JP2009051971A - Composition for interlayer insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an interlayer insulating film used for electronic devices and the like that exhibits good film properties such as a dielectric constant or mechanical strengths, good adhesion to a substrate and excellent stability of a coating liquid. <P>SOLUTION: The composition for an interlayer insulating film comprises the following components. (A) A hydrolyzate obtained by hydrolyzing an alkoxysilane or an acyloxysilane having at least one styryl group optionally bearing one or more substituent group in the molecule. (B) A compound having at least two carbon-carbon triple bonds in the molecule. (C) A solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a film-forming composition, and more particularly, a composition for forming an interlayer insulating film having good film properties such as dielectric constant, mechanical strength, heat resistance, etc. used in electronic devices, and having good temporal stability. Further, the present invention relates to an insulating film obtained using the composition and an electronic device having the insulating film.

  In recent years, in the field of electronic materials, with the progress of higher integration, more functions, and higher performance, circuit resistance and capacitor capacity between wirings have increased, leading to an increase in power consumption and delay time. In particular, an increase in delay time is a major factor in reducing the signal speed of the device and the occurrence of crosstalk. Therefore, in order to reduce the delay time and speed up the device, it is necessary to reduce parasitic resistance and parasitic capacitance. It has been. As a specific measure for reducing this parasitic capacitance, an attempt has been made to cover the periphery of the wiring with a low dielectric interlayer insulating film. In addition, the interlayer insulating film is required to have excellent heat resistance and chemical resistance that can withstand a subsequent process such as a thin film formation process, chip connection, and pinning during manufacturing of a mounting substrate. Furthermore, in recent years, low resistance Cu wiring is being introduced from Al wiring, and along with this, planarization by CMP (Chemical Mechanical Polishing) has become common, and high mechanical strength that can withstand this process is high. It has been demanded.

Polybenzoxazole, polyimide, polyarylene (ether), and the like have been disclosed for a long time as a high heat-resistant interlayer insulating film, but a material having a lower dielectric constant is desired to realize a high-speed device. When a heteroatom such as oxygen, nitrogen or sulfur or an aromatic hydrocarbon unit is introduced into the polymer molecule as in this material, the dielectric constant increases due to high molar polarization, or the dielectric constant over time due to moisture absorption. Improvements are necessary because of the increase in the rate and problems that impair the reliability of the electronic device.
On the other hand, a polymer composed of saturated hydrocarbons has an advantage that it exhibits a lower dielectric constant because it has a smaller molar polarization than a polymer composed of heteroatom-containing units or aromatic hydrocarbon units. However, for example, highly flexible hydrocarbons such as polyethylene have insufficient heat resistance and have been difficult to use for electronic device applications.

Under such circumstances, a low dielectric constant material containing a polycyclic carbocyclic compound having a cage structure has been proposed as an insulating film material having excellent low dielectric properties, insulating properties, heat resistance, and durability. Among them, a polymer obtained by polymerizing a compound having a carbon-carbon unsaturated bond is disclosed as an excellent material (Patent Document 1). These insulating films, as organic compound films, show excellent results of achieving both extremely high heat resistance and low dielectric constant, but have been required to be improved in terms of adhesion to the substrate.
As an adhesive for an interlayer insulating film, studies on silane compounds have been disclosed (Patent Documents 2 and 3). Although these certainly show the effect of improving adhesion, in order to obtain sufficient adhesion, it is necessary to add a large amount so as to adversely affect other performances. There was a problem such as loss of sex, and further improvement was demanded.

US Patent Application Publication No. 2005/0276964 JP 2005-146034 A US Pat. No. 6,184,284

  The present invention relates to a composition for an interlayer insulating film for solving the above-mentioned problems, and more specifically, film characteristics such as dielectric constant and mechanical strength used for electronic devices and the like, and adhesion to a substrate and coating. The present invention relates to a composition for an interlayer insulating film having excellent liquid stability, and further relates to an insulating film obtained using the composition and an electronic device having the same.

It has been found that the above problems are solved by the following <1> to <5> configurations.
<1> A composition for an interlayer insulating film containing the following components.
(A) a hydrolyzate obtained by hydrolyzing an alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule;
(B) a compound having at least two carbon-carbon triple bonds in the molecule, and (C) a solvent.
<2> The composition according to <1>, wherein the compound (B) further has a cage structure in the molecule.
<3> The composition according to <2>, wherein the cage structure is selected from the group consisting of adamantane, biadamantane, diamantane, triamantane, and tetramantane.
<4> An insulating film formed using the composition according to any one of <1> to <3>.
<5> An electronic device having the insulating film according to <4>.

With the interlayer insulating film composition of the present invention, an interlayer insulating film having excellent adhesion and mechanical strength can be formed.
In addition, the interlayer insulating film composition of the present invention can form an interlayer insulating film with improved adhesion and mechanical strength while maintaining the properties of heat resistance and low dielectric constant.
In addition, with the interlayer insulating film composition of the present invention, it is possible to obtain a good interlayer insulating film composition in which adhesion is not lost even when heat treatment at about 400 ° C. is repeated while maintaining other performances.

Hereinafter, the present invention will be described in detail.
The composition for interlayer insulation films of this invention contains the following components.
(A) a hydrolyzate obtained by hydrolyzing an alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule;
(B) a compound having at least two carbon-carbon triple bonds in the molecule, and (C) a solvent.
Each component will be described below.

