JP2000345041A - Composition for forming film, production of composition for forming film, and material for forming insulation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having improved storage stability and giving a film improved in uniformity, permittivity, and leak current characteristics by selecting a composition containing a hydrolyzate of a silane compound or a condensate of the hydrolyzate and having a specified propylene glycol content. SOLUTION: This composition contains at least either of a hydrolyzate and/or a condensate selected from a compound of formula I and a compound of formula II and a solvent of formula III of a purity of 99% (as measured by gas chromatography) and has a propylene glycol content of 10,000 ppm or below. In the formula, R1 is H, F, or a monovalent organic group; R2 to R6 are each a monovalent organic group; a, b, and c are each 0-2; R7 is O or -(CH2)n-; in formula II, n is 1-6; d is 0 or 1 ; R8 and R9 are each a monovalent organic group selected from H, a 1-4C alkyl, and CH3CO-; and e is 1-2. The composition desirably has an iron content and a sodium content each of which is 15 ppb or below and may contain a β-diketone, a compound having a polyalkylene oxide structure, or the like.

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 film having an appropriate uniform thickness as an interlayer insulating film material for a semiconductor device or the like, and having improved storage stability. The present invention relates to a film-forming composition which is excellent and has excellent dielectric constant and leak current characteristics of a coating film.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO2) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor element or the like. And
In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film mainly containing a hydrolysis product of tetraalkoxylan has been used. I have. Also,
With the high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant and mainly composed of polyorganosiloxane called organic SOG has been developed. However, with higher integration and multilayering of semiconductor devices and the like, more excellent electrical insulation between conductors is required, and therefore, an interlayer having good storage stability, a lower dielectric constant, and excellent leak current characteristics is required. An insulating film material is required.

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

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

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

However, when a metal chelate compound such as titanium or zirconium is combined with a silane compound as described above, the uniformity and storage stability of the coating film are not excellent, and the dielectric constant and leak current are well balanced. is not.

[0007]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a film-forming composition as an interlayer insulating film in a semiconductor device or the like, which has a high coating uniformity and storage stability. It is an object of the present invention to provide a material for an interlayer insulating film that is excellent in dielectric constant and leakage current characteristics.

The present invention relates to (A) (A-1) a compound represented by the following general formula (1): R ¹ aSi (OR ² ) 4-a (1) wherein R ¹ is a hydrogen atom , A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) represented by the following general formula (2) compound _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ may be the same or different, each represents a monovalent organic group, b and c may be the same or different, represents the number of 0 to 2, R ⁷ is an oxygen atom or - (CH2 ) _n - represents a group represented by, n
Represents 1 to 6, and d represents 0 or 1. Or (B) a hydrolyzate and / or a condensate of at least one compound selected from the group consisting of (B) a compound represented by the following general formula (3) and having a purity of 9 when measured by gas chromatography.
9% solvent R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (3) (R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 1 selected from CH ₃ CO-
Represents a valent organic group, and e represents an integer of 1 to 2. ), A method for producing the film-forming composition, and a material for forming an insulating film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

Component (A) Component (A-1) In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Can be. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

