JP2005320412A - Film-forming composition, insulating film, method for forming the same and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming composition which is excellent in flattening effect and is useful as a material for an interlayer insulating film used in a semiconductor element etc., a method for forming the insulating film, the insulating film and a semiconductor device. <P>SOLUTION: The film-forming composition contains (A) a hydrolytic condensate obtained by hydrolyzing and condensing an alkoxysilane in the presence of water and at least one of a metal chelate compound and an acid catalyst, (B) a hydrolysis condensate obtained by hydrolyzing and condensing an alkoxysilane in the presence of an alkali catalyst and water, an organic solvent and water. The weight ratio of component (A) is greater than that of component (B). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a film forming composition, a method for forming an insulating film, an insulating film, and a semiconductor device, and more specifically, as a material for an interlayer insulating film used in a semiconductor element or the like, for forming a film having an excellent planarization effect. The present invention relates to a composition, a method for forming an insulating film, an insulating film, and a semiconductor device.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is 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 and the like, an interlayer insulating film having a lower relative dielectric constant is required, and an interlayer insulating film material having excellent flatness is required.

As a material having a low dielectric constant, a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (see Patent Documents 1 and 2), A coating liquid obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia has been proposed (see Patent Documents 3 and 4).
JP-A-5-263045 JP-A-5-315319 Japanese Patent Laid-Open No. 11-340219 Japanese Patent Laid-Open No. 11-340220

  However, with further high integration and multi-layering of semiconductor devices in recent years, further improvement in the planarization effect and the like is desired for interlayer insulating films and the like.

  An object of the present invention is to provide a film-forming composition that is further excellent in flatness and can obtain a film that is suitably used as an interlayer insulating film.

  Another object of the present invention is to provide a method for producing the above-mentioned film forming composition.

  Another object of the present invention is to provide a method for forming an insulating film using the above-mentioned film forming composition.

  Another object of the present invention is to provide an insulating film obtained by the above-described film forming method and suitably used as an interlayer insulating film.

  Another object of the present invention is to provide a semiconductor device including the above-described insulating film.

(1) The film forming composition according to the present invention comprises:
Component (A): a compound represented by the following general formula (1) and at least one compound selected from the compounds represented by the following general formulas (2) to (4), a metal chelate compound and an acid Hydrolysis condensate obtained by hydrolysis and condensation in the presence of water with at least one of the catalyst,
Component (B): a compound represented by the following general formula (1) and at least one compound among the compounds represented by the following general formulas (2) to (4), an alkali catalyst and water Hydrolysis condensate obtained by hydrolysis and condensation in the presence of
Contains an organic solvent, and water,
In the component (A), the ratio of the compound represented by the general formula (1) to the total amount of the compounds represented by the general formulas (1) to (4) is 60 mol% or more,
In the component (B), the ratio of the compound represented by the general formula (1) to the total amount of the compounds represented by the general formulas (1) to (4) is 40 mol% or more, and A composition for film formation in which the weight ratio of component A) is greater than the weight ratio of component (B).
R ¹ Si (OR ² ) ₃ (1)
(Wherein R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and R ² represents a monovalent organic group.)
R ³ ₂ Si (OR ⁴ ) ₂ (2)
(In the formula, R ³ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and R ⁴ represents a monovalent organic group.)
Si (OR ⁵ ) ₄ (3)
(In the formula, R ⁵ represents a monovalent organic group.)
_{^{R 6 a (R 7 O)}} 3-a Si- (R 10) c -Si (OR 8) 3-b R 9 b ····· (4)
[Wherein R ^{6 to} R ⁹ are the same or different, each is a monovalent organic group, a and b are the same or different and each represents an integer of 0 to 2, and R ¹⁰ represents an oxygen atom, a phenylene group or — (CH _{2 N}
-(Wherein n is an integer of 1 to 6), and c represents 0 or 1. ]
According to the film forming composition of the present invention, an insulating film excellent in gap fill performance can be obtained.

(2) In the film forming composition according to the present invention,
The gelation temperature can be 90 ° C. or higher.

  The gelation temperature refers to a film-forming composition applied on a 4-inch silicon substrate to a thickness of 500 nm, heated in the air on a hot plate at a predetermined temperature for 1 minute, and then in a petri dish having a diameter of 120 mm. When immersed in 200 mL of propylene glycol mono-n-propyl ether at 25 ° C. for 1 minute, it can be confirmed silently that the film obtained from the film-forming composition remains on the surface of the 4-inch silicon wafer. This is the lowest temperature among the hot plate temperatures.