(A) A hydrolyzate obtained by hydrolyzing an alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule. Or a styryl group optionally having a plurality of substituents, that is, a group obtained by removing one hydrogen atom from styrene (vinylbenzene), preferably a form obtained by removing one hydrogen atom on the benzene ring of styrene (vinylbenzene). It is a compound obtained by hydrolyzing an alkoxysilane or acyloxysilane having at least one group which is a group and optionally has one or more substituents on the benzene ring. Examples of the substituent include a group represented by R ₂ in formula (1) described later. When a plurality of substituents are present, the substituents may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms of the benzene ring.

Hydrolysis may be performed by adding water to alkoxysilane or acyloxysilane, or adding alkoxysilane or acyloxysilane to water, but is preferably diluted with a solvent.
Since the main solvent used for the hydrolysis also functions as a coating solvent in the interlayer insulating film composition (coating liquid) of the present invention, it is organic from the viewpoints of solubility in the coating liquid and coated surface. It is preferably a solvent, preferably an alcohol, a ketone, an ester or an ether, more preferably a ketone or an ether, and most preferably a ketone.
Moreover, from the viewpoint of the coating surface shape and ease of drying during coating, the main solvent used for the hydrolysis is preferably 90 ° C. to 210 ° C. as the boiling point at normal pressure, and 110 ° C. to 190 ° C. More preferably, it is most preferably 130 ° C to 170 ° C. If the boiling point is too low, the drying rate is too high and unevenness in the surface is likely to occur. If the boiling point is too high, the residual amount in the film tends to be too large.

  Specifically, low-molecular weight (about 4 to 10 carbon atoms) cyclic, branched or linear alkyl ketones such as cyclohexanone and 2-heptanone can be mentioned as the most preferred examples.

Hydrolysis is usually performed by diluting an alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule with the above solvent, and then adding water dropwise to the diluted solution. Alternatively, alkoxysilane or acyloxysilane (or a solution thereof) having at least one styryl group in the molecule may be dropped into a mixed solution of a solvent and water. Preferably, an alkoxysilane or acyloxysilane having at least one styryl group having one or more substituents in the molecule is dropped into a mixed solution of a solvent and water.
The amount of water added is usually 1 equivalent or more, preferably 3 equivalents or more, more preferably 5 equivalents or more, and still more preferably 8 equivalents or more, relative to the silane compound.
The water preferably contains no metal elements, and the content of each metal element is preferably 300 ppb or less, more preferably 100 ppb or less, and even more preferably 10 ppb or less. Therefore, it is preferable to use distilled water, ultrapure water, or the like.

In the hydrolysis, an acid catalyst may be added in order to improve the hydrolysis reaction rate. As the acid catalyst, a Bronsted acid of -1 <pKa <11 is preferable, 0 <pKa <9 is more preferable, and 1 <pKa <7 is most preferable. If the acidity is too weak, the effect of improving the hydrolysis rate is small, and if the acidity is too strong, the condensation reaction of silanol after hydrolysis is promoted, which may cause a problem in stability over time.
Specifically, carboxylic acid is preferable, and considering the volatility at the time of coating and drying, 1 to 10 carbon atoms are preferable, 1 to 8 are more preferable, and 2 to 6 are most preferable.
The addition amount of the acid catalyst can be appropriately determined according to the hydrolysis conditions such as the purpose and temperature. For example, it is 20 ppm to 80% with respect to the total mass of the hydrolysis reaction solution.

Conditions such as the temperature and time of the hydrolysis reaction vary depending on the substrate, and may be appropriately set according to the rate of the hydrolysis reaction. For example, in the case of acyloxysilane, the progress of the hydrolysis reaction can be confirmed by quantifying the carboxylic acid resulting from the hydrolysis by ¹ H-NMR, and in the case of alkoxysilane, the alcohol resulting from the hydrolysis. Can be confirmed by quantitative determination.
In the case of acyloxysilane, the temperature and time of a general hydrolysis reaction are from -30 ° C to 50 ° C for about 1 minute to 6 hours, and in the case of alkoxysilane, from 0 ° C to 120 ° C for 1 minute to 24 hours. It is about time.
After completion of the reaction, it is usually preferable to use the reaction solution as it is as the component (A) and the component (C) of the interlayer insulating film composition. However, as described later, another solvent may be further added as the component (C).

式中、Ｒ₁はアルキル基若しくはアシル基であり、Ｌは、２価の連結基である。
ｎ＝１〜５の整数である。
Ｒ₂は、水素原子、又は、任意の置換基を表し、Ｒ₂が複数存在する場合、Ｒ₂同士は互いに同一であっても異なっていても良く、互いに結合してベンゼン環の炭素原子と共に環構造を形成しても良い。 As an alkoxysilane and an acyloxysilane suitably used in the present invention, it is essential to have a styryl group optionally having one or more substituents in the molecule.
In the present specification, the alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule is preferably a trialkoxysilane or trialumina represented by the following general formula (1). It is a siloxysilane compound.

In the formula, R ₁ is an alkyl group or an acyl group, and L is a divalent linking group.
n is an integer of 1 to 5.
R ₂ is a hydrogen atom, or represents an optional substituent, if R ₂ there are a plurality, R ₂ to each other may be the being the same or different, together with the carbon atoms of the benzene ring bonded to each other A ring structure may be formed.

