JP5729307B2 - Cobalt film forming material and cobalt film forming method - Google Patents

Description

  The present invention relates to a cobalt film forming material and a cobalt film forming method.

2. Description of the Related Art A semiconductor device typified by a DRAM (Dynamic Random Access Memory) is required to change materials of each metal film and metal oxide film constituting the device in accordance with high integration and miniaturization.
Especially, improvement of the conductive metal film for the multilayer wiring use in the semiconductor device is required, and the conversion to copper wiring with high conductivity is newly advanced. For the purpose of improving the conductivity of the copper wiring, a low dielectric constant material (Low-k material) is used as an interlayer insulating film material of the multilayer wiring. However, there is a problem that oxygen atoms contained in the low dielectric constant material are easily taken into the copper wiring and the conductivity is lowered. Therefore, for the purpose of preventing the movement of oxygen from the low dielectric constant material, a technique for forming a barrier film between the low dielectric constant material and the copper wiring has been studied. A metal cobalt film has been attracting attention as a material that is difficult to take up oxygen from a dielectric layer and a material that can be easily processed by dry etching, which are used for the barrier film. Further, in the damascene film forming method in which the copper wiring is embedded by plating, metallic cobalt has attracted attention for the purpose of satisfying both roles of the barrier film and the plating growth film at the same time. As a method for forming a cobalt film, for example, a method for forming a cobalt film using octacarbonyl dicobalt has been proposed (Patent Document 1). However, the compound (octacarbonyl dicobalt) has a problem that it is unstable in the atmosphere.

JP 2006-328526 A

  The present invention has been made in view of the above problems, and an object thereof is to provide a cobalt film forming material that is stable in the air, and a cobalt film forming method using the material.

In order to achieve the above object, the present inventors have conducted intensive studies and found that the above object can be achieved by using a compound represented by the following formula (1), thereby completing the present invention.
That is, the present invention provides the following [1] to [ 8 ].
[1] A cobalt film forming material containing a compound represented by the following formula (1).
Co ₃ (CO) ₉ CZ (1)
(In the formula (1), Z is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom (excluding those having a double bond) , or may be substituted with a halogen atom . A good alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom (excluding those having a double bond) , and may be substituted with a halogen atom An alkylamide group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, and an alkoxyalkyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom are shown. )
[ 2 ] The cobalt film-forming material according to [1], wherein in the general formula (1), Z is an alkoxycarbonyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
[ 3 ] The cobalt film-forming material according to [1] or [2] , which is for chemical vapor deposition.
[ 4 ] A cobalt film forming method using the material for forming a cobalt film according to any one of [1] to [ 3 ].
[ 5 ] A cobalt film forming material supply step for supplying the cobalt film forming material according to [1] to [ 3 ] onto a substrate, and a thermal decomposition of the cobalt film forming material supplied on the substrate. And a film forming step of forming a cobalt film on the substrate.
[ 6 ] The cobalt film forming method according to [ 5 ], wherein the temperature of heat decomposition in the film forming step is 100 ° C to 800 ° C.
[ 7 ] The cobalt film forming method according to [ 5 ] or [ 6 ], wherein the thermal decomposition in the film forming step is performed in an inert gas or a reducing gas.
[ 8 ] A film forming step in which the cobalt film forming material according to [1] or [2] is applied on a substrate, and then heat treatment and / or light treatment is performed to form a cobalt film on the substrate. A method for forming a cobalt film.

  Since the material for forming a cobalt film of the present invention is stable in the atmosphere and excellent in handleability, the cobalt film can be formed by a simple method.

Hereinafter, the present invention will be described in detail.
The cobalt film forming material of the present invention is represented by the following formula (1).
Co ₃ (CO) ₉ CZ (1)
In general formula (1), Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or a carbon atom having 1 to 10 carbon atoms which may be substituted with a halogen atom. An alkoxy group, an acyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, an alkylamide group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or a carbon which may be substituted with a halogen atom An alkoxycarbonyl group having 2 to 10 carbon atoms and an alkoxyalkyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom;

As Z, the melting point of the compound is low, and from the viewpoint that the cobalt film forming material can be easily supplied onto the substrate when forming the cobalt film, the compound having 1 to 4 carbon atoms which may be substituted with a halogen atom An alkoxy group, an acyl group having 2 to 5 carbon atoms that may be substituted with a halogen atom, an alkylamide group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a carbon that may be substituted with a halogen atom An alkoxycarbonyl group having 2 to 4 carbon atoms and an alkoxyalkyl group having 2 to 4 carbon atoms which may be substituted with a halogen atom are preferable.
In Z, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.

  Further, as the hydrocarbon group having 1 to 10 carbon atoms in Z, the vapor pressure of the compound is high, and from the viewpoint that the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film, A hydrocarbon group having 1 to 8 carbon atoms is preferable, and a hydrocarbon group having 1 to 4 carbon atoms is more preferable. Specifically, aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl And aromatic hydrocarbon groups such as phenyl group, methylphenyl group, ethylphenyl group, benzyl group, methyl group, ethyl group, n-propyl group, isopropyl group, A t-butyl group, a phenyl group, and a methylphenyl group are preferable, and a methyl group and an ethyl group are more preferable.

Examples of the hydrocarbon group having 1 to 10 carbon atoms in which at least a part of hydrogen atoms in Z are substituted with halogen atoms include fluorinated hydrocarbon groups, chlorinated hydrocarbon groups, and brominated hydrocarbon groups. More preferably, it is a fluorinated hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably 1 to 4 from the viewpoint that the vapor pressure of the compound is high and the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film.
Specifically, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, perfluoro-n-propyl Group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-t-butyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoro An ethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, and a perfluoro-t-butyl group are preferable, and a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2,2- Trifluoroethyl group, pentaf More preferably Oroechiru group.

