal acid generator, a surfactant, a silane coupling agent, a dissolution promoter, and a crosslinking promoter.
Another object of the present invention is to provide a method for preparing a photosensitive resin composition, comprising the steps of:
s1, carrying out polymerization reaction on a triptycene structure phenolic compound with a structure shown as a formula (7), a phenolic compound component with a structure shown as a formula (8) and a polymerization component with a structure shown as a formula (9) and/or a formula (10) under the action of a catalyst to obtain phenolic resin;
s2, uniformly mixing the phenolic resin with a photoacid generator, a cross-linking agent and an optional thermal acid generator, a surfactant, a silane coupling agent, a dissolution promoter and a cross-linking promoter to obtain the photosensitive resin composition;
in the formula (7), R 14 ～R 17 Each independently selected from hydrogen atom, C 1 ～C 10 And C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (a);
in the formula (8), X is selected from a hydrogen atom and C 2 ～C 10 Alkoxycarbonyl group of (A), C 2 ～C 10 Alkoxycarbonylalkyl of (2), C 2 ～C 10 Of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 18 Is selected from C 1 ～C 10 A hydrocarbon group of (C) 1 ～C 10 M is one of alkoxy, nitro and cyano 6 =1, 2 or 3,m 7 =0, 1 or 2,2 ≦ (m) 6 +m 7 )≤4；
In the formula (9), R 19 And R 20 Each independently selected from hydrogen atom, C 1 ～C 11 And one of a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;
in the formula (10), R 21 ～R 24 Each independently selected from hydrogen atom, C 1 ～C 10 Monovalent aliphatic group ofC having radicals, some or all of the hydrogen atoms substituted by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (a); r is 25 One or more selected from halogen atom, hydroxyl group, carboxyl group, sulfonic group and monovalent organic group, m 8 =1, 2, 3 or 4,Z 1 And Z 2 Each independently selected from hydroxymethyl, alkoxymethyl and haloalkyl.
The third object of the present invention is to provide a photosensitive resin composition prepared by the above method.
The fourth object of the present invention is to provide a cured film obtained by heat-curing the photosensitive resin composition at 150 to 300 ℃.
The fifth object of the present invention is to provide the use of the photosensitive resin composition and/or the cured film for the production of a protective film for a semiconductor device, an interlayer insulating film, and an insulating layer for an organic electroluminescent device.
In some embodiments, the photosensitive resin composition is used to prepare a cured relief pattern, specifically:
forming a photosensitive resin layer on a surface of a substrate using the photosensitive resin composition;
exposing the photosensitive resin layer;
removing exposed parts or unexposed parts in the photosensitive resin layer through a developing solution to obtain a relief pattern;
and heating and curing the relief pattern at the temperature of 150-300 ℃.
Has the advantages that:
(1) The phenolic resin with a triptycene structure and a benzene ring structure in a macromolecular chain is used as a matrix, and the photosensitive resin composition is obtained by adding the components such as a photoacid generator, a cross-linking agent and the like, so that the curing molding temperature is low, the curing can be completely cured at a low temperature, a cured film obtained by curing has good performances on the mechanical properties such as elasticity, tensile elongation and the like, the cured film has good thermal stability, the photosensitive resin composition can still keep a good state under the condition of complex temperature change, and the applicability is excellent;
(2) The phenolic resin with a special structure contained in the photosensitive resin composition provided by the invention has good alkali solubility, and when the phenolic resin is applied to the preparation of the relief pattern, the relief pattern with clear edges can be obtained, the preparation accuracy of the relief pattern is improved, and the phenolic resin can be applied to the production of high-precision semiconductor elements and has a huge application prospect.
Detailed Description
Compared with the most commonly used polyamide-imide resin in the prior art, the photosensitive resin composition provided by the invention can be completely cured at a lower temperature, and the obtained cured film has mechanical properties such as elasticity, tensile elongation and the like, excellent thermal stability and good application prospect. The photosensitive resin composition takes phenolic resin with a special molecular structure as a matrix, and specifically can be a block structure or a random structure, and the structure of the phenolic resin is shown as the formula (1):
in the structure of the phenolic resin, a triptycene structure is taken as a first basic unit, and a disubstituted benzene ring structure is taken as a second basic unit to form a macromolecular chain of the phenolic resin; and R in each first basic unit in the macromolecular chain of the phenolic resin 1 ～R 4 X and R in each second basic unit may be the same, partially the same or different 5 May be identical, partially identical or completely different.
