JP2009079195A - Composition for interlayer insulated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming interlayer insulated films, which is used for electronic devices or the like, has good film characteristics such as good dielectric constant and mechanical strength, has good adhesiveness to substrates, and gives coating liquids excellent in stability. <P>SOLUTION: This composition for forming the interlayer insulated films comprises a polymer obtained by polymerizing raw materials containing at least compounds of general formulas (1) and (2), (wherein, R<SB>0</SB>is H or a 1 to 6C hydrocarbon group; Ar is an aryl group or heteroaryl group which may have one or more substituents; R<SB>A</SB>is H or an organic group; R<SB>c</SB>is an organic group having a cage type structure to whose bridge head position at least one R<SB>A</SB>-C≡C- group is directly bound). <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 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 one 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). However, although these insulating films exhibit a low dielectric constant as an organic compound film, they are insufficient in terms of heat resistance, adhesion to a substrate, and stability over time of relative dielectric constant, and need to be improved. It was.

US Patent Application Publication No. 2005/0276964

  The present invention relates to a film-forming composition for solving the above-mentioned problems. More specifically, the film characteristics such as dielectric constant and heat resistance used for electronic devices are good, and the relative dielectric constant is stable over time. In addition, the present invention relates to a composition for an interlayer insulating film which is excellent in adhesion to a substrate and stability of a coating solution, and further relates to an insulating film obtained using the composition and an electronic device having the same.

式（１）中、Ｒ₀は水素原子または炭素数１〜６のアルキル基を表す。Ａｒは置換基を有しても良いアリール基またはヘテロアリール基を表す。
式（２）中、Ｒ_Aは水素原子または有機基を表す。複数存在するＲ_Aは互いに同一であっても、異なっていても良い。
Ｒ_Cは、少なくとも１つのＲ_A−Ｃ≡Ｃ−基が橋頭位に直接結合したカゴ型構造を有する有機基を表し、前記有機基は更に置換基を有していても良い。
（Ｂ）溶媒。
＜２＞ 上記＜１＞に記載の組成物を用いて形成された絶縁膜。
＜３＞ 上記＜２＞に記載の絶縁膜を有する電子デバイス。 It has been found that the above problems are solved by the following <1> to <3> configurations.
<1> A composition for an interlayer insulating film containing the following components.
(A) A polymer obtained by polymerizing a raw material containing at least the compounds of the following general formulas (1) and (2).

In the formula (1), R ₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar represents an aryl group or a heteroaryl group which may have a substituent.
In formula (2), R _A represents a hydrogen atom or an organic group. A plurality of R _A may be the same or different.
R _C represents an organic group having a cage structure in which at least one R _A —C≡C— group is directly bonded to the bridgehead position, and the organic group may further have a substituent.
(B) Solvent.
<2> An insulating film formed using the composition described in <1> above.
<3> An electronic device having the insulating film according to <2>.

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, according to the present invention, a composition for an interlayer insulating film having good temporal stability can be obtained.

Hereinafter, the present invention will be described in detail.
(A) A polymer obtained by polymerizing a raw material containing at least the compounds of the following general formulas (1) and (2)

In the formula (1), R ₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar represents an aryl group or a heteroaryl group which may have a substituent.
In formula (2), R _A represents a hydrogen atom or an organic group. A plurality of R _A may be the same or different.
R _c represents an organic group having a cage structure in which at least one R _A —C≡C— group is directly bonded to the bridgehead position, and the organic group may further have a substituent.

(A-1) Compound of Formula (1) In Formula (1), R ₀ preferably has 3 or less carbon atoms, more preferably 1 or less, and most preferably a hydrogen atom.
Examples of the aryl group represented by Ar include aryl groups having 6 to 14 carbon atoms, and more specifically, phenyl, naphthyl, phenanthryl, anthryl and the like. Examples of the heteroaryl group represented by Ar include a 5-membered to 8-membered heteroaryl group having at least one heteroatom selected from sulfur, oxygen, and nitrogen on the ring, and more specifically, thienyl. , Furyl, pyridyl, pyrrolyl, quinolyl and the like.
Moreover, the group which two or more groups selected from the aryl group and the heteroaryl group condensed may be sufficient. For example, a group derived from a benzofuran ring or an indole ring.

