JP2001335745A - Composition for forming film, method for forming film, and silica-based film - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a composition capable of forming a silica-based film having excellent low dielectric constant characteristics, oxygen plasma resistance, and excellent crack resistance after PCT. (A) The following general formulas (1), (2),
At least one selected from the group of compounds represented by (3)
A film-forming composition R _a (Si) (OR ¹ ) _4-a · comprising a condensate obtained by hydrolyzing and condensing a species compound and a compound represented by the following formula (4), and an organic solvent: (1) Si (OR ² ) ₄ (2) R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR
⁵ ) _3-c R ⁶ _c (3) R ⁸ _e M (OR ⁹ ) _fe (4) (wherein R is H, F, or a monovalent organic group) , R7 is O, phenylene or _{- (CH 2) n -,} R 8 is a chelating agent, M
Is a metal atom, R ⁹ is an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, a is 1 to 2, b, c is 0 to
2, d is 0 or 1, f is valence, e is 0 to f, n is 1
Represents an integer of from 6 to 6. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming composition, and more particularly, to a material for an interlayer insulating film in a semiconductor device or the like, which has low dielectric constant, oxygen plasma resistance,
The present invention relates to a film-forming composition capable of forming a silica-based film having excellent crack resistance after a CT (Pressure Cooker Test).

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor device or the like. And in recent years,
In order to form a more uniform interlayer insulating film, S
A coating type insulating film called a OG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxylan, has been used. 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. In particular, with higher integration and multilayering of semiconductor devices and the like, more excellent electrical insulation between conductors is required, and therefore, excellent dielectric constant characteristics, oxygen plasma resistance, and crack resistance after PCT are excellent. There is a demand for an interlayer insulating film material having excellent characteristics.

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (Japanese Patent Application Laid-Open No. H5-263045; 5-315
319) and a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219, JP-A-11-34022).
0) has been proposed, but the materials obtained by these methods are not stable in the properties of reaction products, and exhibit variations in film properties such as low dielectric constant properties, oxygen plasma resistance, and crack resistance after PCT. Due to its large size, it was not suitable for industrial production.

[0004]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a low dielectric constant property, an oxygen plasma resistance, as an interlayer insulating film in a semiconductor device or the like. An object of the present invention is to provide a film-forming composition having excellent crack resistance after PCT and a silica-based film obtained from the composition.

[0005]

The present invention provides (A) (A-
1) a compound represented by the following general formula (1) (hereinafter, referred to as “compound (1)”): R _a Si (OR ¹ ) _4-a (1) (where R is hydrogen An atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is an integer of 1 to 2.)
A compound represented by the following general formula (2) (hereinafter, referred to as “compound (2)”) and Si (OR ² ) ₄ ... (2) (where R ² represents a monovalent organic group) The compound represented by the following general formula (3) (hereinafter referred to as “compound (3)”): R ³ _b (R ⁴ O) _3-b Si— (R ⁷ ) _d —Si (OR ⁵ ) _{3 -c} R ⁶ _c ··· (3) wherein R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b to c are the same or different, and an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. At least one selected from the group of
(A-2) a compound represented by the following general formula (4): R ⁸ _e M (OR ⁹ ) _fe (4) (R ⁸ is a chelating agent, M is a metal atom, R ⁹ represents an alkyl group or an aryl group, f represents the valence of the metal M, e represents 0 to
represents an integer of f. And (C) an organic solvent. Next, the present invention provides
The present invention relates to a method for forming a film, which comprises applying the composition for film formation to a substrate and heating the composition. Next, the present invention relates to a silica-based film obtained by the method for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the (A) hydrolyzed condensate is a hydrolyzate of the compound (A-1) and the component (A-2) and / or a condensate thereof. is there. Here, the hydrolyzate in the component (A) refers to the R ¹ O—, R ² O—, and R ⁴ O— groups contained in the compounds (1) to (4) constituting the component (A). , R ⁵ O
It is not necessary that all of the — and R ⁹ O— groups be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. There may be. Further, the condensate in the component (A) includes the compounds (1) to (4) constituting the component (A).
The silanol group of the hydrolyzate of (4) is condensed to form Si—O
In the present invention, it is not necessary that all of the silanol groups are condensed.In the present invention, a mixture of those having a small amount of condensed silanol groups and those having different degrees of condensation are used. Is a concept that also encompasses

