JP5099302B2 - Composition for forming insulating film, polymer and method for producing the same, method for producing insulating film, and silica-based insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer capable of forming an electrical insulation film with low water-adsorbing tendency and dielectric constant, high etching resistance and chemical liquid resistance and high mechanical strength; to provide a method for producing the polymer; to provide an electrical insulation film-forming composition containing the polymer; to provide a method for producing such electrical insulation film; and to provide silica-based electrical insulation film. <P>SOLUTION: The electrical insulation film-forming composition comprises the polymer obtained by co-condensation between (A) at least one silane monomer of the general formula(1), (B) a hydrolysable group-containing silane monomer and (C) a hydrolysable group-containing carbosilane in the presence of a basic catalyst and an organic solvent. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

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

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

  In particular, with further higher integration and 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.

  Therefore, for example, JP-A-6-181201 discloses a coating composition for forming an insulating film having a lower relative dielectric constant as an interlayer insulating film material. This coating-type composition is intended to provide an insulating film of a semiconductor device having low water absorption and excellent crack resistance, and has a constitution of at least one selected from titanium, zirconium, niobium and tantalum. The main component is an oligomer having a number average molecular weight of 500 or more obtained by polycondensing an organometallic compound containing an element and an organosilicon compound having at least one alkoxy group in the molecule.

  In addition, International Publication No. WO96 / 00758 pamphlet is used for forming an interlayer insulating film of a multilayer wiring board, and is capable of thick film coating composed of alkoxysilanes, metal alkoxides other than silane and organic solvents, and the like. A silica-based coating-type insulating film forming material having excellent oxygen plasma resistance is disclosed.

  Further, JP-A-3-20377 discloses a coating solution for forming an oxide film useful as a surface flattening of an electronic component or the like, an interlayer insulating film or the like. This coating solution for forming an oxide film is a uniform coating solution without generation of a gel-like material, and by using this coating solution, even when it is cured at high temperature or treated with oxygen plasma, A good oxide film without cracks can be obtained. The composition of this coating solution is a coating solution for forming an oxide film obtained by hydrolyzing and polymerizing a predetermined silane compound and a predetermined chelate compound in the presence of an organic solvent.

  However, as described above, when a metal chelate compound such as titanium or zirconium is combined with a silane compound, the mechanical properties and crack resistance of the coating film, the storage stability of the solution, the low dielectric constant of the coating film, etc. are well balanced. Difficult to achieve.

On the other hand, the present applicant is used for a film-forming composition for solving the above-mentioned problems, and semiconductor elements, etc., and has excellent mechanical properties, crack resistance, and adhesion with TaN. A method for providing an interlayer insulating film which is excellent and exhibits a low relative dielectric constant is disclosed (Japanese Patent Laid-Open No. 2001-335748). However, when an insulating film is formed using a polymer obtained from this composition, an insulating film having a high carbon atom content that is resistant to various processing steps (etching, chemical cleaning) and the like in semiconductor circuit manufacturing is obtained. May not be possible. Even if a polysiloxane having a high carbon atom content can be synthesized using the above method, the degree of condensation of silanol groups produced by hydrolysis of alkoxysilane and the like is reduced, and water is easily adsorbed. In some cases, only an insulating film in a state can be obtained. Such an insulating film having a high water adsorptivity is known to be inferior in resistance to etching and cleaning chemicals. That is, even if the carbon atom content in the polymer is increased by using the above method, the etching resistance and the chemical resistance are offset by increasing the water adsorbability.
Japanese Patent Laid-Open No. 6-181201 International Publication No. 96/00758 Pamphlet JP-A-3-20377 JP 2001-335748 A

  An object of the present invention is to provide an insulating film-forming composition, a polymer, and a polymer capable of forming an insulating film having a low water adsorption property and a low relative dielectric constant, excellent etching resistance and chemical solution resistance, and excellent mechanical strength. A manufacturing method, a manufacturing method of an insulating film, and a silica type insulating film are provided.

The composition for forming an insulating film according to the first aspect of the present invention includes (A) at least one silane monomer represented by the following general formula (1), (B) a hydrolyzable group-containing silane monomer, C) a polymer obtained by cocondensing a hydrolyzable group-containing carbosilane with (D) at least one of an acidic catalyst and a metal chelate catalyst;
An organic solvent,
Containing.