  When the gelation temperature is 90 ° C. or higher, it is possible to prevent the polymer in the film-forming composition from gelling before filling the gap of the base material when the coating film is dried. Therefore, according to the film forming composition of the present invention, an insulating film excellent in gap fill performance can be obtained.

(3) In the method for forming an insulating film according to the present invention, the film forming composition according to the present invention is applied on a substrate,
Dried at a temperature below the gelation temperature for 1-60 minutes,
Dried for 1 to 60 minutes at a temperature higher than the gelation temperature and less than 200 ° C higher than the gelation temperature
Baking is performed at a temperature of 200 ° C. higher than the gelling temperature and a temperature of 450 ° C. or lower for 1 to 180 minutes.

  (4) The insulating film according to the present invention is formed by the insulating film forming method according to the present invention.

  (5) A semiconductor device according to the present invention includes an insulating film according to the present invention.

  Details of the film forming composition, the insulating film forming method, the insulating film, and the semiconductor device according to the present invention will be described below.

1. Film-Forming Composition The film-forming composition according to the present invention comprises (A) component, (B) component, an organic solvent, and water. Each of (A) component and (B) component is demonstrated below.

1.1. Component (A) and Component (B) The component (A) is represented by a compound represented by the following general formula (1) (hereinafter referred to as “compound 1”) and the following general formulas (2) to (4). Of the compounds (hereinafter referred to as “compound 2”, “compound 3”, and “compound 4”, respectively) with at least one of the metal chelate compound and the acid catalyst in the presence of water. It is a hydrolysis-condensation product obtained by decomposition and condensation.

Component (B) is a hydrolysis condensate obtained by hydrolyzing and condensing compound 1 and at least one compound of compounds 2 to 4 in the presence of an alkali catalyst and water.
R ¹ Si (OR ² ) ₃ (1)
(Wherein R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and R ² represents a monovalent organic group.)
R ³ ₂ Si (OR ⁴ ) ₂ (2)
(In the formula, R ³ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and R ⁴ represents a monovalent organic group.)
Si (OR ⁵ ) ₄ (3)
(In the formula, R ⁵ represents a monovalent organic group.)
_{^{R 6 a (R 7 O)}} 3-a Si- (R 10) c -Si (OR 8) 3-b R 9 b ····· (4)
[Wherein R ^{6 to} R ⁹ are the same or different, each is a monovalent organic group, a and b are the same or different and each represents an integer of 0 to 2, and R ¹⁰ represents an oxygen atom, a phenylene group or — (CH _{2 N}
-(Wherein n is an integer of 1 to 6), and c represents 0 or 1. ]
The hydrolysis condensate in the component (A) and the component (B) is at least one of a hydrolyzate and a condensate of at least one compound among the compound 1 and the compounds 2 to 4. Here, the “hydrolyzate” in the component (A) and the component (B) is an R ² O— group, an R ⁴ O— group, an R ⁵ O— group, or an R ⁷ O contained in the compounds 1 to 4. It is not necessary for all of the groups and R ⁸ O- groups to be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. May be. In addition, here, the “condensate” in the component (A) and the component (B) is a product in which the silanol groups of the hydrolyzates of the compounds 1 to 4 are condensed to form a Si—O—Si bond. However, in the present invention, it is not necessary that all of the silanol groups are condensed, and the concept includes a mixture of a small part of the silanol groups or a mixture of those having different degrees of condensation.

  Moreover, it is preferable that the ratio of the compound 1 is 60 to 95 mol% with respect to the total amount of the compound 1 to the compound 4 in (A) component, and it is more preferable that it is 65 to 90 mol%. When the proportion of Compound 1 is less than 65 mol%, the resulting coating film has high hygroscopicity, and thus the dielectric constant of the coating film may be high, and the proportion of Compound 1 is more than 90 mol%. In some cases, gelation or precipitation may occur during synthesis.

  In the component (B), the proportion of compound 1 is preferably 40 mol% or more and 90 mol% or less, more preferably 50 to 80 mol%, relative to the total amount of compound 1 to compound 4. When the proportion of Compound 1 is less than 50 mol%, the resulting coating film has high hygroscopicity, and thus the dielectric constant of the coating film may be high, and the proportion of Compound 1 is more than 80 mol%. In some cases, gelation or precipitation may occur during synthesis.

  Here, the component (A) has a higher gelation temperature and a higher melt viscosity of the polymer than the component (B). The component (B) has a lower gelation temperature and a lower melt viscosity of the polymer than the component (A). Therefore, the composition for film formation which has favorable gap fill performance can be obtained by mixing (A) component and (B) component by appropriate weight ratio.