Component (A-1) The component (A-1) is at least one silane compound selected from the group of the compounds (1) to (3). Compound (1): In the above general formula (1), R and R
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples include an allyl group and a glycidyl group. Further, in the general formula (1), R 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 preferably have 1 to 1 carbon atoms.
5, these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted by a fluorine atom or the like. In the general formula (1), examples of the aryl group 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, tri- 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 and the like;

[0009] Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n
-Butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n -Butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane,
Ethyl triphenoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-n-propoxy silane, vinyl tri-iso-propoxy silane, vinyl tri-n-butoxy silane, vinyl tri-s
ec-butoxysilane, vinyltri-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-s
ec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, se
c-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, s
ec-butyl-tri-sec-butoxysilane, sec
-Butyl-tri-tert-butoxysilane, sec-
Butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso
-Propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-
Butyl tri-tert-butoxy silane, t-butyl triphenoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tri-n-propoxy silane, phenyl tri-iso-propoxy silane, phenyl tri-n-butoxy silane, phenyl tri -Sec-butoxysilane, phenyltri-tert-
Butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltrimethoxysilane Ethoxysilane and the like;

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-te
rt-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-iso-
Propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxy Silane, 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-s
ec-butyl-di-iso-propoxysilane, di-s
ec-butyl-di-n-butoxysilane, di-sec-
Butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, Di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxy Silane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane,
Diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-
Butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane and the like.

Preferred compounds as compound (1) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Vinyl triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like. These may be used alone or in combination of two or more.

Compound (2): In the above formula (2), examples of the monovalent organic group represented by R ² include the same organic groups as those in the above formula (1). Specific examples of the compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, tetraphenoxysilane and the like.

Compound (3): In the above formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above formula (1). . In the general formula (3), as a compound in which R ⁷ is an oxygen atom,
Hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,
3,3-pentamethoxy-3-methyldisiloxane,
1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3
-Methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3
-Pentaethoxy-3-ethyldisiloxane, 1,1,
1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyl Disiloxane, 1,1,1,3,3-pentaphenoxy-3-phenyldisiloxane, 1,1,
3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,
3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-
1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,
1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-
Trimethyldisiloxane, 1,1,3-triethoxy-
1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane,
1,1,3-trimethoxy-1,3,3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3
Triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,
1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3 -Triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy- 1,1,3
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraethyldisiloxane, 1,3-
Diethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,
3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,
Examples thereof include 3-diphenoxy-1,1,3,3-tetraphenyldisiloxane.

Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane,
1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,1
3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,
Preferred examples include 3-dimethoxy-1,1,3,3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane.

In the general formula (3), the compound in which d is 0 includes hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,1
2,2-pentamethoxy-2-methyldisilane, 1,
1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2
-Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2
-Pentamethoxy-2-phenyldisilane, 1,1,
1,2,2-pentaethoxy-2-phenyldisilane,
1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-
Dimethyldisilane, 1,1,2,2-tetraethoxy-
1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2
-Tetramethoxy-1,2-diethyldisilane, 1,
1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,
2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-
Tetraphenoxy-1,2-diphenyldisilane, 1,
1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2
-Trimethyldisilane, 1,1,2-trimethoxy-
1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,
1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,
2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2
-Dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-
Tetramethyldisilane, 1,2-dimethoxy-1,1,1
2,2-tetraethyldisilane, 1,2-diethoxy-
1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane,
1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,1
2,2-tetraphenyldisilane and the like can be mentioned.

Of these, hexamethoxydisilane,
Hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,
2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,1
Preferred examples include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane.

