JP2007161778A - Film-forming composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming composition capable of providing a good film, even after storage over time, which is used for an electronic device etc., and exerts favorable film characteristics such as dielectric constant and mechanical strength, an insulating film using the composition, and an electronic device having the same. <P>SOLUTION: The film-forming composition contains at least two compounds each having a cage structure. The insulating film is obtained by using the composition. The electronic device has the insulating film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film-forming composition, and more particularly to a film-forming composition having good film properties such as dielectric constant and mechanical strength used for electronic devices, and further, an insulating film obtained using the composition And an electronic device having the same.

  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.

For a long time, polybenzoxazole and polyimide have been widely known as high heat-resistant insulating films. In addition, a highly heat-resistant insulating film made of polyarylene ether is disclosed. However, in order to realize a high-speed device, there is a strong demand for further reduction of the dielectric constant.
Polymers based on saturated hydrocarbons such as polyethylene are characterized by a low dielectric constant due to their low electronic polarization, but are generally composed of carbon-carbon single bonds with low bond dissociation energy. The problem is that the heat resistance is low.

US Pat. No. 6,380,347 US Pat. No. 5,965,679

  The present invention relates to a film-forming composition for solving the above-mentioned problems, more specifically to a composition for forming an insulating film having good film properties such as dielectric constant and mechanical strength used for electronic devices, etc. The present invention relates to an insulating film obtained using the composition and an electronic device having the insulating film.

It has been found that the above problems are solved by the following <1> to <10> configurations.
<1>
A film-forming composition comprising at least two compounds having a cage structure.
<2>
The film forming composition as described in <1>, wherein the compound having a cage structure is a polymer having a cage structure.
<3>
<1> or <2>, wherein the compound having a cage structure is a polymer obtained by polymerizing a monomer having a cage structure in the presence of a transition metal catalyst or in the presence of a radical initiator The composition for film formation as described.
<4>
The film-forming composition according to any one of <1> to <3>, wherein the monomer having a cage structure has a carbon-carbon double bond or a carbon-carbon triple bond.
<5>
The film-forming composition according to any one of <1> to <4>, wherein the cage structure is selected from adamantane, biadamantane, diamantane, triamantane, and tetramantane.
<6>
The film-forming composition according to any one of <1> to <5>, wherein the monomer having a cage structure is selected from the group of compounds represented by the following formulas (I) to (VI): .

In the formulas (I) to (VI),
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.
Y _{1 to} Y ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group.
When a plurality of X _{1 to} X ₈ and Y _{1 to} Y ₈ are present, they may be the same or different.
m ₁ and m ₅ each independently represents an integer of ₁ to 16, and n ₁ and n ₅ each independently represents an integer of 0 to 15.
m ₂ , m ₃ , m ₆ and m ₇ each independently represents an integer of 1 to 15, and n ₂ , n ₃ , n ₆ and n ₇ each independently represents an integer of 0 to 14.
m ₄ and m ₈ each independently represents an integer of 1 to 20, and n ₄ and n ₈ each independently represents an integer of 0 to 19.
<7>
The film-forming composition as described in any one of <1> to <6>, wherein the compound having a cage structure can be dissolved in cyclohexanone or anisole at 3% by mass or more at 25 ° C.
<8>
Furthermore, the organic solvent is contained, The film forming composition in any one of <1>-<7> characterized by the above-mentioned.
<9>
<1>-<8> The insulating film formed using the film forming composition in any one of.
<10>
An electronic device having the insulating film according to <9>.

  The compound having a cage structure used in the present invention is soluble in a coating solvent such as anisole or cyclohexanone, and a film formed using the film forming composition of the present invention has a low dielectric constant and high mechanical strength. Therefore, it is suitable as an interlayer insulating film in an electronic device or the like.

Hereinafter, the present invention will be described in detail.
The film-forming composition of the present invention contains at least two compounds having a cage structure. That is, it contains at least two different compounds as the compound having a cage structure.
The compound having a cage structure may be a low molecular compound or a high molecular compound. Examples of the low molecular compound include a monomer having a cage structure (monomer type compound). Examples of the polymer compound include a polymer having a cage structure (polymer compound).

When the compound having a cage structure is a polymer compound, the weight average molecular weight is preferably 1000 to 500000, more preferably 5000 to 200000, and particularly preferably 10000 to 100,000. The polymer compound having a cage structure may be included in the film forming composition 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 is preferably a polymer compound.

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. .

  The cage structure used in 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 a low dielectric constant.

  The cage structure used in the present invention is preferably adamantane, biadamantane, diamantane, triamantane, and tetramantane, more preferably adamantane, biadamantane, and diamantane, particularly biadamantane in that it has a low dielectric constant. Diamantane is preferred.

  As described above, the compound having a cage structure may be a polymer (for example, a polymer of a compound having a cage structure).

With respect to a compound having a cage structure, the term “different” refers to any of the following cases.
About a unit having a cage structure in a compound having a cage structure (a monomer itself if not a polymer)
a. The type or position of substituents possessed by the cage structure is different.
b. The cage structure is different. (In addition, even if the cage structure is the same, it is different if the number of cage structures in the unit is different.)
b. It is preferable that the points are different.

  Preferred combinations of the cage structure when the cage structures are different include adamantane and diamantane, adamantane and biadamantan, and biadamantan and diamantane. That is, by using a combination of two or more kinds of compounds having a cage structure with different three-dimensional bulkiness, fine and uniform vacancies are formed in the polymer molecule, and low dielectric constant is obtained without impairing mechanical strength. Rate can be achieved.

  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.), a nitro group, a cyano group, a silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl or the like) and the like.

  The insulating film of the present invention preferably contains no nitrogen atoms from the viewpoint of dielectric constant and hygroscopicity of the film, and is particularly preferably an insulating film having no polyimide bond.

  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.

  The monomer having a cage structure used in the present invention preferably has a polymerizable carbon-carbon double bond or carbon-carbon triple bond. Furthermore, compounds represented by the following formulas (I) to (VI) are more preferable.

In the formulas (I) to (VI),
X _{1 to} X ₈ are each independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), an alkenyl group (preferably 2 to 10 carbon atoms), an alkynyl group (preferably 2 to 10 carbon atoms), an aryl group (Preferably 6 to 20 carbon atoms), silyl group (preferably 0 to 20 carbon atoms), acyl group (preferably 2 to 10 carbon atoms), alkoxycarbonyl group (preferably 2 to 10 carbon atoms), carbamoyl group ( Preferably, it represents a carbon number of 1 to 20) 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 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 are each independently a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group (preferably 1 to 10 carbon atoms), an aryl group (preferably 6 to 20 carbon atoms) or a silyl group (preferably carbon). It is preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms which may have a substituent, and particularly preferably an alkyl group (such as a methyl group). It is.
When a plurality of X _{1 to} X ₈ and Y _{1 to} Y ₈ are present, they may be the same or different, and may be further substituted with another substituent.

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

  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.

  The compound having a cage structure used in the present invention is a monomer having a cage structure and, for example, a saturated carbonization having a carbon-carbon triple bond or a carbon-carbon double bond as a polymerizable group and not having a cage structure. It may be a copolymer with a hydrogen monomer or an aromatic hydrocarbon monomer.

The compound having a cage structure used in the present invention is preferably a polymer having a cage structure, and is preferably a polymer obtained by polymerizing a monomer having a cage structure. Here, the term “monomer” refers to a monomer that can be polymerized with each other to form a dimer or higher polymer. This polymer may be a homopolymer or a copolymer. Further, it may be a polymer that can be obtained by polymerizing a plurality of monomers having two or more types of cage structures.
The total amount of the compound having a cage structure is preferably 50% by mass or more, more preferably 65% by mass or more, particularly preferably 80% by mass or more, based on the solid content of the film-forming composition. The mass of the compound having the first cage structure / (the mass of the compound having the first cage structure + the mass of the compound having the second cage structure) is preferably 0.10 to 0.90, more preferably Is 0.25 to 0.75, particularly preferably 0.40 to 0.60.

As a film-forming composition containing two different compounds having a cage structure of the present invention,
(1) Film-forming composition containing monomer-type compound and monomer-type compound (2) Film-forming composition containing monomer-type compound and polymer-type compound (3) Film containing polymer-type compound and polymer-type compound A preferred embodiment is a forming composition. Among the above embodiments, the embodiment (3) is most preferable, and then the embodiment (2) is preferable.

The compound having a cage structure in the present invention may be substituted as a pendant group in the polymer and may be a part of the polymer main chain, but a form that is a part of the polymer main chain is more preferable. . Here, the form which is a part of the polymer main chain means that the polymer chain is cleaved when the cage structure 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 monomer having a cage structure used in the present invention is prepared by reacting bromine atoms with a desired bromine atom by reacting with bromine in the presence or absence of an aluminum bromide catalyst, for example, by using easily available adamantane, biadamantane, or diamantane. In the presence of a Lewis acid such as aluminum bromide, aluminum chloride, iron chloride and the like, followed by Friedel-Crafts reaction with vinyl bromide to introduce a 2,2-dibromoethyl group, followed by de-HBr with a strong base. And can be synthesized by converting to an ethynyl group. Specifically, Macromolecules, 1991, 24, 5266-5268, 1995, 28, 5554-5560, Journal of Organic Chemistry, 39, 2995-3003 (1974). ) And the like.
Moreover, a vinyl body can be easily obtained by reducing an ethynyl group with diisobutylaluminum hydride.
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 polymerization reaction of the monomer used in the present invention is caused by the polymerizable group substituted for the monomer. Here, the polymerizable group refers to a substituent having a reactivity for polymerizing a 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.

  The polymerization reaction of the monomer used in the present invention is preferably carried out in the presence of a transition metal catalyst or in the presence of a polymerization initiator.

As the polymerization initiator, a nonmetallic polymerization initiator is preferable. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond may be polymerized in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating. I can do it.
As the polymerization initiator, an organic peroxide or an organic azo compound is particularly preferably used.
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, peroxydicarbonates such as perroyl TCP, diisobutyryl peroxide, cumylperoxyneodeca Noate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4 -T-Buchi Chlohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) ) Peroxide, t-butylperoxy-2-ethylhexanoate, (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1 -Di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2 -Di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5,- Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl Rumonocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di-t-butylperoxyvalerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl Peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane Hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, 2,4- Dichlorobenzoyl peroxide, o-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, tris- (t-butylperoxy) triazine, 2,4,4-trimethylpentylperoxyneodecanoate, α-cumylperoxy Neodecanoate, t-amylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxytrimethyladipate, di-3- Methoxybutyl par Xidicarbonate, di-isopropyl peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, diethylene glycol bis (t-butylperoxycarbonate), t-hexyl Peroxyneodecanoate and the like 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 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylpropionitrile), 2,2-azobis (2,4-dimethylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo ] Formamide, 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2-azobis [2-methyl-N- (2- Hydroxybutyl) propionamide], 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2-azobis (N-butyl-2-methylpropionamide), 2,2-azobis ( N-cyclohexyl-2-methylpropioamide), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) ) Propane] disulfate dihydrate, 2,2-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} di Drolochloride, 2,2-azobis [2- [2-imidazolin-2-yl] propane], 2,2-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2-azobis (2 -Methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, dimethyl 2,2-azobis (2-methylpropionate), 4, 4-Azobis (4-cyanovaleric acid), 2,2-azobis (2,4,4-trimethylpentane) and the like are preferably used.

Only one polymerization initiator or a mixture of two or more polymerization initiators may be used.
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 with respect to 1 mol of the monomer.

Any transition metal catalyst may be used as long as it can cause the polymerization reaction of the monomer used in the present invention to proceed. For example, Pd-based catalyst such as Pd (PPh ₃ ) ₄ , Pd (OAc) ₂ , Ziegler-Natta catalyst, Ni-based catalyst such as nickel acetylacetonate, W-based catalyst such as WCl ₆ , Mo-based catalyst such as MoCl ₅ , TaCl _5, etc. Ta catalysts, Nb based catalysts, such as NbCl _5, Rh-based catalyst, it is preferable to polymerize a Pt catalyst and the like.

Only one transition metal catalyst or a mixture of two or more transition metal catalysts may be used.
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.

A solvent may be used for the polymerization reaction, and any solvent can 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 resulting polymer. Such a thing may be used. For example, alcohol solvents such as water, methanol, ethanol, propanol, etc., ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate, etc. Ester solvents, ether solvents such as dibutyl ether, anisole, tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, 1,3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, etc. Amide solvents, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene Halogen-based solvents, hexane, heptane, octane, and aliphatic hydrocarbon solvents such as cyclohexane can be used for. Among these, 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, 1,3,5-trimethyl. Isopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, anisole, toluene, xylene, mesitylene, 1,3,4 5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyl Lactones, anisole, mesitylene, 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.

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 220 ° C, more preferably 40 ° C to 210 ° C, and particularly preferably 80 ° C. C. to 200.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 film-forming composition of the present invention may contain an organic solvent, and can also be used as a coating solution. Although it does not specifically limit as an organic solvent, For example, alcohol solvents, such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, 1-methoxy-2-propanol, acetone, acetylacetone, methyl ethyl ketone , Ketone solvents such as methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, ethyl propionate , Ester solvents such as propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone, diisopropyl Ether solvents such as pyr ether, dibutyl ether, ethyl propyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methylpyrrolidinone, dimethylacetamide Examples of these solvents include amide solvents, and the like. These may be used alone or in admixture of two or more.
More preferred organic solvents are 1-methoxy-2-propanol, propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, t-butylbenzene, especially Preferred are 1-methoxy-2-propanol, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole.
The total solid 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.
Here, the total solid content corresponds to all components constituting the insulating film obtained by using this composition.

  The compound having a cage structure used in the present invention preferably has a higher solubility in an organic solvent from the viewpoint of preventing precipitation of insoluble materials during storage of the coating solution. 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.

The film-forming composition of the present invention preferably has a sufficiently low metal content such as impurities. 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 of them is 100 × 10 ¹⁰ atoms · cm ^{−. It} is preferably ² or less, more preferably 50 × 10 ¹⁰ atoms · cm ⁻² or less, and particularly preferably 10 × 10 ¹⁰ atoms · cm ⁻² or less. Further, Br which is halogen can be observed, and the residual amount is preferably 10,000 × 10 ¹⁰ atoms · cm ⁻² or less, more preferably 1000 × 10 ¹⁰ cm ⁻² or less, and particularly preferably 400 × 10 ¹⁰ atoms · cm 2. ^-2 or less. Further, although Cl can be observed as halogen, the remaining amount is preferably 100 × 10 ¹⁰ atoms · cm ⁻² or less, more preferably 50 × 10 ¹⁰ atoms · cm ·, from the viewpoint of damaging the CVD apparatus, the etching apparatus, and the like. cm ⁻² or less, particularly preferably 10 × 10 ¹⁰ atoms · 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 adhesion promoter.

  The radical generator refers to a compound that generates radicals of atoms such as carbon, oxygen, and nitrogen when irradiated with heat or light energy, and has a function of promoting a dural reaction.

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 Etc. can be used.
The colloidal silica used in the present invention may be one type or two or more types.

  Any surfactant may be used in the present invention, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, 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 with respect to the total amount of the film-forming composition. More preferably, it is as follows.

  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 (preferably having 1 to 5 carbon atoms), x represents an integer of 1 to 20, and m and n are each independently an integer of 2 to 100. A plurality of x and R may be the same or different.

