A photosensitive polybenzoxazole resin composition and its applications

Abstract

The present application discloses a photosensitive resin composition based on polybenzoxazole and its applications. The photosensitive resin composition includes a resin, a polysiloxane containing a nitrogen heterocycle, a silane coupling agent, a photosensitive aid, a crosslinking agent, and a solvent. By adding the polysiloxane containing a nitrogen heterocycle, the obtained photosensitive resin composition can exhibit excellent dielectric properties.

Description

Technical Field

[0001] The present application relates to a photosensitive resin composition based on polybenzoxazole and its application, belonging to the technical field of organosilicon compounds. Background Art

[0002] With the development of aerospace and national defense military equipment, the demand for polymer materials with low density, high strength, high modulus and high temperature resistance in high-end fields is increasing. The development of such materials is of great significance for enhancing the competitiveness of the country's high-end frontier science and technology fields. Polybenzoxazole (PBO) is a high-performance resin material. Due to the alternating rigid benzoxazole rings and benzene rings in the PBO chain structure, it has extremely high tensile strength, stiffness, and relatively low density. Polybenzoxazole polymers are high-performance polymers with high-rigidity molecular chain segments, and are usually widely used in the fields of aerospace, navigation, military, etc. in the form of films, fibers, resin matrices, and molecular reinforcing materials. They are important matrix materials for high-temperature and high-strength composite materials.

[0003] The adhesion to the substrate is an important indicator to measure the quality of the material. Now, semiconductor devices in different fields use substrates of different materials, such as silicon, copper, copper alloy, titanium, titanium alloy, silver, aluminum, etc. A good product needs to show good adhesion to different substrates.

[0004] In addition, the interlayer insulating film used for multi-layer metal interconnection circuits in semiconductor packaging is required to have as low a dielectric constant and dielectric loss as possible to minimize parasitic capacitance, thereby preventing signal transmission delay, crosstalk, and noise, etc. Polyimide materials themselves have good heat resistance, mechanical properties, and insulation properties, and are important materials for interlayer insulating films. However, the dielectric constant of traditional polyimide is relatively high (about 3.4), which is difficult to meet the requirements of next-generation semiconductor packaging materials, and its low-dielectric modification is required. Summary of the Invention

[0005] One of the purposes of the present invention is to provide a photosensitive resin composition. The resin used in this photosensitive resin composition is a polybenzoxazole resin, and at the same time, a polysiloxane containing a nitrogen heterocycle is introduced, which has strong dielectric properties and good adhesion to the substrate, and more meets the usage requirements.

[0006] The present application provides a photosensitive resin composition, which has strong dielectric properties. This photosensitive resin composition can be used to form relief patterns such as passivation films, surface protection films, and interlayer insulating films of semiconductor devices.

[0007] The photosensitive resin composition includes a resin, a polysiloxane containing a nitrogen heterocycle, a silane coupling agent, a photosensitive auxiliary agent, a crosslinking agent, and a solvent.

[0008] Among them, the nitrogen-containing heterocyclic polysiloxane is selected from at least one of the structural formulas shown in the following formula (1):

[0009]

[0010] Among them, Y is an organic group containing a nitrogen-containing heterocycle. Optionally, Y is selected from at least one of the structures shown in the following formula (2) to formula (5), and can be one, two or more than two, and * represents the access site:

[0011]

[0012] In formula (2) to formula (5), R1 is selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Specifically, the alkyl group or alkoxy group having 1 to 20 carbon atoms can be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., or can be an alkoxy group such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, etc.

[0013] Preferably, R1 is selected from a hydrogen atom, methyl, ethyl, butyl, 2-hydroxyethyl methacrylate.

[0014] In formula (2) to formula (5), the W group is selected from a nitrogen-containing heterocyclic structure, such as triazolyl, tetrazolyl, triazinyl, imidazolyl, oxazolyl, etc.

[0015] Preferably, W is selected from at least one of the structures shown in the following formula (6), and * represents the access site:

[0016]

[0017] In formula (6), R2, R3, R4, R5, R6, R7, R8, R9 are each independently selected from at least one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, and an ester group. Among them, the hydrocarbon group having 1 to 10 carbon atoms can be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., can be a cycloalkyl group such as cyclopentyl, cyclohexyl, etc., can be an aromatic group such as phenyl, tolyl, etc., can be an aralkyl group such as benzyl, phenethyl, phenylpropyl, etc., and can also be an unsaturated alkenyl group such as vinyl, allyl, butenyl, propenyl, isopropenyl, styrenyl, etc.

[0018] Preferably, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group having 1 to 5 carbon atoms, and an ester group. More preferably, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen atom, a saturated alkyl group having 1 to 3 carbon atoms, and a carboxyl group having 1 to 5 carbon atoms. Even more preferably, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently selected from a hydrogen atom, a methyl group, an ethyl group, and a carboxyl group.

[0019] Furthermore, the nitrogen-containing heterocyclic polysiloxane can be used alone or in combination of two or more. It has a significant promoting effect on the dielectric properties and adhesion of the polybenzoxazole precursor, polybenzoxazole heat-resistant resin, and the substrate.

[0020] Furthermore, the preparation method of the nitrogen-containing heterocyclic polysiloxane includes the following steps:

[0021] Step 1: Under gas protection, an organic solvent, a nitrogen-containing heterocyclic silane coupling agent monomer, and a catalyst are stirred and mixed evenly.

[0022] Step 2: The temperature of the mixture in Step 1 is controlled at 0 to 40 °C, water is added dropwise thereto, after dropping, the mixture is kept at a constant temperature for reaction, and then the temperature is raised to 50 to 100 °C for continuous reaction.

[0023] Step 3: After the reaction, the organic layer is separated, and the volatile matter is removed by distillation to obtain the polysiloxane.

[0024] Furthermore, in Step 1, the nitrogen-containing heterocyclic silane coupling agent monomer is selected from at least one of the structures shown in the following formula (7):

[0025]

[0026] In formula (7), the definitions of R1 and W are the same as those defined above.

[0027] In formula (7), R 10 is selected from a hydrocarbon group having 1 to 10 carbon atoms. Among them, the hydrocarbon group having 1 to 10 carbon atoms can be an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc., can also be a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, etc., can also be an aromatic group such as a phenyl group, a tolyl group, etc., can also be an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, etc., and can also be an unsaturated alkenyl group such as a vinyl group, an allyl group, a butenyl group, a propenyl group, an isopropenyl group, a styryl group, etc. Preferably, R 10 is a saturated alkyl group having 1 to 10 carbon atoms, and more preferably, R 10 is a methyl group or an ethyl group.

