JP2007262256A - POLYMER AND METHOD FOR PRODUCING SAME, COMPOSITION FOR FORMING INSULATING FILM, METHOD FOR PRODUCING INSULATING FILM, AND SILICA BASED INSULATING FILM - Google Patents

Abstract

・・・・・（１）
【選択図】なし
[PROBLEMS] To provide a polymer capable of forming an insulating film having a low relative dielectric constant and excellent in CMP resistance and chemical solution resistance, a method for producing the same, a composition for forming an insulating film, a method for producing the insulating film, and silica-based insulation Providing a membrane.
(A) At least one silane compound represented by the following general formula (1), (B) a compound represented by the following general formula (2), and the following general formula (3) Co-condensation of at least one silane compound selected from the compounds in the presence of at least one of (C) a metal chelate compound or an acid catalyst.
[Chemical 1]

(1)
[Selection figure] None

Description

  The present invention relates to a polymer and a method for producing the same, a composition for forming an insulating film, a method for producing an insulating film, and a silica-based insulating film.

Conventionally, silica (SiO ₂ ) formed by a vacuum process such as a CVD (Chemical Vapor Deposition) method as an interlayer insulating film (Japanese Patent Laid-Open Nos. 5-263045 and 5-315319) used for a semiconductor element or the like. Membranes are frequently used. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant called polyorganosiloxane called organic SOG has been developed (Japanese Patent Laid-Open Nos. 11-340219 and 11-11). No. 340220).
In particular, with further higher integration and multi-layering of semiconductor elements and the like, further improvement in electrical insulation between conductors is required. Therefore, an interlayer insulating film material having a lower relative dielectric constant and excellent mechanical strength is required. It has come to be required.

Furthermore, in recent semiconductor device manufacturing processes, a CMP (Chemical Mechanical Polishing) process is used for the purpose of planarization. Therefore, high CMP resistance is required for the insulating film material. In the manufacturing process of a semiconductor device, cleaning is performed after etching of an interlayer insulating film or ashing of a resist, and a chemical such as dilute hydrofluoric acid is used in this cleaning process. Therefore, high chemical resistance is required for the insulating film material.
It is known that the higher the carbon content in the silica material, the better the mechanical and chemical resistance in the CMP process, etching, and ashing process. Therefore, development of materials with high carbon content such as polycarbosilane (Japanese Patent Laid-Open No. 2001-127152). Recently, materials having an improved carbon content by condensation with hydrolyzable group-containing silane compounds and cyclic silane compounds have been developed, and their resistance has been improved over conventional polyorganosiloxane materials. However, when this cyclic silane compound is used, the ratio of the carbon amount can be increased dramatically theoretically, but in practice it is not always easy to introduce a large amount of cyclic silane compound, and if the ratio is increased too much However, the increase in the number of unreacted silanol sites increases the hygroscopicity and increases the dielectric constant. It is also known that the mechanical strength decreases by increasing the proportion of polycarbosilane.
JP-A-5-263045 JP-A-5-315319 Japanese Patent Laid-Open No. 11-340219 Japanese Patent Laid-Open No. 11-340220 JP 2001-127152 A

  An object of the present invention is to provide a polymer having a low relative dielectric constant and excellent CMP resistance and chemical resistance, a method for producing the same, a composition for forming an insulating film, a method for producing an insulating film, and a silica-based insulating film.

The composition for forming an insulating film of a polymer according to the first aspect of the present invention comprises:
(A) at least one silane compound represented by the following general formula (1), (B) a compound represented by the following general formula (2) and a compound represented by the following general formula (3) And (C) a polymer obtained by cocondensation in the presence of at least one of a metal chelate compound or an acid catalyst, and an organic solvent.

・・・・・（１）
（式中、ＲおよびＲ^１〜Ｒ^３は同一または異なり、アルキル基、アルケニル基、アルキニル基またはアリール基を示し、Ｘはハロゲン原子、ヒドロキシ基、アルコキシ基、またはアシロキシ基を示し、ｎは０〜２の整数を示す。）
（Ｂ）は、下記一般式（２）で表される化合物および下記一般式（３）で表される化合物の群から選ばれた少なくとも１種のシラン化合物である。
Ｒ^４ _ａＳｉＸ’_４−ａ ・・・・・（２）
（式中、Ｒ^４は水素原子、アルキル基、アルケニル基、アルキニル基またはアリール基、Ｘ‘はハロゲン原子あるいはアルコキシル基、ａは０〜３の整数を示す。）
Ｒ^５ _ｂＹ’_３−ｂＳｉ−（Ｒ^７）_ｄ−ＳｉＺ’_３−ｃＲ^６ _ｃ ・・・・・（３）
〔式中、Ｒ^５，Ｒ^６は同一または異なり、それぞれ水素原子、フッ素原子、アルキル基、アルケニル基、アルキニル基またはアリール基、ｂおよびｃは同一または異なり、０〜２の整数、Ｒ^７は酸素原子，フェニレン基または−（ＣＨ_２）_ｅ−で表される基（ここで、ｅは１〜６の整数である）、Ｙ’およびＺ’は同一または異なり、ハロゲン原子またはアルコキシル基、ヒドロキシ基、アシロキシ基を示す。ｄは０または１を示す。〕