  Examples of the silicone-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, - 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-chloropropylmethyldimethoxy Silane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldi Ethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, Benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, - mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, it may be mentioned thiourea compounds. The preferable use amount of the adhesion promoter is preferably 10 parts by mass or less, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass 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, the solubility in a solvent used in the film-forming composition, the polymer of the present invention. It is necessary to satisfy the compatibility with.
A polymer can also be used as the pore-forming agent. Examples of the polymer that can be used as the pore-forming agent include polyvinyl aromatic compounds (polystyrene, polyvinyl pyridine, halogenated polyvinyl aromatic compounds, etc.), polyacrylonitrile, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), polyethylene, poly Lactic acid, polysiloxane, polycaprolactone, polycaprolactam, polyurethane, polymethacrylate (such as polymethyl methacrylate) or polymethacrylic acid, polyacrylate (such as polymethyl acrylate) and polyacrylic acid, polydiene (such as polybutadiene and polyisoprene), polyvinyl chloride , Polyacetal, and amine-capped alkylene oxide, other polyphenylene oxide, poly (dimethyl) Siloxane), polytetrahydrofuran, poly cyclohexyl ethylene, polyethyl oxazoline, polyvinyl pyridine, may be a polycaprolactone.
In particular, polystyrene can be suitably used as a pore forming agent. Examples of polystyrene include anionic polymerized polystyrene, syndiotactic polystyrene, unsubstituted and substituted polystyrene (for example, poly (α-methylstyrene)), and unsubstituted polystyrene is preferred.
Further, a thermoplastic polymer can also be used as the pore forming agent. Examples of thermoplastic pore forming polymers include polyacrylate, polymethacrylate, polybutadiene, polyisoprene, polyphenylene oxide, polypropylene oxide, polyethylene oxide, poly (dimethylsiloxane), polytetrahydrofuran, polyethylene, polycyclohexylethylene, polyethyloxazoline. , Polycaprolactone, polylactic acid, polyvinyl pyridine and the like.
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 heating conditions for drying, it is preferably performed at 100 ° C. to 250 ° C. for 1 minute to 5 minutes. As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, a clean track series (manufactured by Tokyo Electron), a D-spin series (manufactured by Dainippon Screen), an SS series or a CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. The spin coating conditions may be any rotational speed, but 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 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. Further, from the viewpoint of suppressing the consumption of the film-forming composition, a method is used in which only the solvent is preliminarily discharged onto the substrate to form a liquid film, and then the film-forming composition is discharged from the liquid film. You can also. 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 method of heat treatment is not particularly limited, but it is possible to apply commonly used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. 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 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) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.

The polymer of the present invention is particularly preferably cured (baked) by applying heat treatment after coating on a 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 (baking) by causing 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 50 keV or less, more preferably 30 keV or less, and particularly preferably 20 keV or less. The total dose of the electron beam is preferably 5 μC / cm ² or less, more preferably ² μC / cm ² or less, and particularly preferably 1 μC / cm ² or less. 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. 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. In addition, after the etching process, ashing can be performed for the purpose of removing the photoresist or the like used for the processing, 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 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.
Further, 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 of compound (A) having cage structure>
According to the synthesis method described in Macromolecules, 5266 (1991), 4,9-diethynyldiamantane was synthesized, and this compound was reduced with diisobutylaluminum hydride in a conventional manner to give 4,9-divinyl. Diamantane was synthesized. Next, 2 g of 4,9-divinyldiamantane, 0.4 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) and 10 ml of t-butylbenzene were stirred and polymerized at an internal temperature of 150 ° C. for 5 hours under a nitrogen stream. After the reaction solution was brought to room temperature, it was added to 60 ml of isopropyl alcohol, and the precipitated solid was filtered and thoroughly washed with isopropyl alcohol. 0.9g of compound (A) with a weight average molecular weight of about 1 million was obtained.

<Synthesis of compound (B) having a cage structure>
1,3-diethynyladamantane was synthesized according to the synthesis method of compound (A). 2,3 g of 1,3-diethynyladamantane, 0.5 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) and 10 ml of t-butylbenzene were stirred and polymerized at an internal temperature of 150 ° C. for 5 hours under a nitrogen stream. After the reaction solution was brought to room temperature, it was added to 60 ml of isopropyl alcohol, and the precipitated solid was filtered and thoroughly washed with isopropyl alcohol. 0.8 g of the compound (B) having a weight average molecular weight of about 30,000 was obtained.
<Synthesis of compound (C) having cage structure>
3,3′-divinyl-1,1′-biadamantane was synthesized according to the synthesis method of compound (A). Stir 2 g of 3,3′-divinyl-1,1′-biadamantane, 0.25 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) and 10 ml of t-butylbenzene at an internal temperature of 150 ° C. for 5 hours under a nitrogen stream. Polymerized. After the reaction solution was brought to room temperature, it was added to 60 ml of isopropyl alcohol, and the precipitated solid was filtered and thoroughly washed with isopropyl alcohol. 1.2 g of compound (C) having a weight average molecular weight of about 20,000 was obtained.

<Example 1>
A coating solution was prepared by completely dissolving 0.5 g of compound (A) and 0.5 g of compound (B) in 10 g of anisole. The solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and the solvent was dried. Furthermore, as a result of baking for 60 minutes in a 400 ° C. oven purged with nitrogen, a uniform film having a thickness of 0.5 μm and no defects was obtained. The relative dielectric constant of the film was calculated from the capacitance value at 1 MHz by using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard. Moreover, it was 6.5 GPa when the Young's modulus was measured using nano indenter SA2 by MTS.

