JP2006093657A - Organic silica system film and forming method thereof, composition for forming insulating film of semiconductor apparatus, and wiring structure and semiconductor apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic silica system film for a semiconductor apparatus, and a forming method thereof. <P>SOLUTION: The forming method comprises the steps of coating an insulating film forming composition to a substrate, heating the coated film, and performing a hardening process by applying heat and ultraviolet rays to the coated film. The insulating film forming composition is a hydrolytic condensate of a compound expressed by the following formulas (1) to (4), which contains an organic silica sol including 11.8-16.7 mol% of carbon atoms and an organic solvent. (1): R<SP>1</SP>Si(OR<SP>2</SP>)<SB>3</SB>, (2): Si(OR<SP>3</SP>)<SB>4</SB>, (3): (R<SP>4</SP>)<SB>2</SB>Si(OR<SP>5</SP>)<SB>2</SB>, (4): R<SP>6</SP><SB>b</SB>(R<SP>7</SP>O)<SB>3-b</SB>Si-(R<SP>10</SP>)<SB>d</SB>-Si(OR<SP>8</SP>)<SB>3-c</SB>R<SP>9</SP><SB>c</SB>, In the formula, R<SP>1</SP>-R<SP>9</SP>indicate an alkyl group or an aryl group respectively; b and c are same or different and indicate the number of 0-2, and R<SP>10</SP>is expressed by an oxygen atom; a phenylene group, or a group of -(CH<SB>2</SB>)<SB>m</SB>- (where, m is an integer of 1-6); and then d indicates 0 or 1. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as a wiring interlayer insulating film of a semiconductor device in a large scale integrated circuit (LSI) or the like. In recent years, for the purpose of forming a semiconductor wiring interlayer insulating film having a more uniform film thickness, a coating type insulating film called an SOG (Spin on Glass) film, which is mainly composed of a hydrolysis product of alkoxysilane. Also comes to be used. Further, with the high integration of LSI, an interlayer insulating film having a low relative dielectric constant mainly composed of an organic silica sol represented by MSQ (methyl silsesquioxane) has been developed (US Pat. No. 6,235,101). Specification, US Pat. No. 6,413,647, US Pat. No. 6,495,264).

  Curing of these organic silica sols is achieved by dehydrating and condensing silanol groups contained in the sol by heating at 350 ° C. to 500 ° C., and is suitable as an interlayer insulating film for semiconductor devices. An insulating film having durability can be formed. However, this organic silica sol reaction is a solid phase reaction, and dehydration condensation does not proceed easily due to the diffusion law, and there is a difficulty that heating for a long time, at least about 30 minutes, usually 1 hour or more is required. there were. In order to perform this long-time heat treatment, a batch heat treatment furnace capable of processing a plurality of wafers, usually 50 to 150 wafers at a time, is used for the purpose of processing a spin-on low dielectric constant interlayer insulating film. . However, the semiconductor devices that mainly require low dielectric constant interlayer insulation films are in the field of the logic devices, and the wiring manufacturing process of this logic device is a single wafer process that processes wafers one by one in a short time. Transitioning. This is because ASICs and custom ICs, which are the mainstream of logic devices, originate from the production of small quantities of other varieties, and the single wafer process has become the mainstream of the manufacturing process for the purpose of improving the flexibility of the manufacturing process. is there.

  A method using an electron beam has been proposed as a method for curing a low dielectric constant interlayer insulating film composition mainly composed of an organic silica sol in a short time and improving the strength (US Pat. No. 6,204,201, Europe). Patent No. 1122770). These methods irradiate electron beams simultaneously with heating to actively decompose and activate not only the silanol condensation reaction but also the organic groups in the organic silica-based film to form new bridges such as Si-CHx-Si. It has the feature that can be introduced. When an electron beam is used, a film with low moisture absorption and excellent mechanical strength can be obtained by electron beam irradiation treatment usually within 5 minutes, and wafer single wafer processing becomes possible. On the other hand, there is a concern that charge accumulation due to electron beam irradiation may damage the transistor structure in the LSI, and there are pros and cons to curing a low dielectric constant interlayer insulating film composition using an electron beam (E. Mickler et al. Proceedings of the International Interconnect Technology Conference, p190, 2004., Miyajima, et al. Proceedings of the International Interconnect Technology Conference, p222, 2004.).

  As a method for curing the low dielectric constant interlayer insulating film composition containing organic silica sol as a main component using an electron beam other than an electron beam, a method using ultraviolet rays can be considered. Here, the viewpoint is temporarily turned to technologies other than the interlayer insulating film for LSI. The technology to mix silica sol and alkoxysilane with photoacid generators and photobase generators that generate acids and bases by UV irradiation, and to promote the condensation reaction of silanol and alkoxide to gel silica sol is photosol-gel technology. It is known and applied to the formation of optical waveguides (JP 2000-109695 A). A silica film cured using such a photoacid generator or photobase generator generally has a large amount of residual silanol and high hygroscopicity, resulting in a film having a high dielectric constant. Moisture absorption by residual silanol can be reduced by heating at a temperature of about 250 ° C. to 500 ° C. after gelation by ultraviolet irradiation for a certain period of time (usually 30 minutes or more). There is no difference from curing of the silica film by heating. Furthermore, the composition containing these photoacid generator and photobase generator is a photoacid generator, a photobase generator itself, and further, the acid or basic substance generated from these becomes a charge carrier and impairs insulation, Further, there is a problem that the quality as an insulating film of an LSI semiconductor device requiring high insulation reliability cannot be satisfied, for example, the wiring metal is deteriorated.

  Siloxane compounds are highly studied as the main skeleton of F2 photoresist using ultraviolet rays having a wavelength of 157 nm because they are excellent in transparency to ultraviolet rays (JP 2002-288268 A). Although this technology uses siloxane as a backbone, it basically applies the principle of a chemically sensitized photoresist using a KrF or ArF light source. The photoacid generator generates an acidic substance when irradiated with ultraviolet light, and the chemical bond cleaved by this acid generates a functional group that is easily dissolved in a basic developer such as carboxylic acid. Not what you want.

  The surface of the organic silica film cured by heat, electron beam or the like is rich in hydrophobicity, and ultraviolet irradiation may be performed for the purpose of improving the surface hydrophobicity (US Pat. No. 6,383,913, special feature). JP-A 63-248710, JP-A 63-289939, JP-B 8-29932, JP-A 2001-110802, etc.). These technologies oxidize the extreme surface of the organic silica film by ozone generated by irradiating ultraviolet rays in the air, and modify the hydrophobic surface to a hydrophilic surface rich in reactivity such as silanol. Features. This modification is mainly performed for the purpose of improving the adhesion with the film formed on the upper layer.

  As described above, a technique in which a polysiloxane resin solution or an organic silica sol solution is applied to a substrate and irradiated with ultraviolet rays after film formation has been considerably studied. However, so far, no technology has been reported that actively uses ultraviolet rays to cure the organic silica sol for the purpose of forming an interlayer insulating film of an LSI semiconductor device. A few prior examples are found in JP-A-3-30427, JP-A-1-194980, WO03 / 025994, and US Patent Application Publication No. 2004/0058090.