The alkyl group in the general formula (1) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl, ethyl and propyl groups.
The acyl group in the general formula (1) is preferably an alkanoyl group having 1 to 7 carbon atoms (R′C═O: R ′ is hydrogen, an alkyl group having 1 to 6 carbon atoms), more preferably formyl or acetyl. And a propanoyl group.
Examples of the divalent linking group represented by L in the general formula (1) include a single bond or a group represented by -L1-L2-L3-. L 1, L 2 and L 3 are independently a group selected from the group consisting of a single bond, — (CH ₂ ) n — (n is an integer of 1 to 5), NH, S, O, C (═O), and phenylene. Represents.
L is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, or an arylene group having 5 to 12 carbon atoms, and most preferably a single bond.
R ₂ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, carbon An alkoxy group having 1 to 10 atoms, an aryloxy group having 6 to 12 carbon atoms, an acyl group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and an arylcarbonyl group having 6 to 12 carbon atoms , An arylcarbonyloxy group having 6 to 12 carbon atoms. Examples of the ring structure formed by combining a plurality of R ₂ together with the carbon atoms of the benzene ring include cycloalkyl rings such as cyclopentyl and cyclohexyl, and aromatic rings such as phenyl.
More preferred are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and an alkynyl group having 1 to 10 carbon atoms, and most preferred is a hydrogen atom.

The component (A) is typically prepared by diluting an alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule with a reaction solvent, adding water, It can manufacture by performing a hydrolysis reaction.
The reaction substrate concentration (dilution ratio) in carrying out the hydrolysis reaction is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and most preferably 10% by mass. It is as follows. The reaction substrate concentration is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and most preferably 0.5% by mass or more. If the concentration is too low, the amount of solvent may be too large to adjust the target addition amount when preparing the coating solution.

As specific examples of alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule, the following compounds can be exemplified.

(B) Compound having at least two carbon-carbon triple bonds in the molecule (B) The component (B) can be used without particular limitation as long as it is a compound having at least two carbon-carbon triple bonds in the molecule. However, from the viewpoint of film formability, a polymer is preferable, a polymer having a weight average molecular weight of 500 or more is preferable, 1000 or more is more preferable, and 2000 or more is most preferable.

When the component (B) is a polymer, it may be a compound obtained by polymerizing a monomer represented by the following general formula (2) by a method described later.

In the formula, R ₃ is a linear, branched or cyclic m-valent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. Specific examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 10 to 20 carbon atoms. The cage-type structural group of More preferably, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a cage structure group having 10 to 20 carbon atoms can be used. The cage structure group will be described later.
m is 1 or more and is less than the valence of R ₃ . That is, in the general formula (2), m means the number of triple bonds directly bonded to R _3, and therefore the valence represented by R ₃ is the maximum value m can take. m is preferably 2 or more.

Examples of the substituent for R ₃ include a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cage structure group having 10 to 20 carbon atoms, or carbon. A silyl group of several 0-20 is mentioned. More preferred are an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and particularly preferred is an alkyl group having 1 to 10 carbon atoms.

  X is each independently a hydrogen atom or a hydrocarbon group having about 1 to 20 carbon atoms. Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silyl group having 0 to 20 carbon atoms. Group, an acyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, and the like. Among these, Preferably a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, a C0-C20 silyl group, a C2-C10 acyl group, C2-C10 Examples thereof include an alkoxycarbonyl group and a carbamoyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom and an aryl group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.

  In the present specification, the term “monomer” refers to a monomer that is polymerized to be a dimer or higher polymer. This polymer may be a homopolymer or a copolymer.

  The polymerization reaction of the monomer is caused by the polymerizable group substituted for the monomer. Here, the polymerizable group refers to a reactive substituent that polymerizes the monomer. The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, and transition metal catalyst polymerization.

In the present invention, the monomer polymerization reaction is preferably performed in the presence of a nonmetallic polymerization initiator. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond may be polymerized in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating. I can do it.
As the polymerization initiator, an organic peroxide or an organic azo compound is preferably used, and an organic peroxide is particularly preferable.

Examples of the organic peroxide include ketone peroxides such as perhexa H, peroxyketals such as perhexa TMH, hydroperoxides such as perbutyl H-69, park mill D, and perbutyl C, which are commercially available from Nippon Oil & Fats Co., Ltd. Dialkyl peroxides such as perbutyl D, diacyl peroxides such as niper BW, peroxyesters such as perbutyl Z and perbutyl L, and peroxydicarbonates such as peroyl TCP are preferably used.
As organic azo compounds, azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70, which are commercially available from Wako Pure Chemical Industries, Ltd., VA-080, Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidine compounds such as V-50 and VA-057 Etc. are preferably used.

  In the present invention, the polymerization initiator may be used alone or in combination of two or more. In the present invention, the amount of the polymerization initiator used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and particularly preferably 0.05 to 0.5 mol, relative to 1 mol of the monomer. .

In the present invention, the monomer polymerization reaction is also preferably performed in the presence of a transition metal catalyst. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond may be a Pd-based catalyst such as Pd (PPh ₃ ) ₄ , Pd (OAc) ₂ , Ziegler-Natta catalyst, nickel acetylacetonate, etc. polymerized using a Ni-based catalyst, W-based catalyst such as WCl _6, Mo-based catalysts such as MoCl _5, Ta catalysts such as TaCl _5, Nb-based catalyst such as NbCl _5, Rh-based catalyst, a Pt-based catalyst and the like It is preferable.

