JP2012222104A - Method for forming silica-based coating film, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a silica-based coating film by which a hardened material of a silica-based coating film which is excellent in adhesion and has electrically high reliability can be obtained.SOLUTION: The method for forming a silica-based coating film comprises the steps of: forming a coating film by applying, onto a substrate, a photosensitive resin composition which contains a siloxane resin resulting from hydrolysis condensation of a silane compound containing a compound expressed by the following general formula (1), at least one selected from the group consisting of a photoacid generating agent and a photobase generating agent, a solvent into which the siloxane resin can be dissolved, and an onium salt; exposing the coating film to light through a pattern mask; heating the coating film subsequent to the exposing step; removing, by development, an unexposed part of the coating film subsequent to the heating step; and irradiating the remaining coating film with ultraviolet light to form a silica-based coating film with a pattern, subsequent to the removing step.

Description

  The present invention relates to a method for forming a silica-based film and an electronic component.

In recent years, electronic parts such as LSIs and displays have been highly integrated and miniaturized. As insulating films used for these electronic components, SiO ₂ films formed by CVD methods, organic SOG (Spin On Glass) films and inorganic SOG films formed by coating methods are widely used. There is a demand for insulating materials with excellent efficiency and process resistance. Therefore, in order to achieve these requirements, a proposal has been made for an insulating film having a low dielectric constant and high process resistance by irradiating a film formed on the substrate with ultraviolet rays. For example, Patent Document 1 and Patent Document 2 is disclosed.

  However, it is impossible to directly form wiring trenches and via holes in conventional insulating films, and usually after patterning a photoresist on the insulating film, a dry etching process using plasma or a wet etching process using chemicals is performed. Next, a pattern is formed through a resist removal process and a cleaning process. In contrast, if photosensitive properties are imparted to an insulating film material that has excellent heat resistance, electrical reliability, etc., the resist material that is essential in the above process becomes unnecessary, and dry etching processing using plasma or wet etching using chemicals. It becomes possible to omit a process, a resist removal process, and a washing process.

  As such photosensitive polysiloxane material, for example, Patent Document 3 and Patent Document 4 are disclosed, and a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which water and a catalyst have been removed, a photoacid generator, and a solvent. Things have been proposed.

JP-A-6-283520 JP 2004-356508 A Japanese Patent Laid-Open No. 6-148895 Japanese Patent Laid-Open No. 10-246960

The present inventors have studied in detail the patterning using the insulating film material provided with such conventional photosensitive characteristics. As a result, for example, when a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which water and catalyst have been removed, a photoacid generator, and a solvent as disclosed in Patent Document 3 and Patent Document 4 is used, both of them are used in a large amount. It was revealed that the exposure amount was required and the mass productivity was not excellent.
Furthermore, since the film formed from the photosensitive resin composition has insufficient adhesion to the adherend and electrical insulation, film peeling is likely to occur during the process, and there is a problem of low electrical reliability. there were.

  The present invention has been made in view of such circumstances, and has a method for forming a silica-based film that provides a cured product of a silica-based film having excellent adhesion and high electrical reliability, and silica formed by the method. It aims at providing an electronic component provided with a system coat.

  As a result of intensive studies, the present inventors have found that a method for forming a silica-based film using a photosensitive resin composition containing a specific component can solve various conventional problems. The invention has been completed.

［式中、Ｒ^１は、Ｈ原子、Ｆ原子、有機基、又は、Ｂ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子及びＴｉ原子からなる群より選択される少なくとも１種の原子を含む基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示し、４−ｎ個のＸは同一でも異なっていてもよく、ｎが２であるとき、２個のＲ^１は同一でも異なっていてもよい。］ That is, the present invention is at least selected from the group consisting of a siloxane resin obtained by hydrolytic condensation of a silane compound containing a compound represented by the following general formula (1), and a photoacid generator and a photobase generator. A step of applying a photosensitive resin composition containing one type, a solvent capable of dissolving a siloxane resin, and an onium salt on a substrate to obtain a coating; and a step of exposing the coating through a pattern mask; A step of heating the coating after the step of exposing, a step of removing the unexposed portion of the coating by development after the step of heating, and a silica system having a pattern by irradiating the coating remaining after the step of removing with ultraviolet rays And a step of obtaining a coating.

[Wherein R ¹ represents at least one selected from the group consisting of H atom, F atom, organic group, or B atom, N atom, Al atom, P atom, Si atom, Ge atom and Ti atom. A group containing an atom, X represents a hydrolyzable group, n represents an integer of 0 to 2, 4-n Xs may be the same or different, and when n is 2, 2 R ¹ may be the same or different. ]

  According to the present invention, since the specific siloxane resin is used as a constituent component of the photosensitive resin composition, the highly reactive silanol (SiOH) group concentration can be reduced, and as a result, it can be left at room temperature for a long time. It can be set as the photosensitive resin solution excellent in stability. Moreover, since the said siloxane resin contains the functional group which has polarity, it can form the silica-type film excellent in adhesiveness with various to-be-adhered bodies. Furthermore, since the siloxane resin sufficiently undergoes a curing reaction upon irradiation with ultraviolet rays, it is possible to form a silica-based film having excellent low dielectric properties, electrical insulation properties, heat resistance, and transparency.

  In the present invention, since the photosensitive resin composition contains at least one selected from the group consisting of a photoacid generator and a photobase generator, it exhibits negative photosensitivity excellent in transparency and resolution. It is possible to obtain excellent developability at the time of development after exposure when a silica-based film is formed. Furthermore, since the condensation reaction between the silanol groups in the silica-based coating is further accelerated by the acid or base generated by photolysis of the photoacid generator or photobase generator contained in the photosensitive resin composition, the resulting silica The heat resistance, electrical properties and mechanical strength of the system coating are improved.

  Furthermore, in the present invention, since the photosensitive resin composition contains an onium salt, the condensation reaction of silanol groups present in the siloxane resin can be promoted, the resolution during development is improved, and after curing, A silica-based film having excellent insulating properties can be formed.

  In the method for forming a silica-based film according to the present invention, it is preferable to irradiate the film with ultraviolet rays while the film is heated to 150 ° C. or higher in the step of obtaining the silica-based film. In this case, the condensation reaction between the silanol groups in the silica-based coating proceeds sufficiently, so that the low dielectric properties, insulating properties and mechanical strength are further improved.

  The present invention further provides an electronic component comprising a substrate and the silica-based film formed on the substrate by the method described above.

  Since the electronic component of the present invention includes the silica-based film formed by the above method using the above photosensitive resin composition, it has excellent performance.

  According to the present invention, since a photosensitive resin composition having excellent long-term room temperature storage stability and capable of forming a pattern with high accuracy is used, a silica-based film having high adhesion and high electrical reliability can be provided.

  In addition, according to the present invention, it is easy to form a silica-based film having a pattern that can be used as an insulating film, and the in-plane uniformity of film thickness, applicability, solution, and the like of the formed silica-based film are facilitated. It is possible to provide a method for forming a silica-based film having excellent image properties, adhesion, insulating properties, low dielectric properties, heat resistance, transparency and mechanical properties. Furthermore, this invention can provide an electronic component provided with the silica-type film which has the pattern formed by the formation method of the said silica-type film.

It is a schematic cross section which shows one Embodiment of a semiconductor element provided with the silica-type film formed by the formation method of the silica-type film of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  In the present specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve.

