JP2001040092A - Composition for forming membrane and material for forming insulating membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for forming an insulating film and a material for forming the insulating film excellent in uniformity of a coating film, a low permittivity, a mechanical strength, long-term preservation stability, etc., of a solution as a layer insulating film material in a semiconductor element, etc. SOLUTION: This composition for forming a film comprises (A) a compound prepared by hydrolyzing and condensing at least one kind of compound selected from the group consisting of a compound represented by formula I: R1aSi(OR2)4-a [R1 denotes hydrogen atom, fluorine atom or a monovalent organic group; R2 denotes a monovalent organic group; (a) denotes an integer of 0-2] and a compound represented by formula II: R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c (R3, R4, R5 and R6 may be each the same or different and denote each a monovalent organic group; b and c may be each the same or different and denote each a number of 0-2; R7 denotes oxygen atom or (CH2)n; d denotes 0 or 1; n denotes a number of 1-6) in the presence of a metal chelating compound and (B) a compound obtained by hydrolyzing and condensing at least one kind of compound selected from the compound represented by formula I and the compound represented by formula II in the presence of an acidic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a film-forming composition, and more particularly, to a film having uniformity, low dielectric constant, mechanical strength, and long-term storage of a solution as an interlayer insulating film material for a semiconductor device or the like. The present invention relates to a film-forming composition having excellent stability and the like.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO2) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor element 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. Also, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low 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,
There is a demand for an interlayer insulating film material having a lower dielectric constant, excellent CMP resistance, and excellent storage stability.

[0003] Japanese Patent Application Laid-Open No. 6-181201 discloses a coating composition for forming an insulating film having a lower dielectric constant as an interlayer insulating film material. The coating type composition has a low water absorption and is intended to provide an insulating film of a semiconductor device having excellent crack resistance.
Titanium, zirconium, niobium and tantalum; an organometallic compound containing at least one element selected from the group consisting of polycondensation of an organosilicon compound having at least one alkoxy group in the molecule; This is a coating composition for forming an insulating film, which is mainly composed of an oligomer.

[0004] WO96 / 00758 also discloses that
A silica-based coating-type insulating film that is used for forming an interlayer insulating film of a multilayer wiring board and that is made of an alkoxysilane, a metal alkoxide other than silane, and an organic solvent, and that can be applied in a thick film and has excellent oxygen plasma resistance. A forming material is disclosed.

Further, Japanese Patent Application Laid-Open No. Hei 3-20377 discloses a coating liquid for forming an oxide film, which is useful for flattening the surface of electronic parts and the like and for interlayer insulation. The coating solution for forming an oxide film provides a uniform coating solution without generation of a gel-like substance. Further, by using this coating solution, curing at a high temperature and treatment by oxygen plasma are performed. Even so, the purpose is to obtain a good oxide film without cracks. The composition is a coating solution for forming an oxide film obtained by hydrolyzing and polymerizing a predetermined silane compound and a predetermined chelate compound in the presence of an organic solvent.

However, when a metal chelate compound such as titanium or zirconium is combined with a silane compound as described above, the uniformity, low dielectric constant and mechanical strength of the coating film, and the long-term storage stability of the solution are balanced. I don't have much.

[0007]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a film-forming composition for forming an interlayer insulating film in a semiconductor device or the like, which has a high uniformity and a low dielectric constant. It is an object of the present invention to provide a material for an interlayer insulating film which is excellent in mechanical strength, mechanical stability and long-term storage stability of a solution.

The present invention relates to (A) a method of preparing a compound represented by the following general formula (1) and at least one compound selected from the group consisting of a compound represented by the following general formula (2): And at least one compound selected from the group consisting of a compound hydrolyzed and condensed below and (B) a compound represented by the following general formula (1) and a compound represented by the following general formula (2): It is intended to provide a film-forming composition and a material for forming an insulating film, characterized by containing a compound hydrolyzed and condensed in the presence thereof. Formula _{^{1 R 1 a Si (OR 2}} ) 4-a ····· (1) (R 1 represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group , a is an integer of 0 to 2.) formula _{^{2 R 3 b (R 4 O}} ) 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ·· (2) (May be the same or different and each represents a monovalent organic group, b and c may be the same or different and represent a number of 0 to 2, R ⁷ represents an oxygen atom or-(C
H _{2) n} - indicates, d represents 0 or 1, n is a number of 1-6. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

Component (A) Component (A-1) In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Can be. 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, a butyl group and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples include a phenyl group, a naphthyl group, a methylphenyl group, 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. Preferably, 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, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmono Methoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane, triphenylmonoethoxysila It is. These may be used alone or in combination of two or more.

