JP2003179050A - Film-forming method, insulating film, and substrate for semiconductor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a forming method of an insulating film for semiconductors that has superior coherency with a film formed by a CVD (Chemical Vapor Deposition) method as an interlayer insulating film material in a semiconductor device or the like. <P>SOLUTION: In the film-forming method, a substrate is treated by an alkoxy silane compound having a reactivity group and the hydrolysis condensation product or either of them (A), at least one kind of silane compound that is selected from tetrafunctional alkoxy silane, trifunctional alkoxy silane, and difunctional alkoxy silane is heated by applying the hydrolysis condensation product that is subjected to hydrolysis and condensation under the presence of water and a catalyst, and a composition for film formation containing an organic solvent (B). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming method, and more particularly, as a material for an interlayer insulating film in a semiconductor device or the like, a CVD (Chemical Vapor) material.
The present invention relates to a method for forming an insulating film for a semiconductor, which has excellent adhesion to a film formed by the deposition method.

[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
For the purpose of forming 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 the further integration and multilayering of semiconductor elements and the like, there is a demand for an interlayer insulating film material having a lower relative permittivity, preferably a relative permittivity of 2.5 or less and excellent adhesion to a substrate. Has become.

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 have the problems that the adhesion to the substrate is inferior or the relative dielectric constant exceeds 2.5 when used alone.

[0004]

The present invention relates to a film forming method for solving the above problems, and more specifically, a CVD method as an interlayer insulating film in a semiconductor device or the like.
An object of the present invention is to provide a method for forming an insulating film for a semiconductor, which has excellent adhesion to a film formed by a method.

[0005]

[In the formula, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and represent a number of 0 to 2, and R ⁷ is an oxygen atom, a 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. ]

Next, the present invention relates to an insulating film obtained by the above film forming method. Next, the present invention relates to a semiconductor substrate using the above insulating film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate used in the present invention may be the one used in the usual semiconductor formation, and has a CVD film on its surface. This CVD film is
The deposited film contains Si and further contains at least one element selected from the group consisting of O, C, N, and H. As such a deposited film, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, silane, tetramethylsilane, trimethylsilane, dimethylsilane, methylsilane, ethylsilane, Phenylsilane, diphenylsilane, disilanomethane, bis (methylsilano) methane,
1,2-disilanoethane, 1,2-bis (methylsilano) ethane, 2,2-disilanopropane, 1,3,5-
Trisilano-2,4,6-trimethylene, 1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, trimethylsiloxane, 1,3-bis (silanomethylene) disiloxane, bis (1- Methyldisiloxanyl) methane, 2,2-bis (1-methyldisiloxanyl) propane, 2,4,6,8-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 2,4,6- Trisilane tetrahydropyran, 2,
Using 5-disilanetetrahydrofuran and derivatives thereof, oxygen, carbon monoxide, carbon dioxide, nitrogen,
A plasma polymerized deposited film in the presence of argon, water, ozone, ammonia, N ₂ O, etc. can be used.
In the film forming method of the present invention, the substrate with the above CVD film is
The method is characterized in that after treatment with an alkoxysilane compound having a reactive group and / or its hydrolysis-condensation product, the film-forming composition is applied and baked. In the step (A) of the present invention, the alkoxysilane compound has a reactive group such as an epoxy group, an isocyanate group, a vinyl group, a hydroxyl group, an acetoxy group, an amino group and a mercapto group,
The hydrolysis condensate can also be used.