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

(A-2) Component In the above general formula (2), examples of the monovalent organic group include the same organic groups as those in the above general formula (1).
Examples of the divalent organic group represented by R ⁷ in the general formula (2) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (2), as the compound in which R ⁷ is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldimethyl Siloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,
3,3-pentaethoxy-3-phenyldisiloxane,
1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3
-Dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,
3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3
3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,
3-triethoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraphenyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetraphenyldisiloxane and the like. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3
Dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3
Preferred examples include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Compounds in which d is 0 in the general formula (2) include hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,1,2,2-pentamethoxy-2
-Methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2
-Pentaethoxy-2-phenyldisilane, 1,1,
2,2-tetramethoxy-1,2-dimethyldisilane,
1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-
1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,
1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane or the like, wherein R ⁷ in the general formula (2) is-(CH2) n-
Examples of the compound of the group represented by are bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, and bis (diethoxymethylsilyl) methane , Bis (dimethoxyphenylsilyl)
Methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl) ethane , Bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl) ethane, bis (diethoxyphenylsilyl) ethane , Bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane,
Bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1,3-bis (hexamethoxysilyl) propane, 1,3-bis (hexaethoxysilyl) propane, 1,3-bis (hexaphenoxysilyl) Propane, 1,3-bis (dimethoxymethylsilyl) propane, 1,3-bis (diethoxymethylsilyl) propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) Propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3-bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, 1,3-bis (ethoxydiphenylsilyl) propane, etc. Can be mentioned. Of these, hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2
2-tetraethoxy-1,2-dimethyldisilane, 1,
1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis ( Preferred examples include dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane. It can be mentioned as. In the present invention,
As the component (A), the components (A-1) and (A-
Component 2) or one of them may be used, and two or more of each of component (A-1) and component (A-2) may be used.

Component (B) The component (B) of the present invention is a solvent represented by the following general formula (3) (hereinafter referred to as “solvent 1”): R ⁸ O (CHCH ₃ CH ₂ O) _e R ^9. (3) (R ⁸ and R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—
Represents a valent organic group, and e represents an integer of 1 to 2. ). Here, the purity of the solvent 1 measured by gas chromatography is 99% or more, preferably 99.5% or more. Solvent 1 includes propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene Glycol diacetate and the like, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomer Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can be used alone or in combination of two or more.

In the present invention, the term “hydrolysis” refers to R ² O—, R ⁴ O—, and R ² O—
^It is not necessary that all the ⁵ O-groups be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. In the present invention, condensation refers to condensation of a silanol group of the hydrolyzate of the component (A) to form a Si—O—Si bond. In the present invention, however, it is not necessary that all of the silanol groups are condensed. The concept encompasses the formation of a mixture of a small amount of silanol groups and a mixture of those having different degrees of condensation.
In addition, the weight average molecular weight of the hydrolysis-condensation product of the component (A) is usually about 1,000 to 120,000, preferably about 1,200 to 100,000.

In the present invention, the amount of the component (B) used is in the range of 0.3 to 25 times the amount (weight) of the component (A) (in terms of a completely hydrolyzed condensate). In the present invention, the completely hydrolyzed condensate is an R ² O— group contained in the component (A),
R ⁴ O— and R ⁵ O— groups are hydrolyzed to 100%
H group, which is completely condensed.

The film-forming composition of the present invention may further contain the following organic solvent in an amount of 50% by weight or less of the solvent 1. As the organic solvent used in the present invention, for example, n-
Aliphatic hydrocarbons such as pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane Solvent: benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-
Aromatic hydrocarbon solvents such as propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene and trimethylbenzene; acetone, methyl ethyl ketone, methyl-n- Propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone,
Ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, phen Ketone solvents such as Chong; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether;
-Ethylhexyl ether, ethylene oxide, 1,2
-Propylene oxide, dioxolan, 4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene Glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol,
Ether solvents such as tetraethylene glycol di-n-butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate; I-propyl acetate, n-butyl acetate,
I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate,
Methylpentyl acetate, 2-ethylbutyl acetate, 2-acetic acid
Ethylhexyl, 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 acetate,
Diethylene glycol mono-n-butyl ether acetate,
Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate,
Ester solvents such as ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-
Dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-
Dimethylacetamide, N-methylpropionamide,
Nitrogen-containing solvents such as N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These can be used alone or in combination of two or more.

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

Other Additives Components such as colloidal silica, colloidal alumina, organic polymer and surfactant may be further added to the film-forming composition obtained in the present invention. Colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 m.
μ, preferably 10-20 μm, solid content concentration of 10-4
It is about 0% by weight. Examples of such colloidal silica include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industry Co., Ltd .; and Oscar manufactured by Catalyst Chemicals Co., Ltd. Examples of the colloidal alumina include alumina sols 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; and alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemicals Co., Ltd. As the organic polymer, for example, a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound,
Examples include dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, polyquinoxalines, polyoxadiazoles, and fluoropolymers.
As the surfactant, for example, a nonionic surfactant,
Examples thereof include anionic surfactants, cationic surfactants, amphoteric surfactants, and the like, and further include silicone surfactants, polyalkylene oxide surfactants, and poly (meth) acrylate surfactants. be able to.

