JP2001329216A - Film-forming composition, method for forming film and silica film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a film-forming composition capable of forming a silica film excellent in coating uniformity of a coating film, the property of low relative dielectric constant and mechanical strength after PCT(Pressure Cooker Test) as a material for forming an interlaminar insulating film in a semiconductor element or the like. SOLUTION: The film-forming composition comprises (A) a hydrolyzed condensate produced by subjecting at least one silane compound selected from the group consisting of a compound represented by the following formula 1 a compound represented by the following formula 2 and a compound represented by the following formula 3 to hydrolysis and condensation reaction in the presence of (B) a compound represented by the following formula 4 and (C) water, and (D) an organic solvent : Ra(Si)(OR1)4-a 1, Si(OR2)42, R3b(R4O)3-bSi-(R7)d-Si(OR5)3cR6c 3, MFe 4, (wherein R, R3 and R6 each denote H, F or a monovalent organic group; R1, R2, R4 and R5 each denote a monovalent organic group; R7 denotes O, a phenylene group or -(CH2)n-; a denotes an integer of 1 or 2 ; b and c each denote a number of 0 to 2; d denotes 0 or 1; n denotes an integer of 1 to 6; M is a metal atom; and e denotes a valence of the metal atom M).

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 specifically, as a material for an interlayer insulating film in a semiconductor device or the like, coating uniformity of coating film, low relative dielectric constant characteristic,
The present invention relates to a film-forming composition capable of forming a silica-based film having excellent mechanical strength after PCT (Presure 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 is often 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 containing a hydrolysis product of tetraalkoxylane as a main component has also been used. In addition, with the high integration of semiconductor elements and the like, an interlayer insulating film called organic SOG having a low relative dielectric constant containing polyorganosiloxane as a main component has been developed. In particular, with higher integration and multi-layering of semiconductor elements and the like, better electrical insulation between conductors is required, and therefore, an interlayer insulating film material having a lower relative dielectric constant and excellent crack resistance is required. It is like this.

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing an alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of the alkoxysilane (JP-A-5-263045, Same as 5-315
319) or a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219 and JP-A-11-34022).
0) has been proposed, but the materials obtained by these methods are not stable in the properties of the reaction product, and the coating uniformity of the coating film, low relative dielectric constant characteristics, mechanical strength after PCT, etc. Since the film characteristics vary greatly, it was not suitable for industrial production.

[0004]

The present invention relates to a film-forming composition for solving the above problems, and more specifically, as a interlayer insulating film in a semiconductor device or the like, coating uniformity of coating film and low ratio An object of the present invention is to provide a film-forming composition having excellent dielectric constant characteristics and mechanical strength after PCT, and a silica-based film obtained from the composition.

[0005]

[Wherein, R ³ and R ⁶ are the same or different, a hydrogen atom, a fluorine atom or a monovalent organic group, R ⁴ and R ⁵ are a monovalent organic group, b and c are the same or different, and are a number of 0 to 2]. R ⁷ is an oxygen atom, a phenylene group or a group represented by —(CH ₂ ) _n — (where n is an integer of 1 to 6), and d is 0 or 1. ]

(B) A compound represented by the following general formula (4) and MF _e (4) (wherein M represents a metal atom and e represents a valence of the metal M.) (C) Presence of water The present invention relates to a film-forming composition containing a hydrolyzed condensate that is hydrolyzed and condensed under the condition (D) and an organic solvent. Next, the present invention relates to a method for forming a film, which comprises applying the film forming composition to a substrate and heating the substrate. Next, the present invention relates to a silica-based film obtained by the above method for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the (A) hydrolyzed condensate is at least one hydrolyzed product selected from the group of the compounds (1) to (3) and/or its condensate. is there. Here, the hydrolyzate in the component (A) means the R ¹ O-group, R ² O-group and R ⁴ O-group contained in the compounds (1) to (3) constituting the component (A). And R ⁵ O
It is not necessary that all the -groups are hydrolyzed, for example, only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. Further, the condensate in the component (A) is
The silanol groups of the hydrolysates of the compounds (1) to (3) constituting the component (A) are condensed to form Si-O-Si bonds, but in the present invention, all the silanol groups are condensed. However, the concept also includes a thing in which a small amount of a silanol group is condensed, a mixture of things in which the degree of condensation is different, and the like.