  In particular, in the film-forming composition, the weight ratio of the component (A) is preferably larger than the weight ratio of the component (B), and the weight ratio of the component (A) to the component (B), that is, the component (A) / The component (B) is more preferably 1.5 to 9.0. Thereby, the composition for film formation which has sufficient gap fill performance can be obtained.

1.1.1. Compound 1
In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Especially, in General formula (1), it is preferable that R is a monovalent organic group, especially an alkyl group or an aryl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and preferably 1 to 5 carbon atoms. These alkyl groups may be linear or branched, Further, 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, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

  Specific examples of compound 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxy. Silane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane , Ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxy N-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyl Tri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n -Butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxy Run, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert- Butyl-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri- tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxy Silane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , Γ-trifluoropropyltrimethoxysilane, and γ-trifluoropropyltriethoxysilane. These may be used alone or in combination of two or more.

  Particularly preferred compounds as Compound 1 are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane and the like.

1.1.2. Compound 2
In the general formula (2), examples of the monovalent organic group represented by R ³ and R ⁴ include the same organic groups as those shown in the general formula (1).

  Specific examples of compound 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, and dimethyldi-tert-butoxysilane. , Dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyl Diphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopro Xysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldi Ethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di- n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n Butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi- n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di- sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiisopropoxysilane, di-tert-butyldi -N-butoxysilane, di-te rt-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxysilane, diphenyldimethoxysilane, diphenyldi-ethoxysilane, diphenyldi-n-propoxysilane, diphenyldiiso Examples thereof include propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, and divinyltrimethoxysilane. These may be used alone or in combination of two or more.

  Particularly preferred compounds as Compound 2 are dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

1.1.3. Compound 3
In the general formula (3), examples of the monovalent organic group represented by R ⁵ include the same organic groups as those shown in the general formula (1).

  Specific examples of Compound 3 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, Tetraphenoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

  Particularly preferred compounds as compound 3 include tetramethoxysilane and tetraethoxysilane.

1.1.4. Compound 4
In the general formula (4), examples of the monovalent organic group represented by R ^{6 to} R ⁹ include the same organic groups as those shown in the general formula (1).

Among the compounds 4, compounds in which R ¹⁰ in the general formula (4) is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3- Methyldisiloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1,3 3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-pen Taphenoxy-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1 , 3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3- Diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3- Tetraethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3 , 3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3- Trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane Siloxane, 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 the general formula (4), specific examples of the compound 4 with c = 0 include hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1 , 1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2- Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-penta Methoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2 -Tet Methoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2, , 2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, , 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2- Diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2, -Trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2 , 2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy -1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2 -Diphenoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisi Lan, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2 -Tetraphenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, etc. can be mentioned.

  Of these, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1, 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-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 (4), R ¹⁰ is a group represented by — (CH ₂ ) _n — as bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n -Propoxysilyl) methane, bis (tri-iso-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri-iso-propoxy) Silyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1, -Bis (tri-tert-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- ( Di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (tri-iso-propoxysilyl) methane, 1- (di- n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert- Butoxymethylsilyl) -1- (tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso -Propoxymethylsilyl) -2- (tri-iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxy) Methylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis ( Diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethylsilyl) meta Bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1 , 2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2-bis ( Di-n-butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) ethane, 1,2-bis (trimethoxy) Silyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bi (Tri-iso-propoxysilyl) benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert- Butoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis ( Tri-iso-propoxysilyl) benzene, 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-tert-butoxy) Silyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri -N-propoxysilyl) benzene, 1,4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) ) Benzene, 1,4-bis (tri-tert-butoxysilyl) benzene, and the like.

  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.

1.1.5. Metal Chelate Compound The metal chelate compound is represented by the following general formula (5).

^{_{R 11 d M (OR 12)}} e-d ····· (5)
[Wherein R ¹¹ represents a chelating agent, M represents a metal atom, R ¹² represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, e represents a valence of metal M, d represents 1 to 1 e represents an integer. ]