Further, in the general formula (3), R ⁷ is-
Examples of the compound represented by the group represented by (CH ₂ ) _n- include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, and bis (tri-i-propoxy). Silyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-
sec-butoxysilyl) methane, bis (tri-t-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri- n-propoxysilyl) ethane, 1,2-bis (tri-i-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) Ethane, 1,2-bis (tri-t-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl)
-1- (triethoxysilyl) methane, 1- (di-n-
Propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-i-propoxymethylsilyl) -1- (tri-i-propoxysilyl) methane,
1- (di-n-butoxymethylsilyl) -1- (tri-
n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-t-butoxymethylsilyl)
-1- (tri-t-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl)
Ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-i -Propoxymethylsilyl) -2-
(Tri-i-propoxysilyl) ethane, 1- (di-n
-Butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-t-butoxy) Methylsilyl) -2- (tri-t-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl)
Methane, bis (di-n-propoxymethylsilyl) methane, bis (di-i-propoxymethylsilyl) methane,
Bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1, 2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-i-propoxymethylsilyl) ethane, 1,2-
Bis (di-n-butoxymethylsilyl) ethane, 1,2
-Bis (di-sec-butoxymethylsilyl) ethane,
1,2-bis (di-t-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene,
1,2-bis (triethoxysilyl) benzene, 1,2
-Bis (tri-n-propoxysilyl) benzene, 1,
2-bis (tri-i-propoxysilyl) benzene,
1,2-bis (tri-n-butoxysilyl) benzene,
1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-t-butoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene,
1,3-bis (triethoxysilyl) benzene, 1,3
-Bis (tri-n-propoxysilyl) benzene, 1,
3-bis (tri-i-propoxysilyl) benzene,
1,3-bis (tri-n-butoxysilyl) benzene,
1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-t-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene,
1,4-bis (triethoxysilyl) benzene, 1,4
-Bis (tri-n-propoxysilyl) benzene, 1,
4-bis (tri-i-propoxysilyl) benzene,
1,4-bis (tri-n-butoxysilyl) benzene,
Examples thereof include 1,4-bis (tri-sec-butoxysilyl) benzene and 1,4-bis (tri-t-butoxysilyl) benzene.

Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane,
2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1-
(Diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2-
(Trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethyl) (Silyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) )benzene,
1,3-bis (triethoxysilyl) benzene, 1,4
Preferred examples include -bis (trimethoxysilyl) benzene and 1,4-bis (triethoxysilyl) benzene.

In the present invention, the compounds (1) to (3) constituting the component (A) include the above-mentioned compound (1),
One or more of (2) and (3) can be used.