(A) Hydrolytic Condensate The (A) hydrolytic condensate contains (B) at least one silane compound selected from the group of the compounds (1) to (3).
Obtained by hydrolysis and condensation in the presence of components. Compound (1); R and R in the general formula (1)
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples thereof include allyl group and 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, a butyl group, and the like, preferably having 1 to 1 carbon atoms.
5, these alkyl groups may be linear or branched, and the hydrogen atom may be substituted with 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 and 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;

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,
Ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-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-
Butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-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-trifluoropropyltrisilane Ethoxysilane 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-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, J-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 the compound (1) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Examples thereof include vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. These may be used either individually or in combination of two or more.

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

Compound (3): In the above general formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above general formula (1). .. In the general formula (3), as the 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,
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,
Preferred examples include 3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane and the like.

Further, in the general formula (3), as the compound in which d is 0, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 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,
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,
2,2-tetraphenyldisilane etc. 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,
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 (CH ₂ ) _n − include bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(tri-n-propoxysilyl)methane, 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-t-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, 1,
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 compounds (1),
One or more of (2) and (3) can be used.

When hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3) constituting the component (A), 0 is added per 1 mol of the component (A). It is preferable to use 0.5 to 150 mol or less of water, and it is particularly preferable to add 0.5 to 130 mol of water. If the amount of water added is less than 0.5 mol, the crack resistance of the coating film may be poor, and if it exceeds 150 mol, precipitation or gelation of the polymer may occur during the hydrolysis and condensation reaction.

In producing the (A) hydrolysis-condensation product of the present invention, at the time of hydrolyzing and condensing at least one silane compound selected from the group of the compounds (1) to (3), ( The feature is that the component B) is used. (B)
By using the components, it is possible to obtain a silica-based film having excellent coating uniformity of coating film, low relative dielectric constant property, and mechanical strength after PCT. (B) that can be used in the present invention
Examples of the component include lithium fluoride, sodium fluoride, potassium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride and the like. These (B) components may be used either individually or in combination of two or more.

The amount of the component (B) used is the same as that of the compound (1).
In general, 0.00001 to 10 mol per 1 mol of the total amount of the groups represented by R ¹ O-group, R ² O-group, R ⁴ O-group and R ⁵ O-group in (3). , Preferably 0.000
It is from 05 to 5 mol. When the amount of the component (B) used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

In the component (A), when each component is converted into a complete hydrolysis-condensation product, the compound (2) is contained in the total amount of the compounds (1) to (3), preferably 5 to 75% by weight. Is 10 to 70% by weight, more preferably 15 to 70% by weight
Is. Further, the compound (1) and/or (3) is
In the total amount of the compounds (1) to (3), 95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight.
It is 0% by weight. Compound (2) is compound (1)-
When it is 5 to 75% by weight in the total amount of (3), the elastic modulus of the obtained coating film is high and the low dielectric property is particularly excellent. Here, in the present invention, the complete hydrolysis-condensation product means the R ¹ O-group, R ² O-group and R ⁴ O in the compounds (1) to (3).
- group and R ⁵ O-group 100% hydrolyzed to the SiOH
It is a base and is further condensed completely to form a siloxane structure. Further, the component (A) is preferably a hydrolysis-condensation product of the compound (1) and the compound (2), because the storage stability of the obtained composition is more excellent.

