JP2001011377A - Film-forming composition, formation of film and low density film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-forming composition excellent in dielectric characteristics, resistance to oxygen plasma and mechanical strength and useful as a material, etc., for interlayer insulation films by including hydrolyzate, etc., of a specific organosilicon compound and a compound of prescribed boiling point, etc. SOLUTION: This film-forming composition comprises (A) a hydrolyzate of a compound mixture containing compounds of formulas I and II [R1 to R3 are each a monovalent organic group; (n) is 0-2] and its partial condensation product or either one compound thereof and (B) one or more kinds of compounds selected from a group comprising a compound capable of dissolving or dispersing in the component A, having 250-450 deg.C boiling point or decomposition temperature and having polyalkylene dioxide structure, a (meth)acrylic polymer, a polyester, a polycarbonate and a polyanhydride and preferably further comprises (C) an organic solvent such as n-pentane. Furthermore, it is preferable that the film-forming composition is applied to a substrate such as semiconductor and heated to produce a film having 0.3-1.2 g/cm3 film density.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composition for forming a film, and more particularly, to oxygen plasma resistance, mechanical properties, and the like.
The present invention relates to a film-forming composition having excellent dielectric constant and the like, and a film obtained by curing the composition.

[0002]

Conventionally, as an interlayer insulating film in semiconductor devices and the like, silica is formed Te than by a vacuum process such as CVD (SiO ₂₎ film is often used. And in recent years,
In order to form a more uniform interlayer insulating film, S
A coating-type insulating film called a OG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxylan, has also been used. Also, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant, which is mainly composed of organopolysiloxane and is called organic SOG, has been developed. However, with higher integration of semiconductor devices and the like, better electrical insulation between conductors is required, and therefore, an interlayer insulating film material having a lower dielectric constant has been 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. Such a coating composition has a low water absorption and is intended to provide an insulating film of a semiconductor device having excellent crack resistance, and the constitution is
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; It is a coating type composition for forming an insulating film mainly comprising an oligomer. However, the dielectric constant of the conventional inorganic interlayer insulating film material is 3.0 or more, which is insufficient for high integration.

An object of the present invention is to provide a material for an interlayer insulating film which has improved dielectric constant characteristics and a good balance of mechanical characteristics and the like against oxygen plasma. Hereinafter, the present invention will be described in detail.

The present invention relates to (A) a compound represented by the following general formula (1) (hereinafter referred to as "compound (1)") and a compound represented by the following general formula (2) (hereinafter referred to as compound (2) ) hydrolysis of a compound containing hereinafter) and a portion thereof condensate or either one _{^{R 1 n Si (oR 2)}} 4-n (1) HSi (oR 3) 3 (2) (R 1, R 2 and R ³ may be the same or different and each represents a monovalent organic group, and n represents an integer of 0 to 2.) (B) Compatible or dispersed in the component (A), and has a boiling point or decomposition temperature. A compound having a temperature of 250 to 450 ° C., a method for producing a film, comprising applying the composition to a substrate and heating the composition, and a film density obtained by the production method. there is provided a film which is 0.3~1.2g / cm ^3.

Component (A) In the general formulas (1) and (2), examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and are preferably an alkyl group having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched. And a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group and a naphthyl group. Specific examples of the compound (1) include compounds represented by the above general formula (1)
In which n = 0, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n
-Butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, and the like, as specific examples of the compound where n = 1 in the above general formula (1), 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-butyl Butyltri-tert-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
c-butyl-tri-sec-butoxysilane, sec-
Butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltriiso-
Propoxy silane, t-butyl tri-n-butoxy silane, t-butyl tri-sec-butoxy silane, t-butyl tri-tert-butoxy silane, t-butyl triphenoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tri-n- Propoxysilane, phenyltri-iso-propoxysilane,
Phenyltri-n-butoxysilane, phenyltri-s
ec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, and the like, as specific examples of the compound where n = 2 in the general formula (1),
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-s
ec-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-iso-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-butoxy Silane, 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-s
ec-butyl-di-n-propoxysilane, di-sec
-Butyl-di-iso-propoxysilane, di-sec
-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-butoxysilane, di-
tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane , Diphenyl-di-
n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc. it can. These compounds may be used alone or in combination of two or more.

