JP2010106100A - Composition for forming insulating film, insulating film, and method for forming insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming an insulating film that can be suitably used in semiconductor elements in which high integration and multi-layering are desired, and can be used for forming the insulating film with a low relative dielectric constant superior in mechanical strength and working resistance, as well as to provide the insulating film and a method for forming the film. <P>SOLUTION: This composition for forming the insulating film includes: a hydrolysis-condensate that is obtained by hydrolysis-condensation of a silane compound which contains a compound 1 represented by following general formula (1): R<SP>1</SP><SB>b</SB>(R<SP>2</SP>O)<SB>3-b</SB>Si-CH<SB>2</SB>-Si(OR<SP>3</SP>)<SB>3-c</SB>R<SP>4</SP><SB>c</SB>(wherein R<SP>1</SP>-R<SP>4</SP>are the same or different, and are each a monovalent organic group, respectively, b and c are the same or different, and are each a number of 0-1) and an organic solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for forming an insulating film, an insulating film, and a method for forming the same.

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

  However, with further higher integration and multi-layering of semiconductor devices and the like, better electrical insulation between conductors is required, and therefore, storage stability is better, lower relative permittivity, and more mechanical An interlayer insulating film having excellent strength has been demanded.

  In the manufacturing process of the semiconductor device, a CMP (Chemical Mechanical Planarization) process for planarizing the insulating layer and various cleaning processes are performed. Therefore, in order to be applied to an interlayer insulating film or a protective film of a semiconductor device, in addition to dielectric constant characteristics, it is also required to have mechanical strength and plasma resistance enough to withstand erosion by plasma irradiation.

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensation of alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (Japanese Patent Laid-Open No. 5-263045, particularly Kaihei 5-315319) and coating liquids obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (Japanese Patent Laid-Open Nos. 11-340219 and 11-340220) Has been proposed. However, the materials obtained by these methods are not stable in the properties of the reaction products, and have large variations in the dielectric constant, crack resistance, mechanical strength, adhesion, etc. of the coating film. It was unsuitable.
JP-A-5-263045 JP-A-5-315319 Japanese Patent Laid-Open No. 11-340219 Japanese Patent Laid-Open No. 11-340220

  INDUSTRIAL APPLICABILITY The present invention can be suitably used in semiconductor elements and the like that are desired to be highly integrated and multilayered, and can be used to form an insulating film having a low relative dielectric constant and excellent mechanical strength and processing resistance. The object is to provide a film-forming composition.

  Another object of the present invention is to provide an insulating film having a low relative dielectric constant that is excellent in mechanical strength and processing resistance, and a method for forming the same.

The composition for forming an insulating film according to one embodiment of the present invention includes:
A hydrolysis condensate obtained by hydrolytic condensation of a silane compound containing Compound 1 represented by the following general formula (1) and an organic solvent are included.
^{_{R 1 a (R 2 O)}} 3-a Si-CH 2 -Si (OR 3) 3-b R 4 b ····· (1)
(In the formula, R ^{1 to} R ⁴ are the same or different and each represents a monovalent organic group, and a and b are the same or different and represent a number of 0 to 1.)
In the insulating film forming composition, the hydrolysis-condensation product may have a polymerization average molecular weight of 5,000 to 50,000.

  In the said insulating film formation composition, the usage-amount of the said compound 1 can be 20 to 100% of the total amount of the said silane compound in the said hydrolysis condensation.

In the insulating film forming composition, the silane compound may further include a compound 2 represented by the following general formula (2).
R ⁵ _c Si (OR ⁶ ) _4-c (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 2 carbon atoms, a vinyl group, an allyl group, an acetyl group or a phenyl group, c represents an integer of 1 to 2, and R ⁶ represents an alkyl having 1 to 3 carbon atoms. Group, vinyl group, allyl group, acetyl group or phenyl group.)
In this case, the molar ratio of the compound 1 and the compound 2 (compound 1: compound 2) may be 20:80 to 60:40.

  In the insulating film forming composition, the silane compound may further include hydrolyzable polycarbosilane.

  In this case, the weight ratio of the compound 1 to the hydrolyzable polycarbosilane (compound 1: hydrolyzable polycarbosilane) may be 40:60 to 80:20.

  In this case, the hydrolyzable polycarbosilane may have a structural unit represented by the following general formula (3).

・・・・・（３）
（式中、Ｒ^８は水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１０，Ｒ^１１は同一または異なり、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１２〜Ｒ^１４は同一または異なり、置換または非置換のメチレン基、アルキレン基、アルケニレン基、アルキニレン基、またはアリーレン基を示し、ｘ，ｙ，ｚは、それぞれ０〜１０，０００の数を示し、５＜ｘ＋ｙ＋ｚ＜１０，０００の条件を満たす。）
上記絶縁膜形成用組成物において、前記シラン化合物は、下記一般式（２）で表される化合物２および下記一般式（３）で表される化合物３をさらに含み、前記化合物３の使用量１００質量部に対して、前記化合物１および前記化合物２の使用量の合計が１〜１０００質量部であることができる。
Ｒ^５ _ｃＳｉ（ＯＲ^６）_４−ｃ ・・・・・（２）
（式中、Ｒ^５は炭素数１〜２のアルキル基、ビニル基、アリル基、アセチル基またはフェニル基を示し、ｃは１〜２の整数を示し、Ｒ^６は炭素数１〜３のアルキル基、ビニル基、アリル基、アセチル基またはフェニル基を示す。）

(3)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group,, x, y, z are each 0 to 10,000 And the condition 5 <x + y + z <10,000 is satisfied.)
In the insulating film forming composition, the silane compound further includes a compound 2 represented by the following general formula (2) and a compound 3 represented by the following general formula (3). The sum total of the usage-amount of the said compound 1 and the said compound 2 can be 1-1000 mass parts with respect to the mass part.
R ⁵ _c Si (OR ⁶ ) _4-c (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 2 carbon atoms, a vinyl group, an allyl group, an acetyl group or a phenyl group, c represents an integer of 1 to 2, and R ⁶ represents an alkyl having 1 to 3 carbon atoms. Group, vinyl group, allyl group, acetyl group or phenyl group.)