・・・・・（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)

The method for producing the polymer according to the second aspect of the present invention includes:
(A) at least one silane monomer represented by the following general formula (1); (B) a hydrolyzable group-containing silane monomer; and (C) a hydrolyzable group-containing carbosilane. And co-condensation in the presence of at least one of a metal chelate 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。）

(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)

  In the present invention, the “hydrolyzable group” refers to a group that can be hydrolyzed during the production of a polymer. Specific examples of the hydrolyzable group are not particularly limited, and examples thereof include a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, and a trifluoromethanesulfone group.

In the method for producing the polymer, the (B) hydrolyzable group-containing silane monomer is at least one selected from a compound represented by the following general formula (2) and a compound represented by the following general formula (3): It can be a silane compound.
R ⁴ _a SiX ′ _4-a (2)
(Wherein 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, an alkoxy group, or an acyloxy group, and a is 0-3. Indicates an integer.)
_{^{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, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group,, b and c individually represent an integer of 0 to 2, 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 a halogen atom Or an alkoxy group or an acyloxy group, and d represents 0 or 1. ]

  In the polymer production method, the (C) hydrolyzable group-containing carbosilane may be at least one polycarbosilane represented by the following general formula (4).

・・・・・（４）
（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、アリーレン基を示し、ｅ，ｆ，ｇは、それぞれ０〜１０，０００の数を示し、１０＜ｅ＋ｆ＋ｇ＜１０，０００の条件を満たす。）

(4)
(Wherein R ⁸ is a group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ represents a group selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ¹⁰ and R ¹¹ are the same or different, and are halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups having 2 to 6 carbon atoms, aryl A group consisting of a group, an allyl group, and a glycidyl group Shows barrel ^group, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, e, f, g, respectively 0-10,000 And satisfies the condition of 10 <e + f + g <10,000.)

In the polymer production method, the metal chelate catalyst may be a compound represented by the following general formula (5).
R ¹⁵ _h M (OR ¹⁶ ) _j-h (5)
(R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ 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 acidic catalyst may be an organic acid.

  In the polymer production method, the component (D) 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 polymer production method, the cocondensation can be performed in an organic solvent.

  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.

  In the method for manufacturing the insulating film, the heating can be performed while irradiating a high energy beam.

  The silica type insulating film of the 5th aspect of this invention is obtained by the manufacturing method of the said insulating film.

  According to the composition for forming an insulating film, (A) at least one silane monomer represented by the following general formula (1), (B) a hydrolyzable group-containing silane monomer, and (C) hydrolyzable By containing a polymer obtained by cocondensing a group-containing carbosilane with (D) at least one of an acidic catalyst and a metal chelate catalyst, the carbon atom content can be further increased. And since the reactivity of the said monomers is high, content of an unreacted silanol group can be decreased. Therefore, by forming an insulating film using the composition for forming an insulating film, a film having low water adsorptivity is obtained, so that the relative dielectric constant is low, and the mechanical strength and etching resistance (for example, film formation) An insulating film excellent in resistance to subsequent dry etching (RIE)) and chemical resistance (for example, resistance to wet etching using a chemical) can be formed.

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

1. Polymer and Method for Producing the Polymer The method for producing a polymer according to an embodiment of the present invention is also referred to as (A) at least one silane monomer represented by the following general formula (1) (hereinafter also referred to as “component (A)”). ), (B) a hydrolyzable group-containing silane monomer (hereinafter also referred to as “(B) component”), and (C) a hydrolyzable group-containing carbosilane (hereinafter also referred to as “(C) component”). And (D) co-condensation in the presence of at least one of an acidic catalyst and a metal chelate catalyst (hereinafter also referred to as “component (D)”).

・・・・・（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)

  Each of the components (A) to (C) can be used alone or in combination of two or more.

  The weight average molecular weight of the condensate (polymer) obtained by the production method is preferably 1,000 to 200,000, and more preferably 2,000 to 100,000. If the weight average molecular weight of the polymer is larger than 200,000, particles are likely to be formed, and the pores of the polymer become too large, which is not preferable. On the other hand, if the weight average molecular weight of the polymer is lower than 1,000, problems are likely to occur in coating properties and storage stability.

  Moreover, the temperature when (A)-(C) component is co-condensed is 0-100 degreeC normally, Preferably it is 15-80 degreeC.

  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 monomer 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.

  In the polymer production method, the ratio of the component (A) to the total amount of the components (A) to (C) is preferably 10 to 90% by mass, and more preferably 15 to 80% by mass.

