JPWO2005108469A1 - Method for forming organic silica film, organic silica film, wiring structure, semiconductor device, and film forming composition - Google Patents

Abstract

The coating film can be efficiently cured at a lower temperature in a shorter time with a lower electron beam dose, and can be suitably used as an interlayer insulating film in, for example, a semiconductor element, and has a relative dielectric constant of A method for forming an organic silica film that can form a film that is small, excellent in mechanical strength and adhesion, and further excellent in plasma resistance and chemical resistance, a film-forming composition used in the method, and the method It is an object to provide an organic silica film obtained, a wiring structure including the organic silica film, and a semiconductor device including the wiring structure. The method for forming an organic silica film of the present invention includes a step of forming a coating film comprising a silicon compound having a -Si-O-Si- structure and a -Si-CH2-Si- structure on a substrate, and the coating film And a step of performing a curing process by irradiating the coating film with an electron beam.

Description

  The present invention relates to a method for forming an organic silica film, an organic silica film, a wiring structure, a semiconductor device, and a film forming composition.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD (Chemical Vapor Deposition) method has been frequently used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, with high integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG, has been developed.

  In particular, with further higher integration and multilayering of semiconductor elements, etc., better electrical insulation between conductors is required, and therefore, it has a lower relative dielectric constant and excellent crack resistance, mechanical strength and adhesion. An interlayer insulating film material has been demanded.

  However, conventional polysiloxane-based materials are not stable in the properties of the reaction products, and have large variations in the relative permittivity, crack resistance, mechanical strength, adhesion, etc. of the coating film. It was unsuitable for.

  On the other hand, a technique for improving the performance of an insulating film by irradiating an electron beam (EB) without using conventional polysiloxane as a material (US Pat. No. 6,042,994, US Pat. No. 6204201) and a technique (Japanese Patent Laid-Open No. 2001-286821) for generating a —Si—C—Si bond in a film by irradiating a polysiloxane having a methyl group with an electron beam. .

  However, in the formation of a multilayer wiring structure of a semiconductor device, the formed insulating film is subjected to various plasma etching and chemical treatment during processing, but the insulating film obtained by the conventional technique has a low relative dielectric constant and Even with high mechanical strength, there is a problem that plasma etching resistance and RIE resistance are not sufficient.

Plasma damage applied during processing of the insulating film is mainly caused by radicals generated by the plasma pulling out CH ₃ from the Si—CH ₃ structure of polysiloxane. The silyl radical that is secondarily generated by the extraction of CH ₃ from the Si—CH ₃ structure quickly reacts with oxygen atoms and oxygen radicals present in the vicinity, and further draws in hydrogen to produce a silanol group (Si—OH ). Due to the presence of the silanol group, the hygroscopic property of the insulating film is increased, and the relative dielectric constant is increased, the chemical resistance is deteriorated, and the electrical insulating property is decreased.

On the other hand, as a method for improving the plasma resistance, a dense layer is formed on the surface layer by simply increasing the absolute amount of the Si—CH ₃ structure in the insulating film and extracting more CH ₃ on the surface layer. A method of improving plasma resistance and RIE resistance apparently can be considered. However, from the viewpoint of maintaining the performance of the insulating film, particularly the hardness and elastic modulus, there is a limit to introducing Si—CH ₃ structural group into polysiloxane.

  Further, as a material for forming the low dielectric interlayer insulating film, a composition obtained by mixing polycarbosilane itself or polysiloxane and polycarbosilane has been proposed (Japanese Patent Laid-Open No. 2001-127152).

Although this composition is intended to improve heat resistance and moisture absorption resistance, such a material has a steric hindrance or Si—CH ₂ — when the polycarbosilane has a Si—OH structure. This Si-OH structure is considered to be less reactive than the Si-OH group in the polysiloxane unit due to restrictions on the mobility of the Si structure, and it is difficult to form a sufficiently high condensed state by heating. The OH group remains in the obtained insulating film, and the plasma resistance and the chemical resistance are not excellent.
JP 2001-127152 A JP 2001-286821 U.S. Pat. No. 6,042,994 U.S. Pat. No. 6,204,201

  The present invention can efficiently cure the coating film at a lower temperature in a shorter time with a lower electron beam dose, and can be suitably used as an interlayer insulating film in, for example, a semiconductor element, A method for forming an organic silica film capable of forming a film having a small relative dielectric constant, excellent mechanical strength and adhesion, and at the same time excellent in plasma resistance and chemical resistance, and film formation used in the method It is to provide a composition for use.

  Another object of the present invention is to provide an organic silica film obtained by the method for forming an organic silica film of the present invention, a wiring structure including the organic silica film, and a semiconductor device including the wiring structure. There is.

The method for forming the organosilica film of the present invention includes:
Forming a coating film comprising a silicon compound having a —Si—O—Si— structure and a —Si—CH ₂ —Si— structure on a substrate;
Heating the coating film;
Irradiating the coating film with an electron beam and performing a curing treatment;
including.

Here, in the method for forming an organic silica-based film of the present invention, the silicon compound has a —Si—O—Si— structure and a —Si—CH ₂ —Si— structure of —Si—CH ₂ —Si— / -Si-O-Si- (molar ratio) can be present in a ratio of 0.03 to 2.00.

  Here, in the method for forming an organic silica film of the present invention, a carbon content in the silicon compound may be 13 to 24 mol%.

  Here, in the method for forming an organic silica film of the present invention, the silicon compound was obtained by hydrolytic condensation of (B) a hydrolyzable group-containing silane monomer in the presence of (A) polycarbosilane. It can be a hydrolysis condensate.

Here, in the method for forming an organic silica film of the present invention, in the electron beam irradiation, an acceleration voltage of the electron beam is 0.1 to 20 keV, and an irradiation amount of the electron beam is 1 to 1000 μC. / Cm ² .

  Here, in the method for forming an organic silica film of the present invention, heating and electron beam irradiation can be performed simultaneously. In this case, the heating can be performed at 300 to 450 ° C.

  Here, in the method for forming an organic silica film of the present invention, the electron beam irradiation can be performed in the absence of oxygen.

The organic silica film of the present invention is obtained by the method for forming an organic silica film of the present invention, and has a relative dielectric constant of 1.5 to 3.5 and a film density of 0.7 to 1.3 g / cm. Can be ³ .

  The wiring structure of the present invention uses the organic silica film of the present invention as an interlayer insulating film.

  The semiconductor device of the present invention includes the wiring structure of the present invention.

The film forming composition of the present invention comprises:
(A) In the presence of polycarbosilane, (B) a hydrolytic condensate obtained by hydrolytic condensation of a hydrolyzable group-containing silane monomer;
An organic solvent,
Including
In the method for forming an organic silica film of the present invention, it is used for forming the coating film.

