JP4766267B2 - Film, method for forming the same, and semiconductor device - Google Patents

Description

  The present invention relates to a film, a method for forming the film, and a semiconductor device.

  A film made of polycarbosilane is used as, for example, an etching stopper, a hard mask, and an insulating film because it is less damaged by the etching process (Japanese Patent Laid-Open No. 2004-186610).

A film made of polycarbosilane can be obtained, for example, by forming a coating film using a composition containing polycarbosilane and an organic solvent, and curing the coating film by heating. In particular, since a laminated film having a large residual stress of the film causes peeling of the film interface, it is necessary to reduce the residual stress.
JP 2004-186610 A

  The present invention provides a film formation method capable of obtaining a film with reduced residual stress, a film obtained by the method, and a semiconductor device having the film.

A method for forming a film according to one embodiment of the present invention includes:
A step of forming a film by curing a coating film containing polycarbosilane under an atmosphere having an oxygen concentration of 50 to 3,000 ppm;

  In the film forming method, the curing may be performed using at least one selected from heating, ultraviolet irradiation, and electron beam irradiation. In this case, the curing can be performed using heating and ultraviolet irradiation simultaneously. In this case, the heating may be performed at 300 to 450 ° C. Further, in this case, the wavelength of ultraviolet rays used for the ultraviolet irradiation can be 300 nm or less.

  In the film formation method, the polycarbosilane is a polymer having a repeating structural unit represented by the following general formula (1) or a polymer having a repeating structural unit represented by the following general formula (2). Can be.

・・・・・（１）
（式中、Ｒ^１，Ｒ^２は互いに独立に、水素原子、炭素数１〜３０の置換基を有してもよいアルキル基、炭素数１〜３０の置換基を有してもよいアルケニル基、炭素数１〜３０の置換基を有してもよいアルキニル基、または、置換基を有してもよい芳香族基を表し、Ｒ^３は、−Ｃ≡Ｃ−、少なくとも１つの−Ｃ≡Ｃ−と連結した置換基を有してもよい−ＣＨ_２−、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよいアルキレン基、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよいアルケニレン基、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよいアルキニレン基、または、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよい二価の芳香族基を表す。）

(1)
(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent having 1 to 30 carbon atoms, or an alkenyl group which may have a substituent having 1 to 30 carbon atoms. Represents an alkynyl group which may have a substituent having 1 to 30 carbon atoms, or an aromatic group which may have a substituent, and R ³ represents —C≡C—, at least one —C≡. —CH ₂ — which may have a substituent linked to C—, an alkylene group which may have a substituent of 2 to 30 carbon atoms linked to at least one —C≡C—, at least one — Alkenylene group optionally having 2 to 30 carbon atoms linked to C≡C—, Alkynylene optionally having 2 to 30 carbon atoms linked to at least one —C≡C— Or a substituent having 2 to 30 carbon atoms linked to at least one —C≡C—. There represents a divalent aromatic group.)

・・・・・（２）
（式中、Ｒ^４およびＲ^５は互いに独立に、水素原子、１〜４個の炭素原子を有しているアルキル基またはアリール基を表し、Ｒ^６は、メチレン基またはメチン基を表し、ｍおよびｎは、それぞれ、１０＜ｍ＋ｎ＜１０００およびｎ／ｍ＜０．３の条件を満たす正の整数を表す。）

(2)
(Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 4 carbon atoms, R ⁶ represents a methylene group or a methine group, m And n represent positive integers that satisfy the conditions of 10 <m + n <1000 and n / m <0.3, respectively.

  The film according to one embodiment of the present invention can be obtained by the above film formation method.

  The film can be used as an insulating film, an etching stopper, or a hard mask.

  A semiconductor device according to one embodiment of the present invention includes the above film.

  According to the film forming method, oxygen molecules are taken into the film by forming a film by curing a coating film containing polycarbosilane in an atmosphere having an oxygen concentration of 50 to 3,000 ppm. As a result, a film with reduced residual stress (tensile stress) can be obtained. Therefore, the film obtained by the above-described film formation method has little residual stress in the film, so that it is difficult to cause interfacial peeling, and in particular, it is possible to provide a film having a structure that hardly causes interfacial peeling during lamination.

  The film obtained by the film forming method is useful as, for example, an insulating film, an etching stopper, and a hard mask.

  Hereinafter, a film according to an embodiment of the present invention, a method for forming the film, and a semiconductor device will be specifically described.

1. Film and Method for Forming the Film The film forming method according to the present embodiment includes a step of forming a film by curing a coating film containing polycarbosilane in an atmosphere having an oxygen concentration of 50 to 3,000 ppm. Here, when the oxygen concentration in the atmosphere is less than 50 ppm, the residual stress in the film may not be sufficiently reduced. On the other hand, when it exceeds 3,000 ppm, the presence of oxygen indicates the film thickness when the coating film is cured. Tensile stress may increase because it greatly affects shrinkage. The oxygen concentration in the atmosphere is more preferably 100 to 1,000 ppm.