Among the compounds represented by the general formula (1), tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; alkyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; Dialkyldialkoxysilanes such as ethoxysilane and dimethyldimethoxysilane are preferred. Specific examples of the compound (2) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, and tri-n
-Butoxysilane, tri-sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane and the like can be mentioned, and trimethoxysilane and triethoxysilane are preferable.

In the present invention, the ratio of the compound (1) to the compound (2) is 5 to 95% by weight, preferably 40 to 95% by weight based on the total amount of the compound (1) and the compound (2). 90% by weight, 95 to 5% by weight of the compound (2), preferably 60 to 10% by weight. Compound (1)
And when the compound represented by the compound (2) is hydrolyzed and partially condensed, the group 1 represented by R ² O— and R ³ O—
It is preferable to use 0.3 to 5.0 moles of water per mole, and it is particularly preferable to add 0.5 to 2.0 moles of water. If the amount of water to be added is a value within the range of 0.3 to 5.0 mol, there is no possibility that the uniformity of the coating film is reduced,
In addition, the storage stability of the film-forming composition is less likely to be reduced. When the component (A) is a condensate of the compound (1) and the compound represented by the compound (2), the weight average molecular weight in terms of polystyrene is 500 to 100,000.
It is preferable that

Component (B) In the present invention, the compound having a boiling point or a decomposition temperature of from 250 to 450 ° C., which is compatible or dispersed with the component (A), has a polyalkylene oxide structure,
(Meth) acrylate polymers, polyesters,
Examples thereof include polycarbonate and polyanhydride. In the present invention, the boiling point and the decomposition temperature refer to the temperature at 1 atm. Compound having a polyalkylene oxide structure Here, examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene block copolymer Ether-type compounds such as oxyethylene polyoxypropylene alkyl ether, ether-type compounds such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, polyethylene Glycol fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, It can be mentioned Li glycerol fatty acid esters, sorbitan fatty acid esters, 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. - a (A) n- (B) m- (A) l- ( In the formula, A group represented by -CH ₂ CH ₂ O-, the B - (A) n- (B ) m- -
A group represented by CH ₂ CH (CH ₃ ) O—, wherein n is 1 to
90, m is a number from 10 to 99, and l is a number from 0 to 90)

(Meth) acrylic polymer In the present invention, the acrylate and methacrylate constituting the (meth) acrylic polymer include alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate,
Examples thereof include methacrylic acid alkyl esters and methacrylic acid alkoxyalkyl esters. Examples of the alkyl acrylate include those having 1 to 6 carbon atoms such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, and hexyl acrylate. Alkyl esters, alkyl methacrylates, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, pentyl methacrylate,
Alkyl esters having 1 to 6 carbon atoms such as hexyl methacrylate, alkoxyalkyl acrylates include methoxymethyl acrylate, ethoxyethyl acrylate, and alkoxyalkyl methacrylates include methoxymethyl methacrylate and ethoxyethyl methacrylate. Can be mentioned. Among these,
It is preferable to use an alkyl methacrylate, and particularly preferable to use ethyl methacrylate, isobutyl methacrylate, or the like.

In the present invention, the (meth) acrylic polymer is preferably obtained by copolymerizing the above monomer with a monomer having an alkoxysilyl group. Examples of the monomer having an alkoxysyl group include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- [tri (methoxyethoxy) silyl] propyl methacrylate, and 3- (methmethoxysilyl) propyl methacrylate.
(Methyldimethoxysilyl) propyl, methacrylic acid 3
-(Methyldiethoxysilyl) propyl and the like. The monomer having an alkoxysilyl group is usually from 0.5 to all monomers constituting the acrylic polymer.
It is contained in a proportion of 10 mol%, preferably 1 to 7 mol%. In the present invention, the acrylic polymer may be copolymerized with not more than 40 mol% of a radical polymerizable monomer other than the above-mentioned acrylate, methacrylate and monomer having an alkoxysilyl group. Examples of the radical polymerizable monomer include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, N, N-dimethylacrylamide,
Examples include unsaturated amides such as N, N-dimethylmethacrylamide, unsaturated nitriles such as acrylonitrile, unsaturated ketones such as methyl vinyl ketone, and aromatic compounds such as styrene and α-methylstyrene. In the present invention, the (meth) acrylic polymer has a polystyrene reduced number average molecular weight of 1,000 to 100,000,
Preferably it is 1000-20,000. Polycondensates of polyester hydroxycarboxylic acids, ring-opening polymers of lactones, polycondensates of aliphatic polyols and aliphatic polycarboxylic acids and the like can be mentioned. Polycarbonate Polycondensates of carbonic acid and alkylene glycol, such as polyethylene carbonate, polypropylene carbonate, polytrimethylene carbonate, polytetramethylene carbonate, polypentamethylene carbonate, and polyhexamethylene carbonate, can be given. Examples include polycondensates of dicarboxylic acids such as polyanhydride polymalonyl oxide, polyadipoyl oxide, polypimeloyl oxide, polysuberoyl oxide, polyazelayl oxide, and polysebacoil oxide. Also,
As the component (B), poly (N-vinylacetamide), poly (N-vinylpyrrolidone), poly (2-vinylacetamide)
Examples thereof include vinylamide polymers such as methyl-2-oxazoline) and poly (N, N-dimethylacrylamide), and styrene polymers such as polystyrene, polymethylstyrene, and polyα-methylstyrene.

In the present invention, it is preferable to use a compound having an alkylene oxide structure or an acrylate-based polymer as the component (B). Particularly, among the compounds having an alkylene oxide structure, such as a polyoxyethylene polyoxypropylene block copolymer, etc. Polyoxyalkylene block copolymers are preferred. The amount of the component (B) to be used is generally 1 to 80% by weight, preferably 5 to 65% by weight, based on the component (A) (in terms of a completely hydrolyzed condensate). When the use ratio of the component (B) is 1% by weight or less, the effect of lowering the dielectric constant is small, and 80% by weight.
Above, the mechanical strength decreases. In the present invention, the completely hydrolyzed condensate refers to a group represented by —OR ² and —OR ³ in the compound (1) and the compound (2) of 100.
% Hydrolyzed to form OH groups, which are completely condensed.

Component (C) In the present invention, the above components (A) and (B) are usually used by dissolving them in an organic solvent. Examples of the organic solvent used in the present invention include, 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 System solvent: benzene, toluene, xylene, ethylbenzene,
Trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i
-Aromatic hydrocarbon solvents such as -propylbenzene, n-amylnaphthalene and trimethylbenzene; methanol, ethanol, n-propanol, i-propanol and n-
Butanol, i-butanol, sec-butanol, t
-Butanol, n-pentanol, i-pentanol,
2-methylbutanol, 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, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, Monoalcohol solvents such as acetone alcohol and cresol; ethylene glycol,
1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol −
Polyhydric alcohol solvents such as 1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; 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, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone Ketone solvents such as acetone alcohol, acetophenone and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide,
Dioxolan, 4-methyldioxolan, dioxane,
Dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-
n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n- Butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomer Ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-ether solvents such as methyl tetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, .gamma.-butyrolactone,
γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-acetic acid
Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-acetic acid
Ethyl butyl, 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, propylene glycol monomethyl acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl acetate 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 lactate, ethyl lactate, n-butyl lactate, n-lactate
Ester solvents such as amyl, diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen-containing solvents such as dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone;
Dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane,
Examples thereof include sulfur-containing solvents such as 1,3-propane sultone. These can be used alone or in combination of two or more. In the present invention, the boiling point is 2
It is particularly preferred to use an organic solvent below 50 ° C.,
Specifically, alcohols such as methanol, ethanol and isopropanol, polyhydric alcohols such as ethylene glycol and glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monopropyl ether, dipropylene Glycol ether solvents such as glycol monoethyl ether, glycol acetate ether solvents such as ethylene glycol monomethyl acetate, diethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, N, N-dimethylacetamide, N, N-dimethylformamide , N-
Amide solvents such as methyl-2-pyrrolidone, acetone,
One or a combination of two or more of ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and methyl amyl ketone, and carboxylic acid ester solvents such as ethyl lactate, methoxymethyl propionate and ethoxyethyl propionate. Can be mentioned.