・・・・・（３）
（式中、Ｒ^８は水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１０，Ｒ^１１は同一または異なり、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１２〜Ｒ^１４は同一または異なり、置換または非置換のメチレン基、アルキレン基、アルケニレン基、アルキニレン基、またはアリーレン基を示し、ｘ，ｙ，ｚは、それぞれ０〜１０，０００の数を示し、５＜ｘ＋ｙ＋ｚ＜１０，０００の条件を満たす。）
上記絶縁膜形成用組成物において、空孔形成剤をさらに含むことができる。

(3)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group,, x, y, z are each 0 to 10,000 And the condition 5 <x + y + z <10,000 is satisfied.)
The insulating film forming composition may further include a pore forming agent.

  An insulating film forming method according to another embodiment of the present invention includes a step of applying the insulating film forming composition to a substrate and heating the substrate.

  In the method for forming an insulating film, the heating step may include a step of irradiating a high energy beam under heating. In this case, the high energy beam may be at least one selected from an electron beam and an ultraviolet ray.

  The method for forming an insulating film according to another embodiment of the present invention can be obtained by the method for forming an insulating film.

  The composition for forming an insulating film includes a hydrolysis-condensation product obtained by hydrolysis-condensation of a silane compound containing the compound 1 represented by the following general formula (1), and an organic solvent. It can be used for forming an insulating film having high strength and low dielectric constant having excellent processing resistance such as plasma resistance.

  The insulating film has a small relative dielectric constant, and is excellent in mechanical strength and processing resistance.

  Hereinafter, a composition for forming an insulating film, an insulating film, and a method for forming the same according to an embodiment of the present invention will be specifically described.

1. Composition for insulating film formation The composition for insulating film formation which concerns on one Embodiment of this invention is a hydrolysis condensation obtained by hydrolytic condensation of the silane compound containing the compound 1 represented by following General formula (1). And an organic solvent.
^{_{R 1 a (R 2 O)}} 3-a Si-CH 2 -Si (OR 3) 3-b R 4 b ····· (1)
(In the formula, R ^{1 to} R ⁴ are the same or different and each represents a monovalent organic group, and a and b are the same or different and represent a number of 0 to 1.)
Hereinafter, each component used in order to manufacture the composition for film formation which concerns on this embodiment is demonstrated.

1.1. Hydrolysis condensate As described above, the hydrolysis condensate is obtained by hydrolytic condensation of a silane compound containing Compound 1.

1.1.1. Compound 1
Compound 1 contains —Si—CH ₂ —Si—. When the silane compound contains compound 2 by condensation between compounds 1, the condensation between compound 1 and compound 2 causes the silane compound to hydrolyze polycarbohydrate. In the case where silane is contained, a —Si—O—Si— bond can be formed by condensation with Compound 1 hydrolyzable polycarbosilane. In forming the hydrolysis condensate, the use of Compound 1 contributes to an improvement in elastic modulus and an improvement in plasma resistance.

In the general formula (1), examples of the monovalent organic group represented by R ^{1 to} R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert group. -C1-C4 alkyl groups, such as a butyl group, can be mentioned, and a methyl group and an ethyl group are more preferable. In these alkyl groups, a hydrogen atom may be substituted with a fluorine atom or the like.

  In the hydrolytic condensation when preparing the composition for forming an insulating film according to this embodiment, the amount of compound 1 used is preferably 20 to 100% of the total amount of silane compounds. If the amount of compound 1 used is less than 20%, the elastic modulus may be lowered.

  As compound 1, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-iso-propoxysilyl) methane, bis (tri-n-butoxy) Silyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 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-but Sisilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (tri-tert-butoxysilyl) Methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethylsilyl) methane, bis (di-n-butoxy) Examples include methylsilyl) methane, bis (di-sec-butoxymethylsilyl) methane, and bis (di-tert-butoxymethylsilyl) methane.

  Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (tri Preferred examples include ethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, and the like.

  Compound 1 may be used alone or in combination of two or more.

1.2. Compound 2
In the hydrolytic condensation when preparing the composition for forming an insulating film according to this embodiment, the silane compound can further include a compound 2 represented by the following general formula (2).
R ⁵ _c Si (OR ⁶ ) _4-c (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 2 carbon atoms, a vinyl group, an allyl group, an acetyl group or a phenyl group, c represents an integer of 1 to 2, and R ⁶ represents an alkyl having 1 to 3 carbon atoms. Group, vinyl group, allyl group, acetyl group or phenyl group.)
In the general formula (2), examples of the alkyl group having 1 to 2 carbon atoms represented by R ⁵ include a methyl group and an ethyl group, and the alkyl group having 1 to 3 carbon atoms represented by R ^6. Examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. In these alkyl groups, a hydrogen atom may be substituted with a fluorine atom or the like.

R ⁵ is preferably an alkyl group having 1 to 2 carbon atoms, a vinyl group or an allyl group, and R ⁶ is preferably an alkyl group having 1 to 3 carbon atoms or a vinyl group.

  In the above hydrolytic condensation, compound 2 is condensed with compound 1, condensed between compounds 2, and when the silane compound contains hydrolyzable polycarbosilane, by condensation between compound 2 and hydrolyzable polycarbosilane, A -Si-O-Si- bond can be formed. In the formation of the hydrolysis condensate, compound 2 contributes to the improvement of plasma resistance.

