JP2006269402A - Composition for insulation material formation and insulation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound capable of forming an insulation material having a low dielectric constant; to provide a composition for insulation material formation containing the compound; and to provide an insulation material obtained from the composition. <P>SOLUTION: This compound is represented by general formula (1). This composition for insulation material formation is characterized by containing its hydrolysate and/or condensate. In general formula (1), R<SB>1</SB>-R<SB>8</SB>are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a silyloxy group independently of one another. At least one of the groups represented by R<SB>1</SB>-R<SB>8</SB>is an alkyl group, an aryl group, an alkoxy group or a silyloxy group each having a group represented by general formula (S1) as a substituted group. In the general formula (S1), X is a hydrolizable group; R<SB>9</SB>is an alkyl group, an aryl group or a heterocycle group; and n is an integer of 1 to 3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composition for forming an insulating material, and further relates to an insulating material having good characteristics such as dielectric constant and mechanical strength obtained by using the composition.

  Patent Document 1 describes a coating composition for forming an insulating film containing siloxane (silsesquioxane) having a T8 cage structure, and an insulating film having a low dielectric constant can be obtained by polymerizing by crosslinking. It has been shown. There is no description of mechanical strength. On the other hand, with further higher integration and multilayering of semiconductors and the like, better electrical insulation between conductors is required, lower dielectric constant, heat resistance, mechanical strength (chemical mechanical polishing (CMP Interlayer insulating materials having excellent resistance)) have been demanded.

Japanese Patent Laid-Open No. 11-40554

  An object of the present invention is to provide a compound used for an insulating material having a low dielectric constant, a composition for forming an insulating material using the compound, and an insulating film obtained from the composition.

Specifically, the above object of the present invention can be achieved by the following constitution.
(1) A composition for forming an insulating material comprising a compound represented by the following general formula (1), a hydrolyzate and / or a condensate thereof.

In general formula (1), R < ₁ > -R < ₈ > represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or a silyloxy group each independently. However, at least one of the groups represented by R _{1 to} R ₈ represents an alkyl group, aryl group, alkoxy group or silyloxy group having a group represented by the following general formula (2) as a substituent.

In the general formula (S2), X represents a hydrolyzable group, and R ₉ represents an alkyl group, an aryl group or a heterocyclic group. m represents an integer of 1 to 3.
(2) The compound represented by the general formula (1) contains a compound represented by the general formula (2) and / or a compound represented by the general formula (3). A composition for forming an insulating material.

In General Formulas (2) and (3), R _{10 to} R ₁₇ represent a substituent represented by General Formula (S2). n1 to n8 each independently represents 2 or 3.

R _{18 to} R ₁₉ independently represent an alkyl group. m represents an integer of 1 to 3.

(3) The composition for forming an insulating material according to the above (1) or (2), further comprising a compound represented by the general formula (4), a hydrolyzate and / or a condensate thereof.
_An SiX _(4-n) (4)
In the formula, n represents a natural number of 1 to 3. A is a group containing a cage structure formed of 11 or more carbon atoms, which may have a substituent, and X represents a hydrolyzable group.

(4) The composition for forming an insulating material as described in (3) above, wherein in formula (4), A contains a diamantyl group.

(5) For forming an insulating material according to any one of (1) to (4) above, further comprising a compound represented by the general formula (5), a hydrolyzate and / or a condensate thereof. Composition.

In General Formula (5), X ¹ represents a hydrolyzable group, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, n ₁ represents an integer of ₁ to 3, and m ₁ represents 2 or more. Represents an integer. L ¹ represents a divalent linking group, and A represents a group containing a cage structure formed of 11 or more carbon atoms.

(6) The insulating material formed from the composition in any one of said (1)-(5).
(7) An insulating film formed from the composition according to any one of (1) to (5) above.

(8) The compound represented by the general formula (2) or (3) described in (2) above.

  The composition for forming an insulating material of the present invention contains a compound represented by the following general formula (1), a hydrolyzate and / or a condensate thereof.