  Moreover, as a C1-C10 alkoxy group in Z, since the vapor pressure of a compound is high and it can supply the cobalt film formation material on a base | substrate at the time of cobalt film formation, it is C1-C1. Are preferably alkoxy groups of ˜4, specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, methoxy group, An ethoxy group, an n-propoxy group, and an isopropoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

Examples of the alkoxy group having 1 to 10 carbon atoms in which at least a part of hydrogen atoms in Z are substituted with halogen atoms include fluorinated alkoxy groups, chlorinated alkoxy groups, brominated alkoxy groups, and fluorinated alkoxy groups. It is more preferable that The number of carbon atoms of the alkoxy group is preferably 1 to 4 from the viewpoint that the vapor pressure of the compound is high and the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film.
Specifically, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, perfluoro-n- Examples thereof include a propoxy group, a perfluoroisopropoxy group, a perfluoro-n-butoxy group, a perfluoroisobutoxy group, and a perfluoro-t-butoxy group. A fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, 2,2,2 -Trifluoroethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoroisopropoxy group, perfluoro-t-butoxy group are preferred, and fluoromethoxy group, difluoromethoxy group, trifluoromethoate Shi group, 2,2,2-trifluoroethoxy group, and more preferably a pentafluoroethoxy group.

In addition, as the acyl group having 2 to 10 carbon atoms in Z, the vapor pressure of the compound is high, and from the viewpoint that the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film, the number of carbon atoms is 2. Acyl groups of ˜5 are preferred. The acyl group may be either an aliphatic acyl group or an aromatic acyl group. Preferable specific examples of the aliphatic acyl group include, for example, acetyl group, propionyl group, butyryl group, valeryl group, cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group and the like.
Preferable specific examples of the aromatic acyl group include a benzoyl group, a methylphenylcarbonyl group, and an ethylphenylcarbonyl group.

In addition, examples of the acyl group having 2 to 10 carbon atoms in which at least a part of hydrogen atoms in Z are substituted with halogen atoms include fluorinated acyl groups, chlorinated acyl groups, and brominated acyl groups. It is preferable that Further, the number of carbon atoms of the acyl group is preferably 2 to 5 from the viewpoint that the vapor pressure of the compound is high and the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film.
Preferable specific examples include a trifluoroacetyl group, a pentafluoropropionyl group, a heptafluorobutyryl group, and the like.

In addition, as the alkylamide group having 1 to 10 carbon atoms in Z, the vapor pressure of the compound is high, and from the viewpoint that the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film, 1-6 are preferable, and specific examples include a methylamide group, a dimethylamide group, an ethylamide group, a diethylamide group, a propylamide group, a dipropylamide group, a butyramide group, and a dibutylamide group.
Examples of the alkylamide group having 1 to 10 carbon atoms in which at least a part of hydrogen atoms in Z are substituted with halogen atoms include fluorinated alkylamide groups, chlorinated alkylamide groups, and brominated alkylamide groups. A fluorinated alkylamide group is preferred. In addition, the number of carbon atoms of the alkylamide group is preferably 1 to 4 from the viewpoint that the vapor pressure of the compound is high and the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film. .
Preferred examples include chloromethylamide group, dichloromethylamide group, trichloromethylamide group, fluoromethylamide group, difluoromethylamide group, trifluoromethylamide group, 2-chloroethylamide group, 2,2-dichloro Ethylamide group, 2,2,2-trichloroethylamide group, 2-fluoroethylamide group, 2,2-difluoroethylamide group, 2,2,2-trifluoroethylamide group, pentafluoroethylamide group, etc. Can be mentioned.

  In addition, as the alkoxycarbonyl group having 2 to 10 carbon atoms in Z, the vapor pressure of the compound is high, and from the viewpoint that the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film, A C 2-6 alkoxycarbonyl group is preferred, and a C 2 or C 3 alkoxycarbonyl group is preferred. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, t-butoxycarbonyl group, and 2-methylbutoxycarbonyl group. A methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and a 2-methylbutoxycarbonyl group, preferably a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methylbutoxycarbonyl group. More preferred.

Examples of the C2-C10 alkoxycarbonyl group in which at least a part of hydrogen atoms in Z are substituted with halogen atoms include fluorinated alkoxycarbonyl groups, chlorinated alkoxycarbonyl groups, and brominated alkoxycarbonyl groups. More preferably, it is a fluorinated alkoxycarbonyl group. In addition, the number of carbon atoms of the halogenated alkoxycarbonyl group is preferably 2 to 5 from the viewpoint that the vapor pressure of the compound is high and the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film. is there.
Specifically, chloromethoxycarbonyl group, dichloromethoxycarbonyl group, trichloromethoxycarbonyl group, fluoromethoxycarbonyl group, difluoromethoxycarbonyl group, trifluoromethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, pentafluoro Examples thereof include ethoxycarbonyl group, perfluoro-n-propoxycarbonyl group, perfluoroisopropoxycarbonyl group, perfluoro-n-butoxycarbonyl group, perfluoroisobutoxycarbonyl group, perfluoro-t-butoxycarbonyl group, fluoromethoxycarbonyl group, Difluoromethoxycarbonyl group, trifluoromethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, pentafluoroethoxycal Nyl group, perfluoro-n-propoxycarbonyl group, perfluoroisopropoxycarbonyl group, and perfluoro-t-butoxycarbonyl group are preferable. Fluoromethoxycarbonyl group, difluoromethoxycarbonyl group, trifluoromethoxycarbonyl group, 2,2, 2-trifluoroethoxycarbonyl group and pentafluoroethoxycarbonyl group are more preferable.

  As the alkoxyalkyl group having 2 to 10 carbon atoms in Z, the vapor pressure of the compound is high, and from the viewpoint that the cobalt film forming material can be easily supplied onto the substrate at the time of forming the cobalt film, It is preferably an alkoxyalkyl group having 8 carbon atoms, and more preferably an alkoxyalkyl group having 2 to 4 carbon atoms. Specific examples include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, and the like. A propyl group, an ethoxymethyl group, and an ethoxyethyl group are more preferable.