  The metal M in the metal chelate compound represented by the general formula (5) is at least one metal selected from Group IIIB metals (aluminum, gallium, indium, thallium) and Group IVA metals (titanium, zirconium, hafnium). It is preferable that titanium, aluminum, and zirconium are more preferable. Specific examples of the metal chelate compound (A-3) include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonate). Titanium, tri-n-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxy bis (acetylacetate) Nato) titanium, di-n-propoxy bis (acetylacetonato) titanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy.titanium Bis (acetylacetonate) titanium, di tert-Butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, mono-n-propoxy tris (acetylacetonato) titanium, monoisopropoxy tris (acetylacetonato) titanium, mono -N-butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-tert-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy Mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, triisopropoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) ) Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (Ethyl acetoacetate) titanium, diisopropoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-tert -Butoxy bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono- n -Butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetyl) Titanium chelate compounds such as acetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetyl) Acetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, triisopropoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetate) Ruacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-tert-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis ( Acetylacetonato) zirconium, diisopropoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-tert- Butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, monoisopropyl Poxy-tris (acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonate) Zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, triisopropoxy mono (ethyl acetoacetate) zirconium, tri-n- Butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-tert-butoxy mono (ethyl aceto) Acetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl aceto) Acetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (Ethyl acetoacetate) zirconium, monoisopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, -Sec-butoxy-tris (ethylacetoacetate) zirconium, mono-tert-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis Zirconium chelate compounds such as (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium; diethoxy mono (acetylacetonato) aluminum, di-n-propoxy mono (Acetylacetonato) aluminum, diisopropoxy mono (acetylacetonato) aluminum, di-n-butoxy mono (acetylacetonato) a Minium, di-sec-butoxy mono (acetylacetonato) aluminum, di-tert-butoxy mono (acetylacetonato) aluminum, monoethoxy bis (acetylacetonato) aluminum, mono-n-propoxy bis (acetyl) Acetonato) aluminum, monoisopropoxy bis (acetylacetonato) aluminum, mono-n-butoxy bis (acetylacetonato) aluminum, mono-sec-butoxy bis (acetylacetonato) aluminum, mono-tert-butoxy・ Bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, diethoxy mono (ethylacetoacetate) aluminum, di-n-propoxy mono (ethylacetoacetate) ) Aluminum, diisopropoxy mono (ethyl acetoacetate) aluminum, di-n-butoxy mono (ethyl acetoacetate) aluminum, di-sec-butoxy mono (ethyl acetoacetate) aluminum, di-tert-butoxy mono (Ethyl acetoacetate) aluminum, monoethoxy bis (ethyl acetoacetate) aluminum, mono-n-propoxy bis (ethyl acetoacetate) aluminum, monoisopropoxy bis (ethyl acetoacetate) aluminum, mono-n-butoxy Bis (ethyl acetoacetate) aluminum, mono-sec-butoxy bis (ethyl acetoacetate) aluminum, mono-tert-butoxy bis (ethyl acetoacetate) aluminum, One or more of aluminum chelate compounds such as aluminum (ethylacetoacetate) aluminum, mono (acetylacetonato) bis (ethylacetoacetate) aluminum, bis (acetylacetonato) mono (ethylacetoacetate) aluminum Can be mentioned.

In _{particular, (CH 3 (CH 3)} HCO) 4-t Ti (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t ( _{C 4 H 9 O) 4-} t Ti (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Ti (CH 3
COCH ₂ COOC ₂ H ₅ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Ti ( CH ₃ COCH ₂ COO
_{C 2 H 5) t (CH} 3 (CH 3) HCO) 4-t Zr (CH 3 COCH 2 COCH 3) t (CH 3 (CH 3) HCO) 4-t Zr (CH 3 COCH 2 COOC 2 H 5 _{) t (C 4 H 9 O} ) 4-t Zr (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Zr (CH
₃ COCH ₂ COOC ₂ H ₅ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Zr (CH ₃ COCH ₂ CO
_{OC 2 H 5) t (CH} 3 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COCH 3) t (CH 3 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COOC 2 H 5 _{) t (C 4 H 9 O} ) 3-t Al (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 3-t Al (C
_{H 3 COCH 2 COOC 2 H 5} ) t, (C 2 H 5 (CH 3) CO) 3-t Al (CH 3 COCH 2 COCH 3) t, (C 2 H 5 (CH 3) CO) 3-t Al (CH ₃ COCH ₂ C
One type or two or more types such as OOC ₂ H ₅ ) _t are preferred as the metal chelate compound.

  The amount [mol] of the metal chelate compound used is usually 0.000001 to 0.5, preferably 0.000003 to 0.3, based on the total amount [mol] of the silane compounds 1 to 4. More preferably, it is a value within the range of 0.000005 to 0.1. Here, when the amount of the metal chelate compound used is a value within the range of 0.000001 to 0.5, the coating thickness after curing becomes uniform, and the relative dielectric constant of the coating after curing is determined. Can be lowered. Here, if the amount of the metal chelate compound used is less than 0.000001, the hydrolysis and condensation reaction does not proceed sufficiently and the above-mentioned target molecular weight may not be obtained. May exceed the molecular weight.