R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a silyloxy group.
Preferable examples of the alkyl group represented by R _{1 to} R ₈ include a linear, branched or cyclic alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, an isopropyl group, n -Butyl group, 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.).
Preferable examples of the aryl group represented by R _{1 to} R ₈ include a substituted or unsubstituted phenyl group or naphthyl group having 6 to 20 carbon atoms.
Preferred examples of the alkoxy group represented by R _{1 to} R ₈ include substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms (for example, methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group, etc.) Etc.
Preferable examples of the silyloxy group represented by R _{1 to} R ₈ include substituted or unsubstituted silyloxy groups having 1 to 10 carbon atoms (for example, trimethylsilyloxy group, ethyldimethylsilyloxy group, dimethylpropylsilyloxy group, etc.) Is mentioned.

However, at least one of the groups represented by R _{1 to} R ₈ represents an alkyl group, an aryl group, an alkoxy group, or a silyloxy group having a group represented by the following general formula (S1) as a substituent.

In the general formula (S1), examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyloxy group, and a hydroxyl group.
X is preferably a substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group) and a halogen atom. Particularly preferred are a methoxy group, an ethoxy group, and a chlorine atom.

Preferred examples of the alkyl group represented by R ₉ include a linear, branched or cyclic alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group). 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.).
Preferable examples of the aryl group represented by R ₉ include a substituted or unsubstituted phenyl group or naphthyl group having 6 to 20 carbon atoms.
Preferred examples of the heterocyclic group represented by R ₉ include a substituted or unsubstituted hetero 6-membered ring (pyridyl, morpholino group, tetrahydropyranyl, etc.), a substituted or unsubstituted hetero 5-membered ring (furyl, thiophene). Group, 1,3-dioxolan-2-yl group, etc.).

  As the compound represented by the general formula (1), a compound represented by the general formula (2) or (3) is preferable.

In General Formulas (2) and (3), R _{10 to} R ₁₇ represent a substituent represented by General Formula (S2). n1 to n8 each independently represents 2 or 3.

The alkyl group represented by R _{18 to} R ₁₉ is the same as the alkyl group represented by R ₉ , m
Represents an integer of 1 to 3.

  Although the specific example of the organosilicon compound represented by General formula (1) is given, it is not limited to these.

The compound represented by the general formula (1) is, for example, hydrosilylated or halogenated by adding a corresponding silane compound to a cage-type silsesquioxane compound having a corresponding unsaturated group in the presence of a transition metal complex catalyst. Furthermore, it can be easily synthesized by reacting the cage silsesquioxane compound with the corresponding Grignard reagent.

  In addition to the organosilicon compound represented by the general formula (1), other known silicon compounds (for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, etc.) are used in combination for hydrolysis. -It may be condensed to obtain a silicon oxygen crosslinking compound.

  In order to improve the film characteristics of the material, another organosilicon compound may be added to the organosilicon compound represented by the general formula (1) as necessary.

As another organosilicon compound, it is preferable to add an organosilicon compound represented by the following general formula (4), a hydrolyzate and / or a condensate thereof.
_An SiX _(4-n) (4)
In the formula, n represents a natural number of 1 to 3. A is a group containing a cage structure formed of 11 or more carbon atoms, which may have a substituent, and X represents a hydrolyzable group.

In general formula (4), A is a group containing a cage structure formed of 11 or more carbon atoms (a cage structure-containing group). The cage structure-containing group may be a monovalent group of the cage structure itself.
The “cage structure” is a structure in which the volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located within the volume cannot be separated from the volume without passing through the ring.

  For example, an adamantane structure is considered a cage structure. In contrast, a cyclic structure having a single bridge such as norbornane (bicyclo [2,2,1] heptane) is not considered a cage structure because the ring of a single bridged cyclic compound does not define volume. .

