JP2008231383A - Composition for interlayer insulation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating for forming an insulation film which is a composition for forming an insulation film used in electronic devices and the like and gives an insulation film being excellent in film characteristics such as in dielectric constant and mechanical strength, adhesion to substrates and further in the stability of a coating liquid. <P>SOLUTION: The composition for interlayer insulation films comprises the ingredients as described below: (A) an alkoxysilane or a hydrolysate of an acyloxysilane having at least one carbon-carbon double bond, (B) a compound having at least two carbon-carbon double bonds or carbon-carbon triple bonds in the molecule, (C) a ≤16C carboxylic acid and (D) a solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  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 that can withstand post-processes such as a thin film forming process, chip connection, and pinning when manufacturing a mounting substrate, and chemical resistance that can withstand a wet process. 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 performance, and the stability of the coating solution may be NG There was a problem and further improvements were required.

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

It has been found that the above problems are solved by the following configurations <1> to <6>.
<1>
The composition for interlayer insulation films containing the following components.
(A) a hydrolyzate of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond,
(B) a compound having at least two carbon-carbon double bonds or carbon-carbon triple bonds in the molecule;
(C) A carboxylic acid having 16 or less carbon atoms, and (D) a solvent.
<2>
(B) Component is a compound which has a carbon-carbon triple bond, The composition as described in said <1> characterized by the above-mentioned.
<3>
The composition according to <1> or <2> above, wherein the component (B) is a compound having a cage structure in the molecule.
<4>
The composition according to <3>, wherein the cage structure is selected from biadamantane, diamantane, triamantane, and tetramantane.
<5>
The insulating film formed using the composition as described in any one of said <1>-<4>.
<6> An electronic device having the insulating film according to <5>.

With the composition for an interlayer insulating film of the present invention, an interlayer insulating film having excellent adhesion, coated surface shape 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, according to the present invention, it is possible to obtain a composition for an interlayer insulating film that has a very good stability over time of a coating solution and can provide a film showing good interlayer insulating film performance even after being stored for a long time. it can.

The present invention relates to an interlayer insulating film composition (hereinafter, also simply referred to as “film forming composition” or “composition”) containing the following components.
(A) a hydrolyzate of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond,
(B) a compound having at least two carbon-carbon double bonds or carbon-carbon triple bonds in the molecule;
(C) A carboxylic acid having 16 or less carbon atoms, and (D) a solvent.
Hereinafter, each component will be described in detail.

(C) component: C16 or less carboxylic acid (C) component in the composition of this invention is C16 or less carboxylic acid. Such a carboxylic acid has (A) a hydrolyzate of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond, and (B) a carbon-carbon double bond or a carbon-carbon triple bond in the molecule. By adding it together with the compound having at least two, it is possible to obtain a composition for an interlayer insulating film that can provide a film exhibiting good interlayer insulating film performance after storage for a long time, as well as before storage. That is, the composition for an interlayer insulating film of the present invention can form a film exhibiting excellent interlayer insulating film performance such as low dielectric constant, heat resistance, adhesion and mechanical strength even after being stored for a long time. Shows very good storage stability.
Further, the use of the carboxylic acid having such a carbon number is advantageous in that a low k value can be achieved because it is difficult to remain in the film after hardening.
In this specification, carboxylic acid is a general term for organic compounds RCOOH (R is a hydrocarbon group) having a carboxy group —COOH. Also called carboxylic acid.
In the present invention, the carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid such as a dicarboxylic acid or a tricarboxylic acid, but the monocarboxylic acid may be added to the cured film. It is preferable from the viewpoint of persistence.
The carboxylic acid includes linear, branched or cyclic aliphatic carboxylic acids and aromatic carboxylic acids, and further includes saturated carboxylic acids and unsaturated carboxylic acids. From the viewpoint of persistence in the film after curing, an aliphatic carboxylic acid is preferred.