  Here, in the film forming composition of the present invention, the hydrolysis condensate may contain 13 to 24 mol% of carbon atoms.

  Here, in the film-forming composition of the present invention, the component (B) is added in an amount of 1 to 1000 weights with respect to 100 parts by weight of the component (A) converted to a complete hydrolysis condensate of the component (A). Can be part.

  Here, in the film-forming composition of the present invention, the contents of sodium, potassium, and iron can each be 100 ppb or less.

  According to the method for forming an organic silica-based film of the present invention, a step of forming a coating film made of the silicon compound on a substrate, a step of heating the coating film, and irradiating the coating film with an electron beam Including the step of performing the curing treatment, the coating film can be efficiently cured at a lower temperature in a shorter time with a lower electron beam irradiation dose. Thereby, for example, an organic silica-based film that can be suitably used as an interlayer insulating film in a semiconductor element or the like, has a low relative dielectric constant, and is excellent in chemical resistance, plasma resistance, and mechanical strength in a semiconductor manufacturing process can be obtained. I can do it.

FIG. 1 is a diagram showing IR spectra of silica-based films obtained in Example 2 and Comparative Example 2, respectively.

  Hereinafter, the present invention will be described in more detail.

1. Organic Silica Film and Method for Forming the Same The method for forming the organic silica film of the present invention includes a silicon compound having a —Si—O—Si— structure and a —Si—CH ₂ —Si— structure (hereinafter simply referred to as “silicon compound”). And a step of heating the coating film, and a step of irradiating the coating film with an electron beam to perform a curing treatment.

1.1. In the present invention, first, a coating film made of a silicon compound having a —Si—O—Si— structure and a —Si—CH ₂ —Si— structure is formed on a substrate.

In the present invention, the —Si—CH ₂ —Si— structure / —Si—O—Si— structure (molar ratio) in the silicon compound is preferably 0.03 to 2.00. When this molar ratio is less than 0.03 or exceeds 2.00, it is difficult to improve plasma resistance and chemical resistance while maintaining the relative permittivity and mechanical strength.

In the present invention, the number of moles of the —Si—O—Si— structure is based on the assumption that the total amount of the hydrolyzable silane monomer to be used is hydrolyzed and condensed in the silicon compound comprising the hydrolysis condensate described later. The number of moles of the —Si—CH ₂ —Si— structure is the number of moles of the —Si—O—Si— structure present in the polycarbosilane described later.

  In this invention, it is preferable that the carbon atom density | concentration in the coating film consisting of a silicon compound is 13-24 mol%. If the carbon atom concentration in the silicon compound is less than 13 mol%, the resulting film may not be sufficiently plasma-resistant and chemical-resistant. On the other hand, if it exceeds 24 mol%, the resulting film may have interlayer insulation. In some cases, the balance of characteristics as a film is lacking.

  In the present invention, the carbon atom concentration in the coating film composed of a silicon compound is the amount of carbon atoms in the silicon compound composed of a hydrolyzed condensate when all the hydrolyzable silane monomer described below undergoes hydrolytic condensation.

  The film thickness of the coating film made of a silicon compound is usually 1 to 2,000 nm, preferably 10 to 1,000 nm.

  In the present invention, a coating film made of a silicon compound can be formed by applying a solution obtained by dissolving a polymer in an organic solvent and drying it, or by a CVD method or the like. The film | membrane formed by apply | coating the composition for formation to a base material and drying is preferable.

1.2. Film-forming composition and production method thereof In the present invention, a film-forming composition for forming a coating film made of a silicon compound preferably contains polycarbosilane and polysiloxane as polymer components. The film-forming composition of the present invention can be produced by dissolving polycarbosilane and polysiloxane in an organic solvent. In particular, (A) polycarbosilane (hereinafter also referred to as “component (A)”). (B) Hydrolyzed condensate obtained by hydrolytic condensation of a hydrolyzable group-containing silane monomer (hereinafter also referred to as “component (B)”) (hereinafter simply referred to as “hydrolytic condensate”) Is preferably obtained by dissolving in an organic solvent.

  In the present invention, the “hydrolyzable group” refers to a group that can be hydrolyzed during the production of the film-forming composition of the present invention. Specific examples of the hydrolyzable group are not particularly limited, and examples thereof include a halogen atom, a hydroxy group, an alkoxy group, a sulfone group, a methanesulfone group, and a trifluoromethanesulfone group. Hereinafter, each component in the case where the film-forming composition of the present invention contains a hydrolysis condensate and an organic solvent will be described.

1.2.1. Hydrolyzed condensate The polystyrene-converted weight average molecular weight (Mw) of the hydrolyzed condensate is preferably 1,500 to 500,000, more preferably 2,000 to 200,000, and 2,000 to More preferably, it is 100,000. If the polystyrene-converted weight average molecular weight of the hydrolyzed condensate is less than 1,500, the intended relative dielectric constant may not be obtained. On the other hand, if it exceeds 500,000, the in-plane uniformity of the coating film may be reduced. May be inferior.

  In producing the hydrolysis condensate, the mixing ratio of the component (A) and the component (B) is such that the component (B) is 1 to 1000 weights per 100 parts by weight of the complete hydrolysis condensate of the component (A). Parts, preferably 5 to 100 parts by weight, more preferably 5 to 20 parts by weight. When the component (B) is less than 1 part by weight, sufficient chemical resistance may not be exhibited after film formation, and when it exceeds 1000 parts by weight, a reduction in dielectric constant may not be achieved.

1.2-1. (A) Component In the present invention, the (A) polycarbosilane that is the (A) component is, for example, a polycarbosilane compound represented by the following general formula (1) (hereinafter also referred to as “compound 1”). be able to.

・・・・・（１）
（式中、Ｒ^８は、水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基、およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基、およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１０，Ｒ^１１は同一または異なり、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基、およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１２〜Ｒ^１４は同一または異なり、置換または非置換のメチレン基、アルキレン基、アルケニル基、アルキニル基、アリーレン基を示し、ｘ，ｙ，ｚは、それぞれ０〜１０，０００の数を示し、５＜ｘ＋ｙ＋ｚ＜１０，０００の条件を満たす。）

(1)
(Wherein R ⁸ is a group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ represents a group selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ¹⁰ and R ¹¹ are the same or different, and are halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups having 2 to 6 carbon atoms, aryl A group consisting of a group, an allyl group, and a glycidyl group Shows barrel ^group, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenyl group, an alkynyl group, an arylene group, x, y, z are each 0 to 10,000 And satisfies the condition of 5 <x + y + z <10,000.)

  In the general formula (1), examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group, and preferably have 2 to 6 carbon atoms, and these alkylene groups are chain-like. However, it may be branched or may form a ring, and a hydrogen atom may be substituted with a fluorine atom or the like.