  Specific examples of the component (A) include the following (i) to (iii).

  (I) A silane monomer in which n is 0 in the general formula (1). Specifically, the following silane monomers can be mentioned.

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

  (Iii) A silane monomer in which n is 2 in the general formula (1). Specifically, the following silane monomers can be mentioned.

1.2. (B) Component (B) A component is a hydrolysable group containing silane monomer. (B) The hydrolyzable group-containing silane monomer 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)
(Wherein 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, an alkoxy group, or an acyloxy group, and a is 0-3. Indicates an integer.)
_{^{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, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group,, b and c individually represent an integer of 0 to 2, 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 a halogen atom Or an alkoxy group or an acyloxy group, and 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, alkoxy group, or acyloxy group represented by X ′, Y ′, and Z ′, those exemplified as X in the general formula (1) can be used. Can be used.

  In the polymer production method, the ratio of the component (B) to the total amount of the components (A) to (C) is preferably 10 to 80% by mass, and more preferably 20 to 75% by mass.

  Examples of compound 1 and compound 2 include the following.

(I) Compound 1
Specific examples of the compound 1 include, for example, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tri-tert-butoxysilane. 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- ert-butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxy Silane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriiso Propoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butylto Methoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert -Butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxy Silane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, te rt-butylto-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyl Triphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxy Dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, Diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n -Propyl diisopropoxy silane, di-n-propyl di-n-butoxy silane, di-n-propyl di-sec-butoxy silane, di-n-propyl di-tert-butoxy silane, di-n-propyl di-pheno Sisilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyl Diphenoxysilane, 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-butyl Diethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec -Butyldi-tert-butoxysilane, di-sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyl Diisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxysilane, diphenyldimethoxysilane , Giffeni Diethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, tetramethoxysilane , Tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, and the like. 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, and tetraethoxysilane.

  In the production of the polymer, the component (B) preferably contains compound 1, and the proportion thereof is preferably 20 to 100 mol%, more preferably 30 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.

1.3. Component (C) The component (C) is a hydrolyzable group-containing carbosilane. (C) The hydrolyzable group-containing carbosilane may be at least one polycarbosilane represented by the following general formula (4) (hereinafter also referred to as “compound 3”).

・・・・・（４）
（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、アリーレン基を示し、ｅ，ｆ，ｇは、それぞれ０〜１０，０００の数を示し、１０＜ｅ＋ｆ＋ｇ＜１０，０００の条件を満たす。）

(4)
(Wherein R ⁸ is a group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ represents a group selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ¹⁰ and R ¹¹ are the same or different, and are halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups having 2 to 6 carbon atoms, aryl A group consisting of a group, an allyl group, and a glycidyl group Shows barrel ^group, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, e, f, g, respectively 0-10,000 And satisfies the condition of 10 <e + f + g <10,000.)

  In the general formula (4), examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group, and preferably have 2 to 6 carbon atoms, and these alkylene groups are chain-like. However, it may be branched or may form a ring, and a hydrogen atom may be substituted with a fluorine atom or the like.

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

  Moreover, in the said General formula (4), e, f, and g are the same or different, and are 10 <e + f + g <10,000 in the number of 0-10,000. When e + f + g ≦ 10, the storage stability of the film-forming composition may be inferior, and when 10,000 ≦ e + f + g, layer separation may occur and a uniform film may not be formed. Preferably, e, f, and g are 0 <e <800, 0 <f <500, and 0 <g <1,000, and more preferably 0 <e <500, 0 <f <300, 0, respectively. <G <500, and more preferably 0 <e <100, 0 <f <50, 0 <g <100.

  Further, 5 <e + f + g <1,000 is preferable, 5 <e + f + g <500 is more preferable, 5 <e + f + g <250 is further preferable, and 5 <e + f + g <100 is most preferable. .

  In the polymer production method, the ratio of the component (C) to the total amount of the components (A) to (C) is preferably 5 to 80% by mass, and more preferably 5 to 70% by mass.

  Moreover, in the manufacturing method of the said polymer, it is preferable that the ratio of (C) component with respect to the total amount of (B) component and (C) component is 5-70 mass%, and it is more preferable that it is 5-60 mass%. . Obtaining a polymer capable of forming an insulating film having excellent mechanical strength and a low relative dielectric constant when the ratio of the component (C) to the total amount of the component (B) and the component (C) is 5 to 60% by mass. Can do.