  JP-A-3-30427 discloses that a silicon dioxide film is obtained at a low temperature by applying a solution obtained by dissolving tetraalkoxysilane (for example, tetraethoxysilane: TEOS) in collodion on a semiconductor substrate and then irradiating with ultraviolet rays in a nitrogen atmosphere. Technology. It is characterized in that highly volatile TEOS is fixed by collodion and decomposition of collodion and dehydration condensation of TEOS are promoted by ultraviolet irradiation. JP-A-1-194980 discloses that an organic siloxane resin is applied to a substrate, irradiated with ultraviolet light having a main wavelength of 254 nm under heating at a temperature of 200 ° C. or less, and ozone generated by the ultraviolet light is used to form an organic siloxane film. This is a technique for obtaining a dense silicon dioxide film by oxidizing the surface and subsequently heating at 400 ° C. or higher, particularly around 900 ° C.

On the other hand, International Publication No. 03/025994 pamphlet and US Patent Application Publication No. 2004/0058090 disclose a method for curing HSQ (hydrogenated silsesquioxane) or MSQ with ultraviolet rays. This technology mainly oxidizes HSQ or HSQ / MSQ cocondensate in the presence of oxygen by irradiating ultraviolet rays into the system so that active oxygen (for example, ozone) generated in the system oxidizes Si-H in HSQ. To form a silica film rich in SiO ₂ bonds. In addition, it is stated in these previous examples that the same method is effective for MSQ, but even in that case, it is stated that the presence of oxygen is more effective for curing. It can be presumed that SiO ₂ bonding by active oxygen is the main mechanism of the crosslinking reaction. Thus, it is difficult to form SiO ₂ bonds in a short time by other curing methods, and one feature of the technology is that this ultraviolet ray is used, but the silica film formed by this method is The increase in the SiO ₂ bond can provide a film having a high elastic modulus and hardness, but there is also a problem that the hydrophilicity of the film increases, leading to an increase in moisture absorption and a dielectric constant. A film having a high hygroscopic property is generally easily damaged by RIE (reactive ion etching) during processing of an interlayer insulating film for a semiconductor device, and has poor chemical resistance to a wet cleaning solution. In particular, this tendency is remarkable in a low dielectric constant interlayer insulating film having a dielectric constant k of 2.5 or less, in which the insulating film itself has a porous structure. Therefore,
(A) an organic silica sol composition that does not contain an ionic substance such as a photoacid generator, a photobase generator, and a sensitizer, a source of charge carriers or a corrosive compound, and can be cured in a short time;
(B) A method of curing an organic silica film that can be processed by a single wafer process without damaging the transistor structure;
(C) an organic silica-based film that is not hygroscopic and rich in hydrophobicity,
(D) an organosilica film having mechanical strength that can withstand the formation of a copper damascene structure;
Is desired as a low dielectric constant interlayer insulating film of an LSI semiconductor device and a method for forming the same.

In addition, organic silica sol compositions for low dielectric constant insulating films typically used in semiconductor devices are thermoset in consideration of yields in mechanical stress producing processes such as CMP (Chemical Mechanical Polishing) and packaging. The composition of the organic silica sol is controlled so that the organic silica film obtained later exhibits a high elastic modulus (for example, US Pat. No. 6,495,264). Specifically, it is designed to increase the absolute crosslink density in the silica film by increasing the tetrafunctional silane compound (hereinafter also referred to as “Q component”) in the organic silica sol to 40 mol% or more. It has become. By increasing the Q component, the crosslink density increases, and a film having a high elastic modulus and hardness can be obtained. However, it is difficult to completely react the cross-linked site (silanol) of the Q component. If the Q component is increased too much, there will be a large amount of residual silanol after thermosetting, resulting in a hydrophilic and highly hygroscopic film. To compensate for this weakness, co-condensation with an alkoxysilane having a hydrophobic group such as methyltrialkoxysilane is usually performed using a basic catalyst (eg, ammonia or tetraalkylhydroxyammonium) to produce a sol with a high degree of condensation. By doing so, the absolute amount of silanol in the sol is reduced (US Pat. No. 6,413,647), and a hydrophobization treatment is additionally performed on the highly condensed sol (Japanese Patent Laid-Open No. 2004-59737). Publication, Unexamined-Japanese-Patent No. 2004-149714). However, such an organic silica sol containing a large amount of Q component still has a high crosslink density and a low molecular chain mobility, and therefore has a very high diffusion barrier during a solid phase reaction. Even when such an organic silica sol containing a large amount of the Q component is cured by, for example, ultraviolet irradiation at a temperature of 400 ° C. within 5 minutes, there is no sign that the condensation reaction is accelerated. In order to react such an organic silica sol, a curing time of 30 minutes or more is still necessary.
US Pat. No. 6,235,101 US Pat. No. 6,413,647 US Pat. No. 6,495,264 US Pat. No. 6,204,201 European Patent No. 1122770 JP 2000-109695 A JP 2002-288268 A US Pat. No. 6,383,913 JP-A 63-248710 JP-A 63-289939 Japanese Patent Publication No. 8-29932 JP 2001-110802 A JP-A-3-30427 JP-A-1-194980 International Publication No. 03/025944 Pamphlet US Patent Application Publication No. 2004/0058090 JP 2004-59737 A JP 2004-149714 A

  An object of the present invention is to use an insulating film forming composition for a semiconductor device that is cured using heat and ultraviolet rays, and to provide an organic silica film having a low relative dielectric constant, excellent mechanical strength, and high hydrophobicity. An object of the present invention is to provide a method for forming an organic silica film formed in a short heating time, and an organic silica film.

  Another object of the present invention can be suitably used in the manufacture of LSI semiconductor devices for which higher integration and multilayering are desired, and the heating time can be shortened by conventional ultraviolet irradiation. An object of the present invention is to provide a composition for forming an insulating film of a semiconductor device, which can form an insulating film having a low relative dielectric constant and excellent mechanical strength.

  Still another object of the present invention is to provide a wiring structure using the organosilica film of the present invention and a semiconductor device including the wiring structure.

The method for forming an organosilica film according to the present invention includes:
Applying a composition for forming an insulating film of a semiconductor device that is cured using heat and ultraviolet rays to a substrate and forming a coating film; and
Heating the coating film;
A step of curing the coating film by irradiating heat and ultraviolet rays,
The insulating film forming composition is:
Selected from the compound represented by the following general formula (1), the compound represented by the following general formula (2), the compound represented by the following general formula (3), and the compound represented by the following general formula (4) A hydrolyzed condensate obtained by hydrolyzing and condensing the silane compound,
An organic silica sol containing 11.8 to 16.7 mol% of carbon atoms and an organic solvent are included.

R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group or an aryl group.)
Si (OR ³ ) ₄ (2)
(In the formula, R ³ represents an alkyl group or an aryl group.)
(R ⁴ ) ₂ Si (OR ⁵ ) ₂ (3)
(In the formula, R ⁴ represents an alkyl group or an aryl group, and R ⁵ represents an alkyl group or an aryl group.)
_{^{R 6 b (R 7 O)}} 3-b Si- (R 10) d -Si (OR 8) 3-c R 9 c ··· (4)
[Wherein, R ^{6 to} R ⁹ are the same or different and each represents an alkyl group or an aryl group; b and c are the same or different and each represents a number of 0 to 2; R ¹⁰ represents an oxygen atom, a phenylene group or — ( A group represented by CH ₂ ) _m — (wherein m is an integer of 1 to 6), d represents 0 or 1; ]

  In the method for forming an organic silica film according to the present invention, the ultraviolet light may have a wavelength of 250 nm or less.

  In the method for forming an organic silica film according to the present invention, heating and ultraviolet irradiation can be performed simultaneously.

  In the method for forming an organic silica film according to the present invention, the heating may be performed at 300 to 450 ° C.