In the general formula (1), examples of the alkenyl group include an ethenylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, and the like, which may be dienyl, and preferably has 1 to 4 carbon atoms. A hydrogen atom may be substituted with a fluorine atom or the like. Examples of the alkynyl group include acetylene group and propynylene group. Examples of the arylene group include a phenylene group and a naphthylene group, and a hydrogen atom may be substituted with a fluorine atom or the like. R ^{8 to} R ¹¹ may be the same group or different groups.

  Moreover, in the said General formula (1), x, y, z is a number of 0-10,000, and is 5 <x + y + z <10,000. In the case of x + y + z <5, the storage stability of the film-forming composition may be inferior, and in the case of 10,000 <x + y + z, the component (A) is separated and a uniform film is not formed. Sometimes. Preferably, x, y, and z are 0 ≦ x ≦ 800, 0 ≦ y ≦ 500, and 0 ≦ z ≦ 1,000, and more preferably 0 ≦ x ≦ 500, 0 ≦ y ≦ 300, 0, respectively. ≦ z ≦ 500, and more preferably 0 ≦ x ≦ 100, 0 ≦ y ≦ 50, and 0 ≦ z ≦ 100.

  Further, 5 <x + y + z <1,000 is preferable, 5 <x + y + z <500 is more preferable, 5 <x + y + z <250 is further preferable, and 5 <x + y + z <100 is most preferable. .

  Examples of the compound represented by the general formula (1) include chloromethyltrichlorosilane, bromomethyltrichlorosilane, chloromethylmethyldichlorosilane, chloromethylethyldichlorosilane, chloromethylvinyldichlorosilane, chloromethylphenyldichlorosilane, and bromomethyl. Methyldichlorosilane, bromomethylvinyldichlorosilane, chloromethyldimethylchlorosilane, chloromethyldivinylchlorosilane, bromomethyldimethylchlorosilane, (1-chloroethyl) trichlorosilane, (1-chloropropyl) trichlorosilane, chloromethyltrimethoxysilane, bromomethyl Trimethoxysilane, chloromethylmethyldimethoxysilane, chloromethylvinyldimethoxysilane, chloromethylphenyldimethoxysilane, bromine Methylmethyldimethoxysilane, bromomethylvinyldimethoxysilane, bromomethylphenyldimethoxysilane, chloromethyldimethylmethoxysilane, chloromethyldivinylmethoxysilane, chloromethyldiphenylmethoxysilane, bromomethyldimethylmethoxysilane, bromomethyldiisopropylmethoxysilane, chloromethyltrimethyl Ethoxysilane, bromomethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylethyldiethoxysilane, chloromethylvinyldiethoxysilane, chloromethylphenyldiethoxysilane, bromomethylmethyldiethoxysilane, bromomethylvinyldiethoxysilane , Bromomethylphenyldiethoxysilane, chloromethyldimethylethoxysilane, chloromethyldie Reacting at least one compound selected from ruethoxysilane, bromomethyldivinylethoxysilane, chloromethyltriisopropoxysilane and bromomethyltriisopropoxysilane in the presence of at least one of an alkali metal and an alkaline earth metal. If necessary, it can be obtained by further treatment with an alcohol, an organic acid, a reducing agent or the like.

  As the alkali metal, Li, Na and K are preferable, and as the alkaline earth metal, Mg and the like are preferable.

1.2.1-2. (B) Hydrolyzable group-containing silane monomer In the present invention, the (B) hydrolyzable group-containing silane monomer is not particularly limited as long as it is a silane monomer having a hydrolyzable group. For example, the following general formula (2) At least one silane compound selected from the group consisting of a compound represented by formula (hereinafter also referred to as “compound 2”) and a compound represented by the following general formula (3) (hereinafter also referred to as “compound 3”). Can be.
R ¹ _a SiX _4-a (2)
(In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, X represents a halogen atom or an alkoxy group, and a represents an integer of 0 to 3.)
_{^{R 2 b Y 3-b Si-}} (R 4) d -SiZ 3-c R 3 c ····· (3)
(Wherein R ² and R ³ are the same or different and each represents a monovalent organic group, b and c are the same or different and represent an integer of 0 to 2, and R ⁴ represents an oxygen atom, a phenylene group or — ( CH ₂ ) represents a group represented by _e — (wherein e is an integer of 1 to 6), Y and Z are the same or different, represent a halogen atom or an alkoxy group, and d represents 0 or 1 .)
In the general formulas (2) and (3), examples of the halogen atom represented by X and Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, as R in the general formula (3) in the alkoxy group represented by Y (-OR), it may be mentioned the same alkyl groups and aryl groups of R ¹ to R ⁴ to be described later.

1.2.1-2A. Compound 2
In the general formula (2), R ¹ is a hydrogen atom, a fluorine atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. In the general formula (2), R ² is preferably a monovalent organic group, particularly an alkyl group or a phenyl group.

  Here, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned, Preferably it is C1-C5. These alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom, an amino group, or the like.

  Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group.

  Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

As for the hydrocarbon portion of an alkoxy group X, it can be fitted as it is listed as the monovalent organic group R ^2.