(D) Organic Solvent The film-forming composition of the present invention generally contains the component (A)
(D) Dissolved or dispersed in an organic solvent. This (D)
As the organic solvent, alcohol solvents, ketone solvents,
At least one selected from the group consisting of amide-based solvents, ester-based solvents and aprotic solvents. 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 are used. Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2
-Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, s
ec-octanol, n-nonyl alcohol, 2,6-
Dimethylheptanol-4, n-decanol, sec-
Undecyl alcohol, trimethylnonyl alcohol,
monoalcoholic 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-ethylbutyl 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,
Examples thereof include polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. These alcohol solvents are used alone or in combination.
More than one species may be used simultaneously.

As the ketone solvent, 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
-Pentanedione, acetonylacetone, acetophenone, fenchon, etc., as well as 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,
Examples include β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione.
These ketone solvents may be used either individually or in combination of two or more.

As the amide solvent, formamide, N
-Methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,
N-dimethylacetamide, N-ethylacetamide,
Examples include N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Be done. These amide solvents may be used either individually or in combination of two or more.

As the ester solvent, 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, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate
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 Methoxytriglycol, 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 are 1
One kind or two or more kinds may be used at the same time. As the aprotic solvent, acetonitrile, dimethyl sulfoxide, N,N,N',N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N −
Methyl-Δ3-pyrroline, N-methylpiperidine, N-
Ethylpiperidine, 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 and the like can be mentioned.

Among these organic solvents, the organic solvent represented by the following general formula (5) is particularly preferable. ^{_{R 8 O (CHCH 3 CH 2}} O) e R 9 ····· (5) (R 8 and R ⁹ are each independently a hydrogen atom, alkyl group or CH ₃ CO- 1 to 4 carbon atoms 1 chosen
Represents a valent organic group, and e represents an integer of 1 to 2. The above (D) organic solvent may 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 compounds (1) to (3) constituting the component (A) are hydrolyzed and/or condensed.

Specifically, water or water diluted with a solvent is intermittently or continuously added to the solvent in which the compounds (1) to (3) are dissolved. At this time, the component (B) may be added to the solvent in advance, or may be dissolved or dispersed in water when water is added. The reaction temperature at this time is usually 0 to 150° C., preferably 15 to 120° C.
Is.

Other Additives The film-forming composition obtained in the present invention further contains components such as colloidal silica, colloidal alumina, organic polymers, surfactants, silane coupling agents, radical generators and triazene compounds. May be added. Colloidal silica is, for example, a dispersion liquid in which high-purity silicic acid anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 5.
30 mμ, preferably 10 to 20 mμ, solid content concentration is 1
It is about 0 to 40% by weight. Examples of such colloidal silica include those manufactured by Nissan Chemical Industries, Ltd.
Examples include methanol silica sol and isopropanol silica sol; manufactured by Catalyst Kasei Kogyo Co., Ltd., Oscar, and the like. As colloidal alumina, Nissan Chemical Industry Co., Ltd.
Alumina sol 520, 100, 200; Kawaken Fine Chemical Co., Ltd.'s alumina clear sol, alumina sol 10, 132, etc. As the organic polymer, for example, a compound having a sugar chain structure, a vinylamide polymer, a (meth)acrylic polymer, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, a polyquinoxaline,
Examples thereof include polyoxadiazoles, fluoropolymers, compounds having a polyalkylene oxide structure, and the like.

As the compound having a polyalkylene oxide structure, a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples thereof include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene ethylene phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, alkylphenol formalin condensate ethylene oxide derivative, polyoxyethylene polyether Oxypropylene block copolymer, ether type compounds such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Examples thereof include ether ester type compounds, polyethylene glycol fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and 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 -
Represents a group represented by CH ₂ CH(CH ₃ )O-, and j is 1 to
90, k are 10 to 99, 1 is a number of 0 to 90) Among these, polyoxyethylene alkyl ether,
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
More preferred examples include ether type compounds such as These may be used either individually or in combination of two or more.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, and further, fluorine-based surfactants and silicone-based surfactants. Activators, polyalkylene oxide-based surfactants, poly(meth)acrylate-based surfactants and the like can be mentioned, with preference given to fluorine-based surfactants and silicone-based surfactants.