  In the method for forming an organic silica film according to the present invention, the irradiation with ultraviolet rays can be performed in the absence of oxygen.

  The organic silica film according to 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.

  The wiring structure according to the present invention uses the organic silica film according to the present invention as an interlayer insulating film. The semiconductor device according to the present invention includes the wiring structure according to the present invention.

The composition for forming an insulating film of a semiconductor device according to the present invention is used in the method for forming an organic silica-based film according to the present invention,
Selected from the compound represented by the general formula (1), the compound represented by the general formula (2), the compound represented by the general formula (3), and the compound represented by the general formula (4) A hydrolyzed condensate obtained by hydrolyzing and condensing the silane compound,
It contains an organic silica sol containing 11.8 to 16.7 mol% of carbon atoms and an organic solvent, and is cured using heat and ultraviolet rays.

  In the composition for forming an insulating film of a semiconductor device according to the present invention, 60 mol% or more of the silane compound may be a compound represented by the general formula (1).

  In the composition for forming an insulating film of a semiconductor device according to the present invention, the compound represented by the general formula (2) in the silane compound may be 40 mol% or less.

  In the composition for forming an insulating film of a semiconductor device according to the present invention, the silane compound is 65 to 95 mol% of the compound represented by the general formula (1) and the compound 5 represented by the general formula (2). 35 mol% can be contained.

  The composition for forming an insulating film of a semiconductor device according to the present invention can contain no reaction accelerator active against ultraviolet rays. Such a reaction accelerator can be any one of a reaction initiator, an acid generator, a base generator and a sensitizer having an ultraviolet absorbing function, or a combination of two or more.

  In the composition for forming an insulating film of a semiconductor device according to the present invention, the contents of sodium, potassium, and iron can each be 100 ppb or less.

  The composition for forming an insulating film of a semiconductor device of the present invention (hereinafter simply referred to as “film forming composition”) is obtained by applying an organic silica sol composition having a specific composition range to a substrate and drying it, followed by heating. Further, by curing (curing) by irradiation with ultraviolet rays, an insulating film having a low relative dielectric constant and excellent mechanical strength can be formed.

  Hereinafter, the characteristics of the film forming composition and the method for forming the organic silica film of the present invention will be described.

  The present invention will be specifically described below.

1. Film-Forming Composition A film-forming composition according to the present invention comprises a compound represented by the following general formula (1) (hereinafter also referred to as “T component”), a compound represented by the following general formula (2) ( Q component), a compound represented by the following general formula (3) (hereinafter also referred to as “D component”), and a silane compound selected from the compounds represented by the following general formula (4) were hydrolyzed and condensed. A hydrolysis-condensation product, which contains an organic silica sol containing 11.8 to 16.7 mol% of carbon atoms and an organic solvent, and is cured using heat and ultraviolet rays.

R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group or an aryl group.)
Si (OR ³ ) ₄ (2)
(In the formula, R ³ represents an alkyl group or an aryl group.)
(R ⁴ ) ₂ Si (OR ⁵ ) ₂ (3)
(In the formula, R ⁴ represents an alkyl group or an aryl group, and R ⁵ represents an alkyl group or an aryl group.)
_{^{R 6 b (R 7 O)}} 3-b Si- (R 10) d -Si (OR 8) 3-c R 9 c ··· (4)
[Wherein, R ^{6 to} R ⁹ are the same or different and each represents an alkyl group or an aryl group; b and c are the same or different and each represents a number of 0 to 2; R ¹⁰ represents an oxygen atom, a phenylene group or — ( A group represented by CH ₂ ) _m — (wherein m is an integer of 1 to 6), d represents 0 or 1; ]

  Hereinafter, a silane compound, a composition, an organic solvent, an additive, etc. are demonstrated concretely.

1.1. Silane compound A compound represented by the general formula (1) (hereinafter referred to as “compound 1”), a compound represented by the general formula (2) (hereinafter referred to as “compound 2”), and the general formula (3). As the compound represented by (hereinafter referred to as “compound 3”) and the compound represented by the general formula (4) (hereinafter referred to as “compound 4”), the following can be used.

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 and an aryl group. Among them, in the general formula (1), the monovalent organic group represented by R ² is preferably a particular alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and 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 Examples thereof include silane, phenyl tri-tert-butoxy silane, and phenyl triphenoxy silane. 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, phenyltrimethoxysilane, phenyltriethoxy. Such as silane.

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

  Specific examples of Compound 2 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, and particularly preferred compounds include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination of two or more.

1.1.3. Compound 3
In the general formula (3), examples of R ⁴ and R ⁵ include the same groups as those exemplified as R ¹ and R ^{2 in} the general formula (1).

  Specific examples of the compound 3 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- -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- Butyl di-n-butoxysilane, di-t tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxy Examples include silane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, and diphenyldiphenoxysilane.

  Particularly preferred compounds as Compound 3 are dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. These may be used alone or in combination of two or more.

1.1.4. Compound 4
In the general formula (4), examples of R ^{6 to} R ⁹ include the same groups as those exemplified as R ¹ and R ^{2 in} the general formula (1).

  In the general formula (4), examples of the compound where d = 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, , 1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2- Phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy 1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2 -Tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1 , 2,2-Tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2- Trime Rudisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2,2 -Triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1 , 2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy -1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1, 2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane 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 (4), compounds in which R ¹⁰ is d = 1 include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, and 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-propoxysilyl) ethane, 1,2-bis (Tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-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) ethane, 1- (diethoxymethyl) Rusilyl) -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-butoxymethylsilyl) -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) methane, bis (di-n-butoxy) Methylsilyl) 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 (trimethoxysilyl) benzene, 1,2-bis (Triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-iso-propoxy) Sisilyl) 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-butoxysilyl) benzene, 1, 4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) , 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 can be mentioned.

  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.

  The above-mentioned compound 4 may be used alone or in combination of two or more.

1.1.5. Composition of Silane Compound In the film-forming composition of the present invention, the proportion of carbon atoms in the organic silica sol is 11.8 to 16.7 mol%. When the carbon content is less than 11.8 mol%, the diffusion barrier in the solid phase reaction is high, and the reaction is difficult to be accelerated even when irradiated with ultraviolet rays. If the carbon content is more than 16.7 mol%, the mobility of the molecule is too high, the elastic modulus is low, and in some cases, the film shows a glass transition point, which is not preferable.

  In the film-forming composition of the present invention, the compound 1 represented by the general formula (1) is contained in a proportion of preferably 60 mol% or more, more preferably 65 to 95 mol% of the silane compound. Moreover, the compound 2 represented by the said General formula (2) in a silane compound becomes like this. Preferably it is 40 mol% or less, More preferably, it is contained in the ratio of 5-35 mol% of compounds. The film-forming composition of the present invention contains at least Compound 1 and Compound 2 as described above.

  The film-forming composition of the present invention can contain the compound 3 represented by the general formula (3) and the compound 4 represented by the general formula (4) as necessary. The content of these compounds 3 and 4 is desirably 35 mol% or less with respect to the entire silane compound. If the content of compound 3 and compound 4 exceeds 35 mol%, it is extremely difficult to control the molecular weight of the organic silica sol in the stage of obtaining a film-forming composition, and in some cases, gelation may occur, Absent.

  The molecular weight of the organic silica sol in the film-forming composition of the present invention can be 500 to 500,000. If the molecular weight is larger than this range, particles are likely to be formed, and pores in the organic silica film become too large, which is not preferable. On the other hand, if the molecular weight is lower than this range, problems are likely to occur in coating properties and storage stability.