Specific examples of the compound represented by the general formula (2) (hereinafter also referred to as “compound 2”) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra- n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxy Silane, tri-sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluorotri-n -Buto Shishiran, fluorotriazinyl -sec- butoxysilane, fluoro tri -tert- butoxysilane, etc. fluoro triphenoxy silane;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxy Vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri- iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i -Propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri -Ter -Butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxy Silane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxy Silane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl- Triphenoki Sisilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxy Silane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxy Silane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 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-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di- n-propyl- -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-butoxysilane, di-iso-propyl-di-phenoxysilane, di -N-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-pro Xysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert -Butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl -Di-iso-propoxysilane, di-sec-butyl-di-n-butoxysilane, di-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-propoxy Silane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane and the like;
Tetrachlorosilane, tetrabromosilane, tetraiodosilane, trichlorosilane, tribromosilane, triiodosilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, t-butyltri Chlorosilane, cyclohexyltrichlorosilane, phenethyltrichlorosilane, 2-norbornyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyltribromosilane, ethyltribromosilane, n-propyltribromosilane, isopropyltribromosilane, n- Butyltribromosilane, t-butyltribromosilane, cyclohexyltribromosilane, phenethyltribromosilane, 2-norbornyltri Lomosilane, vinyltribromosilane, phenyltribromosilane, methyltriiodosilane, ethyltriiodosilane, n-propyltriiodosilane, isopropyltriiodosilane, n-butyltriiodosilane, t-butyltriiodosilane, cyclohexyltri Iodosilane, phenethyltriiodosilane, 2-norbornyltriiodosilane, vinyltriiodosilane, phenyltriiodosilane, dimethyldichlorosilane, diethyldichlorosilane, di-n-propyldichlorosilane, diisopropyldichlorosilane, di-n -Butyldichlorosilane, di-t-butyldichlorosilane, dicyclohexyldichlorosilane, diphenethyldichlorosilane, di-2-norbornyldichlorosilane, divinyldichlorosilane, diph Nyldichlorosilane, dimethyldibromosilane, diethyldibromosilane, di-n-propyldibromosilane, diisopropyldibromosilane, di-n-butyldibromosilane, di-t-butyldibromosilane, dicyclohexyldibromosilane, diphenethyldibromosilane, di 2-norbornyldibromosilane, divinyldibromosilane, diphenyldibromosilane, dimethyldiiodosilane, diethyldiiodosilane, di-n-propyldiiodosilane, diisopropyldiiodosilane, di-n-butyldiiodosilane, Di-t-butyldiiodosilane, dicyclohexyldiiodosilane, diphenethyldiiodosilane, di-2-norbornyldiiodosilane, divinyldiiodosilane, diphenyldiiodosilane, trimethylchloro Rosilane, triethylchlorosilane, tri-n-propylchlorosilane, triisopropylchlorosilane, tri-n-butylchlorosilane, tri-t-butylchlorosilane, tricyclohexylchlorosilane, triphenethylchlorosilane, tri-2-norbornylchlorosilane, trivinylchlorosilane , Triphenylchlorosilane, trimethylbromosilane, triethylbromosilane, tri-n-propylbromosilane, triisopropylbromosilane, tri-n-butylbromosilane, tri-t-butylbromosilane, tricyclohexylbromosilane, triphenethylbromo Silane, tri-2-norbornylbromosilane, trivinylbromosilane, triphenylbromosilane, trimethyliodosilane, triethyliodosilane, Ri-n-propyliodosilane, triisopropyliodosilane, tri-n-butyliodosilane, tri-t-butyliodosilane, tricyclohexyliodosilane, triphenethyliodosilane, tri-2-norbornyliodosilane, tri Examples thereof include silicon compounds such as vinyliodosilane and triphenyliodosilane. These compounds can be used alone or in a mixture of two or more.

  The compound 2 is preferably methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

  These may be used alone or in combination of two or more.

1.2.1-2B. Compound 3
In the general formula (3), examples of the monovalent organic group represented by R ² and R ³ include the same organic groups as those in the general formula (2).

In the general formula (3), the compound in which R ⁴ is an oxygen atom includes hexachlorodisiloxane, hexabromodisiloxane, hexaiodosidisiloxane, 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 3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pe Tert-ethoxy-3-phenyldisiloxane, 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-diethyl Disiloxane, 1,1,3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetra Methoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldishiro Sun, 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-triethyl Phenoxy-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, 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane, and the like.

  Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane Siloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1, 3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane and the like are preferable. As an example.

  In addition, in the general formula (3), as the compound where d is 0, hexachlorodisilane, hexabromodisilane, hexaiodosidisilane, 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, , 1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2, Pentapentoxy-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, , 1,2,2-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-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-tetraethyl Rudisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2- Examples thereof include tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, and the like.

  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-tetramethyl Preferred examples include disilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, and the like.

Furthermore, in the general formula (3), R ⁴ is a group represented by — (CH ₂ ) _e —, and examples thereof include bis (trichlorosilyl) methane, bis (tribromosilyl) methane, and bis (triiodosilyl). Methane, bis (trichlorosilyl) ethane, bis (tribromosilyl) ethane, bis (triiodosilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) Methane, bis (tri-i-propoxysilyl) 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-pro Xylylyl) ethane, 1,2-bis (tri-i-propoxysilyl) ethane, 1,2-bis (tri-n-1, butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane 1,1,2,2-bis (tri-t-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (tri Ethoxysilyl) 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- (di Ethoxymethylsilyl) -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-butoxymethylsilyl) -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 (trimethoxysilane) L) 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) Examples include benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-t-butoxysilyl) benzene, and the like. it can.

  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- (di Ethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (di Ethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxy) Silyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) Benzene etc. can be mentioned as a preferable example.

  As compound 2 and 3, 1 type (s) or 2 or more types can be used.

  When at least one silane compound selected from the group of compounds 2 and 3 is hydrolyzed and condensed in the presence of the polymers (I) to (IV) described above, 1 mol of compounds 2 and 3 is used. It is preferable to use more than 0.5 mol and not more than 150 mol of water, particularly preferably more than 0.5 mol and not more than 130 mol of water.

1.2.1-3. Method for Producing Hydrolyzed Condensate The hydrolyzed condensate of the present invention is obtained by hydrolytic condensation of the component (A) in the presence of the component (B).

  Here, the component (A) can be hydrolyzed with the component (A) and the component (B) dissolved in an organic solvent. Examples of the organic solvent that can be used in this case include methanol, ethanol, propanol, butanol, tetrahydrofuran, γ-butyrolactone, propylene glycol monoalkyl ethers, and ethylene glycol monoalkyl ethers.

  The reaction temperature in the hydrolysis condensation is 0 to 100 ° C., preferably 20 to 60 ° C., and the reaction time is 30 minutes to 24 hours, preferably 1 to 8 hours.

  Moreover, in order to manufacture a hydrolysis-condensation product, when hydrolyzing and condensing (B) component in presence of (A) component, a specific catalyst can be used. As a catalyst, at least 1 sort (s) chosen from the group of an alkali catalyst, a metal chelate catalyst, and an acid catalyst can be used.

  Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, dia Zabicyclooctane, 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, amines or amine salts are preferable, organic amines or organic amine salts are particularly preferable, and alkylamines and tetraalkylammonium hydroxides are preferable. Most preferred. These alkali catalysts may be used alone or in combination of two or more.

Examples of the metal chelate catalyst include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy Tris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl) Acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di- i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate Tate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) 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 (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) 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 (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) Zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum;
Preferred examples include titanium or aluminum chelate compounds, and particularly preferred are titanium chelate compounds. These metal chelate catalysts may be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric 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, merit acid, Arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid Hydrolysis of 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 Organic acid such as hydrolyzate of maleic anhydride, hydrolyzate of maleic anhydride, hydrolyzate of phthalic anhydride Bets can be, can be exemplified organic carboxylic acids as a more preferable example. These acid catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used is usually 0.00001 to 10 mol, preferably 0.00005 to 5 mol, per 1 mol of the total amount of groups represented by X, Y and Z in the compounds 2 and 3. . If the amount of the catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction. Moreover, in this invention, the temperature when hydrolyzing the compounds 2 and 3 is 0-100 degreeC normally, Preferably it is 15-80 degreeC.