Examples of the alkoxysilane compound having such a reactive group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 3-glycidyl. Sidoxypropylmethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5, 6-epoxyhexyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- [2- (vinylbenzylamino)]-3- Ami Trimethoxysilane, N-
[2- (vinylbenzylamino)]-3-aminopropyltriethoxysilane, N- (hydroxyethyl) -N
-Methylaminopropyltrimethoxysilane, N- (hydroxyethyl) -N-methylaminopropyltriethoxysilane, hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxypropyl Trimethoxysilane, acetoxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxy Silane, 3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N '
-Bis [3- (triethoxysilyl) propyl] ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like can be mentioned. Two or more kinds of these alkoxysilane compounds having a reactive group may be used at the same time.
As the alkoxysilane compound having these reactive groups, an alkoxysilane compound having an amino group is particularly preferable. The processing of the substrate in the step (A) of the present invention means
Specifically, it represents a step of applying the reactive group-containing alkoxysilane compound and / or its hydrolysis-condensation product onto the substrate with the CVD film, and then drying by heating. Examples of the method for applying the alkoxysilane compound having a reactive group and / or its hydrolyzed condensate to the substrate with a CVD film include spin coating, dipping, roll coating, spraying, and scan coating. A method is used. Of these coating methods, the spin coating method is particularly preferable. When applying the alkoxysilane compound having a reactive group and a hydrolysis-condensation product thereof or one of them, the alkoxysilane compound having a reactive group and a hydrolysis-condensation product thereof or any one of It can be diluted with a solvent before use. Examples of the organic solvent include alcohol solvents, ketone solvents, amide solvents,
At least one selected from the group consisting of an ester solvent and an aprotic solvent is included. Here, examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methyl. Butanol,
sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol,
sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, Mono-alcoholic solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol; ethylene glycol, 1,2 -Propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-
Polyhydric alcohol solvents such as 2,4, hexanediol-2,5, heptanediol-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, di Polyethylene 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, dipropylene glycol monopropyl ether, etc. And the like, such as a partial alcoholic ether solvent. These alcohol solvents may be used either individually or in combination of two or more. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl. In addition to ketones, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone and fenchon, 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,
Examples include β-diketones such as 5-heptanedione and 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. Examples of the amide solvent include formamide, N-methylformamide,
N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N
-Methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N -Acetylmorpholine, N-acetyl piperidine, N-acetyl pyrrolidine, etc. are mentioned. 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, s-acetic acid
ec-pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate,
Ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetic acid Propylene glycol monopropyl ether, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-propionate Amyl, diethyl oxalate, di-n-butyl oxalate, Methyl acid, ethyl lactate, n
-Butyl, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used either individually or in combination of two or more. 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 (1
H) -pyrimidinone and the like. Among these organic solvents, the organic solvent represented by the following general formula (4) is particularly preferable. R ¹⁵ O (CHCH ₃ CH ₂ O) _g R ¹⁶ (4) (R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—. The selected monovalent organic group is shown, and g represents an integer of 1 to 2.) The above organic solvents may be used alone or in combination of two or more. A hot plate, an oven, a furnace or the like can be used when the alkoxysilane compound having the reactive group and / or the hydrolysis-condensation product thereof having been coated on the substrate with the CVD film is dried by heating. The heating atmosphere can be performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like.
Drying is usually performed at 60 ° C. to 400 ° C., preferably 60 ° C. to 200 ° C., usually for 30 seconds to 2 hours, preferably for 30 seconds to 1 hour. By the process of the above step (A),
The alkoxysilane compound having a reactive group on the substrate with a CVD film and / or its hydrolysis-condensation product is usually 200 nm or less, preferably 100 nm or less,
Particularly preferably, the deposition is 50 nm or less. By treating the above-mentioned substrate with a CVD film with an alkoxysilane compound having a reactive group and / or a hydrolyzate thereof, the affinity between the CVD film and the (B) insulating film composition described later increases, The adhesion between the CVD film and the insulating film is improved. When the insulating film composition (B) is applied to the CDV film-coated substrate treated as in the above step (A), spin coating, dipping, roll coating, spraying, scan coating, etc. may be used. A coating means is used. Among these coating methods, the spin coating method is particularly preferable. The film thickness at this time is
As a dry film thickness, the thickness is 0.02-2.5 μm after one coating.
A film having a thickness of about 0.04 to 5 μm can be formed by coating twice. Then, it is dried at room temperature, or at a temperature of about 80 to 600 ° C, usually 5 to 240
By heating for about a minute and drying, a glassy or giant polymer 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, and a heating atmosphere can be an atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. It can be carried out. Also, by irradiating with an electron beam or ultraviolet rays
A film can be formed. Since the interlayer insulating film thus obtained has excellent adhesion to the CVD film,
LSI, system LSI, DRAM, SDRAM, RD
An interlayer insulating film for semiconductor elements such as RAM and D-RDRAM, an etching stopper film, a protective film such as a surface coating film of a semiconductor element, an intermediate layer of a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film of a multilayer wiring board, a liquid crystal It is useful for applications such as a protective film or an insulating film for a display element, a protective film or an insulating film for an electroluminescent display element.