Here, the weight average molecular weight (Mw) can be measured using GPC under the following conditions, for example.
(conditions)
Sample: 5 μL
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: RI-monitor manufactured by Hitachi, Ltd., trade name “L-3000”
Integrator: GPC integrator manufactured by Hitachi, Ltd., trade name “D-2200”
Pump: Hitachi, Ltd., trade name “L-6000”
Degassing device: Showa Denko Co., Ltd., trade name "Shodex DEGAS"
Column: Hitachi Chemical Co., Ltd., trade names “GL-R440”, “GL-R430”, “GL-R420” connected in this order and used as eluent: tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 mL / min Measurement time: 45 minutes

［式中、Ｒ^１は、Ｈ原子、Ｆ原子、有機基、又は、Ｂ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子及びＴｉ原子からなる群より選択される少なくとも１種の原子を含む基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示し、４−ｎ個のＸは同一でも異なっていてもよく、ｎが２であるとき、２個のＲ^１は同一でも異なっていてもよい。］
（ｂ）成分：光酸発生剤及び光塩基発生剤からなる群より選択される少なくとも１種
（ｃ）成分：上記シロキサン樹脂を溶解可能な溶媒
（ｄ）成分：オニウム塩 [Photosensitive resin composition]
The photosensitive resin composition used in the present embodiment contains the following components (a) to (d) as essential components.
(A) Component: Siloxane resin obtained by hydrolytic condensation of a silane compound containing a compound represented by the following general formula (1)

[Wherein R ¹ represents at least one selected from the group consisting of H atom, F atom, organic group, or B atom, N atom, Al atom, P atom, Si atom, Ge atom and Ti atom. A group containing an atom, X represents a hydrolyzable group, n represents an integer of 0 to 2, 4-n Xs may be the same or different, and when n is 2, 2 R ¹ may be the same or different. ]
(B) component: at least one selected from the group consisting of a photoacid generator and a photobase generator (c) component: a solvent capable of dissolving the siloxane resin (d) component: onium salt

  Hereinafter, each of (a) component, (b) component, (c) component, and (d) component is demonstrated.

<(A) component>
The component (a) is a siloxane resin obtained by hydrolytic condensation of a silane compound containing the compound represented by the general formula (1). The siloxane resin preferably has a hydroxyl (OH) group at the terminal or side chain of the resin. This is for imparting alkali solubility to an unexposed portion when a film formed using the photosensitive resin composition is developed after exposure. In addition, after exposure, a part of the hydroxyl group in the exposed area undergoes a condensation reaction with the component (b), so that the alkali-soluble contrast with respect to the unexposed area can be improved, and further, when the film in the exposed area is heat-treated. The condensation reaction is more likely to proceed.

The siloxane resin can be obtained by hydrolytic condensation of a silane compound containing the compound represented by the general formula (1).
In the general formula (1), examples of the organic group represented by R ¹ include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. Specific examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Specific examples of the branched aliphatic hydrocarbon group include groups such as isopropyl group and isobutyl group. Specific examples of the cyclic aliphatic hydrocarbon group include groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptylene group, a norbornyl group, and an adamantyl group. Among these, a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and an n-propyl group is more preferable, and a methyl group is more preferable from the viewpoint of availability of raw materials. .

  In the general formula (1), examples of the divalent organic group represented by A include a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group. Among these, from the viewpoint of availability of raw materials, a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms is preferable.

  Preferable specific examples of the linear divalent hydrocarbon group having 1 to 20 carbon atoms include groups such as a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Preferable specific examples of the branched divalent hydrocarbon group having 1 to 20 carbon atoms include groups such as isopropylene group and isobutylene group. Preferred examples of the cyclic divalent hydrocarbon group having 1 to 20 carbon atoms include groups such as a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a group having a norbornane skeleton, and a group having an adamantane skeleton. It is done. Among these, a C1-C7 linear divalent hydrocarbon group such as a methylene group, an ethylene group or a propylene group, a cyclopentylene group or a cyclohexylene group such as a C3-C3 group. 7 cyclic divalent hydrocarbon groups and cyclic divalent hydrocarbon groups having a norbornane skeleton are particularly preferred.

  In the general formula (1), examples of the hydrolyzable group represented by X include an alkoxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group. Among these, an alkoxy group is preferable from the viewpoint of liquid stability of the photosensitive resin composition itself, coating properties, and the like.

  Examples of the compound (alkoxysilane) in which the hydrolyzable group X is an alkoxy group include tetraalkoxysilane, trialkoxysilane, and diorganodialkoxysilane.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. And tetraphenoxysilane.

  Examples of the trialkoxysilane include trimethoxysilane, triethoxysilane, tripropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, and methyltri-iso. -Propoxysilane, methyltri-n-butoxysilane, methyltri-iso-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso -Propoxysilane, ethyltri-n-butoxysilane, ethyltri-iso-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxy N-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri -Iso-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyl Tri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-iso-butoxysilane, iso-propyltri-tert-butoxysilane, iso-propyltriphenoxysilane, n-butyltrimethyl Xylsilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-iso-butoxysilane, n-butyltri-tert -Butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltri-iso-propoxysilane, sec-butyltri-n-butoxy Silane, sec-butyltri-iso-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butylto Ri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-iso-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-iso-butoxysilane, phenyltri-tert-butoxysilane, Phenyltriphenoxysilane, trifluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxy Run, 3-acetoxypropyltrimethoxysilane, 3-acetoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Examples include silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, and dimethyldi-tert. -Butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldi-iso-propoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert- Butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxy Di-n-propyldi-iso-propoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, di-n- Propyl diphenoxy silane, di-iso-propyl dimethoxy silane, di-iso-propyl diethoxy silane, di-iso-propyl di-n-propoxy silane, di-iso-propyl di-iso-propoxy silane, di-iso-propyl di- n-butoxysilane, di-iso-propyldi-sec-butoxysilane, di-iso-propyldi-tert-butoxysilane, di-iso-propyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldi Ethoxysilane, di-n-butyldi-n-propoxy Silane, di-n-butyldi-iso-propoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n- Butyldiphenoxysilane, di-sec-butyldimethoxysilane, di-sec-butylethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldi-iso-propoxysilane, di-sec-butyldi-n -Butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldiphenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxy Silane, di-tert-butyldi-n-propoxysilane Di-tert-butyldi-iso-propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyl Diphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert- Examples include butoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane, and methyl (3,3,3-trifluoropropyl) dimethoxysilane.

In addition, the compound of the general formula (1) in which R ¹ is an organic group having 1 to 20 carbon atoms, and other compounds than the above include, for example, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (Tri-n-propoxysilyl) methane, bis (tri-iso-propoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tri-n-propoxysilyl) ethane, bis ( Tri-iso-propoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (tri-n-propoxysilyl) propane, bis (tri-iso-propoxysilyl) propane, bis (tri Methoxysilyl) benzene, bis (triethoxysilyl) benzene, bis (tri-n-pro Examples thereof include bissilylalkanes such as (poxysilyl) benzene and bis (tri-iso-propoxysilyl) benzene, and bissilylbenzene.

  Moreover, as a compound (halogenated silane) of General formula (1) whose hydrolyzable group X is a halogen atom (halogen group), the alkoxy group in each alkoxysilane molecule mentioned above is substituted with a halogen atom, for example. And the like. Furthermore, examples of the compound (acetoxysilane) of the general formula (1) in which the hydrolyzable group X is an acetoxy group include those in which the alkoxy group in each alkoxysilane molecule described above is substituted with an acetoxy group. It is done. Furthermore, examples of the compound (isocyanate silane) of the general formula (1) in which the hydrolyzable group X is an isocyanate group include those in which the alkoxy group in each alkoxysilane molecule described above is substituted with an isocyanate group. Can be mentioned. Furthermore, examples of the compound (hydroxysilane) of the general formula (1) in which the hydrolyzable group X is a hydroxyl group include those in which the alkoxy group in each alkoxysilane molecule described above is substituted with a hydroxyl group. Can be mentioned.