  In the present invention, only one transition metal catalyst or a mixture of two or more transition metal catalysts may be used. In the present invention, the amount of the transition metal catalyst used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and particularly preferably 0.05 to 0.5 mol with respect to 1 mol of the monomer.

R ₃ in the general formula (2) is a cage structure group (a group derived by removing a hydrogen atom or other group from the cage structure) from the viewpoint of achieving both heat resistance and a low dielectric constant. Particularly preferred.
Hereinafter, a compound in which R ₃ in the general formula (2) is a cage structure group is also referred to as a “monomer having a cage structure group”.
Further, as the compound of the component (B) of the present invention, another compound containing a cage structure group in the molecule may be used. In the following, the term “compound having a cage structure” means not only a compound in which R ₃ is a cage structure group in the polymer of the monomer, but also other compounds containing a cage structure group in the molecule. .

  The “cage structure” described in the present invention is such that 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. Refers to a molecule. 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. .

In the present invention, the cage structure may contain either a saturated or unsaturated bond and may contain a heteroatom such as oxygen, nitrogen or sulfur, but a saturated hydrocarbon is preferred from the viewpoint of a low dielectric constant.
The cage structure in the present invention is preferably adamantane, biadamantane, diamantane, triamantane, tetramantane, dodecahedran, more preferably adamantane, biadamantane, diamantane, and particularly in terms of low dielectric constant, biadamantane, Diamantane is preferred.

  The cage structure in the present invention may have one or more substituents. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), a carbon number of 1 to 10. Linear, branched and cyclic alkyl groups (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups having 2 to 10 carbon atoms (vinyl, propenyl, etc.), alkynyl groups having 2 to 10 carbon atoms (ethynyl, phenyl) Ethynyl, etc.), C6-C20 aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), C2-C10 acyl groups (benzoyl, etc.), C2-C10 alkoxycarbonyl groups (methoxycarbonyl) Etc.), a carbamoyl group having 1 to 10 carbon atoms (N, N-diethylcarbamoyl etc.), an aryloxy group having 6 to 20 carbon atoms (phenoxy etc.), 6 carbon atoms 20 arylsulfonyl group (phenylsulfonyl, etc.), nitro groups, cyano group, a silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl or the like) and the like.

  The cage structure group in the present invention is preferably divalent to tetravalent. At this time, the group bonded to the cage structure may be a monovalent or higher valent substituent or a divalent or higher linking group. The cage structure group is preferably divalent or trivalent, and particularly preferably divalent.

The polymerization reaction of the monomer having a cage structure group is caused by the polymerizable group substituted for the monomer. Here, the polymerizable group refers to a reactive substituent that polymerizes the monomer. The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, and transition metal catalyst polymerization.
As the polymerization method, the method described for the polymerization method of the compound of the general formula (2) can be applied.

In the “compound having a cage structure” in the present invention, the cage structure group may be substituted as a pendant group in the polymer and may be a part of the polymer main chain. The form which is a part is more preferable. Here, the form which is a part of the polymer main chain means that the polymer chain is cleaved when the cage structure group is removed from the polymer. In this form, the cage structure group is directly single-bonded or linked by an appropriate divalent linking group. Examples of the linking group include, for example, —C (R ₁₁ ) (R ₁₂ ) —, —C (R ₁₃ ) ═C (R ₁₄ ) —, —C≡C—, arylene group, —CO—, —O—. , —SO ₂ —, —N (R ₁₅ ) —, —Si (R ₁₆ ) (R ₁₇ ) —, or a combination thereof. Here, R _{11 to} R ₁₇ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. These linking groups may be substituted with a substituent, and for example, the above-described substituents are preferable examples.
Among these, more preferred linking groups are —C (R ₁₁ ) (R ₁₂ ) —, —CH═CH—, —C≡C—, arylene group, —O—, —Si (R ₁₆ ) (R ₁₇ ). — Or a combination thereof, and particularly preferred are —C (R ₁₁ ) (R ₁₂ ) — and —CH═CH— from the viewpoint of low dielectric constant.

  In the present invention, the compound having a cage structure may be a low molecular compound or a high molecular compound (for example, a polymer), but a preferable one is a polymer. When the compound having a cage structure is a polymer, the mass average molecular weight is preferably 1,000 to 500,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000. The polymer having a cage structure may be included in the interlayer insulating film coating solution as a resin composition having a molecular weight distribution. When the compound having a cage structure is a low molecular compound, the molecular weight is preferably 150 to 3000, more preferably 200 to 2000, and particularly preferably 220 to 1000.

In the present invention, the compound having a cage structure is more preferably a polymer of compounds represented by the following formulas (I) to (VI).
However, in the present invention, since the component (B) is a compound having at least two bonds selected from carbon-carbon triple bonds in the molecule, the compound obtained by polymerization has a carbon-carbon triplet in the molecule. The monomers of the formulas (I) to (VI) can be appropriately selected and combined for copolymerization so that the compound has at least two bonds selected from the bonds. For example, the monomer of formula (I) can be used alone, but the monomer of formula (IV) can be used as a monomer for a copolymer with another monomer that provides a carbon-carbon triple bond.