  Examples of the alkoxyalkyl group having 2 to 10 carbon atoms in which at least a part of hydrogen atoms in Z are substituted with halogen atoms include fluorinated alkoxyalkyl groups, chlorinated alkoxyalkyl groups, and brominated alkoxyalkyl groups. An alkoxyalkyl group is preferred. In addition, the number of carbon atoms of the alkoxyalkyl group is preferably 2 to 8, more preferably from the viewpoint that the vapor pressure of the compound is high and the cobalt film forming material can be easily supplied onto the substrate during the formation of the cobalt film. Preferably it is 2-4. Preferable specific examples include chloromethoxymethyl group, chloromethoxyethyl group, chloromethoxypropyl group, chloromethoxybutyl group, 2,2,2-trichloroethoxymethyl group, pentachloroethoxymethyl group, 2,2,2- Trichloroethoxyethyl group, pentachloroethoxyethyl group, fluoromethoxymethyl group, fluoromethoxyethyl group, fluoromethoxypropyl group, fluoromethoxybutyl group, 2,2,2-trifluoroethoxymethyl group, pentafluoroethoxymethyl group, 2 , 2,2-trifluoroethoxyethyl group, pentafluoroethoxyethyl group, etc., such as fluoromethoxymethyl group, fluoromethoxyethyl group, fluoromethoxypropyl group, 2,2,2-trifluoroethoxymethyl group, pentafluoro D Kishimechiru group, 2,2,2-trifluoroethoxy ethyl group, pentafluoroethyl ethoxyethyl group, and the like.

上記式（１）で表される化合物の具体例としては、例えば、ノナカルボニル−μ_３−メチリジントリコバルト、ノナカルボニル−μ_３−エチリジントリコバルト、ノナカルボニル−μ_３−エトキシカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−ｔ−ブトキシカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−ジエチルアミドメチリジントリコバルト、ノナカルボニル−μ_３−ｎ―プロピルカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−フェニルカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−４−メチルフェニルカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−２，２，２−トリフルオロエトキシカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−２，２，３，３，４，４，５，５−オクタフルオロペントキシカルボニルメチリジントリコバルト、ノナカルボニル−μ_３−２−メチルブトキシカルボニルメチリジントリコバルトなどが挙げられる。
これらの化合物は単独でまたは２種以上を混合してコバルト膜形成用材料として使用することができる。製膜条件の設定が容易であるため、１種類の化合物を単独でコバルト膜形成用材料として使用することが好ましい。Specifically, the compound represented by the above formula (1) is preferably a compound having a structure represented by the following formula (2).

Specific examples of the compound represented by the formula (1) include, for example, nonacarbonyl- [mu] ₃ -methylidyne tricobalt, nonacarbonyl- [mu] ₃ -ethylidyne tricobalt, nonacarbonyl- [mu] ₃ -ethoxycarbonylmethylidyne. Tricobalt, nonacarbonyl- [mu] _3- t-butoxycarbonylmethylidyne tricobalt, nonacarbonyl- [mu] ₃ -diethylamidomethylidyne tricobalt, nonacarbonyl- [mu] _3- n-propylcarbonylmethylidyne tricobalt, nonacarbonyl- [mu] ₃ -Phenylcarbonylmethylidyne tricobalt, nonacarbonyl-μ ₃ -4-methylphenylcarbonylmethylidyne tricobalt, nonacarbonyl-μ ₃ -2,2,2-trifluoroethoxycarbonylmethylidyne tricobalt, nonacarbonyl-μ ₃ -2, 2 , 3,3,4,4,5,5-octafluoropentoxycarbonylmethylidyne tricobalt, nonacarbonyl-μ ₃ -2-methylbutoxycarbonylmethylidyne tricobalt, and the like.
These compounds can be used alone or in combination of two or more as a material for forming a cobalt film. Since it is easy to set the film forming conditions, it is preferable to use one kind of compound alone as a material for forming a cobalt film.

Moreover, the cobalt film forming material of the present invention can be used by dissolving in a solvent. The solvent used is not particularly limited as long as it dissolves the compound represented by the above formula (1). Examples of such solvents include hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents. And ketone solvents.
Examples of the hydrocarbon solvent include n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, decane, cyclodecane, dicyclopentadiene hydride, benzene, toluene, Examples include xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene and the like.
Examples of the halogenated hydrocarbon solvent include dimethyl dichloride, chloroform, carbon tetrachloride, tetrachloroethane, chlorobenzene, dichlorobenzene, tetrachlorobenzene, bromobenzene, and fluorobenzene.
Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, and bis. (2-methoxyethyl) ether, p-dioxane, butyl glycidyl ether, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, fentol, 2-methylfentol, 3-methylfentol, 4- Methylfentol, veratrol, 2-ethoxyanisole, 1,4-dimethoxybenzene, etc. It can be mentioned.
Examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, allyl alcohol, n-butanol, i-butanol, t-butanol, n-heptanol, octanol, diethylene glycol, 1,2-butanediol, 1 , 3-butanediol, propylene glycol, cyclopentanol, cyclohexanol, phenol, 3-chloro-1-propanol and the like.
Examples of the ester solvent include ethyl acetate, methyl acetate, vinyl acetate, methyl methacrylate, ethyl chloroacetate, ethyl acetoacetate, chlorocarbonic acid methyl ester, and chlorocarbonic acid ethyl ester.
Examples of the ketone solvent include acetone, methyl ethyl ketone, acetyl acetone, diethyl ketone, methyl hexyl ketone, and cyclohexanone.
These solvents can be used alone or in admixture of two or more.
Of these solvents, it is preferable to use a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent, and a mixed solvent thereof in combination from the viewpoints of solubility and stability of the resulting composition solution. At that time, it is preferable to use cyclohexane, n-heptane, cycloheptane, n-octane, benzene, toluene or xylene as the hydrocarbon solvent. As ether solvents, diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, fentol Preferably, veratrol, 2-ethoxyanisole or 1,4-dimethoxybenzene is used. It is preferable to use ethyl acetate as the ester solvent. Moreover, it is preferable to use acetone, methyl ethyl ketone, and acetylacetone as the ketone solvent.
When the cobalt film forming material of the present invention is used after being dissolved in a solvent, the ratio of the total mass of the components excluding the solvent to the total mass of the cobalt film forming material (hereinafter referred to as “solid content concentration”) is as follows. , Preferably, it is 1-80 mass%, More preferably, it is 20-60 mass%.
The cobalt film forming material of the present invention can contain other cobalt compounds in addition to the compound represented by the above formula (1). Other cobalt compounds include octacarbonyl dicobalt and the like.
In the cobalt film forming material of the present invention, the compound represented by the above formula (1) is preferably 30 to 100% by mass, more preferably 50% to 100% by mass, based on the total of components excluding the solvent. %, More preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

The cobalt film forming method of the present invention uses the above-described cobalt film forming material.
The method for forming a cobalt film of the present invention can be a method known per se except that the above-described material for forming a cobalt film is used. For example, the method can be carried out as follows.