Component (A-2) The component (A-2) is a compound represented by the above formula (4). In the general formula (4), R ⁸ is a chelating agent, and R ⁹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Such compounds include:
For example, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetra-n
-Butoxytitanium, tetra-i-butoxytitanium, tetra-sec-butoxytitanium, tetra-t-butoxytitanium, triethoxymono (acetylacetonato) titanium, tri-n-propoxymono (acetylacetonato) titanium, tri I-propoxy mono (acetylacetonate) titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetyl) Acetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-
Propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate)
Titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n-propoxytris (acetyl) Acetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n
-Butoxy-tris (acetylacetonate) titanium,
Mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n- Propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) 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 compounds such as titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; tetraethoxy Zirconium, tetra-n-propoxy zirconium, tetra-i-propoxy zirconium, tetra-n-butoxy zirconium, tetra-i-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-t-butoxy zirconium, triethoxy mono (acetylacetate Natto) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-
Propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (acetylacetonate) zirconium, tri-sec-butoxy mono (acetylacetonate) zirconium, tri-t-butoxy mono (acetylacetonate) Zirconium, zirconium diethoxy bis (acetylacetonate),
Di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di-n-butoxybis (acetylacetonato) zirconium, di-sec-butoxybis ( Acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxy・ Tris (acetylacetonate) zirconium,
Mono-n-butoxy tris (acetylacetonate)
Zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri- n-propoxy mono (ethyl acetoacetate) 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 (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) 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-propoxytris (ethylacetoacetate) zirconium, mono-i-propoxytris (ethylacetoacetate) 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 (acetylacetate) Zirconium compounds such as (nate) mono (ethylacetoacetate) zirconium; triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, tri-i-butoxyaluminum, tri-sec- Butoxyaluminum, tri-t-butoxyaluminum, diethoxymono (acetylacetonato) aluminum, di-n-propoxymono (acetyla) Tonato) aluminum, di -
i-propoxy mono (acetylacetonate) aluminum, di-n-butoxy mono (acetylacetonate) aluminum, di-sec-butoxy mono (acetylacetonate) aluminum, di-t-butoxy.
Mono (acetylacetonato) aluminum, ethoxybis (acetylacetonato) aluminum, n-propoxybis (acetylacetonato) aluminum, i-propoxybis (acetylacetonato) aluminum, n-butoxybis (acetylacetoacetate) Nate) aluminum, sec-butoxybis (acetylacetonate) aluminum, t-butoxybis (acetylacetonate) aluminum, diethoxymono (ethylacetoacetate) aluminum, di-n-propoxymono (ethylacetoacetate) Aluminum, di-i-propoxy mono (ethyl acetoacetate) aluminum, di-n-butoxy mono (ethyl acetoacetate) aluminum, di-sec-butoxy mono (ethyl acetate) Acetate) aluminum, di -
t-butoxy mono (ethylacetoacetate) aluminum, ethoxybis (ethylacetoacetate) aluminum, n-propoxybis (ethylacetoacetate) aluminum, i-propoxybis (ethylacetoacetate) aluminum, n-butoxy. Aluminum such as bis (ethylacetoacetate) aluminum, sec-butoxybis (ethylacetoacetate) aluminum, t-butoxybis (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and tris (ethylacetoacetate) aluminum And the like, and more preferably a titanium compound.

Component (A-2) is used in an amount of 0.001 to 5 parts by weight (in terms of completely hydrolyzed condensate) with respect to 100 parts by weight of component (A-1) (in terms of completely hydrolyzed condensate). More preferably, it is 0.005 to 2 parts by weight. (A-2)
When the content of the component is less than 0.001 part by weight, the oxygen plasma resistance of the coating film is poor, and when it exceeds 5 parts by weight, the coating uniformity of the coating film may be poor.

When the component (A-2) is hydrolyzed and condensed with at least one silane compound selected from the group of the compounds (1) to (3) constituting the component (A), It is preferable to use more than 0.5 mole and not more than 150 moles of water per mole of the total of components A) and (A-2), and it is particularly preferable to add more than 0.5 mole and 130 moles of water. If the amount of water to be added is 0.5 mol or less, the crack resistance of the coating film may be poor, and if it exceeds 150 mol, precipitation or gelation of the polymer during the hydrolysis and condensation reaction may occur.

In producing the hydrolyzed condensate of the component (A) and the component (A-2) of the present invention, the hydrolysis and condensation of the component (A-1) and the component (A-2) are carried out. It is effective to use a catalyst. Here, preferred examples of the catalyst include an acid catalyst and an alkali catalyst.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and oxalic acid;
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, shikimic 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, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid And organic acids such as succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, a hydrolyzate of glutaric acid, a hydrolyzate of maleic anhydride, and a hydrolyzate of phthalic anhydride. And organic acids can be mentioned as more preferred examples. These compounds may be used alone or in combination of two or more.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine,
Picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, ammonia, methylamine, ethylamine, propyl Amine, butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine, N, N-dimethylamine, N, N-
Diethylamine, N, N-dipropylamine, N, N-
Dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-
Methyl butane, dimethyl glycine, 3-amino-3-methylamine and the like can be mentioned, and organic amines are more preferable, and ammonia, alkylamine and tetramethylammonium hydroxide are preferable in terms of adhesion to the substrate of the silica-based film. Is particularly preferred. One or more of these alkali catalysts may be used simultaneously.