Examples of the fluorinated surfactant include 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-(perfluorooctane sulfone Amido)propyl]-N,N′-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamidopropyl trimethyl ammonium salt,
At least one of the terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. A fluorosurfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the site can be mentioned. Commercially available products are MegaFac F142D, F172, F173, and F1.
83 (above, manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC-430, FC-431.
(Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, same SC-103, same SC-104, same 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 fluorine-based surfactants can be mentioned. Among these, the Megafac F172, BM-1000, BM-11
00, NBX-15 are particularly preferred.

Examples of silicone-based surfactants include SH7PA, SH21PA, SH30PA, ST94P.
A (all are Toray Dow Corning Silicone Co., Ltd.)
It can be manufactured. Among these, the above S
H28PA and SH30PA are particularly preferable.

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 either individually 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-aminopropyltriamine Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-
Examples thereof include aminopropyltrimethoxysilane and N-bis(oxyethylene)-3-aminopropyltriethoxysilane. These may be used either individually or in combination of two or more.

Examples of the radical generator include isobutyryl peroxide, α,α'bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxy neodecanoate, di-npropylperoxydicarbonate, diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutylperoxyneodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutyl peroxydicarbonate, di(3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butyl peroxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di( 2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-
1-methylethylperoxy 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-)
Butyl peroxycyclohexyl)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-hexyl peroxybenzoate, 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-t-butylperoxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned.

The amount of radical generator compounded is 100
0.1 to 10 parts by weight is preferable with respect to parts by weight. These may be used either individually 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 either individually or in combination of two or more.

Method for Preparing Film-Forming Composition When preparing the film-forming composition of the present invention, for example, the compounds (1) to (3) are mixed in a solvent and water is continuously or intermittently added. Add, hydrolyze, condense,
After the component (A) is prepared, the component (D) may be added thereto, and there is no particular limitation.

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

The composition of the present invention was prepared by using a silicon wafer, Si
When applying to a base material such as an O ₂ wafer or SiN wafer, a coating means such as spin coating, dipping, roll coating or spraying is used.

The film thickness at this time is a dry film thickness of about 0.05 to 2.5 μm for one coating, and a thickness of about 0.1 to 5.0 μm for two coatings. be able to. Then, dry at room temperature or 80~600
A glassy or giant polymer insulating film can be formed by heating and drying at a temperature of about C for about 5 to 240 minutes. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere is under air, a nitrogen atmosphere,
It can be performed in an argon atmosphere, under vacuum, under reduced pressure with controlled oxygen concentration, and the like. The coating film can also be formed by irradiating with an electron beam or an ultraviolet ray. Further, in order to control the curing speed of the coating film, it is possible to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, or reduced pressure, if necessary.

The interlayer insulating film thus obtained is excellent in coating uniformity of coating film, low relative permittivity property, and mechanical strength after PCT, so that it is suitable for LSI, system LSI, DRA.
Interlayer insulating film for semiconductor elements such as M, SDRAM, RDRAM, and D-RDRAM, an etching stopper film, a protective film such as a surface coat film of a semiconductor element, an intermediate layer in a semiconductor manufacturing process using a multilayer resist, an interlayer of a multilayer wiring board It is useful for applications such as insulating films, protective films for liquid crystal display devices, and insulating films.

[0047]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the following description generally shows an example of the embodiment of the present invention, and the present invention is not limited to the description by no particular reason. In the examples and comparative examples, parts and% are parts by weight and% by weight, respectively, unless otherwise specified. Also,
Various evaluations were performed as follows.