An example of the cobalt film formation method of the present invention is as follows: (1) The cobalt film formation material of the present invention is vaporized or sublimated under reduced pressure and heating, and the vaporized product or sublimated product is supplied onto a substrate (for example, a substrate). And (2) a step of heating and thermally decomposing the cobalt film forming material supplied onto the substrate to form a cobalt film on the substrate. In addition, even if it decomposes | disassembles the cobalt film formation material of this invention in the said process (1), the effect of this invention is not weakened.
As a material of the substrate that can be used here, for example, glass, silicon semiconductor, quartz, metal, metal oxide, synthetic resin, and other suitable materials can be used. However, the material can withstand the process temperature for thermally decomposing the cobalt compound. It is preferable.

Specifically, the substrate is composed of a metal film such as Ta, Ti, Zr, Hf, Pt, Ir, Cu, Au, and Al, a metal nitride film such as TaN, TiN, ZrN, and AlN, or an insulating film. .
Examples of the insulating film include a thermal oxide film, a PETEOS film (Plasma Enhanced-TEOS film), an HDP film (High Density Plasma Enhanced-TEOS film), a silicon oxide film obtained by a thermal CVD method, and a boron phosphorus silicate film (BPSG film). ), An insulating film called FSG, an insulating film having a low dielectric constant, and the like.
The thermal oxide film is formed by exposing high temperature silicon to an oxidizing atmosphere and chemically reacting silicon and oxygen or silicon and moisture.
The PETEOS film is formed by chemical vapor deposition using tetraethylorthosilicate (TEOS) as a raw material and using plasma as an acceleration condition.
The HDP film is formed by chemical vapor deposition using tetraethylorthosilicate (TEOS) as a raw material and using high-density plasma as a promotion condition.
The silicon oxide film obtained by the thermal CVD method is formed by an atmospheric pressure CVD method (AP-CVD method) or a low pressure CVD method (LP-CVD method).
The boron phosphorus silicate film (BPSG film) can be obtained by an atmospheric pressure CVD method (AP-CVD method) or a low pressure CVD method (LP-CVD method).
The insulating film called FSG can be formed by chemical vapor deposition using high-density plasma as a promotion condition.
Examples of the material for forming the insulating film having a low dielectric constant include organic SOG, hydrogen-containing SOG, a low dielectric constant material made of an organic polymer, a SiOF-based low dielectric constant material, and a SiOC-based low dielectric constant material. it can. Here, “SOG” is an abbreviation of “Spin On Glass”, and means an insulating film material for applying a precursor on a substrate and then forming a film by heat treatment or the like.
The organic SOG is composed of a silicon oxide containing an organic group such as a methyl group. For example, an insulating film made of organic SOG can be obtained by applying a precursor containing, for example, a mixture of tetraethoxysilane and methyltrimethoxysilane on the substrate, followed by heat treatment or the like.
The hydrogen-containing SOG is composed of a silicon oxide containing a silicon-hydrogen bond. An insulating film made of hydrogen-containing SOG can be obtained by applying a precursor containing, for example, triethoxysilane or the like on the substrate, followed by heat treatment or the like.
Examples of the low dielectric constant material made of the organic polymer include low dielectric constant materials mainly composed of polyarylene, polyimide, polybenzocyclobutene, polyfluorinated ethylene and the like.
The SiOF-based low dielectric constant material is composed of silicon oxide containing fluorine atoms. For example, an insulating film made of a SiOF-based low dielectric constant material can be obtained by adding (doping) fluorine to silicon oxide obtained by chemical vapor deposition.
The SiOC-based low dielectric constant material is composed of silicon oxide containing carbon atoms. For example, an insulating film made of a SiOC-based low dielectric constant material can be obtained by chemical vapor deposition using a mixture of silicon tetrachloride and carbon monoxide as a raw material.
Among the insulating films, the insulating film formed using a low dielectric constant material made of organic SOG, hydrogen-containing SOG, and organic polymer may have fine pores (pores) in the formed film. Good.

The base on which the cobalt film is formed may have a trench, and the trench is formed on the base made of the material as described above by a known method such as photolithography.
The trench may have any shape and size, but the opening width of the trench, that is, the minimum distance of the surface opening is 300 nm or less, and the aspect ratio of the trench, that is, the depth of the trench is When the value divided by the minimum distance of the surface opening is 3 or more, the advantageous effects of the present invention are maximized. The opening width of the trench is preferably 10 to 250 nm, and more preferably 30 to 200 nm. The aspect ratio of the trench is preferably 3 to 40, and more preferably 5 to 25.

In the said process (1), the temperature which evaporates a cobalt compound becomes like this. Preferably it is 30-250 degreeC, More preferably, it is 50-200 degreeC.
In the said process (2), the temperature which heat-decomposes the cobalt film formation material becomes like this. Preferably it is 100 to 800 degreeC, More preferably, it is 150 to 600 degreeC, More preferably, it is 300 to 500 degreeC.

The cobalt film forming method of the present invention can be carried out under any condition in the presence or absence of an inert gas, or in the presence or absence of a reducing gas. Moreover, you may implement on the conditions in which both inert gas and reducing gas exist. Here, examples of the inert gas include nitrogen gas, argon gas, helium gas, and the like. Examples of the reducing gas include hydrogen gas and ammonia gas. The cobalt film forming method of the present invention can also be carried out in the presence of an oxidizing gas. Here, examples of the oxidizing gas include oxygen, carbon monoxide, and nitrous oxide.
In particular, for the purpose of reducing the amount of impurities in the formed cobalt film, it is preferable to coexist these reducing gases. When the reducing gas is allowed to coexist, the ratio of the reducing gas in the atmosphere is preferably 1 to 100 mol%, and more preferably 3 to 100 mol%.
The proportion of the oxidizing gas in the atmosphere is preferably 10 mol% or less, more preferably 1 mol% or less, and further preferably 0.1 mol% or less.
The chemical vapor deposition method of the present invention can be carried out under any conditions under pressure, normal pressure and reduced pressure. Especially, it is preferable to implement under a normal pressure or pressure reduction, and it is still more preferable to implement under the pressure of 15,000 Pa or less.