The total solid content of the film-forming composition of the present invention is preferably 2 to 30% by weight, and is appropriately adjusted depending on the purpose of use. When the total solid content of the composition is 2 to 30
When it is% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The composition for film formation of the present invention has a propylene glycol content of 10,000 ppm or less, preferably 5000 ppm or less. When the propylene glycol content exceeds 10,000 ppm, a problem that storage stability of the coating film is deteriorated is likely to occur. Further, the composition of the present invention has a sodium content and an iron content of 15 ppb or less, respectively. If any one of the sodium content and the iron content exceeds 15 ppb, a problem that the leakage current of the coating film increases tends to occur.

The composition of the present invention is produced by dissolving the component (A) in the solvent 1 and hydrolyzing the component (A) usually by adding a catalyst and water. When the above component (A) is hydrolyzed and condensed, the components (A-1) and (A-2)
It is preferable to use 0.25 to 3 mol of water, preferably 0.3 to 2.5 mol of water per 1 mol of the group represented by R ² O—, R ⁴ O— and R ⁵ O— that the component has. It is particularly preferred to add If the amount of water to be added is in the range of 0.25 to 3 mol, there is no possibility that the uniformity of the coating film is reduced,
Further, it is because there is little possibility that the storage stability of the film-forming composition is reduced. Further, the water is preferably added intermittently or continuously. In the present invention, the temperature at which the component (A) is hydrolyzed is usually 0 to 100 ° C, preferably 15 to 80 ° C.

In hydrolyzing and condensing the component (A), a catalyst may be used. Examples of the catalyst used at this time include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base. Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy.
Mono (acetylacetonato) titanium, tri-n-butoxy mono (acetylacetonato) titanium, tri-s
ec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, Di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium, di-sec-butoxy.
Bis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n
-Propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxytris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonate) ) Titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri I-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl) Acetoace Over G) titanium, diethoxy-bis (ethylacetoacetate) titanium, di -n- propoxy bis (ethylacetoacetate) titanium, di -i-
Propoxy bis (ethyl acetoacetate) titanium,
Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) ) 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 (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, Titanium chelate compounds such as mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxymono (Acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) 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, diethoxy ·
Bis (acetylacetonate) zirconium, di-n-
Propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxybis (acetylacetonate) zirconium, di-sec-butoxy.
Bis (acetylacetonate) zirconium, di-t-
Butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (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 (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, Tri-s
ec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy.
Bis (ethylacetoacetate) zirconium, di-i
-Propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) ) Zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-
n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy.
Tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) Zirconium chelate compounds such as mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; and the like.

Examples of the organic acid include 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 and sebacin 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 the like. it can. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclookran, Examples thereof include diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Among these catalysts, metal chelate compounds,
Organic acids and inorganic acids are preferred, and more preferred are titanium chelate compounds and organic acids. These may be used alone or in combination of two or more.

The amount of the catalyst to be used is generally 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the total amount of the component (A) (in terms of complete hydrolysis condensate).
The range is 0 parts by weight. Further, the catalyst may be previously added to the solvent, or may be dissolved or dispersed in water at the time of adding water.

In the present invention, the content of the alcohol having a boiling point of 100 ° C. or less in the film-forming composition is 20% by weight or less,
In particular, it is preferably at most 5% by weight. Boiling point 100 ° C
The following alcohols are used as the component (A-1) and the component (A).
-2) It may occur during hydrolysis and / or condensation of the component, and it is preferable to remove the component by distillation or the like so that the content is 20% by weight or less, preferably 5% by weight or less.