[0028] Furthermore, the preparation method of the nitrogen-containing heterocyclic silane coupling agent monomer shown in formula (7) is:

[0029] Category 1: Amido acid nitrogen-containing heterocyclic silane coupling agent monomers:

[0030] Mix the nitrogen-containing heterocyclic monoamine H with a solvent, and then slowly add the silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in an amount of one molar equivalent of the nitrogen-containing heterocyclic monoamine H. After the addition is complete, continue the reaction at 23-26 °C for 20-22 hr. After the reaction is complete, perform vacuum distillation and purification to obtain the amido acid nitrogen-containing heterocyclic silane coupling agent monomer.

[0031] Category 2: Imide nitrogen-containing heterocyclic silane coupling agent monomers:

[0032] Mix the nitrogen-containing heterocyclic monoamine H with a solvent, and then slowly add the silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in an amount of one molar equivalent of the nitrogen-containing heterocyclic monoamine H. After the addition is complete, continue the reaction at 23-26 °C for 20-22 hr. Then, add a base and an acid anhydride to the reaction system for imidization. After the reaction is complete, perform vacuum distillation to remove the solvent, unreacted raw materials, and by-products in the system to obtain the imide nitrogen-containing heterocyclic silane coupling agent monomer.

[0033] Category 3: Amido ester nitrogen-containing heterocyclic silane coupling agent monomers:

[0034] Mix the nitrogen-containing heterocyclic monoamine H with a solvent, and then slowly add the silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in an amount of one molar equivalent of the nitrogen-containing heterocyclic monoamine H. After the addition is complete, continue the reaction at 23-26 °C for 20-22 hr. Then, add an esterification reagent (such as N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, etc.) to the system for esterification reaction. After the reaction is complete, perform vacuum distillation to obtain the amido ester nitrogen-containing heterocyclic silane coupling agent monomer.

[0035] Among them, the nitrogen-containing heterocyclic monoamine H is selected from at least one of the structures shown in the following formula (8):

[0036]

[0037] In the above formula (8), the definitions of R2, R3, R4, R5, R6, R7, R8, and R9 are the same as the above definitions.

[0038] Optionally, in step 1, the organic solvent is at least one of hydrocarbons, ketones, esters, ethers, alcohols, etc. Examples of the hydrocarbons include toluene, xylene, etc.; examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc.; examples of the esters include ethyl acetate, n-butyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; examples of the ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc. The organic solvents are preferably those that are immiscible with water, and these organic solvents can be used alone or in combination of two or more.

[0039] Optionally, in step 1, the catalyst can be one of acids, alkali metal compounds, organic bases, etc. Examples of the acids include hydrochloric acid, p-toluenesulfonic acid, etc.; examples of the alkali metal compounds include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc.; examples of the organic bases include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole, etc.; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc.; quaternary organic amines such as tetramethylammonium hydroxide, etc. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and tetramethylammonium hydroxide are preferred.

[0040] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the organic solvent is 1:0.25 - 10, such as 1:0.25, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and preferably 1:1 - 5.

[0041] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the catalyst is 1:0.001 - 0.1, such as 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, and preferably 1:0.005 - 0.05.

[0042] Optionally, in step 2, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to water is 1:0.5 to 25, such as 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, preferably 1:1 to 10.

[0043] Optionally, in step 2, the dropping time of water is 0.5 to 5 h, such as 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h.

[0044] Optionally, in step 2, water is dropped at 0 to 40 °C, and this temperature can be 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C. After dropping water, keep the temperature for reaction for 3 to 6 h, such as 3 h, 4 h, 5 h, 6 h. After the reaction, continue to raise the temperature to 50 to 100 °C, such as 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, and keep the temperature for reaction for 6 to 12 h, such as 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h at this temperature.

[0045] Furthermore, in the above photosensitive resin composition, the resin is a resin with a polybenzoxazole precursor structure and a polybenzoxazole structure as the main components. The polybenzoxazole precursor structure is selected from at least one of the polymers with the structural formula shown in the following formula (9), and the polybenzoxazole structure is selected from at least one of the polymers with the structural formula shown in the following formula (10):

[0046]

[0047]

[0048] In formula (9) and formula (10), i1 and i2 each independently selected from integers of 2 to 200, such as 2, 5, 10, 30, 50, 80, 100, 120, 150, 180, 200, etc.

[0049] In formula (9) and formula (10), X1 and X2 each independently selected from tetravalent organic groups with 4 to 40 carbon atoms.

[0050] Optionally, X1 and X2 each independently selected from organic groups with 6 or more carbon atoms containing an aromatic ring;

[0051] Optionally, X1 and X2 each independently selected from at least one of the structures shown in formula (11), * represents the access site:

[0052]

[0053] In Formula (9) and Formula (10), Y1 and Y2 are each independently selected from divalent organic groups having 2 to 40 carbon atoms.

[0054] Optionally, Y1 and Y2 are each independently selected from aromatic groups having 6 or more carbon atoms.

[0055] Optionally, Y1 and Y2 are each independently selected from at least one of the structures shown in Formula (12), where * represents the attachment site:

[0056]

[0057] Furthermore, the resin of the present invention is selected from resins having a polybenzoxazole precursor structure or a polybenzoxazole structure as the main component, and other resins may also be included as needed.

[0058] Optionally, in all the structural units of the resin, more than 50 mol% of the structures are structural units represented by Formula (9) or Formula (10), such as 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, preferably, more than 70 mol% is contained, and more preferably, more than 90 mol% is contained.

[0059] The polybenzoxazole precursor of the present invention can be obtained by a condensation reaction or the like of a bis-aminophenol compound and a dicarboxylic acid or a diacyl chloride with any structure in the presence of a dehydrating agent such as polyphosphoric acid or dicyclohexylcarbodiimide by the acyl chloride method or the activated ester method.

[0060] The polybenzoxazole of the present invention can be obtained by dehydrative cyclization of any polybenzoxazole precursor by a chemical method or a physical method.