  In the hydrolytic condensation, when the silane compound contains compound 2, the molar ratio of compound 1 to compound 2 (compound 1: compound 2) is preferably 20:80 to 60:40. Here, if the amount of compound 2 used relative to the amount of compound 1 used is less than 2/3, the elastic modulus may decrease, whereas if it exceeds 4, the dielectric constant may increase.

Specific examples of the compound 2 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert. -Butoxysilane, 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-propyltriisopro Xysilane, 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- Toxisilane, 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-butyl Rutri-tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec -Butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec- Butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propo Sisilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane Di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi- tert-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxy Silane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane , Di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi- Phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxy Silane, di-sec-butyl di-sec-butoxy Sisilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, Di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-ter - butoxysilane include diphenyl phenoxy silanes. These may be used alone or in combination of two or more.

  Particularly preferred compounds as Compound 2 are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy. Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. These may be used alone or in combination of two or more.

1.1.3. Hydrolyzable polycarbosilane In the hydrolysis condensation at the time of preparing the composition for forming an insulating film according to this embodiment, the silane compound may further contain hydrolyzable polycarbosilane.

  The hydrolyzable polycarbosilane has a Si—C—Si bond, and when the silane compound contains compound 2 by condensation of hydrolyzable polycarbosilane and compound 1, hydrolyzable polycarbosilane and compound 2 -Si-O-Si- bond can be formed by condensation with hydrolyzable polycarbosilane. In the formation of the hydrolysis condensate, the hydrolyzable polycarbosilane contributes to the improvement of chemical resistance.

  When the silane compound further contains hydrolyzable polycarbosilane, the weight ratio of compound 1 to hydrolyzable polycarbosilane (compound 1: hydrolyzable polycarbosilane) is preferably 40:60 to 80:20. . Here, when the amount of hydrolyzable polycarbosilane used relative to the amount of compound 1 used is less than ¼, chemical resistance may decrease, while when it exceeds 3/2, the dielectric constant increases. There is a case.

  The hydrolyzable polycarbosilane can be, for example, a polycarbosilane compound having a structural unit represented by the following general formula (3) (hereinafter referred to as “compound 3”).

・・・・・（３）
（式中、Ｒ^８は水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１０，Ｒ^１１は同一または異なり、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１２〜Ｒ^１４は同一または異なり、置換または非置換のメチレン基、アルキレン基、アルケニレン基、アルキニレン基、またはアリーレン基を示し、ｘ，ｙ，ｚは、それぞれ０〜１０，０００の数を示し、５＜ｘ＋ｙ＋ｚ＜１０，０００の条件を満たす。）
上記一般式（３）において、Ｒ^８〜Ｒ^１１で表されるハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子などを挙げることができ、Ｒ^８〜Ｒ^１１で表されるアルコキシ基としては、例えばメトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基などを挙げることができ、Ｒ^８〜Ｒ^１１で表されるアシロキシ基としては、例えばアセチルオキシ基、プロピオニルオキシ基などを挙げることができ、Ｒ^８〜Ｒ^１１で表されるアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基などを挙げることができ、Ｒ^８〜Ｒ^１１で表されるアリール基としては、例えばフェニル基、ナフチル基、メチルフェニル基、エチルフェニル基、クロロフェニル基、ブロモフェニル基、フルオロフェニル基などを挙げることができる。

(3)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group,, x, y, z are each 0 to 10,000 And the condition 5 <x + y + z <10,000 is satisfied.)
In the said General formula (3), as a halogen atom represented by R < ⁸ > -R < ¹¹ >, a fluorine atom, a chlorine atom, a bromine atom etc. can be mentioned, for example, As an alkoxy group represented by R < ⁸ > -R < ¹¹ > Can include, for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like, and examples of the acyloxy group represented by R ^{8 to} R ¹¹ include an acetyloxy group and a propionyloxy group. Examples of the alkyl group represented by R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, and an aryl group represented by R ^{8 to} R ^11. Examples of groups include phenyl, naphthyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, and phenyl. Or the like can be mentioned Orofeniru group.

In the general formula (3), examples of the alkylene group represented by R ^{12 to} R ¹⁴ include an ethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group. The alkylene group has 2 to 6 carbon atoms, and these alkylene groups may be chain-like or branched or may form a ring, and a hydrogen atom is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom May be substituted. Examples of the alkenylene group represented by R ^{12 to} R ¹⁴ include straight-chain or branched alkenylene groups having 2 to 6 carbon atoms (preferably 1 to 4), such as vinylene group, propenylene group, butenylene group, and pentenylene. Group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, 3-methylpentenylene group, 1-ethylvinylene group, 1-ethylpropenylene group 1-ethylbutenylene group, 3-ethylbutenylene group and the like. The hydrogen atom in these alkenylene groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkynylene group represented by R ^{12 to} R ¹⁴ include straight-chain or branched alkynylene groups having 2 to 6 carbon atoms (preferably 1 to 4), such as ethynylene group, 1-propynylene group, 1- Examples include butynylene, 1-pentynylene, 1-hexynylene, 2-butynylene, 2-pentynylene, 1-methylethynylene, 3-methyl-1-propynylene, and 3-methyl-1-butynylene. it can. The hydrogen atom in these alkynylene groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the arylene group represented by R ^{12 to} R ¹⁴ include a phenylene group and a naphthylene group, and a hydrogen atom is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Also good.

Moreover, in the said General formula (3), x, y, z is the number of 0-10,000, and is 5 <x + y + z <10,000. In the case of x + y + z <5, the storage stability of the polymer may be inferior, and in the case of 10,000 <x + y + z, the obtained polymer may cause layer separation and may not form a uniform film. Preferably, x, y and z are 0 ≦ x ≦ 800, 0 ≦ y ≦ 500 and 0 ≦ z ≦ 1,000, respectively, more preferably 0 ≦ x ≦ 500.
0 ≦ y ≦ 300 and 0 ≦ z ≦ 500, and more preferably 0 ≦ x ≦ 100, 0 ≦ y ≦ 50, and 0 ≦ z ≦ 100.

  In the general formula (3), 5 <x + y + z <1,000 is preferable, 5 <x + y + z <500 is more preferable, 5 <x + y + z <250 is further preferable, and 5 <x + y + z. Most preferred is <100.

  Compound 3 is, for example, chloromethyltrichlorosilane, bromomethyltrichlorosilane, chloromethylmethyldichlorosilane, chloromethylethyldichlorosilane, chloromethylvinyldichlorosilane, chloromethylphenyldichlorosilane, bromomethylmethyldichlorosilane, bromomethylvinyldichlorosilane , Chloromethyldimethylchlorosilane, chloromethyldivinylchlorosilane, bromomethyldimethylchlorosilane, (1-chloroethyl) trichlorosilane, (1-chloropropyl) trichlorosilane, chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethylmethyldimethoxysilane , Chloromethylvinyldimethoxysilane, chloromethylphenyldimethoxysilane, bromomethylmethyldimethoxy Run, bromomethylvinyldimethoxysilane, bromomethylphenyldimethoxysilane, chloromethyldimethylmethoxysilane, chloromethyldivinylmethoxysilane, chloromethyldiphenylmethoxysilane, bromomethyldimethylmethoxysilane, bromomethyldiisopropylmethoxysilane, chloromethyltriethoxysilane, Bromomethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylethyldiethoxysilane, chloromethylvinyldiethoxysilane, chloromethylphenyldiethoxysilane, bromomethylmethyldiethoxysilane, bromomethylvinyldiethoxysilane, bromomethyl Phenyldiethoxysilane, chloromethyldimethylethoxysilane, chloromethyldiethylethoxysilane, bromine At least one compound selected from methyldivinylethoxysilane, chloromethyltriisopropoxysilane and bromomethyltriisopropoxysilane is reacted in the presence of at least one of an alkali metal and an alkaline earth metal, and if necessary Further, it can be obtained by treatment with alcohol, organic acid, reducing agent or the like.

  The weight average molecular weight of the hydrolyzable polycarbosilane is preferably 5,000 to 50,000, and more preferably 8,000 to 30,000. When the weight average molecular weight of the hydrolyzable polycarbosilane is less than 5,000, there may be a problem in coating properties and storage stability. On the other hand, when the weight average molecular weight is more than 50,000, particles are easily generated. The pores in the insulating film formed using the resulting hydrolyzed condensate are undesirably too large.

  In the film-forming composition according to this embodiment, when Compound 1, Compound 2, and hydrolyzable polycarbosilane are used in the formation of the hydrolysis condensate, 100 parts by weight of hydrolyzable polycarbosilane (completely The total of compound 1 and compound 2 is preferably 1 to 1000 parts by weight (in terms of complete hydrolyzate), more preferably 5 to 200 parts by weight, and more preferably 5 to 100 with respect to hydrolyzate. More preferably, it is part by weight. Here, when the total of the compound 1 and the compound 2 with respect to 100 parts by weight of the hydrolyzable polycarbosilane is less than 1 part by weight, it may not be possible to achieve a low dielectric constant of the film. If exceeded, sufficient plasma resistance may not be exhibited after film formation.

1.1.4. Catalyst The catalyst for obtaining the hydrolysis condensate contained in the film forming composition according to this embodiment is preferably at least one compound selected from a basic compound, an acidic compound, and a metal chelate compound. More preferably, it is a basic compound.

1.1.4.1. Metal Chelate Compound A metal chelate compound that can be used as a catalyst is represented by the following general formula (4).

R ¹⁵ _e M (OR ¹⁶ ) _fe (4)
(In the formula, R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ represents an alkyl group or an aryl group, f represents a valence of the metal M, and e represents an integer of 1 to f.)
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. Examples of the alkyl group or aryl group represented by R ¹⁶ include the alkyl group or aryl group represented by R ¹ in the general formula (1).

  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 by weight, with respect to 100 parts by weight (in terms of complete hydrolysis condensate) of the hydrolyzable silane compound. 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.

  When hydrolyzing and condensing a hydrolyzable silane compound in the presence of a metal chelate compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of hydrolyzable silane compound, and 1 to 10 mol of water is used. 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.

1.1.4.2. Acidic compounds Examples of acidic compounds that can be used as a catalyst include organic acids and inorganic acids, with organic acids being preferred. 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 Object can include hydrolysis products 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 organic acids such as 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 hydrolyzable silane compound. When the amount of the acidic compound used is less than 0.0001 parts by weight relative to 100 parts by weight of the total amount of the hydrolyzable silane compound, the coatability of the coating film may be inferior. In some cases, the hydrolytic condensation reaction proceeds to cause gelation.

  When hydrolyzing and condensing a hydrolyzable silane compound in the presence of an acidic compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of hydrolyzable silane compound, 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.

1.1.4.3. Basic compounds Examples of basic compounds that can be used as a catalyst include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, and N-butylmethanol. Amine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethano Amine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyl Dibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) ) Butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanol N- (aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- ( Aminobutyl) propanolamine, N- (aminobutyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, Propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, methylamine, ethyl Ruamine, propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydro Oxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylaminopropyl Amine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethyl Aminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine, Examples include pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. it can.

  The basic compound is particularly preferably a nitrogen-containing compound represented by the following general formula (5) (hereinafter also referred to as compound 5).

(X ¹ X ² X ³ X ⁴ N) _g Y (5)
In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ are the same or different and are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, or a butyl group). Hexyl group), hydroxyalkyl group (preferably hydroxyethyl group etc.), aryl group (preferably phenyl group etc.), arylalkyl group (preferably phenylmethyl group etc.), Y is a halogen atom (preferably fluorine) An atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a 1 to 4 valent anionic group (preferably a hydroxy group), and g represents an integer of 1 to 4.