[0027] The composition of the present invention is applied to a silicon wafer, Si
When applying to a substrate such as an O2 wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used.

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

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

[0030]

The present invention will now be described more specifically with reference to examples. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Further, the evaluation of the film-forming composition in the examples was measured as follows.

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

The composition for forming a uniform film thickness was applied onto an 8-inch silicon wafer using a spin coater under the conditions of a rotation speed of 1,700 rpm and 30 seconds. Thereafter, using a hot plate maintained at a temperature of 95 ° C., the silicon wafer coated with the film forming composition was heated for 5 minutes to disperse the organic solvent.
Next, the silicon wafer coated with the film-forming composition was heated for 5 minutes using a hot plate maintained at a temperature of 210 ° C. to form a coating film on the silicon wafer. The film thickness of the coating film thus obtained is measured by an optical film thickness meter (Ru).
Spec manufactured by dolph Technologies
(tra Laser 200), and 50 points were measured in the coating film surface. 3σ of the obtained film thickness was calculated and evaluated according to the following criteria. ；: 3σ of coating film is less than 35 nm ×: 3σ of coating film is 35 nm or more

Storage stability The film-forming composition stored at 37 ° C. for 35 days was applied on an 8-inch silicon wafer using a spin coater at a rotation speed of 1,700 rpm for 30 seconds. Then, using a hot plate maintained at a temperature of 95 ° C,
The silicon wafer coated with the film-forming composition was heated for 5 minutes to disperse the organic solvent. Next, the silicon wafer coated with the film-forming composition was heated for 5 minutes using a hot plate maintained at a temperature of 210 ° C. to form a coating film on the silicon wafer. The film thickness of the coating film thus obtained is measured using an optical film thickness meter (Rudolph Techno).
Spectra Laser20 manufactured by logies
Using 0), 50 points were measured in the coating film surface. The film thickness of the obtained film thickness was measured, and the film thickness increase rate determined by the following equation was used.
The storage stability was evaluated. Film thickness increase rate (%) = ((film thickness after storage) − (film thickness before storage)) ÷ (film thickness before storage) × 100 〇: film thickness change rate ≦ 10% △: 10% <film Thickness change rate ≦ 20% ×: 20% <Thickness change rate

A composition sample is applied on a silicon wafer having a dielectric constant of 8 inches by a spin coating method, and the substrate is dried on a hot plate at 95 ° C. for 5 minutes and at 210 ° C. for 5 minutes. The substrate was baked for 70 minutes in an oven in an atmosphere. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for permittivity evaluation. Dielectric constants were measured using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd. and an HP4284A.
It was calculated from the capacitance value at 10 kHz using a precision LCR meter.

The leakage current 8-inch silicon on the wafer is coated with a composition sample by spin coating, for 5 minutes at 95 ° C. on a hot plate, and dried for 5 minutes the substrate at 210 ° C., vacuum of more 450 ° C. The substrate was baked for 70 minutes in an oven in an atmosphere. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for evaluating leak current. Leakage current is Keithley
Use Co., Ltd. 6517A and apply 0.2MV / c
The current value when a voltage of m was applied was measured. The leak current of the coating film was evaluated according to the following criteria. ；: Leakage current is less than 7 × 10 ⁻¹⁰ A ×: Leakage current is 7 × 10 ⁻¹⁰ A or more

Synthesis Example 1 In a quartz separable flask, 135.7 g of methyltrimethoxysilane, 48.2 g of bis (triethoxysilyl) methane, and 1.1 g of diisopropoxytitanium bisethylacetyl acetate were placed in a quartz container. Propylene glycol monopropyl ether 135 purified by flash distillation
g, then stirred with a three-one motor,
The solution temperature was stabilized at 60 ° C. Next, ion-exchanged water 7
5 g was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. To this reaction solution, 190 g of propylene glycol monopropyl ether purified twice by distillation using a quartz container was added,
At 50 ° C., 190 g of a solution containing methanol and ethanol was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 5,700.