In the formula (1), R 1 ～R 4 Each independently selected from hydrogen atom, C 1 ～C 10 And C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 Preferably, each of the monovalent aliphatic groups of (a) is independently selected from a hydrogen atom or C 1 ～C 5 An aliphatic group of (2).
In the formula (1), X is selected from hydrogen atom and C 2 ～C 10 Alkoxycarbonyl group of (A), C 2 ～C 10 Alkoxycarbonylalkyl of (C) 2 ～C 10 Of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 5 Is selected from C 1 ～C 10 A hydrocarbon group of (C) 1 ～C 10 And one of alkoxy, nitro and cyano.
In the formula (1), n 1 ≥2，n 2 ≥2，m 1 =1, 2 or 3,m 2 =0, 1 or 2,2 ≦ (m) 1 +m 2 )≤4。
In some preferred embodiments, X is a hydrogen atom, a tert-butoxybutyl group and/or a tetrahydropyranyl group, and m is 1 =1 or 2; when m is 1 And when the relative positions of the two X groups on the benzene ring are meta-positions, the phenolic resin and the photoacid generator in the photosensitive resin composition have a good interaction relationship, and the preparation of a higher-precision relief pattern is facilitated. In other preferred embodiments, R 5 Is C 1 ～C 3 And m is a hydrocarbon group 2 And =1 or 2, in which case the cured film obtained by curing the photosensitive resin composition has more excellent tensile properties.
In the invention, the first basic unit and the second basic unit both contain Y groups, and the Y groups are divalent organic groups with the structures shown in formula (3) and/or formula (4).
In the present invention, the Y group in the first base unit may be identical, partially identical or completely different from the Y group in the second base unit, the Y group in each first base unit may be identical, partially identical or completely different, and the Y group in each second base unit may be identical, partially identical or completely different.
In some embodiments, R 6 And R 7 Each independently selected from hydrogen atom, C 1 ～C 11 And one of a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group-containing group, preferably C 1 ～C 3 Of (2) a hydrocarbon group。
In some embodiments, R 8 ～R 11 Each independently selected from hydrogen atom, C 1 ～C 10 Monovalent aliphatic group of (2), C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (1), R 12 One or more selected from halogen atom, hydroxyl group, carboxyl group, sulfonic group and monovalent organic group, m 3 =1, 2, 3 or 4.
In the invention, when the structure of the Y group is shown as the formula (5), a cured film obtained by curing the photosensitive resin composition has better thermal stability, and is suitable for application scenes with complex temperature change conditions.
Specifically, R in the formula (5) 13 Is C 1 ～C 5 And/or C 1 ～C 5 Alkoxy of (2), preferably C 1 ～C 3 Or C is a hydrocarbon group 1 ～C 3 Alkoxy of (a), m 4 =1, 2 or 3,m 5 =0, 1,2 or 3, and 1 ≦ (m) 4 +m 5 ) Less than or equal to 4; meanwhile, in the formula (5), a plurality of R 13 May be identical, partially identical or completely different.
In the invention, when the structure of the Y group is specifically shown as the formula (6), the photosensitive resin composition has better light sensitivity, so that a relief pattern with a better shape is obtained after exposure and development, and the preparation accuracy of the cured relief pattern is favorably improved.
Specifically, R in the formula (6) 13 Is C 1 ～C 5 And/or C 1 ～C 5 Alkoxy of (3), preferably C 1 ～C 3 Or a hydrocarbon radical of C 1 ～C 3 Alkoxy of (a), m 5 =0, 1,2 or 3. In the formula (6), a plurality of R 13 May be identical, partially identical or completely different.
In the phenolic resin, n 1 Is any integer of 5 to 400, specifically 5, 6, 7, 8, 9, 10, 15, 20, 30, 45, 50, 75, 90, 100, 150, 180, 200, 250, 300, 350, 450, 500 and any value therebetween; n is 2 Specifically, the number is 5 to 400, and may be 5, 10, 20, 25, 35, 40, 55, 80, 105, 120, 140, 190, 210, 280, 320, 350, 385, 400, 423, 453, 492, 500, or any value therebetween.
The phenolic resin is prepared by mixing n in phenolic resin based on the properties of cured film obtained by curing the photosensitive resin composition, such as elasticity, tensile property and thermal stability 1 /(n 1 +n 2 ) Creatively controlled between 0.15 and 0.50, so that each group in the molecular structure of the phenolic resin can exert the optimal synergistic effect, and the prepared cured film has excellent elasticity, tensile property and thermal stability.
