JP5113466B2 - Insulating film manufacturing method and insulating film - Google Patents

Description

  The present invention relates to an insulating film manufacturing method and an insulating film obtained by the manufacturing method.

  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.

In general, a polymer composed of a saturated hydrocarbon is exemplified as a compound exhibiting a low dielectric constant. Since these polymers have a lower molar polarization than polymers composed of heteroatom-containing units and aromatic hydrocarbon units, they exhibit a lower dielectric constant. However, for example, highly flexible hydrocarbons such as polyethylene have insufficient heat resistance and cannot be used for electronic device applications.
On the other hand, polymers in which adamantane and diamantane, which are rigid hydrocarbons having a rigid cage structure, are introduced into the molecule are disclosed, and are disclosed to have a low dielectric constant (Patent Document 1).

JP 2003-292878 A

  An object of the present invention is to provide a method for manufacturing an insulating film that is capable of manufacturing an insulating film having excellent curability and a low dielectric constant, and an insulating film obtained by the manufacturing method.

As a result of intensive studies, the present inventor has found that the above problems are solved by the following <1> and <5> configurations. It is shown below with <2>-<4> which are preferable embodiments.
<1> A step of applying a film-forming composition and a step of irradiating the applied film-forming composition with ultraviolet light, wherein the film-forming composition comprises (A) a radical polymerization initiator and (B -1) A polymer obtained by polymerizing at least a compound represented by the following formula (1) and / or a compound represented by the following formula (1), and / or (B-2) represented by the following formula (2). And / or a polymer obtained by polymerizing at least a compound represented by the following formula (2), and a method for producing an insulating film,

（式（１）中、２つのＲ¹は炭素と水素のみからなる基を表し、それぞれ同一でも異なっていてもよく、お互いに連結し、６員環以上の環構造を形成していてもよい。Ｒ²は水素原子又は下記式（３）で表され、それぞれ同一でも異なっていてもよい。ただし、少なくともＲ²のうち１つは式（３）で表される。）

(In the formula (1), two R ^{1 s} represent groups consisting of only carbon and hydrogen, which may be the same or different, and may be linked to each other to form a 6-membered or higher ring structure. R ² is represented by a hydrogen atom or the following formula (3), which may be the same or different, but at least one of R ² is represented by formula (3).

（式（２）中、Ｒ⁴及びＲ⁵は炭素と水素のみからなる基を表し、それぞれ同一でも異なっていてもよく、Ｒ⁴はＲ⁴と、Ｒ⁵はＲ⁵とお互いに連結し、６員環以上の環構造を形成していてもよい。Ｒ⁶は水素原子又は式（３）で表され、それぞれ同一でも異なっていてもよい。ただし、少なくともＲ⁶のうち１つは式（３）で表される。）

(In the formula (2), R ⁴ and R ⁵ each represent a group consisting of carbon and hydrogen, which may be the same or different, and R ⁴ is linked to R ⁴ and R ⁵ is linked to R ⁵ . A ring structure of 6 or more members may be formed, and R ⁶ is represented by a hydrogen atom or formula (3), and may be the same or different, provided that at least one of R ⁶ is represented by formula ( 3))

（式（３）中、Ｃ₂Ｈ_xにおける２つの炭素原子は２重結合又は３重結合で連結されており、ｘは０又は２を表す。Ｒ³は水素原子、アルキル基、アリール基、置換アリール基、ヘテロアリール基、アリールエーテル基、アルケニル基又はアルキニル基を表す。ｎは４であり、ｎ個のＲ⁷はそれぞれ同一でも異なっていてもよく、水素原子、アルキル基、アリール基、置換アリール基又はハロゲン原子を表す。）

(In Formula (3), two carbon atoms in C ₂ H _x are connected by a double bond or a triple bond, and x represents 0 or 2. R ³ represents a hydrogen atom, an alkyl group, an aryl group, A substituted aryl group, a heteroaryl group, an aryl ether group, an alkenyl group or an alkynyl group, wherein n is 4 and n R ^{7 s} may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, Represents a substituted aryl group or a halogen atom.)

<2> The method according to <1>, wherein the wavelength of the ultraviolet light is 500 nm or less,
<3> The production method according to <1> or <2>, wherein the irradiation time of the ultraviolet rays is 3 minutes or less,
<4> Any of <1> to <3> above, wherein the radical polymerization initiator contains at least one selected from the group consisting of organic peroxides, organic azo compounds, alkylphenone compounds, and oxime ester compounds. Or the production method according to claim 1,
<5> An insulating film obtained by the manufacturing method according to any one of <1> to <4> above.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the insulating film which can manufacture the insulating film which is excellent in sclerosis | hardenability and has a low dielectric constant, and the insulating film obtained by the said manufacturing method were able to be provided.