Weight average molecular weight (Mw) It was measured by a gel permeation chromatography (GPC) method under the following conditions. Sample: Prepared by dissolving 1 g of the hydrolyzed condensate in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemicals was used. Device: High-temperature high-performance gel permeation chromatogram (Model 150-C ALC/GPC) manufactured by US Waters Co., Ltd. Column: SHODEX A-80M manufactured by Showa Denko KK
(Length 50 cm) Measurement temperature: 40° C. Flow rate: 1 cc/min

The composition for forming coating film uniformity was dried on an 8-inch silicon wafer using a spin coater on a hot plate at 90° C. for 3 minutes and in a nitrogen atmosphere at 200° C. for 3 minutes. The film thickness of the coating film thus obtained was measured by an optical film thickness meter (Ru
Made by dolph Technologies, Spec
50 points were measured on the surface of the coating film using a Tra Laser 200). 3σ of the obtained film thickness was calculated and evaluated according to the following criteria. ○: 3σ of the coating film is less than 12 nm ×: 3σ of the coating film is 12 nm or more The composition sample is applied onto a silicon wafer having a relative dielectric constant of 8 inches by the spin coating method, and the composition sample is applied on a hot plate at 90° C. for 3 minutes. Then, the substrate was dried in a nitrogen atmosphere at 200° C. for 3 minutes, and further baked at 425° C. in a nitrogen atmosphere (oxygen concentration 100 ppm) hot plate for 30 minutes, and an aluminum electrode pattern was formed by a vapor deposition method to obtain a relative dielectric constant measurement sample. Created. The sample is HP16 manufactured by Yokogawa/Hewlett-Packard Co. at a frequency of 100 kHz.
451B electrode and HP4284A precision LCR
The relative dielectric constant of the coating film was measured by the CV method using a meter.

Mechanical Strength (Elastic Modulus) After PCT A composition sample was applied onto an 8-inch silicon wafer by a spin coating method, and the composition was applied on a hot plate at 90° C. for 3 minutes and nitrogen atmosphere at 200° C. for 3 minutes. The substrate was dried and further baked on a hot plate at 425° C. in a nitrogen atmosphere (oxygen concentration 100 ppm) for 30 minutes. The obtained film was subjected to PCT for 1 hour under the conditions of 100° C., humidity of 100% RH and 2 atm. The elastic modulus of the obtained film was measured by a continuous stiffness measuring method using Nanoindenter XP (manufactured by Nano Instruments).

Synthesis Example 1 308.48 g of methyltrimethoxysilane and 96.28 g of tetramethoxysilane were placed in a quartz separable flask.
And 333 g of propylene glycol monoethyl ether were added and stirred uniformly. Calcium fluoride 1 in this solution
252 g of ion-exchanged water in which 0.0 g was dissolved was added over 1 hour. The reaction was carried out for 10 hours while keeping the solution at 90°C. To this solution was added 467 g of propylene glycol monoethyl ether, and then a solution containing methanol and water was added to the solution containing 467 g by using an evaporator at 50°C.
g was removed to obtain a reaction solution. The weight average molecular weight of the thus obtained condensate and the like was 980.

Synthetic Example 2 In the same manner as in Synthetic Example 1 except that magnesium fluoride was used in place of calcium fluoride in Synthetic Example 1,
A reaction solution was obtained. The weight average molecular weight of the thus obtained condensate and the like was 1,080.

Comparative Synthesis Example 1 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that calcium chloride was used instead of calcium fluoride. The weight average molecular weight of the thus obtained condensate and the like was 280.

Comparative Synthesis Example 2 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that propionic acid was used in place of calcium fluoride in Synthesis Example 1. The weight average molecular weight of the thus obtained condensate and the like was 1,350.

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 onto a silicon wafer by spin coating. The coating uniformity of the solution is 9.
It was excellent at 2 nm. The relative dielectric constant of the coating film was a low value of 2.81, and the elastic modulus of the coating film after PCT was 8.6 GPa, indicating excellent mechanical strength.

