JP2001286821A - Manufacturing method of silica based film, silica based film, insulated film and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a coating film having proper uniform thickness as the interlayer isolation of a semiconductor device and to obtain the film excellent in preservable stability and having excellent specific dielectric, mechanical strength and hygroscopic resistance. SOLUTION: The manufacturing method of a silica based film is characterized by irradiating the film containing a siloxane compound with electron beam.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a film,
More specifically, as interlayer insulation in semiconductor devices, etc., it is possible to form a coating film with an appropriate uniform thickness, and it has excellent storage stability, and has excellent relative dielectric constant, mechanical strength, and moisture absorption resistance of the coating film. About the membrane.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as an interlayer insulating film in a semiconductor device or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating-type insulating film mainly composed of a hydrolysis product of tetraalkoxylan, which is called an SOG (Spin on Glass) film, may be used. It has become. Further, with the increase in integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. However, with higher integration and multilayering of semiconductor devices and the like, more excellent electrical insulation between conductors is required, and therefore, storage stability is good, lower dielectric constant is excellent, and leakage current characteristics are excellent. An interlayer insulating film has been required.

Therefore, Japanese Patent Application Laid-Open No. 6-181201 discloses an insulating film having a lower relative dielectric constant as an interlayer insulating film. The purpose of this insulating film is to provide an insulating film of a semiconductor device having low water absorption and excellent crack resistance, and has a structure in which at least one element selected from titanium, zirconium, niobium and tantalum is used. Comprising an organometallic compound and an organosilicon compound having at least one alkoxy group in the molecule.
An oligomer having a number average molecular weight of 500 or more as a main component.

As a method for curing SOG with an electron beam, Japanese Patent Application Laid-Open No. Hei 10-237307 and PCT Publication No. 9700535 disclose a technique of irradiating a resin containing a siloxane resin as a main component with an electron beam. . In these methods, a siloxane resin is irradiated with an electron beam to form silica (SiO ₂ ).
The resulting insulating film has a relative dielectric constant of usually 3.5 to 4.2 and is still insufficient for application to a semiconductor device operating at a high frequency.

[0005]

The present invention relates to a method of manufacturing a film for solving the above-mentioned problems, and more particularly, to a method of forming a film having an interlayer insulating film in a semiconductor device or the like to balance the relative dielectric constant and mechanical strength. An object of the present invention is to provide a method for manufacturing an excellent insulating film.

[0006]

SUMMARY OF THE INVENTION The present invention provides a method for producing a silica-based film, which comprises irradiating a film containing a siloxane compound with an electron beam, and a film and an insulating film obtained by the method. It is.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, first, a film containing a siloxane compound (hereinafter, referred to as “coating film”) is formed on a substrate. In order to form a coating film, a coating composition obtained by dissolving a siloxane compound in an organic solvent (hereinafter referred to as “coating composition”) is applied to a substrate, and the organic solvent is removed. In the present invention, (A)
As a component, a compound represented by the following general formula (1) (hereinafter, referred to as “compound (1)”): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is hydrogen Represents an atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and a compound represented by the following general formula (2) (hereinafter referred to as “compound ( 2) ") R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c (2) (R ³ , R ⁴ , R ⁵ and R ^6, which may be the same or different, each represents a monovalent organic group, b and c may be the same or different, represents the number of 0 to 2, R ⁷ is an oxygen atom Or a group represented by-(CH2) _n- ,
Represents 1 to 6, and d represents 0 or 1. Or a hydrolyzate and / or condensate of at least one compound selected from the group consisting of:

In the above general formula (1), R ¹ and R ²
Examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
And these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group, a phenyl group, a naphthyl group, a methylphenyl group,
Examples thereof include an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-silane. sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltrimethylsilane -N-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane,
Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, vinyl tri-tert
-Butoxysilane, vinyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-
n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisilane -Iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc .; dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec
-Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n -Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-
tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso- Propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di- Phenoxysilane, di-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, di-iso-propyl-di-sec-
Butoxysilane, di-iso-propyl-di-tert
-Butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n
-Butyldiethoxysilane, di-n-butyl-di-n-
Propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di- tert-butoxysilane, di-n
-Butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane,
Di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like. Among the above compounds (1), tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-
iso-propoxysilane, tetraphenoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-
iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldimethoxysilane Ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane,
Triphenylmonoethoxysilane.