  In addition, the film forming composition of the present invention may not contain a reaction accelerator for promoting the hydrolysis reaction and / or condensation reaction of the silane compound. Here, the “reaction accelerator” means any one of a reaction initiator, a catalyst (acid generator, base generator) and a sensitizer having an ultraviolet absorption function, or a combination of two or more. As described above, 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 as an insulating film of an LSI semiconductor device that requires high insulation reliability, such as deterioration of wiring metal, may not be satisfied. Since the film-forming composition of the present invention can be cured by heating and ultraviolet irradiation without including such a reaction accelerator, these problems can be avoided.

  In the film forming composition of the present invention, the contents of sodium, potassium, and iron are each preferably 100 ppb or less. Since these elements are sources of contamination of semiconductor devices, it is desirable to eliminate them as much as possible.

1.1.6. Method for Producing Film-Forming Composition The film-forming composition of the present invention contains a hydrolysis-condensation product obtained by hydrolyzing and condensing the silane compounds 1 to 4 described above. Hydrolytic condensation of the silane compounds 1 to 4 can be performed in the presence of a metal chelate compound, an acidic compound, or a basic compound. Hereinafter, each of the metal chelate compound, the acidic compound, and the basic compound will be described.

1.1.6a. Metal chelate compound The metal chelate compound which can be used at the time of the hydrolytic condensation of the silane compounds 1 to 4 is represented by the following general formula (5).

R ¹¹ _β M (OR ¹² ) _α-β (5)
[Wherein R ¹¹ is a chelating agent, M is a metal atom, R ¹² is an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, α is the valence of metal M, β is 1 to represents an integer of α. ]
Here, the metal M is preferably at least one metal selected from Group IIIB metals (aluminum, gallium, indium, thallium) and Group IVA metals (titanium, zirconium, hafnium). Titanium, aluminum, zirconium Is more preferable.

  Specific examples of metal chelate compounds include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium J-tert-but Si-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, Re-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 tri Sus (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) Titanium chelate compounds such as tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonate) Zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, triisopropoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-tert-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nate) zirconium, diisopropoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-tert-butoxy Bis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, monoisopropoxytris Acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonato) 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 acetoacetate) zirconium Konium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) 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, mono-sec-but Si-tris (ethylacetoacetate) zirconium, mono-tert-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetate) Zirconium chelate compounds such as nattobis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium; triethoxy mono (acetylacetonato) aluminum, tri-n-propoxy mono (acetylacetate) Nato) aluminum, triisopropoxy mono (acetylacetonato) aluminum, tri-n-butoxy mono (acetylacetonato) aluminium , Tri-sec-butoxy mono (acetylacetonato) aluminum, tri-tert-butoxy mono (acetylacetonato) aluminum, diethoxybis (acetylacetonato) aluminum, di-n-propoxybis (acetylacetonate) ) Aluminum, diisopropoxy bis (acetylacetonato) aluminum, di-n-butoxy bis (acetylacetonato) aluminum, di-sec-butoxy bis (acetylacetonato) aluminum, di-tert-butoxy bis (Acetylacetonato) aluminum, monoethoxy tris (acetylacetonato) aluminum, mono-n-propoxy tris (acetylacetonato) aluminum, monoisopropoxy tris (acetylacetate) Tonato) aluminum, mono-n-butoxy tris (acetylacetonato) aluminum, mono-sec-butoxy tris (acetylacetonato) aluminum, mono-tert-butoxy tris (acetylacetonato) aluminum, tetrakis (acetylacetate) Natto aluminum, triethoxy mono (ethyl acetoacetate) aluminum, tri-n-propoxy mono (ethyl acetoacetate) aluminum, triisopropoxy mono (ethyl acetoacetate) aluminum, tri-n-butoxy mono (ethyl aceto) Acetate) aluminum, tri-sec-butoxy mono (ethyl acetoacetate) aluminum, tri-tert-butoxy mono (ethyl acetoacetate) aluminum, di Toxi bis (ethyl acetoacetate) aluminum, di-n-propoxy bis (ethyl acetoacetate) aluminum, diisopropoxy bis (ethyl acetoacetate) aluminum, di-n-butoxy bis (ethyl acetoacetate) aluminum, Di-sec-butoxy bis (ethyl acetoacetate) aluminum, di-tert-butoxy bis (ethyl acetoacetate) aluminum, monoethoxy tris (ethyl acetoacetate) aluminum, mono-n-propoxy tris (ethyl acetoacetate) ) Aluminum, monoisopropoxy tris (ethyl acetoacetate) aluminum, mono-n-butoxy tris (ethyl acetoacetate) aluminum, mono-sec-butoxy tris Ethyl acetoacetate) aluminum, mono-tert-butoxy-tris (ethylacetoacetate) aluminum, tetrakis (ethylacetoacetate) aluminum, mono (acetylacetonato) tris (ethylacetoacetate) aluminum, bis (acetylacetonato) bis ( 1 type or 2 types or more of aluminum chelate compounds, such as ethyl acetoacetate) aluminum and tris (acetylacetonato) mono (ethyl acetoacetate) aluminum, etc. are 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 COOC 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 COOC 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 (CH 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 COOC ₂ H ₅ ) One or more types such as _t are preferred as the metal chelate compound used.

  The amount of the metal chelate compound used is 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts per 100 parts by weight (in terms of complete hydrolysis condensate) of the silane compounds 1 to 4 during hydrolysis condensation. Parts by weight. When the use ratio of the metal chelate compound is less than 0.0001 part by weight, the coatability of the coating film may be inferior, and when it exceeds 10 parts by weight, the polymer growth cannot be controlled and gelation may occur. The metal chelate compound may be added in advance to the organic solvent together with the silane compounds 1 to 4 at the time of hydrolysis condensation, or may be dissolved or dispersed in water at the time of addition of water.

  When hydrolyzing and condensing the silane compounds 1 to 4 in the presence of the metal chelate compound, it is preferable to use 0.5 to 20 mol of water per 1 mol of the total amount of the silane compounds 1 to 4, preferably 1 to 10 mol of water. It is particularly preferred to add. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

1.1.6b. Acidic compound Examples of the acidic compound that can be used at the time of hydrolytic condensation of the silane compounds 1 to 4 include organic acids and inorganic acids. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid Acid, butyric acid, meritic 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, benzenesulfone Acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, Citraconic acid, malic acid, malonic acid, hydrolyzed glutaric acid, hydrolyzed maleic anhydride Objects, and the like hydrolyzate of phthalic anhydride. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Of these, organic acids are preferred in that there is little risk of polymer precipitation or gelation during hydrolysis and condensation reactions, and among these, compounds having a carboxyl group are more preferred. Among these, acetic acid, oxalic acid, maleic acid, Particularly preferred are hydrolysates of formic acid, malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid and maleic anhydride. These may be used alone or in combination of two or more.

  The amount of the acidic compound used is 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight (in terms of complete hydrolysis condensate) of the silane compounds 1 to 4 during hydrolysis condensation. Part. If the use ratio of the acidic compound is less than 0.0001 part by weight, the coating property of the coating film may be inferior, and if it exceeds 10 parts by weight, the hydrolysis condensation reaction may proceed rapidly to cause gelation. The acidic compound may be added in advance to the organic solvent together with the silane compounds 1 to 4 at the time of hydrolysis condensation, or may be dissolved or dispersed in water at the time of addition of water.