In the present invention, the weight average molecular weight of the phenol resin is preferably 2000 to 200000, and specifically may be 2000, 5000, 10000, 15000, 50000, 100000, 150000, 200000, and any value therebetween; preferably, the weight average molecular weight of the phenolic resin is 3000 to 120000, more preferably 3000 to 40000.
In the invention, the photo-acid generator can be decomposed and volatilized in the thermal curing process, and only a very small amount of photo-acid generator or no photo-acid generator remains in the finally prepared cured film, so that the influence of the photo-acid generator residue on the properties of the cured film is reduced. The photoacid generator is specifically a quinone diazo compound, and may be a compound having, but not limited to, a diazo 1,2-benzoquinone structure or a diazo 1,2-naphthoquinone structure, and the compound having the diazo 1,2-naphthoquinone structure is preferably a compound having a structure represented by formulas (11) to (14).
Q in the formulae (11) to (14) may be a hydrogen atom or a group represented by the formula (15) or (16).
In the present invention, the crosslinking agent may be, specifically, but not limited to, one or more of epoxy compounds, oxetane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, unsaturated bond-containing compounds, melamine and derivatives thereof, methylol compounds, alkoxymethyl compounds, N-methylol compounds and N-alkoxymethyl compounds. When the crosslinking agent is selected from one or more of an epoxy compound, an oxetane compound, an isocyanate compound, a methylol compound or an alkoxymethyl compound, an N-methylol compound and an N-alkoxymethyl compound, the cured film obtained after curing the photosensitive resin composition has excellent thermal and mechanical properties.
In some specific embodiments, the amount of the phenolic resin, the photoacid generator and the crosslinking agent in the photosensitive resin composition is as follows:
95-120 parts of phenolic resin;
1-30 parts of a photoacid generator;
1-30 parts of a cross-linking agent.
In some embodiments, when the input mass ratio of the photoacid generator to the phenolic resin is (5-30): 100 and the input mass ratio of the crosslinking agent to the phenolic resin is (0.5-50): 100, the three components can well exert synergistic effect, so that the photosensitive resin composition has more excellent performance.
In some embodiments, the photosensitive resin composition further comprises a solvent for dissolving other substances in the photosensitive resin composition to form a solution system, which is advantageous for storage and transportation of the photosensitive resin composition. The solvent may be, but is not limited to, one or more of amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbon solvents, and may be, but is not limited to, one or more of N-methyl-2-pyrrolidone, N-dimethylacetamide, methyl isobutyl ketone, cyclopentanone, cyclohexanone, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, styrene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, and xylene. The mass ratio of the solvent to the phenolic resin is preferably (100 to 1000): 100, in which case the phenolic resin, the photoacid generator, and the crosslinking agent can be dispersed in the solvent well to form a stable solution system, and the content of the solvent is appropriate so as not to affect the film formation of the photosensitive resin composition.
The photosensitive resin composition provided by the invention further comprises a surfactant, a silane coupling agent, a dissolution promoter and a thermal acid generator.
In some specific embodiments, the surfactant may be, but is not limited to, polyethylene glycol nonionic surfactants such as polypropylene glycol and polyoxyethylene lauryl ether, and the input mass ratio of the surfactant to the phenolic resin is (0.01-10): 100.
In the present invention, the addition of a silane coupling agent can improve the stability of the solution system of the photosensitive resin composition, which is advantageous for transportation and storage, and in some embodiments, the silane coupling agent can be, but is not limited to, one or more of phenyl silanetriol, trimethoxyphenyl silane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenyl silane, diethoxydiphenyl silane, dimethoxydi-p-tolyl silane, and triphenyl silanol. The mass ratio of the silane coupling agent to the phenolic resin is (0.1-15): 100.
In some specific embodiments, the dissolution promoter is a compound having a hydroxyl group and/or a carboxyl group, and specifically may be, but is not limited to, one or more of p-cumylphenol, bisphenol, and resorcinol compounds, preferably one or more of 3-phenyllactic acid, 2,4-dimethylbenzoic acid, and 2,4,6-trimethylbenzoic acid. The mass ratio of the dissolution accelerator to the phenolic resin is (0.1-20): 100.
In some embodiments, the thermal acid generator may be, but is not limited to, one or more of ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, p-toluenesulfonic acid, and 2-methoxyethyl ester. The mass ratio of the thermal acid generator to the phenolic resin is preferably (0.5-5): 100.