1.1. Configuration of Polycarbosilane The polycarbosilane used in the film forming method according to this embodiment has a relative dielectric constant of 4 or less, preferably 3.5 or less.

  The polycarbosilane used in the film forming method according to the present embodiment is, for example, a polymer having a repeating structural unit represented by the following general formula (1) (hereinafter referred to as “polymer (1)”), And a polymer having a repeating structural unit represented by the following general formula (2) (hereinafter referred to as “polymer (2)”).

・・・・・（１）
（式中、Ｒ^１，Ｒ^２は互いに独立に、水素原子、炭素数１〜３０の置換基を有してもよいアルキル基、炭素数１〜３０の置換基を有してもよいアルケニル基、炭素数１〜３０の置換基を有してもよいアルキニル基、または、置換基を有してもよい芳香族基を表し、Ｒ^３は、−Ｃ≡Ｃ−、少なくとも１つの−Ｃ≡Ｃ−と連結した置換基を有してもよい−ＣＨ_２−、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよいアルキレン基、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよいアルケニレン基、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよいアルキニレン基、または、少なくとも１つの−Ｃ≡Ｃ−と連結した炭素数２〜３０の置換基を有してもよい二価の芳香族基を表す。）

(1)
(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent having 1 to 30 carbon atoms, or an alkenyl group which may have a substituent having 1 to 30 carbon atoms. Represents an alkynyl group which may have a substituent having 1 to 30 carbon atoms, or an aromatic group which may have a substituent, and R ³ represents —C≡C—, at least one —C≡. —CH ₂ — which may have a substituent linked to C—, an alkylene group which may have a substituent of 2 to 30 carbon atoms linked to at least one —C≡C—, at least one — Alkenylene group optionally having 2 to 30 carbon atoms linked to C≡C—, Alkynylene optionally having 2 to 30 carbon atoms linked to at least one —C≡C— Or a substituent having 2 to 30 carbon atoms linked to at least one —C≡C—. There represents a divalent aromatic group.)

Examples of the alkyl group which may have a substituent having 1 to 30 carbon atoms of R ¹ and R ² include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecanyl group, and trifluoro. Examples include a methyl group, 3,3,3-trifluoropropyl group, chloromethyl group, aminomethyl group, hydroxymethyl group, silylmethyl group, and 2-methoxyethyl group, and having a substituent having 1 to 30 carbon atoms. Suitable alkenyl groups include, for example, vinyl, 2-propenyl, isopropenyl, 3-butenyl, 5-hexenyl, 1,3-butadienyl, 3,3,3-trifluoro-1-propenyl. Examples of the alkynyl group that may have a substituent having 1 to 30 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, Nyl group, trimethylsilylethynyl group, phenylethynyl group can be mentioned, and examples of the aromatic group which may have a substituent include, for example, phenyl group, naphthyl group, pyrazinyl group, 4-methylphenyl group, 4-vinylphenyl group 4-ethynylphenyl group, 4-aminophenyl group, 4-chlorophenyl group, 4-hydroxyphenyl group, 4-carboxyphenyl group, 4-methoxyphenyl group, 4-silylphenyl group, and at least one of R ³ Examples of —CH ₂ — which may have a substituent linked to two —C≡C— include groups in which one or two —C≡C— is bonded to a methylene group, a fluoromethylene group, or the like. Examples of the alkylene group which may have a substituent having 2 to 30 carbon atoms linked to at least one —C≡C— include, for example, ethylene group, propylene Group, tetramethylene group, tetrafluoroethylene group, or the like, or a group in which one or two —C≡C— is bonded to each other, and has at least one substituent having 2 to 30 carbon atoms linked to —C≡C—. Examples of the alkenylene group that may be used include a group in which one or two —C≡C— is bonded to a vinylene group, a propenylene group, a butadienylene group, etc., and a carbon linked to at least one —C≡C—. Examples of the alkynylene group which may have a substituent of 2 to 30 include a group in which one or two —C≡C— is bonded to an ethynylene group, a propynylene group, a butynylene group, etc., and at least one Examples of the divalent aromatic group optionally having a substituent linked to —C≡C— include a phenylene group, a naphthylene group, a biphenylene group, an anthracenedil group, a pyridinedyl group, a thiol group, Phenedylyl group, fluorophenylene group, chlorophenylene group, methylphenylene group, silylphenylene group, hydroxyphenylene group, aminophenylene group, phenylenemethylenephenylene group, phenyleneoxyphenylene group, phenylenepropylidenephenylene group, phenylene (hexafluoropropylidene) And a group in which one or two —C≡C— is bonded to a phenylene group.

  Specific examples of the repeating structural unit of the polymer (1) include silylene ethynylene, methylsilylene ethynylene, phenylsilylene ethynylene, silylene ethynylene-1,3-phenylene ethynylene, and silylene ethynylene-1,4. -Phenyleneethynylene, silyleneethynylene-1,2-phenyleneethynylene, methylsilyleneethynylene-1,3-phenyleneethynylene, methylsilyleneethynylene-1,4-phenyleneethynylene, methylsilyleneethynylene-1, 2-phenyleneethynylene, dimethylsilyleneethynylene-1,3-phenyleneethynylene, dimethylsilyleneethynylene-1,4-phenyleneethynylene, dimethylsilyleneethynylene-1,2-phenyleneethynylene, diethylsilyleneethynylene- 1,3-phenylene ether Nylene, phenylsilyleneethynylene-1,3-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenyleneethynylene, phenylsilyleneethynylene-1,2-phenyleneethynylene, diphenylsilyleneethynylene-1,3- Phenyleneethynylene, hexylsilyleneethynylene-1,3-phenyleneethynylene, vinylsilyleneethynylene-1,3-phenyleneethynylene, ethynylsilyleneethynylene-1,3-phenyleneethynylene, 2-propenylsilyleneethynylene- 1,3-phenyleneethynylene, 2-propynylsilyleneethynylene-1,3-phenyleneethynylene, trifluoromethylrosilyleneethynylene-1,3-phenyleneethynylene, 3,3,3-trifluoropropylsilyleneethynylene -1 3-phenyleneethynylene, 4-methylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-vinylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-ethynylphenylsilyleneethynylene-1,3- Phenyleneethynylene, phenylethynylsilyleneethynylene-1,3-phenyleneethynylene, silyleneethynylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5-methyl-1,3-phenylene) ethynylene Phenylsilylene ethynylene (5-silyl-1,3-phenylene) ethynylene, phenylsilylene ethynylene (5-hydroxy-1,3-phenylene) ethynylene, phenylsilylene ethynylene-2,7-naphthylene ethynylene, silylene Ethynylene-5,1 0-anthracenedylethynylene, phenylsilyleneethynylene-4,4′-biphenyleneethynylene, phenylsilyleneethynylene-1,4-phenylenemethylene-1 ′, 4′-phenyleneethynylene, phenylsilyleneethynylene-1 , 4-phenylene-2,2-propylidene-1 ′, 4′-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenylene-2,2- (1,1,1,3,3,3-hexa Fluoropropylidene) -1 ′, 4′-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenyleneoxy-1 ′, 4′-phenyleneethynylene phenylsilyleneethynylene-2,5-pyridinediethylethynylene , Phenylsilyleneethynylene-2,5-thiophenedyrylethynylene, methylsilylenee Tinylenemethyleneethynylene, phenylsilylene-1,4-phenylene (phenylsilylene) ethynylene-1 ′, 3-phenyleneethylinylene, phenylsilyleneoxy (phenylsilylene) ethynylene, phenylsilyleneoxy (phenylsilylene) ethynylene-1 ′ , 4′-phenyleneethynylene, phenylsilyleneimino (phenylsilylene) ethynylene-1 ′, 3′-phenyleneethynylene, phenylsilyleneimino (phenylsilylene) ethynylene-1 ′, 4′-phenyleneethynylene, silylene-1, 3-phenyleneethynylene, silylene-1,4-phenyleneethynylene, silylene-1,2-phenyleneethynylene, phenylsilylene-1,3-phenyleneethynylene, phenylsilylene-1,4-phenyleneethynylene, fluoro Nylsilylene-1,2-phenyleneethynylene, diphenylsilylene-1,3-phenyleneethynylene, methylsilylene-1,3-phenyleneethynylene, methylsilylene-1,4-phenyleneethynylene, methylsilylene-1,2- Phenyleneethynylene, dimethylsilylene-1,3-phenyleneethynylene, diethylsilylene-1,3-phenyleneethynylene, phenylsilylene-1,3-butadienylene, diphenylsilylene-1,3-butadienylene, phenylsilylenemethyleneethynylene, Diphenylsilylenemethyleneethynylenemethylene, phenylsilylenemethyleneethynylenemethylene, silylene-1,4-phenyleneethynylene-1 ′, 4′-phenylene, methylsilylene-1,4-phenyleneethynylene-1 ′, 4′-fu Ylene, dimethylsilylene-1,4-phenylene ethynylene-1 ', 4'-phenylene, silylene-1,4-phenylene ethynylene-1', 4'-phenylene, and the like.