  Moreover, it is preferable that the usage-amount [mol] of the water used for reaction of the said silane compound and a metal chelate compound is 0.1-12 times the total usage-amount [mol] of the compounds 1-4 to be used, More preferably, it is 0.2 to 10 times. Here, if the amount of water to be added is less than 0.1 times, the crack resistance of the coating film may be inferior. On the other hand, if it exceeds 12 times, precipitation or gelation of the polymer during hydrolysis and condensation reactions May occur.

  Water can be added all at once, or can be added continuously or intermittently.

1.1.6. Acid catalyst 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, and nonanoic acid. , Decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolein Acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, Hydrolyzate of citric acid, tartaric acid, succinic acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid Organic acids such as hydrolyzate of maleic anhydride and hydrolyzate of phthalic anhydride can be mentioned, and organic acids can be mentioned as more preferred examples. These compounds may be used alone or in combination of two or more.

The amount of the acid catalyst used is 1 mol of the total amount of R ² O— group, R ⁴ O— group, R ⁵ O— group, R ⁷ O— group and R ⁸ O— group contained in compounds 1-4. Usually, it is 0.00001-10 mol, Preferably, it is 0.00005-5 mol. Within this range, there is little risk of polymer precipitation or gelation during the reaction.

  Moreover, it is preferable that the usage-amount [mol] of the water used when using an acid catalyst is 0.1-12 times the total usage-amount [mol] of the compounds 1-4 to be used, 0.2- 10 times is more preferable. Here, if the amount of water to be added is less than 0.1 times, the crack resistance of the coating film may be inferior. On the other hand, if it exceeds 12 times, precipitation or gelation of the polymer during hydrolysis and condensation reactions May occur.

  Water can be added all at once, or can be added continuously or intermittently.

1.1.7. Alkali catalyst By using an alkali catalyst, it is possible to obtain an insulating film having a low relative dielectric constant and a high elastic modulus and excellent adhesion to the substrate. Examples of the alkali catalyst that can be used in the present invention include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane. , Diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, N, N -Dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, cerium hydroxide, etc. From the point of adhesion of the insulating film to the substrate, ammonia and alkylamine. Particularly preferred. These alkali catalysts may be used alone or in combination of two or more.

The amount of the alkali catalyst used is based on 1 mol of the total amount of R ² O— group, R ⁴ O— group, R ⁵ O— group, R ⁷ O— group and R ⁸ O— group contained in compounds 1-4. Usually, it is 0.00001-10 mol, preferably 0.00005-5 mol. Within this range, there is little risk of polymer precipitation or gelation during the reaction.

  Moreover, it is preferable that the usage-amount [mol] of the water used when using an alkali catalyst is 0.3-12 times the total usage-amount [mol] of the compounds 1-4 to be used, 0.5- 10 times is more preferable. Here, if the amount of water to be added is less than 0.3 times, the crack resistance of the coating film may be inferior. On the other hand, if it exceeds 12 times, precipitation or gelation of the polymer during hydrolysis and condensation reactions May occur.

  Water can be added all at once, or can be added continuously or intermittently.

1.2. Organic Solvent The film-forming composition according to the present invention contains the above-described component (A), component (B), an organic solvent, and water. Examples of the organic solvent include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.

Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 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, 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, 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, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol solvents such as ethylhexanediol-1,3, 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-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned. These aprotic solvents may be used alone or in combination of two or more.

  As the organic solvent, it is particularly preferable to use a solvent represented by the following general formula (6).

R ¹³ O (CHCH ₃ CH ₂ O) _f R ¹⁴ (6)
(R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monovalent organic group selected from CH ₃ CO—, and f represents an integer of 1 to 2).
Specific examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. Can do. The above organic solvents can be used alone or in combination of two or more.