The preparation method of the photosensitive resin composition provided by the invention comprises the following steps:
s1, carrying out polymerization reaction on a triptycene structure polymerization component with a structure shown as a formula (7), a benzene ring structure polymerization component with a structure shown as a formula (8) and a phenolic compound with a structure shown as a formula (9) and/or a formula (10) under the action of a catalyst to obtain phenolic resin;
s2, uniformly mixing the phenolic resin with a photoacid generator, a cross-linking agent and an optional thermal acid generator, a surfactant, a silane coupling agent, a dissolution promoter and a cross-linking promoter to obtain the photosensitive resin composition;
in the formula (7), R 14 ～R 17 Each independently selected from hydrogen atom, C 1 ～C 10 And C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of monovalent aliphatic groups of (a);
in the formula (8), X is selected from a hydrogen atom and C 2 ～C 10 Alkoxycarbonyl group of (A), C 2 ～C 10 Alkoxycarbonylalkyl of (C) 2 ～C 10 R is one of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl of 18 Is selected from C 1 ～C 10 A hydrocarbon group of 1 ～C 10 Alkoxy and nitro ofAnd one of cyano groups, m 6 =1, 2 or 3,m 7 =0, 1 or 2,2 ≦ (m) 6 +m 7 )≤4；
In the formula (9), R 19 And R 20 Each independently selected from hydrogen atom, C 1 ～C 11 And one of a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;
in the formula (10), R 21 ～R 24 Each independently selected from hydrogen atom, C 1 ～C 10 A monovalent aliphatic group of (A), C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (a); r 25 One or more selected from halogen atom, hydroxyl group, carboxyl group, sulfonic group and monovalent organic group, m 8 =1, 2, 3 or 4,Z 1 And Z 2 Each independently selected from hydroxymethyl, alkoxymethyl and haloalkyl.
In some specific embodiments, the triptycene structural polymeric component may be specifically, but is not limited to, one or more of 1,4-dihydroxytriptycene, 2,6-di-tert-butyl-1,4-dihydroxytriptycene, 2-tert-butyl-5-methyl-1,4-dihydroxytriptycene, 2-fluoromethyl-1,4-dihydroxytriptycene, and 3 (2-fluoroethyl) -6-ethyl-1,4-dihydroxytriptycene; the benzene ring structure polymeric component may be specifically, but not limited to, one or more of phenol, resorcinol, 2-methylresorcinol, 4-methoxyresorcinol catechol, hydroquinone and/or phloroglucinol.
In some specific embodiments, the charging molar ratio of the total amount of the triptycene structure polymeric component and the benzene ring structure polymeric component to the phenolic compound is preferably 1 (1 to 4), more preferably 1 (1 to 2.3), from the viewpoint of reaction control and stability of the resultant photosensitive resin.
In some specific embodiments, the catalyst may be an acidic catalyst, or may be a basic catalyst, preferably an acidic catalyst, and specifically may be, but is not limited to, one or more of inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid.
In some specific embodiments, phenolic compounds and polymeric components are dissolved in an organic solvent at 55-60 ℃, and then reacted at 80-85 ℃ for 10-14 h to obtain a reaction solution containing phenolic resin, and after the reaction solution is diluted by the organic solvent, a large amount of water is added to precipitate solids, namely the phenolic resin.
In some embodiments, the organic solvent used in the polymerization reaction may be, but is not limited to, one or more of bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, triethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
The invention also provides the photosensitive resin composition prepared by the method.
The invention also provides a cured film which is prepared by taking the photosensitive resin composition as a raw material and performing thermal curing at 150-300 ℃. The cured film is excellent in physical properties such as elasticity and tensile properties, and can be kept in a good state without cracking or deformation even when the temperature change is complicated, and has good thermal stability.
The invention also provides application of the photosensitive resin composition and/or the cured film in preparing a protective film, an interlayer insulating film and an organic electroluminescent element insulating layer of a semiconductor element.
When the photosensitive resin composition is used for preparing a cured relief pattern, the method specifically comprises the following steps:
forming a photosensitive resin layer on a surface of a substrate using the photosensitive resin composition;
exposing the photosensitive resin layer;
removing exposed parts or unexposed parts in the photosensitive resin layer through a developing solution to obtain a relief pattern;
and heating and curing the relief pattern at 150-300 ℃.
In some embodiments, in order to improve the bonding force between the relief pattern and the substrate, a silane coupling agent may be previously coated on the surface of the substrate as an adhesion aid.
In some embodiments, the photosensitive resin composition may be formed into a photosensitive resin layer on the surface of the substrate by various methods, such as but not limited to one or more of spin coating, spray coating, dipping, printing, and roll coating.