Synthesis Example 2 In a quartz separable flask, 101.8 g of methyltrimethoxysilane and 1,1,3,3-tetraethoxy-
70.4 g of 1,3-dimethylsiloxane was dissolved in 159 g of propylene glycol monomethyl ether which was distilled and purified twice using a quartz container, and stirred with a three-one motor to stabilize the solution temperature at 60 ° C. next,
70 g of ion-exchanged water in which 4.4 g of maleic acid was dissolved was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. To this reaction solution, 210 g of propylene glycol monomethyl ether twice purified by distillation using a quartz container was added, and a solution containing methanol and ethanol was added at 50 ° C. to the solution.
10 g was removed by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained is
It was 4,000.

Comparative Synthesis Example 1 A reaction was carried out in the same manner as in Synthesis Example 1 except that propylene glycol monopropyl ether which had not been subjected to distillation purification was used to obtain a reaction solution having a weight average molecular weight of 5,500. .

Example 1 The reaction solution obtained in Synthesis Example 1 was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a film-forming composition of the present invention. The obtained composition had a propylene glycol content of 200 ppm, a sodium content of 1.2 ppb, and an iron content of 1.8 ppb. The obtained composition was applied on a silicon wafer by a spin coating method. The thickness of the obtained coating film was 475 nm, and 3σ was as good as 8.4 nm. When the storage stability of the solution was evaluated,
The film increase rate after 5 days was 4.3%, indicating excellent storage stability. When the dielectric constant of the coating film was evaluated, it showed a low dielectric constant of 2.69. Furthermore, it was evaluated the leakage current of the coating film, 1.2 × 10 ^{-1 0} A low leakage current is obtained.

Example 2 Evaluation was performed in the same manner as in Example 1 except that the reaction solution obtained in Synthesis Example 2 was used. The obtained composition had a propylene glycol content of 205 ppm, a sodium content of 1.8 ppb, and an iron content of 2.2 ppb.
The thickness of the obtained coating film was 433 nm, and 3σ was as good as 9.9 nm. When the storage stability of the solution was evaluated, the film growth rate after 35 days was 8.1%, indicating excellent storage stability. Also, when the dielectric constant of the coating film was evaluated,
It showed a low dielectric constant of 2.70. Further, when the leak current of the coating film was evaluated, a low leak current of 1.8 × 10 ⁻¹⁰ A was obtained.

Example 3 Evaluation was carried out in the same manner as in Example 1 except that a solution obtained by adding 1 g of acetylacetone to 100 g of the reaction solution obtained in Synthesis Example 1 was used. The obtained composition had a propylene glycol content of 198 ppm and a sodium content of 1.
1 ppb and the iron content was 1.7 ppb. The thickness of the obtained coating film was 470 nm, and 3σ was 8.4 n.
m and good. When the storage stability of the solution was evaluated, the film growth rate after 35 days was 3.9%, indicating excellent storage stability. When the dielectric constant of the coating film was evaluated, it was 2.7.
It showed a low dielectric constant of 0. Furthermore, it was evaluated the leakage current of the coating film, 1.5 × 10 ^{-1 0} A low leakage current is obtained.

Example 4 Evaluation was performed in the same manner as in Example 1 except that a solution obtained by adding 10 g of polyisopropyl methacrylate having a molecular weight of about 4,000 to 100 g of the reaction solution obtained in Synthesis Example 2 was used. The resulting composition has a propylene glycol content of 205 ppm, a sodium content of 2.5 ppb,
The iron content was 3.3 ppb. The thickness of the obtained coating film was 399 nm, and 3σ was as good as 10.3 nm. When the storage stability of the solution was evaluated, the film growth rate after 35 days was 8.9%, indicating excellent storage stability. When the dielectric constant of the coating film was evaluated, it showed a low dielectric constant of 2.32. Furthermore, it was evaluated the leakage current of the coating film, 0.8 × 10 ^{-1 0} A low leakage current is obtained.