  Specific examples of compound 5 include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-iso-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-hydroxide iso-butylammonium hydroxide, tetra-tert-butylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraheptylammonium hydroxide, tetraoctylammonium hydroxide, tetranonylammonium hydroxide, tetradecylammonium hydroxide, Tetraundecylammonium hydroxide, tetradodecylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, teto chloride Ethylammonium, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, hexadecyltrimethylammonium hydroxide, -n-hexabromide Decyltrimethylammonium hydroxide, hydroxide-n-octadecyltrimethylammonium, bromide-n-octadecyltrimethylammonium bromide, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, benzyltrimethylammonium chloride, didecyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Tridecylmethylammonium, tetrabutylammonium hydrogen sulfate, tributylmethylammonium bromide, trioctyl chloride Methyl ammonium, trilauryl methyl ammonium chloride, benzyl trimethyl ammonium hydroxide, benzyl bromide triethylammonium, and the like are preferable benzyl bromide tributylammonium bromide phenyl trimethyl ammonium, choline and the like. Among these, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethyl bromide are particularly preferable. Ammonium, tetraethylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride. Compound 5 may be used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.00001-10 mol normally with respect to 1 mol of total amounts of the hydrolysable group in a hydrolysable silane compound, Preferably it is 0.00005-5 mol.

1.1.5. Organic solvent Examples of the organic solvent contained in the composition for forming an insulating film according to the present embodiment include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and t-butanol. Alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2, Polyhydric alcohol solvents such as 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Polyhydric alcohol partial ether solvents such as recall monopropyl ether and ethylene glycol monobutyl ether; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, Ether solvents such as dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether; 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 Luketone, methyl-n-hexylketone, di-i-butylketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone And ketone solvents such as diacetone alcohol.

  The reaction temperature in the hydrolytic condensation of the hydrolyzable silane compound is 0 to 100 ° C., preferably 20 to 80 ° C., and the reaction time is 30 to 1000 minutes, preferably 30 to 180 minutes.

1.1.6. Hydrolyzed condensate The weight average molecular weight (Mw) of the hydrolyzed condensate contained in the film-forming composition according to this embodiment is more preferably 5,000 to 50,000, and 8,000 to 30,000. It is more preferable that it is 10,000 to 25,000. If the weight-average molecular weight of the hydrolysis-condensation product is larger than 50,000, gelation tends to occur, and the pores in the obtained insulating film become too large, which is not preferable. On the other hand, if the weight average molecular weight of the hydrolyzed condensate is less than 5,000, problems are likely to occur in coating properties and storage stability.

1.2. Organic Solvent The organic solvent used in the film forming composition according to this embodiment includes alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatics. Examples thereof include at least one selected from the group of system solvents and halogen-containing solvents.

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, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, full Lil alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol 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 solvents, 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 film-forming composition according to the present embodiment, it is desirable to use an organic solvent having a boiling point of less than 150 ° C. Among them, alcohol solvents, ketone solvents, and ester solvents are particularly desirable, and further, 1 It is desirable to use seeds or two or more simultaneously.

  These organic solvents may be the same as those used for the synthesis of the hydrolysis condensate, or the solvent can be replaced with a desired organic solvent after the synthesis of the hydrolysis condensate is completed.

  The total solid concentration of the film-forming composition according to one embodiment of the present invention is preferably 0.1 to 20% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the film-forming composition according to one embodiment of the present invention is 0.1 to 20% by mass, the film thickness of the coating film is in an appropriate range and has better storage stability. It will be a thing. In addition, adjustment of this total solid content concentration is performed by concentration and dilution with an organic solvent, if necessary.

1.3. Other Additives Components such as organic polymers and surfactants may be further added to the film forming composition according to this embodiment.

1.3.1. Organic polymer As the organic polymer, for example, a polymer having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound polymer, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, Examples thereof include polyquinoxaline, polyoxadiazole, a fluorine-based polymer, and a polymer having a polyalkylene oxide structure. These organic polymers can be used as pore forming agents. In the film forming composition according to the present embodiment, when an organic polymer is used as the pore forming agent, the amount of the pore forming agent used is 0 to 100 parts by weight with respect to 100 parts by weight of the solid content in the composition. Preferably there is.

  Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure.

  Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Ether type compounds such as oxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters.

  Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.

− (X ′) ₁ − (Y ′) _m −
-(X ') _1- (Y') _m- (X ') _n-
(Wherein X ′ represents a group represented by —CH ₂ CH ₂ O—, Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, l is 1 to 90, and m is 10 to 99, n represents a number from 0 to 90)
Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, More preferred examples include ether type compounds. The aforementioned organic polymers may be used alone or in combination of two or more.

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.

  The usage-amount of surfactant is 0.00.0-1 weight part normally with respect to 100 weight part of polymers obtained. These may be used alone or in combination of two or more.

2. Method for Forming Insulating Film A method for forming an insulating film (silica-based film) according to an embodiment of the present invention includes a step of applying the insulating film forming composition to a substrate and heating the substrate.

Examples of the substrate on 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 the film-forming composition is applied to the substrate, the solvent is removed to form a coating film. 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. Then, a silica-type film | membrane can be formed by performing a hardening process with respect to the obtained coating film.

  Examples of the curing treatment include heating, irradiation with high energy rays such as electron beams and ultraviolet rays, plasma treatment, and combinations thereof. Heat treatment and / or irradiation with high energy rays are preferable, and high energy rays are applied under heating. Irradiation is more preferable.