  Compound 3 is, for example, chloromethyltrichlorosilane, bromomethyltrichlorosilane, chloromethylmethyldichlorosilane, chloromethylethyldichlorosilane, chloromethylvinyldichlorosilane, chloromethylphenyldichlorosilane, bromomethylmethyldichlorosilane, bromomethylvinyldi Chlorosilane, chloromethyldimethylchlorosilane, chloromethyldivinylchlorosilane, bromomethyldimethylchlorosilane, (1-chloroethyl) trichlorosilane, (1-chloropropyl) trichlorosilane, chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethylmethyldimethoxy Silane, chloromethylvinyldimethoxysilane, chloromethylphenyldimethoxysilane, bromomethylmethyldimethoxy Silane, bromomethylvinyldimethoxysilane, bromomethylphenyldimethoxysilane, chloromethyldimethylmethoxysilane, chloromethyldivinylmethoxysilane, chloromethyldiphenylmethoxysilane, bromomethyldimethylmethoxysilane, bromomethyldiisopropylmethoxysilane, chloromethyltriethoxysilane, Bromomethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylethyldiethoxysilane, chloromethylvinyldiethoxysilane, chloromethylphenyldiethoxysilane, bromomethylmethyldiethoxysilane, bromomethylvinyldiethoxysilane, bromomethyl Phenyldiethoxysilane, chloromethyldimethylethoxysilane, chloromethyldiethylethoxysilane, At least one compound selected from momethyldivinylethoxysilane, chloromethyltriisopropoxysilane and bromomethyltriisopropoxysilane is reacted in the presence of at least one of an alkali metal and an alkaline earth metal, and if necessary And further by treatment with alcohol, organic acid, reducing agent or the like.

  The weight average molecular weight of the component (C) is preferably 300 to 100,000, more preferably 500 to 10,000, and still more preferably 1,000 to 5,000. When the weight average molecular weight of the component (C) is greater than 100,000, particles are likely to be generated, and the pores in the silica-based insulating film become too large, which is not preferable.

  Component (C) is, for example, a condensation polymerization reaction of one or more monomers represented by the following general formula (6), or a ring-opening polymerization of one or more cyclic compounds represented by the following general formula (7) It can be obtained by such a method.

・・・・・（６）
（式中、Ｒ^ａおよびＲ^ｂは同一または異なり、水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、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、アルケニル基、アルキニル基またはアリール基を示し、Ｒ^ｃは置換のアルキレン基、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、Ｙはハロゲン原子を示す）

(6)
(Wherein R ^a and R ^b are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R ^c represents a substituted alkylene group, alkenylene group, alkynylene group, or arylene group, X represents a halogen atom, a hydroxy group, an alkoxy group, or an acyloxy group, and Y represents a halogen atom)

・・・・・（７）
（式中、Ｒ^ｄおよびＲ^ｅは同一または異なり、水素原子、ハロゲン原子、ヒドロキシル基、アルコキシ基、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、アルケニル基、アルキニル基またはアリール基を示し、Ｒ^ｆは置換のメチレン基、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、ｎは２〜４の整数を示す。）

(7)
(Wherein R ^d and R ^e are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. ^Rf represents a substituted methylene group, alkylene group, alkenylene group, alkynylene group or arylene group, and n represents an integer of 2 to 4.)

Formula (6) and the general formula ^(7), R ^a, R b, alkoxy group represented by ^{R d,} and ^{R e,} an alkyl group, an alkenyl group, the alkynyl group and aryl group, in the general The groups exemplified as R ^{8 to} R ¹¹ in the formula (4) can be used, and examples of the alkylene group, alkenylene group, alkynylene group, and arylene group represented by R ^c and R ^f include the general formula (4). ) Can be used as the groups exemplified as R ^{12 to} R ¹⁴ .

1.4. (D) component In manufacture of the polymer which concerns on one Embodiment of this invention, water adsorption property is low by co-condensing (A)-(C) component in presence of at least one of an acidic catalyst and a metal chelate catalyst. In addition, a polymer capable of forming an insulating film excellent in etching resistance and chemical resistance can be obtained.

  As the component (D), either an acidic catalyst or a metal chelate catalyst may be used, or both an acidic catalyst and a metal chelate catalyst may be used.

  The component (D) is preferably 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.