Example 5 Evaluation was performed in the same manner as in Example 1 except that a solution obtained by adding 10 g of polyethylene glycol having a weight molecular weight of about 2,000 to 100 g of the reaction solution obtained in Synthesis Example 2 was used. The propylene glycol content of the obtained composition is 2
05 ppm, the sodium content was 3.4 ppb, and the iron content was 5.2 ppb. The thickness of the obtained coating film was 393 nm, and 3σ was as good as 10.2 nm. When the storage stability of the solution was evaluated, the film growth rate after 35 days was 9.1%, indicating excellent storage stability. When the dielectric constant of the coating film was evaluated, it showed a low dielectric constant of 2.22. Furthermore, when the leakage current of the coating film was evaluated,
0.6 × 10 ^{-1 0} A low leakage current is obtained.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that the reaction solution obtained in Comparative Synthesis Example 1 was used. The obtained composition had a propylene glycol content of 15000 ppm, a sodium content of 53 ppb and an iron content of 88 ppb. The thickness of the obtained coating film was 476 nm,
σ was 40.2 nm, which was inferior to the uniformity of the coating film. When the storage stability of the solution was evaluated, the film increase rate after 35 days was 13.4%, which was inferior to the storage stability. When the dielectric constant of the coating film was evaluated, it showed a high dielectric constant of 3.02. Furthermore, when the leakage current of the coating film was evaluated,
A high leakage current of 19.5 × 10 ⁻¹⁰ A was obtained.

According to the present invention, by dissolving a hydrolyzate of alkoxysilane and / or a condensate thereof in a solvent having a specific purity, uniformity of coating film, storage stability, dielectric constant, and leakage current characteristics can be obtained. Thus, it is possible to provide a film-forming composition (material for an interlayer insulating film) having an excellent balance.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd. (reference) 4J002 CP031 EA016 EE026 EE048 EH026 EP016 EV206 EZ007 GQ01 5F058 AA03 AA10 AC03 AF04 AG01 AH01 AH02 BA06 BA20 BC05 BF46 BH01 BJ01 BJ02

Claims (7)

[Claims] (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound represented by the following general formula (2) _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ May be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH 2) _n represents a group represented by-
Represents 1 to 6, and d represents 0 or 1. Or a hydrolyzate and / or condensate of at least one compound selected from the group consisting of: (B) a solvent represented by the following general formula (3): R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (3) (R ⁸ and R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—
Represents a valent organic group, and e represents an integer of 1 to 2. ) And the content of propylene glycol is 10,000 p
pm or less. 2. The film forming composition according to claim 1, wherein the sodium content and the iron content are each 15 ppb or less. 3. The method for producing a film-forming composition according to claim 2, wherein the catalyst (C) is a metal chelate compound represented by the following general formula (4). R ¹⁰ _f M (OR ¹¹ ) _gf (4) (R ¹⁰ is a chelating agent, M is a metal atom, and R ¹¹ is C 2 to C 2.
5 represents an alkyl group or an aryl group having 6 to 20 carbon atoms, g represents the valence of the metal M, and f represents an integer of 1 to g. ) 4. The method for producing a film-forming composition according to claim 2, wherein the catalyst (C) is an acid catalyst. 5. The composition according to claim 1, further comprising at least one compound selected from the group consisting of a β-diketone, a compound having a polyalkylene oxide structure, and a (meth) acrylic polymer. A film-forming composition. 6. (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound represented by the following general formula (2) _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ May be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH 2) _n represents a group represented by-
Represents 0 or 1. ) At least one compound selected from the group consisting of (B) represented by the following general formula (3);
99% purity as measured by gas chromatography
The above solvent R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (3) (R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH 1 selected from ₃ CO-
Represents a valent organic group, and e represents an integer of 1 to 2. 2. The method according to claim 1, wherein the hydrolysis is carried out in the presence of a catalyst. 7. A material for forming an insulating film, comprising the composition for forming a film according to claim 1. Description: