JP4538343B2 - Silicon-containing compound, hydrolyzate and / or condensate of the compound, composition containing the hydrolyzate and / or condensate, and insulating material and insulating film formed from the composition - Google Patents

Description

The present invention uses a silicon-containing compound, a hydrolyzate and / or condensate of the compound (hereinafter also referred to as “ silicon oxygen crosslinking compound ”) , a composition containing the silicon oxygen crosslinking compound, and the composition. The present invention relates to an insulating material such as an obtained insulating film.

  In Patent Document 1, an attempt is made to achieve both heat resistance and low dielectric constant by introducing an adamantyl group onto siloxane in the formation of an insulating film. However, with 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.

JP 2000-302791 A

  An object of the present invention is to provide a compound capable of providing an insulating material having a low dielectric constant and high mechanical strength, a composition for forming an insulating material using the compound, and an insulating material such as an insulating film obtained from the composition. To do.

一般式（１）中、Ｘ^２１〜Ｘ^２２は、各々独立に、アルコキシ基またはハロゲン原子を表し、Ｒ^２１〜Ｒ^２２は、各々独立に、アルキル基、アリール基又はヘテロ環基を表し、ｎ^２１〜ｎ^２２は１〜３の整数を表す。
ｐ２は０〜２を表し、ｐ２が０の場合、ｍ^２１は２〜４の整数を表し、ｐ２が１の場合、ｍ^２１＋ｍ^２２は２〜４の整数を表し、ｐ２が２の場合、ｍ^２１＋ｍ^２２は２〜６の整数を表す。
Ｌ^２１〜Ｌ^２２は、ビニレン基を表す。
＜２＞ ＜１＞に記載の一般式（１）で表される化合物の加水分解物及び／または縮合物。
＜３＞ 一般式（１）で表される化合物が、一般式（３−２）で表わされる化合物であることを特徴とする上記＜２＞に記載の加水分解物及び／または縮合物。

一般式（３−２）中、Ｘ^２１〜Ｘ^２２は、各々独立に、アルコキシ基またはハロゲン原子を表し、Ｒ^２１〜Ｒ^２２は、各々独立に、アルキル基、アリール基又はヘテロ環基を表し、ｎ^２１〜ｎ^２２は１〜３の整数を表す。
＜４＞ 一般式（３−２）で表わされる化合物において、Ｒ^２１〜Ｒ^２２が、各々独立に、アルキル基を表し、ｎ^２１〜ｎ^２２は２又は３の整数であることを特徴とする上記＜３＞に記載の加水分解物及び／または縮合物。
＜５＞ 上記＜２＞〜＜４＞のいずれか１項に記載の加水分解物及び／または縮合物及び溶媒を含有することを特徴とする絶縁材料形成用組成物。
＜６＞ 上記＜５＞に記載の組成物から形成された絶縁材料。
＜７＞ 上記＜５＞に記載の組成物から形成された絶縁膜。
＜８＞ 式１−５で表わされる化合物。

本発明は、上記＜１＞〜＜８＞に係る発明であるが、以下、他の事項も含めて説明している。
（１）下記一般式（１）で表される化合物を加水分解及び／または縮合して得られるケイ素酸素架橋化合物。 Specifically, the above object of the present invention can be achieved by the following constitution.
<1> A compound represented by the following general formula (1) .

In the general formula (1), X ^{21 to} X ²² each independently represents an alkoxy group or a halogen atom, R ^{21 to} R ²² each independently represents an alkyl group, an aryl group or a heterocyclic group, n ²¹ ~n ²² represents an integer of 1 to 3.
p2 represents 0-2, for p2 is ^{0, m 21} represents an integer of 2-4, when p2 is ^{1, m} 21 ⁺ m ²² represents an integer of 2 to 4, the case of p2 is 2, m ²¹ + m ²² represents an integer of 2 to 6.
L ^{21 to} L ²² represent a vinylene group.
<2> Hydrolyzate and / or condensate of the compound represented by the general formula (1) according to <1>.
<3> The compound represented by the general formula (1) is a hydrolyzate and / or condensate described in <2> which is a compound represented by the general formula (3-2).

In General Formula (3-2), X ^{21 to} X ²² each independently represent an alkoxy group or a halogen atom, and R ^{21 to} R ²² each independently represents an alkyl group, an aryl group, or a heterocyclic group. And n ^{21 to} n ²² represent an integer of 1 to 3.
< 4 > In the compound represented by the general formula (3-2), R ^{21 to} R ²² each independently represent an alkyl group, and n ^{21 to} n ²² are integers of 2 or 3. The hydrolyzate and / or condensate according to < 3 > above .
<5> above <2> to <4> insulating material-forming composition characterized by containing a hydrolyzate and / or condensate and solvent according to any one of.
< 6 > An insulating material formed from the composition described in < 5 > above.
< 7 > An insulating film formed from the composition according to < 5 > above.
< 8 > A compound represented by formula 1-5.

The present invention is an invention according to the above <1> to < 8 >, but will be described below including other matters.
(1) A silicon-oxygen crosslinking compound obtained by hydrolysis and / or condensation of a compound represented by the following general formula (1).

(In the general formula (1), X ^{21 to} X ²² each independently represents a hydrolyzable group, R ^{21 to} R ²² each independently represents an alkyl group, an aryl group or a heterocyclic group, n ²¹ ~n ²² represents an integer of 1 to 3.
p2 represents 0 to 2, when p2 is 0, m ²¹ represents an integer of 2 to 4, when p2 is 1, m ²¹ + m ²² represents an integer of 2 to 4, and when p2 is 2, m ²¹ + m ²² represents an integer of 2-6.
L ^{21 to} L ²² each independently represents a single bond, an alkylene group, a vinylene group, an arylene group, —O—, —S—, —CO—, —NR′— (R ′ represents a hydrogen atom, an alkyl group or an aryl group) Represents a group) or a divalent linking group in which these groups are combined.

(2) The silicon oxygen crosslinking compound as described in (1) above, wherein L ^{21 to} L ²² are an alkylene group or a vinylene group.

(3) A composition containing the silicon oxygen crosslinking compound according to (1) or (2) above.
(4) An insulating material formed from the composition described in (3) above.
(5) An insulating film formed from the composition as described in (3) above.
(6) A compound represented by the general formula (2).

(In General Formula (2), X ^{21 to} X ²² each independently represents a hydrolyzable group, R ^{21 to} R ²² each independently represents an alkyl group, an aryl group, or a heterocyclic group, and n ²¹ ~n ²² is .L ²¹ ~L ²² represents an integer of 1 to 3, each independently, an alkylene group, vinylene group, an arylene group, -O -, - S -, - CO -, - NR '- ( R ′ represents a hydrogen atom, an alkyl group or an aryl group) or a divalent linking group in which these groups are combined.

(7) A compound represented by formula (3-1) or (3-2).

(In the general formulas (3-1) and (3-2), X ^{21 to} X ²² each independently represents a hydrolyzable group, and R ^{21 to} R ²² each independently represents an alkyl group or an aryl group. Alternatively, it represents a heterocyclic group, and n ^{21 to} n ²² represent an integer of 1 to 3.)

  According to the silicon-oxygen crosslinking compound of the present invention, a novel composition capable of forming a highly reliable insulating film having a low relative dielectric constant of 2.4 or less and having no defects caused by moisture absorption or the like can be obtained. . In particular, the present invention can contribute to improving the response speed of a semiconductor device having a multilayer wiring structure.

  The silicon oxygen crosslinking compound of the present invention is obtained by hydrolysis and / or condensation of a silane compound represented by the following general formula (1).

In the general formula (1), X ^{21 to} X ²² each independently represents a hydrolyzable group, R ^{21 to} R ²² each independently represents an alkyl group, an aryl group or a heterocyclic group, and n ²¹ ~n ²² represents an integer of 1 to 3.
p2 represents 0 to 2, when p2 is 0, m ²¹ represents an integer of 2 to 4, when p2 is 1, m ²¹ + m ²² represents an integer of 2 to 4, and when p2 is 2, m ²¹ + m ²² represents an integer of 2-6.
L ^{21 to} L ²² each independently represents a single bond, an alkylene group, a vinylene group, an arylene group, —O—, —S—, —CO—, —NR′— (R ′ represents a hydrogen atom, an alkyl group or an aryl group) Represents a group) or a divalent linking group in which these groups are combined.

In the general formula (1), examples of the hydrolyzable group represented by X ^{21 to} X ²² include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyloxy group, and a hydroxyl group. X ^{21 to} X ²² are preferably an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group) or a halogen atom. Particularly preferred are a methoxy group, an ethoxy group, and a chlorine atom.