In the present invention, the amount of the organic solvent used is
It is in the range of 0.3 to 25 times (weight) the total amount of the component (A) (in terms of complete hydrolysis condensate) and the component (B).

Component (D) In the present invention, a catalyst can be used in addition to the components (A) to (C). Examples of the catalyst include organic acids, inorganic acids, organic salts, inorganic salts, and metal chelates. 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, sebacic acid, gallic acid,
Butyric acid, melitic acid, arachidonic acid, mykimic 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,
Examples include trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. As organic salts,
For example, pyridine, pyrrole, piperazine, pyrrolidine,
Piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine,
Examples thereof include dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. Examples of the inorganic salt include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Also,
Metal chelates can also be used in the compositions of the present invention. Examples of metal chelate compounds include triethoxy mono (acetylacetonate) titanium,
n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetate) (Nato) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis ( Acetylacetonate) titanium, di-n
-Butoxybis (acetylacetonato) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, Mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate) titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-s
ec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy. Mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, Tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di-i-propoxy bis (ethyl acetoacetate) Chita , Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) Acetate) 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 (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris ( Titanium chelate compounds such as acetylacetonate) mono (ethylacetoacetate) titanium; triethoxymono (acetylacetonato) zirconium, tri-n-propoxymono (acetylacetonato) zirconium, tri-i-propoxymono ( (Acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (A Tilacetonate) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di-n-butoxy. Bis (acetylacetonato) zirconium, di-sec-butoxybis (acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n -Propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconium, mono-n-butoxytris (acetylacetonato) zirconium, mono-sec-butyl Carboxymethyl -
Tris (acetylacetonate) zirconium, mono-
t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate)
Zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy. Mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i- 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 (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate)
Zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium,
Mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate)
Zirconium chelate compounds such as zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium; tris (acetylacetonate) aluminum, tris (ethylacetoacetate)
Aluminum chelate compounds such as aluminum; and the like. The amount of the catalyst used is usually 0.000 to 1 mol of the total amount of the compound (1) and the compound (2).
It is 1 to 1 mol, preferably 0.001 to 0.1 mol.