(1)
Wherein R and R ^{1 to} R ³ are the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X represents a halogen atom, a hydroxy group, an alkoxy group or an acyloxy group, and n is 0 Represents an integer of ~ 2)
(B) is at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
R ⁴ _a SiX ′ _4-a (2)
(Wherein R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X ′ represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 5 b Y '3-b}} Si- (R 7) d -SiZ' 3-c R 6 c ····· (3)
[In the formula, R ⁵ and R ⁶ are the same or different, respectively, a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, b and c are the same or different, an integer of 0 to 2, and R ⁷ is An oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _e — (wherein e is an integer of 1 to 6), Y ′ and Z ′ are the same or different, a halogen atom or an alkoxyl group, a hydroxy group Group represents an acyloxy group. d represents 0 or 1; ]

The method for producing the polymer according to the second aspect of the present invention includes:
(A) at least one silane compound represented by the following general formula (1), (B) a compound represented by the following general formula (2) and a compound represented by the following general formula (3) A method for producing a polymer obtained by co-condensing at least one silane compound in the presence of at least one of (C) a metal chelate compound or an acid catalyst.

・・・・・（１）
（式中、ＲおよびＲ^１〜Ｒ^３は同一または異なり、アルキル基、アルケニル基、アルキニル基またはアリール基を示し、Ｘはハロゲン原子、ヒドロキシ基、アルコキシ基、またはアシロキシ基を示し、ｎは０〜２の整数を示す。）
（Ｂ）は、下記一般式（２）で表される化合物および下記一般式（３）で表される化合物の群から選ばれた少なくとも１種のシラン化合物である。
Ｒ^４ _ａＳｉＸ’_４−ａ ・・・・・（２）
（式中、Ｒ^４は水素原子、アルキル基、アルケニル基、アルキニル基またはアリール基、Ｘ‘はハロゲン原子あるいはアルコキシル基、ａは０〜３の整数を示す。）
Ｒ^５ _ｂＹ’_３−ｂＳｉ−（Ｒ^７）_ｄ−ＳｉＺ’_３−ｃＲ^６ _ｃ ・・・・・（３）
〔式中、Ｒ^５，Ｒ^６は同一または異なり、それぞれ水素原子、フッ素原子、アルキル基、アルケニル基、アルキニル基またはアリール基、ｂおよびｃは同一または異なり、０〜２の整数、Ｒ^７は酸素原子，フェニレン基または−（ＣＨ_２）_ｅ−で表される基（ここで、ｅは１〜６の整数である）、Ｙ’およびＺ’は同一または異なり、ハロゲン原子またはアルコキシル基、ヒドロキシ基、アシロキシ基を示す。ｄは０または１を示す。〕
前記ポリマーの製造方法において、前記（Ｃ）成分が、下記一般式（４）で示される金属キレート化合物であることができる。
Ｒ^８ _ｈＭ（ＯＲ^９）_ｊ−ｈ ・・・・・（４）
（Ｒ^８はキレート剤を示し、Ｍは金属原子を示し、Ｒ^９はアルキル基またはアリール基を示し、ｊは金属Ｍの原子価を示し、ｈは１〜ｊの整数を表す。）

(1)
Wherein R and R ^{1 to} R ³ are the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X represents a halogen atom, a hydroxy group, an alkoxy group or an acyloxy group, and n is 0 Represents an integer of ~ 2)
(B) is at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
R ⁴ _a SiX ′ _4-a (2)
(Wherein R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X ′ represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 5 b Y '3-b}} Si- (R 7) d -SiZ' 3-c R 6 c ····· (3)
[In the formula, R ⁵ and R ⁶ are the same or different, respectively, a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, b and c are the same or different, an integer of 0 to 2, and R ⁷ is An oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _e — (wherein e is an integer of 1 to 6), Y ′ and Z ′ are the same or different, a halogen atom or an alkoxyl group, a hydroxy group Group represents an acyloxy group. d represents 0 or 1; ]
In the method for producing the polymer, the component (C) may be a metal chelate compound represented by the following general formula (4).
R ⁸ _h M (OR ⁹ ) _j-h (4)
(R ⁸ represents a chelating agent, M represents a metal atom, R ⁹ represents an alkyl group or an aryl group, j represents a valence of the metal M, and h represents an integer of 1 to j.)

In the polymer production method, the component (C) may be at least one compound selected from the group consisting of a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and an organic carboxylic acid.

In the manufacturing method of the said polymer, it can carry out in the organic solvent represented by following General formula (5).
R ¹⁰ O (CHCH ₃ CH ₂ O) _k R ¹¹ (5)
[R ¹⁰ and R ¹¹ 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 k represents an integer of 1 to 2. ]

The polymer of the third aspect of the present invention is obtained by the method for producing the polymer.
The manufacturing method of the insulating film of the 4th aspect of this invention includes apply | coating the said composition for insulating film formation to a board | substrate, and heating at 30-450 degreeC.
The insulating film manufacturing method according to the fifth aspect of the present invention includes applying the insulating film forming composition to a substrate and irradiating the substrate with high energy rays.
The silica type insulating film of the 6th aspect of this invention is obtained by the manufacturing method of the said insulating film.