(A-2) Component In the above general formula (2), examples of the monovalent organic group include the same organic groups as those in the above general formula (1).
In the general formula (2), as the compound in which R ⁷ is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1
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
3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,3
Dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3
Examples thereof include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,
3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-
1,3-diphenyldisiloxane, 1,3-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,
Preferred examples include 3,3-tetraphenyldisiloxane. In the general formula (2), d
As compounds having 0, 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-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,1
Examples of the compound in which R ⁷ is — (CH ₂ ) _n — in the general formula (2) include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane. (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, 1,3-bis (hexa Methoxysilyl) 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- Examples thereof include bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, and 1,3-bis (ethoxydiphenylsilyl) propane. 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-1,1,2,2-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 (diethoxyphenyl) Preferred examples include (silyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane.
In the present invention, the component (A) includes the above (A-1)
Component and / or Component (A-2) are used, and Component (A-1) and Component (A-2) are 2
More than one species can be used.

In the present invention, the component (A) is replaced with a solvent represented by the following general formula (4): R ¹⁰ O (CHCH ₃ CH ₂ O) _g R ¹¹ (4) (R ¹⁰ and R ^{And 11} independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monovalent organic group selected from CH ₃ CO—, and g represents an integer of 1 to 2) in the presence of water. Decompose. As the solvent at this time, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene Propylene glycol monomethyl ether,
Dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether,
Dipropylene glycol dibutyl 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, dipropylene glycol Monopropyl ether acetate,
Dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, propylene glycol, and the like.Especially, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol Dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate are preferred. These can be used alone or in combination of two or more.

In the present invention, after dissolving the component (A) in a solvent, the catalyst and water are usually added to hydrolyze the component (A). When the component (A) is hydrolyzed and condensed,
R ² O of component (A-1) and component (A-2)
—, R ⁴ O— and R ⁵ O—
It is preferable to use 0.25 to 3 mol of water,
It is particularly preferred to add ~ 2.5 mol of water. When the amount of water to be added falls within the range of 0.25 to 3 mol, there is no possibility that the uniformity of the coating film is reduced, and the storage stability of the film-forming composition is less likely to be reduced. That's why. Further, the water is preferably added intermittently or continuously.

The component (A-1) and / or (A-2)
When the components are hydrolyzed and condensed, a metal chelate compound (B) represented by the general formula (3) and an acid catalyst (D) are used.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, -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 chelating 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 chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; and titanium. A particularly preferred example is a metal chelate compound containing

Examples of the acid catalyst include organic acids and inorganic acids. Examples of the organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and decane acid. Acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid,
Gallic acid, butyric acid, melitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene Examples thereof include sulfonic acid, monochloroacetic acid, 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. Among these, organic acids can be mentioned as preferred examples, acetic acid, propionic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid,
Tartaric acid is particularly preferred.

The amount of the metal chelate compound and the acid catalyst used is the total amount of component (A) (in terms of complete hydrolysis condensate) of 1
0.001 to 10 parts by weight, usually 0.001 to 10
Parts by weight, preferably in the range of 0.01 to 10 parts by weight. In the present invention, the complete hydrolysis condensate is
The component represented by -OR ² , -OR ⁴ , and -OR ⁵ in the component (A) is hydrolyzed 100% to form an OH group, which is completely condensed. Also, the metal chelate compound and the acid catalyst
It may be added to the solvent in advance, or may be dissolved or dispersed in water at the time of adding water. In the present invention, the hydrolysis refers to R ² contained in the component (A).
O- group, those not required to R ⁴ O-, and R ⁵ O- groups everything is hydrolyzed, for example, only one is hydrolyzed, those two or more are hydrolyzed, Alternatively, a mixture of these is formed. In the production method of the present invention, the component (A) may be condensed after hydrolysis. In the present invention, condensation refers to condensation of a silanol group of the hydrolyzate of the component (A) to form a Si—O—Si bond. In the present invention, however, it is not necessary that all of the silanol groups are condensed. The concept encompasses the formation of a mixture of a small amount of silanol groups and a mixture of those having different degrees of condensation. In the present invention, the temperature at which the component (A) is hydrolyzed is usually 0 to 100 ° C, preferably 15 to 80 ° C.