In the present invention, the carboxylic acid preferably has 12 or less carbon atoms, more preferably 8 or less carbon atoms, and most preferably 5 or less carbon atoms.
The boiling point of the carboxylic acid is not particularly limited, but is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and still more preferably 140 ° C. or higher. If the volatility is too high, the coated surface may be deteriorated when the amount added is large.

The carboxylic acid having 16 or less carbon atoms of the present invention is preferably a carboxylic acid represented by the following formula (1).
R ¹ —COOH (Formula 1)
In Formula 1, R ¹ is a hydrocarbon group having 15 or less carbon atoms.
More preferably, R ¹ is a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 15 carbon atoms, a linear or branched chain having 2 to 15 carbon atoms. A chain or cyclic alkynyl group, an aryl group having 6 to 15 carbon atoms, an alkylaryl group having 7 to 15 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, a carboxyl group-substituted alkyl group having 1 to 15 carbon atoms (provided that carbon When the number is 1, it represents oxalic acid). More preferably, R ¹ is an alkyl group.
Further, each of the above groups is a hydroxyl group, a carboxyl group, an alkyl group having 1 to 3 carbon atoms (however, the total carbon number is 16 or less), and an alkoxy group having 1 to 3 carbon atoms (however, the total carbon number is 16 or less). , Keto group, thiol group, and thio group may be substituted.

Specific examples of the carboxylic acid having 16 or less carbon atoms in the present invention include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid. Alkanoic acids such as tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 2-methylpropionic acid, 2-methylbutanoic acid,
Unsaturated bond-containing monocarboxylic acid such as acrylic acid, methacrylic acid, 2-butenoic acid, 2-butynoic acid, cinnamic acid, propionic acid,
Aromatic monocarboxylic acid glycolic acid such as benzoic acid, p-methylbenzoic acid, salicylic acid, mesitylene acid, anisic acid, monocarboxylic acid containing hydroxyl group or keto group such as lactic acid, pyruvic acid, mevalonic acid,
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
Hydroxyl group-containing dicarboxylic acids such as malic acid and tartaric acid,
Unsaturated group-containing dicarboxylic acid such as fumaric acid and maleic acid,
Aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimesic acid,
Hydroxyl group-containing tricarboxylic acids such as citric acid and isocitric acid,
Etc. can be illustrated.

The content of the component (C) in the composition of the present invention is preferably 0.1% by mass, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and 0.5% The mass% or more is most preferable. By increasing the amount added, the stability of the coating solution is improved.
On the other hand, if the addition amount is too large, the coated surface state may be deteriorated, so that it is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less.
In addition, when using the solution which hydrolyzed the acyloxysilane of (A) component for the composition of this invention as it is, the composition of this invention will contain the carboxylic acid derived from an acyloxysilane. Accordingly, when the carboxylic acid derived from the acyloxysilane as the component (A) is present, this is considered as a part of the component (C).

(A) Component: Hydrolyzate of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond (A) Component is an alkoxysilane or acyloxysilane having at least one carbon-carbon double bond. It is a component obtained by hydrolysis.
Therefore, the component (A) has at least one carbon-carbon double bond obtained by hydrolysis of an alkoxysilane or acyloxysilane having at least one carbon-carbon double bond, and at least one It is a siloxane polymer obtained by dehydration condensation of a compound having a hydroxyl group or silanol. Although the manufacturing method of (A) component is mentioned later, the (A) component obtained by the manufacturing method is a mixture of a siloxane polymer or a silanol monomer compound having a hydroxyl group and / or an oligomer thereof. The number average molecular weight Mn of (A) is preferably 1000 or less, more preferably 750 or less, and most preferably 500 or less.
The content of the component (A) in the composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass or more, and further preferably 2 to 20% by mass or more.
If the amount is too small, the effect of improving the adhesion cannot be obtained. If the amount is too large, an increase in the k value and a problem of etching property occur.

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. Solvents are preferred, alcohols, ketones, esters and ethers are preferred, ketones and ethers are more preferred, and ketone compounds are most preferred.
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, cyclohexanone, 2-heptanone, etc. can be mentioned as the most preferred examples.