Hereinafter, the present invention will be described in detail.
The method for producing an insulating film of the present invention comprises a step of applying a film-forming composition and a step of irradiating the applied film-forming composition with ultraviolet rays, wherein the film-forming composition comprises (A) a radical. Polymerized by using at least a polymerization initiator and (B-1) a compound represented by the above formula (1) and / or a compound represented by the above formula (1) (hereinafter referred to as component (B-1) And / or (B-2) a polymer obtained by polymerizing at least a compound represented by the above formula (2) and / or a compound represented by the above formula (2) (hereinafter referred to as (B- 2) also referred to as a component)).

  In the present invention, the film-forming composition is constituted by adding a radical polymerization initiator to the component (B-1) and / or the component (B-2). By adding a radical polymerization initiator to a compound having an unsaturated bond linked to an aromatic ring, such as component (B-1) or component (B-2), the reaction efficiency is improved, and the machine after hardening The strength can be improved, and the k value (dielectric constant) can be reduced by reducing unreacted groups.

  In addition, the conventionally used film curing process by heat treatment has a problem that the processing time is long and the manufacturing takes time. In the present invention, the curing reaction is accelerated by irradiating with ultraviolet rays, and the time required for production can be greatly reduced. A radical polymerization initiator is added so that the curing reaction is further accelerated by irradiation with ultraviolet rays, and the curing reaction is further accelerated. Therefore, the processing time per wafer can be shortened by irradiation with ultraviolet rays, and the curing reaction can be performed more quickly than the curing reaction by heat, so that a film with higher mechanical strength can be formed. It becomes possible.

(Film forming composition)
The film-forming composition used in the present invention (also referred to as the film-forming composition of the present invention) comprises (A) a radical polymerization initiator, (B-1) component and / or (B-2) component. And other additives as required.

<(A) Radical polymerization initiator>
The radical polymerization initiator used in the present invention preferably exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by ultraviolet rays (UV). In particular, organic peroxides, organic azo compounds, alkylphenone compounds, and oxime ester compounds are preferably used.

  Organic peroxides include diisobutyryl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate , Di (2-ethylhexyl) peroxydicarbonate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1 , 1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethyhexanoylperoxy) hexane, t-hexyl peroxy-2-ethylhexanoate, di (4-methylbenzoyl ) peroxide, t-butyl peroxy-2-ethylhexanoate, di (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) cyclohe xane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t -butyl peroxylaurate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2, 2-di- (t-butylperoxy) butane, t-butyl peroxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, p-menthane 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-butyl peroxy) triazine, 2,4,4-trimethyl pe ntyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, t-amyl peroxy 2-ethyl hexanoate, t-butyl peroxy isobutylate, di-t-butyl peroxy hexahydro terephthalate, di-t-butylperoxy trimethyl adipate, di-3-methoxy butyl peroxy dicarbonate Di-isopropyl peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, 1,6-bis (t-butyl peroxycarbnyloxy) hexane, diethyleneglycol bis (t-butyl peroxycarbonate), t-hexylperoxy neodecanoate and the like are preferably used.

  As organic azo compounds, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylpropionitrile), 2,2 -azobis (2,4-dimethylbuthyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2-azobis {2-methyl-N -[1,1-bis (hydroxymethyl) -2-hydroxyethyle] propionamide}, 2,2-azobis {2-methyl-N- [2- (1-hydroxybuthyl)] propionamide}, 2,2-azobis [2- methyl-N- (2-hydroxyethyl) -propionamide], 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2-azobis (N-buthyl-2-methylpropionamide), 2,2 -azobis (N-cyclohexyl-2-methylpropionamide), 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} dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) ) propane], 2,2-azobis (1-imino-1-pyrrolidino-2-methyl-propane) dihydrochloride, 2,2-azobis (2-methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-car boxyethyl) -2-methyl-propionamidine] tetrahydrate, dimethyl 2,2-azobis (2-methylpropionate), 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2,4,4-trimethylpentane), etc. Is preferably used.

  Alkylphenone compounds include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 -Methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like are preferably used.

In the present invention, only one radical polymerization initiator may be used, or two or more radical polymerization initiators may be used in combination.
In this invention, the usage-amount of a polymerization initiator shall be 0.005-20 mol with respect to 1 mol of total moles of (B-1) component, (B-2) component, and another polymeric compound. Is more preferable, 0.01 to 8 mol is more preferable, and 0.1 to 2 mol is particularly preferable. Here, the total number of moles is the sum of monomer units constituting the polymer when the component (B-1) is a polymer polymerized using at least the compound represented by formula (1). This means the number of moles. Similarly, when the component (B-2) is a polymer polymerized using at least the compound represented by formula (2), the total of monomer units constituting the polymer It means the number of moles.

<(B-1) component and (B-2) component>
In the present invention, the film-forming composition contains the component (B-1) and / or the component (B-2) as an essential component.
[(B-1) component]
In the present invention, the component (B-1) is a polymer obtained by polymerizing at least a compound represented by the following formula (1) and / or a compound represented by the following formula (1).

-Compound represented by Formula (1)-
The compound represented by formula (1) will be described.