In the present invention, the hydrolytic condensate described in (B) means at least one hydrolyzate selected from the group of the compounds (1) to (3) and its condensate or either one. is there. In the present invention, the hydrolyzate is an alkoxysilane compound having a reactive group and R ¹ O-group and R ² O- contained in the compounds (1) to (3).
It is not necessary that all groups, R ⁴ O-groups and R ⁵ O-groups, be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or , Or a mixture thereof. Further, in the present invention, the condensate is one in which the silanol groups of the hydrolyzates of the compounds (1) to (3) are condensed to form a Si—O—Si bond, but in the present invention, the silanol groups are It is not necessary to condense all, and it is a concept including a compound in which a small amount of a silanol group is condensed, a mixture of compounds having different degrees of condensation, and the like.

Compound (1): In the above general formula (1), examples of the monovalent organic group of R and R ¹ include an alkyl group, an aryl group and an allyl 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 carbon atom.
To 5 and 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), as the aryl group, a phenyl group, a naphthyl group, a methylphenyl group,
Examples thereof include an ethylphenyl group, a chlorophenyl group, a bromophenyl group and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-. 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, 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-tert-butoxysilane, n
-Butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, s
ec-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-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n -Butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-te
rt-Butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-
n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane and the like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane,
Dimethyl-di-iso-propoxysilane, dimethyl-
Di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n
-Propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-te
rt-butoxysilane, diethyldiphenoxysilane,
Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di -N-butoxysilane, di-n-propyl-di-sec-butoxysilane,
Di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-
Propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxy. Silane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n -Butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl -Di-sec-butoxysilane, di-n-
Butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, The-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 and the like can be mentioned.

Preferred compounds as the compound (1) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy For example, silane. 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 and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane.

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 −
(CH _{2) n} - Examples of the compound group represented by bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri -n- propoxy) 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, as the compounds (1) to (3) constituting the alkoxysilane hydrolysis condensate, one kind or two or more kinds of the compounds (1), (2) and (3) can be used.

When the alkoxysilane compound having a reactive group used in the present invention and the compounds (1) to (3) are hydrolyzed and condensed, 0.5 to 150 mol of the alkoxysilane hydrolyzed condensate is used per mol of the alkoxysilane hydrolyzed condensate. Water is preferably used, and it is particularly preferable to add 1 to 100 mol of water. If the amount of water added is 1 mol or less, the crack resistance of the film may be poor, and if it exceeds 150 mol, precipitation or gelation of the polymer may occur during the hydrolysis and condensation reaction.

When the alkoxysilane compound having a reactive group used in the present invention and at least one silane compound selected from the group of the compounds (1) to (3) are hydrolyzed and condensed, the above-mentioned reactive group is used. When the alkoxysilane compound and at least one silane compound selected from the group of compounds (1) to (3) are hydrolyzed and condensed, an alkali catalyst, an acid catalyst, and a metal chelate compound are used.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine,
Picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, ammonia,
Methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine,
N, N-dimethylamine, N, N-diethylamine,
N, N-dipropylamine, N, N-dibutylamine,
Trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine and the like can be mentioned, and amines or amine salts are preferable. ,
Organic amines or organic amine salts are particularly preferable, and alkylamines and tetraalkylammonium hydroxides are most preferable. These alkali catalysts may be used either individually or in combination of two or more.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tritium. -N-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy.
Bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) titanium, di-i-
Propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) Titanium, monoethoxy tris (acetylacetonate) titanium, mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy.
Tris (acetylacetonate) titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate)
Titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate)
Titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium, tri-n-butoxy mono (ethylacetoacetate) Acetate) Titanium, Tri-s
ec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, di-sec-butoxy bis (ethylacetoacetate) titanium, di-t.
-Butoxy bis (ethylacetoacetate) titanium,
Monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy tris (ethylacetoacetate). ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelate compounds such as titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy・ Mono (acetylacetonato) zirconium, tri-
n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylaceto) Nart) zirconium,
Tri-t-butoxy mono (acetylacetonato) zirconium, diethoxy bis (acetylacetonato) zirconium, di-n-propoxy bis (acetylacetonato) zirconium, di-i-propoxy.
Bis (acetylacetonato) zirconium, di-n-
Butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono -N-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy tris (acetylacetonato) zirconium, mono-n-butoxy tris (acetylacetonato) zirconium, mono-sec-butoxy tris (acetyl) Acetonato) zirconium, mono-t-butoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethylacetoacetate) zirconium Tri -n- propoxy mono (ethylacetoacetate) zirconium, tri -i
-Propoxy mono (ethylacetoacetate) zirconium, tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-
Butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di- n-butoxy bis (ethylacetoacetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium , Mono-n
-Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-
sec-Butoxy tris (ethyl acetoacetate)
Zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate). Zirconium, a zirconium chelate compound such as tris (acetylacetonato) mono (ethylacetoacetate) zirconium; an aluminum chelate compound such as tris (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum; Is a chelate compound of titanium or aluminum, particularly preferably a chelate compound of titanium. These metal chelate compounds may be used either individually or in combination of two or more.