<Example 2>
A coating solution was prepared by completely dissolving 0.5 g of the compound (A) and 0.5 g of the compound (C) in 10 g of anisole. The solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and the solvent was dried. Furthermore, as a result of baking for 60 minutes in a 400 ° C. oven purged with nitrogen, a uniform film having a thickness of 0.5 μm and no defects was obtained. The relative dielectric constant of the film was calculated from the capacitance value at 1 MHz by using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard. Moreover, it was 5.0 GPa when the Young's modulus was measured using Nano Indenter SA2 from MTS.

<Reference Example 1>
A coating solution was prepared by completely dissolving 1.0 g of compound (A) in 10 g of anisole. The solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and the solvent was dried. Furthermore, as a result of baking for 60 minutes in a 400 ° C. oven purged with nitrogen, a uniform film having a thickness of 0.5 μm and no defects was obtained. The relative dielectric constant of the film was calculated from the capacitance value at 1 MHz by using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard. Moreover, it was 4.5 GPa when the Young's modulus was measured using Nano Indenter SA2 manufactured by MTS.

<Reference Example 2>
A coating solution was prepared by completely dissolving 1.0 g of compound (B) in 10 g of anisole. The solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and the solvent was dried. Furthermore, as a result of baking for 60 minutes in a 400 ° C. oven purged with nitrogen, a uniform film having a thickness of 0.5 μm and no defects was obtained. 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 Yokogawa Hewlett-Packard. Moreover, it was 6.5 GPa when the Young's modulus was measured using nano indenter SA2 by MTS.

<Reference Example 3>
A coating solution was prepared by completely dissolving 1.0 g of compound (C) in 10 g of anisole. The solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and the solvent was dried. Furthermore, as a result of baking for 60 minutes in a 400 ° C. oven purged with nitrogen, a uniform film having a thickness of 0.5 μm and no defects was obtained. The relative dielectric constant of the film was calculated from the capacitance value at 1 MHz by using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard. Moreover, it was 4.5 GPa when the Young's modulus was measured using Nano Indenter SA2 manufactured by MTS.

  It can be seen that the insulating film of the present invention is excellent in relative dielectric constant and Young's modulus.

Claims (10)

  A film-forming composition comprising at least two compounds having a cage structure.   The film-forming composition according to claim 1, wherein the compound having a cage structure is a polymer having a cage structure.   3. The compound having a cage structure is a polymer obtained by polymerizing a monomer having a cage structure in the presence of a transition metal catalyst or in the presence of a radical initiator. A film forming composition.   The film-forming composition according to any one of claims 1 to 3, wherein the monomer having a cage structure has a carbon-carbon double bond or a carbon-carbon triple bond.   The film-forming composition according to any one of claims 1 to 4, wherein the cage structure is selected from adamantane, biadamantane, diamantane, triamantane, and tetramantane. The film-forming composition according to any one of claims 1 to 5, wherein the monomer having a cage structure is selected from the group of compounds represented by the following formulas (I) to (VI).

In the formulas (I) to (VI),
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.
Y _{1 to} Y ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group.
When a plurality of X _{1 to} X ₈ and Y _{1 to} Y ₈ are present, they may be the same or different.
m ₁ and m ₅ each independently represents an integer of ₁ to 16, and n ₁ and n ₅ each independently represents an integer of 0 to 15.
m ₂ , m ₃ , m ₆ and m ₇ each independently represents an integer of 1 to 15, and n ₂ , n ₃ , n ₆ and n ₇ each independently represents an integer of 0 to 14.
m ₄ and m ₈ each independently represents an integer of 1 to 20, and n ₄ and n ₈ each independently represents an integer of 0 to 19.   The film-forming composition according to any one of claims 1 to 6, wherein the compound having a cage structure can be dissolved in cyclohexanone or anisole at 3% by mass or more at 25 ° C.   Furthermore, the organic solvent is included, The composition for film formation in any one of Claims 1-7 characterized by the above-mentioned.   The insulating film formed using the film forming composition in any one of Claims 1-8.   An electronic device having the insulating film according to claim 9.