The cage structure of the present invention is characterized by being composed of at least 11 carbon atoms. The cage structure is preferably composed of 11 to 30, more preferably 12 to 20, and still more preferably 12 to 14 carbon atoms. When the number of carbon atoms is 11 or more, sufficient dielectric constant characteristics can be obtained.
The carbon atom here does not include a linking group substituted with a cage structure or a carbon atom of the substituent. For example, 1-methyladamantane is composed of 10 carbon atoms.

  The compound having a cage structure of the present invention is preferably a saturated aliphatic hydrocarbon, and examples thereof include diamantane, triamantane, tetramantane, dodecahedrane, etc., particularly low dielectric constant and good solubility in coating solvents. In addition, diamantane is preferable from the viewpoint of suppressing the generation of defects in the insulating film.

The cage structure in the present invention may have one or more substituents, and examples of the substituent include -Si (Am) (X) _(3-m) (m is an integer of 0 to 2 _). A and X are as defined in Formula (4)), halogen atom (fluorine atom, chloro atom, bromine atom, or iodine atom), linear, branched, or cyclic alkyl having 1 to 10 carbon atoms. Groups (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.), C2-C10 alkenyl groups (vinyl, propenyl, etc.), C2-C10 alkynyl groups (ethynyl, phenylethynyl, etc.), C6-C20 Aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), C2-C10 acyl groups (benzoyl, etc.), C6-C20 aryloxy groups (phenoxy, etc.), C6-C20 aryl Sulfonyl group Nirusuruhoniru etc.), a nitro group, a cyano group, a silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl or the like) and the like. Further preferred substituents are a fluorine atom, a bromine atom, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, and a silyl group. These substituents may be further substituted with another substituent.

  The cage structure in the present invention is preferably divalent to tetravalent. More preferably, it is divalent or trivalent, and particularly preferably divalent.

The bond between the cage structure-containing group as A and the silicon atom can be performed at any position of the cage structure-containing group as long as the effect of the present invention is not adversely affected.
Preferably, the number of atoms constituting the group connecting the cage structure and the silicon atom (the number of atoms existing on the shortest path not including the substituent) is 6 or less, and the cage structure and the silicon atom are directly connected. It is particularly preferable.

  Examples of the hydrolyzable group as X include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a silyloxy group. X is preferably a substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group, etc.).

  When n = 2 or 3, the plurality of R may be the same group or different from each other. When n = 1 or 2, the plurality of X may be the same group or different from each other.

  As a compound represented by Formula (4), the compound represented by a following formula is preferable. In the following formula, X is an alkoxy group.

  As another organosilicon compound, a compound represented by the following general formula (5) is preferable.

In General Formula (5), X ¹ represents a hydrolyzable group, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, n ₁ represents an integer of ₁ to 3, and m ₁ represents 2 or more. Represents an integer. L ¹ represents a divalent linking group, and A represents a group containing a cage structure formed of 11 or more carbon atoms.
Examples of the hydrolyzable group as X ¹ include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyloxy group, and a hydroxyl group. X ¹ is preferably a substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group, etc.).

R ¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Preferable examples of the alkyl group represented by R ¹ include a linear, branched or cyclic alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group). , 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.), and preferred examples of the aryl group represented by R ¹ include substituted or non-substituted groups having 6 to 20 carbon atoms. Examples of the heterocyclic group represented by R ¹ include a substituted phenyl group and a naphthyl group. Preferred examples of the heterocyclic group represented by R ¹ include a substituted or unsubstituted hetero 6-membered ring (pyridyl, morpholino group, tetrahydropyranyl, etc.), substituted Alternatively, an unsubstituted hetero 5-membered ring (furyl, thiophene group, 1,3-dioxolan-2-yl group, etc.) and the like can be mentioned.

In the case of n1 = 2 or 3, a plurality of X ¹ may be the same group or different from each other. When n1 = 1, the plurality of R ¹ may be the same group or different from each other.

L ¹ represents a divalent linking group. Examples of the linking group include an alkylene group, an alkenylene group, an arylene group, -O-, -S-, -CO-, -NR'- (R 'is a hydrogen atom, an alkyl group or an aryl group), or 2 Examples thereof include a linking group formed by combining two or more. Of the linking groups, an alkylene group and an alkenylene group are preferable, and an ethylene group and a vinylene group are particularly preferable.

When A is diamantane, m ₁ is preferably 2 to 4, and when it is triamantane, m ₁ is preferably 2 to 6.

  As the compound represented by the general formula (5), a compound represented by the general formula (6) is preferable.

In General Formula (6), X ^{31 to} X ³⁴ each represent a hydrolyzable group, R ^{3 to} R ³⁴ each represent an alkyl group, an aryl group, or a heterocyclic group, and n _{31 to} n ₃₄ represent 1 to 3 represents an integer, and m ₃₁ + m ₃₂ + m ₃₃ + m ₃₄ represents an integer of 1 to 4. L ^{31 to} L ³⁴ are each alkylene, vinylene, arylene, —O—, —S—, —CO—, —NR′— (R ′ represents a hydrogen atom, an alkyl group or an aryl group) or a combination thereof. Represents a divalent linking group.
The hydrolyzable group represented by X ^{31 to} X ³⁴ has the same meaning as that represented by X ¹ , and the preferred embodiment is also the same.
The alkyl group, aryl group or heterocyclic group represented by R ^{31 to} R ³⁴ has the same meaning as that represented by R ¹ , and the preferred embodiments are also the same.

  Although the specific example of a compound represented by General formula (5) is given, it is not limited to these.

  When using together the compound represented by General formula (4) or (5), it is preferable to use in the range of 1-1000 mol% with respect to the compound represented by General formula (1), 10-800 mol% It is more preferable to use in the range.

The molecular weight of the compound represented by the general formula (4) is generally 250 to 1000, preferably 280 to 700.
The molecular weight of the compound represented by the general formula (5) is generally 400 to 2000, preferably 450 to 1500.

  The compound represented by the general formula (4) or (5) can be easily prepared by using a technique well known in the chemistry of silicon. For example, a compound having a corresponding unsaturated group can be converted into a transition metal complex. It can be easily synthesized by a hydrosilylation reaction in which a corresponding silane compound is added in the presence of a catalyst or a reaction between a halogenated cage structure-containing compound and a Grignard reagent.

  Examples of still other organosilicon compounds used in combination include organosilicon compounds represented by the following general formula (A) or polymers containing these as monomers.

In general formula (A), R _a represents an alkyl group, an aryl group or a heterocyclic group, and R _b represents a hydrogen atom, an alkyl group, an aryl group or a silyl group. These groups may further have a substituent.
q represents an integer of 0 to 4, and when q or 4-q is 2 or more, R _a or R _b may be the same or different. In addition, the compounds may be connected to each other by a substituent of R _a or R _b to form a multimer.

Q in the general formula (A) is preferably 0 to 2, and R _b is preferably an alkyl group. Further, examples of preferable compounds when q is 0 include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and the like, and examples of preferable compounds when q is 1 or 2 include the following compounds: Can be mentioned.

  When using together the compound represented by general formula (A), it is preferable to use in the range of 1-200 mol% with respect to the silane compound represented by general formula (1), and the range of 1-100 mol% It is more preferable to use it.

A method for obtaining a compound having a silicon-oxygen cross-linked structure by hydrolysis and condensation using an organosilicon compound represented by the general formula (1) and, if necessary, another organosilicon compound in combination is as follows. The silicon oxygen cross-linked structure refers to a cross-linked structure composed of a siloxane bond (-(Si-O) n-) that is naturally formed by condensation.
When hydrolyzing and condensing the silane compound, 0.5 to 150 mol of water per 1 mol of the total amount of the organosilicon compound represented by the general formula (1) and, if necessary, other organosilicon compounds is included. It is preferable to use 1 to 100 mol of water. The amount of water to be added is preferably 0.5 mol or more from the viewpoint of crack resistance of the film, and is preferably 150 mol or less from the viewpoint of polymer precipitation and prevention of gelation during hydrolysis and condensation reactions.

  When hydrolyzing and condensing the organosilicon compound, it is preferable to use an alkali catalyst, an acid catalyst, or a metal chelate compound.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, dia Zabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine,

  Butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, And tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and the like, preferably amines or amine salts, organic amines or Organic amine salts are particularly preferred, and alkylamines and tetraalkylammonium hydroxides are most preferred. These alkali catalysts may be used alone or in combination of two or more.

The acid catalyst is preferably an inorganic or organic proton acid.
Examples of inorganic protonic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acids (H ₃ PO ₄ , H ₃ PO ₃ , H ₄ P ₂ O ₇ , H ₅ P ₃ O ₁₀ , metaphosphoric acid, hexafluorophosphoric acid, etc. ), Boric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid and the like, or solid acids such as tungstophosphoric acid and tungten peroxo complexes.

Organic protonic acids include carboxylic acids (oxalic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, maleic acid, methylmaleic acid, adipic acid, sebacic acid , Gallic acid, butyric acid, melottic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, p-aminobenzoic acid, Formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, anhydrous Hydrolyzate of maleic acid, trifluoroacetic acid, benzoic acid, substituted benzoic acid, etc.), phosphate esters (For example, carbon number 1-30, phosphoric acid methyl ester, phosphoric acid propyl ester, phosphoric acid dodecyl ester, phosphoric acid phenyl ester, phosphoric acid dimethyl ester, phosphoric acid dododecyl ester, etc.), phosphorous acid esters (for example, carbon number 1-30, phosphorous acid methyl ester, phosphorous acid dodecyl ester, phosphorous acid diethyl ester, phosphorous acid diisopropyl, phosphorous acid didodecyl ester, etc.), sulfonic acids (for example, carbon number 1-15, benzenesulfonic acid, Toluenesulfonic acid, hexafluorobenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid, etc.), imides (eg bis (trifluoromethanesulfonyl) imidic acid, trifluoromethanesulfonyltrifluoroacetamide, etc.), phosphonic acid Low molecular weight compounds such as (for example, having 1 to 30 carbon atoms, methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, 1,5-naphthalene bisphosphonic acid), or perfluorocarbon sulfonic acid polymers represented by Nafion , Poly (meth) acrylate having a phosphate group in the side chain (Japanese Patent Laid-Open No. 2001-14834), sulfonated polyether ether ketone (Japanese Patent Laid-Open No. 6-93111), sulfonated polyether sulfone (Japanese Patent Laid-Open No. 10-45913) ) And sulfonated polysulfone (Japanese Patent Laid-Open No. 9-245818).

Examples of metal chelate compounds include triethoxy mono (acetylacetonate).
Titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy.titanium Mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i- Propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium, di-t-butoxy bis (acetylacetonato) Titanium, monoethoxy tris (acetylacetonate) Tan, mono -n- propoxy tris (acetylacetonate) 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-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethylacetate) Acete G) 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 (ethyl acetoacetate) ) Titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl acetoacetate) ) Titanium chelate compounds such as titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetate) Inert) zirconium, tri -n- propoxy mono (acetylacetonate) zirconium, tri -i- propoxy mono (acetylacetonate) 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 (acetylacetonate) Zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy Bis (acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonate) Luconium, mono-n-butoxy tris (acetylacetonato) zirconium, mono-sec-butoxy tris (acetylacetonato) zirconium, mono-t-butoxytris (acetylacetonato) zirconium, tetrakis (acetylacetonato) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) 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) Cetoacetate) 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 (ethyl acetoacetate) zirconium,

  Tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, etc. Zirconium chelate compounds; aluminum chelate compounds such as tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum; and the like, preferably titanium or aluminum chelate compounds, particularly preferably titanium chelate compounds Can be mentioned. These metal chelate compounds may be used alone or in combination of two or more.