As the acid catalyst, for example, hydrochloric acid,
Inorganic acids such as nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid; acetic acid, propionic acid, butanoic acid, pentanoic acid,
Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic 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, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, An organic acid such as a hydrolyzate of phthalic anhydride can be mentioned, and an organic carboxylic acid can be mentioned as a more preferable example. These acid catalysts may be used either individually or in combination of two or more.

The amount of the above catalyst used is the alkoxysilane compound having a reactive group and the alkoxyl group or R ¹ O-group, R ² O-group, R ⁴ O in the compounds (1) to (3).
− Group and R ⁵ O— group based on the total amount of 1 mol, usually 0.00001 to 10 mol, preferably 0.1.
It is from 00005 to 5 mol. When the amount of the catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction. In the present invention, the temperature for hydrolyzing the alkoxysilane compound having a reactive group and the compounds (1) to (3) is usually 0 to 100 ° C, preferably 15
~ 80 ° C.

When the compounds (1) to (3) are converted into complete hydrolysis-condensation products, 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 the total amount of (3) is 5 to 75% by weight, the elastic modulus of the obtained film is high and the low dielectric property is particularly excellent. Here, in the present invention, the complete hydrolysis-condensation product means an alkoxysilane compound having a reactive group and an alkoxyl group or R ¹ O— group in the compounds (1) to (3),
R ² O-group, R ⁴ O-group and R ⁵ O-group 100% hydrolyzed to become SiOH groups, more fully condensed refers to became siloxane structure.

The film-forming composition used in the present invention usually comprises an alkoxysilane hydrolyzed condensate dissolved or dispersed in an organic solvent. Examples of the organic solvent include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents and aprotic solvents. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol, t-butanol, n-pentanol,
i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, se
c-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2
-Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4,
n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol,
Cyclohexanol, methylcyclohexanol, 3,
Monoalcoholic solvents such as 3,5-trimethylcyclohexanol, benzyl alcohol and 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 may be 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., 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. To be These amide solvents may be used either individually or in combination of two or more.

Ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ.
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, 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 (4) is particularly preferable. R ¹⁵ O (CHCH ₃ CH ₂ O) _g R ¹⁶ (4) (R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—. The selected monovalent organic group is shown, and g represents an integer of 1 to 2.) The above organic solvents may be used alone or in combination of two or more.

Other Additives Components such as colloidal silica, an organic polymer, a surfactant, a silane coupling agent and a radical generator may be further added to the film forming composition used in the present invention.
Examples of the compound having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether,
Ether type such as polyoxyethylene phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether Compound, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, ether ester type compound such as polyoxyethylene fatty acid alkanolamide sulfate, polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride , Polyglycerin fatty acid ester, sorbitan fatty acid Ether, propylene glycol fatty acid esters, ether-ester type compounds such as sucrose fatty acid esters, and the like. 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, and 1 is a number from 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. 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 fluorine-based 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, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl phosphate) -N-ethylaminoethyl), monoperfluoroalkylethyl phosphoric acid ester and the like, and a fluorosurfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain sites. be able to. Also, as commercially available products, Megafac F142D, F172, F173, 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, the same 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, S
H30PA and ST94PA (both manufactured by Toray Dow Corning Silicone Co., Ltd., etc. can be used.
Among these, SH28PA and SH30PA are particularly preferable. The amount of the surfactant used is usually 0.0001 to 10 parts by weight based on the alkoxysilane hydrolysis condensate (complete hydrolysis 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-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triacetate 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 and 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 per Cide, 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 blending amount of the radical generator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer. These may be used either individually or in combination of two or more.

The total solid content concentration of the film-forming composition used in the present invention thus obtained is preferably 1 to 3.
It is 0% by weight and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 1 to 30% by weight, the film thickness of the film is in an appropriate range, and the storage stability is more excellent. The total solid content concentration is adjusted, if necessary, by concentration and dilution with the above organic solvent.