  These compounds represented by the general formula (1) are used singly or in combination of two or more.

  Further, a resin obtained by hydrolytic condensation of a partial condensate such as a multimer of the compound represented by the general formula (1), a partial condensate such as a multimer of the compound represented by the general formula (1) and the general Resin obtained by hydrolytic condensation of the compound represented by formula (1), resin obtained by hydrolytic condensation of the compound represented by general formula (1) and other compounds, general formula (1) It is also possible to use a resin obtained by hydrolytic condensation of a partial condensate such as a multimer of the compound represented by general formula (1) and another compound.

  Examples of partial condensates such as multimers of the compound represented by the general formula (1) include hexamethoxydisiloxane, hexaethoxydisiloxane, hexa-n-propoxydisiloxane, hexa-iso-propoxydisiloxane, and the like. Examples include hexaalkoxydisiloxane, trisiloxane having advanced partial condensation, tetrasiloxane, and oligosiloxane.

  Examples of the “other compounds” include compounds having a polymerizable double bond or triple bond. Examples of the compound having a polymerizable double bond include ethylene, propylene, isobutene, butadiene, isoprene, vinyl chloride, vinyl acetate, vinyl propionate, vinyl caproate, vinyl stearate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether. , Acrylonitrile, styrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, methacrylate-iso-propyl, methacrylate-n-butyl, acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid Examples thereof include phenyl, vinylpyridine, vinylimidazole, acrylamide, allylbenzene, diallylbenzene and the like, and those obtained by partial condensation of these compounds. Examples of the compound having a triple bond include acetylene and ethynylbenzene.

  The resins thus obtained are used alone or in combination of two or more.

  The amount of water used when hydrolyzing and condensing the compound represented by the general formula (1) is preferably 0.1 to 1000 mol, more preferably 1 mol per mol of the compound represented by the general formula (1). Is 0.5 to 100 mol. If the amount of water is less than 0.1 mol, the hydrolysis-condensation reaction tends not to proceed sufficiently, and if the amount of water exceeds 1000 mol, gelation tends to occur during hydrolysis or condensation.

  Moreover, it is also preferable to use a catalyst in the hydrolysis condensation of the compound represented by the general formula (1). Examples of such a catalyst include an acid catalyst, an alkali catalyst, and a metal chelate compound.

  Examples of the acid catalyst include organic acids and inorganic acids. Examples of organic acids include formic acid, maleic acid, fumaric acid, phthalic acid, malonic acid, succinic acid, tartaric acid, malic acid, lactic acid, citric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid , Octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p- Examples thereof include toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, and the like. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and hydrofluoric acid. These are used singly or in combination of two or more.

  Examples of the alkali catalyst include inorganic alkalis and organic alkalis. Examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like. Examples of the organic alkali include pyridine, monoethanolamine, diethanolamine, triethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, methylamine, and ethylamine. Propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, cyclopentylamine, cyclohexylamine, N, N-dimethylamine, N, N-diethylamine, N , N-dipropylamine, N, N-dibutylamine, N, N-dipentylamine, , N-dihexylamine, N, N-dicyclopentylamine, N, N-dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tricyclopentylamine, tricyclohexylamine, etc. It is done. These are used singly or in combination of two or more.

  Examples of the metal chelate compound include trimethoxy mono (acetyl acetonate) titanium, triethoxy mono (acetyl acetonate) titanium, tri-n-propoxy mono (acetyl acetonate) titanium, tri-iso-propoxy mono ( Acetyl acetonate) titanium, tri-n-butoxy mono (acetyl acetonate) titanium, tri-sec-butoxy mono (acetyl acetonate) titanium, tri-tert-butoxy mono (acetyl acetonate) titanium, dimethoxy Mono (acetylacetonate) titanium, diethoxy-di (acetylacetonate) titanium, di-n-propoxy-di (acetylacetonate) titanium, diiso-propoxy-di (acetylacetonate) titanium, di-n-butoxy-di (Acetylacetonate) titanium, di-s c-butoxy-di (acetylacetonate) titanium, ditert-butoxy-di (acetylacetonate) titanium, monomethoxy-tris (acetylacetonate) titanium, monoethoxy-tris (acetylacetonate) titanium, mono-n- Propoxy tris (acetyl acetonate) titanium, mono iso-propoxy tris (acetyl acetonate) titanium, mono n-butoxy tris (acetyl acetonate) titanium, mono sec-butoxy tris (acetyl acetonate) titanium, mono tert-butoxy-tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, trimethoxy-mono (ethylacetoacetate) titanium, triethoxy-mono (ethylacetoacetate) titanium, tri-n-propoxy-mono (ethyl) Acetoacetate) titanium, tri-iso-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert -Butoxy mono (ethyl acetoacetate) titanium, dimethoxy mono (ethyl acetoacetate) titanium, diethoxy di (ethyl acetoacetate) titanium, di-n-propoxy di (ethyl acetoacetate) titanium, diiso-propoxy di (Ethyl acetoacetate) titanium, di-n-butoxy di (ethyl acetoacetate) titanium, disec-butoxy di (ethyl acetoacetate) titanium, di tert-butoxy di (ethyl acetoacetate) titanium, monomethoxy Lith (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono n-propoxy tris (ethyl acetoacetate) titanium, monoiso-propoxy tris (ethyl acetoacetate) titanium, mono n-butoxy Metal chelate compounds having titanium such as tris (ethyl acetoacetate) titanium, mono sec-butoxy tris (ethyl acetoacetate) titanium, mono tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, Examples thereof include compounds in which titanium of the metal chelate compound having titanium is substituted with zirconium, aluminum, or the like. These are used singly or in combination of two or more.

  In the hydrolytic condensation of the compound represented by the general formula (1), it is preferable to carry out hydrolysis using such a catalyst. However, when the stability of the composition is deteriorated or the catalyst is contained, corrosion to other materials is caused. In some cases, the effects of In such a case, for example, the above catalyst may be removed from the composition after hydrolysis, or the function as a catalyst may be deactivated by reacting with another compound. There is no particular limitation on the method of removing or reacting, but it may be removed using distillation, ion chromatography column or the like. Moreover, the hydrolyzate obtained from the compound represented by the general formula (1) may be taken out of the composition by reprecipitation or the like. In addition, as a method of deactivating the function as a catalyst by reaction, for example, when the catalyst is an alkali catalyst, a method of adding an acid catalyst and neutralizing it by an acid-base reaction or bringing the pH to the acidic side can be mentioned. It is done.

  The amount of the catalyst used is preferably in the range of 0.0001 to 1 mol with respect to 1 mol of the compound represented by the general formula (1). If the amount used is less than 0.0001 mol, the reaction does not tend to proceed substantially, and if it exceeds 1 mol, gelation tends to be promoted during hydrolysis condensation.

  Furthermore, since the alcohol by-produced by this hydrolysis is a protic solvent, it is preferably removed using an evaporator or the like.

  The weight average molecular weight of the resin thus obtained is preferably 5,000 to 100,000, preferably 5,000 to 50,000, from the viewpoint of solubility in a solvent, mechanical properties, moldability, room temperature storage stability, and the like. More preferably, it is further preferably 5000 to 30000, particularly preferably 6000 to 20000, and most preferably 6000 to 15000. If the weight average molecular weight is less than 5,000, the room temperature storage stability of the solution tends to be inferior. If the weight average molecular weight exceeds 100,000, the compatibility with the solvent tends to decrease.