In the general formula (2), examples of the monovalent organic group include the same organic groups as those in the general formula (1). Examples of the divalent organic group represented by R ⁷ in the general formula (2) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (2), R
Compounds in which ⁷ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 1,1,1,3 , 3-pentaethoxy-3-methyldisiloxane, 1,1,1,
3,3-pentamethoxy-3-phenyldisiloxane,
1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3
-Dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3
-Tetramethoxy-1,3-diphenyldisiloxane,
1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3
-Trimethyldisiloxane, 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-
Trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3
3-tetramethyldisiloxane, 1,3-diethoxy-
1,1,3,3-tetramethyldisiloxane, 1,3-
Examples thereof include dimethoxy-1,1,3,3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,1
3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,
3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3
-Tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraphenyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetraphenyldisiloxane and the like can be mentioned as preferred examples.
In the general formula (2), examples of the compound in which d is 0 include hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1 , 2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-
Pentamethoxy-2-phenyldisilane, 1,1,1,
2,2-pentaethoxy-2-phenyldisilane, 1,
1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2
-Diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2
-Triethoxy-1,2,2-trimethyldisilane,
1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,1
2,2-tetramethyldisilane, 1,2-diethoxy-
1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane,
And 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, R ⁷ in the general formula (2) is - (CH
2) As compounds of the group represented by n-, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl)
Methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) Methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl) ethane, bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, Bis (dimethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) ethane,
Bis (dimethoxyphenylsilyl) ethane, bis (diethoxyphenylsilyl) ethane, bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane, bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1 1,3-bis (hexamethoxysilyl) propane, 1,3-bis (hexaethoxysilyl) propane, 1,3-bis (hexaphenoxysilyl) propane, 1,3-bis (dimethoxymethylsilyl) propane, 1,3 -Bis (diethoxymethylsilyl) propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3 -Bis (ethoxydimethylsilyl) propane 1,3-bis (methoxydiphenylsilyl) propane, 1,3-bis (ethoxydiphenylsilyl) propane can be cited. Of these, hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,
2,2-tetraethoxy-1,2-dimethyldisilane,
1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-
Diphenyldisilane, 1,2-dimethoxy-1,1,1
2,2-tetramethyldisilane, 1,2-diethoxy-
1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane,
1,2-diethoxy-1,1,2,2-tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl)
Methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane Can be mentioned as a preferable example.

When the compounds represented by the compounds (1) and (2) are hydrolyzed and partially condensed, R ² O—, R ⁴ O— and R ⁴ in the general formulas (1) and (2)
It is preferable to use 0.3 to 10 mol of water per 1 mol of the group represented by ⁵ O-. When the siloxane compound is a condensate, the weight average molecular weight in terms of polystyrene is preferably from 500 to 100,000. In addition,
In a completely hydrolyzed condensate present invention, a group represented by -OR ² and -OR ³ of the siloxane compound component 10
A substance which is hydrolyzed by 0% to become an OH group and completely condensed.