  In the present invention, the “completely hydrolyzed condensate” means that (A) the polycarbosilane and the hydrolyzable groups in the compounds 2 and 3 are 100% hydrolyzed to become SiOH groups, and further completely condensed to form a siloxane structure. The thing that became.

  Moreover, as a hydrolysis condensate, it is preferable that it is a hydrolysis condensate of (A) polycarbosilane and the compound 2 at the point which the storage stability of the composition obtained is more excellent. In the present invention, the amount of the compounds 2 and 3 used relative to (A) polycarbosilane is such that the total amount of the compounds 2 and 3 is 500 to 4000 parts by weight, more preferably 1000 parts per 100 parts by weight of (A) polycarbosilane. -3000 parts by weight.

1.2.2. Organic Solvent In the film-forming composition of the present invention, the hydrolysis condensate and other components described later can be dissolved or dispersed in an organic solvent as necessary.

  The organic solvent used as a component of the film-forming composition of the present invention is not particularly limited as long as it can be removed before the final film is obtained, but more specifically, it is a protic solvent and an aprotic solvent. An organic solvent. Examples of the protic solvent include alcohol solvents. Examples of the aprotic solvent include ketone solvents, ester solvents, ether solvents, amide solvents, and other aprotic solvents described later.

Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2- Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 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, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether;
And so on. These alcohol solvents may be used alone or in combination of two or more.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-hexyl. In addition to ketones, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, 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, - heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents 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-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide solvents may be used alone or in combination of two or more.

  Examples of 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, and i-acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl acetate Glycol mono-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, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester solvents may be used alone or in combination of two or more.

As aprotic solvents, acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methyl- [Delta] ₃ -pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl- Examples include 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. These aprotic solvents may be used alone or in combination of two or more.

  Among the aprotic solvents, ketone solvents such as 2-heptanone, methyl isobutyl ketone, diethyl ketone, and cyclohexanone are preferable, and propylene glycol monopropyl ether and the like are preferable as the alcohol solvent.

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

1.2.3. Other Components In the film-forming composition of the present invention, a reaction accelerator for accelerating the hydrolysis reaction and / or condensation reaction of the component (A) and / or the component (B) can be excluded. Here, the “reaction accelerator” means any one of a reaction initiator, a catalyst (acid generator, base generator) and a sensitizer having an electron beam absorption function, or a combination of two or more thereof. To do.

  A silica film cured using an acid generator or a base generator generally has a large amount of residual silanol and high hygroscopicity, resulting in a film having a high dielectric constant. Furthermore, the composition containing these acid generators and base generators may be acid generators, base generators themselves, and acids and basic substances generated from these may become charge carriers and impair the insulating properties of the film. In some cases, the quality of an insulating film of an LSI semiconductor device that requires high insulation reliability, such as deterioration of wiring metal, may not be satisfied.

  On the other hand, according to the film-forming composition of the present invention, the coating film can be cured through the heating step and the electron beam irradiation step even without including such a reaction accelerator. The problem can be avoided.

  In the film-forming composition of the present invention, it is desirable that the contents of sodium, potassium, and iron are each 100 ppb or less. Since these elements become a contamination source of the semiconductor device, it is desirable to eliminate them as much as possible from the film forming composition of the present invention.

  You may add components, such as an organic polymer, surfactant, and a silane coupling agent, to the film forming composition of this invention. These additives may be added to a solvent in which each component is dissolved or dispersed before the film-forming composition is produced.

1.2.3-1. Organic polymer The organic polymer used by this invention can be added as an easily decomposable component for forming a void | hole in a silica type film | membrane. Adding such an organic polymer is disclosed in JP 2000-290590, JP 2000-313612, Hedrick, JL, et al. “Templating Nanoporosity in Thin Film Dielectric Insulators”. Adv. Mater., 10 (13), 1049, 1998. etc., and similar organic polymers may be added.

  Examples of organic polymers include polymers having a sugar chain structure, vinylamide polymers, (meth) acrylic polymers, aromatic vinyl compound polymers, dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, polyquinoxalines. , Polyoxadiazole, a fluorine-based polymer, a polymer having a polyalkylene oxide structure, and the like.

1.2.3-2. Surfactant Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and further, fluorine surfactants, silicone surfactants, and the like. Activators, polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1, 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8, 8,9,9,10,10-Decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluoro Kutansulfonamido) propyl] -N, N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorophosphate) Octylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate ester and the like, a fluorosurfactant comprising a compound having a fluoroalkyl or fluoroalkylene group at at least one of its terminal, main chain and side chain Can be mentioned.

  Commercially available products include Megafax F142D, F172, F173, and F183 (above, manufactured by Dainippon Ink and Chemicals, Inc.), Ftop EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.). ] Fluorad FC-430, FC-431 [manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15 (Neos Co., Ltd.) and other commercially available fluorines There may be mentioned system surfactants. Among these, the above-mentioned Megafac F172, BM-1000, BM-1100, and NBX-15 are particularly preferable.

  As the silicone surfactant, for example, SH7PA, SH21PA, SH30PA, ST94PA [all manufactured by Toray Dow Corning Silicone Co., Ltd.] can be used. Of these, SH28PA and SH30PA are particularly preferable.

  The amount of the surfactant used is usually 0.00001 to 1 part by weight with respect to 100 parts by weight of the film-forming composition. These may be used alone or in combination of two or more.

1.2.3-3. Silane coupling agent Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-glycidyloxypropylmethyl. Dimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxy Silyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-dia Zanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxy Silane, N-bi (Oxyethylene) -3-aminopropyltrimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. These may be used alone or in combination of two or more.

1.3. Formation of Organic Silica Film As described above, the method for forming an organic silica film of the present invention includes a step of forming a coating film made of a silicon compound on a substrate, a step of heating the coating film, and the coating method. Irradiating the film with an electron beam and performing a curing treatment.

  Moreover, in the formation method of the organic silica film of the present invention, the step of heating the coating film and the step of irradiating the coating film with an electron beam may be performed simultaneously. In the curing treatment of the present invention, by simultaneously performing heating and electron beam irradiation, the condensation reaction of the organic silica sol can be sufficiently achieved at a relatively low temperature and in a short time with a smaller amount of electron beam irradiation. The intended organic silica film can be obtained. When heating and electron beam irradiation are performed simultaneously, the curing treatment can be preferably performed for 30 seconds to 10 minutes, more preferably 30 seconds to 7 minutes. Hereinafter, each process in the formation method of the organic silica film of the present invention will be described.

1.3.1. Formation of Coating Film In the method for forming an organic silica film of the present invention, when forming a coating film made of a silicon compound, for example, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used. . The substrate to be coated is not particularly limited, for _{example, Si, SiO 2, SiN,} SiC, SiCN, Si containing layer SiON, and the like. Specific examples of the substrate include semiconductor substrates made of the above materials.