The amount of the catalyst to be used is determined according to the amount of the compound (1)
R in (4)¹ O-group, R^Two O-group, R ^Four O-group, R^Five 
O-group and R⁹ Per mole of the total amount of the group represented by O-
And usually, 0.00001 to 10 mol, preferably
0.00005 to 5 mol. The amount of catalyst used is within the above range
Within the range, the polymer may precipitate or gel during the reaction.
Less is.

In the component (A-1), when each component is converted into a complete hydrolysis condensate, the compound (2) is 5 to 75% by weight based on the total amount of the compounds (1) to (3). , Preferably 10 to 70% by weight, more preferably 15 to 70% by weight. Compound (1) and / or (3)
Is 95 to 25% by weight, preferably 90 to 30% by weight, more preferably 8% by weight, based on the total amount of the compounds (1) to (3).
5 to 30% by weight. Compound (2) is compound (1)
When the content is 5 to 75% by weight in the total amount of (3), the resulting coating film has a high elastic modulus and is particularly excellent in low dielectric properties.
Here, in the present invention, the completely hydrolyzed condensate refers to R ¹ O—, R ² O—, R ^{4 in} compounds (1) to (3).
O-group and R ⁵ O-group are hydrolyzed by 100% to form SiO
It is an H group, which is completely condensed to form a siloxane structure. Further, the component (A-1) is preferably a hydrolyzed condensate of the compound (1) and the compound (2) because the obtained composition has better storage stability.

(B) Organic Solvent The film-forming composition of the present invention comprises the component (A-1) and the component (A-
2) The hydrolysis-condensation product with the component is usually dissolved or dispersed in (B) an organic solvent. Examples of the (B) organic solvent include alcohol solvents, ketone solvents, amide solvents,
At least one selected from the group consisting of ester solvents and aprotic solvents is exemplified. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol,
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, mono-alcohol solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethyl butyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl 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,
Polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether; and the like. One or two of these alcohol solvents are used.
More than one species may be used simultaneously.

Examples of ketone solvents include 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, 2-hexanone, methylcyclohexanone, 2,4
-In addition to pentanedione, acetonylacetone, acetophenone, fenchone, etc., 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,
Β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione and the like can be mentioned.
These ketone solvents may be used alone or in combination of two or more.

As amide solvents, formamide, N
-Methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide,
N-dimethylacetamide, N-ethylacetamide,
N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Can be One or two or more of these amide solvents may be used simultaneously.

Examples of the ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, 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-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl 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, acetic acid Methoxy triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents include 1
Species or two or more species may be used simultaneously. Examples of aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, −
Methyl-Δ3-pyrroline, N-methylpiperidine, N-
Ethyl piperidine, N, N-dimethylpiperazine, N-
Methylimidazole, N-methyl-4-piperidone, N
-Methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3
-Dimethyltetrahydro-2 (1H) -pyrimidinone.

Among these organic solvents, an organic solvent represented by the following general formula (5) is particularly preferred. R ¹⁰ O (CHCH ₃ CH ₂ O) _g R ¹¹ ... (5) (R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—. It represents a selected monovalent organic group, and e represents an integer of 1 or 2.) The organic solvent (C) or more can be used alone or in combination of two or more.

In the film-forming composition of the present invention, the same solvent can be used when the component (A-1) and the component (A-2) are hydrolyzed and / or condensed.

Specifically, water or water diluted with a solvent is added intermittently or continuously to a solvent in which the compounds (1) to (4) are dissolved. At this time, the catalyst may be previously added to the solvent, or may be dissolved or dispersed in water at the time of adding water. As the reaction temperature at this time,
Usually, it is 0 to 100 ° C, preferably 15 to 90 ° C.

Other Additives The film-forming composition obtained by the present invention further comprises β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, radical generator, triazene Components such as compounds may be added.