Since the interlayer insulating film obtained by the method according to the present invention has excellent adhesion to the CVD film, LS
I, system LSI, DRAM, SDRAM, RDRA
Interlayer insulating films and etching stopper films for semiconductor elements such as M and D-RDRAM, protective films such as surface coating films for semiconductor elements, intermediate layers in semiconductor manufacturing processes using multilayer resists, interlayer insulating films for multilayer wiring boards, liquid crystals It is useful for applications such as a protective film or an insulating film for a display element, a protective film or an insulating film for an electroluminescent display element.

[0040]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the following description is a general description of example embodiments of the present invention, and the present invention is not limited to the description without particular reason. In addition, unless otherwise indicated, the part and% in an Example and a comparative example have shown that it is a weight part and weight%, respectively. Also,
Various evaluations were performed as follows.

Radius of inertia Measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) method under the following conditions. Sample solution: The alkoxysilane hydrolysis condensate was diluted with methanol containing 10 mM LiBr so that the solid content concentration became 0.25%, and GPC (refractive index,
A sample solution for viscosity and light scattering measurement) was used. Apparatus: Tosoh Corp., GPC system model GPC-8020 Tosoh Corp., column Alpha5000 / 3000 Viscotech Co., viscosity detector and light scattering detector model T-60 dual meter Carrier solution: 10 mM LiBr Containing methanol Carrier delivery rate: 1 ml / min Column temperature: 40 ° C

The composition sample was applied onto a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, and the substrate was dried on a hot plate at 80 ° C. for 1 minute and in a nitrogen atmosphere at 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for measuring relative permittivity. Frequency of the sample is 100k
Yokogawa / Hewlett Packard Co., Ltd. at a frequency of Hz
Manufactured by HP16451B electrode and HP4284A precision LCR meter, the relative dielectric constant of the film was measured by CV method.

Adhesion of Laminated Film Regarding the adhesiveness of the laminated film, ten stud pins were fixed to the uppermost layer of the substrate using an epoxy resin and dried at 150 ° C. for 1 hour. This stud pin was subjected to a pull-out test using the Sebastian method, and the adhesion was evaluated according to the following criteria. ○: 10 stud pins, no peeling at the interface between the CVD film and the film ×: Peeling occurred at the interface between the CVD film and the film

Synthesis Example 1 Distilled ethanol 570 was placed in a quartz separable flask.
g, 160 g of ion-exchanged water, and 30 g of a 10% tetramethylammonium hydroxide aqueous solution were added and uniformly stirred. A mixture of 136 g of methyltrimethoxysilane and 209 g of tetraethoxysilane was added to this solution. 60 solution
The reaction was carried out for 5 hours while maintaining the temperature at ℃. 300 g of propylene glycol monopropyl ether was added to this solution, and then the solution was added to 1 by using an evaporator at 50 ° C.
The solution was concentrated until it became 0% (completely hydrolyzed condensate), and then 10 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a reaction solution. The radius of gyration of the condensate and the like thus obtained is 17.8 nm.
And the relative dielectric constant was 2.23.

Synthesis Example 2 In a quartz separable flask, distilled ethanol 470.
9 g, ion-exchanged water 226.5 g and 10% potassium hydroxide aqueous solution 10.2 g were added and stirred uniformly. A mixture of 44.9 g of methyltrimethoxysilane and 68.6 g of tetraethoxysilane was added to this solution over 30 minutes. The reaction was carried out for 2 hours while keeping the solution at 55 ° C.
To this solution, 80 g of 20% maleic acid aqueous solution was added, and after sufficiently stirring, it was cooled to room temperature. 400 g of propylene glycol monopropyl ether was added to this solution, and then the solution was adjusted to 10% using an evaporator at 50 ° C.
It concentrated until it became (completely hydrolyzed condensate conversion), and then 10 g of a 10% propylene glycol monopropyl ether solution of maleic acid was added to obtain a reaction solution. The radius of gyration of the condensate or the like thus obtained is 23.4.
nm, and the relative dielectric constant was 2.14.