Further, the step of forming the photosensitive resin layer on the surface of the substrate by the photosensitive resin composition further comprises the step of baking: and (3) drying the substrate with the photosensitive resin composition on the surface at 80-120 ℃ for a period of time to volatilize the solvent in the photosensitive resin composition, and forming a photosensitive resin layer on the surface of the substrate.
When the photosensitive resin layer is exposed to light, the light source used may be X-rays, electron beams, ultraviolet rays, etc., and preferably chemical rays having a wavelength of 200 to 500 nm; to further improve the resolution of the cured relief pattern, the light source used is more preferably g-ray, h-ray or i-ray of a mercury lamp.
In some specific embodiments, the developing solution may be, but is not limited to, one or more aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and when the concentration of the aqueous solution is 0.5 to 10wt%, the optimum developing effect can be achieved.
In the invention, after development, the substrate needs to be rinsed with a rinsing liquid to remove the developing liquid on the surface. The washing solution may be, but is not limited to, distilled water, methanol, ethanol, isopropyl alcohol, and the like.
The examples of embodiment are intended to illustrate the invention and should not be construed as limiting the invention. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, are according to the techniques or conditions described in the literature of the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Preparation example 1.1,4-dihydroxy triptycene Synthesis method
S1, 12.1g of p-benzoquinone (112 mmol) and 10g of anthracene (56 mmol) are added into a three-neck flask with a magnetic stirring device, a nitrogen protection device and a reflux device, then 100mL of toluene is added, after the solid is completely dissolved, the temperature is continuously increased to reflux and kept for 6 hours.
And S2, cooling the reaction solution in the S1 to room temperature, separating out a large amount of solid, filtering, washing a filter cake by using a small amount of toluene, and drying in vacuum to obtain 13.6g of an orange product with the yield of 85%.
S3, adding the orange product into a three-necked bottle with a magnetic stirring device, a nitrogen protection device and a reflux device, adding 300mL of acetic acid, and heating to reflux; slowly dropping 4mL hydrobromic acid after the product is completely dissolved, continuing to react for 2h, cooling, filtering and vacuum drying to obtain white 1,4-dihydroxy triptycene powder, wherein the structure is shown as a formula (17), and the yield is 88%.
Preparation 2.2,6-di-tert-butyl-1,4-dihydroxytriptycene Synthesis method
S1, adding 12.1g of p-benzoquinone (112 mmol) and 16.3g of 2,6-di-tert-butylanthracene (56 mmol) into a three-neck flask with magnetic stirring, nitrogen protection and reflux devices, then adding 100mL of toluene, heating until the solid is completely dissolved, and continuing to heat to reflux for 6 hours.
And S2, cooling the reaction solution in the S1 to room temperature, separating out a large amount of solid, filtering, washing a filter cake by using a small amount of toluene, and drying in vacuum to obtain 17.9g of an orange product with the yield of 80%.
S3, adding the orange product into a three-neck bottle with a magnetic stirring device, a nitrogen protection device and a reflux device, adding 400mL of acetic acid, and heating to reflux; slowly dropping 4mL hydrobromic acid after the product is completely dissolved, continuing to react for 2h, cooling, filtering and vacuum drying to obtain white 2,6-di-tert-butyl-1,4-dihydroxy triptycene powder, wherein the structure is shown as a formula (18), and the yield is 88%.
Example 1.
The photosensitive resin composition provided in this example comprises 38wt% of a phenol resin, 4.9 wt% of a photosensitizer, 3.7wt% of a crosslinking agent, and 53.4wt% of γ -butyrolactone, and the above components were mixed uniformly and filtered through a membrane filter having a pore size of 1 μm. The phenolic resin is prepared by carrying out polymerization reaction on 1,4-dihydroxy triptycene, resorcinol and 2,6-bis (hydroxymethyl) -p-cresol provided by preparation example 1 under the catalysis of p-toluenesulfonic acid, and specifically the preparation method comprises the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was purged with nitrogen, and then 91.8g of resorcinol (0.833 mol), 128.8g of 1,4-dihydroxytriptycene (0.45 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 83g of 2,6-bis (hydroxymethyl) -p-cresol (0.50 mol), and 166g of propylene glycol monomethyl ether were added, mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under the above conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 50g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 6L of water under high-speed stirring to disperse and separate out the resin, filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 74%. The weight average molecular weight of the phenolic resin was 6500.
In the positive photosensitive resin composition provided in this example, the structure of the photosensitizer is represented by formula (19), 83% of Q in the photosensitizer is represented by formula (20), and 17% of Q is hydrogen atoms. The structure of the cross-linking agent is shown as the formula (21).