In the present invention, the siloxane compound is usually dissolved in an organic solvent to obtain a coating composition. As the organic solvent used in the present invention, examples of the organic solvent used in the present invention include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,
Aliphatic hydrocarbon solvents such as 2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propyl Bensen,
Aromatic hydrocarbon solvents such as diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene and trimethylbenzene;
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-
Butanol, t-butanol, n-pentanol, i-
Pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol,
n-hexanol, 2-methylpentanol, sec-
Hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-
Decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,
Monoalcohol solvents such as 3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,3
-Butylene glycol, pentanediol-2,4,2
-Methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc. Polyhydric alcohol solvents: acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl Ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,
Ketone solvents such as 4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-
Butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan,
Dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2
-Ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n
-Butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether,
Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran,
Ether solvents such as -methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate,
I-propyl acetate, n-butyl acetate, i-butyl acetate,
Sec-butyl acetate, n-pentyl acetate, sec-acetic acid
Pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate,
Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono acetate -N-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, Methoxytriglycol acetate,
Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-oxalate
-Butyl, methyl lactate, ethyl lactate, n-butyl lactate,
Ester solvents such as n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N
-Nitrogen-containing solvents such as diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane And sulfur-containing solvents such as 1,3-propane sultone. These can be used alone or in combination of two or more.

In the present invention, it is particularly preferable to use an organic solvent having a boiling point of less than 250 ° C. Specifically, alcohols such as methanol, ethanol and isopropanol, polyhydric alcohols such as ethylene glycol and glycerin, and ethylene glycol monomethyl Ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monopropyl ether,
Glycol ether solvents such as dipropylene glycol monoethyl ether and the like, ethylene glycol monomethyl acetate, diethylene glycol monobutyl ether acetate, ethylene glycol diacetate, glycol acetate ether solvents such as propylene glycol methyl ether acetate, N, N-dimethylacetamide, N, N- Dimethylformamide, N-methyl-2-
Amide solvents such as pyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone,
Examples thereof include one kind alone or a combination of two or more kinds such as ketone solvents such as methyl amyl ketone and carboxylic acid esters such as ethyl lactate, methoxymethyl propionate and ethoxyethyl propionate. In the present invention, the amount of the organic solvent used is in the range of 0.3 to 25 times (by weight) the siloxane compound (in terms of a completely hydrolyzed condensate).

In the present invention, the coating composition may contain a catalyst in addition to the siloxane compound component. Examples of the catalyst include an organic acid, an inorganic acid, an organic base, an inorganic base, and a metal chelate. Organic acids include, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,
Decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melitic acid,
Arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid,
Examples thereof include dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Examples of the organic base include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, and N-methylethanolamine. , N-
Ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanol Amine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N -Dimethylethanolamine, N, N-
Diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine,
N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-
Dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine,
N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N −
Butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-propyldibutanol Amine, N
-Butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N-
(Aminomethyl) butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine,
N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (aminopropyl)
Ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine,
N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine, N- (aminobutyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, Ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine,
Butoxybutylamine, methylamine, ethylamine,
Propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide , Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, Methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropyl Piruamin, ethylamino tributylamine, propylamino methylamine, propylamino ethylamine, propylamine aminopropyl amine, propylamino butyl amine, butyl amino methyl amine,
Butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole,
Piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocran,
Examples thereof include diazabicyclononane and diazabicycloundecene. Examples of metal chelates include triethoxy mono (acetylacetonate) titanium,
Tri-n-propoxy mono (acetylacetonate)
Titanium, tri-i-propoxy mono (acetylacetonate) titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy. Mono (acetylacetonate) titanium, diethoxy
Bis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-
Propoxy bis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonate) Titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy.
Tris (acetylacetonate) titanium, mono-n-butoxytris (acetylacetonate) titanium, mono-sec-butoxytris (acetylacetonate)
Titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate)
Titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Acetate) titanium, tri-s
ec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t
-Butoxy bis (ethyl acetoacetate) titanium,
Monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxytris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelate compounds such as titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; Triethoxy mono (acetylacetonate) zirconium, tri-
n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonate) Nart) zirconium,
Tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxy.
Bis (acetylacetonate) zirconium, di-n-
Butoxy bis (acetylacetonate) zirconium, di-sec-butoxy bis (acetylacetonate) zirconium, di-t-butoxybis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono -N-propoxy tris (acetylacetonate) zirconium, mono-i-propoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetyl) (Acetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium Tri -n- propoxy mono (ethylacetoacetate) zirconium, tri -i
-Propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-
Butoxy mono (ethylacetoacetate) zirconium, diethoxybis (ethylacetoacetate) zirconium, di-n-propoxybis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di- n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium , Mono-n
-Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-
sec-butoxy tris (ethyl acetoacetate)
Zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) Zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium,
And the like; aluminum chelate compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); and the like. The amount of the catalyst to be used is generally 0.00 mol per 1 mol of the total amount of the compounds (1) and (2).
It is 001 to 1 mol, preferably 0.001 to 0.1 mol.