  Further, as another example of the cobalt film forming method of the present invention, the cobalt film forming material is applied on a substrate, then subjected to heat treatment and / or light treatment, and expressed by the above formula (1) on the substrate. A cobalt film is formed by converting a compound into a cobalt film.

When applying the above-described cobalt film-forming material on the substrate as described above, an appropriate method such as a spin coating method, a roll coating method, a curtain coating method, a dip coating method, a spray method, a droplet discharge method, or the like is used. Can be used. In these coating steps, coating conditions are adopted such that the cobalt film forming material reaches every corner of the substrate depending on the shape and size of the substrate. For example, when the spin coating method is employed as the coating method, the spinner rotation speed can be set to 300 to 2,500 rpm, and further to 500 to 2,000 rpm.
After the coating step, heat treatment may be performed to remove low-boiling components such as a solvent contained in the coated cobalt film forming material. The temperature and time for heating vary depending on the type of solvent used and the boiling point (vapor pressure), but can be, for example, 100 to 350 ° C. and 5 to 90 minutes. At this time, the solvent can be removed at a lower temperature by reducing the pressure of the entire system. Preferably, it is 10 to 60 minutes at 100 to 250 ° C.

Next, the coating film formed as described above is subjected to heat treatment and / or light treatment to form a cobalt film on the substrate.
The temperature of the heat treatment is preferably 100 to 800 ° C, more preferably 150 to 600 ° C, and further preferably 300 to 500 ° C. The heat treatment time is preferably 30 seconds to 120 minutes, more preferably 1 to 90 minutes, still more preferably 10 to 60 minutes.
Examples of the light source used for the light treatment (for example, light irradiation) include a mercury lamp, a deuterium lamp, a rare gas discharge light, a YAG laser, an argon laser, a carbon dioxide gas laser, and a rare gas halogen excimer laser. . Examples of the mercury lamp include a low-pressure mercury lamp and a high-pressure mercury lamp. Examples of the rare gas used for the discharge light of the rare gas include argon, krypton, and xenon. Examples of the rare gas halogen used in the rare gas halogen excimer laser include XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, and the like.
The output of these light sources is preferably 10 to 5,000 W, more preferably 100 to 1,000 W. Although the wavelength of these light sources is not specifically limited, Preferably it is 170 nm-600 nm. Further, the use of laser light is particularly preferable from the viewpoint of the quality of the cobalt film to be formed. Further, for the purpose of forming a better cobalt film, plasma oxidation can be performed in an oxidizing gas atmosphere. As oxidation conditions for the plasma oxidation at this time, for example, RF power is 20 to 100 W, oxygen gas is 90 to 100% as an introduction gas, the remainder is argon gas, and the introduction pressure of the introduction gas is 0.05 to 0.2 Pa. And the plasma oxidation time can be set to 10 seconds to 240 seconds.

  The atmosphere during the coating step and the heat treatment and / or the light treatment step is preferably made of an inert gas such as nitrogen, helium, or argon. Furthermore, you may mix reducing gas, such as hydrogen and ammonia, as needed.

  Only one of the heat treatment and the light treatment may be performed, or both the heat treatment and the light treatment may be performed. When both heat treatment and light treatment are performed, the heat treatment and light treatment may be performed at the same time regardless of the order. Of these, it is preferable to perform only heat treatment or perform both heat treatment and light treatment. Further, for the purpose of forming a better cobalt film, plasma oxidation may be performed separately from the heat treatment and / or light treatment step.

The cobalt film-forming material of the present invention is excellent in long-term storage stability. Even if the cobalt film forming material of the present invention is held in the air, the material does not deteriorate. Since this is excellent in handling of the cobalt film forming material, it is very advantageous for filling the container, installing the container in the chemical vapor deposition apparatus, and stabilizing the operation of the chemical vapor deposition apparatus.
The cobalt film obtained as described above has high purity and electrical conductivity, and can be suitably used for, for example, a barrier film of a wiring electrode, a plating growth film, a capacitor electrode, and the like.

Hereinafter, the present invention will be described specifically by way of examples. The following operations were all performed in a dry nitrogen atmosphere unless otherwise specified.
(Synthesis example 1) Synthesis | combination of nonacarbonyl- (micro | micron | mu) ₃ -methylidyne tricobalt 18.7 g of dicobalt octacarbonyl and 150 ml of tetra dehydration hydrofurans were put into the Schlenk tube substituted with nitrogen, and were stirred. After dissolution of dicobalt octacarbonyl, 7.8 g of bromoform was slowly added using a syringe and heated to reflux at 50 ° C. for 3 hours. After completion of the reflux, filtration was performed, and the solvent was distilled off under vacuum and extracted with hexane. The hexane solution was washed with 10% hydrochloric acid and ultrapure water, added with magnesium sulfate anhydride, and dried for 12 hours. Filtration was performed after drying, and the solvent was distilled off under vacuum to obtain 3.7 g of nonacarbonyl-μ ₃ -methylidyne tricobalt as a solid. The yield was 34% by mass.
When the elemental analysis of the solid obtained here was implemented, they were carbon: 27.20% and hydrogen 0.24%. The theoretical value as nonacarbonyl-μ ₃ -methylidyne tricobalt was 27.18% carbon and 0.23% hydrogen.
^{_{IR (CCl 4, cm -1)}} : 2105m, 2060vs, 2045s, 2025w, 1980vw.

Synthesis Example 2 Synthesis of Nonacarbonyl-μ ₃ -Ethyridine Tricobalt In Synthesis Example 1, the same procedure as in Synthesis Example 1 was performed except that 7.8 g of bromoform was changed to 4.1 g of 1,1,1-trichloroethane. 4.8 g of nonacarbonyl-μ ₃ -ethylidene tricobalt was obtained as a solid. The yield was 43% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the obtained solid, it was confirmed that nonacarbonyl-μ ₃ -ethylidyne tricobalt was obtained.