According to the polymer production method, the carbon atom in the polymer is obtained by co-condensing the silane compound of the component (A) and the silane compound of the component (B) in the presence of the component (C). The content of can be further increased, and the content of unreacted silanol groups can be reduced. Therefore, by forming an insulating film using the polymer obtained by the above manufacturing method, a film having low hygroscopicity can be obtained, so that the relative dielectric constant is low and the mechanical strength, CMP resistance, and chemical resistance ( For example, an insulating film excellent in resistance to wet etching using a chemical solution can be formed.

  Hereinafter, a polymer and a manufacturing method thereof, a composition for forming an insulating film, a manufacturing method of an insulating film, and a silica-based insulating film according to an embodiment of the present invention will be described.

1. Polymer and production method thereof The production method of a polymer according to an embodiment of the present invention includes:
(A) at least one silane compound represented by the following general formula (1) (hereinafter also referred to as “component (A)”), (B) a compound represented by the following general formula (2), and At least one silane compound selected from the compound represented by the general formula (3) (hereinafter also referred to as “component (B)”) is used as (C) at least one of a metal chelate compound and an acid catalyst (hereinafter referred to as “component (B)”). And co-condensation in the presence of “(C) component”).

・・・・・（１）
（式中、ＲおよびＲ^１〜Ｒ^３は同一または異なり、アルキル基、アルケニル基、アルキニル基またはアリール基を示し、Ｘはハロゲン原子、ヒドロキシ基、アルコキシ基、またはアシロキシ基を示し、ｎは０〜２の整数を示す。）

(1)
Wherein R and R ^{1 to} R ³ are the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X represents a halogen atom, a hydroxy group, an alkoxy group or an acyloxy group, and n is 0 Represents an integer of ~ 2)

(B) is at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
R ⁴ _a SiX ′ _4-a (2)
(Wherein R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X ′ represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 5 b Y '3-b}} Si- (R 7) d -SiZ' 3-c R 6 c ····· (3)
[In the formula, R ⁵ and R ⁶ are the same or different, respectively, a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, b and c are the same or different, an integer of 0 to 2, and R ⁷ is An oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _e — (wherein e is an integer of 1 to 6), Y ′ and Z ′ are the same or different, a halogen atom or an alkoxyl group, a hydroxy group Group represents an acyloxy group. d represents 0 or 1; ]

(A) component and (B) component can each be used 1 type or in combination of 2 or more types.
Hereinafter, each component used for manufacture of the polymer which concerns on one Embodiment of this invention is each demonstrated.

1.1. Component (A) The component (A) is at least one silane compound represented by the general formula (1).
In the general formula (1), examples of the alkyl group represented by R and R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, and a butyl group, preferably having 1 to 5 carbon atoms. These alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group. Examples of the alkynyl group include an enityl group, a propargyl group, a 3-butynyl group, a 3-pentynyl group, and a 3-hexynyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Among these, as R and ^R 1 to R ^3, an alkyl group, a phenyl group, or an alkenyl group.

  In the general formula (1), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, A propyloxy group and a butyloxy group can be mentioned. The acyloxy group is a monovalent atomic group in which an acyl group is bonded to oxygen, and examples thereof include an acetyloxy group, a trifluoroacetyloxy group, a benzoyloxy group, and an isobutyryloxy group.

(A) A component can be used individually or in combination of 2 or more types.
Specific examples of the component (A) include the following (i) to (iii).
(I) A silane compound in which n is 0 in the general formula (1). Specifically, the following silane compounds can be mentioned.

(Ii) A silane compound in which n is 1 in the general formula (1). Specifically, the following silane compounds can be mentioned.

  (Iii) A silane compound wherein n is 2 in the general formula (1). Specifically, the following silane compounds can be mentioned.

1.2. (B) component (B) A component is a hydrolysable group containing silane compound. (B) The hydrolyzable group-containing silane compound includes a compound represented by the following general formula (2) (hereinafter referred to as “compound 1”) and a compound represented by the following general formula (3) (hereinafter referred to as “compound 2”). At least one silane compound selected from.
R ⁴ _a SiX ′ _4-a (2)
(In the formula, R ⁴ represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, X ′ represents a halogen atom or an alkoxy group, and a represents an integer of 0 to 3. )
_{^{R 5 b Y '3-b}} Si- (R 7) d -SiZ' 3-c R 6 c ····· (3)
[Wherein, R ⁵ and R ⁶ are the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, b and c are the same or different, each represents an integer of 0 to 2, and R ⁷ represents an oxygen atom] , A phenylene group, or a group represented by — (CH ₂ ) _x — (wherein x is an integer of 1 to 6), Y ′ and Z ′ are the same or different and are a halogen atom or an alkoxy group. D represents 0 or 1. ]

In the general formula (2) and the general formula (3), examples of the alkyl group, alkenyl group, alkynyl group, and aryl group represented by R ^{4 to} R ⁶ include R and R ¹ in the general formula (1). To R ³ can be used, and as the halogen atom and alkoxy group represented by X ′, Y ′ and Z ′, those exemplified as X in the general formula (1) can be used. .
Examples of compound 1 and compound 2 include the following.