  When hydrolyzing and condensing silane compounds 1 to 4 in the presence of an acidic compound, it is preferable to use 0.5 to 20 mol of water per 1 mol of the total amount of silane compounds 1 to 4, and 1 to 10 mol of water is added. It is particularly preferred. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

1.1.6c. Basic compounds Examples of basic compounds that can be used during the hydrolytic condensation of silane compounds 1 to 4 include sodium hydroxide, potassium hydroxide, lithium hydroxide, cerium hydroxide, barium hydroxide, calcium hydroxide, pyridine, Pyrrole, piperazine, pyrrolidine, piperidine, picoline, ammonia, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine , Dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, urea, Examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline. Among these, ammonia, organic amines, and ammonium hydroxides can be given as preferred examples, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide are particularly preferable. These basic compounds may be used alone or in combination of two or more.

The use amount of the basic compound is represented by R ⁿ O— (n = 2, 3, 5, 7, 8) in the general formulas (1) to (4), which is the total amount of alkoxyl groups of the silane compounds 1 to 4. The amount is usually 0.00001 to 1 mol, preferably 0.00005 to 0.5 mol, per 1 mol of the total group. If the usage-amount of a basic compound is in the said range, there is little possibility of polymer precipitation or gelation during reaction.

  When hydrolyzing and condensing the silane compounds 1 to 4 in the presence of a basic compound, it is preferable to use 0.5 to 150 mol of water per 1 mol of the total amount of the silane compounds 1 to 4, It is particularly preferred to add water. If the amount of water to be added is less than 0.5 mol, the hydrolysis and condensation reaction takes a long time, which is not preferable from the viewpoint of productivity. If it exceeds 150 moles, polymer precipitation or gelation may occur during hydrolysis and condensation reactions.

  In this case, it is preferable to use alcohol having a boiling point of 100 ° C. or lower together with water. Here, examples of the alcohol having a boiling point of 100 ° C. or lower include methanol, ethanol, n-propanol, and isopropanol. The amount of alcohol having a boiling point of 100 ° C. or less is usually 3 to 100 mol, preferably 5 to 80 mol, per 1 mol of the total amount of silane compounds 1 to 4.

  Alcohol having a boiling point of 100 ° C. or lower may be generated during hydrolysis and / or condensation of the silane compounds 1 to 4, and distilled so that the content thereof is 20% by weight or less, preferably 5% by weight or less. It is preferable to remove by, for example. Further, as additives, a dehydrating agent such as methyl orthoformate, a further metal complex, or a leveling agent may be contained.

  Moreover, after obtaining a hydrolysis-condensation product from the silane compounds 1-4 in presence of a basic compound, it is preferable to adjust the pH of the film forming composition of this invention to 7 or less. As a method for adjusting the pH, 1) a method of adding a pH adjusting agent, 2) a method of distilling a basic compound from the composition under normal pressure or reduced pressure, and 3) bubbling a gas such as nitrogen or argon. To remove the basic compound from the composition, 4) a method to remove the basic compound from the composition with an ion exchange resin, and 5) to remove the basic compound from the system by extraction or washing. Method, etc. Each of these methods may be used in combination.

  Here, examples of the pH adjusting agent include inorganic acids and organic acids. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid, and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, and sebacic acid. Gallic acid, butyric acid, meritic 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, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid , Malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, phthalic anhydride Water decomposition products, and the like. These compounds may be used alone or in combination of two or more.

  The pH of the composition by the pH adjuster is adjusted to 7 or less, preferably 1 to 6. By adjusting the pH within the above range with the pH adjusting agent, the effect of improving the storage stability of the film-forming composition can be obtained. The amount of the pH adjusting agent used is an amount that makes the pH of the film-forming composition within the above range, and the amount used is appropriately selected.

1.1.6d. Organic Solvent In the present invention, silane compounds 1 to 4 can be hydrolytically condensed in an organic solvent. Here, the organic solvent is preferably a solvent represented by the following general formula (6) among the organic solvents described later.

R ¹³ O (CHCH ₃ CH ₂ O) _γ 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 γ represents an integer of 1 to 2. ]
In the said General formula (6), as a C1-C4 alkyl group, the thing similar to what was shown as an alkyl group in previous General formula (1) can be mentioned.

  Specific examples of the organic solvent represented by the general formula (6) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether. , Propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di Propylene glycol dipropyl ether, di Lopylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono Propyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, etc., especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can use 1 type (s) or 2 or more types simultaneously. In addition to the solvent represented by the general formula (6), other solvents such as an ester solvent and an amide solvent may be included to some extent.

  The total solid concentration of the film-forming composition of the present invention is preferably 0.1 to 10% by weight, and is appropriately adjusted according to the purpose of use. When the total solid concentration of the film-forming composition of the present invention is 0.1 to 10% 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 an organic solvent, if necessary.

1.2. Organic Solvents Organic solvents that can be used in the present invention include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents, and halogen-containing solvents. The at least 1 sort (s) chosen from the group is mentioned.

Examples of alcohol solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furf 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 And the like; monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. 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. Ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, Mention may be made of ketone solvents such as fenchon. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents include N, N-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- Examples thereof include nitrogen-containing solvents such as methylpropionamide and N-methylpyrrolidone. These amide solvents may be used alone or in combination of two or more.

  As ether solvent systems, ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene Glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether , Ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether Le, can be mentioned ether solvents such as anisole. These ether solvents may be used alone or in combination of two or more.

  Examples of ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-acetate. Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate , Ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n acetate -Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy acetate Triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate And ester solvents such as dimethyl phthalate and diethyl phthalate. These ester solvents may be used alone or in combination of two or more.

  Examples of the aliphatic hydrocarbon solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, Examples thereof include aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-propyl benzene, Aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene can be mentioned. These aromatic hydrocarbon solvents may be used alone or in combination of two or more. Examples of the halogen-containing solvent include halogen-containing solvents such as dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, and dichlorobenzene.

  In the present invention, it is desirable to use an organic solvent having a boiling point of less than 150 ° C., and as the solvent species, alcohol solvents, ketone solvents, and ester solvents are particularly desirable. It is desirable to use them simultaneously.

1.3. Other Additives The insulating film forming composition of the present invention may further contain components such as an organic polymer, a surfactant, and a silane coupling agent. These additives may be added to a solvent in which each component is dissolved or dispersed before the film-forming composition is produced.

1.3.1. 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. The addition of such an organic polymer is described 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.

1.3.2. 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, and fluorine surfactants and silicone surfactants can be preferably exemplified.

  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, F183 [above, manufactured by Dainippon Ink & Chemicals, Inc.], Ftop EF301, 303, 352 [produced 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.

1.3.3. 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.

2. Method for Forming Film The method for forming the organic silica film of the present invention comprises a step of applying the film-forming composition to a substrate to form a coating film, a step of heating the coating film, And a step of performing a curing process by irradiating with ultraviolet rays. In the curing treatment of the present invention, it is desirable to perform heating and ultraviolet irradiation simultaneously. Thus, by simultaneously performing heating and ultraviolet irradiation, the condensation reaction of the organic silica sol can be sufficiently achieved at a relatively low temperature and in a short time, and the organic silica film targeted by the present invention can be obtained. When heating and ultraviolet irradiation are performed simultaneously, the curing treatment can be preferably performed for 30 seconds to 10 minutes, more preferably 30 seconds to 7 minutes.