1.3.2. Heating of the coating film The formed coating film is then dried at room temperature, or usually heated for about 5 to 240 minutes at a temperature of about 80 to 600 ° C. The coating 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 is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do.

1.3.3. In the method for forming an organic silica film of the present invention, the energy (acceleration voltage) when irradiating an electron beam is 0.1 to 20 keV, and the electron beam irradiation amount is 1-1000 μC / cm ² ( It is preferably 10 to 500 μC / cm ² , more preferably 10 to 300 μC / cm ² ). When the acceleration voltage is 0.1 to 20 keV, the electron beam penetrates the film and does not damage the lower semiconductor element, and the electron beam can sufficiently enter the coating film. Moreover, when the electron beam irradiation amount is 1-1000 μC / cm ² , the entire coating film can be reacted, and damage to the coating film is reduced.

  Moreover, the heating temperature of the base material at the time of electron beam irradiation is 300-450 degreeC normally. When the heating temperature is lower than 300 ° C., the mobility of the molecular chain in the organic silica sol does not become active, and a sufficiently high condensation rate cannot be obtained. On the other hand, when the heating temperature is higher than 450 ° C., the molecules in the organic silica sol are easily decomposed. Further, if the heating temperature is higher than 450 ° C., it is not possible to match the steps in the semiconductor device manufacturing process, for example, the copper damascene process that is usually performed at 450 ° C. or lower. As a means for heating at the same time as the electron beam irradiation, for example, a hot plate or infrared lamp annealing can be used. In addition, the time required for the coating film to be cured by electron beam irradiation is about 1 minute to 5 minutes, which is significantly shorter than 15 minutes to 2 hours required for thermosetting. For this reason, it can be said that electron beam irradiation is suitable for wafer-by-leaf processing.

  Prior to the electron beam irradiation of the coating film of the present invention, the coating film of the present invention is pre-cured in a state where the substrate is heated to 250 ° C. or more and 500 ° C. or less, and the relative dielectric constant is 3.0 or less (preferably 2.7 or less), the organic silica film can be irradiated with an electron beam. Irradiation with an electron beam after the coating film is thermally cured can reduce film thickness unevenness depending on the non-uniformity of the electron beam irradiation amount.

  In addition, in the method for forming an organic silica film of the present invention, in order to control the curing rate of the coating film, it is necessary to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, or reduced pressure as necessary. Can be.

  The coating treatment of the present invention can be performed under an inert atmosphere or under reduced pressure. In particular, in this curing treatment, it is desirable that the electron beam irradiation be performed in the absence of oxygen. Here, “the absence of oxygen” means that the oxygen partial pressure is preferably 0.1 kPa or less, more preferably 0.01 kPa or less. When the oxygen partial pressure is higher than 0.1 kPa, ozone is generated at the time of electron beam irradiation, and the silicon compound is oxidized by the ozone, so that the hydrophilicity of the obtained organic silica film is increased, and the hygroscopicity and ratio of the film are increased. It tends to increase the dielectric constant. Therefore, by performing the curing treatment in the absence of oxygen, an organic silica-based film having high hydrophobicity and hardly causing an increase in relative dielectric constant can be obtained.

In the present invention, the electron beam irradiation may be performed in an inert gas atmosphere. Here, examples of the inert gas used include N ₂ , He, Ar, Kr and Xe, preferably He and Ar. By performing electron beam irradiation in an inert gas atmosphere, the film is hardly oxidized, and the low dielectric constant of the obtained coating film can be maintained.

  In the present invention, the electron beam irradiation may be performed under pressure or in a reduced pressure atmosphere. The pressure at that time is preferably 0.001 to 1000 kPa, more preferably 0.001 to 101.3 kPa. If the pressure is out of the above range, in-plane non-uniformity may occur in the degree of curing. Moreover, in order to control the curing rate of the coating film, it is possible to heat stepwise, or to select atmospheric conditions such as an inert gas such as nitrogen and a reduced pressure state, as necessary.

  According to the method for forming an organic silica-based film of the present invention, by including a step of heating a coating film made of a silicon compound and a step of performing a curing treatment by irradiating the coating film with an electron beam, fewer electrons are produced. The coating film can be cured in a shorter time and at a lower temperature with the irradiation dose.

1.4. Organic Silica Film The organic silica film of the present invention is obtained by the method for forming an organic silica film of the present invention. In the organic silica film of the present invention, the carbon content (number of atoms) is 13 to 24 mol%, preferably 13 to 20 mol%. When the carbon content is in the above range, curing can be performed with a smaller amount of electron beam irradiation, and the mechanical strength can be improved while maintaining the low dielectric constant of the obtained organic silica film. If the carbon content is less than 13 mol%, the diffusion barrier in the solid-phase reaction is high, and the reaction is difficult to promote even when irradiated with an electron beam. On the other hand, if the carbon content is more than 24 mol%, the molecular mobility is high. It is not preferable because it is too high and the elastic modulus is low, and in some cases, the film exhibits a glass transition point.

The organic silica film of the present invention has an extremely high elastic modulus and film density and a low dielectric constant, as will be apparent from Examples described later. More specifically, the film density of the organic silica film of the present invention is usually 0.7 to 1.3 g / cm ³ , preferably 0.7 to 1.2 g / cm ³ , and more preferably 0.7 to 1.2 g / cm ³ . 1.0 g / cm ³ . When the film density is less than 0.7 g / cm ³ , the mechanical strength of the coating film is lowered. On the other hand, when it exceeds 1.3 g / cm ³ , a low dielectric constant cannot be obtained. The relative dielectric constant of the organic silica film of the present invention is usually 1.5 to 3.5, preferably 1.9 to 3.1, and more preferably 2.0 to 3.0. From these, it can be said that the organic silica film of the present invention is extremely excellent in insulating film properties such as mechanical strength and relative dielectric constant.

  Further, the organic silica film of the present invention has a water contact angle of preferably 60 ° or more, more preferably 70 ° or more. This indicates that the organosilica film of the present invention is hydrophobic, has low hygroscopicity, and can maintain a low relative dielectric constant. Furthermore, since such an organic silica film has low hygroscopicity, it is not easily damaged by RIE used in a semiconductor process, and is excellent in chemical resistance to a wet cleaning liquid. In particular, this tendency is remarkable in an organic silica film having a dielectric constant k of 2.5 or less, in which the insulating film itself has a porous structure.