Example 2 Example 1 except that the reaction solution obtained in Synthesis Example 2 was used.
It evaluated similarly to. Application uniformity of solution is 8.7 nm
And was excellent. The relative permittivity of the coating film was a low value of 2.79, and the elastic modulus of the coating film after PCT was 8.9 GPa, indicating excellent mechanical strength.

Comparative Example 1 Evaluations were made in the same manner as in Example 1 except that the reaction solution obtained in Comparative Synthesis Example 1 was used, but the molecular weight of the solution was too small to form a coating film.

Comparative Example 2 Evaluations were made in the same manner as in Example 1 except that the reaction solution obtained in Comparative Synthesis Example 2 was used. The coating uniformity of the solution is 11.
Although it was excellent at 2 nm, the relative dielectric constant of the coating film was as high as 3.11, and the elastic modulus of the coating film after PCT was 3.9 GPa, which was inferior in mechanical strength.

[0059]

According to the present invention, the alkoxysilane is hydrolyzed and/or condensed in the presence of a specific metal fluoride salt and water, whereby the coating uniformity of the coating film and the low relative dielectric constant characteristics,
It is possible to provide a film forming composition (material for an interlayer insulating film) having excellent mechanical strength after PCT.

Front page continuation (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) H01L 21/316 H01L 21/316 GF term (reference) 4G072 AA25 BB09 FF01 FF02 FF09 GG02 HH30 JJ28 KK17 LL11 LL13 LL15 MM31 MM36 NN21 TT30 UU01 4J038 DL021 DL031 DL041 DL161 GA12 HA116 JA18 JA20 JA26 JA28 JA32 JA34 JA56 JA57 JB13 JB27 JB30 JB32 JB38 JB39 KA04 KA06 MA07 MA10 NA11 NA21 NA24 NA26 PA19 PB09 5F058 AA10 AC03 AF04 AH02

Claims (6)

[Claims] 1. At least one selected from the group consisting of: (A) a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3). One kind of silane compound is represented by R _a Si(OR ¹ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, and R ¹ is a monovalent organic group. , A represents an integer of 1 to 2) Si(OR ² ) ₄ (2) (In the formula, R ² represents a monovalent organic group.) R ³ _b (R ⁴ O) _3-b Si-(R ⁷ ) _d -Si(OR ⁵ ) _3-c R ⁶ _c ··· (3) [In the formula, R ³ and R ⁶ are the same or different and each is a hydrogen atom,
Fluorine atom or monovalent organic group, R ⁴ and R ⁵ are monovalent organic groups, b and c are the same or different and represent a number of 0 to 2, R ⁷ is oxygen atom, phenylene group or —(CH
₂ ) A group represented by _n − (where n is an integer of 1 to 6), and d represents 0 or 1. ] (B) A compound represented by the following general formula (4) and MF _e (4) (In the formula, M represents a metal atom and e represents a valence of the metal M.) (C) Water A film-forming composition comprising a hydrolyzed condensate which is hydrolyzed and condensed in the presence of the above, and (D) an organic solvent. 2. The film-forming composition according to claim 1, wherein the metal atom of the component (B) is one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium and calcium. 3. The amount of the component (B) used is 0.00001 to 1 mol based on 1 mol of the total amount of alkoxyl groups in the component (A).
The film-forming composition according to claim 1, wherein the composition is 10 mol. 4. The film-forming composition according to claim 1, wherein the organic solvent (D) is a solvent represented by the following general formula (5). ^{_{R 8 O (CHCH 3 CH 2}} O) f R 9 ····· (5) (R 8 and R ⁹ are each independently a hydrogen atom, alkyl group or CH ₃ CO- 1 to 4 carbon atoms 1 chosen
Represents a valent organic group, and f represents an integer of 1 to 2. ) 5. A method for forming a film, which comprises applying the composition for forming a film according to claim 1 to a substrate and heating the substrate. 6. A silica-based film obtained by the method for forming a film according to claim 5.