R ^{21 to} R ²² represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Preferable examples of the alkyl group represented by R ^{21 to} R ²² 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.), and preferred examples of the aryl group represented by R ^{21 to} R ²² include 6 carbon atoms. 20 substituted or unsubstituted phenyl group, a naphthyl group and the like, and preferred examples of the heterocyclic group represented by R ²¹ to R ²² is a substituted or unsubstituted of hetero 6-membered ring (pyridyl, morpholino Group, tetrahydropyranyl, etc.), substituted or unsubstituted hetero 5-membered rings (furyl, thiophene group, 1,3-dioxolan-2-yl group, etc.) and the like.

In the case of n ^{21 to} n ²² = 2 or 3, the plurality of X ^{21 to} X ²² may be the same group or different from each other. When n ^{21 to} n ²² = 1, the plurality of R ^{21 to} R ²² may be the same group or different from each other.

L ^{21 to} L ²² represent 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, and a linking group having 10 or less carbon atoms is preferable. Of the linking groups, an alkylene group and an alkenylene group are preferable, and an ethylene group and a vinylene group are particularly preferable.

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

In the general formula (2), each of X ^{21 to} X ²² , R ^{21 to} R ²² , n ^{21 to} n ²² , and L ^{21 to} L ²² is the same as that in the general formula (1).

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

In the general formulas (3-1) and (3-2), X ^{21 to} X ²² , R ^{21 to} R ²² , and n ^{21 to} n ²² are the same as those in the general formula (1).

  The compound represented by the general formula (1) includes, for example, a hydrosilylation reaction in which a corresponding silane compound is added to a compound having a corresponding unsaturated group in the presence of a transition metal complex catalyst or a halogenated adaamantane and a corresponding Grignard reagent. It can be easily synthesized by this reaction.

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

  In order to improve the film characteristics of the material, another silane compound may be added to the silane compound represented by the general formula (1) as necessary. Examples of other silane compounds include organosilicon compounds represented by the following general formula (A) or polymers having 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 of general formula (1), and to use in the range of 10-100 mol%. More preferred.

The method for obtaining a silicon oxygen cross-linked compound by hydrolysis and condensation using the silane compound represented by the above general formula (1) and, if necessary, other silane compounds in combination is as follows. Note that 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 is used per 1 mol of the total amount of the silane compound represented by the general formula (1) and, if necessary, other silane compounds. It is particularly preferable to add 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 silane 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, Examples thereof include tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and ammonia, amine or amine salt is preferable, and ammonia Organic amines or organic amine salts are particularly preferred, and ammonia, 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, 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.), Examples thereof include boric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid, and solid acids such as tungstophosphoric acid and tungten peroxo complex.
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, methylmalonic 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, dichloroacetic 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 Phthalic acid hydrolysates, trifluoroacetic acid, benzoic acid, substituted benzoic acid, etc.), phosphate esters For example, C 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 didodecyl ester, etc.), phosphorous acid esters (for example, C number 1 ~ 30,
Phosphorous acid methyl ester, phosphorous acid dodecyl ester, phosphorous acid diethyl ester, diisopropyl phosphite, phosphorous acid dododecyl ester, etc.), sulfonic acids (for example, C 1-15, benzene sulfonic acid, toluene sulfonic acid, Hexafluorobenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid, etc.), imides (for example, bis (trifluoromethanesulfonyl) imidic acid, trifluoromethanesulfonyltrifluoroacetamide, etc.), phosphonic acids (for example, C 1) To 30, low molecular weight compounds such as methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, 1,5-naphthalene bisphosphonic acid), or perfluorocarbon sulfone represented by Nafion Acid polymer, poly (meth) acrylate having a phosphate group in the side chain (Japanese Patent Application Laid-Open No. 2001-14834), sulfonated polyetheretherketone (Japanese Patent Application Laid-Open No. 6-93111), sulfonated polyethersulfone (Japanese Patent Application Laid-Open 45913) and sulfonated polysulfone (Japanese Patent Laid-Open No. 9-245818).

  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 (Acetylacetonate) titanium, monoethoxy-tris (acetylacetonate) titanium, 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 and tris (ethylacetoacetate) aluminum; 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 silane 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 condensing and hydrolyzing the silane 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.
Thus, the hydrolyzate and condensate of the silane compound represented by the general formula (1), that is, the silicon oxygen crosslinking compound of the present invention can be prepared.