The ratio of the polymer 1 and the polymer 2 in the film-forming composition of the present invention is based on 100 parts by weight of the total amount of the polymer 1 and the polymer 2 (complete hydrolyzed condensate). The combined ratio of the combined 1 is 10 to 90 parts by weight (in terms of a complete hydrolysis condensate), preferably 20 to 80 parts by weight. When the use ratio of the polymer 1 is less than 10 parts by weight, the long-term storage stability of the solution may be poor, and the use ratio of the polymer 1 is 90%.
If the amount exceeds the weight part, the mechanical strength of the coating film may decrease.

The film-forming composition of the present invention is a composition obtained by the above-mentioned production method, and the content of alcohol having a boiling point of 100 ° C. or less in the composition is 20% by weight or less, particularly 5% by weight or less. Preferably, there is. The alcohol having a boiling point of 100 ° C. or lower may be generated during hydrolysis and / or condensation of the component (A-1) and the component (A-2), and the content thereof is 20% by weight or less, preferably 5% by weight. %
It is preferable to remove by distillation or the like so as to be as follows.

The film-forming composition of the present invention may further contain the following organic solvents. As the organic solvent used in the present invention, for example, n-pentane, i-pentane,
aliphatic hydrocarbon solvents such as n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane; benzene, toluene, Xylene, ethylbenzene, trimethylbenzene,
Methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene,
aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene; 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,
Ketone solvents such as trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-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- Ether solvents such as butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate; γ-butyrolactone, γ-valerola Kuton, n-propyl acetate, i-acetate
-Propyl, n-butyl acetate, i-butyl acetate, s-acetic acid
ec-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, acetoacetate Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate, 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,
Nitrogen-containing solvents such as N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide;
Examples thereof include sulfur-containing solvents such as sulfolane and 1,3-propane sultone. These can be used alone or in combination of two or more.

The film-forming composition of the present invention may further contain the following components. β-diketones β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2
6,6-tetramethyl-3,5-heptanedione, 1,
One or more kinds such as 1,1,5,5,5-hexafluoro-2,4-heptanedione. In the present invention, the β-diketone content in the film-forming composition,
Total amount of component (A) (in terms of complete hydrolysis condensate) 100
It is usually in the range of 0.1 to 100 parts by weight, preferably 0.2 to 80 parts by weight based on parts by weight. Β in such a range
Addition of a diketone can provide a certain storage stability and reduce the risk of deterioration of properties such as coating uniformity of the film-forming composition. This β-diketone is preferably added after the hydrolysis and condensation reaction of the component (A).

Other Additives Components such as colloidal silica, colloidal alumina, organic polymers, and surfactants may be further added to the film-forming composition obtained in the present invention. 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 m.
μ, preferably 10-20 μm, solid content concentration of 10-4
It is about 0% by weight. Examples of such colloidal silica include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industry Co., Ltd .; and Oscar manufactured by Catalyst Chemicals Co., Ltd. Examples of the colloidal alumina include alumina sols 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; and alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemicals Co., Ltd. As the organic polymer, for example, a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound,
Examples include dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, polyquinoxalines, polyoxadiazoles, and fluoropolymers.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a silicone surfactant, a polyalkylene oxide surfactant And fluorinated surfactants and acrylic surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (Sumitomo 3M Limited)
Asahi Guard, Surflon (above, Asahi Glass Co., Ltd.)
), Disperbyk (manufactured by BYK Japan KK), Solsperse (manufactured by Zeneca Corporation), and the like. These surfactants can be used alone or
More than one species can be used in combination.