The coating composition of the present invention can be produced by mixing the above siloxane compound and, if necessary, other components. Other Additives In the present invention, the coating composition may further contain components such as colloidal silica, colloidal alumina, and a surfactant. Colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 1 to 30 nm.
It has a solid content of about 0 to 20 nm and a solid concentration of about 10 to 40% by weight. Examples of such colloidal silica include, for example, methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .;
And Oscar. Examples of the colloidal alumina include alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.
Examples 100 and 200 include alumina clear sol, alumina sol 10 and 132, manufactured by Kawaken Fine Chemicals Co., Ltd. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like.
Examples include a silicone-based surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant.

The total solid content of the coating composition used in the present invention is preferably 2 to 30% by weight, and is appropriately adjusted depending on the purpose of use. The total solid content of the composition is 2-3
When the content is 0% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The content of alcohol having a boiling point of 100 ° C. or less in the coating composition used in the present invention is preferably 20% by weight or less, particularly preferably 5% by weight or less. Alcohol having a boiling point of 100 ° C. or lower may be generated during hydrolysis and condensation of compounds (1) and (2), and the content thereof is 20% by weight or less, preferably 5% by weight or less.
It is preferable to remove it by distillation or the like so as to be not more than% by weight. In the present invention, the substrate on which the coating composition is applied is a silicon wafer, a SiO 2 wafer,
N wafers and the like, and application means such as spin coating, dipping, roll coating, and spraying are used. In the present invention, the coating film is obtained by applying the coating composition to a substrate and removing the organic solvent, but the thickness of the coating film is
Usually 0.05 to 3 μm, preferably 0.1 to 2.5 μm
It is.

In the present invention, the coating film formed as described above or the organic silica-based film obtained by curing the coating film is irradiated with an electron beam. In the present invention, the energy when irradiating an electron beam is 0.1 to 50 keV, preferably 1 to 30 keV,
The amount of electron beam irradiation is 1 to 1000 μC / cm ² , preferably 10 to 500 μC / cm ² . Also, the acceleration voltage is
When the voltage is 0.1 to 50 keV, the electron beam can penetrate into the coating film sufficiently without penetrating the film and damaging the underlying semiconductor element. further,
When the electron beam irradiation amount is 1 to 1000 μC / cm ² , the whole coating film is reacted and damage to the coating film is reduced. Furthermore, the substrate temperature during electron beam irradiation is usually 25
-500 ° C, preferably 25-450 ° C. The time required for the electron beam curing of the coating film is about 1 minute to 5 minutes, which is significantly shorter than the time required for the thermal curing of 15 minutes to 2 hours. It can be said that it is suitable for. In addition, the siloxane component of the present invention is heat-cured in advance with the substrate heated to 250 ° C. or more and 500 ° C. or less prior to electron beam irradiation of the coating film of the present invention. The relative dielectric constant is 2.8 or less, preferably 2. After forming the organic silica film of 7 or less, the electron beam can be irradiated. The method of irradiating an electron beam after thermal curing of a coating film is effective because it can reduce the film thickness unevenness depending on the non-uniformity of the electron beam irradiation amount. In the present invention, the electron beam irradiation has an oxygen concentration of 10,000.
It is preferable to carry out in an atmosphere of not more than ppm, preferably 1,000 ppm. In the present invention, the electron irradiation can be performed in an inert gas atmosphere. Here, the inert gas used includes N ₂ , He, Ar, Kr and Xe, preferably He and Ar. By performing electron beam irradiation in an inert gas atmosphere, the film is less likely to be oxidized, and the resulting silica-based film can maintain a low dielectric constant. This electron beam irradiation may be performed in a reduced-pressure atmosphere, and the degree of reduced pressure is usually 133 Pa or less, preferably in the range of 0.133 to 26.7 Pa.