1.4.1. Metal Chelate Catalyst The metal chelate catalyst is preferably a compound represented by the following general formula (5).
R ¹⁵ _h M (OR ¹⁶ ) _j-h (5)
(R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ 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 above general formula (5), examples of the chelating agent represented by R ¹⁵ 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 ¹⁶ , 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 usage-amount of a metal chelate catalyst is 0.0001-1 mol normally with respect to 1 mol of total amounts of (A) component-(C) component, Preferably it is 0.001-0.1 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 usage-amount of an acidic catalyst is 0.0001-1 mol normally with respect to 1 mol of total amounts of (A)-(C) component, Preferably it is 0.001-0.1 mol.

1.5. Organic solvent In the production of the polymer, co-condensation of the components (A) to (C) can be carried out in an organic solvent. Here, as the organic solvent, among the organic solvents described later, it is preferable to use a solvent represented by the following general formula (8) alone or in combination with another solvent.
R ¹⁵ O (CHCH ₃ CH ₂ O) _γ R ¹⁶ (8)
[R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monovalent organic group selected from CH ₃ CO—, and γ represents an integer of 1 to 2. ]

  In the general formula (8), 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).

  Examples of the organic solvent represented by the general formula (8) 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, and 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, Dipropylene glycol di Propyl ether, dipro Lenglycol 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 Examples include propyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, and dipropylene glycol diacetate. Especially, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Recall 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 (8), 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 12.5-22.0 atomic%. When the content of carbon atoms in the polymer is less than 12.5 atomic%, the etching resistance and chemical resistance are low. On the other hand, when the content of carbon atoms in the polymer is more than 22.0 atomic%, molecular motion This is not preferable because the properties are too high, the elastic modulus is low, and in some cases, the film exhibits a glass transition point. The carbon atom content (atomic%) is such that the hydrolyzable groups contained in the components (A) to (C) 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 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

  According to the method for producing a polymer according to an embodiment of the present invention, (A) at least one silane monomer represented by the general formula (1), (B) a hydrolyzable group-containing silane monomer, For example, a polymer described in JP-A-2001-335748 includes co-condensation with C) a hydrolyzable group-containing carbosilane in the presence of at least one of an acidic catalyst and a metal chelate catalyst. As compared with the above, it is possible to obtain a polymer having a small amount of unreacted silanol groups and a higher carbon atom content. Thereby, using the film-forming composition containing the polymer, it is possible to form an insulating film having a low water adsorptivity and a relative dielectric constant and excellent in mechanical strength, etching resistance and chemical resistance.

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 one embodiment of the present invention can be added as an easily decomposable component for forming pores in the silica-based film. The addition of such an organic polymer is described in JP 2000-290590, JP 2000-313612, Hedrick, JL, et al. “Templating Nanoporosity in Thin Film Dielectric Insulators”. Adv. Mater., 10 (13), 1049, 1998. etc., and similar organic polymers may be added.

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

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 and 3-aminoglycidyloxypropyltriethoxysilane. 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltri Methoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltri Metoki Sisilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxy Silylpropyltriethylenetriamine, 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-Fe -3-aminopropyltriethoxysilane, 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.

  In this case, as a dry film thickness, a coating film having a thickness of about 0.05 to 2.5 μm can be formed by one coating, and a coating film having a thickness of about 0.1 to 5.0 μm can be formed by two coatings. . Thereafter, it is dried at room temperature, or usually heated at a temperature of about 80 to 600 ° C. for about 5 to 240 minutes to dry, thereby forming a glassy or macromolecular coating film.

  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). Or you may form an insulating film by apply | coating the composition for film formation which concerns on one Embodiment of this invention to a board | substrate, and heating to 30-450 degreeC under high energy ray irradiation.

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 etching resistance and chemical resistance as well as low in water adsorbability and relative dielectric constant, as will be apparent from examples described later.

Specifically, the silica-based insulating film according to one embodiment of the present invention has a relative dielectric constant of preferably 1.5 to 3.5, more preferably 1.8 to 3.0, The elastic modulus is preferably 4.0 to 15.0 GPa, more preferably 4.0 to 12.0 GPa, and the film density is preferably 0.7 to 1.3 g / cm ^3. Preferably it is 0.8-1.27 g / cm < ³ >. From these facts, it can be said that the silica-based insulating film according to an embodiment of the present invention is extremely excellent in insulating film characteristics such as mechanical strength and relative dielectric constant.