An example of a substituent on Ar includes —X—R ₁ .
In the above formula, -X- represents a single bond, a hydrocarbon group having 1 to 20 carbon atoms (alkylene, alkenylene, alkynylene, other divalent or higher hydrocarbon group), -CO-, -COO-, -CONR _2. -, - OCO -, - O -, - S -, - SO -, - SO 2 -, - NR 2 CO-, represents either.
R ₁ is a hydrogen atom, a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.) ), An alkenyl group having 2 to 10 carbon atoms (vinyl, propenyl, etc.), an alkynyl group having 2 to 10 carbon atoms (ethynyl, phenylethynyl, etc.), an aryl group having 6 to 20 carbon atoms (phenyl, 1-naphthyl, 2- Naphthyl, etc.), alkynyl aryl groups having 6 to 20 carbon atoms (ethynylphenyl, diethynylphenyl, etc.), cage structure groups having 10 to 20 carbon atoms (the cage structure groups will be described later), nitro groups, cyano groups, The group selected from a carboxy group is represented. Examples of the substituent include those in which a 4- to 8-membered ring such as a cycloalkane or a furan ring is condensed on an aryl group. Examples of R ₂ include a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.).
There may be a plurality of substituents on Ar.

Further, the compound represented by the formula (1) may further be a compound represented by X ′-{(Ar ′)-≡-R ₀ } n. X ′ is an n-valent group, and n hydrogen atoms are removed from a group defined for X and a group derived from a hydrocarbon group having 6 to 20 carbon atoms, for example, a hydrocarbon group such as benzene and alkane. Represents a group derived by this. Ar ′ is a divalent arylene group or heteroarylene group derived by removing a hydrogen atom from the aryl group or heteroaryl group represented by Ar. n is an integer of 1-6. R ₀ is as defined above.

Preferred specific examples of the compound of the formula (1) are shown below.

(A-2) Compound of Formula (2) In Formula (2), R _C represents an organic group having a cage structure in which at least one R _A —C≡C— group is directly bonded to the bridgehead position, The organic group may further have a substituent.
R _A represents a hydrogen atom or an organic group. A plurality of R _A may be the same or different.

The organic group represented by R _C has at least one cage structure, and if an R _A —C≡C— group is bonded to at least one bridgehead position of the cage structure, It may be bonded. Another group is, for example, a linear, branched or cyclic divalent hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the hydrocarbon group include alkanes having 1 to 10 carbon atoms, alkenes having 1 to 10 carbon atoms, alkynes having 1 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 10 to 20 carbon atoms. Or a combination thereof. “Divalent hydrocarbon group” means a divalent group derived by removing at least two hydrogen atoms from a hydrocarbon group such as alkane. More preferable examples of the hydrocarbon group include an alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a cage structure group having 10 to 20 carbon atoms.

The organic group of R _C may further have a substituent, such as a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), a straight chain having 1 to 10 carbon atoms, branched, Cyclic alkyl group (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.), alkenyl group having 2-10 carbon atoms (vinyl, propenyl, etc.), alkynyl group having 2-10 carbon atoms (ethynyl, phenylethynyl, etc.), carbon number 6-20 aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), C2-C10 acyl groups (benzoyl, etc.), C2-C10 alkoxycarbonyl groups (methoxycarbonyl, etc.), C1 -10 carbamoyl group (N, N-diethylcarbamoyl etc.), C6-C20 aryloxy group (phenoxy etc.), C6-C20 arylsulfo Le group (phenylsulfonyl, etc.), a nitro group, a cyano group, a silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl or the like) and the like.
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.

Examples of the organic group represented by R _A include, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a trialkylsilyl group, or a triarylsilyl group, more preferably 1 to 10 carbon atoms. An alkyl group, 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, a silyl group having 0 to 20 carbon atoms (trialkylsilyl group, triarylsilyl group, etc. A substituted silyl group (hereinafter the same), 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. Of these, hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, silyl groups having 0 to 20 carbon atoms, acyl groups having 2 to 10 carbon atoms, and 2 to 10 carbon atoms are particularly preferable. 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.

  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.

As the compound represented by the formula (2), compounds represented by the following formulas (I) to (III) are more preferable.