In the formula (1), two R ^{1 s} represent groups consisting of only carbon and hydrogen, and may be the same or different, and may be connected to each other to form a 6-membered or higher ring structure. .
Examples of R ¹ include an alkyl group, an alkylene group, an alkenyl group, and an aryl group. Among these, an alkyl group is preferable. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 carbon atom, that is, a methyl group.
The two R ¹ are preferably linked to each other to form a 6-membered or higher ring structure, more preferably a 6-8 membered ring, and still more preferably a 6 membered ring. It is forming. When R ¹ forms a 6-membered ring, the compound represented by the formula (1) has an adamantane skeleton.

In the formula (1), R ² is represented by a hydrogen atom or the following formula (3), and may be the same or different. However, at least one of R ² is represented by Formula (3).

Two carbon atoms in C ₂ H _x in the formula (3) are connected by a double bond (—CH═CH—) or a triple bond (—C≡C—), and x is 0 or 2. To express. C ₂ H _x is preferably connected by a triple bond, that is, —C≡C—.

In the formula (3), R ³ represents a hydrogen atom, an alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, an aryl ether group, an alkenyl group or an alkynyl group. R ³ is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a t-butyl group or a phenyl group. Among these, R ³ is preferably a hydrogen atom or a phenyl group, and particularly preferably a hydrogen atom.

In the formula (3), n is 4, R ⁷ is a hydrogen atom or a substituent bonded to the benzene ring, and there are n (4). R ⁷ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a substituted aryl group or a halogen atom. Examples of the aryl group include a phenyl group or a biphenyl group. R ⁷ is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom.

  Although the preferable example of a compound represented by Formula (1) is shown below, this invention is not limited to this.

  150-3,000 are preferable, as for the molecular weight of the compound represented by Formula (1), 200-2,000 are more preferable, and 220-1,000 are especially preferable.

-Polymer polymerized using at least compound represented by formula (1)-
In this invention, it is preferable that the composition for film formation contains the polymer which polymerized using the compound represented by Formula (1) and / or the compound represented by Formula (1) at least. That is, the polymer has a compound represented by the formula (1) as a monomer unit.
The polymer polymerized using at least the compound represented by the formula (1) preferably contains 10 mol% or more of monomer units derived from the compound represented by the formula (1) in the structure. It is preferably contained in an amount of at least mol%, more preferably at least 50 mol%.
Moreover, the polymer polymerized using at least the compound represented by the formula (1) is a polymer (homopolymer) obtained by polymerizing only the compound represented by the formula (1), or other polymer having an adamantane skeleton. It is preferably a copolymer with a compound, and more preferably a polymer obtained by polymerizing only the compound represented by the formula (1).
The preferable compound in the compound represented by Formula (1) used for the polymer is the same as the preferable compound in the compound represented by Formula (1) described above.
The compound represented by Formula (1) used for the polymer may be used alone or in combination of two or more.

  The method for producing a polymer obtained by polymerization using at least the compound represented by the formula (1) is not particularly limited, but is represented by the formula (1) in the presence of a polymerization initiator or a transition metal catalyst. A method including a step of polymerizing using at least a compound is preferable, and a method including a step of polymerizing using a compound represented by formula (1) in the presence of a radical polymerization initiator is more preferable.

The polymerization initiator is preferably a radical polymerization initiator, and an organic peroxide or an organic azo compound is preferably used as the radical polymerization initiator, and an organic peroxide is particularly preferable.
As the organic peroxide and the organic azo compound, those described above can be preferably used.

Only one polymerization initiator may be used, or two or more polymerization initiators may be mixed and used.
The amount of the polymerization initiator used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and 0.05 to 0.5 mol with respect to 1 mol of the monomer. It is particularly preferred.

The polymerization reaction of the monomer 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 is converted into a Pd-based catalyst such as tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ ) or palladium acetate (Pd (OAc) ₂ ). , Ziegler-Natta catalyst, Ni catalyst such as nickel acetyl acetonate, 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 Polymerization is preferably performed using a catalyst, a Pt catalyst, or 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.

The weight average molecular weight of the polymer polymerized using at least the compound represented by the formula (1) is preferably 800 to 200,000, more preferably 2,000 to 100,000, and 5,000 to 50,000. Particularly preferred.
The polymer polymerized using at least the compound represented by the formula (1) may be contained in the film-forming composition of the present invention as a resin composition having a molecular weight distribution.

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, propanol, alcohol solvents such as alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate Ester solvents such as dibutyl ether and anisole, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t- Butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1- Aromatic hydrocarbon solvents such as tilnaphthalene and 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Halogen solvents such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene and aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane can be used.
Among these, more preferred solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1, 2, 4, 5-tetramethylbenzene, isopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methyl Naphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, Anisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, Chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyrolactone, anisole, mesitylene, t-butylbenzene, 1,3,5-triisopropylbenzene, 1,2- Dichlorobenzene and 1,2,4-trichlorobenzene. These may be used alone or in admixture of two or more.
The concentration of the monomer in the reaction solution is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.

Optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, monomer, solvent type, concentration, and the like, but preferably the internal temperature is 0 ° C to 200 ° C, more preferably 50 ° C to 170 ° C, and particularly preferably 100. C. to 150.degree. C., preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours, and particularly preferably 0.75 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.