(I) Compound 1
Specific examples of the compound 1 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, diphenyldiphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane , Tetraphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, And vinyltriphenoxysilane. Compound 1 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. Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane.
In the production of the polymer, compound (B) preferably contains compound 1, and the proportion is preferably 30 to 100 mol%, more preferably 50 to 100 mol%.

(Ii) Compound 2
In the general formula (3), examples of R ⁵ and R ⁶ include the same groups as those exemplified as R and R ^{1 to} R ^{3 in the} general formula (1).
As the compound 3 in which d = 0 in the general formula (3), 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.

  In addition, as the compound 3 in which d = 1 in the general formula (3), bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-iso-) Propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri-iso-propoxysilyl) ethane, 1,2-bis (tri- n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri-tert-butoxy) L) 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- (diethoxymethylsilyl) 2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso-propoxymethylsilyl) -2- (tri -Iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-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-butoxymethylsilyl) ) Methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ) Ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (Triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-iso-propoxysilyl) , 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) benzene, , 4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis ( And tri-tert-butoxysilyl) benzene.

  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. Compound 2 may be used alone or in combination of two or more.

  In the polymer production method, the ratio of the component (B) to the total amount of the components (A) and (B) is 10 to 2000 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). More preferably, it is 50-1000 weight part. When the ratio of the component (B) is 10 to 2000 parts by weight with respect to 100 parts by weight of the component (A), a polymer capable of forming an insulating film having excellent mechanical strength and low relative dielectric constant can be obtained. .

1.3. Metal Chelate Catalyst The metal chelate catalyst is preferably a compound represented by the following general formula (4).
R ⁸ _h M (OR ⁹ ) _j-h (4)
(R ⁸ represents a chelating agent, M represents a metal atom, R ⁹ represents an alkyl group or an aryl group, j represents a valence of the metal M, and h represents an integer of 1 to j.)
In the general formula (4), examples of the chelating agent represented by R ⁸ include acetylacetonate and ethylacetoacetate. Examples of the metal represented by M include titanium, zirconium, and aluminum. In addition, as the alkyl group or aryl group represented by R ⁹ , for example, those exemplified as the alkyl group or aryl group represented by R and R ^{1 to} R ³ in the general formula (1) may be used. it can.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy bi (Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n- Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy-mono ( Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri- se -Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di -I-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl) Acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy Tris (ethylacetoa Cetate) titanium, mono-sec-butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonato) tris (ethylacetate) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;
Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n- Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) Zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum;
And so on. These metal chelate compounds may be used alone or in combination of two or more. Of these, titanium chelate compounds are particularly preferred.
The amount of the metal chelate catalyst used is usually 0.0001 to 1 mol, preferably 1 mol per 1 mol of the total amount of substituents X, X ′, Y ′ and Z ′ contained in the component (A) and component (B). 0.0005 to 0.1 mol.

1.4.2. Acidic catalyst Examples of the acidic catalyst include inorganic acids and organic acids, with organic acids being more preferred, and organic carboxylic acids being even more preferred. One or two or more acidic catalysts may be used at the same time.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and the like.

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, mikimic 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, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, anhydrous Hydrolysates of barrel acid.
Among these, the addition of acetic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid, maleic anhydride A decomposition product is particularly preferred.

  The amount of the acidic catalyst used is usually 0.0001 to 1 mol, preferably 0 with respect to 1 mol of the total amount of substituents X, X ′, Y ′ and Z ′ contained in the component (A) and component (B). .0005 to 0.1 mol. If the amount of the catalyst used is within the above range, the possibility of polymer precipitation or gelation during the reaction is small. Moreover, the temperature at the time of hydrolyzing the compounds 1-3 is 0-100 degreeC normally, Preferably it is 15-80 degreeC.

1.5. Organic Solvent In the production of the polymer, co-condensation of the component (A) and the component (B) can be performed in an organic solvent. Here, as an organic solvent, it is preferable to use the solvent represented by the following general formula (5) alone or in combination with another solvent among organic solvents described later.
R ¹⁰ O (CHCH ₃ CH ₂ O) _γ R ¹¹ (5)
[R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a C 1-4 alkyl group or a monovalent organic group selected from CH ₃ CO—, and γ represents an integer of 1 to 2. ]
In the general formula (5), examples of the alkyl group having 1 to 4 carbon atoms include the same as those shown as the alkyl group in the general formula (1).

  Specific examples of the organic solvent represented by the general formula (5) 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 organic solvent represented by the general formula (7), other solvents such as ester solvents and amide solvents may be included to some extent.

Content of the carbon atom in the polymer obtained by the said manufacturing method is 12-35 atomic%. When the content of carbon atoms in the polymer is less than 12 atomic%, the CMP resistance and chemical resistance are low. On the other hand, when the content of carbon atoms in the polymer is more than 35 atomic%, the mobility of the molecule is too high. , The elastic modulus is low, and in some cases, the film exhibits a glass transition point, which is not preferable. The carbon atom content (atomic%) is such that the hydrolyzable groups contained in the components (A) and (B) are completely hydrolyzed to form silanol groups, and the generated silanol groups are completely condensed. It is calculated | required from the elemental composition at the time of forming a siloxane bond, and is specifically calculated | required from the following formula | equation.
Carbon atom content (%) = (number of carbon atoms in polymer) / (total number of atoms in polymer) × 100

2. Composition for Forming Insulating Film A composition for forming an insulating film according to an embodiment of the present invention (hereinafter, also simply referred to as “film forming composition”) contains a polymer obtained by the production method and an organic solvent. To do.
The total solid concentration of the film-forming composition according to one embodiment of the present invention is preferably 0.1 to 20% by weight, 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 weight, the film thickness of the coating film is in an appropriate range and has better storage stability. It will be a thing. The total solid content concentration is adjusted by concentration and dilution with an organic solvent, if necessary.