The composition of the present invention can be produced by mixing the above components (A) and (B) and, if necessary, other components. In order to form a film using the composition of the present invention, first, the composition of the present invention is applied to a substrate to form a coating film. Here, examples of the substrate on which the composition of the present invention can be applied include semiconductors, glass, ceramics, and metals, and examples of the application method include spin coating, dipping, and roller blades. The thickness of the coating film to be formed is usually 0.2 to 20 μm for an interlayer insulating film.
m. Next, the formed coating film is heated, and the heating temperature at this time is lower than the decomposition temperature of the component (B). In the present invention, the density can be reduced by selecting the heating conditions for the cured film of the composition of the present invention. As the heating method, the formed coating film of the present composition is heated at a temperature lower than the decomposition temperature of the component (B) to partially cure the component (A), and then the decomposition temperature of the component (B) is reduced. A method of heating from the above temperature to the final curing temperature to obtain a porous cured product, and the like. Further, in order to control the curing rate of the component (A) and the decomposition rate of the component (B), if necessary, heating may be performed stepwise or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. Can be.
In the heating step of the coating film, the decomposition temperature of the component (B) is 25.
Since the temperature is from 0 to 450 ° C., it usually includes a step in which the coating film is finally heated to the decomposition temperature or higher, and this step is preferably performed under reduced pressure or under an inert gas. The film obtained by heating the composition of the present invention by the method of the present invention has a film density of 0.3 to 1.2 g / cm ³ , and has a pore diameter of 10 nm or less when it has pores. The dielectric constant of the film of the present invention is usually 2.6 to 1.2. The film of the present invention is suitable as an insulating film, and is particularly suitable as an interlayer insulating film for highly integrated circuits.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below based on examples. However, the following description generally shows an example of the embodiment of the present invention, and the present invention is not limited by the description without any particular reason. Parts and% in Examples and Comparative Examples indicate parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 (1) In a mixed solution of 168.7 g of trimethoxysilane, 182.7 g of methyltrimethoxysilane and 394.0 g of propylene glycol monopropyl ether, 10.0 g of maleic acid was dissolved in 116.8 g of water. The resulting aqueous solution was added dropwise at room temperature over 1 hour. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 1 hour, and the produced methanol was distilled off under reduced pressure to obtain a polysiloxane sol. (2) 100 g of the polysiloxane sol obtained in the above (1),
8.9 g of a polyethylene oxide block-polypropylene oxide block-polyethylene oxide block copolymer (Newport PE61 manufactured by Sanyo Chemical Co., Ltd.) was added, and the obtained mixture was applied on an 8-inch silicon wafer by a spin coating method, and then heated at 80 ° C. 5 minutes, then 20
After heating at 0 ° C. under nitrogen for 5 minutes, the mixture was further heated under vacuum for 34 minutes.
The mixture was heated at 0 ° C., 360 ° C., and 380 ° C. for 30 minutes each, and further heated at 425 ° C. for 1 hour to form a colorless and transparent film. Further, the obtained film was evaluated as follows. Table 1 shows the results. (Evaluation of composition for film formation)

1. Oxygen plasma ashing property The absorption intensity of organic groups in the obtained coating film was measured using a Fourier transform infrared spectrophotometer (FT-IR) (JEOL Ltd.
Manufactured by JIR-5500). Next, using a barrel-type oxygen plasma ashing device, the coating film was subjected to oxygen plasma treatment under the conditions of 1 torr, 800 W, and 500 Sccm for 20 minutes. Then, 127 of the organic groups in the coating film after the oxygen plasma treatment were obtained.
The intensity of the bending vibration of the methyl group bonded to Si near 0 cm ^-1 was measured using the FT-IR. From the change in the intensity measured in this way, the oxygen plasma ashing property was evaluated according to the following criteria. 〇: Change in absorption strength of organic group is less than 40% Δ: Change in absorption strength of organic group is 40% or more and less than 60% ×: Change in absorption strength of organic group is 60% or more Dielectric constant An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for dielectric constant measurement. Using the sample at a frequency of 100 kHz, the dielectric constant of the coating film was measured by a CV method using an HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd. and an HP4284A precision LCR meter. Table 1 shows the results
Shown in