When adhesion to the substrate and mechanical strength are required, H atom, F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom with respect to 1 mol of Si atom in the general formula (1) , The total content of at least one atom selected from the group consisting of Ti atoms and C atoms (this is the total number (M) of specific bonding atoms (R ¹ in the general formula (1)). 1.3 to 0.20 mol, more preferably 1.0 to 0.20 mol, still more preferably 0.90 to 0.20 mol, and 0.80 to 0. Particularly preferred is 20 moles. If it does in this way, the adhesiveness to the other film | membrane (layer) of hardened | cured material and the fall of mechanical strength can be suppressed.

  When the total number (M) of the specific bonding atoms is less than 0.20, the dielectric properties when the cured product is used as an insulating film tend to be inferior. Adhesiveness with other films (layers) and mechanical strength tend to be inferior. Further, among the above-mentioned specific bonding atoms, at least one kind selected from the group consisting of H atom, F atom, N atom, Si atom, Ti atom and C atom in terms of film formability of the cured product. It is preferable that an atom is included, and among them, in terms of dielectric properties and mechanical strength, at least one atom selected from the group consisting of H atom, F atom, N atom, Si atom and C atom is included. Is more preferable.

In addition, the total number (M) of a specific bond atom can be calculated | required from the preparation amount of a siloxane resin, for example, following formula (A);
M = (M1 + (M2 / 2) + (M3 / 3)) / Msi (A)
It can be calculated using the relationship represented by In the formula, M1 represents the total number of atoms bonded to a single (only one) Si atom among specific bond atoms, and M2 is bonded to two silicon atoms among the specific bond atoms. M3 represents the total number of atoms bonded to three of the specific bonding atoms, and Msi represents the total number of Si atoms.

  Such siloxane resins are used alone or in combination of two or more. As a method of combining two or more types of siloxane resins, for example, a method of combining two or more types of siloxane resins having different weight average molecular weights, or two or more types of siloxane resins obtained by hydrolytic condensation using different compounds as essential components The method of combining, etc. are mentioned.

<(B) component>
The component (b) is at least one selected from the group consisting of a photoacid generator and a photobase generator, and the component (a) can be photocured (hydrolytic polycondensation) by irradiation with radiation. Defined as a compound capable of releasing an acidic or basic active substance.

  Examples of the photoacid generator include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, oximes. Examples include sulfonic acid esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonic acid esters. These are used singly or in combination of two or more. It can also be used in combination with other sensitizers.

  Examples of the photobase generator include compounds represented by the following general formulas (2) to (5), nonionic photobase generators such as nifedipines, cobalt amine complexes, the following general formula (6), Examples thereof include ionic photobase generators such as quaternary ammonium salts represented by the following general formula (7). These may be used alone or in combination of two or more. It can also be used in combination with other sensitizers.

_{^{(R 2 -OCO-NH) m}} -R 3 ... (2)
Here, in the formula, R ² represents a monovalent organic group having 1 to 30 carbon atoms, may include an aromatic ring having a methoxy group or a nitro group in the side chain, and R ³ represents 1 to 1 carbon atoms. 20 represents a 1-4 valent organic group, and m is an integer of 1-4.

^{(R 4 R 5 C = N} -OCO) m -R 3 ... (3)
Here, in the formula, R ³ and m are the same as those in the general formula (2), and R ⁴ and R ⁵ each independently represent a monovalent organic group having 1 to 30 carbon atoms, and are bonded to each other. An annular structure may be formed.

R ² —OCO—NR ⁶ R ⁷ (4)
Here, in the formula, R ² has the same meaning as that in the general formula (2), and R ⁶ and R ⁷ each independently represent a monovalent organic group having 1 to 30 carbon atoms and are bonded to each other to form a ring. A structure may be formed, and one of them may be a hydrogen atom.

^{R 8 -CO-R 9 -NR 6} R 7 ... (5)
Here, in the formula, R ⁶ and R ⁷ have the same meanings as those in the general formula (4), R ⁸ represents a monovalent organic group having 1 to 30 carbon atoms, and an alkoxy group or nitro group is present in the side chain. An aromatic ring having an amino group, an alkyl-substituted amino group or an alkylthio group, R ⁹ represents a divalent organic group having 1 to 30 carbon atoms.

ここで、式中、Ｒ^１０は炭素数１〜３０の１価の有機基を示し、Ｒ^１１及びＲ^１２は各々独立に炭素数１〜３０の１価の有機基又は水素原子を示し、Ｘ^１は、下記一般式（６Ａ）、（６Ｂ）、（６Ｃ）、（６Ｄ）、（６Ｅ）及び（６Ｆ）（以下、「（６Ａ）〜（６Ｆ）」のように表記する。）のいずれかで表される１価の基を示し、Ｚ⁻はアンモニウム塩の対イオンを示し、ｔは１〜３の整数であり、ｐ及びｑは０〜２の整数であり、ｔ＋ｐ＋ｑ＝３である。

Here, in the formula, R ¹⁰ represents a monovalent organic group having 1 to 30 carbon atoms, R ¹¹ and R ¹² each independently represents a monovalent organic group having 1 to 30 carbon atoms or a hydrogen atom, and X ¹ is any ^one of the following general formulas (6A), (6B), (6C), (6D), (6E) and (6F) (hereinafter referred to as “(6A) to (6F)”). Z ⁻ represents a counter ion of an ammonium salt, t is an integer of 1 to 3, p and q are integers of 0 to 2, and t + p + q = 3 .

ここで、式中、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は各々独立に炭素数１〜３０の１価の有機基を示し、Ｒ^１７、Ｒ^１８及びＲ^１９は各々独立に炭素数１〜３０の２価の有機基又は単結合を示し、Ｒ^２０及びＲ^２１は各々独立に炭素数１〜３０の３価の有機基を示す。

Here, in the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a monovalent organic group having 1 to 30 carbon atoms, and R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent 1 carbon atom. Represents a divalent organic group or single bond of ˜30, and R ²⁰ and R ²¹ each independently represents a trivalent organic group having 1 to 30 carbon atoms.

ここで、式中、Ｒ^１０、Ｒ^１１及びＲ^１２、Ｚ⁻、ｔ、ｐ及びｑは上記一般式（６）におけるものと同様であり、Ｘ^２は下記一般式（７Ａ）〜（７Ｄ）のいずれかで表される２価の基を示す。

Here, in the formula, R ¹⁰ , R ¹¹ and R ¹² , Z ⁻ , t, p and q are the same as those in the above general formula (6), and X ² is the following general formula (7A) to (7D). The bivalent group represented by either of these is shown.

ここで、式中、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は、上記一般式（６Ａ）〜（６Ｆ）におけるものと同義である。

Here, in formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> , R < ²⁰ > and R < ²¹ > are synonymous with those in the above general formulas (6A) to (6F). .

  The amount of component (b) used is not particularly limited, but depends on the sensitivity and efficiency of the photoacid generator or photobase generator used, the light source used, the desired thickness of the cured product, etc. The range is wide. Specifically, the use amount of the component (b) is preferably 0.0001 to 50% by weight, and is 0.001 to 20% by weight with respect to the total amount of the component (a) in the radiation curable composition. More preferably, it is 0.01 to 10% by weight. If the amount used is less than 0.0001% by weight, the photocurability tends to be reduced, or a large amount of exposure tends to be required for curing. The film properties and the like tend to be inferior, and the electrical properties and process suitability of the cured product tend to decrease.

  Moreover, you may use a photosensitizer together with the photo-acid generator or photobase generator mentioned above. By using a photosensitizer, radiation energy rays can be efficiently absorbed, and the sensitivity of the photoacid generator or photobase generator can be improved. Examples of the photosensitizer include anthracene derivatives, perylene derivatives, anthraquinone derivatives, thioxanthone derivatives, and coumarins.

  In order to improve the storage stability, when storing the photosensitive resin composition, for example, it is preferable to store at a temperature of 5 ° C. or lower. The lower limit of this temperature is preferably equal to or higher than the freezing point of the solvent in the photosensitive resin composition, and is preferably −50 ° C.