2.1. Organic solvent Examples of the organic solvent that can be used in the film forming composition according to an embodiment of the present invention include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and aliphatic carbonization. Examples thereof include at least one selected from the group consisting of hydrogen solvents, aromatic 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, 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- Examples thereof include aliphatic hydrocarbon solvents such as octane, cyclohexane, and methylcyclohexane. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-propyl. Aromatic hydrocarbon solvents such as benzene, n-amylnaphthalene, and trimethylbenzene can be listed. 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 one embodiment of 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. Further, it is desirable to use one or more of them at the same time.

2.2. Other Additives A film-forming composition according to an embodiment of the present invention includes an organic polymer (hereinafter referred to as “other organic polymer”) different from the polymer obtained by the production method, a surfactant, You may further contain components, such as 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 according to one embodiment of the present invention is produced.

2.2.1. Other organic polymers Other organic polymers that can be used in the film-forming composition according to an embodiment of the present invention include, for example, compounds having a sugar chain structure, vinylamide polymers, (meth) acrylic polymers, aromatics. Group vinyl compounds, dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, polyquinoxalines, polyoxadiazoles, fluoropolymers, compounds having a polyalkylene oxide structure, and the like.
Examples of the compound 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.
− (P) _j − (Q) _k −
− (P) _j − (Q) _k − (P) ₁ −
(In the formula, P represents a group represented by —CH ₂ CH ₂ O—, Q represents a group represented by —CH ₂ CH (CH ₃ ) O—, j represents 1 to 90, and k represents 10 to 10). 99 and l are numbers 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. These may be used alone or in combination of two or more.

Another organic polymer can be added as an easily decomposable component for forming pores in the silica-based insulating film. The addition of such an organic polymer is disclosed in JP 2000-290590, JP 2000-313612, Hedrick, J. et al. L. , Et al. “Templating Nanoporosity in Thin Film Dielectric Insulators” Adv. Mater. , 10 (13), 1049, 1998. And similar organic polymers may be added.

2.2.2. Surfactant Examples of the surfactant that can be used in the film forming composition according to an embodiment of the present invention include, for example, nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Furthermore, fluorine surfactants, silicone surfactants, polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned, preferably fluorine surfactants Agents and silicone surfactants.

  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.
2.2.3. Silane coupling agent

  Examples of the silane coupling agent that can be used in the film forming composition according to an embodiment of the present invention include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, and 3-methacrylic acid. Loxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3 -Uray Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl- 3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3 -Aminopro Le triethoxysilane, N- bis (oxyethylene) -3-aminopropyltrimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. These may be used alone or in combination of two or more.

3. Method for Manufacturing Insulating Film A method for manufacturing an insulating film according to an embodiment of the present invention includes applying the film forming composition according to the embodiment of the present invention to a substrate and heating to 30 to 450 ° C. .
When the film-forming composition according to one embodiment of the present invention is applied to a substrate such as a silicon wafer, a SiO ₂ wafer, or a SiN wafer, the coating such as spin coating, dipping method, roll coating method, spray method, etc. Means are used.

The thickness of the insulating film according to an embodiment of the present invention is about 0.05 to 2.5 μm in thickness when applied once, and about 0.1 to 5.0 μm in thickness when applied twice. A coating film can be formed. Thereafter, it is dried at room temperature, or usually 30 to 500 ° C., preferably 30 to 450 ° C., more preferably 60 to 430 ° C. Alternatively, a coating film of a large polymer can be formed.
As a heating method at this time, for example, a hot plate, an oven, a furnace, or the like can be used. As a heating atmosphere, for example, the atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, or a reduced pressure with a controlled oxygen concentration. Etc.
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.

In addition, the film forming composition according to one embodiment of the present invention may be applied to a substrate, and an insulating film may be formed under irradiation of high energy rays (for example, electron beams and ultraviolet rays). Alternatively, the film-forming composition according to one embodiment of the present invention is applied to a substrate and heated to usually 25 to 500 ° C., preferably 30 to 450 ° C., more preferably 60 to 430 ° C. under irradiation with high energy rays. Thus, an insulating film may be formed.
The high energy ray can be at least one kind of high energy ray selected from electron beam, ultraviolet ray and X-ray. Below, the irradiation conditions at the time of using an electron beam as an example are described.

When the electron beam is irradiated, the acceleration voltage is 0.1 to 50 keV, preferably 1 to 30 keV. When the accelerating voltage is 0.1 to 50 keV, the electron beam penetrates the film and does not damage the lower semiconductor element, and the electron beam can sufficiently enter the coating film. Further, the electron beam irradiation amount is 1-1000 μC / cm ² , preferably 10-500 μC / cm ² . When the electron beam irradiation amount is 1-1000 μC / cm ² , the entire coating film is reacted, and damage to the coating film is reduced.