The total solid content of the film-forming composition of the present invention is preferably 2 to 30% by weight, and is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30
When it is% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The weight average molecular weight of all the polyorganosiloxane components [the hydrolyzed condensate of the component (A)] in the composition thus obtained is as follows:
Usually 1,000 to 120,000, preferably 1,2
It is about 100 to 100,000.

[0025] The composition of the present invention is applied to a silicon wafer, Si
When applying to a substrate such as an O2 wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used.

In this case, the film thickness may be about 0.05 to 1.5 μm in a single coating, and about 0.1 to 3 μm in a double coating. it can. Thereafter, by drying at room temperature or by heating at a temperature of about 80 to 600 ° C., usually for about 5 to 240 minutes, a glassy or macromolecular insulating film can be formed. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used. As a heating atmosphere, the heating is performed in the atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Can be.

The interlayer insulating film thus obtained is excellent in insulating properties, uniformity of coating film, dielectric constant, crack resistance of coating film, and surface hardness of coating film.
System L, DRAM, SDRAM, RDRAM, D
-It is useful for applications such as interlayer insulating films for semiconductor devices such as RDRAMs, protective films such as surface coat films for semiconductor devices, interlayer insulating films for multilayer wiring boards, protective films for liquid crystal display devices, and insulating films.

[0028]

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. Further, the evaluation of the film-forming composition in the examples was measured as follows.

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions. Sample: Prepared by dissolving 1 g of a hydrolyzed condensate in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA was used. Apparatus: High-temperature, high-speed gel permeation chromatogram (model 150-C ALC / GPC) manufactured by Waters, Inc. Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1cc / min

A composition sample is applied on a silicon wafer having a dielectric constant of 8 inches by a spin coating method, and is coated on a hot plate at 100 ° C. for 4 hours.
For 4 minutes at 250 ° C.
The substrate was baked in a vacuum oven for 120 minutes. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for permittivity evaluation. Dielectric constants were measured using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd. and an HP4284A.
Calculated from the capacitance value at 10 kHz using a precision LCR meter

The mechanical strength 8-inch silicon on the wafer is coated with a composition sample by spin coating, at 100 ° C. on a hot plate 4
For 4 minutes at 250 ° C.
The substrate was baked in a vacuum oven for 120 minutes. The obtained film was measured by a continuous stiffness measuring method using a nanoindenter XP (manufactured by Nano Instruments) to measure the elastic modulus.

The composition for forming a uniform film thickness was applied on an 8-inch silicon wafer using a spin coater under the conditions of a rotation speed of 2,000 rpm and 17 seconds. Thereafter, using a hot plate maintained at a temperature of 85 ° C., the silicon wafer coated with the film-forming composition was heated for 4 minutes to disperse the organic solvent. Next, using a hot plate maintained at a temperature of 200 ° C., the silicon wafer coated with the film-forming composition was heated for 4 minutes to form a coating film on the silicon wafer.
The film thickness of the coating film thus obtained was measured using an optical film thickness meter (manufactured by Rudolph Technologies, S
Spectra Laser 200) was used to measure 50 points in the coating film surface. 3σ of the obtained film thickness was calculated and evaluated according to the following criteria. ；: 3σ of coating film is less than 35 nm ×: 3σ of coating film is 35 nm or more

Long-term storage stability The film-forming composition stored at 20 ° C. for 5 months was applied on an 8-inch silicon wafer using a spin coater under the conditions of a rotation speed of 2,000 rpm and 17 seconds. Then, using a hot plate maintained at a temperature of 85 ° C,
The silicon wafer coated with the film-forming composition was heated for 4 minutes to disperse the organic solvent. Next, using a hot plate maintained at a temperature of 200 ° C., the silicon wafer coated with the film-forming composition was heated for 4 minutes to form a coating film on the silicon wafer. The film thickness of the coating film thus obtained is measured using an optical film thickness meter (Rudolph Techno).
Spectra Laser20 manufactured by logies
Using 0), 50 points were measured in the coating film surface. The thickness of the obtained film thickness was measured, and the film thickness increase rate determined by the following equation was used to calculate the film thickness.
The storage stability was evaluated. Film thickness increase rate (%) = ((film thickness after storage) − (film thickness before storage)) ÷ (film thickness before storage) × 100 〇: film thickness change rate ≦ 10% △: 10% <film Thickness change rate ≦ 20% ×: 20% <Thickness change rate