<(C) component>
The component (c) is a solvent capable of dissolving the component (a), and examples thereof include an aprotic solvent and a protic solvent, and it is preferable to contain an aprotic solvent. The inventors presume that an aprotic solvent is effective in reducing the exposure dose and improving the pattern accuracy.

  A protic solvent typified by alcohol has a hydrogen atom bonded to an oxygen atom having a large electronegativity. For this purpose, protic solvent molecules solvate by forming hydrogen bonds with nucleophiles and the like. That is, since the protic solvent solvates with the siloxane resin obtained by hydrolyzing the compound represented by the general formula (1), in order for the siloxane resin to condense, this solvent molecule must be removed. It is considered that there is a tendency to inhibit the curing at the same time.

  On the other hand, an aprotic solvent is a solvent that does not have a hydrogen atom on an element having a large electronegativity, and is considered to have a smaller factor of reaction inhibition than a protic solvent. Therefore, the curing reaction proceeds with the generation of the acidic active substance and the basic active substance in the exposed portion, and the pattern accuracy is unlikely to decrease due to the diffusion of acid or base, and the pattern accuracy tends to be improved. This is different from the mechanism of improving the pattern accuracy by deactivating (neutralizing) the acid generated by the conventional acid diffusion control agent. Thereby, when the aprotic solvent is contained in the component (c), it is considered that the effects of improving the pattern accuracy and reducing the exposure amount are more effectively exhibited.

  Examples of the aprotic solvent contained in the component (c) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, and methyl-n-. Pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, γ-butyrolactone Ketone solvents such as γ-valerolactone; diethyl ether, methyl ethyl ether, methyl-n-di-n-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyl Ludioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl mono-n-propyl ether, diethylene glycol methyl mono -N-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl mono-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethyl N-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetradiethylene glycol methyl ethyl ether, tetraethylene glycol methyl Mono-n-butyl ether, diethylene glycol di-n-butyl ether, tetraethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether , Propylene glycol dibutyl ether, dipropylene glycol Dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl mono- n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl mono-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl mono-n- Hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol Diethyl ether, tetradipropylene glycol methyl ethyl ether, tetrapropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-butyl ether, tetrapropylene glycol methyl mono-n-hexyl ether, tetrapropylene glycol di-n-butyl ether Ether solvents such as methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-acetate Methoxybutyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene acetate Recall monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid dipropylene glycol monoethyl ether, diacetic acid glycol, acetic acid methoxytriglycol, acetic acid ethyl ethyl, propionic acid n- Ester solvents such as butyl, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate; ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl Ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, Ether acetate solvents such as ethylene glycol-n-butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate; acetonitrile, N- Methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, etc. In-plane film thickness uniformity during coating, sensitivity and pattern accuracy during pattern formation, and cured product From the viewpoint of mechanical strength, ether solvents, ester solvents, ether acetate solvents and ketone solvents are preferred. Moreover, it is preferable that it is a solvent which does not have a nitrogen atom.

  Among these, from the viewpoint of being able to improve the compatibility between the siloxane resin and the solvent and forming a film with excellent in-plane uniformity with less film thickness on the film surface, an ether acetate solvent, an ether solvent, and Ketone solvents are preferred, ether acetate solvents and ether solvents are more preferred, and ether acetate solvents are even more preferred. These are used singly or in combination of two or more.

  The proportion of the aprotic solvent used is preferably 50% by weight or more in the total solvent, more preferably 70% by weight or more, still more preferably 90% by weight or more, and 95% by weight or more. It is particularly preferred. If the use ratio is small, the exposed area tends not to be cured sufficiently when the exposure amount is small. Alternatively, if the use ratio is small, heat treatment at a higher temperature is required for sufficient curing, and the generated acid or base tends to diffuse, and the pattern accuracy tends to deteriorate.

  (C) Although the method using a component is not specifically limited, For example, (a) The method used as a solvent at the time of preparing a component, (a) The method of adding after preparing a component, The method of performing solvent exchange, (a) There is a method of taking out the components by evaporating the solvent and adding (c) a solvent.

  The amount of this solvent (the total of the aprotic solvent and the protic solvent) is preferably such that the concentration of the component (a) (siloxane resin) is 3 to 60% by weight. If the amount of the solvent is excessive and the concentration of the component (a) is less than 3% by weight, it tends to be difficult to form a cured product having a desired film thickness, and the amount of the solvent is too small and the concentration of the component (a) is 60. When it exceeds wt%, the film formability of the cured product is deteriorated and the stability of the composition itself tends to be lowered.

<(D) component>
The component (d) is a curing accelerating catalyst, and when added to the photosensitive resin composition, the condensation reaction is accelerated, and the photoacid generator amount or photobase generator amount reducing effect, the exposure amount reducing effect, Or it is thought that the temperature lowering effect of PEB can be expected. This curing accelerating catalyst is different from a normal photoacid generator or photobase generator that generates an active substance by the light of component (b). Therefore, onium salts that can be used as curing accelerator catalysts are usually distinguished from onium salts that are used as photoacid generators or photobase generators.

  It is considered that the curing accelerating catalyst which is the component (d) is a unique one which does not show a catalytic action in a solution and shows activity in a coated film. In the exposed area, the condensation reaction by the curing accelerating catalyst, that is, the curing reaction proceeds with the generation of the acidic active substance or basic active substance, so the pattern accuracy is less likely to deteriorate due to diffusion of acid or base, that is, the pattern accuracy is further improved. It is estimated that.

  Means for examining the curing acceleration catalytic ability of the curing acceleration catalyst are shown in 1-4 below.

1. A composition comprising the component (a) and the component (c) is prepared.
2. The composition prepared in 1 above is applied to a silicon wafer so that the film thickness after baking is 1.0 ± 0.1 μm, and the film is baked at a predetermined temperature for 30 seconds to measure the film thickness.
3. The silicon wafer on which the film is formed is immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ± 2 ° C. for 30 seconds, and the film thickness of the film after rinsing and drying is observed. At this time, the minimum temperature at the time of baking at which the change in film thickness before and after immersion in the TMAH aqueous solution is within 20% is defined as the insoluble temperature.
4). In the composition prepared in 1 above, 0.01% by weight of the compound whose curing acceleration catalytic ability is to be confirmed is added to the total amount of the component (a) to obtain a composition. Determine the insoluble temperature. If the insolubility temperature is lowered by adding a compound for which curing acceleration catalytic ability is desired, the compound has curing acceleration catalytic ability.

  As the curing accelerating catalyst as component (d), an onium salt is used as an essential component, but as other curing accelerating catalysts, for example, alkali metals such as sodium hydroxide, sodium chloride, potassium hydroxide, potassium chloride, etc. Etc. can be used together. These may be used alone or in combination of two or more.

  The onium salt is preferably a quaternary ammonium salt from the viewpoint of improving the electrical properties and mechanical strength of the resulting cured product and further improving the stability of the photosensitive resin composition.

  More specifically, as the onium salt, ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium phosphate salt, ammonium nitrate salt, ammonium borate salt, ammonium sulfate salt, ammonium formate salt, maleic acid Ammonium salt, ammonium fumarate, ammonium phthalate, ammonium malonate, ammonium succinate, ammonium tartrate, ammonium malate, ammonium lactate, ammonium citrate, ammonium acetate, ammonium propionate, Ammonium butanoate, ammonium pentanoate, ammonium hexanoate, ammonium heptanoate, ammonium octanoate, ammonium nonanoate Salt, ammonium decanoate, ammonium oxalate, ammonium adipate, ammonium sebacate, ammonium butyrate, ammonium oleate, ammonium stearate, ammonium linoleate, ammonium linoleate, ammonium salicylate Benzene sulfonic acid ammonium salt, benzoic acid ammonium salt, p-aminobenzoic acid ammonium salt, p-toluenesulfonic acid ammonium salt, methanesulfonic acid ammonium salt, trifluoromethanesulfonic acid ammonium salt, trifluoroethanesulfonic acid ammonium salt, etc. The ammonium salt compound of these is mentioned.