(Synthesis Example 3) Synthesis of Nonacarbonyl-μ ₃ -ethoxycarbonylmethylidinetricobalt In Synthesis Example 1, except that 7.8 g of bromoform was changed to 5.9 g of ethyl trichloroacetate, Synthesis was performed in the same manner as in Synthesis Example 1, and Nona 6.7 g of carbonyl- [mu] ₃ -ethoxycarbonylmethylidyne tricobalt was obtained as a solid. The yield was 53% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the obtained solid, it was confirmed that nonacarbonyl-μ ₃ -ethoxycarbonylmethylidyne tricobalt was obtained.

(Synthesis Example 4) Synthesis of Nonacarbonyl-μ ₃ -t-butoxycarbonylmethylidinetricobalt In Synthesis Example 1, except that 7.8 g of bromoform was changed to 6.8 g of t-butoxytrichloroacetate, the same as Synthesis Example 1 As a result, 0.5 g of nonacarbonyl-μ ₃ -t-butoxycarbonylmethylidyne tricobalt was obtained as a solid. The yield was 4% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the solid obtained here, it was confirmed that nonacarbonyl-μ ₃ -t-butoxycarbonylmethylidyne tricobalt was obtained.

(Synthesis Example 5) Synthesis of Nonacarbonyl-μ ₃ -Diethylamidomethylidyne Tricobalt In Synthesis Example 1, except that 7.8 g of bromoform was changed to 6.8 g of diethylamide trichloroamide, Synthesis was performed in the same manner as in Synthesis Example 1, and nonacarbonyl 2.5 g of -μ ₃ -diethylamidomethylidyne tricobalt was obtained as a solid. The yield was 19% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the obtained solid, it was confirmed that nonacarbonyl-μ ₃ -diethylamidomethylidyne tricobalt was obtained.

(Synthesis Example 6) Synthesis of Nonacarbonyl-μ ₃ -n-propylcarbonylmethylidyne tricobalt In Synthesis Example 1, except that 7.8 g of bromoform was changed to 5.9 g of n-propyltrichloromethylketone, the same as Synthesis Example 1 In this way, 6.1 g of nonacarbonyl-μ ₃ -n-propylcarbonylmethylidyne tricobalt was obtained as a solid. The yield was 49% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the obtained solid, it was confirmed that nonacarbonyl-μ ₃ -n-propylcarbonylmethylidyne tricobalt was obtained.

(Synthesis Example 7) Synthesis of nonacarbonyl-μ ₃ -phenylcarbonylmethylidyne tricobalt In Synthesis Example 1, except that 7.8 g of bromoform was changed to 6.9 g of phenyltrichloromethyl ketone, this was carried out in the same manner as in Synthesis Example 1. 4.4 g of nonacarbonyl-μ ₃ -phenylcarbonylmethylidyne tricobalt was obtained as a solid. The yield was 33% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the solid obtained here, it was confirmed that nonacarbonyl-μ ₃ -phenylcarbonylmethylidyne tricobalt was obtained.

(Synthesis Example 8) Synthesis of Nonacarbonyl-μ ₃ -4-methylphenylcarbonylmethylidinetricobalt Synthesis Example 1 except that 7.8 g of bromoform was changed to 7.4 g of 4-methylphenyltrichloromethylketone in Synthesis Example 1. In the same manner as above, 5.6 g of nonacarbonyl-μ ₃ -4-methylphenylcarbonyltricobalt was obtained as a solid. The yield was 41% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the obtained solid, it was confirmed that nonacarbonyl-μ ₃ -4-methylphenylcarbonylmethylidyne tricobalt was obtained.

(Synthesis Example 9) Synthesis of Nonacarbonyl-μ ₃ -2,2,2-trifluoroethoxycarbonylmethylidinetricobalt In Synthesis Example 1, 7.8 g of bromoform was converted to 2,2,2-trifluoroethoxytrichloromethylketone 7 Except that the amount was 0.6 g, the same procedure as in Synthesis Example 1 was performed to obtain 7.2 g of nonacarbonyl-μ ₃ -2,2,2-trifluoroethoxycarbonylmethylidyne tricobalt as a solid. The yield was 52% by mass.
Elemental analysis of the obtained ^solid, 1 H-NMR analysis, and a result of IR analysis, that Nona carbonyl - [mu] ₃ -2,2,2-trifluoro ethoxycarbonylmethylidene lysine triisocyanate cobalt was obtained confirmed.

(Synthesis Example 10) Synthesis of Nonacarbonyl-μ ₃ -2,2,3,4,4,5,5-octafluoropentoxycarbonylmethylidinetricobalt In Synthesis Example 1, 7.8 g of bromoform was added to 2, Except that 11.7 g of 2,3,3,4,4,5,5-octafluoropentoxytrichloromethylketone was used, the same procedure as in Synthesis Example 1 was carried out, and nonacarbonyl-μ ₃ -2,2,3 8.6 g of 3,4,4,5,5-octafluoropentoxycarbonylmethylidyne tricobalt was obtained as a liquid. The yield was 50% by mass.
As a result of conducting elemental analysis, ¹ H-NMR analysis, and IR analysis of the solid obtained here, nonacarbonyl-μ ₃ -2, 2,3,3,4,4,5,5-octafluoropentoxy was obtained. It was confirmed that carbonylmethylidyne tricobalt was obtained.

Synthesis Example 11 Synthesis of Nonacarbonyl-μ ₃ -2-methylbutoxycarbonylmethylidinetricobalt Synthesis Example 1 except that 7.8 g of bromoform was changed to 7.2 g of 2-methylbutoxytrichloromethylketone in Synthesis Example 1. In the same manner as described above, 7.5 g of nonacarbonyl-μ ₃ -2-methylbutoxycarbonylmethylidyne tricobalt was obtained as a liquid. The yield was 55% by mass.
Elemental analysis of the obtained solid, ^{1 H-NMR} analysis, and a result of IR analysis, it was confirmed that Nona carbonyl - [mu] _{3-2-methyl-butoxycarbonyl} methylate lysine triisocyanate cobalt was obtained.

Example 1
-Stability evaluation After preparing 1 g of nonacarbonyl-μ ₃ -methylidyne tricobalt obtained in Synthesis Example 1 as a sample and allowing it to stand at 25 ° C. in the atmosphere (humidity 40%) for 24 hours, TG / DTA was determined. Was used to measure stability. Specifically, the measurement results of the samples before and after standing for 24 hours were compared, and the reaction rate of the sample was calculated from the difference in the decrease amount of the sample. As a result, the reaction rate of the sample of nonacarbonyl-μ ₃ -methylidyne tricobalt was 0% by mass.