  Since the silica-based insulating film according to an embodiment of the present invention has low water adsorptivity, a low dielectric constant can be maintained. Furthermore, since such a silica-based insulating film has low water adsorbability, it is not easily damaged by etching such as RIE used in a semiconductor process, and has excellent resistance to wet cleaning liquid. In particular, this tendency is remarkable in a silica-based insulating film having a dielectric constant k of 2.5 or less, in which the insulating film itself has a porous structure.

As described above, the silica-based insulating film according to one embodiment of the present invention is
(A) Since there is very little damage to the transistor structure by a semiconductor process such as RIE, the etching resistance (for example, dry etching resistance) is excellent.
(B) Excellent chemical resistance (for example, wet etching resistance),
(C) Since the film-forming composition has a specific composition and carbon atom content, it has excellent insulating film properties such as relative dielectric constant and elastic modulus,
(D) Since the hydrophobicity is high and the water adsorptivity is low, a low dielectric constant can be maintained,
(E) excellent mechanical strength such as elastic modulus, for example, being able to withstand the formation of a copper damascene structure;
It has the features such as.

  The silica-based insulating film according to an embodiment of the present invention is excellent in mechanical strength, etching resistance and chemical resistance, and has a low relative dielectric constant. Therefore, LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM It is particularly excellent as an interlayer insulating film for semiconductor devices such as an etching stopper film, a protective film such as a surface coat film of a semiconductor element, an intermediate layer of a semiconductor device manufacturing process using a multilayer resist, and an interlayer of a multilayer wiring board It can be suitably used for applications of semiconductor devices such as insulating films. For example, a silica-based insulating film according to an embodiment of the present invention is useful for a semiconductor device including a copper damascene process.

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. Examples and Comparative Examples Production of a polymer, production of a film-forming composition using the polymer, and formation of a silica-based film were performed by the following methods.

  In addition, the (C) hydrolyzable group containing carbosilane used by the Example and comparative example which are mentioned later is dimethoxypolycarbosilane (C-1). Dimethoxypolycarbosilane (C-1) is a polymer having a weight average molecular weight of 2,200 obtained by ring-opening polymerization of a cyclic compound represented by the following general formula (9).

・・・・・（９）
（式中、ｎは２以上の整数である。）

(9)
(In the formula, n is an integer of 2 or more.)

5.1.1. Production method of polymer 5.1.1.1-1. Synthesis example 1
In a quartz separable flask, 15.8 g of dimethoxypolycarbosilane (C-1) (component (C)), 50.1 g of ((trimethylsilyl) methyl] triethoxysilane (component (A)), methyltri 68.1 g of methoxysilane and 45.7 g of tetramethoxysilane (component (B)) were dissolved in 1,000 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, 30.1 g of ion-exchanged water in which 0.43 g of oxalic acid (component (D)) was dissolved was added to the solution over 1 hour.

  Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Methanol and ethanol were removed by evaporation at 50 ° C. to obtain a reaction solution (I). The condensate (polymer) thus obtained had a weight average molecular weight of 12,000.

5.1.1-2. Comparative Synthesis Example 1
In a quartz separable flask, 15.8 g of dimethoxypolycarbosilane (C-1) (component (C)), 115.1 g of methyltrimethoxysilane and 55.3 g of tetramethoxysilane (component (B)) After being dissolved in 1,000 g of propylene glycol monoethyl ether, the solution temperature was stabilized at 55 ° C. by stirring with a three-one motor. Next, 44.3 g of ion-exchanged water in which 0.55 g of oxalic acid (component (D)) was dissolved was added to the solution over 1 hour.

  Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Methanol and ethanol were removed by evaporation at 50 ° C. to obtain a reaction solution (II). The condensate (polymer) thus obtained had a weight average molecular weight of 14,000.

5.1.1-3. Synthesis example 2
In a quartz separable flask, 15.8 g of dimethoxypolycarbosilane (C-1) (component (C)), 50.1 g of ((trimethylsilyl) methyl] triethoxysilane (component (A)), methyltri 68.1 g of methoxysilane and 45.7 g of tetramethoxysilane (component (B)) and 0.025 g of tetrakis (acetylacetonato) titanium (component (D)) were dissolved in 1,000 g of propylene glycol monoethyl ether. After that, the solution temperature was stabilized at 55 ° C. by stirring with a three-one motor. Next, 30.1 g of ion-exchanged water was added to the solution over 1 hour.

  Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Methanol and ethanol were removed by evaporation at 50 ° C. to obtain a reaction liquid (III). The condensate (polymer) thus obtained had a weight average molecular weight of 10,000.

5.1.1-4. Comparative Synthesis Example 2
In a quartz separable flask, 15.8 g of dimethoxypolycarbosilane (C-1) (component (C)), 115.1 g of methyltrimethoxysilane and 55.3 g of tetramethoxysilane (component (B)), Tetrakis (acetylacetonato) titanium 0.025 g (component (D)) was dissolved in 1,000 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, 44.3 g of ion-exchanged water was added to the solution over 1 hour.

  Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Methanol and ethanol were removed by evaporation at 50 ° C. to obtain a reaction solution (IV). The condensate (polymer) thus obtained had a weight average molecular weight of 11,000.

5.1.1-5. Synthesis example 3
In a quartz separable flask, 9.0 g of dimethoxypolycarbosilane (C-1) (component (C)), 5.3 g of ((trimethylsilyl) methyl] phenyldimethoxysilane (component (A)), methyltri 25.1 g of methoxysilane and 8.3 g of tetramethoxysilane (component (B)) were dissolved in 1,000 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, 35.5 g of ion-exchanged water in which 0.59 g of acetic acid (component (D)) was dissolved was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Methanol and ethanol were removed by evaporation at 50 ° C. to obtain a reaction solution (V). The condensate (polymer) thus obtained had a weight average molecular weight of 13,000.

5.1.1-6. Comparative Synthesis Example 3
In a quartz separable flask, 44.8 g (component (C)) of dimethoxypolycarbosilane (C-1) was dissolved in 1,000 g of propylene glycol monoethyl ether, and then stirred with a three-one motor, and the solution temperature was adjusted. Stabilized to 55 ° C. Next, 31.1 g of ion-exchanged water in which 0.52 g of acetic acid (component (D)) was dissolved was added to the solution over 1 hour.

  Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. Methanol and ethanol were removed by evaporation at 50 ° C. to obtain a reaction solution (VI). The condensate (polymer) thus obtained had a weight average molecular weight of 12,000.

5.1.2. Method for Producing Film Forming Composition The reaction liquids (I) to (VI) obtained in the above synthesis examples and comparative synthesis examples were filtered with a Teflon (registered trademark) filter having a pore size of 0.2 μm. 3 and Comparative Examples 1 to 3 were obtained.

  After applying the obtained composition onto a silicon wafer by spin coating, 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, and further in a nitrogen atmosphere at 400 ° C. The substrate was baked on a hot plate for 60 minutes. The polymer film (hereinafter referred to as “silica film”) obtained after firing was evaluated according to the following evaluation method. The evaluation results are shown in Table 1.

5.2. Evaluation method 5.1.1. And the condensate (polymer) obtained in 5.1.2. Various evaluations on the silica-based film obtained in the above were performed by the following methods.

5.2.1. Polymer weight average molecular weight (Mw)
It measured by the gel permeation chromatography (GPC) method by the following conditions.

  Sample: Tetrahydrofuran was used as a solvent, and 1 g of a polymer (cocondensate) was dissolved in 100 cc of tetrahydrofuran.

  Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.

Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA
Column: SHODEX A-80M (length: 50 cm) manufactured by Showa Denko K.K.
Measurement temperature: 40 ° C
Flow rate: 1cc / min

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

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

5.2.3. Mechanical strength (elastic modulus / hardness) of silica film
About the silica type | system | group film | membrane formed by the above-mentioned method, mechanical strength (elastic modulus and hardness) was measured by the continuous rigidity measuring method using Nanoindenter XP (made by a nano instrument company).