The substrate temperature at the time of electron beam irradiation is usually 25 to 500 ° C., preferably 30 to 450 ° C. Prior to the electron beam irradiation of the coating film, the substrate can be heated to 250 to 500 ° C., and the coating film of the present invention can be pre-cured and then irradiated with an electron beam. According to this method, it is possible and effective to reduce film thickness unevenness depending on the non-uniformity of the electron beam dose.

The electron beam irradiation is preferably performed in an atmosphere having an oxygen concentration of 10,000 ppm or less, preferably 1,000 ppm. Electron beam irradiation can also be performed in an inert gas atmosphere. Examples of the inert gas include N ₂ , He, Ar, Kr and Xe, preferably He and Ar. By performing the electron beam irradiation in an inert gas atmosphere, the film is hardly oxidized, and the low dielectric constant of the obtained coating film can be maintained.

The electron beam irradiation may be performed in a reduced pressure atmosphere, and the degree of reduced pressure is usually 1000 mTorr or less, preferably 1 to 200 mTorr. In addition, the time required for electron beam curing is about 1 to 5 minutes, which is much shorter than 15 minutes to 2 hours required for thermosetting, and electron beam irradiation is used for wafer single wafer processing. It can be said that it is suitable.

4). Silica Insulating Film A silica insulating film according to an embodiment of the present invention is obtained by the above insulating film manufacturing method.
The silica-based insulating film according to one embodiment of the present invention is excellent in mechanical strength, CMP resistance and chemical resistance, and has a low relative dielectric constant, as will be apparent from examples described later.
Specifically, the silica-based insulating film according to an embodiment of the present invention has a relative dielectric constant of 1.2 to 3.2, preferably 1.5 to 3.0, and more preferably 1.8. 2.7, and the film density is 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , more preferably 0.5 to 1.0 g / cm ^3. It is. When the film density is less than 0.35 g / cm ³ , the mechanical strength of the coating film decreases, and when it exceeds 1.2 g / cm ³ , a low relative dielectric constant cannot be obtained.

  The polymer film obtained by the present invention is characterized by having many silicon-carbon bonds in the film structure. This is derived from the monomer asymmetric silicon monomer, and the polymer obtained by the condensation of this asymmetric silicon monomer and siloxane has a constant dielectric constant due to its structural features. Can be obtained, and a polymer film excellent in mechanical strength, CMP resistance and chemical resistance can be obtained.

Since the polymer film of the present invention has a low relative dielectric constant and excellent mechanical strength, CMP resistance and chemical resistance, an interlayer insulating film for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM Useful for applications such as etching stopper films, protective films such as semiconductor element surface coat films, intermediate layers in semiconductor fabrication processes using multilayer resists, interlayer insulating films on multilayer wiring boards, protective films and insulating films for liquid crystal display elements It is.

5). 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 weight%, respectively, unless otherwise specified.
5.1. Synthesis Examples, Examples, and Comparative Examples Production of a polymer, production of a film-forming composition using the polymer, and formation of a silica-based insulating film were performed by the following methods.

5.1.1. Production method of polymer 5.1.1.1-1. Synthesis example 1
In a mixed solution of 10 g of 10% formic acid aqueous solution, 25 g of ultrapure water and 40 g of ethanol, 10.7 g of methyltriethoxysilane (5.3 g in terms of complete hydrolysis condensate) and 12.0 g of tetramethoxysilane (complete hydrolysis) Condensate conversion 4.7 g) was added and reacted at 60 ° C. for 2 hours to obtain a solution (B-1).
5.1.1-2. Synthesis example 2
10.7 g of methyltrimethoxysilane (5.3 g in terms of complete hydrolysis condensate) in a mixed solution of 0.65 g of tri-i-propoxy mono (acetylacetonate) titanium, 55.0 g of ultrapure water and 50 g of ethanol And 12.0 g of tetraethoxysilane (4.7 g in terms of complete hydrolysis condensate) were added and reacted at 60 ° C. for 3 hours to obtain a solution (B-2).

5.1.2. Method for producing film-forming composition 5.1.1.2-1. Example 1
After 2.5 g of (trimethylsilyl) methyltriethoxysilane (A-1) is added to 88.8 g of the polysiloxane solution (B-1) obtained in Synthesis Example 1, and reacted at 60 ° C. for 2 hours, propylene glycol 400 g of monoethyl ether was added and then concentrated under reduced pressure to a total solution amount of 214 g to obtain a film-forming composition (H-1) having a solid content of 10%.

5.1-2. Example 2
After adding 2.5 g of (trimethylsilyl) methyltriethoxysilane (A-1) to 128.35 g of the polysiloxane solution (B-2) obtained in Synthesis Example 2, the mixture is reacted at 60 ° C. for 2 hours, and then propylene glycol. 500 g of monoethyl ether was added, and then concentrated under reduced pressure to a total solution amount of 250 g to obtain a film-forming composition (H-2) having a solid content of 10%.