Formation and Evaluation of Cobalt Film 0.1 g of nonacarbonyl-μ ₃ -methylidinetricobalt was transferred to a quartz boat container in nitrogen gas and set in a quartz reaction vessel. A silicon wafer with a thermal oxide film was placed near the downstream side of the air flow in the reaction vessel, and nitrogen gas was allowed to flow into the reaction vessel at a flow rate of 300 mL / min for 20 minutes at room temperature. Thereafter, nitrogen gas was allowed to flow into the reaction vessel at a flow rate of 100 mL / min, the system was further set to 133 Pa, and the reaction vessel was heated to 450 ° C. for 15 minutes. Mist was generated from the boat-type container, and deposits were observed on the quartz substrate installed in the vicinity. After the generation of mist is completed, the decompression is stopped, nitrogen gas is introduced into the system to return the pressure, and then nitrogen gas is flowed at a flow rate of 200 mL / min at 101.3 kPa, the temperature of the reaction vessel is raised to 420 ° C., When kept for 1 hour, a film having metallic luster was obtained on the substrate.
The film thickness was 1100 mm. When this film was analyzed by SIMS, it was found to be metallic cobalt. Further, when the resistivity of this cobalt film was measured by a four-terminal method, it was 35 μΩ · cm. The film density of this film was 7.6 g / cm ³ . The cobalt film formed here was evaluated for adhesion to the substrate by a cross-cut tape method, and no peeling between the substrate and the cobalt film was observed.

-Test of vaporization characteristics As a confirmation of vaporization characteristics, the amount of vaporization was measured by the following test method. In a glove box at room temperature in a dry nitrogen atmosphere, 1 g of nonacarbonyl-μ ₃ -methylidyne tricobalt was placed in a pressure-resistant stainless steel container with a 100 mL capacity valve and sealed. Thereafter, the container was placed on a hot plate, the valve was opened, and the interior of the container was decompressed at 13 Pa for 5 minutes while heating at 80 ° C. After closing the valve, the container was returned to room temperature by cooling for 3 hours, and the valve was slowly opened in the glove box to return the pressure in the container to normal pressure. Thereafter, the container was opened and the amount of the remaining sample was measured to calculate the amount of vaporization during the decompression process. The amount of vaporization was 0.31 g. The results are shown in Table 1.

(Example 2)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the compound to be evaluated was nonacarbonyl-μ ₃ -ethylidinetricobalt obtained in Synthesis Example 2. The results are shown in Table 1.
(Example 3)
Evaluation was performed in the same manner as in Example 1 except that in Example 1, the compound to be evaluated was nonacarbonyl-μ ₃ -ethoxycarbonylmethylidinetricobalt obtained in Synthesis Example 3. The results are shown in Table 1.

Example 4
Evaluation was performed in the same manner as in Example 1 except that the compound to be evaluated was nonacarbonyl-μ ₃ -t-butoxycarbonylmethylidyne tricobalt obtained in Synthesis Example 4 in Example 1. The results are shown in Table 1.
(Example 5)
Evaluation was performed in the same manner as in Example 1, except that the compound to be evaluated was nonacarbonyl-μ ₃ -diethylamidomethylidyne tricobalt obtained in Synthesis Example 5. The results are shown in Table 1.

(Example 6)
Evaluation was performed in the same manner as in Example 1 except that the compound to be evaluated was nonacarbonyl-μ ₃ -n-propylcarbonylmethylidyne tricobalt obtained in Synthesis Example 6 in Example 1. The results are shown in Table 1.
(Example 7)
Evaluation was performed in the same manner as in Example 1 except that in Example 1, the compound to be evaluated was nonacarbonyl-μ ₃ -phenylcarbonylmethylidinetricobalt obtained in Synthesis Example 7. The results are shown in Table 1.

(Example 8)
Evaluation was performed in the same manner as in Example 1, except that the compound to be evaluated was nonacarbonyl-μ ₃ -4-methylphenylcarbonylmethylidyne tricobalt obtained in Synthesis Example 8. The results are shown in Table 1.
Example 9
In Example 1, except for using nona carbonyl - [mu] ₃ -2,2,2-trifluoro ethoxycarbonylmethylidene lysine triisocyanate cobalt obtained was evaluated compound in Synthesis Example 9, in the same manner as in Example 1, Evaluation was performed. The results are shown in Table 1.

(Example 10)
In Example 1, it was Nona carbonyl - [mu] _{3-2,2,3,3,4,4,5,5-octafluoro-pentoxycarbonyl} methylate lysine triisocyanate cobalt obtained was evaluated compound in Synthesis Example 10 Except for the above, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
(Example 11)
Evaluation was performed in the same manner as in Example 1 except that the compound to be evaluated was nonacarbonyl-μ ₃ -2-methylbutoxycarbonylmethylidyne tricobalt obtained in Synthesis Example 11 in Example 1. The results are shown in Table 1.

(Example 12)
Dry toluene is added to 1.00 g of nonacarbonyl-μ ₃ -methylidene tricobalt obtained in Synthesis Example 1 to make the total amount 4.00 g, and 25% by mass of nonacarbonyl-μ ₃ -methylidyne tricobalt is contained. A cobalt film forming material was prepared.
The following experiment was conducted in a glove box controlled in a dry nitrogen atmosphere. A silicon substrate was mounted on a spin coater, 2 mL of a cobalt film-forming material containing 25% by mass of nonacarbonyl-μ ₃ -methylidene tricobalt prepared by the above method was dropped, and spin was performed at a rotation speed of 300 rpm for 10 seconds. . The substrate was heated on a hot plate at 100 ° C. for 10 minutes and on a hot plate at 200 ° C. for 10 minutes. Thereafter, when the substrate was further heated at 350 ° C. for 30 minutes, the substrate surface was covered with a film having a metallic luster. The film thickness was 164 mm. When the SIMS spectrum of this film was measured, it was found to be metallic cobalt. Further, when the resistivity of this cobalt film was measured by the 4-terminal method, it was 48 μΩcm. The film density of this film was 7.4 g / cm ³ .