Synthesis Example 3 324.40 g of methyltrimethoxysilane and 123.64 of triethoxysilane were placed in a quartz separable flask.
g, propylene glycol monoethyl ether 298
After dissolving in g, stir with a three-one motor,
The solution temperature was stabilized at 50 ° C. Next, phthalic acid 0.20
254 g of ion-exchanged water having g dissolved therein was added to the solution over 1 hour. Then, after reacting at 50 ° C. for 3 hours, 502 g of propylene glycol monoethyl ether
Was added and the reaction solution was cooled to room temperature. A solution containing methanol and ethanol was removed from the reaction solution at 50 ° C. by 502 g of evaporation to obtain a reaction solution. The thus obtained condensate or the like had a radius of gyration of 0.2 nm and a relative dielectric constant of 2.75.

Synthesis Example 4 77.04 g of distilled trimethoxysilane and 0.48 g of distilled tetrakis (acetylacetonate) titanium were dissolved in 290 g of distilled propylene glycol monopropyl ether in a separable flask made of quartz, and then three-one motor was used. The solution temperature was stabilized at 60 ° C. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, 25 g of distilled acetylacetone was added, and the reaction was further continued for 30 minutes, and the reaction solution was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain 149 g of a reaction solution. The thus obtained condensate and the like had an inertial radius of 0.3 nm and a relative dielectric constant of 2.99.

Synthesis Example 5 In a quartz separable flask, 324.40 g of vinyltrimethoxysilane was dissolved in 298 g of propylene glycol monoethyl ether, and the mixture was stirred with a three-one motor to stabilize the solution temperature at 50 ° C. next,
254g of ion-exchanged water with 0.20g of phthalic acid dissolved
Was added to the solution over 1 hour. Then, after reacting at 50 ° C. for 1 hour, 502 g of propylene glycol monoethyl ether was added and the reaction solution was cooled to room temperature. Fifty
Add a solution containing methanol and ethanol from the reaction solution at 5 ℃.
After removing by 02 g evaporation, 300 g of propylene glycol monopropyl ether was added to obtain a reaction solution.

Synthesis Example 6 In a quartz separable flask, 324.40 g of 3-mercaptotrimethoxysilane was dissolved in 298 g of propylene glycol monoethyl ether, and the mixture was stirred with a three-one motor to stabilize the solution temperature at 50 ° C. It was Next, 254 g of ion-exchanged water having 0.20 g of maleic acid dissolved therein was added to the solution over 1 hour. afterwards,
After reacting at 50 ° C. for 1 hour, 502 g of propylene glycol monoethyl ether was added and the reaction solution was cooled to room temperature. After removing 502 g of a solution containing methanol and ethanol from the reaction solution by evaporation at 50 ° C., 300 g of propylene glycol monopropyl ether was added to obtain a reaction solution.

Example 1 Applied Mate on an 8-inch silicon wafer
Using Producer S manufactured by Rial, a CVD film of tetraethoxysilane was formed at 1000 Å. The elemental composition of this film is Si (32 atomic%), O (64a)
tomic%) and H (4 atomic%). Propylene glycol monopropyl ether in which 3-glycidoxypropyltriethoxysilane was dissolved in a concentration of 2% was coated on this film for 20 seconds at a rotation speed of 1500 rpm, and this substrate was coated at 80 ° C for 1 minute and at 200 ° C for 1 minute. The substrate was dried for a minute. Further, 50 reaction liquid is applied on this substrate.
After applying 00Å, the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 2 Applied Mate on an 8-inch silicon wafer
Using Producer S manufactured by Rial, a CVD film of tetramethylsilane was formed in an amount of 1000Å. The elemental composition of this film is Si (26 atomic%), O (3 atom%).
ic%), C (26atomic%), H (45ato)
mic%). On this film, propylene glycol monopropyl ether in which N- [2- (vinylbenzylamino)]-3-aminopropylpyrimethoxysilane was dissolved in a concentration of 2% was applied at a rotation speed of 1500 rpm for 20 seconds, and the temperature was adjusted to 80 ° C. The substrate was dried for 1 minute at 200 ° C. for 1 minute. Furthermore, 4000 Å reaction liquid on this substrate
After coating, the substrate was dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 3 Sever made by Nevelus on an 8-inch silicon wafer
C. of trimethylsilane by using uel Express
A VD film of 1000 Å was formed. The elemental composition of this film is
Si (25 atomic%), O (4 atomic)
%), C (21 atomic%), N (14 atomi)
c%) and H (36 atomic%). On this film, propylene glycol monopropyl ether in which 3-isocyanatopropyltriethoxysilane was dissolved at a concentration of 2% was applied at a rotation speed of 1500 rpm for 20 seconds, and the substrate was dried at 80 ° C for 1 minute and 200 ° C for 1 minute. did. Further, 4000 liters of the reaction solution was applied onto this substrate, and then the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 4 Seq from Nevellus on an 8-inch silicon wafer
Using uel Express, a CVD film of silane and ammonia was formed to 1000 Å. The elemental composition of this film is Si (50 atomic%), O (4 atomic%).
%), C (3 atomic%), N (40 atomic)
%) And H (4 atomic%). On this film, propylene glycol monopropyl ether in which N- (hydroxyethyl) -N-methylpropyltrimethoxysilane was dissolved in a concentration of 2% was rotated at a rotation speed of 1500 rpm.
For 20 seconds and dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute. In addition, the reaction solution is placed on this substrate 4 times.
After applying 000Å, the substrate was dried at 80 ° C for 1 minute and at 200 ° C for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 5 Seq made by Nevelus on an 8-inch silicon wafer
C. of trimethylsilane by using uel Express
A VD film of 1000 Å was formed. The elemental composition of this film is
Si (25 atomic%), O (4 atomic)
%), C (21 atomic%), N (14 atomi)
c%) and H (36 atomic%). On this film, acetoxymethyltriethoxysilane with a concentration of 2%
The propylene glycol monopropyl ether dissolved in was applied at a rotation speed of 1500 rpm for 20 seconds, and the substrate was dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute. Further, 4000 g of a mixed solution of 20 g of the reaction solution and 20 g of the reaction solution was applied on this substrate, and then the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes.