  The amount of the catalyst and chelate compound used is generally 0.00001 to 10 mol, preferably 0.00005 to 5 mol, relative to 1 mol of the organosilicon compound as a total amount. If the amount of the catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

The temperature for the condensation and hydrolysis of the organosilicon compound is usually 0 to 100 ° C, preferably 10 to 90 ° C. The time is usually 5 minutes to 200 hours, preferably 15 minutes to 40 hours.
In this way, a hydrolyzate or condensate of the organosilicon compound represented by the general formula (1) can be prepared.

The solvent used in the above reaction is not particularly limited as long as it dissolves a solute organosilicon compound, but preferably ketones (cyclohexanone, cyclopentanone, 2-heptanone, methyl isobutyl ketone, methyl ethyl ketone, acetone. Etc.), carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, dimethylimidazolidinone, N-methylpyrrolidone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), chain-like Ethers (diethyl ether, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, etc.), alcohols (methanol, ethanol, isopropanol, ethylene) Recall monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), triethylene glycol monobutyl ether, propylene glycol monopropyl ether, triethylene glycol monomethyl ether, etc.), polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene) Glycol, polypropylene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile,
Propionitrile, benzonitrile, etc.), esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, 2-methoxyethyl) Acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone, phosphate ester, phosphonate ester, etc.), aprotic polar substance (dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, dimethyl) Acetamide, etc.), nonpolar solvents (toluene, xylene, mesitylene, etc.), chlorinated solvents (methylene dichloride, ethylene dichloride, etc.), diisopropylbenzene, water, etc. Kill.

  Among these, alcohols such as propylene glycol monopropyl ether and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), esters such as γ-butyrolactone, carbonates such as ethylene carbonate, ketones such as cyclohexanone, non- Protic polar substances, cyclic ethers such as tetrahydrofuran, nonpolar solvents, and water are preferred. These may be used alone or in combination of two or more.

  Among these, preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, Mention may be made of mesitylene and diisopropylbenzene.

〔Composition〕
The composition containing the silicon-oxygen crosslinking compound of the present invention is usually at least one of the organosilicon compound represented by the general formula (1) itself, the hydrolyzate and condensate of the organosilicon compound prepared above. Is dissolved in a solvent in an organic solvent, water or the like as exemplified as a solvent used for hydrolysis and condensation, if necessary.

  The total solid content concentration of the composition of the present invention is preferably 2 to 30% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 2 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability of the composition is more excellent.

  A good insulating material can be formed by applying, drying, and preferably heating the composition of the present invention. In particular, a good insulating film can be provided.

When the composition of the present invention is applied to a substrate such as a silicon wafer, SiO ₂ wafer, or SiN wafer, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used.

  In this case, as a dry film thickness, it is possible to form a coating film having a thickness of about 0.05 to 1.5 μm by one coating and a thickness of about 0.1 to 3 μm by two coatings. Thereafter, it is dried at room temperature, or heated at a temperature of about 80 to 600 ° C., usually for about 5 to 240 minutes, to form an insulating film of vitreous or giant polymer or a mixture thereof. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do.

  More specifically, the composition of the present invention is applied onto a substrate (usually a substrate having metal wiring) by, for example, a spin coating method, and a first heat treatment is performed at a temperature of 300 ° C. or lower to remove the solvent. While drying, the siloxane contained in the composition is crosslinked, and then a second heat treatment (annealing) at a temperature higher than 300 ° C. and lower than 450 ° C. (preferably 330 to 400 ° C.), generally for 1 minute to 10 hours. ), A low dielectric constant insulating film can be formed.

  A pore forming agent such as a thermally decomposable compound may be added to the composition of the present invention. Examples of the pore forming agent include pore generators described in JP-T-2002-530505.