[0061] Optionally, representative examples of the bis-aminophenol compound include: 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis(4-amino-3-hydroxyphenyl)propane, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2'-bis(3-amino-4-hydroxy-2-trifluoromethyl)propane, 2,2'-bis(4-amino-3-hydroxy-2-trifluoromethyl)propane, 2,2'-bis(3-amino-4-hydroxy-5-trifluoromethyl)propane, 2,2'-bis(4-amino-3-hydroxy-5-trifluoromethyl)propane, 2,2'-bis(3-amino-4-hydroxy-6-trifluoromethyl)propane, 2,2'-bis(4-amino-3-hydroxy-6-trifluoromethyl)propane, 2,2'-bis(3-amino-4-hydroxy-2-trifluoromethyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-2-trifluoromethyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxy-5-trifluoromethyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-5-trifluoromethyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxy-6-trifluoromethyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-6-trifluoromethyl)hexafluoropropane, 3,3'-diamino-4,4'-dihydroxy-2,2'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-2,2'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-trifluoromethylbiphenyl, and the like.

[0062] Optionally, examples of the dicarboxylic acid and the diacyl chloride include isophthaloyl chloride, terephthaloyl chloride, 4,4'-diphenylether dicarbonyl chloride, isophthalic acid, terephthalic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-biphenyl dicarbonyl chloride, and the like.

[0063] In the present invention, from the perspective of improving storage stability, it is desirable to cap the terminal groups. When capping, derivatives including aliphatic groups or cyclic compound groups having at least one alkenyl or alkynyl group can be introduced at the terminals of the polybenzoxazole precursor or polybenzoxazole as acid derivatives or amine derivatives.

[0064] After the condensation reaction is completed, if necessary, the by-products of the dehydrating condensing agent in the reaction solution are filtered out, and then the reaction solution is poured into a poor solvent such as water, lower aliphatic alcohols, or their mixture to precipitate the polymer. If necessary, operations such as re-dissolution and re-precipitation are repeated to purify the polymer, and then vacuum drying is carried out to obtain the precursor. In order to improve the polymer purity, the polymer solution can also be passed through an anion and cation exchange resin-packed column infiltrated with a suitable organic solvent to remove ionic impurities.

[0065] From the perspective of heat resistance and mechanical properties after heat treatment, the weight-average molecular weight (Mw) of the above resin, based on the polystyrene conversion value measured by gel permeation chromatography (GPC), is preferably 1000 or more, more preferably 5000 or more. From the perspective of the solubility of the photosensitive resin composition in the developer, the weight-average molecular weight of the above resin is preferably 60000 or less, more preferably 40000 or less. As the eluent for gel permeation chromatography, N-methyl-pyrrolidone or tetrahydrofuran is recommended. The molecular weight is determined from the standard curve made using standard monodisperse polystyrene.

[0066] Optionally, the weight-average molecular weight of the resin is 10000 to 40000, such as 10000, 12000, 15000, 18000, 20000, 21000, 22000, 23000, 24000, 25000, 28000, 30000, 32000, 35000, 38000, 40000.

[0067] Optionally, the weight-average molecular weight of the resin is 15000 to 30000.

[0068] Optionally, the weight-average molecular weight of the resin is 15000 to 25000.

[0069] Optionally, the weight-average molecular weight of the resin is 21000 to 25000.

[0070] Furthermore, in the above photosensitive resin composition, the silane coupling agent includes at least one of a nitrogen-containing heterocyclic group silane coupling agent, a ureido silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, and an epoxy group-containing silane coupling agent.

[0071] It can be exemplified that the nitrogen-containing heterocyclic group coupling agent can be selected from at least one of the structural formulas of formula (13-1), formula (13-2), and formula (13-3):

[0072]

[0073]

[0074]

[0075] It can be listed that the ureido silane coupling agent can be selected from 3-ureidopropyltriethoxysilane (Nanjing Xuanhao New Materials Technology Co., Ltd., XH-1160), 3-ureidopropyltrimethoxysilane (Nanjing Dimont, DMT-116), 1-propyl-1-(triethoxysilyl)methylurea (Nanjing Xuanhao New Materials Technology Co., Ltd., XH-712), etc., or at least one of the structural formulas of the following formula (14):

[0076]

[0077] The ureido silane coupling agent with the structure of formula (14) can be prepared by referring to Patent CN111825884B.

[0078] It can be cited that the epoxy group-containing silane coupling agent can be selected from (3-glycidoxypropyl)trimethoxysilane (KH-560), (8-glycidoxyoctyl)trimethoxysilane (Shin-Etsu Chemical Co., Ltd., Japan, KBM-4803), (3-glycidoxypropyl)trimethoxysilane (Shin-Etsu Chemical Co., Ltd., Japan, KBM-403), etc.

[0079] It can be cited that the mercapto group-containing silane coupling agent can be selected from 3-(triethoxysilylthio)propyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., Japan, X-12-1056ES), 3-(trimethoxysilyl)-1-propanethiol (Momentive Performance Materials Inc., A-189), γ-mercaptopropyltriethoxysilane (Nanjing Xuanhao New Materials Technology Co., Ltd., KH-580), etc.;

[0080] It can be cited that the vinyl silane coupling agent can be selected from vinyltriethoxysilane (Nanjing Dimont, KH-151), p-vinylphenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., Japan, KBM-1403), etc., but not limited to these.

[0081] Through experimental verification, the preferred silane coupling agent is one or two of the nitrogen-containing heterocyclic group-containing silane coupling agent and the mercapto group-containing silane coupling agent. More preferably, the nitrogen-containing heterocyclic group-containing silane coupling agent and the mercapto group-containing silane coupling agent are used in combination. At least one of the nitrogen-containing heterocyclic group-containing silane coupling agent can be selected, and at least one of the mercapto group-containing silane coupling agent can also be selected.

[0082] Furthermore, in the above photosensitive resin composition, the photosensitizer is selected from at least one of diazoquinone compounds, onium salts, and halogen-containing compounds. From the viewpoints of solvent solubility and storage stability, an ester compound obtained by bonding a quinone diazide sulfonic acid to a polyhydroxy compound through an ester bond is preferred. Examples of the polyhydroxy compound include, but are not limited to, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxy-p-cresol, 2,6-diacetoxymethyl-p-cresol, tetrahydroxybenzophenone, etc. Commercially available quinone diazide compounds are preferred objects. For example, NT-300 (esterification reaction product of 2,3,4-trihydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), 4NT-350, 4NT-300 (esterification reaction product of 2,3,4,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), tris(4-hydroxyphenyl)ethane (HP-190) and (esterification reaction product of 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid) (manufactured by Toyo Gosei Co., Ltd., Japan).