(Example 13)
Nona carbonyl obtained in Synthesis Example 3 - [mu] ₃ - nona carbonyl - [mu] ₃ added to bring the total amount ethoxycarbonylmethylidene lysine triisocyanate cobalt 1.00g in dry ethylene glycol methyl ethyl ether as 1.67 g - ethoxycarbonylmethylidene lysine A cobalt film forming material containing 60% by mass of tricobalt was prepared.
Instead of the cobalt film-forming material containing 25% by mass of nonacarbonyl-μ ₃ -methylidyne tricobalt prepared in Example 12, 60 of nonacarbonyl-μ ₃ -ethoxycarbonylmethylidyne tricobalt prepared by the above method was used. A film was formed in the same manner as in Example 12 except that the cobalt film forming material containing mass% was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metallic cobalt film were evaluated in the same manner as in Example 12. The results are shown in Table 1.

(Example 14)
The dried i-propanol was added to 1.00 g of nonacarbonyl-μ ₃ -diethylamidomethylidyne tricobalt obtained in Synthesis Example 5 to make the total amount 4.00 g, and 25 g of nonacarbonyl-μ ₃ -diethylamidomethylidyne tricobalt was added. A cobalt film-forming material containing mass% was prepared.
Instead of the cobalt film-forming material containing 25% by mass of nonacarbonyl-μ ₃ -methylidyne tricobalt prepared in Example 12, 25 mass of nonacarbonyl-μ ₃ -diethylamide methylidyne tricobalt prepared by the above method was used. A film was formed in the same manner as in Example 12 except that the cobalt film forming material containing 1% was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metallic cobalt film were evaluated in the same manner as in Example 12. The results are shown in Table 1.

(Example 15)
Nona carbonyl -μ obtained in Synthesis Example 7 ₃ - nona carbonyl -μ added to bring the total amount to cyclohexanone and dried phenylcarbonyl methylate lysine triisocyanate cobalt 1.00g as 5.00 g ₃ - 20 phenylcarbonyl methylate lysine triisocyanate cobalt A cobalt film-forming material containing mass% was prepared.
Nona carbonyl - [mu] adjusted in Example 12 ₃ - nona carbonyl was adjusted by the above method instead of the cobalt film material methylol lysine triisocyanate cobalt containing 25 wt% - [mu] ₃ - 20 phenylcarbonyl methylate lysine triisocyanate cobalt A film was formed in the same manner as in Example 12 except that the cobalt film forming material containing mass% was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metallic cobalt film were evaluated in the same manner as in Example 12. The results are shown in Table 1.

(Example 16)
Nona carbonyl - [mu] added to bring the total amount to nona carbonyl - [mu] ₃ -2,2,2 p-dioxane and dried in trifluoroacetic ethoxycarbonylmethylidene lysine triisocyanate cobalt 1.00g obtained in Synthesis Example 9 as 2.00g ₃ -2,2,2 trifluoro ethoxycarbonylmethylidene lysine triisocyanate cobalt was prepared cobalt-film forming material containing 50% by weight.
Nona carbonyl - [mu] ₃ was adjusted in Example 12 - nona carbonyl was adjusted by the above method instead of the cobalt film material methylol lysine triisocyanate cobalt containing 25 wt% - [mu] ₃ -2,2,2-trifluoro A film was formed in the same manner as in Example 12 except that a cobalt film forming material containing 50% by mass of ethoxycarbonylmethylidyne tricobalt was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metallic cobalt film were evaluated in the same manner as in Example 12. The results are shown in Table 1.

(Example 17)
Nonacarbonyl-μ ₃ -2-methylbutoxycarbonyl was prepared by adding dry xylene to 1.00 g of nonacarbonyl-μ ₃ -2-methylbutoxycarbonylmethylidene tricobalt obtained in Synthesis Example 11 to give a total amount of 3.00 g. A cobalt film-forming material containing 33% by mass of methylidyne tricobalt was prepared.
Nona carbonyl - [mu] ₃ was adjusted in Example 12 - nona carbonyl - [mu] _{3-2-methyl-but-adjusted} by the above method instead of the cobalt film material methylol lysine triisocyanate cobalt containing 25 wt% alkoxycarbonyl methylate lysine triisocyanate A film was formed in the same manner as in Example 12 except that the cobalt film forming material containing 33% by mass of cobalt was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metallic cobalt film were evaluated in the same manner as in Example 12. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the compound to be evaluated was dicobalt octacarbonyl. The results are shown in Table 1. From Table 1, it can be seen that the cobalt film forming materials used in Examples 1 to 11 are stable in the air. Moreover, in Examples 1-11, it turns out that the adhesiveness etc. of a board | substrate and a cobalt film are also favorable. On the other hand, the cobalt film forming material used in Comparative Example 1 is inferior in stability in the atmosphere.

Claims (8)

A cobalt film-forming material containing a compound represented by the following formula (1).
Co ₃ (CO) ₉ CZ (1)
(In the formula (1), Z is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom (excluding those having a double bond) , or may be substituted with a halogen atom . A good alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom (excluding those having a double bond) , and may be substituted with a halogen atom An alkylamide group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, and an alkoxyalkyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom are shown. )   The cobalt film-forming material according to claim 1, wherein, in the general formula (1), Z is an alkoxycarbonyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom. The material for forming a cobalt film according to claim 1 or 2 , which is used for chemical vapor deposition. The cobalt film formation method using the cobalt film formation material of any one of Claims 1-3 . A cobalt film forming material supply step for supplying the cobalt film forming material according to any one of claims 1 to 3 onto a substrate, and the cobalt film forming material supplied onto the substrate is thermally decomposed, And a film forming step of forming a cobalt film on the substrate. The cobalt film formation method according to claim 5 , wherein the temperature of heat decomposition in the film formation step is 100 ° C. to 800 ° C. 6. The cobalt film formation method according to claim 5 or 6 , wherein the thermal decomposition in the film formation step is performed in an inert gas or a reducing gas. A method for forming a cobalt film, comprising: a film forming step in which the material for forming a cobalt film according to claim 1 or 2 is applied on a substrate and then heat-treated and / or light-treated to form a cobalt film on the substrate. .