[(B-2) component]
In the present invention, the component (B-2) is a general term for a polymer obtained by polymerization using at least a compound represented by the formula (2) and / or a compound represented by the following formula (2).
Hereinafter, the compound represented by Formula (2) is demonstrated.
-Compound represented by Formula (2)-
The compound represented by formula (2) will be described.

In the formula (2), two R ⁴ and R ⁵ are composed of carbon and hydrogen, and may be the same or different. R ⁴ is linked to R ⁴ and R ⁵ is linked to R ^5, and is a 6-membered ring. The above ring structure may be formed.
In the compound represented by the formula (2), R ⁴ and R ⁴ , R ⁵ and R ⁵ are preferably connected to each other to form a 6-membered ring. That is, it is preferable that the compound represented by Formula (2) has a diamantane skeleton.

In formula (2), R ⁶ is represented by a hydrogen atom or the above formula (3), and may be the same or different. However, at least one of R ⁶ is represented by Formula (3). Formula (3) is synonymous with that in Formula (1), and its preferred range is also the same.

  Preferred examples ((2-1) to (2-4)) of the compound represented by the formula (2) are shown below, but the present invention is not limited thereto.

  The molecular weight of the compound represented by the formula (2) is preferably 270 to 3,000, more preferably 275 to 2,000, and particularly preferably 285 to 1,000.

-Polymer polymerized using at least compound represented by formula (2)-
In the present invention, the film-forming composition can include a polymer obtained by polymerization using at least the compound represented by the formula (2) and / or the compound represented by the formula (2). The polymer has a compound represented by the formula (2) as a monomer unit.
The polymer polymerized using at least the compound represented by the formula (2) preferably contains 10 mol% or more of monomer units derived from the compound represented by the formula (2) in the structure. It is preferably contained in an amount of at least mol%, more preferably at least 50 mol%.
Moreover, the polymer polymerized using at least the compound represented by the formula (2) is a polymer (homopolymer) obtained by polymerizing only the compound represented by the formula (2), or other polymer having a diamantane skeleton. A copolymer with the compound is preferable, and a polymer obtained by polymerizing only the compound represented by the formula (2) is more preferable.
The preferable compound in the compound represented by Formula (2) used for the polymer is the same as the preferable compound in the compound represented by Formula (2) described above.
The compound represented by Formula (2) used for the polymer may be used alone or in combination of two or more.

  As a method for producing a polymer polymerized using at least the compound represented by formula (2), a method similar to the method for producing a polymer polymerized using at least the compound represented by formula (1) is used. The preferred reaction conditions are also the same.

The weight average molecular weight of the polymer polymerized using at least the compound represented by the formula (2) is preferably 800 to 200,000, more preferably 2,000 to 100,000, and 5,000 to 50,000. Particularly preferred.
The polymer polymerized using at least the compound represented by formula (2) may be contained in the film-forming composition of the present invention as a resin composition having a molecular weight distribution.

-Addition amount-
In the present invention, the total amount of component (B-1) and component (B-2) in the film-forming composition is preferably 0.1 to 50% by weight with respect to the film-forming composition. 1 to 40% by weight is more preferable, and 1.5 to 20% by weight is particularly preferable.
Moreover, it is preferable to add 20-99.9 weight% with respect to solid content of the composition for film formation, It is more preferable to add 40-99.7 weight%, 60-609.5 weight% is added. More preferably. Here, the solid content corresponds to all components constituting the film obtained by using the film forming composition of the present invention.
In the present invention, the component (B-1) and the component (B-2) in the film-forming composition may be used alone or in combination of two or more. Therefore, a plurality of (B-1) components can be used, and a plurality of (B-2) components can also be used. Moreover, (B-1) component and (B-2) component can also be used together. Among these, it is preferable to use only the component (B-1) or the component (B-2) and not use both.

<Metal content>
In the present invention, the film-forming composition 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 inductively coupled plasma mass spectrometry (ICP-MS), and the metal content other than the transition metal in that case is preferably 30 ppm or less, more preferably Is 3 ppm or less, particularly preferably 300 ppb or less.
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 of the present invention can also be evaluated by performing total reflection fluorescent X-ray measurement on a film obtained using the film forming composition of the present invention.
When a W (tungsten) ray is used as an X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, each of which is 100 × 10 ¹⁰ atoms. · Cm ⁻² or less is preferable, 50 × 10 ¹⁰ atom · cm ⁻² or less is more preferable, and 10 × 10 ¹⁰ atom · cm ⁻² or less is particularly preferable.
Further, Br which is halogen can be observed, and the residual amount is preferably 10,000 × 10 ¹⁰ atom · cm ⁻² or less, more preferably 1,000 × 10 ¹⁰ atom · cm ⁻² or less, and 400 × 10 ^10. Atom · cm ⁻² or less is particularly preferable. In addition, Cl can be observed as halogen, and the remaining amount is preferably 100 × 10 ¹⁰ atom · cm ⁻² or less, and 50 × 10 ¹⁰ atom · cm ⁻² or less from the viewpoint of damaging a CVD apparatus, an etching apparatus, or the like. Is more preferable, and 10 × 10 ¹⁰ atom · cm ⁻² or less is particularly preferable.