3. Film density The composition sample is applied on an 8-inch Si wafer by using a spin coating method, and is placed on a hot plate at 80 ° C. for 5 minutes.
The substrate was dried at 200 ° C. for 5 minutes, and baked at 450 ° C. for 60 minutes in a vacuum oven at 450 ° C. The film density of the coating was determined by Rutherford back scattering method. 4. Elastic Modulus The obtained film was measured by a continuous stiffness measuring method using a nano indenter XP (manufactured by Nano Instruments). 5. CMP resistance The obtained film was polished under the following conditions. Slurry: silica-hydrogen peroxide polishing pressure: 300 g / cm ² polishing time: 60 seconds The evaluation was performed according to the following criteria. ：: No change Δ: Partly peeling or flaws ×: All peeling Also, the polishing rate was calculated as follows. Polishing rate (angstrom / min) = (initial film thickness)-
(Film thickness after 60-second polishing) Synthesis Example Synthesis of (meth) acrylic polymer Isobutyl methacrylate 18.32 in 100 ml flask
g, 3- (trimethoxysilyl) propyl methacrylate 1.68 g, azoisobutyronitrile (AIBN) 0.
33 g, 0.20 g of 2-mercaptoethanol and 3
30 g of -methoxymethyl propionate was added and dissolved. After the inside of the system was replaced with nitrogen gas, the mixture was stirred for 7 hours while heating in an oil bath at 80 ° C. to obtain a viscous polymer solution. When the average molecular weight in terms of polystyrene was measured by GPC, the number average molecular weight was 4,830 and the weight average molecular weight was 8,900. Example 2 (1) An aqueous solution in which 10.0 g of maleic acid was dissolved in 119.4 g of water was mixed at room temperature with a mixed solution of 73.2 g of trimethoxysilane and 292.3 g of methyltrimethoxysilane and 387.0 g of propylene glycol monopropyl ether. For 1 hour. After the addition of the mixture is completed, the
After reacting at 1 ° C. for 1 hour, the produced methanol was distilled off under reduced pressure to obtain a polysiloxane sol. (2) 21.2 g of the (meth) acrylic polymer solution obtained in the synthesis example in 100 g of the silica sol obtained in (1) above
(Solid content 8.5 g) was added and stirred at 60 ° C. for 1 hour. The resulting solution was applied on an 8-inch wafer by spin coating, and heated at 80 ° C. for 5 minutes on a hot plate for 20 minutes.
After drying at 0 ° C. for 5 minutes, it was baked at 425 ° C. for 1 hour under vacuum to obtain a transparent coating film. Evaluation was performed in the same manner as in Example 1. Table 1 shows the results. Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that the polyethylene oxide block-polypropylene oxide block-polyethylene oxide block copolymer was not used, and the composition was applied to a substrate and heated to form a film. Was formed. Evaluation of the obtained film was performed in the same manner as in Example 1. Table 1 shows the results.

[0021]

[Table 1]

[0022]

The film obtained by curing the composition of the present invention is excellent in dielectric properties, oxygen plasma resistance, mechanical strength and oxygen plasma resistance.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) H01L 21/312 H01L 21/312 C 21/316 21/316 H F term (reference) 4J038 CG142 DD002 DE002 DF022 DL021 DL031 JC32 KA06 5F058 AA10 AC03 AF04 AG01 BA20 BC05 BF46 BH01 BJ01 BJ02

Claims (7)

[Claims] (A) a hydrolyzate of a compound represented by the following general formula (1) and a compound containing a compound represented by the following general formula (2) and / or a partial condensate thereof: R ¹ _n Si (OR ² ) _4-n (1) HSi (OR ³ ) ₃ (2) (R ¹ , R ² and R ³ may be the same or different and each represents a monovalent organic group, and n is (B) represents an integer of 0 to 2.) (B) A film-forming composition comprising a compound compatible or dispersed in the component (A) and having a boiling point or a decomposition temperature of 250 to 450 ° C. 2. The method according to claim 1, wherein the component (B) is at least one selected from the group consisting of a compound having a polyalkylene oxide structure, a (meth) acrylic polymer, a polyester, a polycarbonate, and a polyanhydride. 2. The composition for film formation according to 1. 3. The film-forming composition according to claim 1, further comprising (C) an organic solvent. 4. A method for producing a film, comprising applying the composition according to claim 1 to a substrate and heating the substrate. 5. Applying the composition according to claim 1 to a substrate,
The component (A) is partially cured by heating at a temperature lower than the boiling point or decomposition temperature of the component (B), and then cured by heating at a temperature higher than the boiling point or decomposition temperature of the component (B). Method for forming a film. 6. Applying the composition according to claim 1 to a substrate,
A method for forming a film, comprising curing the component (A) at a temperature equal to or higher than the boiling point or decomposition temperature of the component (B). 7. A low-density film having a film density of 0.3 to 1.2 g / cm ³ obtained by the formation method according to claim 4.