As described above, the organosilica film of the present invention is
(A) Since the silicon compound has a specific composition and carbon content, it has excellent insulating film properties such as relative dielectric constant, elastic modulus, plasma resistance, and chemical resistance, and can be formed at a low temperature in a short time.
(B) The film-forming composition of the present invention used for forming a coating film generates an ionic substance such as an electron beam active acid generator, a base generator, and a sensitizer, a charge carrier or a corrosive compound. Source does not need to contain any contaminants to the semiconductor device,
(C) It is possible to adopt a curing method in which damage to the transistor structure due to a semiconductor process such as RIE is extremely small and can be processed by a single wafer process;
(D) Since it has high hydrophobicity and low hygroscopicity, it can maintain a low relative dielectric constant, and (e) it has excellent mechanical strength such as elastic modulus and can withstand the formation of a copper damascene structure, for example.
It has the features such as. Due to this feature, it is excellent in insulation, coating film uniformity, dielectric constant characteristics, coating film elastic modulus, coating film adhesion, plasma resistance, and chemical resistance.

  The organosilica film of the present invention has a low relative dielectric constant, excellent mechanical strength and adhesion, and is excellent in plasma resistance and chemical resistance. Therefore, LSI, system LSI, DRAM, SDRAM, RDRAM, D- Interlayer insulating film for semiconductor elements such as RDRAM, etching stopper film, protective film such as surface coat film of semiconductor element, intermediate layer of semiconductor manufacturing process using multilayer resist, interlayer insulating film of multilayer wiring board, for liquid crystal display element It can be suitably used for applications such as a protective film and an insulating film. Moreover, the organic silica film of the present invention can be suitably used for a semiconductor device including a wiring structure such as a copper damascene wiring structure.

2. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the examples and comparative examples, “parts” and “%” indicate parts by weight and% by weight, respectively, unless otherwise specified.

2.1. Evaluation method Various evaluations were performed as follows.

2.1.1. Polymer weight average molecular weight (Mw)
It measured by the gel permeation chromatography (GPC) method by the following conditions.
Sample: Prepared by dissolving 1 g of polymer in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent.
Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.
Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA
Column: SHODEX A-80M (length: 50 cm) manufactured by Showa Denko K.K.
Measurement temperature: 40 ° C
Flow rate: 1cc / min

2.1.2. Relative permittivity An aluminum electrode pattern was formed on the obtained polymer film by vapor deposition to prepare a sample for measuring relative permittivity. The relative permittivity of the coating film at room temperature was measured by the CV method using the HP16451B electrode and HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd., at a frequency of 100 kHz.

2.1.3 Delta k
The relative permittivity at 200 ° C. was measured in the same manner as 2.1.2, and the difference from the relative permittivity at 2.1.2 was shown.

2.1.4. Mechanical strength (elastic modulus)
The obtained polymer film was measured by a SAW (Surface Acoustic Wave) method.

2.1.5 Plasma Resistance Measurement Method After the cured organic silica film was irradiated with ammonia plasma for 30 seconds, the relative dielectric constant of the film was measured, and rated according to the value of the relative dielectric constant increased before and after the plasma irradiation.
A: Increase in relative dielectric constant is less than 0.2 B: Increase in relative dielectric constant is 0.2 or more and less than 0.5 C: Increase in relative dielectric constant is 0.5 or more

2.1.6 Chemical resistance test The cured organic silica film was immersed in a triethanolamine aqueous solution of pH 12 at room temperature for 10 minutes and then washed with water. After drying the water droplets on the surface with nitrogen blow, the relative dielectric constant was measured. The rating was based on the value of the relative dielectric constant increased before and after the test.
A: Increase in relative dielectric constant is less than 0.1 B: Increase in relative dielectric constant is 0.1 or more and less than 0.3 C: Increase in relative dielectric constant is 0.3 or more

2.1.7. Carbon content In each synthesis example, the carbon content in the hydrolysis condensate obtained when the silane monomer used in the synthesis of the silicon compound (hydrolysis condensate) was 100% hydrolytically condensed was calculated by calculation.

2.2. Examples and Comparative Examples 2.2.1. Synthesis example 1
In a quartz separable flask, 2.2 g of polycarbosilane A1 (weight average molecular weight 800) having a structural unit represented by the following formula (4), 33.3 g of methyltrimethoxysilane, 21.8 g of tetraethoxysilane, and After 0.0031 g of triethylamine was dissolved in 250 g of ethanol, the solution was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 50.4 g of ion-exchanged water and 203.2 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

Then, after making it react at 55 degreeC for 4 hours, 10 g of 10% propylene glycol monopropyl ether solutions of acetic acid were added, it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. At 50 ° C., 298 g of a solution containing methanol and water was removed from the reaction solution by evaporation, and the carbon content was 13.2 mol%, the weight average molecular weight was 45,000, and —Si—CH ₂ —Si — / — Si—O. A film-forming composition A containing a hydrolysis-condensation product having a —Si— (molar ratio) of 0.034 was obtained. This film-forming composition (hereinafter also simply referred to as “composition”) had a sodium content of 0.5 ppb, a potassium content of 0.8 ppb, and an iron content of 0.7 ppb.

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2.2.2. Synthesis example 2
After dissolving 18.4 g of polycarbosilane A used in Synthesis Example 1, 33.4 g of methyltrimethoxysilane, 9.0 g of tetraethoxysilane, and 0.0030 g of triethylamine in 253 g of methanol in a separable flask made of quartz. The solution temperature was stabilized at 55 ° C. by stirring with a three-one motor. Next, a mixed solution of 50.2 g of ion-exchanged water and 200.3 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

Then, after making it react at 55 degreeC for 4 hours, 10 g of 10% propylene glycol monopropyl ether solutions of acetic acid were added, it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. 299 g of a solution containing methanol and water was removed from the reaction solution by evaporation at 50 ° C., and the carbon content was 15.3 mol%, the weight average molecular weight was 42,000, —Si—CH ₂ —Si — / — Si—O—Si. A film-forming composition B containing a hydrolysis condensate having a molar ratio of 0.153 was obtained. This composition B had a sodium content of 1.1 ppb, a potassium content of 0.4 ppb, and an iron content of 0.6 ppb.

2.2.3. Synthesis example 3
In a quartz separable flask, 16.4 g of polycarbosilane A2 (weight average molecular weight 750) having a structural unit represented by the following formula (5), 21.3 g of methyltrimethoxysilane, 5.7 g of tetraethoxysilane, And 248 g of methanol was dissolved in 201 g of a propylene glycol monopropyl ether solution, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, 24 g of ion-exchanged water in which 0.12 g of succinic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. A solution containing 272 g of water was removed from the reaction solution at 50 ° C. by evaporation, and the carbon content was 19.7 mol%, the weight average molecular weight was 3200, —Si—CH ₂ —Si — / — Si—O—Si— (molar ratio). ) A film forming composition C containing 0.487 hydrolysis condensate was obtained. This composition C had a sodium content of 0.7 ppb, a potassium content of 0.5 ppb, and an iron content of 0.8 ppb.