・・・・・（２）
（式中、Ｒ^４およびＲ^５は互いに独立に、水素原子、１〜４個の炭素原子を有しているアルキル基またはアリール基を表し、Ｒ^６は、メチレン基またはメチン基を表し、ｍおよびｎは、それぞれ、１０＜ｍ＋ｎ＜１０００およびｎ／ｍ＜０．３の条件を満たす正の整数を表す）

(2)
(Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 4 carbon atoms, R ⁶ represents a methylene group or a methine group, m And n represent positive integers that satisfy the conditions of 10 <m + n <1000 and n / m <0.3, respectively)

In the polymer (2), examples of the alkyl group represented by R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecanyl group, a trifluoromethyl group, 3, 3, Examples include 3-trifluoropropyl group, chloromethyl group, aminomethyl group, hydroxymethyl group, silylmethyl group, 2-methoxyethyl group, etc. Examples of the aryl group of R ⁴ and R ⁵ include, for example, phenyl group, naphthyl Group, pyrazinyl group, 4-methylphenyl group, 4-vinylphenyl group, 4-ethynylphenyl group, 4-aminophenyl group, 4-chlorophenyl group, 4-hydroxyphenyl group, 4-carboxyphenyl group, 4-methoxyphenyl Group, 4-silylphenyl group.

In the polymer (2), the alkyl group represented by R ⁶ includes methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, octyl group, dodecanyl group, trifluoromethyl group, 3,3,3-trimethyl. Examples thereof include a fluoropropyl group, a chloromethyl group, an aminomethyl group, a hydroxymethyl group, a silylmethyl group, and a 2-methoxyethyl group. Examples of the aryl group for R ⁶ include a phenyl group, a naphthyl group, a pyrazinyl group, 4 -Methylphenyl group, 4-vinylphenyl group, 4-ethynylphenyl group, 4-aminophenyl group, 4-chlorophenyl group, 4-hydroxyphenyl group, 4-carboxyphenyl group, 4-methoxyphenyl group, 4-silylphenyl Group and the like.

  Although there is no restriction | limiting in particular in the weight average molecular weight of the polycarbosilane represented by the said General formula (1) and (2), Preferably it is 500-500,000. These polycarbosilanes are usually solid or liquid at room temperature.

  The polycarbosilane represented by the general formulas (1) and (2) can be produced by, for example, dehydrogenation of a diethynyl compound and a silane compound using a basic oxide, a metal hydride, or a metal compound as a catalyst. A method for performing polymerization (Japanese Patent Laid-Open Nos. 7-90085, 10-120687, 11-158187), a method for dehydrogenating an ethynylsilane compound using a basic oxide as a catalyst (Japanese Patent Laid-Open No. No. 9-143271), a method of reacting an organomagnesium reagent with dichlorosilane (Japanese Patent Laid-Open Nos. 7-102069 and 11-029579), a diethynyl compound using cuprous chloride and a tertiary amine as a catalyst. Method for Dehydrogenation Copolymerization of Silane and Silane Compound (Hua Qin Liu and John F. Harrod, The Can dian Journal of Chemistry, Vol. 68, 1100-1105 (1990)), and dehydrogenation copolymerization of a diethynyl compound and a silane compound using magnesium oxide as a catalyst (JP-A-7-90085 and JP-A-10-204181). However, it is not particularly limited to these methods.

1.2. Formation of Coating Film In the film forming method according to this embodiment, it is preferable to form a coating film using a film forming composition in which polycarbosilane is dissolved or dispersed in an organic solvent.

1.2.1. Organic solvent Examples of the organic solvent used in the film-forming composition include ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents, and halogen-containing solvents. And at least one selected from.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n. -Hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, Examples include acetophenone and fenchon. These ketone solvents may be used alone or in combination of two or more.

  Examples of the amide solvent include N, N-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, Examples thereof include N-methylpropionamide and N-methylpyrrolidone. These amide solvents may be used alone or in combination of two or more.

  Examples of ether solvents include ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane. , Ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2- Ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethyl Glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl Ether, mention may be made of the anisole. These ether solvents may be used alone or in combination of two or more.

  Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetic acid. sec-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, aceto Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate Mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, Mention may be made of diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used alone or in combination of two or more.

  Examples of the aliphatic hydrocarbon solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Examples include octane, cyclohexane, and methylcyclohexane. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-propyl. Examples include benzene, n-amylnaphthalene, trimethylbenzene, and the like. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of the halogen-containing solvent include dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, dichlorobenzene, and the like.

  In the film forming composition according to the present embodiment, it is preferable to use an organic solvent having a boiling point of less than 250 ° C., and examples of the organic solvent species include ketone solvents, ester solvents, and aromatic hydrocarbon solvents. Preferably, one or more of these solvents are used at the same time.

1.2.2. Other Additives The film-forming composition according to this embodiment further contains components such as a curing accelerator, colloidal silica, colloidal alumina, an organic polymer, a surfactant, a silane coupling agent, and a triazene compound. Also good.

  Examples of the curing accelerator include organic peroxides and organic azo compounds. As the organic peroxide, for example, BPO (benzoyl peroxide), pertetra A, parkmill D (dicumyl peroxide), BTTB (3,3 ′, 4,4′-tetrabutylperoxycarbonylbenzophenone) (all Nippon Oil & Fats Co., Ltd.). Examples of the organic azo compound include 2,2′-azobisisobutyronitrile (AIBN), dimethyl-2,2′-azobis (2-methylpropionate) (V-601, Wako Pure Chemical Industries, Ltd.) Product), 1,1′-azobis (1-acetoxy-1-phenylethane) (OT (azo) -15, manufactured by Otsuka Chemical Co., Ltd.), and the like.