Example 2.
The photosensitive resin composition provided in this example was substantially the same as that of example 1, except that the phenolic resin contained in the photosensitive resin composition was different. In this example, the phenolic resin was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was purged with nitrogen, 113.8g of resorcinol (1.033 mol), 71.6g of 1,4-dihydroxytriptycene (0.25 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 83g of 2,6-bis (hydroxymethyl) -p-cresol (0.50 mol), and 166g of propylene glycol monomethyl ether were added thereto, mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under these conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 50g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 6L of water under high-speed stirring to disperse and separate out the resin, and filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 77%. The weight average molecular weight of the phenolic resin was 6900.
Example 3.
The photosensitive resin composition provided in this example was substantially the same as that of example 1, except that the phenolic resin contained in the photosensitive resin composition was different. In this example, the phenolic resin was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was purged with nitrogen, 113.8g of resorcinol (1.033 mol), 71.6g of 1,4-dihydroxytriptycene (0.25 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 149g of 2,6-bis (hydroxymethyl) -p-cresol (0.90 mol), and 200g of propylene glycol monomethyl ether were added, mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under the conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 100g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 8L of water under high-speed stirring to disperse and separate out the resin, filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 82%. The weight average molecular weight of the phenolic resin was 10500.
Example 4.
The photosensitive resin composition provided in this example is substantially the same as that of example 3, except that the crosslinking agent in the photosensitive resin composition has the following formula (22).
Example 5.
The photosensitive resin composition provided in this example is substantially the same as that of example 4, except that the structure of the sensitizer in the photosensitive resin composition is as shown in formula (23).
Example 6.
The photosensitive resin composition provided in this example was substantially the same as that of example 1, except that the phenolic resin contained in the photosensitive resin composition was different. In this example, it was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was purged with nitrogen, 113.8g of resorcinol (1.033 mol), 71.6g of 1,4-dihydroxytriptycene (0.25 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 73.8g of 37wt% formalin (0.90 mol), and 150g of propylene glycol monomethyl ether were added thereto, and the mixture was mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept in this condition to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 50g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 8L of water under high-speed stirring to disperse and separate out the resin, filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 80%. The weight average molecular weight of the phenolic resin was 10800.
Example 7.
The photosensitive resin composition provided in this example was substantially the same as that of example 1, except that the phenolic resin contained in the photosensitive resin composition was different. In this example, it was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was purged with nitrogen, 113.8g of resorcinol (1.033 mol), 99.6g of 2,6-di-tert-butyl-1,4-dihydroxytriptycene (0.25 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 149g of 2,6-bis (hydroxymethyl) -p-cresol (0.90 mol), and 200g of propylene glycol monomethyl ether were added, mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under these conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 100g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 8L of water under high-speed stirring to disperse and separate out the resin, filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 75%. The weight average molecular weight of the phenolic resin was 9100.
Example 8.
The photosensitive resin composition provided in this example was substantially the same as that of example 1, except that the phenolic resin contained in the photosensitive resin composition was different. In this example, it was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was subjected to nitrogen substitution, and then 113.8g of resorcinol (1.033 mol), 99.6g of 2,6-di-tert-butyl-1,4-dihydroxytriptycene (0.25 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 73.8g of 37wt% formalin (0.90 mol), and 150g of propylene glycol monomethyl ether were added thereto, and mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under the conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 100g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 8L of water under high-speed stirring to disperse and separate out the resin, and filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 83%. The weight average molecular weight of the phenolic resin was 9600.
Comparative example 1.
This comparative example provides a photosensitive resin composition which is substantially the same as that of example 1, except that the photosensitive resin composition contains a different phenol resin. In this comparative example, a phenolic resin was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was subjected to nitrogen substitution, and then 141.0g of resorcinol (1.28 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 149g of 2,6-bis (hydroxymethyl) -p-cresol (0.90 mol) and 200g of propylene glycol monomethyl ether were added thereto, and mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under the conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 100g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 8L of water under high-speed stirring to disperse and separate out the resin, filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 70%. The weight average molecular weight of the phenolic resin was 11500.
Comparative example 2.
This comparative example provides a photosensitive resin composition which is substantially the same as that of example 1, except that the photosensitive resin composition contains a different phenol resin. In this comparative example, a phenolic resin was prepared by the following steps:
s1, a 1L three-necked flask with a dean-Stark trap device was subjected to nitrogen substitution, and then 141.0g of resorcinol (1.28 mol), 3.81g of p-toluenesulfonic acid (0.02 mol), 73.8g of 37wt% formalin (0.9 mol) and 150g of propylene glycol monomethyl ether were added and mixed and stirred at 60 ℃ until the solid was completely dissolved, and the mixed solution was heated to 80 ℃ by an oil bath and kept under the conditions to react for 12 hours.