  In the case of curing by heating, the coating film is heated to 80 to 450 ° C. (preferably 300 ° C. to 450 ° C.) under an inert atmosphere or reduced pressure. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere can be performed under an inert atmosphere or under reduced pressure. More specifically, the oxygen concentration at the time of curing the coating film is preferably 50 ppm or less from the viewpoint of suppressing an increase in dielectric constant.

  Moreover, in order to control the curing rate of the coating film, it can be heated stepwise or an atmosphere such as nitrogen, air, oxygen, or reduced pressure can be selected as necessary. Through such a process, a silica-based film can be manufactured.

3. Insulating Film An insulating film (silica-based film) according to an embodiment of the present invention has a low dielectric constant, high mechanical strength, and excellent processing resistance such as plasma resistance. Therefore, LSI, system LSI, DRAM, SDRAM It is particularly excellent as an interlayer insulating film for semiconductor elements such as RDRAM and D-RDRAM, and it is an etching stopper film, a protective film such as a surface coating film of a semiconductor element, an intermediate layer of a semiconductor manufacturing process using a multilayer resist, and a multilayer It can be suitably used for an interlayer insulating film of a wiring board, a protective film for a liquid crystal display element, an insulating film and the like. In addition, the insulating film according to the present embodiment is useful for a semiconductor device including a copper damascene process, for example.

The dielectric film according to this embodiment has a relative dielectric constant of preferably 1.5 to 3.5, more preferably 1.8 to 3.0, and still more preferably 1.8 to 2.8. The elastic modulus is preferably 2.5 GPa or more, more preferably 3.0 GPa or more, and the film density is preferably 0.7 to 1.3 g / cm ³ , more preferably 0.8 to 1.27 g / cm ³ . From these facts, the insulating film according to the present embodiment has high mechanical strength, excellent processing resistance, and a low relative dielectric constant. Therefore, it can be said that the insulating film characteristics are extremely excellent.

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 mass%, respectively, unless otherwise specified.

4.1. Evaluation method Various evaluations were performed as follows.

  For the elastic modulus and processing resistance (plasma resistance), a polymer film (silica film) formed by the following method was used. That is, the composition obtained in each example and comparative example was applied on a silicon wafer by spin coating, and then the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. Further, the substrate was baked on a hot plate for 60 minutes in a nitrogen atmosphere at 400 ° C. to obtain a polymer film having a film thickness of 500 μm, and this polymer film was used for the various evaluations described above.

4.1.1. Dielectric constant measurement, Δk
A film-forming composition was applied onto an 8-inch N-type silicon wafer having a resistivity of 0.1 Ω · cm or less by using a spin coating method, and then on a hot plate at 90 ° C. for 3 minutes, and then in a nitrogen atmosphere The film was dried at 200 ° C. for 3 minutes and further baked for 1 hour in a vertical furnace at 420 ° C. under reduced pressure of 50 mTorr (vacuum atmosphere) to obtain a film.

  An aluminum electrode pattern was formed on the obtained film by a vapor deposition method, and a sample for measuring relative permittivity was prepared. With respect to the sample, the relative dielectric constant of the film at 200 ° C. was measured at a frequency of 100 kHz by the CV method using an HP 16451B electrode and an HP4284A precision LCR meter manufactured by Agilent.

4.1.2. Evaluation of Elastic Modulus (Young's Modulus) of Membrane 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 following method was measured by a continuous stiffness measurement method.

4.1.3. Plasma Resistance The relative dielectric constant of the film was measured before and after the plasma irradiation of the polymer film for 30 seconds, and was rated according to the following criteria based on the value of the relative dielectric constant increased before and after the plasma irradiation.

A: Increase value of relative dielectric constant is less than 0.2 B: Increase value of relative dielectric constant is 0.2 or more and less than 0.5 C: Increase value of relative dielectric constant is 0.5 or more 4.1.4. Weight average molecular weight Mw
The weight average molecular weight (Mw) of the hydrolysis condensate was measured by a size exclusion chromatography (SEC) method under the following conditions.

Sample: A 2-methoxyethanol solution of LiBr—H ₃ PO _{4 at} a concentration of 10 mmol / L was used as a solvent, and 0.1 g of a hydrolysis condensate was added to 100 cc of 10 mmol / L LiBr—H ₃ PO _{4 in} a 2-methoxyethanol solution. And dissolved.

  Standard sample: Polyethylene oxide manufactured by WAKO was used.

  Apparatus: A high-speed GPC apparatus (model HLC-8120GPC) manufactured by Tosoh Corporation was used.

  Column: Tosoh Co., Ltd. product, TSK-GEL SUPER AWM-H (15 cm in length) was installed in series and used.

Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: Detected by RI of a built-in high-speed GPC device (model HLC-8120GPC) manufactured by Tosoh Corporation.

4.2. Production of composition for film formation 4.2.1. Synthesis example 1
A quartz separable flask was charged with solution (1): 261 g of distilled ethanol, 37 g of ion-exchanged water, and 111 g of 10% tetramethylammonium hydroxide aqueous solution, and stirred uniformly. Next, a mixed solution of solution (2): 28 g of methyltrimethoxysilane, 30 g of bis (triethoxysilyl) methane, 19 g of polycarbosilane (Mw800) having a structure represented by the following formula (6), and 213 g of distilled ethanol The dropping funnel was filled. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The hydrolysis-condensation product obtained in this synthesis example had a weight average molecular weight of 14,300.