[0083] Furthermore, in the above photosensitive resin composition, the crosslinking agent includes at least one of DMOM-PTBP-MF, TMOM-BP, HMOM-TPHAP, DML-PC, DMOM-MBPC, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), MX-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.); it can undergo a polymerization reaction or the addition-polymerizable compound itself undergoes a polymerization reaction to form a crosslinked network structure. The addition-polymerizable compound can further improve the heat resistance and chemical resistance of the cured film formed by the photosensitive resin composition.

[0084] Furthermore, in the above photosensitive resin composition, the solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol diethylmethyl ether.

[0085] Furthermore, the mass ratio of the resin to the nitrogen-containing heterocyclic polysiloxane is 100:0.01 to 10, for example, 100:0.01, 100:0.03, 100:0.05, 100:0.08, 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6,

[0086] Any value among 100:7, 100:8, 100:9, 100:10 or a range value between any two of them.

[0087] Optionally, the mass ratio of the resin to the polysiloxane containing a nitrogen heterocycle is 100:0.1 to 5.

[0088] Optionally, the mass ratio of the resin to the polysiloxane containing a nitrogen heterocycle is 100:1 to 5.

[0089] Furthermore, the mass ratio of the resin to the silane coupling agent is 100:0.1 to 5, such as any value among 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5 or a range value between any two of them.

[0090] Optionally, the mass ratio of the resin to the silane coupling agent is 100:1 to 5.

[0091] Furthermore, the mass ratio of the resin to the photosensitive aid is 100:0.1 to 30, such as any value among 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28,

[0092] Any value among 100:29, 100:30 or a range value between any two of them.

[0093] Optionally, the mass ratio of the resin to the photosensitive aid is 100:0.5 to 25.

[0094] Optionally, the mass ratio of the resin to the photosensitive aid is 100:0.5 to 20.

[0095] Further, the mass ratio of the resin to the crosslinking agent is 100:0.5 to 30, such as any value among 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28, 100:29, 100:30 or the range value between any two of them.

[0096] Optionally, the mass ratio of the resin to the crosslinking agent is 100:1 to 20.

[0097] Further, the mass ratio of the resin to the solvent is 100:80 to 5000, such as any value among 100:80, 100:100, 100:130, 100:150, 100:180, 100:200, 100:230, 100:250, 100:280, 100:300, 100:330, 100:350, 100:380, 100:400, 100:500, 100:600, 100:700, 100:800, 100:900, 100:1000, 100:1500, 100:2000, 100:2500, 100:3000, 100:3500, 100:4000, 100:4500, 100:5000 or the range value between any two of them.

[0098] Optionally, the mass ratio of the resin to the solvent is 100:100 to 1000.

[0099] Optionally, the mass ratio of the resin to the solvent is 100:150 to 400.

[0100] According to another aspect of the present application, a preparation method of the above photosensitive resin composition is provided, which at least includes the following steps:

[0101] Mix the resin, the polysiloxane containing nitrogen heterocycle, the silane coupling agent, the photosensitive auxiliary agent, the crosslinking agent and the solvent to obtain the photosensitive resin composition.

[0102] Optionally, specifically including:

[0103] In a three-necked flask equipped with stirring, dissolve the resin in a solvent, add a polysiloxane containing a nitrogen heterocycle and a silane coupling agent, and continue stirring until completely dissolved. Then, sequentially add a photosensitive aid and a crosslinking agent, continue stirring and dissolving, and then perform pressure filtration (filter with a filter having a pore size of 0.1 μm to 5 μm) to obtain the photosensitive resin composition.

[0104] According to another aspect of the present application, a resin cured film is provided, which is obtained by curing the above-mentioned photosensitive resin composition.

[0105] According to another aspect of the present application, a method for preparing the above-mentioned resin cured film is provided, which at least includes the following steps:

[0106] Coat the photosensitive resin composition on the surface of a substrate, and perform heat treatment in an inert gas atmosphere to obtain the resin cured film.

[0107] Specifically, it includes the following steps:

[0108] Coat the photosensitive resin composition on a 4-inch substrate by a spin coater, then perform soft baking at 120 °C for 3 minutes using a hot plate, and then place the prepared resin cured film in a vacuum and oxygen-free oven to keep nitrogen flowing for heat treatment. Specifically as follows: After ensuring that the oxygen content in the oven cavity is reduced to below 50 ppm, first raise the temperature to 170 °C and keep it constant for 30 minutes, then, after 1 hour, raise the temperature to 350 °C, and treat it at 350 °C for 1 hour to obtain the resin cured film.

[0109] The resin cured film shows excellent adhesion to the substrate in the PCT experiment.

[0110] Substrates such as: copper sheets, copper alloy sheets, silicon wafers, ceramic sheets, titanium sheets, glass sheets, ITO glasses, etc., but not limited thereto. As coating methods, the following can be cited: spraying method, spin coating method, knife coating method and other coating methods. Among them, due to differences in coating methods, rotation speeds, viscosities, composition components, etc., the coating film thickness will also vary. In the present invention, it is preferred to use a 4-inch copper sheet as the substrate for coating the film, and it is preferred to use the spin coating method for coating, and control the thickness of the cured film on the copper sheet to be 10 to 20 μm.

[0111] Subsequently, heat treatment is performed on the substrate coated with the photosensitive resin composition to obtain the resin cured film. The heat treatment method is usually an oven, a hot plate, an infrared lamp, etc. It is preferred to use a hot plate, and it is preferred to perform drying in the range of 50 to 150 °C for 1 minute to 1 hour, and measure the thickness of the cured film after natural cooling to 25 °C. It is preferred to perform drying at a temperature of 100 to 130 °C for 2 to 5 minutes.

[0112] According to another aspect of the present application, there is provided an application of the above photosensitive resin composition or resin cured film as a semiconductor interlayer insulating film, a protective film for a semiconductor, and a protective film for etching.

[0113] According to another aspect of the present application, there is provided a semiconductor device containing the above resin cured film.

[0114] According to another aspect of the present application, there is provided a method for preparing the above semiconductor device, which at least includes the following steps:

[0115] Coat the photosensitive resin composition on the surface of the substrate, and obtain a resin cured film through treatment. Expose, develop, and heat-treat the resin cured film to obtain the semiconductor device.

[0116] Specifically, it includes the following steps:

[0117] (1) Coat the photosensitive resin composition on the substrate to form a photosensitive resin layer on the substrate;

[0118] (2) Expose the photosensitive resin layer;

[0119] (3) Develop the exposed photosensitive resin layer to form a relief pattern;

[0120] (4) Heat-treat the relief pattern to form a cured relief pattern and obtain the semiconductor device.