1.3 Other Additives The insulating film forming composition of the present invention may further contain components such as colloidal silica, colloidal alumina, a surfactant, and a silane coupling agent. The colloidal silica is, for example, a dispersion in which high-purity silicic acid is dispersed in the hydrophilic organic solvent. Usually, the average particle size is 5 to 30 nm, preferably 10 to 20 nm, and the solid content concentration is 10 to 10. About 40% by weight. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol; Catalyst Chemical Industries, Ltd., Oscar. Examples of the colloidal alumina include Alumina Sol 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; Alumina Clear Sol, Alumina Sol 10, and 132 manufactured by Kawaken Fine Chemical Co., Ltd., and the like.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and further, fluorine surfactants, silicone surfactants, Polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned, and fluorine surfactants and silicone surfactants can be preferably mentioned.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8 , 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluoroo Tansulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorophosphate) Octylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate ester, etc., a fluorine-based surfactant comprising a compound having a fluoroalkyl or fluoroalkylene group at least at any one of its terminal, main chain and side chain Can be mentioned. Commercially available products include MegaFuck F142D, F172, F173, and F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Kasei). , FLORARD FC-430, FC-431 (manufactured by Sumitomo 3M Limited), 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.), etc. Mention may be made of surfactants. Among these, the Megafac F172, BM-1000, BM-1100, and NBX-15 are particularly preferable.

  As the silicone-based surfactant, for example, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd., etc.) can be used. Among these, the SH28PA and SH30PA are particularly preferable. The amount of the agent used is usually 0.0001 to 10 parts by weight based on component (A) (completely hydrolyzed condensate), and these may be used alone or in combination of two or more.

  Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1- Methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl 3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 , 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N -Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (Oxyethylene)- - aminopropyltrimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. These may be used alone or in combination of two or more.

2. Film Formation Method and Insulating Film Next, a film formation method will be described.

  The method for forming an insulating film of the present invention includes applying the above-described composition for forming an insulating film to a substrate and heating. First, examples of the method for applying to the substrate include spin coating, dipping, roller blades, and spraying. In this case, as a dry film thickness, it is possible to form a coating film having a thickness of about 0.01 to 1.5 μm by one coating and a thickness of about 0.02 to 3 μm by two coatings.

  Next, the coating film is dried by heating at a temperature lower than the gelation temperature for about 1 to 60 minutes. The gelation temperature refers to a film-forming composition applied on a 4-inch silicon substrate to a thickness of 500 nm, heated in the air on a hot plate at a predetermined temperature for 1 minute, and then in a petri dish having a diameter of 120 mm. When immersed in 200 mL of propylene glycol mono-n-propyl ether at 25 ° C. for 1 minute, it can be confirmed silently that the film obtained from the film-forming composition remains on the surface of the 4-inch silicon wafer. It is the lowest temperature among the hot plate temperatures.

  The gelation temperature is preferably 90 ° C. or higher and 200 ° C. or lower. More preferably, it is 90-180 degreeC.

  Next, the coating film is heated for 1 to 60 minutes at a temperature equal to or higher than the gelation temperature and lower than 200 ° C higher than the gelation temperature, and dried. Preferably, it is preferable to heat to 160 to 300 ° C. More preferably, it is preferable to heat to 180 to 250 ° C.

  Next, the coating film is baked at a temperature of 200 ° C. higher than the gelling temperature and a temperature of 450 ° C. or lower for 1 to 180 minutes to form an insulating film. Preferably, heating to 300 to 450 ° C is preferable. More preferably, heating to 350 to 420 ° C is preferable.

  By performing the above three-step baking, a coating film having no defects and excellent flatness can be obtained.

  In this case, a hot plate, an oven, a furnace, or the like can be used as the heating method, and the heating atmosphere can be an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can be done. In heat curing, it is preferable to heat in an inert atmosphere or under reduced pressure. Moreover, a coating film can be formed also by irradiating an electron beam or an ultraviolet-ray, and this case is preferable at the point which can shorten drying time.

  The insulating film of the present invention is obtained by the film forming method described above. Thus, in the component (A), the ratio of the compound 1 is 60 mol% or more with respect to the total amount of the compounds 1 to 4, and in the component (B), the ratio of the compound 1 to the total amount of the compounds 1 to 4 is An insulating film obtained using a film-forming composition having a ratio of 40 mol% or more and a weight ratio of the component (A) larger than the weight ratio of the component (B) is excellent in gap fill performance. As a result, according to the present invention, an interlayer insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, a protective film such as a surface coat film of the semiconductor device, and a semiconductor using a multilayer resist An insulating layer useful for applications such as an intermediate layer in a manufacturing process, an interlayer insulating film of a multilayer wiring board, a protective film or an insulating film for a liquid crystal display device can be provided.

4). Semiconductor Device The semiconductor device of the present invention includes the above-described insulating film. In the case where the insulating film is used as, for example, a planarization insulating film, a highly reliable semiconductor device can be provided because the insulating film has excellent gap fill properties.