  In these onium salts, ammonium salts such as tetramethylammonium nitrate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium maleate, and tetramethylammonium sulfate are used from the viewpoint of accelerating the curing of the cured product. preferable.

  These are used singly or in combination of two or more.

  The amount of component (d) used is preferably 0.0001 to 5% by weight, more preferably 0.0001 to 1% by weight, based on the total amount of component (a) in the photosensitive resin composition. preferable. When the amount used is less than 0.0001% by weight, a large amount of exposure tends to be required to cure the component (a). When the amount used exceeds 5% by weight, the stability of the composition and the film formability tend to be inferior, and the electrical properties and process suitability of the cured product tend to be lowered.

  In addition, an onium salt can be added so that it may become a desired density | concentration, after melt | dissolving or diluting in water or a solvent as needed. Further, the timing of addition is not particularly limited, and examples include the time when the component (a) is hydrolyzed, during the hydrolysis, at the end of the reaction, before and after the solvent is distilled off, and when the acid generator is added.

<Other ingredients>
The photosensitive resin composition used in the present embodiment may further contain a pigment. When the photosensitive resin composition contains a pigment, for example, an effect of adjusting sensitivity, an effect of suppressing a standing wave effect, and the like are obtained.

  In addition, the photosensitive resin composition used in the present embodiment is a thermally decomposable material such as a surfactant, a silane coupling agent, a thickener, an inorganic filler, and polypropylene glycol as long as the object and effect of the present invention are not impaired. You may further contain a compound, a volatile compound, etc. The thermally decomposable compound and the volatile compound are preferably capable of being decomposed or volatilized by heat (preferably 250 to 500 ° C.) to form voids. Moreover, you may provide void | hole formation ability to the siloxane resin which is (a) component.

  In addition, when using the photosensitive resin composition for an electronic component, it is desirable not to contain an alkali metal or an alkaline earth metal, and even if it is included, the metal ion concentration in the composition may be 1000 ppm or less. Preferably, it is 1 ppm or less. When these metal ion concentrations exceed 1000 ppm, the metal ions easily flow into electronic components such as semiconductor elements having a cured product obtained from the composition, which may adversely affect the device performance itself. Therefore, it is effective to remove alkali metal or alkaline earth metal from the composition using an ion exchange filter or the like, if necessary. However, when used for optical waveguides, other uses, etc., this is not limited as long as the purpose is not impaired.

[Method of forming silica-based film]
Next, a method for forming a silica-based film according to this embodiment will be described. The method for forming a silica-based film according to the present embodiment includes a film forming process for applying the photosensitive resin composition on a substrate to obtain a film, an exposure process for exposing the film through a pattern mask, and an exposure process. A heating step for heating the coating, a development step for removing unexposed portions of the coating by development after the heating step, and irradiating the coating remaining after the development step with ultraviolet rays to obtain a silica-based coating having a pattern An ultraviolet irradiation step.

<Film formation process>
A method for forming a patterned cured product on a substrate using the photosensitive resin composition will be described with reference to a spin coating method that is generally excellent in film formability and film uniformity. However, the cured product forming method is not limited to the spin coating method. Further, the substrate may be one having a flat surface or one having electrodes or the like and having irregularities.

As the substrate, a substrate made of a material such as Si, SiN, SiCN, SiC, SiO ₂ , glass, ITO, or metal, or a substrate made of a composite material of these materials can be used.

  First, the photosensitive resin composition is spin-coated on a substrate such as a silicon wafer or a glass substrate, preferably at 500 to 5000 revolutions / minute, more preferably 500 to 3000 revolutions / minute, to form a film. If the rotational speed is less than 500 revolutions / minute, the film uniformity tends to deteriorate, and if it exceeds 5000 revolutions / minute, the film formability may deteriorate.

  The film thickness of the cured product varies depending on the intended use. For example, the film thickness when used for an interlayer insulating film such as LSI is preferably 0.01 to 2 μm, and the film thickness when used for a passivation layer is 2 to 2 μm. It is preferable that it is 40 micrometers. The film thickness when used for liquid crystal is preferably 0.1 to 20 μm, the film thickness when used for a photoresist is preferably 0.1 to 2 μm, and the film when used for an optical waveguide The thickness is preferably 1 to 50 μm. Usually, this film thickness is generally preferably from 0.01 to 10 μm, more preferably from 0.01 to 5 μm, still more preferably from 0.01 to 3 μm, and preferably from 0.01 to 2 μm. Is particularly preferable, and it is very preferably 0.1 to 2 μm. In order to adjust the film thickness of the cured product, for example, the concentration of the component (a) in the composition may be adjusted. When using the spin coating method, the film thickness can be adjusted by adjusting the number of rotations and the number of coatings. When the film thickness is controlled by adjusting the concentration of the component (a), for example, when the film thickness is increased, the concentration of the component (a) is increased, and when the film thickness is decreased, the component (a) It can be controlled by lowering the concentration. In addition, when adjusting the film thickness using the spin coating method, for example, when increasing the film thickness, the rotational speed is decreased or the number of coatings is increased, and when reducing the film thickness, the rotational speed is increased. Or by reducing the number of coatings.

  Subsequently, the film is dried with a hot plate or the like at 50 to 200 ° C., more preferably at 70 to 150 ° C., and the solvent contained in the film is removed. It is necessary to adjust the drying temperature so that this film dissolves under various conditions during the subsequent development. Moreover, the drying method at this time may be performed by a normal pressure, and may be dried by reduced pressure depending on the case. If the drying temperature is less than 50 ° C., the solvent tends not to be sufficiently dried. If the drying temperature exceeds 200 ° C., the solvent may not be dissolved during development and a pattern may not be formed.

<Exposure process>
Next, the film is exposed by irradiating the film with radiation through a pattern mask having a desired pattern. Preferably this dose is 5~5000mJ / cm ^2, more preferably 5~1000mJ / cm ^2, further preferably 5~750mJ / cm ^2, is 5~500mJ / cm ² It is particularly preferred. This exposure is less than 5 mJ / cm ^2, is by the light source there is a risk that the control becomes difficult, and when it exceeds 5000 mJ / cm ^2, the exposure time becomes long, there is a tendency that the productivity is deteriorated.

  For example, visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays and the like can be used as the radiation in this case, and ultraviolet rays are particularly preferable. Examples of the ultraviolet ray generation source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer lamp.

  The unexposed area is sufficiently soluble in the developer, but an acidic active substance and a basic active substance are generated in the exposed area, a hydrolysis condensation reaction occurs, and the solubility in the developer decreases. Thereby, a pattern is formed.

<Heating process>
Next, heating (post-exposure baking: PEB) is performed after exposure. This heating is to heat the film with a hot plate or the like, but it is preferable to heat in a temperature range where the solubility of the unexposed portion in the developer does not decrease. This temperature is preferably 50 to 200 ° C, more preferably 70 to 150 ° C, and further preferably 70 to 120 ° C. In general, when the temperature is high, the generated acid is likely to diffuse, so this temperature should be low.

<Development process>
For removal of unexposed portions of the photosensitive resin composition, that is, development, for example, a developer such as an alkaline aqueous solution can be used. Examples of the alkaline aqueous solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-n. -Secondary amines such as propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide and the like And quaternary ammonium salts. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant to these alkaline aqueous solutions can also be suitably used. Since the electronic component dislikes alkali metal contamination, a tetramethylammonium hydroxide aqueous solution is preferable as the developer.