5.1.2-3. Example 3
In a mixed solution of 1.1 g of 10% formic acid aqueous solution, 26.8 g of ultrapure water and 80.1 g of ethanol, 13.3 g of methyltrimethoxysilane (6.5 g in terms of complete hydrolysis condensate) and 3.7 g of tetraethoxysilane (1.5 g of fully hydrolyzed condensate) and 2.5 g of (trimethylsilyl) methyltriethoxysilane (A-1) were added and reacted at 60 ° C. for 2 hours, and then 318 g of propylene glycol monoethyl ether was added. Then, it concentrated until it became the total solution amount of 96 g under reduced pressure, and the composition for film formation (H-3) with a solid content of 10% was obtained.

5.1.2-4. Comparative Example 1
In a mixed solution of 1.1 g of 10% formic acid aqueous solution, 23.2 g of ultrapure water and 86.9 g of ethanol, 5.0 g of methyltrimethoxysilane (2.47 g in terms of complete hydrolysis condensate) and 10.0 g of tetraethoxysilane (3.95 g in terms of complete hydrolysis condensate) was added and reacted at 60 ° C. for 2 hours, then 200 g of propylene glycol monoethyl ether was added, and then concentrated under reduced pressure to a total solution amount of 62 g. A film-forming composition (H-4) having a content of 10% was obtained.

5.1.2-5. Comparative Example 2
A commercially available polycarbosilane (“NIPUSI Type-S”, manufactured by Nippon Carbon Co., Ltd., carbosilanized polymer of polydimethylsilane) is mixed in a propylene glycol monoethyl ether: cyclohexanone = 50: 50 (weight ratio) mixed solution with a solid content. It melt | dissolved so that content might be 10%, and obtained the composition solution (H-5). Next, the film-forming composition (H-4) obtained in Comparative Example 1 and the composition solution (H-5) were (H-4) :( H-5) = 90: 10 (weight ratio). By mixing, a film-forming composition (H-6) was obtained.

5.1.2-6. Comparative Example 3
In a mixed solution of 1.1 g of 10% formic acid aqueous solution, 21.8 g of ultrapure water and 86.1 g of ethanol, 8.0 g of methyltrimethoxysilane (4.0 g in terms of complete hydrolysis condensate) and 8.0 g of tetraethoxysilane (2.3 g of fully hydrolyzed condensate) and 0.85 g of 1,3-dimethyl-1,3-dimethoxy-1,3-disilacyclobutane were added and reacted at 60 ° C. for 2 hours. 218 g of glycol monoethyl ether was added, and then concentrated under reduced pressure to a total solution amount of 62 g to obtain a film-forming composition (H-7) having a solid content of 10%.

5.1.2-7. Examples 4, 5, 6 and Comparative Examples 4, 5, 6
The obtained film-forming compositions (H-1), (H-2), (H-3), (H-4), (H-5), (H-6), and (H-7) were respectively spin-coated. After coating on an 8-inch silicon wafer, the substrate is dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, and further on the hot plate in a nitrogen atmosphere at 400 ° C. for 60 minutes. Was fired to obtain a coating film having a thickness of 0.5 μm. The polymer film obtained after firing (hereinafter referred to as “silica-based insulating film”) was evaluated according to the evaluation method of 5.2 below. The evaluation results are shown in Table 1.

5.1.2-8. Examples 7, 8, and 9
The film-forming compositions (H-1), (H-2), and (H-3) were each applied onto an 8-inch silicon wafer using a spin coating method to obtain a coating film having a thickness of 0.5 μm. . Using a hot plate, the substrate was heated in a nitrogen atmosphere at 90 ° C. for 3 minutes and then at 200 ° C. for 3 minutes. Thereafter, the coating film was irradiated with an electron beam under the conditions of an acceleration voltage of 5 keV, an irradiation amount of 100 uC / m ² , an HP temperature of 100 ° C., a pressure of 1.33 Pa, and an atmospheric gas He. The coating film obtained after electron beam irradiation was evaluated according to the evaluation method of 5.2 below. The evaluation results are shown in Table 1.

5.2. Evaluation method 5.1.2. And the polymer obtained in 5.1.2. Various evaluations on the silica-based insulating film obtained in the above were performed by the following methods.

5.2.1. Dielectric constant of silica-based insulating film, Δk
Sample for measuring relative permittivity by forming an aluminum electrode pattern on a silica-based insulating 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. It was created. The relative dielectric constant of the silica-based insulating film was measured for the sample at a frequency of 100 kHz by the CV method using an HP 16451B electrode and an HP4284A precision LCR meter manufactured by Argent.
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, when Δk is 0.20 or more, it can be said that the silica-based insulating film has high hygroscopicity.

5.2.2. Mechanical strength (elastic modulus / hardness) of silica-based insulating film
For the silica-based insulating film formed by the method described above, a Berkovich indenter is attached to Nanoindenter XP (manufactured by Nanoinstrument), and the mechanical strength (elastic modulus and universal hardness) is measured by the continuous stiffness measurement method. did.

5.2.3. CMP Resistance The silica-based insulating film formed by the above method was polished under the following conditions.
Slurry: Silica-hydrogen peroxide system Polishing pressure: 280 g / cm ²
Polishing time: 200 seconds The appearance of the film after CMP was observed with a light source of 350,000 lux and evaluated according to the following criteria.
○: No change.
X: Scratches and peeling are confirmed on the film.