<Organic solvent>
The film forming composition of the present invention may contain an organic solvent (coating solvent).
Although it does not specifically limit as an organic solvent (coating solvent), For example, alcohol solvents, such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, 1-methoxy-2-propanol, Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, acetic acid Esters such as pentyl, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, and γ-butyrolactone , Ether solvents such as diisopropyl ether, dibutyl ether, ethyl propyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methylpyrrolidinone, dimethyl Examples thereof include amide solvents such as acetamide, and 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, Particularly preferred organic solvents are 1-methoxy-2-propanol, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole.

<Concentration of solid content>
The solid content concentration of the film-forming composition of the present invention is preferably 1 to 50% by weight, more preferably 2 to 15% by weight, and particularly preferably 3 to 10% by weight.
Here, the solid content corresponds to all components constituting the film obtained using this composition.
The solubility of the component (B-1) and the component (B-2) is preferably 3% by weight or more, more preferably 5% by weight or more, particularly preferably 10% by weight or more with respect to cyclohexanone or anisole at 25 ° C. It is.

<Other additives>
Furthermore, the film-forming composition of the present invention includes colloidal silica as long as the properties (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) of the obtained film (preferably insulating film) are not impaired. In addition, additives such as a surfactant, a silane coupling agent, and an adhesion promoter may be added.

[Colloidal silica]
Any colloidal silica may be used as the colloidal silica that can 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, preferably an average particle size of 5 to 30 nm, more preferably 10 to 20 nm, and a solid content concentration of preferably 5 to 40% by weight. belongs to.

[Surfactant]
As the surfactant that can be used in the present invention, any surfactant may be used. For example, nonionic surfactants, anionic surfactants, cationic surfactants, and the like, silicone surfactants, fluorine-containing surfactants, polyalkylene oxide surfactants, acrylic surfactants Agents. The surfactant that can be 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 that can be used in the present invention is preferably 0.01% by weight or more and 1% by weight or less, and preferably 0.1% by weight or more and 0.00% by weight based on the total amount of the film-forming composition. More preferably, it is 5% by weight or less.

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

  In said formula, R is a hydrogen atom or a C1-C5 alkyl group, x is an integer of 1-20, m and n are the integers of 2-100 each independently. Further, when there are a plurality of R, they may be the same or different.

  Examples of silicone surfactants that can be used in the present invention include BYK-306, BYK-307 (manufactured by BYK Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 ( Troy Chemical Co., Ltd.).

  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, an acrylic acid copolymer or a methacrylic acid copolymer can be used.

〔Silane coupling agent〕
Any silane coupling agent may be used as the silane coupling agent that can be used in the present invention.
Examples of the silane coupling agent include 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-ethoxycarboni -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-aminopropyltriethoxysilane, N- Bis (oxyethylene) 3-aminopropyltrimethoxysilane, N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.
The silane coupling agent that can be used in the present invention may be used alone or in combination of two or more.

[Adhesion promoter]
Any adhesion promoter may be used as the adhesion promoter that can be used in the present invention.
Examples of the adhesion promoter include 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-chloropropylto Limethoxysilane, 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-mercaptobenzimidazole, 2-mercaptobenzothiazole 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, thiourea compound and the like. Functional silane coupling agents are preferred as adhesion promoters.
The amount of adhesion promoter used is preferably 10 parts by weight or less, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total solid content.

[Void formation factor]
In the film-forming composition 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 achieve a low dielectric constant.
The pore-forming factor as an additive that serves as a pore-forming agent is not particularly limited, but a nonmetallic compound is preferably used, and solubility in a solvent used in the film-forming composition, (B- It is necessary to satisfy the compatibility with the component 1) and / or component (B-2) at the same time.
Further, 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.
The molecular weight is preferably 200 to 50,000, more preferably 300 to 10,000, and particularly preferably 400 to 5,000.
The addition amount is preferably 0.5 to 75% by weight, more preferably 0.5 to 30% by weight, and particularly preferably 1 to 20% by weight 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. It is. The content of the decomposable group is preferably 0.5 to 75 mol%, more preferably 0.5 to 30 mol%, and particularly preferably 1 to 20 mol% with respect to the polymer forming the film.

(Insulating film manufacturing method)
The method for producing an insulating film of the present invention includes (a) a step of applying the film forming composition of the present invention, and (b) a step of irradiating the applied film forming composition with ultraviolet rays. Hereinafter, each process will be described.

<(A) The process of apply | coating the composition for film formation>
The process of apply | coating the composition for film formation of this invention is not specifically limited, It can apply | coat on a board | substrate by a well-known method. Specific examples include spin coating, roller coating, dip coating, and scanning. 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 Co., Ltd.), D-spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS series or 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 1,300 rpm is preferable for a 300 mm silicon substrate.
In addition, the method for discharging the film forming composition may be either dynamic discharge for discharging the film forming composition onto a rotating substrate or static discharge for discharging the film forming composition onto a stationary substrate. However, dynamic ejection is preferable from the viewpoint of in-plane uniformity of the film. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.