In formulas (I) to (III),
X _{1 to} X ₄ 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 ₄ each independently represent 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.).
Group: X ₁ -≡- (when there are a plurality of groups), Group: X ₂ -≡- or X ₃ -≡- (at least one when there are a plurality of groups), Group: X ₄ -≡- ( In the case where there are a plurality, at least one) is bonded to the bridgehead position of the cage structure.
X _{1 to} X ₄ and Y _{1 to} Y ₄ may be further substituted with another substituent.

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

In the present invention, the compound represented by (2) is preferably the above formula (II) or (III), and particularly preferably the compound represented by the above formula (III).
In the present invention, two or more compounds represented by (2) may be copolymerized.

  In the present invention, the compound represented by (2) 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 represented by (2) in the present invention include polybenzoxazoles described in JP-A-11-322929, JP-A-2003-12802, JP-A-2004-18593, and JP-A-2001-2899. Quinoline resin, JP 2003-530464, JP 2004-535497, JP 2004-504424, JP 2004-504455, JP 2005-501131, JP 2005-516382, JP 2005-514479 , JP-T-2005-522528, JP-A No. 2000-100808, U.S. Pat. -292878, JP-A-2004-27 No. 7, 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 compound represented by the formula (2) are described below.

In the present invention, the compound represented by (2) 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 bromination. Carrying out Friedel-Crafts reaction with vinyl bromide in the presence of Lewis acids such as aluminum, aluminum chloride, iron chloride, etc. to introduce 2,2-dibromoethyl groups, followed by de-HBr conversion with strong bases to convert to ethynyl groups Can be synthesized. 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.

The polymer (A) of the present invention can be obtained by polymerizing a raw material (hereinafter also referred to as “monomer”) containing the above formulas (1) and (2).
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.

  The optimal ratio of (1) and (2) varies depending on the combination of monomers, but the ratio of (1) and (2) is preferably 100: 0 to 1:99 by weight ratio of the monomers, 98: 2 to 2:98 is more preferable, and 95: 5 to 5:95 is still more preferable.

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 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, a peroxide or an organic azo compound is preferably used, and a peroxide, and further 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.

  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- 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.

一般式（S）
式中、Ｒ¹はアルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、を表し、更に任意の置換基を有していても良い。Ｒ²は、アルキル基、アリール基、アルコキシ基、アリールオキシ基を表し、複数存在する場合は、互いに同一でも異なってもよく、互いに結合して環構造を形成しても良い。ｎは０〜５の整数を表す。
反応液中のモノマーの濃度は好ましくは１〜５０重量％、より好ましくは５〜３０重量％、特に好ましくは１０〜２０重量％である。 The polymerization solvent is preferably an organic solvent having an aromatic ring, and an organic solvent having a benzene ring is particularly preferable. In particular, in the case of polymerization using an organic peroxide, it is most preferable to use a solvent represented by the following general formula (S).

General formula (S)
In the formula, R ¹ represents an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and may further have an arbitrary substituent. R ² represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and when a plurality of R ² are present, they may be the same as or different from each other, and may be bonded to each other to form a ring structure. n represents an integer of 0 to 5.
The concentration of the monomer in the reaction solution is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.

The optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, monomer, solvent type, concentration, etc., but preferably the internal temperature is 0 ° C. to 230 ° C., more preferably 50 ° C. to 200 ° C., particularly preferably 100. C. to 180.degree. C., preferably 0.1 to 50 hours, more preferably 0.2 to 20 hours, particularly preferably 0.3 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 3000 to 200000, and particularly preferably 50000 to 100000. If it is too small, there is a concern about the film forming property, and if it is too large, there is a concern about the filterability when it is used as a coating solution.
In the present invention, the polymers may be used alone or in admixture of two or more.

(B) Solvent The coating solvent used in the present invention is not particularly limited. For example, alcohols such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, and 1-methoxy-2-propanol are used. Solvents, acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone and other ketone solvents, ethyl acetate, propyl acetate, butyl acetate, acetic acid Such as isobutyl, pentyl acetate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, and γ-butyrolactone Ter solvents, 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-methyl Examples include amide solvents such as pyrrolidinone and dimethylacetamide, 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, 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 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.

(C) Other components 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 fluorescent X-ray 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 a CVD apparatus, an etching apparatus, or 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 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 that can be 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-based surfactant that can be 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.

  The nonionic surfactant that can be used in the present invention may be any nonionic surfactant. 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.

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

  The acrylic surfactant that can be 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 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. 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) can be preferably used. The spin coating conditions may be any rotational speed, but from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate. In addition, the composition solution discharging method may be either dynamic discharge in which the composition solution is discharged onto a rotating substrate or static discharge in which the composition solution is discharged onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. Further, 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 ejected on the substrate to form a liquid film, and then the composition is ejected from the liquid film. 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. As the hot plate, a commercially available device can be preferably used, and the 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 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 peeling 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.

  A film obtained by 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 in order to remove residues 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 flatten 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, Ebara, etc.) can be used as appropriate. Further, cleaning can be performed to remove slurry residues 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.
<Example 1>
Macromolecules. 4,9-diethynyldiamantane was synthesized according to the synthesis method described in pp. 5266 (1991).
Next, 59 g of 4,9-diethynyldiamantane, 32 g of 1,3-diethynylbenzene and 514 g of diphenyl ether were placed in a reaction vessel and heated to an internal temperature of 150 ° C. with stirring under a nitrogen stream. Next, a solution obtained by dissolving 6.76 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) in 6.2 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 7 L of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 300 ml of THF, added to 10 L of methanol, and purified by reprecipitation. After vacuum drying, 30 g of polymer (1) having a weight average molecular weight of about 20,000 was obtained.
A coating solution was prepared by completely dissolving 1.00 g of the polymer (1) in 9.00 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 200 ° 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 heat resistance was evaluated as follows.
The fired sample was heated at 400 ° C. for 30 seconds on a hot plate in the atmosphere, and the film thickness reduction rate (%) before and after heating was used as an index of heat resistance.
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. After film formation, the sample stored for 2 weeks was measured again, and the fluctuation range of the relative dielectric constant was measured.

<Example 2>
59 g of 4,9-diethynyldiamantane, 25 g of ethynylbenzene and 480 g of diphenyl ether were placed in a reaction vessel and heated to an internal temperature of 150 ° C. with stirring under a nitrogen stream. Next, 20.3 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) was added to the reaction solution. After stirring for 2 hours, 20.3 g of dicumyl peroxide was additionally added, and the mixture was stirred for 2 hours.
After the reaction, the reaction solution was cooled to 50 ° C., added to 10 L of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 300 ml of THF, added to 6 L of methanol, and purified by reprecipitation. After vacuum drying, 30 g of a polymer having a weight average molecular weight of about 20,000 was obtained.
A coating solution was prepared by completely dissolving 1.00 g of this polymer in 9.00 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 200 ° 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.

<Comparative Example 1>
Next, 91 g of 4,9-diethynyldiamantane was charged with 514 g of diphenyl ether in a reaction vessel and heated to an internal temperature of 150 ° C. with stirring under a nitrogen stream. Next, a solution obtained by dissolving 6.76 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) in 6.2 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 7 L of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 300 ml of THF, added to 10 L of methanol, and purified by reprecipitation. After vacuum drying, 30 g of a polymer having a weight average molecular weight of about 15,000 was obtained.
A coating solution was prepared by completely dissolving 1.00 g of this 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 and heat resistance of the film were evaluated in the same manner as in Example 1.

<Examples 3 to 8>
Instead of 1,3-diethynylbenzene of Example 1, a polymer using the monomers listed in Table 1 at the stated weight ratio was synthesized, and the same coating solution as in Example 1 was prepared and evaluated. It was.

As is clear from Table 1, the insulating films of the present invention (Examples 1 to 8) exhibited high heat resistance while keeping the relative dielectric constant at a low level. It was also found that the relative permittivity is excellent in that the variation with time is small.
In contrast, the insulating film obtained by using only one kind of monomer (Comparative Example 1) was a result in which the heat resistance was greatly inferior, and the change in relative permittivity with time was also large.

Claims (3)

The composition for interlayer insulation films containing the following components.
(A) A polymer obtained by polymerizing a raw material containing at least the compounds of the following general formulas (1) and (2).

In the formula (1), R ₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar represents an aryl group or a heteroaryl group which may have a substituent.
In formula (2), R _A represents a hydrogen atom or an organic group. A plurality of R _A may be the same or different.
R _c represents an organic group having a cage structure in which at least one R _A —C≡C— group is directly bonded to the bridgehead position, and the organic group may further have a substituent.
(B) Solvent.   An insulating film formed using the composition according to claim 1.   An electronic device having the insulating film according to claim 2.