  Although suitable development time depends on the film thickness and the solvent, it is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 3 minutes, and further preferably 30 seconds to 2 minutes. If the development time is less than 5 seconds, it may be difficult to control the time on the entire surface of the wafer or the substrate, and if it exceeds 5 minutes, the productivity tends to deteriorate. The processing temperature during development is generally 20-30 ° C. As the developing method, for example, methods such as spraying, paddle, dipping, and ultrasonic waves are possible. Next, the pattern formed by development can be rinsed with distilled water or the like, if necessary.

<Ultraviolet irradiation process>
Next, final curing is performed by irradiating the patterned film remaining in the development step with ultraviolet rays. Thereby, the silica-type film (cured material) which has a pattern can be obtained as an insulating film. This final curing can be carried out in the atmosphere or under reduced pressure in an inert atmosphere such as N ₂ , Ar, and He, and is not particularly limited as long as it satisfies the characteristics required for the intended use.

  In the ultraviolet irradiation step, it is preferable to irradiate the film with ultraviolet rays while the film is heated to 150 ° C. or higher (preferably 150 to 500 ° C.). If this heating temperature is less than 150 ° C., sufficient curing tends to be not achieved, and electrical insulation tends to be inferior. If it exceeds 500 ° C., the underlying material may be deteriorated.

  Further, the final curing heating / ultraviolet irradiation time is preferably 2 to 120 minutes, more preferably 2 to 60 minutes, and further preferably 2 to 30 minutes. When this heating / irradiation time exceeds 120 minutes, the coating tends to deteriorate.

Moreover, it is preferable that the ultraviolet rays to irradiate have a wavelength of 150 nm to 800 nm, and more preferably a wavelength of 200 nm to 800 nm. The wavelength may be a single wavelength or distributed over a wavelength range of 150 nm to 800 nm.
Examples of the ultraviolet light source include a deuterium lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, and a xenon lamp.

[Electronic parts]
Examples of the electronic component having such a cured product include devices having an insulating film such as a semiconductor element and a multilayer wiring board. Specifically, in a semiconductor element, it can be used as a surface protective film (passivation film), a buffer coat film, an interlayer insulating film, and the like. On the other hand, in a multilayer wiring board, it can be suitably used as an interlayer insulating film.

  FIG. 1 is a schematic cross-sectional view showing one embodiment when the cured product is used as a surface protective film of a semiconductor element. In the semiconductor device shown in FIG. 1, the photosensitive resin composition is applied onto a silicon substrate 1 having a silicon nitride film 2 on which metal wirings 5 are formed, and the formed film is patterned and cured to form a silica-based material. The film 3 is formed, and then the metal wiring 4 is formed.

  As semiconductor elements, for example, individual semiconductors such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAMs (dynamic random access memories), SRAMs (static random access memories), EPROMs (erasables) Programmable read-only memory (ROM), mask ROM (mask read-only memory), EEPROM (electrically erasable programmable read-only memory), memory elements such as flash memory, microprocessor, DSP, ASIC, etc. Theoretical circuit elements, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), light emitting diodes De, and the like photoelectric conversion element such as a charge coupled device. Examples of the multilayer wiring board include a high-density wiring board such as MCM.

  Moreover, although it can be used also as uses, such as a component for liquid crystals, an optical waveguide, a photoresist, a use application is not this limitation.

  Hereinafter, specific examples according to the present invention will be described, but the present invention is not limited thereto.

  In the following examples, the photosensitive resin composition is used until the development step of the photosensitive resin composition is completed so that the photoacid generator or photobase generator is not excited. Working in an environment that does not include the photosensitive wavelength of the sensitizer and sensitizer.

Example 1
In a solution obtained by dissolving 74.8 g of tetraethoxysilane, 128.7 g of methyltriethoxysilane, and 3.1 g of a tetramethylammonium nitrate aqueous solution (pH 3.6) prepared in 2.38% by weight in 447.3 g of diethylene glycol dimethyl ether, An aqueous nitric acid solution obtained by diluting 0.6 g of 60% nitric acid with 48.7 g of ion-exchanged water was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then a portion of the ethanol and diethylene glycol dimethyl ether produced were distilled off in a warm bath under reduced pressure, followed by further heating in a warm bath at 80 ° C. for 5 hours to obtain 383.2 g of a polysiloxane solution. Obtained. To this, 116.8 g of diethylene glycol dimethyl ether was added to obtain a polysiloxane solution for a photosensitive resin composition. It was 6450 when the weight average molecular weight of polysiloxane was measured by GPC method.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 0.1 g was blended with 10.0 g of this polysiloxane solution for a photosensitive resin composition to prepare a photosensitive resin composition.

<Pattern accuracy>
2 mL of the photosensitive resin composition is dropped onto the center of a low-resistance 5-inch silicon wafer, and a film is formed by spin coating so that the film thickness becomes 0.5 μm. The film is applied on a hot plate at 100 ° C. for 60 seconds. Dried. Thereafter, ultraviolet light was irradiated at 200 mJ / cm ² with an exposure machine (PLA-600F, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 10 μm. The wafer with the exposed coating film is heated on a hot plate at 100 ° C. for 60 seconds, allowed to cool naturally until the wafer reaches room temperature, and then developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. It was immersed in the liquid for 60 seconds. Thereafter, the wafer was washed with water and spin-dried. Next, the spin-dried wafer was irradiated with ultraviolet rays having a wavelength in the range of 150 nm to 800 nm for 5 minutes on a hot plate heated to 400 ° C. in a nitrogen atmosphere to obtain a cured product of a photosensitive resin on the wafer. . When the pattern shape of the cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

<Adhesion test>
Moreover, except the operation which exposes the whole surface of a coating film with an exposure machine without going through a negative mask, operation similar to the method mentioned above was performed, and the cured | curing material of the photosensitive resin without a pattern was obtained. The cured product was scratched in a grid pattern with a razor blade, and an adhesion test was conducted by peeling off the tape. When the surface was observed from above with an optical microscope, it was confirmed that the cured product was not peeled off from the wafer.

<Insulation characteristics>
In addition, the relative dielectric constant and the leakage current were measured using the cured film wafer prepared in the above adhesion test. First, Al metal was vacuum-deposited on the cured product with a vacuum deposition apparatus so as to have a thickness of about 0.1 μm in a circle having a diameter of 2 mm. For the relative dielectric constant, the charge capacity between the Al metal and the wafer was measured using an impedance analyzer (Yokogawa Electric: HP4192A). When the frequency at the time of measurement was 1 MHz and the film thickness of the coating film was calculated using the film thickness measured with an ellipsometer L116B manufactured by Gartner, it was found to be 2.7.
Next, the leak current was measured at 2 MV / cm by applying a voltage from 0 V to dielectric breakdown between the Al metal and the wafer using an ohmmeter (ADVANTEST: R8340). 1.0E-09 A / cm ² or less.

(Example 2)
A solution prepared by dissolving 74.8 g of tetraethoxysilane, 128.7 g of methyltriethoxysilane and 3.1 g of tetramethylammonium nitrate aqueous solution (pH 3.6) prepared in 2.38 wt% in 447.3 g of propylene glycol methyl ether acetate. A nitric acid aqueous solution in which 0.6 g of 60% nitric acid was diluted with 48.4 g of ion-exchanged water was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the produced ethanol and propylene glycol methyl ether acetate was distilled off in a warm bath under reduced pressure, followed by further heating in a warm bath at 80 ° C. for 5 hours to obtain a polysiloxane solution 397. 0.2 g was obtained. To this, 102.8 g of propylene glycol methyl ether acetate was added to obtain a polysiloxane solution for a photosensitive resin composition. It was 5650 when the weight average molecular weight of polysiloxane was measured by GPC method.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) (0.04 g) was blended with 10.0 g of the polysiloxane solution for the photosensitive resin composition to prepare a photosensitive resin composition.