  As described above, according to the method for forming an organic silica-based film of the present invention, the curing process can be performed at a low temperature and in a short time, so that the semiconductor device is not damaged, and the single wafer processing can be performed in the LSI process. .

  Hereinafter, the film curing method will be described in detail.

  The irradiation with ultraviolet rays can be performed with ultraviolet rays including a wavelength of preferably 250 nm or less, more preferably 150 to 250 m. By using an ultraviolet ray having a wavelength in this range, the condensation reaction of molecules in the organic silica sol can be performed at a low temperature in a short time without using a reaction accelerator active to the ultraviolet ray. When the wavelength of the ultraviolet light is longer than 250 nm, a sufficient condensation reaction promoting effect is not observed in the organic silica sol. On the other hand, when the wavelength of the ultraviolet light is shorter than 150 nm, the organic silica sol is likely to be decomposed or detached from the silicon atoms.

  In addition, in ultraviolet irradiation, a light source including a plurality of wavelengths of 250 nm or less is used in order to prevent local change in film quality due to standing waves due to reflection from the substrate on which the film-forming composition is applied. desirable.

  In the curing treatment of the coating film of the present invention, heating can be preferably performed at a temperature of 300 to 450 ° C. 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 method of heating at the same time as the ultraviolet irradiation, a hot plate, an infrared lamp annealing or the like can be used.

  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 irradiation with ultraviolet light 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. If the oxygen partial pressure is higher than 0.1 kPa, ozone is generated during ultraviolet irradiation, and the condensate of the organic silica sol is oxidized by the ozone, thereby increasing the hydrophilicity of the obtained organic silica film and the hygroscopicity of the film. And the relative dielectric constant is likely to increase. Therefore, by performing the curing treatment in the absence of oxygen, it is possible to obtain an organic silica-based film that has high hydrophobicity and is unlikely to raise the dielectric constant.

In the present invention, irradiation with ultraviolet rays can also 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 ultraviolet 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, ultraviolet irradiation may be performed in a reduced pressure atmosphere under pressure. 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 select stepwise heating, an inert gas such as nitrogen, and atmospheric conditions such as a reduced pressure state, as necessary.

Examples of the substrate to which the film forming composition is applied include Si-containing layers such as Si, SiO ₂ , SiN, SiC, and SiCN. As a method for applying the film-forming composition to the substrate, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used. After apply | coating the composition for film formation to a base material, a solvent is removed and a coating film is formed. In this case, as a dry film thickness, a coating film having a thickness of 0.05 to 2.5 μm can be formed by one coating and a thickness of 0.1 to 5.0 μm can be formed by two coatings. Thereafter, an organic silica-based film can be formed by subjecting the obtained coating film to the curing treatment described above.

3. Organic Silica Film 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. Moreover, it can be said that the organosilica film of the present invention has a sufficiently high crosslink density from the knowledge of the shrinkage rate and elastic modulus of the film. Specifically, the organic silica film of the present invention has a relative dielectric constant of preferably 1.5 to 3.5, more preferably 1.8 to 3.0, and an elastic modulus of preferably 4. 0.0-15.0 GPa, more preferably 4.0-12.0 GPa, and the film density is preferably 0.7-1.3 g / cm ³ , more preferably 0.8-1.27 g / cm ^3. It is. 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. This tendency is particularly 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 film-forming composition has a specific composition and carbon concentration, it has excellent insulating film properties such as relative dielectric constant and elastic modulus, and can be formed at a low temperature in a short time.
(B) Since the film-forming composition does not need to contain an ionic substance such as an ultraviolet-active acid generator, base generator, and sensitizer, a source of charge carriers or corrosive compounds, Free of pollutants,
(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,
(E) excellent mechanical strength such as elastic modulus, for example, being able to withstand the formation of a copper damascene structure;
It has the features such as.

  In the film-forming composition of the present invention, the Q component is relatively reduced, and the trifunctional silane compound (T component) is increased to make the T component rich, thereby increasing the mobility of the molecular chain and remaining after curing. Silanol can be reduced. Such a film-forming composition is an organic silica film having a lower hygroscopicity when applied and dried, preferably in the presence of non-oxygen, when heated and irradiated with ultraviolet light, as compared with a film that requires long-term thermosetting. Was found to be obtained. Although the detailed mechanism by which such an organic silica-based film is obtained has not been elucidated, the diffusion barrier during the solid-phase reaction is lowered by reducing the Q component and in addition to heating, and at the excitation site by ultraviolet rays. This is thought to be due to the improved probability of reaction.

  That is, according to the film-forming composition of the present invention, it can be said that the degree of condensation is increased by short-time heating and ultraviolet irradiation as compared with conventional compositions that require long-time thermosetting. The improvement in the degree of condensation means reduction of residual silanol, which contains 11.8 to 16.7 mol% of carbon atoms in the organic silica sol, and is compared with the prior art (for example, US Pat. No. 6,413,647, Example 1). In addition to the characteristics of the composition containing a large amount of the carbon component, the hydrophobicity of the cured organic silica film is dramatically improved due to the improved degree of condensation. Furthermore, an improvement in the degree of condensation also means an improvement in crosslink density, and mechanical strength such as elastic modulus is improved. In a system having a low Q component such as the film forming composition of the present invention, when thermosetting is performed, it is more elastic than an organic silica film obtained by thermosetting a composition rich in the Q component. It was not enough in terms of rate. However, by curing the film-forming composition of the present invention by heating and ultraviolet irradiation, the elastic modulus shows a value equal to or surpassing that of the composition having a rich Q component. Thus, according to the film forming composition of the present invention, an organic silica film having sufficient hydrophobicity and high elastic modulus can be obtained.

  Since the organosilica film of the present invention has such characteristics, it is particularly excellent as an interlayer insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM. Etching stopper film It can be suitably used for semiconductor device applications such as a protective film such as a surface coat film of a semiconductor element, an intermediate layer in a manufacturing process of a semiconductor device using a multilayer resist, and an interlayer insulating film of a multilayer wiring board. The organosilica film of the present invention is useful for a semiconductor device including a copper damascene process.

4). 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.

4.1. Examples and Comparative Examples Production of a film-forming composition and formation of a silica-based film were performed as follows.

4.1.1. Production Method of Film Forming Composition Film forming compositions of Examples 1 to 3 and Comparative Example 1 were obtained with the compositions shown in Table 1.

4.1.1a. Example 1
In a quartz flask equipped with a condenser, 69.3 g of tetramethoxysilane as a Q component, 135.3 g of methyltrimethoxysilane as a T component, 74.6 g of dimethyldimethoxysilane as a D component, and 202.8 g of propylene glycol monoethyl ether Then, the mixture was stirred with a three-one motor to stabilize the temperature of the solution at 55 ° C. Next, 217.6 g of ion-exchanged water in which 0.45 g of oxalic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 55 degreeC for 3 hours, propylene glycol monoethyl ether 837.2g was added and the reaction liquid was cooled to room temperature. The reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, whereby a film-forming composition 1 was obtained. The organic silica sol contained in Composition 1 had a carbon content of 15.9 mol%, a sodium content of 0.7 ppb, a potassium content of 0.4 ppb and an iron content of 1.7 ppb. The weight average molecular weight of the condensate was 2,100.