Hydrolysis may be performed by diluting an alkoxysilane or acyloxysilane having at least one carbon-carbon double bond in the above solvent and then adding water dropwise thereto, or adding a mixture of solvent and water to a carbon-carbon dioxygen solution. Alkoxysilane or acyloxysilane having at least one heavy bond may be dropped. Further, water may be added dropwise (neat) without diluting alkoxysilane or acyloxysilane having at least one carbon-carbon double bond, or may be added dropwise to 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.

Furthermore, in the present invention, an acid catalyst may be used in the hydrolysis.
As an acid catalyst that can be used, any acid such as hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, carboxylic acid and the like may be used. Preferred are organic acids such as sulfonic acid and carboxylic acid, and most preferred is carboxylic acid.
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% of the total amount of hydrolysis reaction (total amount of solvent, silane compound, catalyst and water).

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, the reaction solution can be used as it is as the component (A) and the component (D) or (C) of the film-forming composition. However, you may add another solvent as (D) component so that it may mention later.

  The alkoxysilane and acyloxysilane preferably used in the present invention must have a carbon-carbon double bond, but the carbon-carbon double bond includes those constituting a part of the aromatic ring. Absent.

式中、Ｒ₁はアルキル基若しくはアシル基である。 In the present specification, the alkoxysilane or acyloxysilane having at least one carbon-carbon double bond is preferably a trialkoxysilane or triacyloxysilane compound represented by the following general formula (1).

In the formula, R ₁ is an alkyl group or an acyl group.

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 propanoyl groups.

The component (A) is typically added neat without adding or diluting the alkoxysilane or acyloxysilane having at least one carbon-carbon double bond to a solvent containing water. It can manufacture by adding water and performing a hydrolysis reaction.
When the hydrolysis reaction is performed after dilution, the reaction substrate concentration (dilution ratio) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. Most preferably, it is 2.5 mass% or less. The reaction substrate concentration is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and most preferably 0.2% 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.

Specific examples of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond include trimethoxy (vinyl) silane, allyl (trimethoxy) silane, styryl (trimethoxy) silane, trimethoxy (vinyl) silane, 3-methacryloyl Roxypropyl (trimethoxy) silane, triethoxy (vinyl) silane, allyl (triethoxy) silane, styryl (triethoxy) silane, 3-methacryloyloxypropyl (triethoxy) silane, triacetoxy (vinyl) silane, allyl (triacetoxy) silane, Examples include styryl (triacetoxy) silane and 3-methacryloyloxypropyl (triacetoxy) silane.
Acyloxysilane is preferable from the viewpoint of excellent hydrolysis reaction rate, and vinyl group is preferable from the viewpoint of heat resistance. Therefore, triacetoxy (vinyl) silane is most preferable.

Component (B): Compound having at least two carbon-carbon double bonds or carbon-carbon triple bonds in the molecule. (B) Component includes carbon-carbon double bond and carbon-carbon triple bond in the molecule. Any compound having at least two bonds selected from the above can be used without any particular limitation, but from the viewpoint of film formability, a polymer is preferable, and a polymer having a weight average molecular weight of 500 or more is preferable. The above is more preferable, and 2000 or more is most preferable.
The content of the component (B) in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

When the component (B) is a polymer, it may be a compound obtained by polymerizing a monomer represented by the following general formula (2) and / or (3) by a method described later.

In the formula, R ₂ 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.
m is 1 or more, preferably 2 or more, and less than the valence of R ₂ . That is, in the general formulas (2) and (3), m means the number of double bonds or triple bonds directly bonded to R _2, and therefore the valence represented by R ₂ is the maximum value that m can take.

  Examples of the substituent 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 0 carbon atoms. ˜20 silyl groups. 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.