  When the same operation as in Example 1 was performed and the pattern shape of the cured product was observed, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

  Similarly, when the entire surface of the exposed photosensitive resin-free cured product is scratched with a razor blade in a grid pattern, an adhesion test is performed by peeling the tape, and the surface is observed from above with an optical microscope. It was found that there was no peeling of the cured product.

Furthermore, similarly, when the relative dielectric constant and leakage current of the cured product were measured, the relative dielectric constant was 2.7, and the leakage current at 2 MV / cm was 1.0E-09 A / cm ² or less. I understood it.

(Example 3)
A photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd.) (0.040 g) was blended with 10.0 g of the polysiloxane solution for a photosensitive resin composition obtained in Example 2 to prepare a photosensitive resin composition.

  Similar to Example 1, when the pattern shape of the cured product was observed, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

  Similarly, when the entire surface of the exposed photosensitive resin-free cured product is scratched with a razor blade in a grid pattern, an adhesion test is performed by peeling the tape, and the surface is observed from above with an optical microscope. It was found that there was no peeling of the cured product.

Furthermore, similarly, when the relative permittivity and leakage current of the cured product were measured, the relative permittivity was 2.8, and the leakage current at 2 MV / cm was 1.0E-09 A / cm ² or less. I understood it.

(Example 4)
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) (0.04 g) was blended with 10.0 g of the polysiloxane solution for the photosensitive resin composition obtained in Example 2 to prepare a photosensitive resin composition.

  The pattern was formed on the wafer by performing the same operation as in Example 1 except that the coating film on which the pattern was formed was irradiated on the hot plate heated to 150 ° C. with ultraviolet rays having a wavelength in the range of 150 nm to 800 nm for 30 minutes. The cured | curing material of the photosensitive resin which has this was obtained. When the pattern shape of the cured product was observed, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

  Similarly, the cured film of the photosensitive resin exposed on the entire surface was scratched with a razor blade in a grid pattern, and the adhesion test was performed by peeling the tape. The surface was observed from the top with an optical microscope. I found out that there was no.

Furthermore, similarly, when the relative dielectric constant and the leakage current were measured, it was found that the relative dielectric constant was 2.9 and the leakage current at 2 MV / cm was 1.0E-08 A / cm ² or less. It was.

(Comparative Example 1)
A solution of nitric acid obtained by diluting 0.6 g of 60% nitric acid with 48.7 g of ion-exchanged water in a solution dissolved in 74.8 g of tetraethoxysilane, 128.7 g of methyltriethoxysilane, and 447.3 g of propylene glycol monomethyl ether The solution was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the produced ethanol and propylene glycol monomethyl ether was distilled off in a warm bath under reduced pressure to obtain 398.8 g of a polysiloxane solution. To this, 101.2 g of propylene glycol monomethyl ether was added to obtain a polysiloxane solution for a photosensitive resin composition. The weight average molecular weight of the polysiloxane measured by GPC method was 910.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 0.1 g was blended with 10.0 g of this polysiloxane solution for a photosensitive resin composition to prepare a photosensitive resin composition.

Similarly to Example 1, 200 mJ / cm ² of ultraviolet light was irradiated by an exposure machine (PLA-600F, manufactured by Canon Inc.) through a negative mask having a line pattern having a minimum line width of 10 μm. The wafer with the exposed coating film is heated on a hot plate at 100 ° C. for 60 seconds, allowed to cool naturally until the wafer reaches room temperature, and then developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. The unexposed part was dissolved by immersing in the solution for 60 seconds. Thereafter, the wafer was washed with water and spin-dried. Next, the spin-dried wafer was heated on a hot plate heated to 400 ° C. in a nitrogen atmosphere for 30 minutes, to obtain a cured photosensitive resin having a pattern on the wafer. When the pattern shape of the cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, it was found that the unexposed part was insoluble and no pattern was formed.

  Moreover, except the operation which exposes the whole surface of a film with an exposure machine without going through a negative mask, the same operation as the above-mentioned comparative example 1 was performed, and the cured | curing material of the photosensitive resin without a pattern was obtained. The cured film of the photosensitive resin exposed on the entire surface was scratched with a razor blade in a grid pattern, the adhesion test was performed by peeling the tape, and when the surface was observed from above with an optical microscope, it was found that the film peeled off. .

Furthermore, similarly, when the relative dielectric constant and the leakage current were measured, the relative dielectric constant was 3.5, the leakage current at 2 MV / cm was 1.0E-04 A / cm ² or more, and the dielectric constant It was also found that the leakage current was high.

(Comparative Example 2)
A photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd.) (0.040 g) was blended with 10.0 g of the polysiloxane solution for photosensitive resin composition of Comparative Example 1 to prepare a photosensitive resin composition.
Using the photosensitive resin solution, a cured product of a photosensitive resin having a pattern on a wafer was obtained in the same manner as in Comparative Example 1. When the pattern shape of the cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, it was found that the unexposed part was insoluble and no pattern was formed.
In addition, the cured product of the photosensitive resin with no pattern exposed on the entire surface was scratched with a razor blade in a grid pattern, and the adhesion test was performed by peeling the tape. When the surface was observed from above with an optical microscope, the film was peeled off. I found out that
Furthermore, when the relative dielectric constant and leakage current of the cured film of the photosensitive resin exposed on the entire surface were measured, the relative dielectric constant was 3.7, and the leakage current at 2 MV / cm was 1.0E-04 A / cm. ² or more, it was found that the dielectric constant and leakage current is high.

  The results are shown in Table 1 for Examples 1-4 and Comparative Examples 1-2. “PB” in Table 1 means the heating temperature after application of the resin composition and before exposure, and “PEB” means the heating time after exposure and before development.

  According to the present invention, a cured product having high pattern accuracy and excellent adhesion and electrical reliability can be obtained by a method for forming a silica-based film having a pattern using an excellent photosensitive resin composition. Therefore, the present invention is useful for electronic components.

  DESCRIPTION OF SYMBOLS 1 ... Silicon substrate, 2 ... Silicon nitride film, 3 ... Silica-type film, 4, 5 ... Metal wiring.

Claims (3)

A siloxane resin obtained by hydrolytic condensation of a silane compound containing a compound represented by the following general formula (1):
At least one selected from the group consisting of a photoacid generator and a photobase generator;
A solvent capable of dissolving the siloxane resin;
Onium salt,
A step of applying a photosensitive resin composition containing the composition on a substrate to obtain a film;
Exposing the coating through a pattern mask;
Heating the coating after the exposing step;
Removing the unexposed portion of the coating by development after the heating step;
Irradiating the coating film remaining after the removing step with ultraviolet light to obtain a silica-based coating film having a pattern.

[Wherein R ¹ represents at least one selected from the group consisting of H atom, F atom, organic group, or B atom, N atom, Al atom, P atom, Si atom, Ge atom and Ti atom. A group containing an atom, X represents a hydrolyzable group, n represents an integer of 0 to 2, 4-n Xs may be the same or different, and when n is 2, 2 R ¹ may be the same or different. ]   The method for forming a silica-based coating according to claim 1, wherein in the step of obtaining the silica-based coating, the coating is irradiated with the ultraviolet rays in a state where the coating is heated to 150 ° C. or higher.   An electronic component comprising: the substrate; and the silica-based coating formed on the substrate by the method according to claim 1.

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