The silica-based film obtained according to the present invention has a carbon content (atomic number) of 5 to 17 mol%, preferably 9 to 15.5%. When the carbon content is in the above range, the mechanical strength can be improved while maintaining a low dielectric constant of the obtained silica-based film. Further, it has a feature of having a silicon carbide bond (Si-C-Si) in the film structure. Here, characteristic absorption of silicon carbide bonds is observed at around 890 cm ^{-1 in an} infrared absorption spectrum. Due to these characteristics, the insulating properties, the uniformity of the coating film, the dielectric constant characteristics, the crack resistance of the coating film, and the hardness of the coating film are excellent. For these reasons, LSI, system LSI, DRAM, SDRAM, RDRAM, D-RD
Interlayer insulating films for semiconductor devices such as RAMs, protective films such as surface coating films for semiconductor devices, interlayer insulating films for multilayer wiring boards,
It is useful for applications such as a protective film for a liquid crystal display element and an insulating prevention film.

[0019]

The present invention will now be described more specifically with reference to examples. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Production Example 1 101.3 g of tetramethoxysisilane (completely hydrolyzed condensate: 40.0 g), methyltrimethoxysilane 2
33.0 g (in terms of complete hydrolysis condensate: 100.0 g)
g), 97.3 g of dimethyldimethoxysilane (completely hydrolyzed condensate conversion: 60.0 g), 559.3 g of propylene glycol monopropyl ether, and 239.7 g of methyl-n-pentyl ketone were added to a mixed solution of maleic acid 1.
An aqueous solution in which 0 g was dissolved in 157.7 g of water was added dropwise at room temperature over 1 hour. After completion of the dropwise addition of the mixture, the mixture was further reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure until the total solution amount reached 1000 g, to obtain a component liquid (A) having a solid content of 20%.

Production Example 2 152.0 g of tetramethoxysilane (completely hydrolyzed condensate: 60.0 g), methyltrimethoxysilane 2
84.1 g (in terms of complete hydrolysis condensate: 140.0 g)
g), propylene glycol monomethyl ether 79
To a mixed solution of 8.8 g, 1.2 g of maleic acid was added in water 15.
An aqueous solution dissolved in 7.7 g was added dropwise at room temperature over 1 hour. After completion of the dropwise addition of the mixture, the mixture was further reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure until the total solution amount reached 1000 g, to obtain a component liquid (A) having a solid content of 20%.

Production Example 3 In a mixed solution of 5 g of a 25% aqueous ammonia solution, 320 g of ultrapure water and 600 g of ethanol, 15 g of methyltrimethoxysilane (7.4 g in terms of completely hydrolyzed condensate) and 20 g of tetraethoxysilane (completely hydrolyzed) Condensate 5.8
g) and reacted at 60 ° C. for 3 hours, and then 200 g of propylene glycol monopropyl ether was added.
Thereafter, the solution was concentrated under reduced pressure until the total solution amount reached 140 g,
Thereafter, 10 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added, and the solid content was 8.3%.
Was obtained. Production Example 4 In a quartz separable flask, 77.04 g of methyltrimethoxysilane and 24.05 g of tetramethoxysilane
And tetrakis (acetylacetonate) titanium 0.48
g of propylene glycol monopropyl ether 29
After dissolving in 0 g, the mixture was stirred with a three-one motor, and the solution temperature was stabilized at 60 ° C. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then 60
After the reaction at 2 ° C. for 2 hours, 25 g of acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. At 50 ° C., 149 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution.
The weight average molecular weight of the condensate and the like thus obtained is
8,900. Production Example 5 In a mixed solution of 6 g of a 40% aqueous solution of methylamine, 228 g of ultrapure water, and 570 g of ethanol, 13.6 g of methyltrimethoxysilane (6.7% in terms of complete hydrolysis condensate).
g) and 20.9 g of tetraethoxysilane (6 g of completely hydrolyzed condensate) were added and reacted at 60 ° C. for 2 hours.
g, and then concentrated under reduced pressure to a total solution amount of 116 g. Thereafter, 10 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a coating composition 5 having a solid content of 10%. .