Examples of the β-diketone include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, and 2,4-hexanedione. Nonanion,
3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- Examples thereof include 2,4-heptanedione, and more preferred are acetylacetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5-heptanedione. These may be used alone or in combination of two or more.

The 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 10 to 30 nm.
It has a thickness of 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 organic polymer include a compound having a sugar chain structure, a vinylamide polymer, and (meth)
Acrylic polymer, aromatic vinyl compound, dendrimer, polyimide, polyamic acid, polyarylene, polyamide, polyquinoxaline, polyoxadiazole,
Examples include a fluorine-based polymer and a compound having a polyalkylene oxide structure.

Compounds having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyether Oxypropylene block copolymers, ether compounds such as polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamide sulfates and the like Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. - (X) j- (Y) k- - (X) j- (Y) k- (X) l- ( wherein, X is a group represented by -CH ₂ CH ₂ O-, Y is -
And represents a group represented by CH ₂ CH (CH ₃ ) O—, wherein j is 1 to
90, k is a number from 10 to 99, and l is a number from 0 to 90) Among them, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene Ether-type compounds such as glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitol fatty acid ester can be mentioned as more preferable examples. These may be used alone or in combination of two or more.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of the surfactant include a surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant, and preferably a fluorine-based surfactant and a silicone-based surfactant.

As the fluorine-based surfactant, for example, 1,
1,2,2-tetrafluorooctyl (1,1,2,2-
Tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl)
Ether, hexaethylene glycol (1, 1, 2,
2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro) Pentyl) ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfone Amido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. And a fluorine-based surfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the position (1). Commercially available products are MegaFac F142D, F172, F173, F1
83 (manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC-430, and FC-431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, SC-103, SC-104, SC-1
05, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
(Neos Co., Ltd.) and other commercially available fluorosurfactants. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred.

Examples of the silicone surfactant include SH7PA, SH21PA, SH30PA and ST94P.
A (All are Dow Corning Toray Silicone Co., Ltd.)
And the like can be used. Among them, the above S
H28PA and SH30PA are particularly preferred.

The amount of the surfactant used is usually 0.0001 to 10 parts by weight based on the component (A) (completely hydrolyzed condensate). These may be used alone or in combination of two or more.

As the silane coupling agent, for example, 3
-Glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- 1,4,7-triazadecane, 10-
Triethoxysilyl-1,4,7-triazadecane, 9
-Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-
Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the radical generator include isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate and diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl par Oxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy ) Hexane, 1-cyclohexyl-
1-methylethyl peroxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, t-butylcumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The amount of the radical generator is
0.1 to 10 parts by weight is preferable based on 100 parts by weight of the component (A). These may be used alone or in combination of two or more.

As the triazene compound, for example, 1,
2-bis (3,3-dimethyltriazenyl) benzene,
1,3-bis (3,3-dimethyltriazenyl) benzene, 1,4-bis (3,3-dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis ( 3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3 ,
3-dimethyltriazenylphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)- 9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3- Phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl-4- (3,3 -Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyltriazenyl) phenyl] Fluorene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3
-Dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene and the like. These may be used alone or in combination of two or more.

The total solid content of the composition of the present invention thus obtained is preferably 2 to 30% by weight.
It is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid content concentration is performed, if necessary, by concentration and dilution with the above (D) organic solvent.

When the composition of the present invention is applied to a silicon wafer, Si
When coating on a substrate such as an O ₂ wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used. The film thickness at this time is about 0.05 to 2.5 μm in a single coating as a dry film thickness, and a coating film of about 0.1 to 5.0 μm in a double coating can be formed. . Then, it is dried at room temperature, or at a temperature of about 80 to 600 ° C., usually for 5 to 240 ° C.
By heating and drying for about a minute, 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. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray. In order to control the curing speed of the coating film, if necessary, heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. Furthermore, the relative permittivity of the silica-based film of the present invention is usually 3.0 to 1.2, preferably 3.0 to 1.8, and more preferably 3.0 to 2.0.