5.2.4. Chemical-resistant of silica-based film An 8-inch wafer on which a hybrid polymer film is formed is immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 1 minute and 3 minutes, and the silica-based film formed by the above-described method. The film thickness change before and after immersion was observed. When the remaining film rate defined below was 99% or more, it was judged that the chemical solution resistance was good, and when the remaining film rate was less than 99%, it was judged that the chemical solution resistance was poor. In Table 1, “A” indicates that the chemical resistance is good, and “B” indicates that the chemical resistance is poor.
Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100

5.3. Evaluation Results The silica-based films obtained in Examples 1 to 3 had good chemical resistance tests, and Δk, which is a measure of water adsorption, was also an appropriate value. In contrast, in Comparative Examples 1 and 2, when the polymer was produced, the amount of component (C) was the same as in Example 1, but component (A) was not used. For this reason, when the silica type | system | group film | membrane obtained by the comparative examples 1 and 2 was immersed in dilute hydrofluoric acid aqueous solution for 3 minutes, chemical | medical solution tolerance fell. In Comparative Example 3, in the production of the polymer, without using the component (A) having a high carbon atom content, the content of the carbon atom is increased by increasing the amount of the component (C) in the monomer. The carbon atom content of the polymer produced in Example 3 was adjusted. As a result, the silica-based film obtained in Comparative Example 3 had a large Δk although it had good chemical resistance.

  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, water adsorption and relative dielectric constant are improved. A silica-based insulating film having a low mechanical strength, etching resistance, and chemical resistance can be formed. Therefore, the silica-based film of the present invention is excellent in mechanical strength, etching resistance, and chemical solution resistance, and has low water adsorbability and low relative dielectric constant. Therefore, it can be suitably used as an interlayer insulating film of a semiconductor device.

Claims (10)

(A) Group consisting of at least one silane monomer 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) At least one hydrolyzable group-containing silane monomer selected from: (C) a polycarbosilane having a weight average molecular weight of 300 to 100,000 represented by the following general formula (4): (D) an acidic catalyst And a polymer having a weight average molecular weight of 1,000 to 200,000 and a carbon atom content of 12.5 to 22.0 atomic% obtained by cocondensation in the presence of at least one of a metal chelate catalyst,
An organic solvent,
The composition for insulating film formation containing this.

(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)
R ⁴ _a SiX ′ _4-a (2)
(Wherein 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, an alkoxy group, or an acyloxy group, and a is 0-3. Indicates an integer.)
_{^{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, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group,, b and c individually represent an integer of 0 to 2, 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 a halogen atom Or an alkoxy group or an acyloxy group, and d represents 0 or 1. ]

(4)
(Wherein R ⁸ is a group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ represents a group selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ¹⁰ and R ¹¹ are the same or different, and are halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups having 2 to 6 carbon atoms, aryl A group consisting of a group, an allyl group, and a glycidyl group Shows barrel ^group, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, e, f, g, respectively 0-10,000 And satisfies the condition of 10 <e + f + g <10,000.) (A) Group consisting of at least one silane monomer 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) At least one hydrolyzable group-containing silane monomer selected from: (C) a polycarbosilane having a weight average molecular weight of 300 to 100,000 represented by the following general formula (4): (D) an acidic catalyst And a method for producing a polymer having a weight average molecular weight of 1,000 to 200,000 and a carbon atom content of 12.5 to 22.0 atomic% , comprising co-condensation in the presence of at least one of a metal chelate 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)
R ⁴ _a SiX ′ _4-a (2)
(Wherein 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, an alkoxy group, or an acyloxy group, and a is 0-3. Indicates an integer.)
_{^{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, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group,, b and c individually represent an integer of 0 to 2, 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 a halogen atom Or an alkoxy group or an acyloxy group, and d represents 0 or 1. ]

(4)
(Wherein R ⁸ is a group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ represents a group selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ¹⁰ and R ¹¹ are the same or different, and are halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups having 2 to 6 carbon atoms, aryl A group consisting of a group, an allyl group, and a glycidyl group Shows barrel ^group, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, e, f, g, respectively 0-10,000 And satisfies the condition of 10 <e + f + g <10,000.) In claim 2,
The said metal chelate catalyst is a manufacturing method of a polymer which is a compound represented by following General formula (5).
R ¹⁵ _h M (OR ¹⁶ ) _j-h (5)
(R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ 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 claim 2 or claim 3,
The method for producing a polymer, wherein the acidic catalyst is an organic acid. In any one of Claims 2 thru | or 4,
The method for producing a polymer, wherein the component (D) 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 any one of Claims 2 thru | or 5,
A method for producing a polymer, wherein the cocondensation is performed in an organic solvent.   The polymer obtained by the manufacturing method of the polymer as described in any one of Claims 2 thru | or 6.   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. In claim 8,
A method for manufacturing an insulating film, wherein the heating is performed while irradiating a high energy beam.   The silica type insulating film obtained by the manufacturing method of the insulating film of Claim 8 or Claim 9.