  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 represented by the general formula (2) and / or (3) is caused by a polymerizable group (carbon-carbon double bond or carbon-carbon triple bond) substituted on 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 polymerization reaction of the monomer represented by the general formula (2) and / or (3) is preferably performed in the presence of a nonmetallic polymerization initiator. For example, a polymerizable carbon-carbon double bond or carbon-carbon triple bond can 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.
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, perbutyl C, etc. 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 polymerization reaction of the monomer represented by the general formula (2) and / or (3) 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 ₂ in the general formulas (2) and (3) is particularly preferably a group including a cage structure from the viewpoint of achieving both heat resistance and a low dielectric constant. Moreover, the compound of General formula (3) which has a carbon-carbon triple bond is more preferable from a heat resistant viewpoint.

  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 points 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. .

  The cage structure of the present invention 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 low dielectric constant.

  The cage structure of the present invention is preferably adamantane, biadamantane, diamantane, triamantane, tetramantane, dodekahedran, more preferably adamantane, biadamantane, diamantane, and particularly beadamantane in that it has a low dielectric constant. 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) ), 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 to 6 carbon atoms 20 arylsulfonyl groups (such as phenylsulfonyl), nitro groups, cyano groups, silyl groups (such as triethoxysilyl, methyldiethoxysilyl, trivinylsilyl) and the like.

  The cage structure 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 is preferably divalent or trivalent, particularly preferably divalent.

In the present invention, the “compound having a cage structure in the molecule” is preferably a polymer of a monomer having a cage structure. Here, 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.
As the polymerization method of the monomer, the method described for the polymerization method of the compounds of the general formulas (2) and (3) can be applied.

The cage structure in the “compound having a cage structure in the molecule” may be substituted as a pendant group in the polymer and may be a part of the polymer main chain, but it becomes a part of the polymer main chain. The form 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 compound is removed from the polymer. In this form, the cage structure is directly single-bonded or connected 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.

  The “compound having a cage structure in the molecule” of the present invention may be a low molecular compound or a high molecular compound (for example, a polymer), but is preferably 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 contained in the insulating film forming 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.

The “compound having a cage structure in the molecule” of the present invention is preferably a polymer of a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond, and further represented by the formula (2) or ( The compound represented by 3) and R ₂ is a group having the cage structure described above is more preferable. Furthermore, a polymer of a compound represented by the following formulas (I) to (VI) is more preferable.

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 2 to 3, 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, and particularly preferably 2.
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 2 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.

  The monomer having a cage structure of the present invention is preferably the above formula (II), (III), (V), (VI), more preferably the above formula (II), (III), particularly preferably. It is a compound represented by the above formula (III).

Two or more compounds having the cage structure of the present invention may be used in combination, or two or more monomers having the cage structure of the present invention may be copolymerized.
Monomers of formulas (I) to (VI) so that the compound obtained by polymerization is a compound having at least two bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond in the molecule. Can be appropriately selected and combined for copolymerization.

  The compound having a cage structure of the present invention 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 of the present invention include polybenzoxazoles described in JP-A Nos. 11-322929, 2003-12802, and 2004-18593, and quinoline resins 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., JP2004-2787 , 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 monomer having a cage structure that can be used in the present invention are described below, but the present invention is not limited thereto.

As the solvent used in the polymerization reaction, any solvent may be used 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 obtained polymer. . For example, alcohol solvents such as water, methanol, ethanol and 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-methylnaphtha Aromatic hydrocarbon solvents such as 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1 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, anisole, 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, 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 of 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, chloride. Synthesis by introducing 2,2-dibromoethyl group by reacting with vinyl bromide and Friedel-Crafts in the presence of Lewis acids such as aluminum and iron chloride, followed by dehydrobration with a strong base and conversion to ethynyl group. be able to. Specifically, it is synthesized according to the method described in Macromolecules., 1991, 24, 5266-5268, 1995, 28, 5554-5560, Journal of Organic Chemistry., 39, 2995-3003 (1974), etc. I can do it.
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.
The polymer of this invention may be used individually or may be used in mixture of 2 or more types.