The interlayer insulating film thus obtained is excellent in low dielectric constant characteristics, oxygen plasma resistance, and crack resistance after PCT.
M, SDRAM, RDRAM, D-RDRAM, and other interlayer insulating films for semiconductor devices and etching stopper films, protective films such as surface coating films for semiconductor devices, intermediate layers in the semiconductor manufacturing process using a multilayer resist, and layers between multilayer wiring substrates. It is useful for applications such as insulating films, protective films for liquid crystal display elements and insulating films.

[0050]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following description generally shows an embodiment of the present invention, and the present invention is not limited by the description without any particular reason. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Also,
Various evaluations were performed 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, USA Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1 cc / min

A composition sample was applied on a silicon wafer having a relative dielectric constant of 8 inches by spin coating, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked on a hot plate at 25 ° C. in a nitrogen atmosphere for 25 minutes. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for relative dielectric constant measurement. The sample was made at a frequency of 100 kHz and manufactured by Yokogawa Hewlett-Packard Co., Ltd.
The relative permittivity of the coating film was measured by a CV method using a B electrode and an HP4284A precision LCR meter.

A composition sample was applied on an oxygen plasma resistant 8-inch silicon wafer by spin coating, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked on a hot plate in a nitrogen atmosphere at 25 ° C. for 25 minutes. Using a barrel-type oxygen plasma incinerator (PR-501A manufactured by Yamato Scientific Co., Ltd.) on the obtained film, 200
O ₂ treatment with W for 15 seconds. The film thickness of the coating film before and after the treatment was measured and evaluated according to the following criteria. ：: Change in film thickness is 20 nm or less. X: The change in film thickness exceeds 20 nm.

A composition sample was applied on a crack-resistant 8-inch silicon wafer after PCT using a spin coating method, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, Further, the substrate was baked on a hot plate at 400 ° C. in a nitrogen atmosphere for 25 minutes. At this time, the thickness of the coating film was 1.2 μm. The obtained film was subjected to PCT for 1 hour at 100 ° C., 100% RH and 3 atm. A part of the obtained coating film was scratched with a knife and immersed in pure water for 4 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. ×: Propagation of cracks observed

Synthesis Example 1 In a quartz separable flask, 256.56 g of methyltrimethoxysilane and 80.07 g of tetramethoxysilane
g and tetrakis (acetylacetonato) titanium 3.8
After dissolving 3 g in 310 g of propylene glycol monoethyl ether ethyl, the mixture was stirred with a three-one motor, and the solution temperature was stabilized at 60 ° C. Next, 264 g of ion-exchanged water in which 0.4 g of maleic acid was dissolved was added to the solution over 1 hour. Then, after reacting at 50 ° C. for 2 hours, 50 g of acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. Add propylene glycol monoethyl ether ethyl 4 to this solution.
90 g was added, and 490 g of a solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 6,300.

Synthesis Example 2 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that tetra-i-propoxytitanium was used instead of tetrakis (acetylacetonato) titanium. The weight average molecular weight of the condensate and the like thus obtained was 8,700.

Synthesis Example 3 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that the amount of tetrakis (acetylacetonato) titanium used was changed to 15.2 g. The weight average molecular weight of the condensate and the like thus obtained was 10,700.

Synthesis Example 4 A separable flask made of quartz was charged with 570 g of ethanol, 160 g of ion-exchanged water and 90 g of a 10% dimethylamine ion-exchange aqueous solution, and uniformly stirred. 13.6 g of methyltrimethoxysilane, 20.9 g of tetraethoxysilane, and tetrakis (acetylacetonate) were added to this solution.
A mixture of 0.22 g of titanium was added over 30 minutes.
The reaction was performed for 2 hours while maintaining the solution at 45 ° C. Add propylene glycol monopropyl ether 30 to this solution.
Then, the solution was concentrated to 10% (in terms of complete hydrolysis condensate) using an evaporator at 50 ° C. A solution of 10% maleic acid in distilled propylene glycol was added to the solution, and the pH of the solution was adjusted to 4 to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 1,120,000.