Moreover, after apply | coating the composition for film formation, it is preferable to heat-process in order to remove the solvent contained in the composition for film formation.
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. Commercially available equipment can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron Ltd.), D-Spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS series or CS series (Tokyo Ohka Kogyo Co., Ltd.) )) And the like can be preferably used. As the furnace, α series (manufactured by Tokyo Electron Ltd.) and the like can be preferably used.
The heating temperature and heating time for removing the solvent are preferably selected as appropriate depending on the type and amount of the solvent used in the film-forming composition, the coating amount of the film-forming composition, and the like. For example, 40-300 degreeC can be illustrated, 50-250 degreeC is preferable, and 60-200 degreeC is more preferable.
The heating time can be exemplified by 60 seconds, for example, preferably 10 to 300 seconds, and more preferably 20 to 200 seconds. It is preferable for the heating temperature to be within the above range since the solvent can be effectively removed.
The above heat treatment may be used not only for the purpose of removing the solvent but also for causing a polymerization reaction. In that case, the heating temperature is preferably 40 to 400 ° C., more preferably 50 to 350. The heating time is preferably from 1 to 30 minutes, more preferably from 5 to 45 minutes, and further preferably from 10 to 30 minutes.
The above heat treatment can be performed using an atmosphere around the substrate as an inert atmosphere such as Ar, He, or nitrogen.

<(B) The process of irradiating the applied film-forming composition with ultraviolet rays>
In the present invention, the applied film-forming composition is irradiated with ultraviolet rays to cure the film-forming composition.
The irradiation wavelength region of ultraviolet rays preferably includes a wavelength of 500 nm or less, more preferably includes ultraviolet rays of 150 to 400 nm, and further preferably includes ultraviolet rays of 160 to 350 nm. It is preferable for the wavelength region to be within the above range because the organic material can be easily modified.
Preferably the output is 0.1～5,000MWcm ^-2 immediately above the substrate, more preferably 1～2,000MWcm ^-2, and more preferably a 10~1,000mWcm ^-2. If the output directly above the substrate is within the above range, the higher the illuminance, the shorter the processing is possible. However, since the irradiation effect is dependent on the film thickness, the output is preferably low to some extent.
The irradiation time of ultraviolet rays is preferably 15 minutes or less, more preferably 10 minutes or less, and further preferably 3 minutes or less. Moreover, it is preferable that it is 10 seconds or more, More preferably, it is 20 seconds or more, More preferably, it is 30 seconds or more. It is preferable that the irradiation time of ultraviolet rays be within the above range because the film can be uniformly cured.
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, 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.
Further, the ultraviolet irradiation may be performed a plurality of times. In this case, the ultraviolet irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Heat treatment can also be performed after the ultraviolet irradiation. The heat treatment temperature is preferably 200 to 400 ° C.
In addition, it is preferable to use inert atmosphere, such as Ar, He, and nitrogen, for the atmosphere around a board | substrate from a viewpoint of preventing the oxidation of a polymer for the heating after ultraviolet irradiation. The pressure at that time is preferably 0 to 133 kPa.

Moreover, in this invention, it hardens | cures by raise | generating the polymerization reaction of the carbon triple bond etc. which exist in (B-1) component and / or (B-2) component by irradiating a high energy ray before and behind ultraviolet irradiation. You may let them. 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 . 0-450 degreeC is preferable, as for the substrate temperature at the time of irradiating an electron beam, 0-400 degreeC is more preferable, and 0-350 degreeC is especially preferable. 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, it is preferable to use an inert atmosphere such as Ar, He, or nitrogen as the atmosphere around the substrate. 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. In the present invention, the electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same every time, and may be performed under different conditions each time.

(Insulating film)
The insulating film of the present invention is a film obtained by the insulating film manufacturing method of the present invention.
The insulating film obtained by using the film-forming composition of the present invention preferably has a desired relative dielectric constant depending on the application, but preferably has a low relative dielectric constant and a relative dielectric constant of 2. It is preferably 6 or less, and more preferably 2.5 or less.

Further, the film obtained using the film forming composition of the present invention preferably has a high hardness and preferably has a high Young's modulus. The Young's modulus is preferably 5 GPa or more, more preferably 5.5 to 12 GPa, and even more preferably 6 to 11 GPa.
In addition, as a method for measuring the Young's modulus in the insulating film of the present invention, it is preferable to use MTS Nanoindenter SA2.
Note that it is particularly preferable that the insulating film obtained according to the present invention has a relative dielectric constant and a Young's modulus both in the above range.

The film obtained by the present invention is an insulating film and can be more suitably used as an interlayer insulating film for semiconductors. That is, the insulating film of the present invention can be suitably used for electronic devices.
For example, when used as an interlayer insulating film for a semiconductor, in the wiring structure, there may be a barrier layer on the side surface of the wiring to prevent metal migration, and CMP (chemical In addition to a cap layer and an interlayer adhesion layer that prevent peeling by mechanical mechanical polishing, there may be an etching stopper layer, etc. Furthermore, the interlayer insulating film layer may be divided into a plurality of layers with other materials as required. Also good.