[0121] Among them, the substrate includes silicon, copper, copper alloy, titanium, titanium alloy, and aluminum.

[0122] The preparation method of the photosensitive resin layer in step (1) is the same as the preparation method of the above resin cured film.

[0123] The exposure treatment is to place the above resin cured film under a photomask or mask with a pattern or directly under a mask plate with a desired pattern for the formed resin film, and perform exposure treatment using ultraviolet rays, X-rays, electron beams, etc. Common actinic rays include ultraviolet rays, X-rays, electron beams, etc. In the present invention, a mercury lamp is preferably used, which includes i-line (365 nm), h-line (405 nm), and g-line (436 nm).

[0124] In order to improve the sensitivity, etc., if necessary, post-exposure baking and / or pre-development baking based on any combination of temperature and time can be carried out. The baking conditions are a temperature of 40 to 120 °C and a time of 10 to 240 seconds. As long as the characteristics of the photosensitive resin composition of the present invention are not affected, it is not limited by this range.

[0125] After exposure, a pattern is formed by removing the unexposed part using a developer. Common developers include: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, isopropanol, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, isobutyl ketone, aqueous solution of tetramethylammonium hydroxide, etc. After development, it is preferably rinsed with deionized water, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, etc. For example, pour the developer and the rinsing solution into two glass petri dishes respectively. Control the temperature of the developer at 25 ± 1 °C, immerse the exposed resin film into the developer, and then start timing. When the unexposed part is completely exposed to the substrate, the development ends, stop timing, and record the time required for the whole process.

[0126] Finally, the resin pattern obtained after development is subjected to thermal imidization at 200 - 500 °C to convert it into a cured film. This heat treatment usually selects stepwise temperature increase and maintains a certain time at different temperatures or selects a certain temperature range for continuous temperature increase. For example, a heat treatment method of performing heat treatment at 180 °C, 240 °C, and 350 °C for 30 minutes respectively, or a method of linearly increasing the temperature from 25 °C to 400 °C over 2 hours, etc.

[0127] The cured relief pattern can be used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

[0128] The beneficial effects that this application can produce include:

[0129] The photosensitive resin composition provided by this application, by introducing a nitrogen-containing heterocyclic polysiloxane into the photosensitive resin composition, makes the resin cured film made from the photosensitive resin composition have excellent dielectric properties and excellent adhesion to the substrate. The cured film formed by this photosensitive resin composition can be used for semiconductor interlayer insulating films, protective films for semiconductors, and protective films for etching, and has broad application prospects in semiconductor-related fields. Description of the Drawings

[0130] Figure 1 Infrared spectra of polysiloxanes PS-11, PS-17, PS-19, and PS-20. Detailed Description of the Embodiments

[0131] The technical solutions of the present invention will be described clearly and completely below. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0132] The following are several specific synthesis examples and implementation examples to illustrate the present invention, which helps those of ordinary skill in the art to more comprehensively understand the present invention. However, the present invention is not limited to these examples. It should be noted that the evaluation of the products prepared in the following synthesis examples and implementation examples is carried out according to the following methods.

[0133] (1) Infrared spectrum test

[0134] The synthesized polysiloxane sample was tested by the KBr tablet method using an infrared spectrometer (Shimadzu, IRAffinity-1S) to detect whether the polysiloxane in the present invention was successfully prepared.

[0135] (2) Molecular weight test

[0136] The weight-average molecular weight (Mw) of the resin was determined by gel permeation chromatography (standard polystyrene conversion). The gel permeation chromatograph used in the determination was LC-20AD of Shimadzu Corporation, Japan, the chromatographic column was KF-804 of Showa Denko, and the detector was differential RID-20A of Shimadzu Corporation, Japan. The mobile phase was N-methylpyrrolidone (NMP).

[0137] (3) Viscosity test

[0138] Take 0.5 mL of the resin composition sample and put it into the sample cell of a rotational viscometer (BROOKFIELD DV2T RV). Select an appropriate range, control the temperature at 25 ± 0.1 °C, and conduct a viscosity test.

[0139] (4) Adhesion peel test of the cured film with different substrates

[0140] The resin composition sample was uniformly coated onto a silicon wafer and an aluminum sheet respectively using a spin coater, and then placed on a heating table at 120 °C for 3 minutes of soft baking to obtain a resin film with a film thickness of 10 - 20 μm. Use a scribing tool (BYK-Gardner A-5125) to scribe the resin film into a grid of 10 rows × 10 columns, and then place the film in a vacuum and oxygen-free oven (MOLZK-32D1) for heat treatment: heat treatment at 170 °C for 30 minutes, then heat up to 350 °C over 1 hour, and treat at 350 °C for 1 hour to finally obtain a cured film. Place the cured film in a PCT test chamber for a 400-hour PCT aging test (121 °C, 2 atmospheric pressures of saturated steam; Dongguan Hongjin Technology PCT-30). After the PCT test is completed, use a tape (special transparent 3M tape) to conduct a peel test with reference to the cross-cut test of the paint film in the national standard GB / T 9286-1998, and record the number of peeled grids as the peeling situation after the PCT test.

[0141] When the number of peeled-off pieces in the adhesion peeling experiment is less than 5, it is regarded as "optimal"; when it is less than 10, it is regarded as "good"; when it is less than 30, it is regarded as "slightly good"; when it is greater than or equal to 30, it is regarded as "poor".

[0142] (5) Dielectric constant

[0143] Refer to the national standard GB / T 31838.6-2021 Dielectric and resistive properties of solid insulating materials, and use the DMS2000 high and low temperature dielectric impedance temperature spectrum analyzer to measure the dielectric constant at 25°C, and record the value at a frequency of 1 MHz.