Comparative Synthesis Example 1 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that tetrakis (acetylacetonato) titanium was not used. The weight average molecular weight of the condensate and the like thus obtained was 1,700.

Example 1 The reaction solution obtained in Synthesis Example 1 was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm 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 coating film is 2.7
The value was as low as 8, and the film thickness of the coating film after the oxygen plasma treatment was as good as 12 nm. Further, even when the coating film after PCT was immersed in water, no crack propagation was observed.

Examples 2 to 4 Evaluations were made in the same manner as in Example 1 except that the reaction solution shown in Table 1 was used instead of the reaction solution. The evaluation results are also shown in Table 1.

[0062]

[Table 1]

Comparative Example 1 A coating film was evaluated in the same manner as in Example 1 except that the reaction solution obtained in Comparative Synthesis Example 1 was used. Although the relative dielectric constant of the coating film was a low value of 2.89, the reduction of the coating film by oxygen plasma treatment was as poor as 45 nm. Also, P
When the coating film after CT was immersed in water, propagation of cracks was observed.

[0064]

According to the present invention, a composition for forming a film (interlayer having excellent low dielectric constant characteristics, oxygen plasma resistance and crack resistance after PCT) by hydrolyzing and condensing an alkoxysilane and a specific metal compound. Material for an insulating film).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/316 H01L 21/316 G F-term (Reference) 4J035 AA02 BA14 CA052 CA062 CA162 HA01 HA02 HA05 LB20 4J038 DL021 DL022 DL041 DL042 DL071 DL072 DL161 DL162 DM022 GA12 GA13 GA14 JA18 JA20 JA26 JA33 JA38 JA39 JA56 JB13 JB27 JB30 JB39 JC13 JC14 JC22 JC30 KA04 KA06 KA09 MA07 MA10 NA11 NA12 NA21 NA26 NA19

Claims (7)

[Claims] (A) (A-1) a compound represented by the following general formula (1): R _a Si (OR ¹ ) _4-a (1) wherein R is hydrogen Atom, fluorine atom or monovalent organic group, R ¹ is a monovalent organic group, and a represents an integer of 1 to 2.)
A compound represented by the following general formula (2), and Si (OR ² ) ₄ ... (2) (wherein, R ² represents a monovalent organic group.) compound ^{_{R 3 b (R 4 O)}} 3-b Si- (R 7) d -SiOR 5) 3-c R 6 c ····· (3) wherein represented, R ³ to R ⁶ is The same or different, each monovalent organic group, b to c are the same or different, an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. At least one selected from the group of
(A-2) a compound represented by the following general formula (4): R ⁸ _e M (OR ⁹ ) _fe (4) (R ⁸ is a chelating agent, M is a metal atom, R ⁹ represents an alkyl group or an aryl group, f represents the valence of the metal M, e represents 0 to
represents an integer of f. And (A-2) an organic solvent. 2. The film forming composition according to claim 1, wherein M in the general formula (4) is at least one selected from titanium, zirconium and aluminum. 3. The film-forming composition according to claim 1, wherein the component (A) is hydrolyzed and condensed in the presence of an acid catalyst and / or an alkali catalyst. 4. The composition according to claim 1, wherein the component (A-4) is a component (A-1),
0.001 to 5 based on a total of 100 parts by weight of the component (A-2) and the component (A-3) (in terms of a completely hydrolyzed condensate).
The composition for forming a film according to any one of claims 1 to 3, which is in parts by weight. 5. The method according to claim 1, wherein (A-2) the organic solvent is a solvent represented by the following general formula (5).
The composition for forming a film according to the above. R ¹⁰ O (CHCH ₃ CH ₂ O) _g R ¹¹ ... (5) (R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—. Represents a selected monovalent organic group, and g represents an integer of 1 or 2.) 6. A method for forming a film, comprising applying the film-forming composition according to claim 1 to a substrate and heating the composition. 7. A silica-based film obtained by the method for forming a film according to claim 6.