Synthesis Example 1 In a quartz separable flask, 154.1 g of methyltrimethoxysilane, 48.1 g of tetramethoxysilane, and 0.96 g of diisopropoxytitanium bisethylacetyl acetate were dissolved in 200 g of propylene glycol monomethyl ether. The solution was stirred with a three-one motor to stabilize the solution temperature at 65 ° C. Next, 92 g of ion-exchanged water was added to the solution over 2 hours. Then 6
After reacting at 5 ° C. for 4 hours, the reaction solution was cooled to room temperature. 299 g of propylene glycol monomethyl ether was added to this reaction solution, and at 50 ° C., 299 g of a solution containing methanol 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 was 6,400.

Synthesis Example 2 In a quartz separable flask, 154.1 g of methyltrimethoxysilane, 48.1 g of tetramethoxysilane and maleic acid 1 were dissolved in 200 g of propylene glycol monomethyl ether, followed by stirring with a three-one motor. The solution temperature was stabilized at 65 ° C. Next, 92 g of ion-exchanged water was added to the solution over 2 hours. afterwards,
After reacting at 65 ° C. for 4 hours, the reaction solution was cooled to room temperature. 299 g of propylene glycol monomethyl ether was added to this reaction solution, and at 50 ° C., 299 g of a solution containing methanol 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 was 3,100.

Example 1 20 g of the reaction solution obtained in Synthesis Example 1 and 20 g of the reaction solution obtained in Synthesis Example 2 were mixed, and the mixture was filtered through a Teflon filter having a pore size of 0.2 μm. I got something. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the obtained coating film was as low as 2.56, and the elastic modulus of the coating film was 6.6 GPa, which was excellent in mechanical strength. When the 3σ of the coating film was measured, it was 9.3 nm
And the coating film uniformity was excellent. In addition, when the storage stability of the solution was evaluated, the film increase rate after 5 months was 6.3%, showing excellent storage stability.

Example 2 6 g of the reaction solution obtained in Synthesis Example 1 and 34 g of the reaction solution obtained in Synthesis Example 2 were mixed, and the mixture was filtered through a Teflon filter having a pore diameter of 0.2 μm to form a film-forming composition of the present invention. I got something. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the obtained coating film was as low as 2.79, and the elastic modulus of the coating film was 7.4 GPa, which was excellent in mechanical strength. When the 3σ of the coating film was measured, it was 10.2n
m and coating film uniformity. In addition, when the storage stability of the solution was evaluated, the film increase rate after 5 months was 8.9%, indicating excellent storage stability.

Example 3 34 g of the reaction solution obtained in Synthesis Example 1 and 6 g of the reaction solution obtained in Synthesis Example 2 were mixed and filtered through a Teflon filter having a pore size of 0.2 μm to form a film-forming composition of the present invention. I got something. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the obtained coating film was as low as 2.54, and the elastic modulus of the coating film was 5.2 GPa, which was excellent in mechanical strength. When 3σ of the coating film was measured, it was 8.6 nm.
And the coating film uniformity was excellent. When the storage stability of the solution was evaluated, the film increase rate after 5 months was 6.0%, indicating excellent storage stability.

Example 4 20 g of the reaction solution obtained in Synthesis Example 1 and 20 g of the reaction solution obtained in Synthesis Example 2 were mixed with 0.8 g of acetylacetone, and the mixture was filtered through a Teflon filter having a pore diameter of 0.2 μm to obtain the present invention. Was obtained. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the obtained coating film was as low as 2.56, and the elastic modulus of the coating film was 6.4 GPa, which was excellent in mechanical strength. 3σ of coating film
Was found to be 9.4 nm, showing excellent uniformity of the coating film. When the storage stability of the solution was evaluated, the film increase rate after 5 months was 4.8%, showing excellent storage stability.