Example 1 The coating composition 1 obtained in Production Example 1 was applied on an 8-inch silicon wafer by a spin coating method to form a film having a thickness of 0.7 μm.
Was obtained. 5 minutes at 80 ° C in air and then under nitrogen 2
After heating at 00 ° C. for 5 minutes, an electron beam was irradiated under the conditions shown in Table 1. The obtained film was evaluated as follows. Table 2 shows the results.

1. Relative dielectric constant An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for measuring a relative dielectric constant. The dielectric constant of the coating film of the sample was measured at a frequency of 100 kHz by a CV method using an HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.

2. Hardness A Berkovich type indenter was attached to an ultra-fine altimeter (Nanoindentator XP) manufactured by MTS, and the universal hardness of the organic silica-based film formed on the silicon wafer was determined. 3. Carbon content The number of carbon atoms was determined by using Rutherford back scattering method and hydrogen forward coil scattering method, and was shown as a ratio (mol%) to the total number of atoms. 4. Confirmation of the presence or absence of silicon carbide bond The silicon carbide bond was identified by the infrared spectrum method based on the presence or absence of absorption near 890 cm ^−1, which is the stretching vibration of Si—C—Si. 5. Crack resistance A composition sample was applied on an 8-inch silicon wafer by spin coating. At this time, the film thickness was adjusted so that the film thickness of the cured coating film was 1.6 μm. This coating,
Nitrogen atmosphere 200 at 90 ° C for 3 minutes on hot plate
The substrate was dried at 3 ° C. for 3 minutes, and further reduced at 420 ° C. (6.
The substrate was baked in a vacuum oven at 65 Pa) for 60 minutes. A part of the obtained coating film was scratched with a knife and immersed in pure water for 5 hours. The scar of the knife in the coating film was observed with a microscope, and evaluated according to the following criteria. ：: No crack propagation was observed. X: Crack propagation is observed.

Examples 2 to 7 and Reference Example 1 The compositions shown in Table 1 were used as the coating compositions.
In the same manner as in Example 1, a coating film having the thickness shown in Table 1 was obtained. The obtained coating film was exposed to air at 80 ° C. for 5 minutes and then at 200 ° C. under nitrogen for 5 minutes.
Heated for minutes. Next, electron beams were irradiated under the conditions shown in Table 1.
The obtained film was evaluated in the same manner as in Example 1. Table 2 shows the results.

Reference Example 1 The coating composition 1 obtained in Production Example 1 was applied on an 8-inch silicon wafer by a spin coating method, and the film thickness was 0.8 μm.
Was obtained. 5 minutes at 80 ° C in air and then under nitrogen 2
Heating was performed at 00 ° C. for 5 minutes, inserted into an electron beam irradiation apparatus, and heated at 400 ° C. for 5 minutes, but no electron beam irradiation was performed. The obtained film was evaluated in the same manner as in Example 1. Table 2 shows the results. All of the electron beam irradiation times required for Examples 1 to 7 were completed within 7 minutes.