In formulas (I) to (VI),
X _{1 to} X ₈ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. A silyl group having 0 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms and the like are represented. Among these, Preferably a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, a C0-C20 silyl group, a C2-C10 acyl group, C2-C10 An alkoxycarbonyl group and a carbamoyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom and an aryl group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.
Y _{1 to} Y ₈ each independently represents a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a silyl group having 0 to 20 carbon atoms; Preferably they are a C1-C10 alkyl group and C6-C20 aryl group which may have a substituent, Especially preferably, they are an alkyl group (methyl group etc.).
X _{1 to} X ₈ and Y _{1 to} Y ₈ may be further substituted with another substituent.

m ₁ and m ₅ each independently represents an integer of 1 to 16, preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2.
n ₁ and n ₅ each independently represents an integer of 0 to 15, preferably 0 to 4, more preferably 0 or 1, and particularly preferably 0.
m ₂ , m ₃ , m ₆ and m ₇ each independently represents an integer of 1 to 15, preferably 1 to 4, more preferably 1 to 3, particularly preferably 1.
n ₂ , n ₃ , n ₆ and n ₇ each independently represents an integer of 0 to 14, preferably 0 to 4, more preferably 0 or 1, and particularly preferably 0.
m ₄ and m ₈ each independently represents an integer of 1 to 20, preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2.
n ₄ and n ₈ each independently represents an integer of 0 to 19, preferably 0 to 4, more preferably 0 or 1, and particularly preferably 0.

  In the present invention, the compound having a cage structure is preferably a polymer of the above formulas (II), (III), (V), (VI), more preferably a polymer of the above formulas (II), (III). Particularly preferred is a polymer of the above formula (III).

  In the present invention, two or more compounds having a cage structure may be used in combination. Moreover, you may use what copolymerized 2 or more types of monomers which have a cage structure group.

  In the present invention, the compound having a cage structure preferably has sufficient solubility in an organic solvent. The solubility is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more in cyclohexanone or anisole at 25 ° C.

  Examples of the compound having a cage structure in the present invention include polybenzoxazole described in JP-A-11-322929, JP-A-2003-12802, JP-A-2004-18593, and quinoline resin described in JP-A-2001-2899. Special table 2003-530464, Special table 2004-535497, Special table 2004-504424, Special table 2004-504455, Special table 2005-501131, Special table 2005-516382, Special table 2005-514479, JP-A-2005-522528, JP-A-2000-100808, US Pat. No. 6,509,415, polyaryl resins, JP-A-11-214382, JP-A-2001-332542, JP-A-2003-252882, JP-A-2003-292878 No., JP2004-2 No. 87, JP 2004-67877, poly adamantane described in JP 2004-59444, JP 2003-252992, polyimides and the like described in JP 2004-26850.

  Specific examples of the compounds represented by formulas (I) to (VI) that can be used in the present invention are described below, but the present invention is not limited thereto.

When the above monomers are polymerized, any solvent can be used in the polymerization reaction as long as the raw material monomer can be dissolved at a necessary concentration and does not adversely affect the characteristics of the film formed from the resulting polymer. You may use anything. For example, alcohol solvents such as water, methanol, ethanol, propanol, alcohol solvents such as alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate Ester solvents such as dibutyl ether and anisole, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t- Butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1- Aromatic hydrocarbon solvents such as tilnaphthalene and 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Halogen solvents such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene and aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane can be used. Among these, more preferred solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1, 2, 4, 5 -Tetramethylbenzene, isopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methylnaphthalene 1,3,5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, Sole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, Chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyrolactone, anisole, mesitylene, t-butylbenzene, 1,3,5-triisopropylbenzene, 1,2- Dichlorobenzene and 1,2,4-trichlorobenzene. These may be used alone or in admixture of two or more.
The concentration of the monomer in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

Optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, monomer, solvent type, concentration, and the like, but preferably the internal temperature is 0 ° C to 200 ° C, more preferably 50 ° C to 170 ° C, and particularly preferably 100. C. to 150.degree. C., preferably 1 to 50 hours, more preferably 2 to 20 hours, and particularly preferably 3 to 10 hours.
Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
The preferable range of the weight average molecular weight of the polymer obtained by polymerization is 1000 to 500000, more preferably 5000 to 300000, and particularly preferably 10000 to 200000.

The compound having a cage structure in the present invention is prepared, for example, by using commercially available diamantane as a raw material and reacting with bromine in the presence or absence of an aluminum bromide catalyst to introduce a bromine atom at a desired position, followed by aluminum bromide, Synthesis by introducing 2,2-dibromoethyl group by reaction with vinyl bromide and Friedel-Crafts in the presence of Lewis acids such as aluminum chloride and iron chloride, followed by dehydrobration with strong base and conversion to ethynyl group can do. Specifically, Macromolecules. 1991, 24, 5266-5268, 1995, 28, 5554-5560, Journalof Organic Chemistry. , 39, 2995-3003 (1974) and the like.
Moreover, an alkyl group or a silyl group can be introduced by anionizing a hydrogen atom of a terminal acetylene group with butyllithium or the like and reacting this with an alkyl halide or a silyl halide.
In the present invention, the polymers may be used alone or in admixture of two or more.

(C) Solvent As the solvent used in the composition for an interlayer insulating film of the present invention, the solvent used at the time of hydrolysis of the component (A) is mainly used as it is. Therefore, the main solvent at the time of hydrolysis also functions as a coating solvent for the coating solution. However, the following coating solvent may be further used as the main solvent.
The coating solvent used in the present invention is not particularly limited. For example, alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol and 1-methoxy-2-propanol, acetone , Ketone solvents such as acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate Ester solvents such as ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone , Ether solvents such as diisopropyl ether, dibutyl ether, ethyl propyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methylpyrrolidinone, dimethyl Examples include amide solvents such as acetamide, and these may be used alone or in admixture of two or more.