(D) Component: Solvent The solvent used in the composition for an interlayer insulating film of the present invention may be the solvent used at the time of hydrolysis of the component (A), or the following coating solvent may be newly added. . When the solvent used at the time of hydrolysis of the component (A) is used as it is, 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.
Although 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, 1-methoxy-2-propanol, Ketone solvents such as acetone, 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, acetic acid Esters such as pentyl, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, and 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 preferable coating solvents are 1-methoxy-2-propanol, propanol, acetylacetone, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, t-butyl. Benzene, particularly preferably 1-methoxy-2-propanol, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole.
The solid content concentration of the film-forming composition 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.

The film-forming composition of the present invention preferably has a sufficiently low metal content as an impurity. The metal concentration of the film-forming composition can be measured with high sensitivity by the ICP-MS method. In that case, the metal content other than the transition metal is preferably 30 ppm or less, more preferably 3 ppm or less, particularly preferably 300 ppb or less. It is. 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 film forming composition can also be evaluated by performing total reflection X-ray fluorescence measurement on the film obtained using the film forming 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 the CVD apparatus, the etching apparatus and the like. Particularly preferably, it is 10 × 10 ¹⁰ cm ⁻² or less.

  Furthermore, the composition for forming a film of the present invention includes a radical generator, colloidal silica, and the like within a range that does not impair the properties of the obtained insulating film (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.). You may add additives, such as surfactant, a silane coupling agent, and an adhesive agent.

  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 mass 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 silicone 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, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are 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 silicone-based surfactant is a surfactant containing at least one Si atom. The silicone surfactant used in the present invention may be any silicone 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-based surfactant used in the present invention include BYK306, BYK307 (manufactured by Big 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.

  Any silane coupling agent may be used in 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-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6 -Diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Triethoxysilane, N-bis Oxyethylene) -3-aminopropyltrimethoxysilane, 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.

  Any adhesion promoter may be used in 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-chloropropylmethyldimethoxysila 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, benz Imidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mer Hept benzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, may be mentioned thiourea compounds. Functional silane coupling agents are preferred as adhesion promoters.

  The amount of the silane coupling agent or adhesion promoter used is preferably an amount that does not impair the effects of the present invention, particularly adhesion and storage stability. Specifically, it is preferably about 0 to 20 parts by mass with respect to the total solid content. When the silane coupling agent or adhesion promoter is a compound having an alkoxysilane group or an acyloxysilane group having at least one carbon-carbon double bond, the sum of the compound and the component (A) The concentration is preferably 30% by mass or less.

In the composition for forming a 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 to reduce the dielectric constant.
The pore-forming factor as an additive that becomes a pore-forming agent is not particularly limited, but a non-metallic compound is preferably used, and the solubility in a solvent used in a coating solution for film formation, the polymer of the present invention. It is necessary to satisfy the compatibility with. 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 film forming composition of the present invention is obtained by applying the film forming composition to a substrate by any method such as spin coating, roller coating, dip coating, or scanning, and then using a solvent. Can be formed 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 truck 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) 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 preferred 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. 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, the pressure at that time is preferably 0 to 133 kPa.

  When the film obtained by using the film forming composition of the present invention is used as an interlayer insulating film for a semiconductor, the wiring structure thereof 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 interlayer adhesion layer that prevent separation by CMP on the bottom surface of the upper surface of the wiring and interlayer insulating film, and other layers of the interlayer insulating film may be added as necessary. The seed material may be divided into a plurality of layers.

  The film obtained using the film forming composition 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 by using the film forming composition 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), commercially available slurries (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 suitably. Furthermore, it can be washed to remove the slurry residue after CMP.