  The blending amount of the curing accelerator is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the film-forming composition.

  Colloidal silica is, for example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent, and usually has an average particle size of 5 to 30 μm, preferably 10 to 20 μm, and has a solid content. The concentration is usually 10 to 40% by mass. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol (Catalyst Chemical Industries, Ltd., trade name “Oscar”).

  Examples of the colloidal alumina include trade names “Alumina Sol 520”, “Alumina Sol 100”, “Alumina Sol 200” manufactured by Nissan Chemical Industries, Ltd., and “Alumina Clear Sol” manufactured by Kawaken Fine Chemical Co., Ltd. “Alumina sol 10” and “Alumina sol 132” can be mentioned.

  Examples of the organic polymer include a polymer having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound polymer, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, and a polyquinoxaline. , Polyoxadiazole, a fluorine-based polymer, a polymer having a polyalkylene oxide structure, and the like.

  Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Ether type compounds such as oxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters.

  Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.

− (X ′) ₁ − (Y ′) _m −
− (X ′) ₁ − (Y ′) _m − (X ′) _n −
[Wherein, X ′ represents a group represented by —CH ₂ CH ₂ O—, Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, and l represents 1 to 90] , M represents 10 to 99, and n represents a number of 0 to 90. ]

Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, More preferred examples include ether type compounds.
These may be used alone or in combination of two or more.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and further, fluorine surfactants, silicone surfactants, Polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned, and fluorine surfactants and silicone surfactants can be preferably mentioned.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1, 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8, 8,9,9,10,10-Decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluoro Kutansulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorophosphate) Octylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate ester and the like, a fluorosurfactant comprising a compound having a fluoroalkyl or fluoroalkylene group at at least one of its terminal, main chain and side chain Can be mentioned.

  Commercially available fluorosurfactants include Megafac F142D, F172, F173, and F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ftop EF301, 303, and 352 (new) Akita Kasei Co., Ltd.], Florard FC-430, FC-431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 [Asahi Glass Co., Ltd.], BM-1000, BM-1100 (Yusho Co., Ltd.), NBX-15 [Neos Co., Ltd.] And fluorine-based surfactants that are commercially available. Among these, Megafac F172, BM-1000, BM-1100, and NBX-15 are particularly preferable.

  As the silicone surfactant, for example, SH7PA, SH21PA, SH30PA, ST94PA [all manufactured by Toray Dow Corning Silicone Co., Ltd.] can be used. Among these, SH28PA and SH30PA are particularly preferable.

  The usage-amount of surfactant is 0.00001-1 mass part normally with respect to 100 mass parts of polymers (1) and (2). These surfactants may be used alone or in combination of two or more.

  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. These silane coupling agents may be used alone or in combination of two or more.

  Examples of the triazene compound include 1,2-bis (3,3-dimethyltriazenyl) benzene, 1,3-bis (3,3-dimethyltriazenyl) benzene, and 1,4-bis (3,3 -Dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis (3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, Bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) ben 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3- Dimethyltriazenyl) -9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9, 9-bis [3-phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl- 4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyl) Triazenyl) phenyl] fluorene, 2,7-bis ( , 3-Dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazeni) ) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene and the like. These triazene compounds may be used alone or in combination of two or more.

  The total solid concentration of the film-forming composition according to this embodiment is preferably 1 to 30% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the film-forming composition according to this embodiment is 1 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability is more excellent.

  When a coating film is formed by applying the film-forming composition according to this embodiment to a substrate, examples of the coating means include spin coating, dipping method, roll coating method, spray method, and scan coating method. It is done. The coating film is preferably dried at room temperature as required.

1.3. Curing of Coating Film In the method for forming a film according to this embodiment, curing of the coating film can be performed using at least one selected from heating, ultraviolet irradiation, and electron beam irradiation. It is preferable to use them simultaneously. In addition, the film forming method according to the present embodiment includes silicon oxide (SiO ₂ ), fluorine-doped silicon oxide (FSG), organosilicate glass (OCG), carbon-doped silicon oxide (SiOC), methylsilsesquioxane (MSQ). ), Hydrogen silsesquioxane (HSQ), spin-on-glass (SOG), silicon oxide interlayer insulating films such as polyorganosiloxane, organic polymer interlayer insulating films such as polyarylene, polyarylene ether, polyimide, and fluororesin ( These are hereinafter referred to as “interlayer insulating films”) and are suitably used when a film is formed by curing a coating film containing polycarbosilane.