・・・・・（６）
４．２．２．合成例２
石英製セパラブルフラスコに、溶液（１）：蒸留エタノール２４９ｇ、イオン交換水６９ｇ、および１０％水酸化テトラメチルアンモニウム水溶液９２ｇを入れ、均一に攪拌した。次に、溶液（２）：メチルトリメトキシシラン３３ｇ、ビス（トリエトキシシリル）メタン５４ｇ、および蒸留エタノール２０４ｇの混合溶液を滴下ロートに充填した。次いで、溶液（１）を６０℃で攪拌しながら溶液（２）を１時間かけて滴下し、さらにその後２時間反応を行った。反応液を室温まで冷却した後、この溶液にプロピレングリコールモノプロピルエーテル３００ｇおよび１０％酢酸水溶液３０ｇを加えた。その後、５０℃のエバポレーターを用いて溶液を１５％となるまで濃縮して、加水分解縮合物を含む膜形成用組成物を得た。本合成例で得られた加水分解縮合物の重量平均分子量は１９，４００であった。

(6)
4.2.2. Synthesis example 2
A quartz separable flask was charged with solution (1): 249 g of distilled ethanol, 69 g of ion-exchanged water, and 92 g of 10% tetramethylammonium hydroxide aqueous solution, and stirred uniformly. Next, a dropping funnel was filled with a mixed solution of solution (2): 33 g of methyltrimethoxysilane, 54 g of bis (triethoxysilyl) methane, and 204 g of distilled ethanol. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The weight average molecular weight of the hydrolysis condensate obtained in this synthesis example was 19,400.

4.2.3. Synthesis example 3
Into a quartz separable flask, 237 g of solution (1): distilled ethanol, 61 g of ion-exchanged water, and 111 g of 10% tetramethylammonium hydroxide aqueous solution were added and stirred uniformly. Next, a mixed solution of solution (2): methyltrimethoxysilane 18 g, bis (triethoxysilyl) methane 45 g, polycarbosilane (Mw800) 19 g having the structure represented by the above formula (6), and distilled ethanol 208 g The dropping funnel was filled. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The weight average molecular weight of the hydrolysis-condensation product obtained in this synthesis example was 18,700.

4.2.4. Synthesis example 4
A quartz separable flask was charged with solution (1): 261 g of distilled ethanol, 37 g of ion-exchanged water, and 111 g of 10% tetramethylammonium hydroxide aqueous solution, and stirred uniformly. Next, solution (2): 24 g of methyltrimethoxysilane, 4 g of vinyltrimethoxysilane, 30 g of bis (triethoxysilyl) methane, 19 g of polycarbosilane (Mw800) having the structure represented by the above formula (6), and distillation A dropping funnel was filled with a mixed solution of 213 g of ethanol. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The weight average molecular weight of the hydrolysis-condensation product obtained in this synthesis example was 16,300.

4.2.5. Synthesis example 5
A quartz separable flask was charged with solution (1): 263 g of distilled ethanol, 12 g of ion-exchanged water, and 133 g of 10% tetramethylammonium hydroxide aqueous solution, and stirred uniformly. Next, solution (2): mixed solution of 27 g of methyltrimethoxysilane, 30 g of bis (triethoxysilyl) ethane, 19 g of polycarbosilane (Mw800) having the structure represented by the above formula (6), and 216 g of distilled ethanol In a dropping funnel. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The weight average molecular weight of the hydrolysis-condensation product obtained in this synthesis example was 17,500.

4.2.6. Synthesis Example 6
A quartz separable flask was charged with solution (1): 253 g of distilled ethanol, 13 g of ion-exchanged water, and 144 g of 10% tetramethylammonium hydroxide aqueous solution, and stirred uniformly. Next, a dropping funnel was filled with a mixed solution of solution (2): methyltrimethoxysilane 31 g, bis (triethoxysilyl) ethane 53 g, and distilled ethanol 207 g. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The hydrolysis-condensation product obtained in this synthesis example had a weight average molecular weight of 14,700.

4.2.7. Synthesis example 7
Into a quartz separable flask, 189 g of solution (1): distilled ethanol, 144 g of ion-exchanged water, and 134 g of 10% tetramethylammonium hydroxide aqueous solution were added and stirred uniformly. Next, a solution (2): a mixed solution of 17 g of methyltrimethoxysilane, 44 g of bis (triethoxysilyl) ethane, 19 g of polycarbosilane (Mw800) having the structure represented by the above formula (6), and 154 g of distilled ethanol The dropping funnel was filled. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The weight average molecular weight of the hydrolysis condensate obtained in this synthesis example was 17,100.

4.2.8. Synthesis example 8
A quartz separable flask was charged with solution (1): 231 g of distilled ethanol, 16 g of ion-exchanged water, and 176 g of a 10% tetramethylammonium hydroxide aqueous solution, and stirred uniformly. Next, a dropping funnel was filled with a mixed solution of solution (2): 71 g of methyltrimethoxysilane, 19 g of polycarbosilane (Mw800) having the structure represented by the above formula (6), and 189 g of distilled ethanol. Next, while stirring the solution (1) at 60 ° C., the solution (2) was added dropwise over 1 hour, followed by further reaction for 2 hours. After cooling the reaction solution to room temperature, 300 g of propylene glycol monopropyl ether and 30 g of 10% aqueous acetic acid solution were added to this solution. Thereafter, the solution was concentrated to 15% using an evaporator at 50 ° C. to obtain a film-forming composition containing a hydrolysis-condensation product. The weight average molecular weight of the hydrolysis condensate obtained in this synthesis example was 13,700.

4.3. Formation of film (Examples 1 to 16 and Comparative Examples 1 to 12)
The composition obtained in each synthesis example was mixed at a weight ratio shown in Table 1 to prepare a coating composition. In addition, regarding an example in which “PE-61” (trade name, polyoxyethylene polyoxypropylene block copolymer manufactured by Sanyo Chemical Industries, Ltd.) is used as an additive, “PE-61” has a solid content of 100% by weight. 25 parts by weight with respect to parts was added. Next, this was applied onto an 8-inch silicon wafer by spin coating, and heated in air at 80 ° C. for 5 minutes and then at 200 ° C. for 5 minutes in nitrogen to obtain a coating film. Furthermore, the crosslinking process was implemented by the method shown by each example, and the colorless and transparent film | membrane (500 nm) was formed. The evaluation results of the solution and the film are shown in Table 1. The crosslinking treatment method is as follows.