[0144] The abbreviations of the components used in this application are as follows:[[]]END]]

[0145] NMP: N-methylpyrrolidone

[0146] MIBK: Methyl isobutyl ketone

[0147] ODPA: 4,4'-Oxydiphthalic anhydride

[0148]

[0149] BAHF: 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane Silane coupling agent SCA:

[0150] SCA-1:

[0151]

[0152] SCA-2:

[0153]

[0154] SCA-3:

[0155]

[0156] SCA-4:

[0157]

[0158] SCA-5:

[0159]

[0160] SCA-6:

[0161]

[0162] SCA-7:

[0163]

[0164] SCA-8:

[0165]

[0166] SCA-9:

[0167]

[0168] SCA-10:

[0169]

[0170] SCA-11:

[0171]

[0172] SCA-12:

[0173]

[0174] SCA-13:

[0175]

[0176] SCA-14:

[0177]

[0178] SCA-15:

[0179]

[0180] SCA-16:

[0181]

[0182] SCA-17:

[0183]

[0184] SCA-18:

[0185]

[0186] SCA-19:

[0187]

[0188] SCA-20:

[0189]

[0190] SCA-21:

[0191]

[0192] Preparation of silane coupling agents SCA-1 to SCA-21:

[0193] Preparation of SCA-1:

[0194] Into a 500 mL three-necked flask equipped with a stirrer and a thermometer, sequentially add 250.00 g of the solvent N-methylpyrrolidone and 0.1 mol of 4-aminotriazole. Start stirring. After 4-aminotriazole is fully dissolved, slowly add 0.1 mol of the silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride. After the addition is complete, continue the reaction at 25 °C for 20 hr. After the reaction is completed, perform vacuum distillation purification to obtain SCA-1.

[0195] Preparation of SCA-2:

[0196] Into a 500 mL three-necked flask equipped with a stirrer and a thermometer, sequentially add 250.00 g of the solvent N-methylpyrrolidone and 0.1 mol of 4-aminotriazole. Start stirring. After 4-aminotriazole is fully dissolved, slowly add 0.1 mol of the silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride. After the addition is complete, continue the reaction at 25 °C for 20 hr. Then add 0.2 mol of pyridine to the reaction system, stir evenly, and slowly add 0.2 mol of acetic anhydride. React at 25 °C for 20 hr. After the reaction is completed, perform vacuum distillation to remove the solvent, acetic anhydride, and the generated acetic acid and pyridine in the system to obtain SCA-2.

[0197] Preparation of SCA-3:

[0198] Except that 0.1 mol of 3-(trimethoxysilyl)propyl succinic anhydride is replaced with 0.1 mol of the silane coupling agent SANAH (Shin-Etsu Chemical Co., Ltd.), the others are the same as SCA-1.

[0199] Preparation of SCA-4:

[0200] Except that 0.1 mol of 3-(trimethoxysilyl)propyl succinic anhydride is replaced with 0.1 mol of the silane coupling agent SANAH, the others are the same as SCA-2.

[0201] Preparation of SCA-5:

[0202] Except that 0.1 mol of 4-aminotriazole is replaced with 0.1 mol of 3-amino-1,2,4-triazole, the others are the same as SCA-1.

[0203] Preparation of SCA-6:

[0204] Except that 0.1 mol of 4-aminotriazole is replaced with 0.1 mol of 5-amino-1H-1,2,4-triazole-3-carboxylic acid, the others are the same as SCA-1.

[0205] Preparation of SCA-7:

[0206] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 5-aminotetrazole, the others are the same as SCA-1.

[0207] Preparation of SCA-8:

[0208] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 5-aminotetrazole, the others are the same as SCA-2.

[0209] Preparation of SCA-9:

[0210] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 5-aminotetrazole, the others are the same as SCA-3.

[0211] Preparation of SCA-10:

[0212] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 5-aminotetrazole, the others are the same as SCA-4.

[0213] Preparation of SCA-11:

[0214] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 1-methyl-5-aminotetrazole, the others are the same as SCA-1.

[0215] Preparation of SCA-12:

[0216] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 2-aminoimidazole, the others are the same as SCA-1.

[0217] Preparation of SCA-13:

[0218] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 2-aminoimidazole, the others are the same as SCA-3.

[0219] Preparation of SCA-14:

[0220] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 2-aminooxazole, the others are the same as SCA-1.

[0221] Preparation of SCA-15:

[0222] Except for replacing 0.1 mol of 4-aminotriazole with 0.1 mol of 2-aminooxazole, the others are the same as SCA-3.

[0223] Preparation of SCA-16:

[0224] To a 500 mL three-necked flask equipped with a stirrer and a thermometer, 250.00 g of the solvent N-methylpyrrolidone and 0.1 mol of 2-aminoimidazole were successively added. Stirring was started. After 2-aminoimidazole was completely dissolved, 0.1 mol of the silane coupling agent SANAH was slowly added. After the addition was completed, the reaction was continued at 25 °C for 20 h. Then, 0.2 mol of N,N-dimethylformamide dimethyl acetal was added to the system, and the reaction was continued at 25 °C for 4 h. After the reaction was completed, distillation under reduced pressure was carried out to obtain SCA-16.

[0225] Preparation of SCA-17:

[0226] Except that 0.1 mol of 2-aminoimidazole was replaced with 0.1 mol of 2-aminooxazole, the others were the same as SCA-16.

[0227] Preparation of SCA-18:

[0228] Except that 0.1 mol of 4-aminotriazole was replaced with 0.1 mol of 3-aminophenol, the others were the same as SCA-1.

[0229] Preparation of SCA-19:

[0230] Except that 0.1 mol of 4-aminotriazole was replaced with 0.1 mol of p-aminobenzoic acid, the others were the same as SCA-1.

[0231] Preparation of SCA-20:

[0232] SCA-20 was prepared according to the method of Example 3 in Patent ZL202111145299.6.

[0233] Preparation of SCA-21:

[0234] SCA-21 was prepared according to the method of Example 2 in Patent ZL202111145299.6.

[0235] The silane coupling agent was characterized by 1H NMR, and some of the 1H NMR information is as follows:

[0236]

[0237]

[0238] Synthesis Example 1

[0239] Under nitrogen protection, 100 g of methyl isobutyl ketone (MIBK), 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1, and 0.5 g of p-toluenesulfonic acid were added to a 250 ml three-necked flask, stirred and mixed evenly, and the system temperature was maintained at 10 °C (reaction temperature 1) to obtain a mixed solution; 150 g of deionized water was added dropwise to the above mixed solution within 4 h. After the addition was completed, the mixture was kept at 10 °C for reaction for 4 h, then heated to 70 °C (reaction temperature 2), and the reaction was continued for 10 h; after the reaction was completed, the organic layer was taken out, and the volatile substances in the organic layer were evaporated by a rotary evaporator to obtain polysiloxane PS-1.

[0240] Synthesis Example 2-23

[0241] Referring to the steps of Synthesis Example 1, polysiloxanes PS-2 to PS-23 were synthesized. The difference was that the reaction conditions used were selected according to Table 1 below.