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

  The insulating film obtained by the present invention can be used for various purposes. For example, it is suitable as an insulating film in electronic devices such as semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and multi-chip 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. Can do.

  The following examples illustrate the invention and are not intended to limit its scope.

<Example 1>
1,3-diphenylethynyladamantane 2 parts by weight, dicumyl peroxide (Parkmill D, manufactured by NOF Corporation) 0.4 part by weight, t-butylbenzene 8.6 parts by weight at an internal temperature of 130 ° C. for 1 hour under a nitrogen stream Stir and polymerize. After the reaction solution was brought to room temperature, it was added to 79.1 parts by weight of methanol, and the precipitated solid was filtered and washed with methanol. 1.0 part by weight of polymer (A) having a weight average molecular weight of about 8,000 was obtained.
The solubility of the polymer (A) in cyclohexanone was 20% by weight or more at 25 ° C.

A coating solution was prepared by completely dissolving 1.0 part by weight of polymer (A) and 0.2 part by weight of dicumyl peroxide in 10 parts by weight of cyclohexanone. The solution was filtered through a 0.1 micron tetrafluoroethylene filter, spin-coated on a silicon wafer, and the coating film was heated on a hot plate at 120 ° C. for 60 seconds under a nitrogen stream to obtain a film thickness of 0. A uniform film free of 5 microns was obtained.
Using the dielectric barrier discharge lamp manufactured by Ushio Electric Co., Ltd., which can irradiate the obtained film with ultraviolet light having a wavelength of 172 nm, ultraviolet light is irradiated for 3 minutes on a film placed on a hot plate at 350 ° C. in a nitrogen atmosphere at 1 Pa. Irradiation gave an insulating film. At this time, the output right above the substrate was 10 mWcm ⁻² .
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 9.5 GPa when the Young's modulus was measured using nano indenter SA2 by MTS.

<Comparative Example 1>
1,3-diphenylethynyladamantane 2 parts by weight and dicumyl peroxide (Parkmill D, manufactured by NOF Corporation) 0.4 part by weight, t-butylbenzene 8.6 parts by weight at an internal temperature of 130 ° C. for 1 hour under a nitrogen stream Stir and polymerize. After the reaction solution was brought to room temperature, it was added to 79.1 parts by weight of methanol, and the precipitated solid was filtered and washed with methanol. 1.0 part by weight of polymer (A) having a weight average molecular weight of about 8,000 was obtained.
The solubility of the polymer (A) in cyclohexanone was 20% by weight or more at 25 ° C.

  A coating solution was prepared by completely dissolving 1.0 part by weight of polymer (A) and 0.2 part by weight of dicumyl peroxide in 10 parts by weight of cyclohexanone. The solution was filtered through a 0.1 micron tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 120 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen. As a result of firing on a hot plate at 400 ° C. for 3 minutes at 1 Pa, 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, when the Young's modulus was measured using Nano Indenter SA2 manufactured by MTS, it was 3.2 GPa.

<Example 2>
1,3-diphenylethynyladamantane 2 parts by weight, dicumyl peroxide (Parkmill D, manufactured by NOF Corporation) 0.4 part by weight, t-butylbenzene 8.6 parts by weight at an internal temperature of 130 ° C. for 1 hour under a nitrogen stream Stir and polymerize. After the reaction solution was brought to room temperature, it was added to 79.1 parts by weight of methanol, and the precipitated solid was filtered and washed with methanol. 1.0 part by weight of polymer (A) having a weight average molecular weight of about 8,000 was obtained.
The solubility of the polymer (A) in cyclohexanone was 20% by weight or more at 25 ° C.

A coating solution was prepared by completely dissolving 1.0 part by weight of polymer (A) and 0.2 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone in 10 parts by weight of cyclohexanone. The solution was filtered through a 0.1 micron tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and then irradiated with UV (wavelength 222 nm, dielectric barrier discharge lamp manufactured by USHIO ELECTRIC CO., LTD. Was performed for 10 minutes on a 300 ° C. hot plate in a nitrogen substitution atmosphere. As a result, a uniform film having a thickness of 0.5 microns was obtained. The UV irradiation was performed at 1 Pa. At this time, the output right above the substrate (silicon wafer) was 5 mWcm ⁻² .
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 9.8 GPa when the Young's modulus was measured using nano indenter SA2 by MTS.

<Example 3>
1,3,5-triphenylethynyladamantane 2 parts by weight, dicumyl peroxide (Parkmill D, manufactured by NOF Corporation) 0.4 part by weight, t-butylbenzene 8.6 parts by weight under nitrogen flow 130 ° C. And polymerized with stirring for 1 hour. After the reaction solution was brought to room temperature, it was added to 79.1 parts by weight of methanol, and the precipitated solid was filtered and washed with methanol. 1.0 part by weight of polymer (B) having a weight average molecular weight of about 17,000 was obtained.
The solubility of the polymer (B) in cyclohexanone was 20% by weight or more at 25 ° C.