  When the coating is cured by heating, it is preferably performed at 300 to 450 ° C, more preferably 350 to 400 ° C. In this case, the heating time is usually preferably less than 60 minutes, and more preferably 30 minutes. Moreover, when hardening a coating film by ultraviolet irradiation, it is preferable that the wavelength of the ultraviolet-ray used for ultraviolet irradiation is 300 nm or less, and it is more preferable that it is 220-270 nm. In this case, the heating and ultraviolet irradiation time is preferably less than 10 minutes, and more preferably 1 to 5 minutes.

  As the heating means, for example, a hot plate, an oven, a furnace, or the like can be used.

  Examples of constituents of the atmosphere other than oxygen include nitrogen and argon. The pressure is preferably normal pressure.

2. Film and Semiconductor Device The film according to the present embodiment is obtained by the film formation method described above and has a polycarbosilane skeleton. Examples of the film according to this embodiment include silicon oxide (SiO ₂ ), fluorine-doped silicon oxide (FSG), organosilicate glass (OCG), carbon-doped silicon oxide (SiOC), methylsilsesquioxane (MSQ), and hydrogen. Silsesquioxane (HSQ), spin-on-glass (SOG), silicon oxide-based interlayer insulating films such as polyorganosiloxane, organic polymer-based interlayer insulating films such as polyarylene, polyarylene ether, polyimide, and fluororesin (hereinafter referred to as these) It is preferably used in combination with “interlayer insulating film”.

  The film according to the present embodiment is suitably used as an insulating film, an etching stopper, or a hard mask, for example.

  In the plasma dry etching conditions optimized for the silicon oxide-based interlayer insulating film and the organic polymer-based interlayer insulating film, the film according to the present embodiment has a dry etching rate of the silicon-based interlayer insulating film and the organic polymer-based interlayer. Compared to that of the insulating film, it is at least 1/3 or less, and generally 1/5 or less. Therefore, the film according to the present embodiment functions as an etch stopper or a hard mask.

  More specifically, when the film according to the present embodiment is formed below the interlayer insulating film, the film according to the present embodiment functions as an etch stopper, while the film according to the present embodiment is used as the interlayer insulating film. When formed in the upper layer, the film according to this embodiment functions as a hard mask. Hereinafter, an example in which the film according to the present embodiment is applied to an etching stopper and a hard mask will be described.

2.1. Example 1 (etching stopper)
In this specific example, an example in which the film according to this embodiment is used as an etching stopper will be described.

  1 and 2 are diagrams schematically showing a patterning method for an interlayer insulating film using the film according to the present embodiment as an etching stopper.

  First, as shown in FIG. 1, an interlayer insulating film 2 is formed on the etching stopper 1, and then a mask film 3 having an opening 8 a is formed on the interlayer insulating film 2.

  Various methods can be applied as a method for forming the opening 8a of the mask film 3. For example, a photosensitive polymer (photoresist) is applied to the mask film 3 by lithography using visible light, ultraviolet light, or an electron beam. Can be used to form the opening 8a.

  Next, by etching the interlayer insulating film 2 with the mask film 3 having the opening 8a provided on the interlayer insulating film 2, the interlayer insulating film 2 having the opening 8 is formed as shown in FIG. Form. Thereby, a specific pattern can be formed in the interlayer insulating film 2. The etching method of the interlayer insulating film 2 may be dry etching or wet etching. Examples of the specific pattern formed in the interlayer insulating film 2 include a wiring pattern of an electric circuit.

  The etching rate of the interlayer insulating film 2 is preferably the same regardless of the location. When using dry etching, it is affected by unevenness of etching gas concentration, non-uniformity of the flow of etching gas, uneven temperature, etc. When using wet etching, uneven concentration of etching chemical, uneven convection of etching chemical, temperature The etching rate may vary depending on the location due to the influence of unevenness. For this reason, the etching time is the time during which etching can be performed at the slowest etching place, so that the etching gas or the etching chemical solution reaches the lower layer of the interlayer insulating film 2 except for the slowest etching speed, and the chemical reaction occurs. Occur.

  Therefore, by providing the etching stopper 1 below the interlayer insulating film 2, it is possible to prevent a chemical reaction caused by the etching gas or the etching chemical solution from reaching the lower layer than the etching stopper 1.

2.2. Example 2 (hard mask)
In this specific example, an example in which the film according to this embodiment is used as an etching stopper will be described.

  3 and 4 are diagrams schematically showing a patterning method of the interlayer insulating film using the film according to the present embodiment as a hard mask.

  For example, when the etching selectivity between the mask film 3 made of photoresist and the interlayer insulating film 2 is not sufficient, or the film thickness of the mask film 3 does not have a film thickness that can withstand the etching of the interlayer insulating film 2. In this case, after the pattern of the opening 8a of the mask film 3 is once transferred to the hard mask 9 having a high etching selectivity, the interlayer insulating film 2 can be etched using the opening pattern of the hard mask 9.

  First, as shown in FIG. 3, the hard mask 9 is formed on the interlayer insulating film 2, and the mask film 3 having an opening is formed on the hard mask 9. The method described above can be used as a method for forming the mask film 3.