[0242] Table 1

[0243]

[0244]

[0245] Using an infrared spectrometer (Shimadzu, IRAffinity-1S), the synthesized polysiloxane samples were tested by the KBr tablet method to detect whether the polysiloxane in the present invention was successfully prepared. From the infrared characterization results, it can be seen that the stretching vibration peak of Si-O-Si appears at 1035-1160 cm -1 indicating that the alkoxy group has been successfully transformed into the Si-O-Si structure by hydrolysis. Among them, the infrared spectra of PS-11, PS-17, PS-19, and PS-20 are as shown in Figure 1 shown.

[0246] Synthesis Comparative Example 1

[0247] Polysiloxane PS-24 was prepared according to the method of Synthesis Example 1, except that 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 20 g of silane coupling agent monomer SCA-18.

[0248] Synthesis Comparative Example 2

[0249] Polysiloxane PS-25 was prepared according to the method of Synthesis Example 1, except that 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 20 g of silane coupling agent monomer SCA-19.

[0250] Synthesis Example 24

[0251] Synthesis of polybenzoxazole precursor C-1:

[0252] Under a nitrogen stream, 36.63 g (0.10 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 100.00 g of N-methylpyrrolidone (NMP), and 52.87 g (0.6 mol) of glycidyl methyl ether were added to a 500 ml three-necked flask. After complete dissolution, the temperature of the solution was cooled to -15°C. A solution prepared by dissolving 29.51 g (0.10 mol) of 4,4'-diphenylether dicarbonyl chloride in 50.00 g of N-methylpyrrolidone was added dropwise to the flask, and the reaction materials were controlled below 0°C during the dropping process. After the dropping was completed, the reaction was continued to stir for 6 hours at -10 to -15°C, and the reaction ended. The reaction solution was poured into 3 L of 10 wt% methanol aqueous solution to precipitate a polymer to obtain a white precipitate. After filtration, it was washed three times with deionized water and placed in a vacuum oven for drying at 50°C for 72 h to obtain the polybenzoxazole precursor resin C-1. The molecular weight of the polymer powder was measured by gel permeation chromatography (standard polystyrene conversion), and the result showed that the weight-average molecular weight (Mw) was 21,000 - 25,000.

[0253] Synthesis Example 25

[0254] Synthesis of polybenzoxazole precursor C-2:

[0255] Under a nitrogen stream, 36.63 g (0.10 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 100.00 g of N-methylpyrrolidone (NMP), and 52.87 g (0.6 mol) of glycidyl methyl ether were added to a 500 ml three-necked flask. After complete dissolution, the temperature of the solution was cooled to -15°C. A solution prepared by dissolving 27.91 g (0.10 mol) of 4,4'-biphenyl dicarbonyl chloride in 50.00 g of N-methylpyrrolidone was added dropwise to the flask, and the reaction materials were controlled below 0°C during the dropping process. After the dropping was completed, the reaction was continued to stir for 6 hours at -10 to -15°C, and the reaction ended. The reaction solution was poured into 3 L of 10 wt% methanol aqueous solution to precipitate a polymer to obtain a white precipitate. After filtration, it was washed three times with deionized water and placed in a vacuum oven for drying at 50°C for 72 h to obtain the polybenzoxazole precursor resin C-2. The molecular weight of the polymer powder was measured by gel permeation chromatography (standard polystyrene conversion), and the result showed that the weight-average molecular weight (Mw) was 21,000 - 25,000.

[0256] Synthesis Example 26

[0257] Synthesis of polybenzoxazole C-3:

[0258] Under a nitrogen stream, 40 g of polybenzoxazole precursor C-1 was placed into a 500 mL three-necked flask, 100.00 g of NMP was added, and the mixture was stirred and dissolved at room temperature. Then, 22.46 g (0.22 mol) of acetic anhydride and 17.40 g (0.22 mol) of pyridine were added, and the reaction was carried out at 30 °C for 2 h.

[0259] The obtained reaction solution was added to 5 L of deionized water to precipitate a polymer. After filtering out the obtained precipitate, it was washed repeatedly with deionized water three times and dried under vacuum at 50 °C for 72 h to obtain a polymer powder, namely polybenzoxazole C-3. The molecular weight of the polymer powder was measured by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 21,000 - 25,000.

[0260] Examples and Comparative Examples

[0261] In a three-necked flask equipped with stirring, 25.00 g of the synthesized polybenzoxazole resin was dissolved in 60.00 g of N-methylpyrrolidone (NMP). After the resin was completely dissolved, polysiloxane and a silane coupling agent were added according to the ratio in Table 2, and stirring was continued until completely dissolved. Then, 4 g of a photosensitive auxiliary quinone diazide compound NT-300 (manufactured by Toyo Gosei Co., Ltd., Japan) and 2.00 g of a thermal crosslinking agent TMOM-BP (manufactured by Honshu Chemical Industry) were added in sequence. After complete dissolution, filtration was carried out using a 1.0 μm filter membrane to obtain photosensitive resin compositions P-1 to P-41, and the viscosity measured at 25 °C was 1800 - 2200 cP.

[0262] Table 2

[0263]

[0264]

[0265]

[0266] The above-prepared photosensitive resin compositions were evaluated according to the test method described above, and the results are shown in Table 3.

[0267] Table 3

[0268]

[0269]

[0270] It can be seen from the above table that:

[0271] From the experimental results of Example 1, Examples 11 to 33, Comparative Example 5, and Comparative Example 8, it can be seen that the polybenzoxazole photosensitive resin composition containing the nitrogen-containing heterocyclic polysiloxane compound of the present invention exhibits more excellent dielectric properties than those without addition, and at the same time, the adhesion on silicon and aluminum substrates also has an obvious improvement effect.

[0272] From the experimental results of Example 1 and Comparative Examples 1 to 2, it can be seen that the photosensitive composition containing the nitrogen-containing heterocyclic polysiloxane compound of the present invention has a more obvious improvement effect on adhesion and dielectric properties than the photosensitive composition containing a polysiloxane compound without a nitrogen-containing heterocyclic ring.

[0273] From the experimental results of Example 1 and Examples 4 to 8, it can be seen that in terms of the effect of improving the adhesion to the substrate, the combination of three types of additives, namely, the nitrogen-containing heterocyclic polysiloxane compound, the nitrogen-containing heterocyclic group silane coupling agent, and the mercapto silane coupling agent, shows the best performance.