Example 6 Applied Mate on an 8-inch silicon wafer
Using Producer S manufactured by Rial, a CVD film of tetramethylsilane was formed in an amount of 1000Å. The elemental composition of this film is Si (26 atomic%), O (3 atom%).
ic%), C (26atomic%), H (45ato)
mic%). On this film, propylene glycol monopropyl ether in which N- (2-aminoethyl) -3-aminopropylpyrimethoxysilane was dissolved in a concentration of 2% was applied at a rotation speed of 1500 rpm for 20 seconds, and 8
The substrate was dried at 0 ° C. for 1 minute and 200 ° C. for 1 minute. Further, after applying 4000 Å of a mixed solution of 20 g of the reaction solution and 20 g of the reaction solution on this substrate, the mixture was applied at 80 ° C. for 1 minute for 20 minutes.
The substrate was dried at 0 ° C for 1 minute. In addition, this substrate 405
The substrate was baked for 30 minutes on a hot plate in a nitrogen atmosphere at 0 ° C. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 7 Sever made by Nevelus on an 8-inch silicon wafer
C. of trimethylsilane by using uel Express
A VD film of 1000 Å was formed. The elemental composition of this film is
Si (25 atomic%), O (4 atomic)
%), C (21 atomic%), N (14 atomi)
c%) and H (36 atomic%). On this film, propylene glycol monopropyl ether in which 3-mercaptopropyltriethoxysilane was dissolved in a concentration of 2% was applied at a rotation speed of 1500 rpm for 20 seconds, and 8
The substrate was dried at 0 ° C. for 1 minute and 200 ° C. for 1 minute. Furthermore, after applying 4000 Å reaction solution on this substrate,
The substrate was dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 8 Sever made by Nevelus on an 8-inch silicon wafer
Using uel Express, a CVD film of silane and ammonia was formed to 1000 Å. The elemental composition of this film is Si (50 atomic%), O (4 atomic%).
%), C (3 atomic%), N (40 atomic)
%) And H (4 atomic%). On this membrane, the reaction liquid obtained in Synthesis Example 5 was rotated at a rotation speed of 1500 rp.
m for 20 seconds and dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute. Furthermore, after applying 4000 Å of the reaction solution on this substrate, it is heated at 80 ° C for 1 minute and at 200 ° C for 1 minute.
The substrate was dried for a minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes. When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Example 9 Seq from Nevelus on an 8-inch silicon wafer
C. of trimethylsilane by using uel Express
A VD film of 1000 Å was formed. The elemental composition of this film is
Si (25 atomic%), O (4 atomic)
%), C (21 atomic%), N (14 atomi)
c%) and H (36 atomic%). On this membrane, the reaction solution obtained in Synthesis Example 6 was rotated at a rotation speed of 1500r.
pm for 20 seconds, 80 ℃ for 1 minute, 200 ℃ for 1 minute
The substrate was dried for a minute. Further, 4000 liters of the reaction solution was applied onto this substrate, and then the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. Further, this substrate was baked on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes.
When the adhesion of this laminated film was evaluated, no peeling was observed at the interface between the CVD film and the film.