The film obtained using the film forming composition 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, 1100 g of cyclohexanone and 5.81 g of ultrapure water were measured, and 25.0 g of triacetoxy (vinyl) silane was added while stirring at 25 ° C. It was dripped slowly. The obtained reaction solution was used for preparing a coating solution as a solution containing Compound A-1.
(Concentration of acetic acid derived from acetoxy group: about 0.57% by mass)

<Synthesis Example 2> Synthesis of Compound A-2 In a light-shielded non-glass reaction vessel, 25.0 g of triacetoxy (vinyl) silane was measured, stirred sufficiently, and cooled so that the internal temperature was 5 ° C. or less. Then, 5.81 g of ultrapure water was slowly added dropwise. After stirring at 25 ° C. for 2 hours, the resulting reaction solution was diluted with 1100 g of cyclohexanone to prepare a solution containing Compound A-2 and used for coating solution preparation.
(Concentration of acetic acid derived from acetoxy group: about 0.57% by mass)

<Synthesis Example 3> Synthesis of Compound A-3 In a light-shielded non-glass reaction vessel, 25.0 g of trimethoxy (vinyl) silane containing about 20 ppm of hydrochloric acid was measured and stirred sufficiently, and the internal temperature was 5 ° C. or less. While cooling so that 5.81 g of ultrapure water was slowly added dropwise. After stirring at 20 ° C. for 10 minutes, the obtained reaction solution was diluted with 1100 g of cyclohexanone to prepare a solution containing Compound A-3 and used for preparing a coating solution.
(Acetic acid-containing concentration: 0.00% by mass)

<Synthesis Example 4> Synthesis of Compound A-4 In a light-shielded non-glass reaction vessel, 10.0 g of trimethoxy (vinyl) silane, 40.5 g of acetic acid, and 80.6 g of cyclohexanone were measured and stirred sufficiently, and the internal temperature was While cooling to 5 ° C. or lower, 12.1 g of ultrapure water was slowly added dropwise. After stirring at 25 ° C. for 8 hours, the resulting reaction solution was diluted with 573 g of cyclohexanone to prepare a solution containing Compound A-4 and used for coating solution preparation.
(Acetic acid-containing concentration: about 5.65 mass%)

Polymer synthesis
According to the synthesis method described in Macromolecules., Page 5266 (1991), 4,9-diethynyldiamantane was synthesized.
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 reacted 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.

<Example 1>
A solution containing 1.00 g of the polymer (1) and 3.00 g (acetic acid content: about 0.017 g) containing the compound (A-1) prepared in Synthesis Example 1 was completely dissolved in 30.00 g of cyclohexanone. 1 was prepared. (Concentration of acetic acid in coating solution 1: approx. 0.05%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen at 400 ° C. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 2>
A solution containing 1.00 g of the polymer (1) and the compound (A-1) prepared in Synthesis Example 1 (3.00 g (acetic acid content: about 0.017 g)) and 0.10 g of acetic acid were completely dissolved in 29.90 g of cyclohexanone. Dissolved to prepare coating solution 2. (Concentration of acetic acid in coating solution 2: about 0.345%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 3>
A solution containing 3.00 g of polymer (1) and compound (A-1) prepared in Synthesis Example 1 (acetic acid content: about 0.017 g) and 0.50 g of acetic acid completely into 29.50 g of cyclohexanone. A coating solution 3 was prepared by dissolving. (Concentration of acetic acid in coating solution 3: about 1.52%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 4>
A solution containing 1.00 g of the polymer (1) and the compound (A-3) prepared in Synthesis Example 3 (3.00 g (acetic acid content: about 0.00 g)) and 0.10 g of acetic acid completely into 29.90 g of cyclohexanone. Dissolved to prepare coating solution 2. (Acetic acid content concentration of coating solution 4: about 0.294%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 5>
A solution containing 3.00 g (acetic acid content: about 0.017 g) of the polymer (1) 1.00 g and the compound (A-2) prepared in Synthesis Example 2 is completely dissolved in 30.00 g of cyclohexanone. 5 was prepared. (Concentration of acetic acid in coating solution 5: about 0.05%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen at 400 ° C. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 6>
A solution containing 1.00 g of the polymer (1) and the compound (A-3) prepared in Synthesis Example 3 (3.00 g of acetic acid content: about 0.00 g) and 0.10 g of lactic acid were completely dissolved in 29.90 g of cyclohexanone. Dissolved to prepare coating solution 2. (Concentration of lactic acid in coating solution 6: about 0.294%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen at 400 ° C. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 7>
A solution containing 1.00 g of the polymer (1) and the compound (A-1) prepared in Synthesis Example 1 (3.00 g of acetic acid content: about 0.017 g) and 0.50 g of propionic acid were completely added to 29.50 g of cyclohexanone. A coating solution 7 was prepared by dissolving in (Carboxylic acid-containing concentration of coating solution 7: about 1.52%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen at 400 ° C. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Example 8>
A solution containing 3.00 g of a solution containing 1.00 g of the polymer (1) and the compound (A-4) prepared in Synthesis Example 4 (acetic acid content: about 0.170 g) in 30.00 g of cyclohexanone is completely dissolved. 8 was prepared. (Concentration of carboxylic acid in coating solution 8: about 0.5%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen at 400 ° C. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