[0027]

[Table 1]

[0028]

[Table 2]

Examples 8 to 14 The coating compositions shown in Table 3 were applied to an 8-inch silicon wafer by spin coating to obtain a coating having a thickness of 0.8 μm. 5 minutes at 80 ° C. in air and then at 200 ° C. under nitrogen
An organic silica film having a relative dielectric constant of 2.8 or less, which was heated for 400 minutes and further cured at 400 ° C. for 30 minutes, was formed on the substrate. The results of electron beam irradiation of these organic silica films under the conditions shown in Table 3 are shown as Examples 8 to 14. All of the electron beam irradiation times required for Examples 8 to 14 were completed within 7 minutes. The obtained film was evaluated in the same manner as in Example 1. Table 4 shows the results.

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

According to the present invention, a film having a low dielectric constant and excellent mechanical strength can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/00 CFH C08J 7/00 CFH 302 302 C09D 183/04 C09D 183/04 C08L 83:04 C08L 83: 04 F-term (reference) 4D075 BB26Z BB47Z BB56Z BB93Z BB94Z CA21 DC22 EB42 EB43 EB56 4F073 AA07 AA18 AA32 BA33 BB01 BB09 CA42 DA09 FA08 4J035 BA01 BA02 BA03 BA04 BA11 BA01 BA03 CA01 CA03 CA01 CA03 CA01 CA01 CA03 NA17 NA21 PA17 PB09 5F058 AA03 AA04 AA10 AC03 AF04 AG01 AG10 AH01 AH02 BA06 BA07 BA20 BC05 BF46 BJ01 BJ02

Claims (17)

[Claims] 1. A method for producing a silica-based film, comprising irradiating a film containing a siloxane compound with an electron beam. 2. A compound wherein the siloxane compound is represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ is a monovalent organic group or a hydrogen atom And R ² represents a monovalent organic group, a represents an integer of 0 to 2) and a compound represented by the following general formula (2): R ³ _b (R ⁴ O) _3-b Si— (R ⁷ ) _d -Si (OR ⁵ ) _{3 -c} R ⁶ _c (2) (R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is monovalent And b and c may be the same or different and represent a number of 0 to 2, R ⁷ represents an oxygen atom or a group represented by — (CH 2) _n —, and n
Represents 1 to 6, and d represents 0 or 1. The method according to claim 1, wherein the compound is at least one of a hydrolyzate and a condensate of at least one compound selected from the group consisting of: 3. The method according to claim 1, wherein the film containing the siloxane compound is an organic silica film. 4. The method for producing a silica-based film according to claim 3, wherein the relative permittivity of the organic-based silica film is 2.8 or less. 5. The method according to claim 1, wherein the film further contains a catalyst. 6. A film containing a siloxane compound having a thickness of 0.
2. The method according to claim 1, wherein the thickness is from 0.5 to 3 [mu] m. 7. An electron beam irradiation with an energy of 0.1 to 20 k
^{2. The} method according to claim 1, wherein the irradiation is performed at an eV and an irradiation amount of 1 to 1000 [mu] C / cm < ² >. 8. The method according to claim 1, wherein the electron beam irradiation is performed at 25 to 500 ° C. 9. The method according to claim 1, wherein the electron beam irradiation is performed in an atmosphere having an oxygen concentration of 10,000 ppm or less. 10. The method according to claim 1, wherein the electron beam irradiation is performed in an inert gas atmosphere. 11. The method according to claim 1, wherein the electron beam irradiation is performed at 133.3 Pa or less. 12. A film containing a siloxane compound is heated at 300 ° C.
2. The method according to claim 1, wherein the composition is heat-cured at a temperature of about 500 [deg.] C. and then irradiated with an electron beam. 13. A silica-based film obtained by the production method according to claim 1. 14. The method according to claim 14, wherein the carbon content is 5 to 17 mol%. 15. The silica-based film according to claim 14, having a Si—C—Si (silicon carbide) bond in the film. 16. An insulating film comprising the silica-based film according to claim 15. 17. A semiconductor device comprising the insulating film according to claim 17.