Example 5 20 g of the reaction solution obtained in Synthesis Example 1 and 20 g of the reaction solution obtained in Synthesis Example 2 were mixed with 4 g of polyisopropyl methacrylate having a molecular weight of about 4,000, and Teflon having a pore diameter of 0.2 μm was mixed. Filtration was carried out with a filter made of a filter, to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the obtained coating film is 2.3.
3, a very low value, and the elastic modulus of the coating film was 4.0 GPa.
And very low dielectric constant but excellent mechanical strength.
When the 3σ of the coating film was measured, it was 10.3 nm and was excellent in coating film uniformity. When the storage stability of the solution was evaluated, the film growth rate after 5 months showed an excellent storage stability of 6.6%.

Example 5 20 g of the reaction solution obtained in Synthesis Example 1 and 20 g of the reaction solution obtained in Synthesis Example 2 were mixed with polyethylene glycol having a weight molecular weight of about 2,000, and the mixture was filtered through a Teflon filter having a pore diameter of 0.2 μm. Filtration was performed to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the obtained coating film was very low at 2.30, and the elastic modulus of the coating film was excellent in mechanical strength instead of a very low dielectric constant of 3.9 GPa. Coating 3
When σ was measured, it was 10.1 nm, which was excellent in coating film uniformity. In addition, the storage stability of the solution was evaluated.
The film growth rate after 6.5 months was 6.5%, indicating excellent storage stability.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 1 was used. The dielectric constant of the obtained coating film was as low as 2.59, but the elastic modulus of the coating film was 3.2 G.
Pa and mechanical strength were inferior.

Comparative Example 2 Evaluation was performed in the same manner as in Example 1 except that only the reaction solution obtained in Comparative Synthesis Example 2 was used. The elastic modulus of the coating film is 7.
Although the mechanical strength was excellent at 6 GPa, the dielectric constant of the obtained coating film was a high value of 3.03. When the storage stability of the solution was evaluated, the film increase rate after 5 months was 14.4.
% And poor storage stability.

[0044]

According to the present invention, the alkoxysilane is hydrolyzed in the presence of a metal chelate compound and an acid catalyst to achieve a balance between coating uniformity, dielectric constant, mechanical strength, and long-term storage stability. It is possible to provide an excellent film-forming composition (material for an interlayer insulating film).

Continued on the front page (72) Inventor Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 4J035 AA03 BA16 CA162 HA01 HB03 4J038 CG142 CH142 CH152 DL021 DL022 DL031 DL032 JC38 NA21 5F058 AA03 AA10 AC03 AF04 AG01 AH01 AH02

Claims (6)

[Claims] (A) at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in the presence of a metal chelate compound: Hydrolyzing and condensing a compound and (B) at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in the presence of an acid catalyst A film-forming composition comprising a compound that has been hydrolyzed and condensed. Formula _{^{1 R 1 a Si (OR 2}} ) 4-a ····· (1) (R 1 represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group , a is an integer of 0 to 2.) 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 represents a monovalent organic group, and b and c may be the same or different; R ⁷ represents an oxygen atom or — (CH ₂ ) _n —, and d represents 0 or 1.
And n represents a number of 1 to 6. ) 2. The metal chelate compound represented by the following general formula (3)
The film forming composition according to claim 1, which is a compound represented by the formula: R ⁸ _e M (OR ⁹ ) _fe (3) (R ⁸ is a chelating agent, M is a metal atom, and R ⁹ is a carbon atom having 2 to 5 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 20 carbon atoms, f represents the valence of the metal M, and e represents an integer of 1 to f. ) 3. The film-forming composition according to claim 1, wherein the acid catalyst is an organic acid. 4. The film-forming composition according to claim 1, comprising a solvent represented by the following general formula (4). R ¹⁰ O (R ¹² O) _g R ¹¹ ... (4) (R ¹⁰ and R ¹¹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. Represents a monovalent organic group, R ¹² represents an alkylene group, and g represents an integer of 1 to 2.) 5. The film according to claim 1, further comprising at least one compound selected from the group consisting of a β-diketone, a compound having a polyalkylene oxide structure, and a (meth) acrylic polymer. Forming composition. 6. A material for forming an insulating film, comprising the composition for forming a film according to claim 5.