More preferred coating solvents are 1-methoxy-2-propanol, propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, t-butylbenzene, especially Preferred are 1-methoxy-2-propanol, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene and anisole.
The solid content concentration of the composition for interlayer insulating films of the present invention is preferably 1 to 50% by mass, more preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass.

(D) Other components The composition for an interlayer insulating film of the present invention preferably has a sufficiently low metal content as an impurity. The metal concentration of the composition for interlayer insulating film can be measured with high sensitivity by ICP-MS method, and the metal content other than transition metal in that case is preferably 30 ppm or less, more preferably 3 ppm or less, particularly preferably 300 ppb. It is as follows. In addition, the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the prebaking and thermosetting processes, the content is preferably smaller. Preferably it is 10 ppm or less, More preferably, it is 1 ppm or less, Most preferably, it is 100 ppb or less.
The metal concentration of the interlayer insulating film composition can also be evaluated by performing total reflection X-ray fluorescence measurement on a film obtained using the interlayer insulating film composition of the present invention. When W line is used as the X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, and each is 100 × 10 ¹⁰ cm ⁻² or less. Is more preferably 50 × 10 ¹⁰ cm ⁻² or less, and particularly preferably 10 × 10 ¹⁰ cm ⁻² or less. Further, Br which is halogen can be observed, and the residual amount is preferably 10000 × 10 ¹⁰ cm ⁻² or less, more preferably 1000 × 10 ¹⁰ cm ⁻² or less, particularly preferably 400 × 10 ¹⁰ cm ⁻² or less. is there. Further, although Cl can be observed as halogen, the remaining amount is preferably 100 × 10 ¹⁰ cm ⁻² or less, more preferably 50 × 10 ¹⁰ cm ⁻² or less from the viewpoint of damaging a CVD apparatus, an etching apparatus, or the like. Particularly preferably, it is 10 × 10 ¹⁰ cm ⁻² or less.

  Furthermore, the composition for an interlayer insulating film of the present invention includes a radical generator and colloidal silica as long as the properties of the obtained insulating film (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) are not impaired. Further, additives such as a surfactant, a silane coupling agent, and an adhesive may be added.

  Any colloidal silica may be used in the present invention. For example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water, usually having an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of about 5 to 40% by weight It is.

  Any surfactant may be used in the present invention, and examples thereof include nonionic surfactants, anionic surfactants, and cationic surfactants, and also include silicon surfactants and fluorine-containing interfaces. Activators, polyalkylene oxide surfactants, and acrylic surfactants can be mentioned. The surfactant used in the present invention may be one type or two or more types. As the surfactant, a silicon-based surfactant, a nonionic surfactant, a fluorine-containing surfactant, and an acrylic surfactant are preferable, and a silicon-based surfactant is particularly preferable.

  The addition amount of the surfactant used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and 0.1% by mass or more and 0.5% by mass or less with respect to the total amount of the film-forming coating solution. More preferably.

  In the present invention, the silicon-based surfactant is a surfactant containing at least one Si atom. The silicon-based surfactant used in the present invention may be any silicon-based surfactant, and preferably has a structure containing alkylene oxide and dimethylsiloxane. A structure including the following chemical formula is more preferable.

  In the formula, R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, x is an integer of 1 to 20, and m and n are each independently an integer of 2 to 100. A plurality of R may be the same or different.

  Examples of the silicon surfactant used in the present invention include BYK306, BYK307 (manufactured by BYK Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 (manufactured by Troy Chemical). Can be mentioned.

  Any nonionic surfactant may be used as the nonionic surfactant used in the present invention. For example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, sorbitan fatty acid esters, fatty acid-modified polyoxyethylenes, polyoxyethylene-polyoxypropylene block copolymers, etc. Can do.

  As the fluorine-containing surfactant used in the present invention, any fluorine-containing surfactant may be used. For example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.

  The acrylic surfactant used in the present invention may be any acrylic surfactant. For example, a (meth) acrylic acid type copolymer etc. are mentioned.

  A silane coupling agent may be further used in the composition of the present invention. For example, 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimeth Sisilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10 -Triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-amino Propyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3 -Aminopropyltrimethoxy Silane, N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. The silane coupling agent used in the present invention may be one type or two or more types.

  An adhesion promoter may be further used in the composition of the present invention. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3 -Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane , Diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercapto Benzimidazole, 2-mercaptobenzothiazole, 2-mercaptobe Zookisazoru can urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, be mentioned thiourea compounds. Functional silane coupling agents are preferred as adhesion promoters. The preferred use amount of the adhesion promoter is preferably 10 parts by weight or less, particularly 0.05 to 5 parts by weight with respect to 100 parts by weight of the total solid content.

In the composition for an interlayer insulating film of the present invention, a pore forming factor can be used within the range allowed by the mechanical strength of the film to make the film porous and reduce the dielectric constant.
There is no particular limitation as a pore-forming factor as an additive that serves as a pore-forming agent, but a nonmetallic compound is preferably used, and solubility in a solvent used in a coating solution for forming an interlayer insulating film, It is necessary to satisfy the compatibility with the polymer of the present invention at the same time. Moreover, the boiling point or decomposition temperature of the pore-forming agent is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C. As molecular weight, it is preferable that it is 200-50000, More preferably, it is 300-10000, Most preferably, it is 400-5000. The addition amount is preferably 0.5 to 75%, more preferably 0.5 to 30%, and particularly preferably 1% to 20% by mass% with respect to the polymer forming the film. The polymer may contain a decomposable group as a pore-forming factor, and the decomposition temperature is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C. Good to have. The content of the decomposable group is 0.5 to 75%, more preferably 0.5 to 30%, and particularly preferably 1 to 20% in terms of mol% with respect to the polymer forming the film.