5. Examples Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, “%” indicates wt% unless otherwise specified. Using the components (A) and (B) obtained in Synthesis Example 1 and Synthesis Example 2, film-forming compositions were obtained in Example 1 and Comparative Example 1. A coating film was formed using the composition obtained in Example 1. The obtained insulating film was evaluated for gelation temperature, film thickness reduction rate, film thickness uniformity, relative dielectric constant, and gap fill property.

5.1. Synthesis example 1
In a quartz separable flask, 77.04 g of distilled methyltrimethoxysilane, 24.05 g of distilled tetramethoxysilane and 0.48 g of distilled tetrakis (acetylacetonate) titanium were dissolved in 290 g of distilled propylene glycol monoethyl ether. The solution temperature was stabilized at 60 ° C. by stirring with a three-one motor. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after making it react at 60 degreeC for 2 hours, 25 g of distilled acetylacetone was added, it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by 149 g evaporation to obtain Reaction Solution 1.

5.2. Synthesis example 2
In a quartz separable flask, 470.9 g of distilled ethanol, 226.5 g of ion-exchanged water, and 17.2 g of 25% tetramethylammonium hydroxide aqueous solution were added and stirred uniformly. To this solution, a mixture of 44.9 g of methyltrimethoxysilane and 68.6 g of tetraethoxysilane was added over 2 hours. The reaction was carried out for 6 hours while maintaining the solution at 58 ° C. To this solution, 80 g of a 20% maleic acid aqueous solution was added and stirred sufficiently, and then cooled to room temperature. To this solution was added 400 g of propylene glycol monopropyl ether, and then the solution was concentrated to 10% (in terms of complete hydrolysis condensate) using an evaporator at 50 ° C., and then 10% propylene glycol monopropyl maleate. 10 g of an ether solution was added to obtain a reaction solution 2.

5.3. Example 70 g of the reaction solution 1 obtained in Synthesis Example 1 and 30 g of the reaction solution 2 obtained in Synthesis Example 2 and 2.9 g of ion-exchanged water were added and sufficiently stirred. This solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a film-forming composition A.

5.4. Comparative Example 30 g of the reaction solution 1 obtained in Synthesis Example 1 and 70 g of the reaction solution 2 obtained in Synthesis Example 2 and 2.9 g of ion-exchanged water were added and sufficiently stirred. This solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a film-forming composition B.

5.5. Evaluation of Film Forming Composition The gelation temperature, film thickness reduction rate, film thickness uniformity, relative dielectric constant, and gap fill property of the film forming composition were evaluated. Each evaluation was performed according to the following conditions.

5.5.1. Gelation temperature A film-forming composition was applied on a 4-inch silicon wafer using a spin coating method, dried on a hot plate in an air atmosphere at a predetermined temperature for 1 minute, and then the coating film was propylene glycol mono-n- When immersed in propyl ether for 30 seconds, the lowest temperature at which the coating film remains is defined as the gelation temperature.

5.5.2. Film thickness reduction rate A film-forming composition was applied onto a 4-inch silicon wafer using a spin coating method, dried on a hot plate in the atmosphere at a temperature 10 ° C. lower than the gelation temperature for 1 minute, and then gelled. Drying was performed at a temperature 120 ° C. higher than the temperature for 1 minute. The film thickness before and after drying at a temperature 120 ° C. higher than the gelling temperature was measured with an ellipsometer, the film thickness reduction rate was calculated from the following formula, and evaluated according to the following criteria.

Film thickness reduction rate (%) = 100 × film thickness after drying ÷ film thickness before drying ○; film thickness reduction rate <20%
×: Film thickness reduction rate ≧ 20%

5.5.3. Film thickness uniformity A film-forming composition is applied onto an 8-inch silicon wafer by spin coating, dried on a hot plate in the air at a temperature 10 ° C. lower than the gelation temperature for 1 minute, and then the gelation temperature. The film was dried at a temperature higher by 120 ° C. for 1 minute and further baked in a furnace at 420 ° C. for 60 minutes in a nitrogen atmosphere. The film thickness of the coating film after baking was measured at 49 points per wafer with an ellipsometer, the average film thickness and the standard deviation (σ) were calculated, and evaluated according to the following criteria.
○; 3σ <3%
×; 3σ ≧ 3%

5.5.4. Relative permittivity A film-forming composition was applied onto an 8-inch silicon wafer using a spin coating method, dried on a hot plate in air at a temperature 10 ° C. lower than the gelation temperature for 1 minute, and then from the gelation temperature. It was dried for 1 minute at a temperature higher by 120 ° C., and further baked in a furnace at 420 ° C. for 60 minutes in a nitrogen atmosphere. On the obtained film, an aluminum electrode pattern was formed by a vapor deposition method to obtain a sample for measuring relative permittivity. The relative dielectric constant of the sample at a frequency of 100 kHz was measured by the CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd.