And S2, after the reaction is finished, cooling the reaction container in the atmosphere, adding 100g of propylene glycol monomethyl ether into the reaction container, uniformly stirring and mixing, then dropwise adding the reaction diluent into 8L of water under high-speed stirring to disperse and separate out the resin, filtering, washing with water, dehydrating and drying in vacuum to obtain the phenolic resin, wherein the yield is 68%. The weight average molecular weight of the phenolic resin was 11900.
And (4) testing examples.
(1) Testing of elongation and Young's modulus: the photosensitive resins provided in examples 1 to 8 and comparative examples 1 and 2 were spin-coated on a silicon wafer, heated on a 120 ℃ hot plate for 3 minutes, and then cured at 230 ℃ for 1 hour under the protection of chlorine gas to obtain a cured film having a thickness of 10 μm, the cured film was divided into a plurality of samples having a width of 3mm and a length of 40mm by a dicing saw, the samples were peeled from the wafer using an aqueous hydrofluoric acid solution, the samples were allowed to stand in an atmosphere having a temperature of 23 ℃ and a humidity of 50% for 24 hours or more, and the measurement was carried out by a periscope with an experiment speed of 40mm/min and a load sensor rating of 2kgf, and the results of the experiment were averaged to obtain the maximum five values, and are shown in table 1.
(2) Testing thermal cycle performance: examples 1 to 8 and comparative examples 1 and 2 were spin-coated on ghost wafers, and after heating for 3min with a 120 ℃ hot plate, cured for 1h at 230 ℃ under the protection of chlorine gas to obtain cured films having a thickness of 10 μm, 500 cycles of experiments were performed at-65 ℃ to 135 ℃ for 30min each using a thermal cycling oven, and then the presence or absence of cracks on the film surface was observed using an optical microscope, with the results shown in table 1.
TABLE 1 mechanical Properties and thermal cycling Properties of the cured films
From the experimental results, it can be seen that, in examples 1 to 8, compared with comparative examples 1 and 2, the cured films obtained by curing the photosensitive resin compositions provided by the present invention at a lower temperature of 230 ℃ have higher young's modulus and elongation, i.e., good elasticity and elongation. It is noted that the cured films obtained by thermosetting the phenolic resin prepared by the method provided in example 4 as the matrix have better elasticity and elongation properties than those of examples 1 and 6 to 8. In addition, from the experimental results of the thermal cycle test, it is seen that the cured films provided in examples 1 to 8 of the present invention maintain a good state after 500 cycles of temperature-65 ℃ to 135 ℃, have no cracks on the surface, have more excellent thermal stability than those of comparative examples 1 and 2, can be applied to scenes with complicated temperature changes, and have good applicability.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (11)
1. A photosensitive resin composition characterized by: comprises phenolic resin with a structure shown as a formula (1), a photoacid generator and a cross-linking agent;
in the formula (1), R 1 ～R 4 Each independently selected from hydrogen atom, C 1 ～C 10 And C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 And n is one of monovalent aliphatic groups of 1 Not less than 2; x is selected from hydrogen atom, C 2 ～C 10 Alkoxycarbonyl group of (A), C 2 ～C 10 Alkoxycarbonylalkyl of (C) 2 ～C 10 R is one of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl of 5 Is selected from C 1 ～C 10 A hydrocarbon group of 1 ～C 10 And one of alkoxy, nitro and cyano, and n 2 ≥2，m 1 =1, 2 or 3,m 2 =0, 1 or 2,2 ≦ (m) 1 +m 2 ) N is less than or equal to 4, and n 2 Not less than 2; y is a divalent organic group with a structure shown as a formula (3) or a formula (4):
-CR 6 R 7 -formula (3),
in the formula (3), R 6 And R 7 Each independently selected from hydrogen atom, C 1 ～C 11 And one of a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;
in the formula (4), R 8 ～R 11 Each independently selected from hydrogen atom, C 1 ～C 10 A monovalent aliphatic group of (A), C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (a); r 12 One or more selected from halogen atom, hydroxyl group, carboxyl group, sulfonic group and monovalent organic group, m 3 =1, 2, 3 or 4.