5.2.4. Chemical resistance of silica-based insulating film An 8-inch wafer with a polymer film formed is immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 3 minutes, and the silica-based insulating film formed by the above method is immersed. The film thickness change before and after was observed. If the remaining film rate defined below is 99% or more, it can be determined that the chemical resistance is good.
Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100

5.2.5. Confirmation of presence / absence of phase separation of membrane For the silica-based insulating film formed by the above method, the silica-based insulating film is processed by a focused ion beam method so that the cross-section of the film can be observed, and 18,000 times using TEM The cross-sectional shape of the film was observed. The judgment results are shown as follows.
○: A uniform film is obtained.
X: Sea-island domain phase separation is confirmed in the membrane.

5.3. Evaluation Results The silica-based insulating films obtained in Examples 1 to 6 had good CMP resistance and chemical resistance residual film ratio, and Δk, which is a measure of hygroscopicity, was also an appropriate value. The domain phase separation structure that deteriorates the film properties was not observed even by TEM observation.
In contrast, in Comparative Examples 1 and 2, the CMP resistance and chemical resistance residual film rate deteriorated. In Comparative Example 3, the chemical solution-resistant residual film rate deteriorated.

As is clear from the above examples, by using the method for producing a polymer of the present invention to form a polymer, and using an insulating film forming composition containing the polymer, the relative dielectric constant is low, and It is possible to form a silica-based insulating film having excellent CMP resistance and chemical solution resistance. Therefore, the silica-based insulating film of the present invention is excellent in CMP resistance and chemical solution resistance and has a low relative dielectric constant, and can be suitably used as an interlayer insulating film of a semiconductor device.

Claims (9)

(A) at least one silane compound represented by the following general formula (1), (B) a compound represented by the following general formula (2) and a compound represented by the following general formula (3) An insulating film-forming composition comprising: (C) a polymer obtained by cocondensing at least one silane compound in the presence of at least one of a metal chelate compound or an acid catalyst; and an organic solvent.

(1)
Wherein R and R ^{1 to} R ³ are the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X represents a halogen atom, a hydroxy group, an alkoxy group or an acyloxy group, and n is 0 Represents an integer of ~ 2)
(B) is at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
R ⁴ _a SiX ′ _4-a (2)
(Wherein R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X ′ represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 5 b Y '3-b}} Si- (R 7) d -SiZ' 3-c R 6 c ····· (3)
[In the formula, R ⁵ and R ⁶ are the same or different, respectively, a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, b and c are the same or different, an integer of 0 to 2, and R ⁷ is An oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _e — (wherein e is an integer of 1 to 6), Y ′ and Z ′ are the same or different, a halogen atom or an alkoxyl group, a hydroxy group Group represents an acyloxy group. d represents 0 or 1; ] (A) at least one silane compound represented by the following general formula (1), (B) a compound represented by the following general formula (2) and a compound represented by the following general formula (3) A method for producing a polymer obtained by co-condensing at least one silane compound in the presence of at least one of (C) a metal chelate compound or an acid catalyst.

(1)
Wherein R and R ^{1 to} R ³ are the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X represents a halogen atom, a hydroxy group, an alkoxy group or an acyloxy group, and n is 0 Represents an integer of ~ 2)
(B) is at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
R ⁴ _a SiX ′ _4-a (2)
(Wherein R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, X ′ represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 5 b Y '3-b}} Si- (R 7) d -SiZ' 3-c R 6 c ····· (3)
^Wherein, R 5, ^{R 6} are the same or different, each represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, b and c are the same or different, an integer of 0 to 2, ^{R 7} is An oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _e — (wherein e is an integer of 1 to 6), Y ′ and Z ′ are the same or different, a halogen atom or an alkoxyl group, a hydroxy group Group represents an acyloxy group. d represents 0 or 1; ] The method for producing a polymer according to claim 2, wherein the component (C) is a metal chelate compound represented by the following general formula (4).
R ⁸ _h M (OR ⁹ ) _j-h (4)
(R ⁸ represents a chelating agent, M represents a metal atom, R ⁹ represents an alkyl group or an aryl group, j represents a valence of the metal M, and h represents an integer of 1 to j.)   4. The method for producing a polymer according to claim 3, wherein the metal chelate compound is at least one compound selected from the group consisting of a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and an organic carboxylic acid. In claim 2,
A method for producing a polymer, wherein the cocondensation is performed in an organic solvent represented by the following general formula (5).
R ¹⁰ O (CHCH ₃ CH ₂ O) _k R ¹¹ (5)
[R ¹⁰ and R ¹¹ 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 k represents an integer of 1 to 2. ]   A polymer obtained by the method for producing a polymer according to any one of claims 2 to 5.   The manufacturing method of an insulating film including apply | coating the composition for insulating film formation of Claim 1 to a board | substrate, and heating to 30-450 degreeC.   The manufacturing method of an insulating film including apply | coating the composition for insulating film formation of Claim 1 to a board | substrate, and irradiating a high energy ray. A silica-based insulating film obtained by the method for manufacturing an insulating film according to claim 7 or 8.