  A film obtained using the composition for interlayer insulating film of the present invention is obtained by applying the composition for interlayer insulating film to a substrate by any method such as spin coating, roller coating, dip coating, or scanning. It can be formed by removing the solvent by heat treatment. As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, a clean track series (manufactured by Tokyo Electron), a D-spin series (manufactured by Dainippon Screen), an SS series or a CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. The spin coating conditions may be any rotational speed, but a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate from the viewpoint of in-plane uniformity of the film. In addition, the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate. The heat treatment method is not particularly limited, but generally used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. are applied. Can do. A heating method using hot plate heating or furnace is preferable. A commercially available apparatus can be preferably used as the hot plate, and a clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.

In the present invention, it is particularly preferable that the polymer is cured by heat treatment after coating on the substrate. For example, a polymerization reaction during post-heating of the carbon triple bond remaining in the polymer can be used. The conditions for this post-heat treatment are preferably 100 to 450 ° C., more preferably 200 to 420 ° C., particularly preferably 350 to 400 ° C., preferably 1 minute to 2 hours, more preferably 10 minutes to 1.5 ° C. Time, particularly preferably in the range of 30 minutes to 1 hour. The post-heating treatment may be performed in several times. Further, this post-heating is particularly preferably performed in a nitrogen atmosphere in order to prevent thermal oxidation by oxygen.
Moreover, in this invention, you may make it harden | cure by raise | generating the polymerization reaction of the carbon triple bond which remains in a polymer by irradiating a high energy ray instead of heat processing. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.

The energy when an electron beam is used as the high energy beam is preferably 0 to 50 keV, more preferably 0 to 30 keV, and particularly preferably 0 to 20 keV. The total dose of the electron beam is preferably 0 to 5 μC / cm ² , more preferably 0 to ² μC / cm ² , and particularly preferably 0 to 1 μC / cm ² . The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 450 ° C, more preferably 0 to 400 ° C, and particularly preferably 0 to 350 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation in the present invention may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when using ultraviolet rays is preferably 190 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C. In the present invention, from the viewpoint of preventing oxidation of the polymer, it is preferable to use an inert atmosphere such as Ar, He, or nitrogen as the atmosphere around the substrate. Further, the pressure at that time is preferably 0 to 133 kPa.

  When the film obtained by using the composition for an interlayer insulating film of the present invention is used as an interlayer insulating film for a semiconductor, the wiring structure may have a barrier layer for preventing metal migration on the wiring side surface. In addition, there may be an etching stopper layer, etc. in addition to a cap layer and an interlayer adhesion layer for preventing separation by CMP on the bottom surface of the upper surface of the wiring and the interlayer insulating film. You may divide into multiple layers with other kinds of materials.

  The film obtained by using the composition for interlayer insulating film of the present invention can be etched for copper wiring or other purposes. Etching may be either wet etching or dry etching, but dry etching is preferred. For dry etching, either ammonia-based plasma or fluorocarbon-based plasma can be used as appropriate. These plasmas can use not only Ar but also oxygen, or gases such as nitrogen, hydrogen, and helium. Further, after the etching process, ashing can be performed for the purpose of removing the photoresist or the like used in the process, and further, cleaning can be performed to remove a residue at the time of ashing.

  The film obtained using the composition for an interlayer insulating film of the present invention can be subjected to CMP (Chemical Mechanical Polishing) in order to planarize the copper plating portion after the copper wiring processing. As the CMP slurry (chemical solution), a commercially available slurry (for example, manufactured by Fujimi, manufactured by Rodel Nitta, manufactured by JSR, manufactured by Hitachi Chemical, etc.) can be used as appropriate. Moreover, as a CMP apparatus, a commercially available apparatus (Applied Materials Co., Ltd., Ebara Corporation, etc.) can be used as appropriate. Further, cleaning can be performed to remove slurry residues after CMP.

The film obtained by using the composition for interlayer insulating film of the present invention can be used for various purposes. For example, it is suitable as an insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, interlayer insulating film for semiconductor, etching stopper film, surface protection In addition to films, buffer coat films, LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper clad cover coats, solder resist films, liquid crystal alignment films, etc. I can do it.
Furthermore, as another application, the film of the present invention can be provided with conductivity by doping with an electron donor or acceptor, and used as a conductive film.

The following examples illustrate the invention and are not intended to limit its scope.
<Synthesis Example 1> Synthesis of Compound A-1 In a light-shielded non-glass reaction vessel, 118 g of cyclohexanone, 8.0 g of ultrapure water, and 26.8 g of acetic acid were weighed and stirred at 25 ° C. while stirring with p-styryltrimethoxy. After dripping 10.0 g of silane (distilled and purified product of KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.), the mixture was heated to 80 ° C. and stirred for 12 hours. To the obtained reaction liquid, 650 g of cyclohexanone was added and used for preparing a coating liquid as a solution containing Compound A-1.