4.3.1. Heat treatment The coating was heated at 420 ° C. under vacuum for 1 hour.

4.3.2. Electron beam irradiation In a chamber with an oxygen partial pressure of 0.01 kPa, an electron beam was irradiated for 4 minutes under an irradiation dose of 300 μC / cm ² and an acceleration voltage of 7 keV while heating the coating film at 350 ° C. on a hot plate. .

4.3.3. Ultraviolet irradiation In a chamber having an oxygen partial pressure of 0.01 kPa, ultraviolet rays were irradiated for 8 minutes while heating the coating film at 400 ° C. on a hot plate. As the ultraviolet light source, white ultraviolet light having a wavelength of 250 nm or less was used. Since this ultraviolet light is white ultraviolet light, the illuminance cannot be measured by an effective method.

4.4. Discussion of Results (1) In Table 1, Examples 1 to 4 and Comparative Examples 1 to 4 are examples in which a curing treatment by heat is performed. According to Table 1, it is clear that Comparative Examples 1 to 4 not containing Compound 1 have low plasma resistance.

  (2) Moreover, in Table 1, Examples 5-12 and Comparative Examples 5-12 are examples which performed the hardening process by electron beam irradiation. All of the films obtained in Examples 5 to 12 have good elastic modulus and plasma resistance at a relative dielectric constant of 2.5 or less. Although the film | membrane obtained by Comparative Examples 5-10 has an elasticity modulus exceeding 10 GPa, it turns out that plasma tolerance is low. Furthermore, it can be seen that the films obtained in Comparative Examples 11 and 12 have good plasma resistance but low elastic modulus. From the above results, it can be understood that the film obtained by electron beam irradiation has a higher elastic modulus than the film obtained by heat treatment as the curing treatment.

  (3) Examples 13 to 16 are examples in which crosslinking treatment by ultraviolet irradiation was performed. According to Examples 13-16, it turns out that the film | membrane which has a high elasticity modulus can be obtained similarly to the case where the bridge | crosslinking process by electron beam irradiation is performed.

  As described above, the insulating film obtained by the present invention is excellent in mechanical strength, has a low relative dielectric constant, and is excellent in processing resistance such as plasma resistance, and is therefore suitable as an interlayer insulating film for semiconductor elements and the like. Is clear.

  This is the end of the description of the present embodiment. The present invention is not limited to the above-described embodiments, and various modifications can be made. The present invention also includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same purposes and results). In addition, the present invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. Further, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (14)

The composition for insulating film formation containing the hydrolysis condensate obtained by hydrolytic condensation of the silane compound containing the compound 1 represented by following General formula (1), and an organic solvent.
^{_{R 1 a (R 2 O)}} 3-a Si-CH 2 -Si (OR 3) 3-b R 4 b ····· (1)
(In the formula, R ^{1 to} R ⁴ are the same or different and each represents a monovalent organic group, and a and b are the same or different and represent a number of 0 to 1.) In claim 1,
The composition for insulating film formation whose polymerization average molecular weights of the said hydrolysis-condensation product are 5,000-50,000. In claim 1 or 2,
In the hydrolysis condensation, the amount of the compound 1 used is 20 to 100% of the total amount of the silane compound. In any of claims 1 to 3,
The said silane compound is a composition for insulating film formation which further contains the compound 2 represented by following General formula (2).
R ⁵ _c Si (OR ⁶ ) _4-c (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 2 carbon atoms, a vinyl group, an allyl group, an acetyl group or a phenyl group, c represents an integer of 1 to 2, and R ⁶ represents an alkyl having 1 to 3 carbon atoms. Group, vinyl group, allyl group, acetyl group or phenyl group.) In claim 4,
The composition for insulating film formation whose molar ratio of the said compound 1 and the said compound 2 (compound 1: compound 2) is 20: 80-60: 40. In any of claims 1 to 5,
The composition for forming an insulating film, wherein the silane compound further comprises hydrolyzable polycarbosilane. In claim 6,
The composition for insulating film formation whose weight ratio (Compound 1: Hydrolyzable polycarbosilane) of the said compound 1 and the said hydrolyzable polycarbosilane is 40: 60-80: 20. In claim 6 or 7,
The hydrolyzable polycarbosilane is a composition for forming an insulating film having a structural unit represented by the following general formula (3).

(3)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group,, x, y, z are each 0 to 10,000 And the condition 5 <x + y + z <10,000 is satisfied.) In any of claims 1 to 3,
The silane compound further includes a compound 2 represented by the following general formula (2) and a compound 3 represented by the following general formula (3),
The composition for insulating film formation whose sum total of the usage-amount of the said compound 1 and the said compound 2 is 1-1000 mass parts with respect to the usage-amount of the said compound 3 100 mass parts.
R ⁵ _c Si (OR ⁶ ) _4-c (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 2 carbon atoms, a vinyl group, an allyl group, an acetyl group or a phenyl group, c represents an integer of 1 to 2, and R ⁶ represents an alkyl having 1 to 3 carbon atoms. Group, vinyl group, allyl group, acetyl group or phenyl group.)

(3)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group,, x, y, z are each 0 to 10,000 And the condition 5 <x + y + z <10,000 is satisfied.) In any one of Claim 1 thru | or 9,
An insulating film forming composition further comprising a pore forming agent.   A method for forming an insulating film, comprising the steps of applying the composition for forming an insulating film according to claim 1 to a substrate and heating the substrate. In claim 11,
The method for forming an insulating film includes a step of irradiating a high energy ray under heating in the heating step. In claim 12,
The method for forming an insulating film, wherein the high energy beam is at least one selected from an electron beam and an ultraviolet ray.   An insulating film obtained by the method for forming an insulating film according to claim 11.