  Next, by etching the hard mask 9 with the mask film 3 having openings provided on the hard mask 9, a specific pattern (opening 8b) can be formed in the hard mask 9. Etching of the hard mask 9 may be dry etching or wet etching. After the mask film 3 is removed by dry (ashing) or wet (wet stripping), the interlayer insulating film 2 is etched using the pattern transferred to the hard mask 9 as a mask to form an opening 8 in the interlayer insulating film 2 (See FIG. 4).

2.3. Example 3 (Etching stopper in damascene structure)
In this specific example, an example in which the film according to this embodiment is used as an etching stopper will be described.

  5 and 6 are views schematically showing a method for manufacturing a damascene structure using the film according to the present embodiment as an etching stopper.

  As a method for forming the damascene structure 21, a single damascene method in which wiring grooves (trench) and holes (via holes) are individually processed and metal is embedded after each processing, and wiring grooves and holes are simultaneously formed to form metal. There is a dual damascene method to be embedded.

  In this specific example, a method of forming a damascene structure 21 including first and second insulating films 4 and 6 and an etching stopper (also a hard mask) 5 therebetween by a dual damascene method will be described (FIG. 5). And FIG. 6).

  In the laminated structure 20 shown in FIG. 5, a second insulating film 6 is formed on the barrier film 7 by a plasma CVD method or a coating method, and etching is performed on the second insulating film 6 by a plasma CVD method or a coating method. The stopper 5 is formed, and the second insulating film 4 is sequentially laminated on the etching stopper 5 by a plasma CVD method or a coating method.

  A wiring groove 10 and a hole 11 are formed in the first insulating film 4 and the second interlayer insulating film 6 by photolithography and etching, respectively. Here, by providing the etching stopper 5 between the first insulating film 4 and the second insulating film 6, in-plane uniformity during etching can be ensured. Further, the hole 11 can be formed in the second insulating film 6 by transferring the hole pattern to the etching stopper 5.

  Next, after covering the wiring groove 10 and the hole 11 with a barrier film (not shown), as shown in FIG. 6, a metal (copper) is embedded in the wiring groove 10 and the hole 11, and the excess metal is removed by a chemical mechanical polishing method. By removing by (CMP), the (copper) wiring layer 12 can be formed. Thereby, the damascene structure 21 can be obtained.

  Since the etching stopper and the hard mask according to the present embodiment are excellent in resistance to etching processing, they can be suitably used for semiconductor devices such as LSI, system LSI, MPU, CPU, DRAM, SDRAM, RDRAM, and D-RDRAM. it can.

3. Examples Hereinafter, the present invention will be described more specifically with reference to examples. In addition, unless otherwise indicated, the part and% in an Example and a comparative example have shown that they are the mass part and the mass%, respectively.

3.1. Evaluation Method Evaluation of the film forming compositions in Examples and Comparative Examples was performed as follows.

3.1.1. Weight average molecular weight (Mw)
The weight average molecular weight (Mw) was measured by a gel permeation chromatography (GPC) method under the following conditions.
Sample: Tetrahydrofuran was used as a solvent, and 1 g of a sample was prepared by dissolving in 100 cc of tetrahydrofuran.
Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.
Apparatus: High-temperature, high-speed gel permeation chromatogram (trade name “Model 150-C ALC / GPC”) manufactured by Waters, USA
Column: Showa Denko Co., Ltd., trade name “SHODEX A-80M (length 50 cm)”
Measurement temperature: 40 ° C
Flow rate: 1cc / min

3.1.2. Residual stress of film The residual stress of the film was measured by the following method.
Using FLX-2320 (manufactured by KLA), the warpage of the substrate before and after film formation was measured with a laser to calculate the film stress.

3.2. Preparation of Composition 1 for Film Formation Commercially available polycarbosilane (trade name “NIPUSI Type-S”, a carbosilanized polymer of polydimethylsilane available from Nippon Carbon Co., Ltd., hereinafter referred to as “polycarbosilane 1”. Is dissolved in a mixed solvent of n-butyl acetate and cyclohexanone (n-butyl acetate: cyclohexanone = 80: 20 (weight ratio)), and the weight ratio of polycarbosilane 1 to the mixed solvent is polycarbosilane 1 : A solution (film-forming composition 1) having a mixed solvent = 10: 90 was prepared.
The weight average molecular weight of polycarbosilane 1 was 4,700.