A coating solution was prepared by completely dissolving 1.0 part by weight of polymer (B) and 0.2 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone in 10 parts by weight of cyclohexanone. This solution was filtered through a 0.1 micron tetrafluoroethylene filter, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and then 110 ° C. As a result of irradiating with UV for 5 minutes (wavelength 222 nm) and baking for 3 minutes on a 300 ° C. hot plate purged with nitrogen, a uniform film having a thickness of 0.5 microns was obtained. The UV irradiation was performed at 1 Pa. At this time, the output right above the substrate (silicon wafer) was 5 mWcm ⁻² .
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 8.0 GPa when the Young's modulus was measured using nano indenter SA2 by MTS.

<Comparative example 2>
1,3,5-triphenylethynyladamantane 2 parts by weight, dicumyl peroxide (Parkmill D, manufactured by NOF Corporation) 0.4 part by weight, t-butylbenzene 8.6 parts by weight under nitrogen flow 130 ° C. And polymerized with stirring for 1 hour. After the reaction solution was brought to room temperature, it was added to 79.1 parts by weight of methanol, and the precipitated solid was filtered and washed with methanol. 1.0 part by weight of polymer (B) having a weight average molecular weight of about 17,000 was obtained.
The solubility of the polymer (B) in cyclohexanone was 20% by weight or more at 25 ° C.

Only the polymer (B) was completely dissolved in 10 parts by weight of cyclohexanone to prepare a coating solution. This solution was filtered through a 0.1 micron tetrafluoroethylene filter and then spin-coated on a silicon wafer. The coating film was heat-treated on a 300 ° C. hot plate for 10 minutes in a nitrogen atmosphere. As a result, a uniform film having a thickness of 0.5 microns was obtained. The UV irradiation was performed at 1 Pa.
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, when the Young's modulus was measured using Nano Indenter SA2 manufactured by MTS, it was 3.5 GPa.

  The results are shown in Table 1 below.

  The insulating film obtained by the present invention was found to have excellent curability (strength) and low dielectric constant.

Claims (7)

Applying a film-forming composition to a substrate ;
Irradiating the applied film-forming composition with ultraviolet light,
The film-forming composition is
(A) a radical polymerization initiator;
(B-1) A polymer obtained by polymerizing at least a compound represented by the following formula (1) and / or a compound represented by the following formula (1), and / or (B-2) the following formula (2) in looking contains at least used and polymerized polymer compound and / or a compound represented by the following formula (2) expressed,
The ultraviolet irradiation time in the ultraviolet irradiation step is 10 minutes or less, the substrate temperature at the time of ultraviolet irradiation is 250 to 450 ° C., the wavelength of the ultraviolet light is 150 to 400 nm, and the output of the ultraviolet light immediately above the substrate is 1. A method for producing an insulating film, characterized in that it is ˜2,000 mWcm ⁻² .

(In the formula (1), two R ^{1 s} represent groups consisting of only carbon and hydrogen, which may be the same or different, and may be linked to each other to form a 6-membered or higher ring structure. R ² is represented by a hydrogen atom or the following formula (3), which may be the same or different, but at least one of R ² is represented by formula (3).

(In the formula (2), R ⁴ and R ⁵ each represent a group consisting of carbon and hydrogen, which may be the same or different, and R ⁴ is linked to R ⁴ and R ⁵ is linked to R ⁵ . A ring structure of 6 or more members may be formed, and R ⁶ is represented by a hydrogen atom or formula (3), and may be the same or different, provided that at least one of R ⁶ is represented by formula ( 3))

(In Formula (3), two carbon atoms in C ₂ H _x are connected by a double bond or a triple bond, and x represents 0 or 2. R ³ represents a hydrogen atom, an alkyl group, an aryl group, A substituted aryl group, a heteroaryl group, an aryl ether group, an alkenyl group or an alkynyl group, wherein n is 4 and n R ^{7 s} may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, Represents a substituted aryl group or a halogen atom.)   In the formula (3), C ₂ H _x Are bonded by a triple bond, x represents 0, R ^Three The method for manufacturing an insulating film according to claim 1, wherein represents a hydrogen atom.   The usage-amount of the said radical polymerization initiator is 0.005-20 mol with respect to 1 mol of total moles of the said (B-1) component, (B-2) component, and another polymeric compound. 3. A method for producing an insulating film according to 1 or 2. The production method according to claim 1, wherein the irradiation time of the ultraviolet rays is 3 minutes or less.   The compound represented by the formula (1) is a compound selected from the following (1-1) to (1-4), and the compound represented by the formula (2) is the following (2-1) to (2 The method for producing an insulating film according to any one of claims 1 to 4, which is a compound selected from -4).

The production according to any one of claims 1 to 5, wherein the radical polymerization initiator contains at least one selected from the group consisting of an organic peroxide, an organic azo compound, an alkylphenone compound, and an oxime ester compound. Method. The insulating film obtained by the manufacturing method as described in any one of Claims 1-6 .