4.1.1b. Example 2
In a quartz flask equipped with a condenser, 41.2 g of tetramethoxysilane and 180.1 g of methyltrimethoxysilane were dissolved in 227.3 g of propylene glycol monoethyl ether. Next, 136.5 g of ion-exchanged water was added to the solution and stirred at room temperature for 1 hour. Thereafter, 0.106 g of tetrakis (acetylacetonato) titanium dissolved in 79.9 g of propylene glycol monoethyl ether was added, and the mixture was reacted at a temperature of 50 ° C. for 3 hours, followed by reaction with 887.4 g of propylene glycol monoethyl ether. The liquid was cooled to room temperature. The reaction solution is concentrated under reduced pressure until the solid concentration is 15% or more, 35.0 g of acetylacetone is added, and propylene glycol monoethyl ether is further added to a solid content concentration of 10%. 2 was obtained. The carbon content of the organic silica sol contained in the composition 2 was 14.1 mol%, the sodium content was 0.3 ppb, the potassium content was 0.1 ppb, and the iron content was 2.4 ppb. The weight average molecular weight of the condensate was 1,500.

4.1.1c. Example 3
In a quartz flask equipped with a condenser, 5.2 g of 25% tetrabutylammonium hydroxide aqueous solution, 124.1 g of ultrapure water, and 536.7 g of ethanol were weighed and stirred at 25 ° C. Next, 13.5 g of tetraethoxysilane as the Q component and 20.5 g of methyltriethoxysilane as the T component were continuously added over 1 hour, and the mixture was further stirred at 60 ° C. for 1 hour. After cooling the reaction solution to room temperature, 1321.6 g of propylene glycol monopropyl ether and 34.1 g of a 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 3 was obtained. The carbon content of the organic silica sol contained in Composition 3 was 12.8 mol%, the sodium content was 0.3 ppb, the potassium content was 0.2 ppb, and the iron content was 1.9 ppb. The weight average molecular weight of the condensate was 58,000.

4.1.1d. Comparative Example 1
In a quartz flask equipped with a condenser, 8.3 g of a 20% tetrabutylammonium hydroxide aqueous solution, 118.6 g of ultrapure water, and 516.1 g of isopropyl alcohol were weighed and stirred at 40 ° C. Next, after 34.4 g of tetraethoxysilane and 22.5 g of methyltriethoxysilane were continuously added over 1 hour, the mixture was further stirred at 80 ° C. for 1 hour. After cooling the reaction solution to room temperature, 1269.4 g of propylene glycol monopropyl ether and 55.5 g of a 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 4 was obtained. The carbon content of the organic silica sol contained in Composition 4 was 10.5 mol%, the sodium content was 0.4 ppb, the potassium content was 0.1 ppb, and the iron content was 1.4 ppb. Moreover, the weight average molecular weight of the condensate was 52,000.

4.2. Method for Forming Organic Silica Film Using the compositions and curing conditions shown in Table 2, organic silica films of Examples 4 to 8, Comparative Examples 2 to 7, and Reference Example 1 were obtained.

4.2.1. Examples 4-8, Comparative Examples 2-7, Reference Example 1
The film-forming composition obtained in (1) was applied onto an 8-inch silicon wafer by using a spin coating method, and the coating film was applied on a hot plate at 90 ° C. for 1 minute and in a nitrogen atmosphere at 200 ° C. for 1 minute. Dried. Thereafter, the coating film was cured by irradiating ultraviolet rays while heating the coating film on a hot plate to obtain a sample of an organic silica film. Table 2 shows the types of film-forming compositions and the curing conditions.

  Two types of ultraviolet rays were used: white ultraviolet rays (ultraviolet rays 1) having a wavelength of 250 nm or less and mercury lamps (ultraviolet rays 2) having almost no wavelength of 250 nm or less. In addition, since the ultraviolet ray 1 was white ultraviolet light, the illuminance could not be measured by an effective method.

  In Examples 4 to 8, heating and irradiation with ultraviolet rays 1 were simultaneously performed in the curing treatment. On the other hand, in Comparative Examples 2, 3, 5, and 7, instead of irradiating with ultraviolet rays, only the heat treatment at 420 ° C. for 60 minutes was performed to cure the coating film to obtain a sample. In Comparative Examples 4, 6, and Reference Example 1, heating and ultraviolet irradiation were performed simultaneously, but differed from the examples in the following points. That is, although the ultraviolet ray 1 was used in the reference example 1, the oxygen partial pressure was 1 kPa, the ultraviolet ray 2 was used in the comparative example 4, and the composition 4 of the comparative example 1 was used in the comparative example 6.

4.2.2. Evaluation method 4.1. Various evaluations regarding the organic silica film obtained in (2) were performed as follows.

4.2.2a. Dielectric constant, Δk
A sample for measuring relative permittivity is prepared by forming an aluminum electrode pattern on an organic silica film formed by the above-described method on an 8-inch N-type silicon wafer having a resistivity of 0.1 Ω · cm or less by vapor deposition. Created. The relative permittivity of the organic silica-based film was measured by the CV method using an HP 16451B electrode and an HP4284A precision LCR meter manufactured by Argent Co. at a frequency of 100 kHz.

  Δk is the difference between the relative dielectric constant (k @ RT) measured in an atmosphere of 24 ° C. and 40% RH and the relative dielectric constant (k @ 200 ° C.) measured in an atmosphere of 200 ° C. and dry nitrogen (Δk = k @ RT-k @ 200 ° C.). With this Δk, the increase in dielectric constant due to moisture absorption of the film can be mainly evaluated. Usually, it can be said that it is an organic silica film | membrane with high water absorption as (DELTA) k is 0.15 or more.

4.2.2b. Elastic Modulus of Silica-Based Film A Berkovich indenter was attached to an ultra-small hardness meter (Nanoindentator XP) manufactured by MTS, and the elastic modulus of the insulating film formed by the above method was measured by a continuous stiffness measurement method.

4.2.2c. Contact angle In order to measure the hydrophobicity of the membrane, ultrapure water droplets were dropped on the surface of the insulating film formed by the above method using a contact angle measuring device (DropMaster 500) manufactured by Kyowa Interface Science Co., Ltd. Corner measurements were taken.

4.2.2 d. Condensation rate For the purpose of measuring the condensation rate of siloxane bonds, the area of the ²⁹ Si-NMR spectrum signal was determined for the coated film (organic silica film) after curing using a nuclear magnetic resonance (NMR) method.

Specifically, the organosilica film obtained by the above-described method was scraped off from a silicon wafer, and a solid powder sample was obtained using an agate mortar. This sample was packed in a zirconia rotor having an outer diameter of 7 mm, and ²⁹ Si-NMR was subjected to bipolar decoupled-magic angle spining ( ²⁹ Si-DD-MAS N MR) using a 300 MHz Fourier transform NMR spectrometer (Avance 300 manufactured by Bruker). ) Since the integrated intensity of the signal obtained by this method reflects the abundance ratio of Si, the condensation rate can be measured. Measurement was performed under the following conditions. Measurement was performed at a measurement temperature of 30 ° C., a pulse interval of 10 seconds, a sample tube rotation speed of 3000 to 7000 Hz, an observation center frequency of 59.62 MHz, an observation frequency range of 15.53 kHz, a data point of 16 k, and an integration number of 5,000 to 50,000. . Polydimethylsiloxane was measured in advance as a standard sample for chemical shift, and the decoupler frequency offset value when the polydimethylsiloxane peak was corrected to -34 ppm was read and corrected by inputting the value when measuring each sample.

4.2.2e. Molecular weight (weight average molecular weight; Mw)
The molecular weight (weight average molecular weight; Mw) of the film-forming composition was measured by a size exclusion chromatography (SEC) method under the following conditions.