3.3. Synthesis example 1
A solution obtained by dissolving 30 g of chloromethyltrichlorosilane in 300 ml of THF was dropped into 100 ml of THF containing 10 g of magnesium at room temperature over 2 hours. Next, after the obtained reaction solution was reacted at 60 ° C. for 10 hours, 10 ml of a THF solution of vinylmagnesium bromide having a concentration of 1.0 M was added dropwise at room temperature. Subsequently, after removing the produced magnesium salt, 50 g of lithium aluminum hydride was added to this solution in an ice bath, and the mixture was reacted at room temperature for 10 hours. Subsequently, 100 ml of 3M hydrochloric acid aqueous solution was added in an ice bath to deactivate the reaction solution, and then the organic phase and the aqueous phase were separated. By concentrating the obtained organic phase, 9.5 g of polycarbosilane 2 having a structural unit represented by the following formula (3) and having a weight average molecular weight of 2,200 was obtained. This polycarbosilane 2 has a carbon-carbon double bond to which a silicon-hydrogen bond can be added.
A solution (film-forming composition 2) in which the weight ratio of the polycarbosilane 2 to the mixed solvent was polycarbosilane 1: mixed solvent = 10: 90 was prepared.

3.4. Example 1 Contact and Comparative Example 1-7
A film-forming composition 1 or a film-forming composition 2 is applied onto an 8-inch silicon wafer by spin coating, and the substrate is formed at 90 ° C. for 3 minutes on a hot plate and at 200 ° C. for 3 minutes in a nitrogen atmosphere. after drying the respective under temperature conditions and atmosphere are shown in table 1, by firing a substrate 60 minutes on a hot plate to form a film of example 1 Contact and Comparative example 1-7. Nitrogen was used as the atmosphere, and the final film thickness was 0.5 μm. In Example 1 , heating and ultraviolet irradiation were performed simultaneously. Here, the wavelength of the irradiated ultraviolet rays was 0.3 μm .

  According to Table 1, it can be understood that the residual stress of the film increases when the oxygen concentration in the atmosphere is less than 50 ppm or when the oxygen concentration in the atmosphere exceeds 3,000 ppm. On the other hand, according to Examples 1 to 5, the film remains by curing a coating film containing polycarbosilane under an atmosphere having an oxygen concentration of 50 to 3,000 ppm. It was confirmed that the stress can be reduced.

FIG. 1 is a diagram schematically showing a method for patterning an interlayer insulating film using a film (etching stopper) according to an embodiment of the present invention. FIG. 2 is a diagram schematically showing a method for patterning an interlayer insulating film using a film (etching stopper) according to an embodiment of the present invention. FIG. 3 is a diagram schematically showing an interlayer insulating film patterning method using a film (hard mask) according to an embodiment of the present invention. FIG. 4 is a diagram schematically showing a method for patterning an interlayer insulating film using a film (hard mask) according to an embodiment of the present invention. FIG. 5 is a diagram schematically showing a method for manufacturing a wiring structure (dual damascene structure) using a film (etching stopper) according to an embodiment of the present invention. FIG. 6 is a diagram schematically showing a method for manufacturing a wiring structure (dual damascene structure) using a film (etching stopper) according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Mask film 2 Insulating film 3 Etching stopper 4 1st insulating film 5 Etching stopper 6 2nd insulating film 7 Barrier film 8, 8a, 8b Opening 9 Hard mask 10 Wiring groove 11 Hole 12 Wiring layer 20 Multilayer structure 21 Wiring structure Body (damascene structure)

Claims (7)

A film forming method comprising a step of curing a coating film containing polycarbosilane to form a film by simultaneously using heating and ultraviolet irradiation in an atmosphere having an oxygen concentration of 50 to 3,000 ppm. In claim 1 ,
The method for forming a film, wherein the heating is performed at 300 to 450 ° C. In claim 1 or claim 2 ,
The method for forming a film, wherein the wavelength of ultraviolet rays used for the ultraviolet irradiation is 300 nm or less. In claims 1 to any one of claims 3,
The method for forming a film, wherein the polycarbosilane is a polymer having a repeating structural unit represented by the following general formula (1) or a polymer having a repeating structural unit represented by the following general formula (2).

(1)
(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent having 1 to 30 carbon atoms, or an alkenyl group which may have a substituent having 1 to 30 carbon atoms. Represents an alkynyl group which may have a substituent having 1 to 30 carbon atoms, or an aromatic group which may have a substituent, and R ³ represents —C≡C—, at least one —C≡. —CH ₂ — which may have a substituent linked to C—, an alkylene group which may have a substituent of 2 to 30 carbon atoms linked to at least one —C≡C—, at least one — Alkenylene group optionally having 2 to 30 carbon atoms linked to C≡C—, Alkynylene optionally having 2 to 30 carbon atoms linked to at least one —C≡C— Or a substituent having 2 to 30 carbon atoms linked to at least one —C≡C—. There represents a divalent aromatic group.)

(2)
(Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 4 carbon atoms, R ⁶ represents a methylene group or a methine group, m And n represent positive integers that satisfy the conditions of 10 <m + n <1000 and n / m <0.3, respectively. The film | membrane obtained by the formation method of the film | membrane as described in any one of Claim 1 thru | or 4 . The film according to claim 5 , which is used as an insulating film, an etching stopper, or a hard mask. A semiconductor device having the film according to claim 5 .

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