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2.2.4. Synthesis example 4
In a quartz separable flask, 232.8 g of polycarbosilane A used in Synthesis Example 3 and 248 g of methanol were dissolved in 201 g of propylene glycol monopropyl ether solution, and then stirred with a three-one motor, and the solution temperature was 55 ° C. Stabilized. Next, 20 g of ion-exchanged water in which 0.08 g of succinic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. 250 g of a solution containing water was removed from the reaction solution by evaporation at 50 ° C., and the carbon content was 23.5 mol%, the weight average molecular weight was 2,700, —Si—CH ₂ —Si — / — Si—O—Si— ( A film-forming composition D containing a hydrolysis condensate having a molar ratio of 2.00 was obtained. This composition D was 23.5 mol%, had a sodium content of 0.8 ppb, a potassium content of 0.5 ppb, and an iron content of 0.9 ppb.

2.2.5. Synthesis example 5
In a quartz separable flask, 50.4 g of methyltrimethoxysilane, 77.1 g of tetraethoxysilane, and 0.0034 g of triethylamine were dissolved in 267 g of methanol, and then stirred with a three-one motor to bring the solution temperature to 55 ° C. Stabilized. Next, a mixed solution of 56.2 g of ion-exchanged water and 200.3 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

Then, after making it react at 55 degreeC for 4 hours, 10 g of 10% propylene glycol monopropyl ether solutions of acetic acid were added, it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. 299 g of a solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation, and the carbon content was 10.5 mol%, the weight average molecular weight was 45,000, —Si—CH ₂ —Si — / — Si—O—Si. A film-forming composition E containing polysiloxane having a-(molar ratio) of 0.000 was obtained. This composition E had a sodium content of 0.6 ppb, a potassium content of 0.7 ppb, and an iron content of 0.9 ppb.

2.2.6. Synthesis Example 6
In a quartz separable flask, 4.9 g of polycarbosilane A3 (weight average molecular weight 2300) having a structural unit represented by the following formula (6), 20.5 g of methyltrimethoxysilane, 31.3 g of tetraethoxysilane, and After 258 g of methanol was dissolved in 209 g of propylene glycol monopropyl ether solution, the solution was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, 20 g of ion-exchanged water in which 0.08 g of succinic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 60 degreeC for 12 hours, the reaction liquid was cooled to room temperature. At 50 ° C., 250 g of a solution containing water was removed from the reaction solution by evaporation, and the carbon content was 16.7 mol%, the weight average molecular weight was 4,400, —Si—CH ₂ —Si — / — Si—O—Si— ( A film-forming composition F containing a hydrolysis condensate having a molar ratio of 0.132 was obtained. The carbon content of Composition F was 16.7 mol%, the sodium content was 0.8 ppb, the potassium content was 0.5 ppb, and the iron content was 0.9 ppb.

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2.3. Examples and Comparative Examples Each of the compositions obtained in Synthesis Examples 1-6 was applied on a silicon wafer by a spin coating method, then on a hot plate at 90 ° C. for 3 minutes, and then at 200 ° C. in a nitrogen atmosphere. The substrate was dried for 3 minutes, and the substrate was further fired under the curing conditions shown in Table 1. The polymer film (hereinafter referred to as “silica film”) obtained after firing was evaluated according to the evaluation method. The evaluation results are shown in Table 1. In Example 1-6, the coating film was cured by irradiating a predetermined dose of electron beam within the heating time under the heating conditions shown in Table 1, whereas in Comparative Example 1-5, heating was performed. The coating was cured only by treatment.

  Furthermore, IR spectra of the silica-based films obtained in Example 2 and Comparative Example 2 were measured, and the results are shown in FIG. In FIG. 1, it can be seen that there are peaks that appear only after EB irradiation at the locations indicated by A and B.

  As is apparent from the above, according to Example 1-6, it is possible to form an organic silica-based film with significantly improved characteristics, particularly elastic modulus, as compared with Comparative Example 1-5. confirmed. For this reason, it is clear that the organic silica film obtained by the present invention is excellent in mechanical strength, has a low relative dielectric constant, has a low hygroscopic property, and can be suitably used as an interlayer insulating film of a semiconductor device.

Claims (15)

Forming a coating film comprising a silicon compound having a —Si—O—Si— structure and a —Si—CH ₂ —Si— structure on a substrate;
Heating the coating film;
Irradiating the coating film with an electron beam and performing a curing treatment;
A method for forming an organic silica-based film. In claim 1,
In the silicon compound, the —Si—O—Si— structure and the —Si—CH ₂ —Si— structure are 0.03 to (Si—CH ₂ —Si — / — Si—O—Si— (molar ratio)). A method for forming an organic silica-based film present at a ratio of 2.00. In claim 1,
The formation method of the organic silica type film | membrane whose carbon content in the said silicon compound is 13-24 mol%. In claim 1,
The method for forming an organic silica film, wherein the silicon compound is a hydrolysis condensate obtained by hydrolytic condensation of (B) a hydrolyzable group-containing silane monomer in the presence of (A) polycarbosilane. In claim 1,
The method for forming an organic silica film, wherein, in the irradiation with the electron beam, an acceleration voltage of the electron beam is 0.1 to 20 keV, and an irradiation amount of the electron beam is 1 to 1000 μC / cm ² . In claim 1,
A method for forming an organic silica film, in which heating and electron beam irradiation are performed simultaneously. In claim 1,
The said heating is a 300-450 degreeC formation method of the organic silica type film | membrane. In claim 1,
A method for forming an organic silica film, wherein the electron beam irradiation is performed in the absence of oxygen. It is obtained by the method for forming an organic silica film according to any one of claims 1 to 8, and has a relative dielectric constant of 1.5 to 3.5 and a film density of 0.7 to 1.3 g / cm ^3. An organic silica film.   A wiring structure using the organic silica-based film according to claim 9 as an interlayer insulating film.   A semiconductor device comprising the wiring structure according to claim 10. (A) In the presence of polycarbosilane, (B) a hydrolytic condensate obtained by hydrolytic condensation of a hydrolyzable group-containing silane monomer;
An organic solvent,
A film-forming composition used for forming the coating film in the method for forming an organic silica-based film according to claim 1. In claim 12,
The hydrolysis-condensation product is a film-forming composition containing 13 to 24 mol% of carbon atoms. In claim 12,
The composition for film formation whose said (B) component is 1-1000 weight part with respect to 100 weight part which converted the said (A) component into the complete hydrolysis condensate of (A) component. In claim 12,
The composition for film formation whose content of sodium, potassium, and iron is 100 ppb or less, respectively.

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