[0274] From the experimental results of Example 1 and Examples 16 to 33, it can be seen that different types of nitrogen-containing heterocyclic polysiloxane compounds have slightly different improvement effects on adhesion and dielectric properties. Among them, oxazole and imidazole show better performance, and the mixed use of two different types of nitrogen-containing heterocyclic polysiloxane compounds shows the best performance.

[0275] As described above, only several embodiments of the present application are provided, and it does not impose any form of limitation on the present application. Although the present application is disclosed with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications by using the disclosed technical content within the scope of the technical solution of the present application, which are equivalent to equivalent embodiments and all belong to the scope of the technical solution.

Claims

1. A photosensitive resin composition, characterized in that, It includes a resin, a nitrogen-containing heterocyclic polysiloxane, a silane coupling agent, a photosensitive auxiliary, a crosslinking agent, and a solvent; the resin is selected from resins with polybenzoxazole precursor and / or polybenzoxazole as the main component; The nitrogen-containing heterocyclic polysiloxane is selected from at least one of the structural formulas shown in the following formula (1): Among them, Y is selected from at least one of the structures shown in formulas (2) to (5), and * represents the access site: (2)； (3)； (4)； (5)； Among them, R1 is a hydrogen atom or an alkyl group with 1 to 20 carbon atoms; among them, W is selected from at least one of the structures shown in the following formula (6), and * represents the access site: （6）； Among them, R2, R3, R4, R5, R6, R7, R8, and R9 each independently represent a hydrogen atom, a hydrocarbon group with 1 to 10 carbon atoms, a carboxyl group, or an ester group.

2. The photosensitive resin composition according to claim 1, characterized in that, R1 is selected from a hydrogen atom, a methyl group, an ethyl group, or a butyl group; R2, R3, R4, R5, R6, R7, R8, and R9 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a carboxyl group.

3. The photosensitive resin composition according to claim 1, characterized in that The resin is selected from resins with polybenzoxazole precursor and / or polybenzoxazole as the main component. The polybenzoxazole precursor is selected from at least one of the polymers with the structural formula shown in the following formula (9), and the polybenzoxazole is selected from at least one of the polymers with the structural formula shown in the following formula (10); Among them, i1 and i2 each independently are selected from integers from 2 to 200; X1 and X2 each independently are selected from tetravalent organic groups with 4 to 40 carbon atoms; Y1 and Y2 each independently are selected from divalent organic groups with 2 to 40 carbon atoms.

4. The photosensitive resin composition according to claim 3, characterized in that, The sum of the polybenzoxazole precursor and polybenzoxazole accounts for more than 50 mol% of the entire structure of the resin.

5. The photosensitive resin composition according to claim 3, wherein The sum of the polybenzoxazole precursor and polybenzoxazole accounts for more than 70 mol% of the entire structure of the resin.

6. The photosensitive resin composition according to claim 3, wherein, The sum of the polybenzoxazole precursor and polybenzoxazole accounts for more than 90 mol% of the entire structure of the resin.

7. The photosensitive resin composition according to claim 3, wherein The weight-average molecular weight of the resin is 10,000 to 40,000.

8. The photosensitive resin composition according to claim 3, wherein The weight-average molecular weight of the resin is 15,000 to 30,000.

9. The photosensitive resin composition according to claim 3, wherein The weight-average molecular weight of the resin is 15,000 to 25,000.

10. The photosensitive resin composition according to claim 3, wherein The weight-average molecular weight of the resin is 21,000 to 25,000.

11. The photosensitive resin composition according to claim 3, wherein X1 and X2 each independently are selected from at least one of the structures shown in formula (11), and * represents the access site: （11） Y1 and Y2 each independently are selected from at least one of the structures shown in formula (12), and * represents the access site: 。 12. The photosensitive resin composition according to claim 1, wherein The silane coupling agent is selected from at least one of a nitrogen-containing heterocyclic group silane coupling agent, a ureido silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, and an epoxy group silane coupling agent; The photosensitive auxiliary is selected from at least one of a diazoquinone compound, an onium salt, and a halogen-containing compound; The crosslinking agent is selected from at least one of DMOM-PTBP-MF, TMOM-BP, DML-PC, DMOM-MBPC, HMOM-TPHAP, and MX-100LM; The solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol diethylmethyl ether.

13. The photosensitive resin composition according to claim 12, wherein The silane coupling agent is a composition of a nitrogen-containing heterocyclic group silane coupling agent and a ureido silane coupling agent.

14. The photosensitive resin composition according to claim 3, wherein The mass ratio of the resin to the polysiloxane containing a nitrogen-containing heterocycle is 100:0.01 - 10; The mass ratio of the resin to the silane coupling agent is 100:0.1 - 5; The mass ratio of the resin to the photosensitive auxiliary agent is 100:0.1 - 30; The mass ratio of the resin to the crosslinking agent is 100:0.5 - 30; The mass ratio of the resin to the solvent is 100:80 - 5000.

15. The photosensitive resin composition according to claim 14, characterized in that, The mass ratio of the resin to the polysiloxane containing a nitrogen-containing heterocycle is 100:0.1 - 5.

16. The photosensitive resin composition according to claim 14, wherein The mass ratio of the resin to the polysiloxane containing a nitrogen-containing heterocycle is 100:1 - 5.

17. The photosensitive resin composition according to claim 14, wherein, The mass ratio of the resin to the silane coupling agent is 100:1 - 5.

18. The photosensitive resin composition according to claim 14, wherein, The mass ratio of the resin to the photosensitive auxiliary agent is 100:0.5 - 25.

19. The photosensitive resin composition according to claim 14, wherein The mass ratio of the resin to the photosensitive auxiliary agent is 100:0.5 - 20.

20. The photosensitive resin composition according to claim 14, wherein, The mass ratio of the resin to the crosslinking agent is 100:1 - 20.

21. The photosensitive resin composition according to claim 14, wherein The mass ratio of the resin to the solvent is 100:100 - 1000.

22. The photosensitive resin composition according to claim 14, wherein The mass ratio of the resin to the solvent is 100:150 - 400.

23. A resin curing film, characterized in that, It is obtained by curing the photosensitive resin composition according to any one of claims 1 - 22.

24. A semiconductor device, characterized in that, It includes the resin cured film according to claim 23.

25. Application of the resin cured film according to claim 23 as an interlayer insulating film of a semiconductor, a protective film of a semiconductor, and a protective film for etching.

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