  On the insulating film formed of the composition of the present invention, another insulating film such as a silicon oxide film may be formed by, for example, a vapor deposition method. This is because the insulating film formed according to the present invention is effective in blocking the outside air and suppressing the reduction of hydrogen and fluorine remaining in the film. In addition, this other insulating film is also effective in preventing the insulating film according to the present invention from being damaged by processing in a subsequent process (for example, processing such as planarization by CMP).

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[Synthesis Example 1: Synthesis of Compound 1-1]

In a nitrogen stream, a xylene solution of M-1 (Aldrich) (3.2 g) and platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Aldrich) ) 20 μl was dissolved in 25 ml toluene and heated to 70 ° C. Thereto, triethoxysilane (10.0 g) was gradually added dropwise while paying attention to heat generation. After completion of the dropwise addition, the mixture was further reacted at 90 ° C. for 3 hours, and then the reaction mixture was concentrated and purified by silica gel column chromatography to obtain 5.3 g of 1-1 (white crystals). 1H-NMR (CDCl ₃ ) δ3.8 (48H, q) 1.2 (7
2H, t) 0.6 (32H, m)

[Synthesis Example 2: Synthesis of Compound 1-4]

In a nitrogen stream, a xylene solution of M-2 (manufactured by Aldrich) (2.0 g) and platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (manufactured by Aldrich) ) 20 μl was dissolved in 15 ml toluene and heated to 70 ° C. Thereto, diethoxymethylvinylsilane (3.0 g) was gradually added dropwise while paying attention to heat generation. After completion of the dropwise addition, the mixture was further reacted at the same temperature for 1 hour, and then the reaction mixture was concentrated and purified by silica gel column chromatography to obtain 3.5 g of 1-4 (oil). 1H-NMR (CDCl ₃ ) δ 3.7 (32H, q) 1.2 (48H, t) 0.54 (32H, broad s) 0.14-0.10 (72H, m)

[Synthesis Example 3: Synthesis of Compound 1-5]

In a nitrogen stream, a xylene solution of M-3 (manufactured by Aldrich) (2.0 g) and platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (manufactured by Aldrich) ) 20 μl was dissolved in 15 ml toluene and heated to 70 ° C. Thereto, triethoxyvinylsilane (3.6 g) was gradually added dropwise while paying attention to heat generation. After completion of the dropwise addition, the mixture was further reacted at the same temperature for 1 hour, and then the reaction mixture was concentrated and purified by silica gel column chromatography to obtain 4 g of 1-5 (oil). 1H-NMR (CDCl ₃ ) δ3.8 (48H, q) 1.2 (72H, t) 0.5-0.6 (32H, m) 0.14 (48H, s)

[Example 1: Preparation of coating solution]
7 mmol of the compound 1-1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a 10% by mass solution.

[Examples 2-3: Preparation of coating solution]
A coating solution was prepared in the same manner as in Example 1, using the compounds shown in Table 1 and the solvent.

[Example 4: Preparation of coating solution]
7 mmol of compound 1-1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a 10% by mass solution. A 42 mmol aqueous nitric acid solution (concentration 200 ppm) was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration.

[Examples 5 to 7: Preparation of coating solution]
Example 4 was repeated to prepare a coating solution, except that the compounds and solvents used were changed to those described in Table 2.

Compound A is the following compound.

[Comparative example: Preparation of coating solution]
A coating solution was prepared using Compound A under the same conditions as in Example 4.

[Preparation of insulating film]
The coating solution prepared as described above was spin-coated on a silicon substrate to a film thickness of 4000 mm, dried on a hot plate at 150 ° C. for 1 minute, and the solvent was removed. Next, the dried silicon substrate was transferred to a clean oven and heat-treated at 400 ° C. for 30 minutes in nitrogen having an oxygen concentration of 10 ppm or less. The intended insulating film was obtained.

[Measurement of dielectric constant]
After being allowed to stand for 24 hours at a temperature of 24 ° C. and a humidity of 50%, 1 MHz using a Four Dimensions mercury probe and a Hewlett Packard HP4285A LCR meter.
The dielectric constant (measurement temperature: 25 ° C.) was measured. The measurement results are shown in Table 2.