  The solvent used in the reaction is not particularly limited as long as it dissolves the solute silane 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 ethers ( Diethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, etc.), alcohols (methanol, ethanol, etc.) Isopropanol, ethylene glycol 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, methoxypropion) Methyl acetate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, 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, dimethylacetamide, etc.), nonpolar solvents (toluene, xylene, mesitylene, etc.), chlorinated solvents (methylene dichloride, ethylene dichloride, etc.), diisopropylbenzene, water and the like can be used.

  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 usually contains at least one of the silane compound itself represented by the general formula (1), the hydrolyzate of the silane compound prepared above, and the condensate. If necessary, it is prepared by dissolving in a solvent such as an organic solvent or water exemplified as a solvent used for hydrolysis and condensation.

  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, roll coating, or spraying 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 solvent of the present invention is applied by applying the composition of the present invention on a substrate (usually a substrate having metal wiring) by, for example, spin coating, and performing a first heat treatment at a temperature of 300 ° C. or lower. 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. In addition, this invention is not limited by the following Example. Examples 1, 2, 4 and 5 are reference examples.

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

In a nitrogen stream, 20 μl of M-1 (3.8 g) and platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene (Aldrich) 25 ml of toluene And heated to 80 ° C. Thereto, triethoxysilane (8.3 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 5.7 g of 1-1 (white crystals).

[Synthesis Example 2: Synthesis of Compound 1-3]
5.3 g of 1-3 (white crystals) was obtained in the same manner as in Synthesis Example 1 except that 6.7 g of diethoxymethylsilane was used instead of triethoxysilane.

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

  In a nitrogen stream, 10 μl of M-2 (1.5 g) and platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene (Aldrich) 5 ml of toluene And heated to 80 ° C. To this, triethoxysilane (3.3 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 2.8 g of 1-5 (white crystals).

[Example 1: Preparation of coating solution]
7 mmol of the compound 1-1 was dissolved in a 3: 1 (volume ratio) mixed solvent of propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) 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 2 to 5: Preparation of coating solution]
A coating solution was prepared in the same manner as in Example 1, except that the compounds shown in Table 1 and the solvent were used. PGP in Table 1 is propylene glycol monopropyl ether.

[Comparative example: Preparation of coating solution]
A coating solution was prepared under the same conditions as in Example 1 using adamantyltriethoxysilane.
In addition, the ratio of the solvent in Table 1 is a volume ratio.

[Preparation of insulating film]
The coating solution prepared as described above was spin-coated on a silicon substrate so as to have a film thickness of 4000 A, and dried on a hot plate at 150 ° C. for 1 minute to remove the solvent. 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 left for 24 hours at a temperature of 24 ° C. and a humidity of 50%, the dielectric constant was measured at 1 MHz using a mercury probe manufactured by Four Dimensions and an HP4285A LCR meter manufactured by Hewlett-Packard. The measurement results are shown in Table 2.

[Measurement of elastic modulus (Young's modulus)]
The elastic modulus at 1/10 depth of the film thickness was measured using 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 high Young's modulus, a low dielectric constant, and excellent performance.

Claims (8)

A compound represented by the following general formula (1) .

In the general formula (1), X ^{21 to} X ²² each independently represents an alkoxy group or a halogen atom, R ^{21 to} R ²² each independently represents an alkyl group, an aryl group or a heterocyclic group, n ²¹ ~n ²² represents an integer of 1 to 3.
p2 represents 0-2, for p2 is ^{0, m 21} represents an integer of 2-4, when p2 is ^{1, m} 21 ⁺ m ²² represents an integer of 2 to 4, the case of p2 is 2, m ²¹ + m ²² represents an integer of 2 to 6.
L ^{21 to} L ²² represent a vinylene group. A hydrolyzate and / or condensate of the compound represented by formula (1) according to claim 1. The hydrolyzate and / or condensate according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the general formula (3-2).

In general formula (3-2), X ²¹ ~ X ²² Each independently represents an alkoxy group or a halogen atom; ²¹ ~ R ²² Each independently represents an alkyl group, an aryl group or a heterocyclic group, and n ²¹ ~ N ²² Represents an integer of 1 to 3. In the compound represented by the general formula (3-2), R ²¹ ~ R ²² Each independently represents an alkyl group, n ²¹ ~ N ²² The hydrolyzate and / or condensate according to claim 3, wherein is an integer of 2 or 3. An insulating material forming composition comprising the hydrolyzate and / or condensate according to any one of claims 2 to 4 and a solvent. An insulating material formed from the composition according to claim 5. An insulating film formed from the composition according to claim 5. A compound represented by formula 1-5.