Comparative Example 1 Applied Mate on an 8-inch silicon wafer
Using Producer S manufactured by Rial, a CVD film of tetraethoxysilane was formed at 1000 Å. The elemental composition of this film is Si (32 atomic%), O (64a)
tomic%) and H (4 atomic%). After applying 5000 Å of the reaction solution on this film, 80 ℃
The substrate was dried for 1 minute at 200 ° C. for 1 minute. Further, this substrate was heated on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes.
The substrate was baked for minutes. When the adhesion of this laminated film was evaluated, peeling at the interface between the CVD film and the film was observed with seven stud pins.

Comparative Example 2 Applied Mate was formed on an 8-inch silicon wafer.
Using Producer S manufactured by Rial, a CVD film of tetraethoxysilane was formed at 1000 Å. The elemental composition of this film is Si (32 atomic%), O (64a)
tomic%) and H (4 atomic%). After applying 4000 Å of reaction solution on this film,
The substrate was dried for 1 minute at 200 ° C. for 1 minute. Further, this substrate was heated on a hot plate in a nitrogen atmosphere at 405 ° C. for 30 minutes.
The substrate was baked for minutes. When the adhesion of this laminated film was evaluated, peeling was observed at the interface between the CVD film and the film with four stud pins.

[0061]

EFFECTS OF THE INVENTION According to the present invention, a film forming method is applied in which an alkoxysilane compound having a reactive group and / or a hydrolysis-condensation product thereof is treated and then a hydrolysis-condensation product of an alkoxysilane is laminated. By that, C
Interlayer insulating film with excellent adhesion to VD film (semiconductor substrate)
It is possible to provide.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/25 C09D 5/25 183/02 183/02 183/04 183/04 183/14 183/14 H01L 21/312 H01L 21/312 C 21/768 21/90 QS (72) Inventor Mitsunori Nishikawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Kinji Yamada Chuo-ku, Tokyo Tsukiji 2-chome 11-24 F-Term in JSR Co., Ltd. (reference) 4D075 BB26Z CA13 CA23 CA47 DA06 DB13 DB14 DC22 DC24 EA07 EC03 EC54 4J038 DL021 DL022 DL031 DL032 DL041 DL042 DL071 DL072 DL161 DL162 JA26 KA04 KA06 PA07 PA14 NA14 PA14 PA14 PB09 5F033 HH08 PP19 RR04 RR23 SS04 SS11 SS22 TT03 TT04 VV15 VV16 XX12 XX24 5F058 AA08 AC03 AD05 AD10 AD12 AF04 AG01 AH02 BA10 BC05 BD01 BD04 BD15 BF46 BH03 BH04 BJ02

Claims (6)

[Claims] 1. A substrate is treated with (A) an alkoxysilane compound having a reactive group and / or a hydrolysis-condensation product thereof, and then (B) a compound represented by the following general formula (1), and the following general formula: Hydrolysis condensation in which at least one silane compound selected from the group of compounds represented by formula (2) and compounds represented by the following general formula (3) is hydrolyzed and condensed in the presence of water and a catalyst. A film-forming method comprising applying a film-forming composition containing a substance and an organic solvent and heating the composition. R _a Si (OR ¹ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom, an alkyl group or an aryl group, R ¹ is a monovalent organic group, and a is 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) wherein, R ³ to R ⁶ are the same or different, each represents an alkyl group or an aryl group, b and c are the same or different, Represents a number of 0 to 2 and R ⁷ is an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _n — (where n is 1
Is an integer of 6), and d represents 0 or 1. ] 2. The reactive group contained in the alkoxysilane compound in the step (A) is at least one selected from the group consisting of an epoxy group, an isocyanate group, a vinyl group, a hydroxyl group, an acetoxy group, an amino group and a mercapto group. The film forming method according to claim 1, which is characterized in that. 3. The film forming method according to claim 1, wherein the catalyst used in the hydrolytic condensation of the silane compound in step (B) is an alkali catalyst. 4. The substrate contains Si and contains O, C, N,
The film forming method according to claim 1, further containing at least one element selected from the group H. 5. An insulating film obtained by the film forming method according to claim 1. 6. A semiconductor substrate using the insulating film according to claim 5.