Sample: Concentration 10 mmol / L LiBr—H ₃ PO ₄ 2-methoxyethanol solution was used as a solvent, and hydrolysis condensate 0.1 g was dissolved in 100 cc 10 mmol / L LiBr—H ₃ PO ₄ 2-methoxyethanol solution. Adjusted.
Standard sample: Polyethylene oxide manufactured by WAKO was used.
Equipment: High-speed GPC equipment (model HLC-8120GPC) manufactured by Tosoh Corporation
Column: Three TSK-GEL SUPER AWM-H (length: 15 cm) manufactured by Tosoh Corporation were used in series.
Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: Detected by UV-8220 RI manufactured by Tosoh Corporation.

4.3. Evaluation results 4.3.1. Specific permittivity, Δk, elastic modulus, contact angle These evaluation results are shown in Table 2.

  From the comparison of Examples 4 to 8 and Comparative Examples 2, 3, and 5, it was found that when the carbon content of the organic silica sol was 12.8 mol%, 14.1 mol%, and 15.9 mol%, ultraviolet rays were heated under heating. It was found that an organic silica-based film having a low Δk, a high elastic modulus, and an excellent mechanical strength can be obtained when used for curing.

  On the other hand, from Comparative Examples 6 and 7, when the carbon content of the organic silica sol is 10.5 mol%, the organic silica film obtained by curing with ultraviolet rays 1 and heating is an organic silica film obtained by curing by heating. It was found that the elastic modulus and Δk characteristics were inferior.

  Further, from Reference Example 1, when a heating and ultraviolet irradiation were performed in an atmosphere having a high oxygen partial pressure, a decrease in contact angle and an increase in Δk, which were considered to be due to oxidation of the film, were observed.

  Furthermore, it was found from Comparative Example 4 that the properties of elasticity and Δk were particularly inferior when ultraviolet rays not including a wavelength of 250 nm or less were used.

4.3.2. Molecular weight (weight average molecular weight; Mw)
From Examples 2 and 3 and Comparative Example 1, the weight average molecular weight of the condensate was about 1,000 to about 60,000. From the results of Examples 4 to 8, it was found that an organic silica-based film having a low Δk, a high elastic modulus, and excellent mechanical strength in a wide molecular weight range was obtained. Further, from comparison between Example 8 and Comparative Example 6, it was found that Δk was low only in Example 8 having a carbon content of 12.8 mol% at substantially the same weight average molecular weight.

4.3.3. ²⁹ Si-DDMAS NMR
The results of ²⁹ Si-DDMAS NMR obtained for Example 7 and Comparative Example 3 are shown in FIG. In FIG. 1, the line indicated by the symbol a indicates the result of Example 7, and the line indicated by the symbol b indicates the result of Comparative Example 3.

  From FIG. 1, it was confirmed that in the spectrum of Comparative Example 3, a peak T2 containing Si—OH was observed, whereas in Example 7, this peak was small. Further, from FIG. 1, it was confirmed that the Si—O peak T3 in the spectrum of Example 7 was larger than the peak T3 of Comparative Example 3. Specifically, in Example 1, the peak area ratio (T3 / T2) was 8.6, whereas in Comparative Example 1, the peak area ratio (T3 / T2) was 3.1.

  From these facts, it was found that the condensation reaction did not proceed in mere heating cure, whereas in this example, the component containing Si—OH decreased and the condensation reaction proceeded sufficiently.

  As is clear from the above, according to the present invention, it was confirmed that it is possible to form an organic silica-based film in which properties, in particular, elastic modulus, Δk and hydrophobicity are remarkably improved as compared with the comparative example. It was. For this reason, 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.

It is a diagram showing the ²⁹ Si-DDMAS NMR spectrum obtained for Example.

Claims (15)

Applying a composition for forming an insulating film of a semiconductor device that is cured using heat and ultraviolet rays to a substrate and forming a coating film; and
Heating the coating film;
A step of curing the coating film by irradiating heat and ultraviolet rays,
The insulating film forming composition is:
Selected from the compound represented by the following general formula (1), the compound represented by the following general formula (2), the compound represented by the following general formula (3), and the compound represented by the following general formula (4) Hydrolysis condensate obtained by hydrolyzing and condensing the resulting silane compound, comprising an organic silica sol containing 11.8 to 16.7 mol% of carbon atoms, and an organic solvent, and a method for forming an organic silica film .
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group or an aryl group.)
Si (OR ³ ) ₄ (2)
(In the formula, R ³ represents an alkyl group or an aryl group.)
(R ⁴ ) ₂ Si (OR ⁵ ) ₂ (3)
(In the formula, R ⁴ represents an alkyl group or an aryl group, and R ⁵ represents an alkyl group or an aryl group.)
_{^{R 6 b (R 7 O)}} 3-b Si- (R 10) d -Si (OR 8) 3-c R 9 c ··· (4)
[Wherein, R ^{6 to} R ⁹ are the same or different and each represents an alkyl group or an aryl group; b and c are the same or different and each represents a number of 0 to 2; R ¹⁰ represents an oxygen atom, a phenylene group or — ( A group represented by CH ₂ ) _m — (wherein m is an integer of 1 to 6), d represents 0 or 1; ] In claim 1,
The method of forming an organic silica film, wherein the ultraviolet light has a wavelength of 250 nm or less. In claim 1 or 2,
A method for forming an organic silica film, in which heating and ultraviolet irradiation are simultaneously performed. In any one of Claims 1 thru | or 3,
The said heating is a 300-450 degreeC formation method of the organic silica type film | membrane. In any of claims 1 to 4,
A method for forming an organic silica film, wherein the ultraviolet irradiation is performed in the absence of oxygen. Organic silica having a relative dielectric constant of 1.5 to 3.5 and a film density of 0.7 to 1.3 g / cm ³ obtained by the method for forming an organic silica-based film according to any one of claims 1 to 5. System membrane.   A wiring structure using the organic silica-based film according to claim 6 as an interlayer insulating film.   A semiconductor device comprising the wiring structure according to claim 7. It is used in the method for forming an organosilica film according to any one of claims 1 to 5,
Selected from the compound represented by the general formula (1), the compound represented by the general formula (2), the compound represented by the general formula (3), and the compound represented by the general formula (4) A hydrolyzed condensate obtained by hydrolyzing and condensing the silane compound,
A composition for forming an insulating film of a semiconductor device, comprising an organic silica sol containing 11.8 to 16.7 mol% of a carbon atom, and an organic solvent, and is cured using heat and ultraviolet rays. In claim 9,
The composition for insulating film formation of a semiconductor device whose 60 mol% or more of the said silane compound is a compound represented by the said General formula (1). In claim 9 or 10,
The composition for insulating film formation of a semiconductor device whose compound represented by the said General formula (2) in the said silane compound is 40 mol% or less. In any of claims 9 to 11,
The composition for forming an insulating film of a semiconductor device, wherein the silane compound contains 65 to 95 mol% of the compound represented by the general formula (1) and 5 to 35 mol% of the compound represented by the general formula (2). . In any one of claims 9 to 12,
A composition for forming an insulating film of a semiconductor device, which does not contain a reaction accelerator active to ultraviolet rays. In claim 13,
The composition for forming an insulating film of a semiconductor device, wherein the reaction accelerator is any one of a reaction initiator, an acid generator, a base generator and a sensitizer having an ultraviolet absorption function, or a combination of two or more thereof. In any of claims 9 to 14,
A composition for forming an insulating film of a semiconductor device, wherein the contents of sodium, potassium, and iron are each 100 ppb or less.

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