<Comparative Example 1>
A coating solution P1 was prepared by completely dissolving 1.00 g of the polymer (1) and 3.00 g (without acetic acid) containing the compound (A-3) prepared in Synthesis Example 3 in 30.00 g of cyclohexanone. (Acetic acid-containing concentration of coating solution P1: about 0.00%)
This solution was filtered with a 0.02 μm Nylon filter manufactured by Nippon Pole Co., Ltd., spin-coated on a silicon wafer, this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen at 400 ° C. The film was baked in an oven for 60 minutes to form a film with a thickness of 100 nm.

The dielectric constant, adhesion, and defects on the coated surface of the obtained film were evaluated as shown below.
In addition, a film is formed using the coating liquid after being stored at 45 ° C. for one month, and the adhesion of the obtained film and defects on the coated surface of the film are evaluated, and compared with the film before storage. The aging stability of the liquid was evaluated. The obtained results are shown in Table 1 below.

The relative dielectric constant of the film was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Hewlett-Packard Yokogawa at a measurement temperature of 25 ° C.
-Adhesion of film to substrate: 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 peeling area ratio, and A: 0%, B: <10%, C: <50%, D:> 50%.
-Defect evaluation on the coated surface: The number of defects on the entire wafer surface was measured by KLA-Tencor No. 2360, and the number of defects was evaluated as A, 1000 or less as B, 3000 or less as C, and 3000 or more as D.

As is clear from the above table, (A) hydrolyzate of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond, (B) carbon-carbon double bond or carbon-carbon in the molecule All of the films obtained from the composition of the present invention containing a compound having at least two triple bonds, (C) a carboxylic acid having 16 or less carbon atoms, and (D) a solvent have high relative dielectric constant and adhesion. Furthermore, the temporal stability of the coating solution was high. In particular, when a sufficient amount of carboxylic acid such as acetic acid, lactic acid or propionic acid is added in addition to acetic acid derived from a hydrolyzate of acetoxysilane, remarkable stability over time is observed, and adhesion and coating are also observed after storage. The coating liquid which the performance of a surface did not change at all was able to be obtained (Examples 2-4, 6-8).
On the other hand, the coating solution containing no carboxylic acid had poor stability over time, and when a solution stored for one month was used, the adhesion of the obtained film was deteriorated (Comparative Example 1). In addition, the coating surface of the film obtained using the coating solution before storage had few defects, whereas the coating surface of the film obtained using the coating solution after storage had many defects. (Comparative Example 1).

Claims (6)

The composition for interlayer insulation films containing the following components.
(A) a hydrolyzate of alkoxysilane or acyloxysilane having at least one carbon-carbon double bond,
(B) a compound having at least two carbon-carbon double bonds or carbon-carbon triple bonds in the molecule;
(C) A carboxylic acid having 16 or less carbon atoms, and (D) a solvent.   The composition according to claim 1, wherein the component (B) is a compound having a carbon-carbon triple bond.   The composition according to claim 1 or 2, wherein the component (B) is a compound having a cage structure in the molecule.   4. The composition according to claim 3, wherein the cage structure is selected from biadamantane, diamantane, triamantane, and tetramantane.   The insulating film formed using the composition as described in any one of Claims 1-4.   An electronic device having the insulating film according to claim 5.