<Synthesis Example 2> Comparative Example: Synthesis of Adhesive 1 In a light-shielded non-glass reaction vessel, 118 g of cyclohexanone, 8.0 g of ultrapure water, and 26.8 g of acetic acid were weighed and stirred at 25 ° C. After dropwise adding 10.0 g of methacryloxypropyltrimethoxysilane, the mixture was heated to 80 ° C. and stirred for 12 hours. 650 g of cyclohexanone was added to the obtained reaction solution to prepare a solution containing the adhesive 1 and used for preparing a coating solution.

<Example 1>
Macromolecules. 4,9-diethynyldiamantane was synthesized according to the synthesis method described in pp. 5266 (1991).
Next, 100 g of 4,9-diethynyldiamantane and 563 g of diphenyl ether were placed in a reaction vessel and heated to an internal temperature of 155 ° C. with stirring under a nitrogen stream to completely dissolve 4,9-diethynyldiamantane. did. Next, a solution obtained by dissolving 21.6 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) in 18.9 g of diphenyl ether was added to the reaction solution over 1 hour while maintaining the internal temperature of the reaction solution at 150 ° C. to 160 ° C. It was dripped.
After the reaction, the reaction solution was cooled to 50 ° C., added to 4 L of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 400 ml of THF, added to 4 L of methanol, and purified by reprecipitation. After vacuum drying, 62 g of polymer (1) having a weight average molecular weight of about 38,000 was obtained.
A coating solution was prepared by completely dissolving 1.00 g of the polymer (1) and 3.00 g of the compound (A-1) prepared in Synthesis Example 1 in 6.00 g of cyclohexanone. This solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen 400 As a result of baking in an oven at 60 ° C. for 60 minutes, a uniform film having a thickness of 0.5 μm and no defects was obtained.

The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
The relative dielectric constant of the film (measurement temperature: 25 ° C., the same applies hereinafter) was calculated from the capacitance value at 1 MHz using a Four Dimensions mercury probe and Yokogawa Hewlett Packard HP4285ALCR meter.
Further, the adhesion of the membrane to the support was evaluated by the method described below.

The Young's modulus of the film was measured as an index of the mechanical strength of the film. MTS Nanoindenter SA2 was used for the measurement.
The adhesion of the membrane to the support was evaluated as a peeled area by a tape peel test. That is, a cross-cut tape peeling test was performed on the coated surface of the silicon wafer in accordance with JIS D0202-1988. Using cellophane tape ("CT24", manufactured by Nichiban Co., Ltd.), the film was adhered to the film with the belly of the finger and then peeled off. Judgment was a peel area ratio, and A: 0%, B: <10%, C: 10-50%, D:> 50%.

<Comparative Example 1>
A coating solution was prepared by completely dissolving 1.00 g of the polymer (1) in 9.00 g of cyclohexanone. The solution was filtered through a 0.1 μm tetrafluoroethylene filter and spin-coated on a silicon wafer. The obtained coating film was heated at 250 ° C. for 60 seconds on a hot plate under a nitrogen stream, and then baked in a 400 ° C. oven substituted with nitrogen for 60 minutes. was gotten.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
The relative dielectric constant of the film and the adhesion of the film to the support were evaluated in the same manner as in Example 1.

<Comparative example 2>
A coating solution was prepared by completely dissolving 1.00 g of the polymer (1) and 3.00 g of the adhesive 1 prepared in Synthesis Example 2 in 6.00 g of cyclohexanone. This solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen 400 As a result of baking in an oven at 60 ° C. for 60 minutes, a uniform film having a thickness of 0.5 μm and no defects was obtained.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
The relative dielectric constant of the film and the adhesion of the film to the support were evaluated in the same manner as in Example 1.

<Comparative Example 3>
A coating solution was prepared by completely dissolving 1.00 g of the polymer (1) and 6.00 g of the adhesive 1 prepared in Synthesis Example 2 in 3.00 g of cyclohexanone. This solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen 400 As a result of baking in an oven at 60 ° C. for 60 minutes, a uniform film having a thickness of 0.5 μm and no defects was obtained.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
The relative dielectric constant of the film and the adhesion of the film to the support were evaluated in the same manner as in Example 1.

Table 1

As is clear from Table 1, the insulating film of the present invention (Example 1) exhibited high adhesion while keeping the relative dielectric constant at a low level. Further, it was found that the adhesion of the insulating film of the present invention is an excellent film in that it is not lost even when heat treatment is performed.
On the other hand, the insulating film manufactured from the composition which does not contain the hydrolyzate (component (A)) obtained by hydrolyzing the alkoxysilane or acyloxysilane which has a styryl group in a molecule | numerator (Comparative Examples 1-3) Was inferior in adhesiveness, and it was found that the adhesiveness was greatly reduced particularly after heat treatment.

Claims (5)

The composition for interlayer insulation films containing the following components.
(A) a hydrolyzate obtained by hydrolyzing an alkoxysilane or acyloxysilane having at least one styryl group optionally having one or more substituents in the molecule;
(B) a compound having at least two carbon-carbon triple bonds in the molecule, and (C) a solvent. The composition according to claim 1, wherein the compound (B) further has a cage structure in the molecule. The composition according to claim 2, wherein the cage structure is selected from the group consisting of adamantane, biadamantane, diamantane, triamantane, and tetramantane. The insulating film formed using the composition as described in any one of Claims 1-3. An electronic device having the insulating film according to claim 4.