[Measurement of elastic modulus (Young's modulus)]
The elastic modulus (measurement temperature 25 ° C.) at a depth of 1/10 of the film thickness was measured using a nanoindenter SA2 (manufactured by MTS). The measurement results are shown in Table 2.

  It can be seen that the insulating film formed from the composition of the present invention has a low dielectric constant, high mechanical strength, and excellent performance.

[Example 8: Preparation of coating solution]
7 mmol of the compound 1-1 and 1.75 mmol of the compound 2-1 were dissolved in propylene glycol monomethyl ether (PGME) to prepare a 10% by mass solution. A 55 mmol aqueous nitric acid solution (concentration 200 ppm) was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration.

[Examples 9 to 12: Preparation of coating solution]
A coating solution was prepared in the same manner as in Example 8 using the compounds shown in Table 4 and the solvent. The organosilicon compounds in Table 4 are those exemplified above.

  Using the coating liquids of Examples 8 to 12, an insulating film was prepared and evaluated in the same manner as the coating liquids of Examples 1 to 7. The results are shown in Table 5.

  It can be seen that the insulating film formed from the composition using another organosilicon compound according to the present invention exhibits a low dielectric constant, higher mechanical strength, and excellent performance.

Claims (9)

A composition for forming an insulating material, comprising a compound represented by the following general formula (1), a hydrolyzate and / or a condensate thereof.

In general formula (1), R < ₁ > -R < ₈ > represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or a silyloxy group each independently. However, at least one of the groups represented by R _{1 to} R ₈ represents an alkyl group, an aryl group, an alkoxy group, or a silyloxy group having a group represented by the following general formula (S1) as a substituent.

In the general formula (S1), X represents a hydrolyzable group, and R ₉ represents an alkyl group, an aryl group, or a heterocyclic group. n represents an integer of 1 to 3. The insulating material according to claim 1, wherein the compound represented by the general formula (1) contains a compound represented by the general formula (2) and / or a compound represented by the general formula (3). Forming composition.

In General Formulas (2) and (3), R _{10 to} R ₁₇ represent a substituent represented by General Formula (S2). n1 to n8 each independently represents 2 or 3.

R _{18 to} R ₁₉ independently represent an alkyl group. m represents an integer of 1 to 3. Furthermore, the composition for insulating material formation of Claim 1 or 2 containing the compound represented by General formula (4), its hydrolyzate, and / or a condensate.
_An SiX _(4-n) (4)
In the formula, n represents a natural number of 1 to 3. A is a group containing a cage structure formed of 11 or more carbon atoms, which may have a substituent, and X represents a hydrolyzable group.   The composition for forming an insulating material according to claim 3, wherein A in formula (4) contains a diamantyl group. Furthermore, the composition for insulating material formation in any one of Claims 1-4 containing the compound represented by General formula (5), its hydrolyzate, and / or a condensate.

In General Formula (5), X ¹ represents a hydrolyzable group, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, n ₁ represents an integer of ₁ to 3, and m ₁ represents 2 or more. Represents an integer. L ¹ represents a divalent linking group, and A represents a group containing a cage structure formed of 11 or more carbon atoms.   The insulating material formed from the composition in any one of Claims 1-5.   The insulating film formed from the composition in any one of Claims 1-5. A compound represented by the general formula (2).

In General Formula (2), R _{10 to} R ₁₇ each independently represent a substituent represented by General Formula (S2). n1 to n8 each independently represents 2 or 3.

In general formula (S2), R _{18 to} R ₁₉ independently represent an alkyl group. m represents an integer of 1 to 3. A compound represented by the general formula (3).

In general formula (3), R _{10 to} R ₁₇ represent a substituent represented by general formula (S2). n1 to n8 each independently represents 2 or 3.

R _{18 to} R ₁₉ independently represent an alkyl group. m represents an integer of 1 to 3.