5.5.5. Gap fill property L / S = 200 nm / 200 nm, A film forming composition is applied on a patterned wafer having an aspect ratio of 5 using a spin coating method, and is 10 ° C. lower than the gelation temperature on a hot plate in an air atmosphere. The substrate was dried at a temperature for 1 minute, and then the substrate was dried at a temperature 120 ° C. higher than the gelation temperature for 1 minute, and further baked at 420 ° C. furnace in a nitrogen atmosphere for 60 minutes. The pattern cross section of this substrate was observed with a scanning electron microscope, and the embedding property was evaluated according to the following criteria.
○: The film is embedded in the pattern groove without any defects.
X: The film | membrane is not completely embedded in the groove | channel of a pattern, but a space | gap and a defect are recognized.

5.6. Evaluation Results The gelation temperature, film thickness reduction rate, film thickness uniformity, relative dielectric constant, and gap fill property of the film forming composition A and the film forming composition B were evaluated, and the evaluation results are shown in Table 1.

  As shown in Table 1, according to the examples, the gelation temperature of the obtained insulating film is 90 ° C., the film thickness reduction rate is low, the film thickness uniformity is excellent, and the relative dielectric constant is also low. It was confirmed. Due to the low film thickness reduction rate, it becomes difficult to generate minute irregularities and bubbles on the surface due to a sudden change in the film thickness. In particular, it was confirmed from the comparative example that the insulating film is excellent in gap fill property.

  As shown in the result of the comparative example, when the gelation temperature is less than 90 ° C., the polymer in the film-forming composition gels before filling the gap of the base material when the coating film is dried. A gap-filling film-forming composition could not be obtained.

  On the other hand, as shown in the results of the examples, when the gelation temperature is 90 ° C. or higher, it is possible to maintain a low viscosity without gelation when the coating film is dried. A composition for use could be obtained.

Claims (5)

Component (A): a compound represented by the following general formula (1) and at least one compound selected from the compounds represented by the following general formulas (2) to (4), a metal chelate compound and an acid Hydrolysis condensate obtained by hydrolysis and condensation in the presence of water with at least one of the catalyst,
Component (B): a compound represented by the following general formula (1) and at least one compound among the compounds represented by the following general formulas (2) to (4), an alkali catalyst and water Hydrolysis condensate obtained by hydrolysis and condensation in the presence of
Contains an organic solvent, and water,
In the component (A), the ratio of the compound represented by the general formula (1) to the total amount of the compounds represented by the general formulas (1) to (4) is 60 mol% or more,
In the component (B), the ratio of the compound represented by the general formula (1) to the total amount of the compounds represented by the general formulas (1) to (4) is 40 mol% or more, and A composition for film formation in which the weight ratio of component A) is greater than the weight ratio of component (B).
R ¹ Si (OR ² ) ₃ (1)
(Wherein R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and R ² represents a monovalent organic group.)
R ³ ₂ Si (OR ⁴ ) ₂ (2)
(In the formula, R ³ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and R ⁴ represents a monovalent organic group.)
Si (OR ⁵ ) ₄ (3)
(In the formula, R ⁵ represents a monovalent organic group.)
_{^{R 6 a (R 7 O)}} 3-a Si- (R 10) c -Si (OR 8) 3-b R 9 b ····· (4)
[Wherein R ^{6 to} R ⁹ are the same or different, each is a monovalent organic group, a and b are the same or different and each represents an integer of 0 to 2, and R ¹⁰ represents an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _n- (wherein n is an integer of 1 to 6), and c represents 0 or 1. ] In claim 1,
A film-forming composition having a gelling temperature of 90 ° C or higher. Applying the film-forming composition according to claim 1 or 2 on a substrate;
Dried at a temperature below the gelation temperature for 1-60 minutes,
Dried for 1 to 60 minutes at a temperature higher than the gelation temperature and less than 200 ° C higher than the gelation temperature,
A method for forming an insulating film, in which baking is performed at a temperature of 200 ° C. to 450 ° C. for 1 to 180 minutes above the gelling temperature.   An insulating film formed by the method for forming an insulating film according to claim 3.   A semiconductor device comprising the insulating film according to claim 4.