2. The photosensitive resin composition according to claim 1, wherein: y in the phenolic resin structure is a divalent organic group with the structure shown in a formula (5),
in the formula (5), R 13 Is C 1 ～C 5 And/or C 1 ～C 5 Alkoxy of (a), m 4 =1, 2 or 3,m 5 =0, 1,2 or 3, and 1 ≦ (m) 4 +m 5 )≤4；
Preferably, Y in the phenolic resin structure is a divalent organic group with the structure shown in the formula (6),
in the formula (6), R 13 Is C 1 ～C 5 And/or C 1 ～C 5 Alkoxy of (a), m 5 =0, 1,2 or 3.
3. The photosensitive resin composition according to claim 1, wherein: in the phenolic resin, n 1 /(n 1 +n 2 ) = 0.15-0.50; the weight average molecular weight of the phenolic resin is 2000-200000 Da.
4. The photosensitive resin composition according to claim 1, wherein: the photo-acid generator is a quinone diazo compound; preferably, the photoacid generator is a compound with a diazo-1,2-benzoquinone structure and/or a compound with a diazo-1,2-naphthoquinone structure;
the crosslinking agent is selected from one or more of epoxy compound, oxetane compound, oxazoline compound, carbodiimide compound, aldehyde, isocyanate compound, compound containing unsaturated bond, melamine and its derivative, methylol compound, alkoxymethyl compound, N-methylol compound and N-alkoxymethyl compound.
5. The photosensitive resin composition according to claim 1, wherein: the photosensitive resin composition comprises the following raw materials in parts by weight:
95-120 parts of phenolic resin;
1-30 parts of a photoacid generator;
1-30 parts of a cross-linking agent.
6. The photosensitive resin composition according to claim 1, wherein: the photosensitive resin composition further includes one or more of a thermal acid generator, a surfactant, a silane coupling agent, a dissolution accelerator, and a crosslinking accelerator.
7. A method for producing a photosensitive resin composition, characterized in that: the method comprises the following steps:
s1, carrying out polymerization reaction on a triptycene structure phenolic compound with a structure shown as a formula (7), a phenolic compound component with a structure shown as a formula (8) and a polymerization component with a structure shown as a formula (9) and/or a formula (10) under the action of a catalyst to obtain phenolic resin;
s2, uniformly mixing the phenolic resin with a photoacid generator, a cross-linking agent and an optional thermal acid generator, a surfactant, a silane coupling agent, a dissolution promoter and a cross-linking promoter to obtain the photosensitive resin composition;
in the formula (7), R 14 ～R 17 Each independently selected from hydrogen atom, C 1 ～C 10 And C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (a);
in the formula (8), X is selected from a hydrogen atom and C 2 ～C 10 Alkoxycarbonyl group of (A), C 2 ～C 10 Alkoxycarbonylalkyl of (C) 2 ～C 10 Of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 18 Is selected from C 1 ～C 10 A hydrocarbon group of 1 ～C 10 M is one of alkoxy, nitro and cyano 6 =1, 2 or 3,m 7 =0, 1 or 2,2 ≦ (m) 6 +m 7 )≤4；
In the formula (9), R 19 And R 20 Each independently selected from hydrogen atom, C 1 ～C 11 One of a monovalent organic group of (1) and a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;
in the formula (10), R 21 ～R 24 Each independently selected from hydrogen atom, C 1 ～C 10 A monovalent aliphatic group of (A), C having some or all of the hydrogen atoms replaced by fluorine atoms 1 ～C 10 One of the monovalent aliphatic groups of (a); r is 25 One or more selected from halogen atom, hydroxyl group, carboxyl group, sulfonic group and monovalent organic group, m 8 =1, 2, 3 or 4,Z 1 And Z 2 Each independently selected from hydroxymethyl and alkoxymethylAnd a haloalkyl group.
8. A photosensitive resin composition prepared by the method of claim 7.
9. A cured film obtained by thermally curing the photosensitive resin composition according to any one of claims 1 to 6 and 8 at 150 to 300 ℃.
10. Use of the photosensitive resin composition according to any one of claims 1 to 6 and 8 and/or the cured film according to claim 9 for producing a protective film for a semiconductor device, an interlayer insulating film, and an insulating layer for an organic electroluminescent device.
11. Use according to claim 10, wherein the photosensitive resin composition is used for the preparation of a cured relief pattern, in particular:
forming a photosensitive resin layer on a surface of a substrate using the photosensitive resin composition;
exposing the photosensitive resin layer;
removing exposed parts or unexposed parts in the photosensitive resin layer through a developing solution to obtain a relief pattern;
and heating and curing the relief pattern at 150-300 ℃.
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