JP5741443B2 - Ruthenium film forming material and ruthenium film forming method - Google Patents

Description

  The present invention relates to a ruthenium film forming material and a ruthenium 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 increasing 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, a technique for forming a barrier film between the low dielectric constant material and the copper wiring has been studied for the purpose of preventing oxygen migration from the low dielectric constant material. A metal ruthenium film has attracted 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 for embedding the copper wiring by the plating method, metal ruthenium has attracted attention for the purpose of satisfying both roles of the barrier film and the plating growth film at the same time.
Also in semiconductor device capacitors, metal ruthenium films have high oxidation resistance and high conductivity as electrode materials of high dielectric constant materials such as alumina, tantalum pentoxide, hafnium oxide, barium strontium titanate (BST). It is attracting attention from sex.

Sputtering methods have been used in the past for the formation of the above-mentioned metal ruthenium films, but in recent years, chemical vapor deposition methods have been investigated as measures for miniaturization of structures, thinning, and improvement of mass productivity. Has been.
However, in general, metal films formed by chemical vapor deposition have poor surface morphology, such as the sparse state of microcrystals, and bis (dipivaloylmethanate) is a means of solving the above morphological problems. ) The use of ruthenium, ruthenocene, or bis (alkylcyclopentadienyl) ruthenium as a chemical vapor deposition material has been studied (see Patent Documents 1 to 3).
Furthermore, when these chemical vapor deposition materials are used in the production process, good storage stability of the materials is required for the purpose of stabilizing the production conditions. However, existing ruthenocene, bis (alkylcyclopentadienyl) ruthenium, etc. cause material oxidation in a short period of time due to air contamination and the resulting performance degradation, resulting in a decrease in the conductivity of the deposited ruthenium. Therefore, there is a problem in the storage stability and the stable handling property in the air.

JP-A-6-283438 JP 11-35589 A JP 2002-114795 A

  The present invention has been made in view of the above problems, and its object is to provide a ruthenium film-forming material capable of obtaining a high-quality ruthenium film having excellent storage stability and low residual impurities, and to form a ruthenium film using the material. It is to provide a simple way to do this.

（一般式（１）中、Ｒ^１〜Ｒ^４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜１０の炭化水素基、または炭素数１〜１０のハロゲン化炭化水素基、Ｒ^５は、炭素数１〜１２の２価の炭化水素基、または炭素数１〜１２の２価のハロゲン化炭化水素基である。）
［２］ 化学気相成長法用である、前記［１］に記載のルテニウム膜形成用材料。
［３］ 前記［１］または［２］に記載のルテニウム膜形成用材料を用いる、ルテニウム膜形成方法。
［４］ 前記［２］に記載のルテニウム膜形成用材料を、基体上に供給するルテニウム膜形成用材料供給工程と、該ルテニウム膜形成用材料を加熱分解して、上記基体上にルテニウム膜を形成させる膜形成工程とを含む、ルテニウム膜形成方法。
［５］ 上記膜形成工程における加熱分解の温度が１００℃〜８００℃である、前記［４］に記載のルテニウム膜形成方法。
［６］ 上記膜形成工程における加熱分解を不活性気体または還元性気体中で行う、前記［４］または［５］に記載のルテニウム膜形成方法。
［７］ 前記［１］に記載のルテニウム膜形成用材料を、基体上に塗布し、次いで熱処理及び／又は光処理して、上記基体上にルテニウム膜を形成させる膜形成工程を含む、ルテニウム膜形成方法。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 [7].
[1] A ruthenium film-forming material containing a compound represented by the following general formula (1).

(In General Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group having 1 to 10 carbon atoms, R ⁵ is a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms.)
[2] The ruthenium film-forming material according to [1], which is for chemical vapor deposition.
[3] A ruthenium film forming method using the ruthenium film forming material according to [1] or [2].
[4] A ruthenium film forming material supply step for supplying the ruthenium film forming material according to [2] onto a substrate, and the ruthenium film forming material is thermally decomposed to form a ruthenium film on the substrate. A ruthenium film forming method including a film forming step of forming the film.
[5] The ruthenium film forming method according to [4], wherein the temperature of heat decomposition in the film forming step is 100 ° C to 800 ° C.
[6] The ruthenium film forming method according to [4] or [5], wherein the thermal decomposition in the film forming step is performed in an inert gas or a reducing gas.
[7] A ruthenium film comprising a film forming step in which the ruthenium film-forming material according to [1] is applied on a substrate and then heat-treated and / or light-treated to form a ruthenium film on the substrate. Forming method.

  According to the ruthenium film forming material of the present invention, a good quality ruthenium film having excellent long-term storage stability and a small amount of residual impurities can be obtained. Further, a ruthenium film can be formed by a simple method using the ruthenium film forming material of the present invention.

Hereinafter, the present invention will be described in detail.
The ruthenium film-forming material of the present invention contains a compound represented by the following general formula (1).

In General Formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group having 1 to 10 carbon atoms.
Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.
Moreover, as a C1-C10 hydrocarbon group, a C1-C7 hydrocarbon group is preferable.
Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, neopentyl group, n-hexyl group, cyclohexyl group, phenyl group, and benzyl group. And methylphenyl group.
Moreover, as a C1-C10 halogenated hydrocarbon group, a C1-C6 halogenated hydrocarbon group is preferable. Specific examples thereof include, for example, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, perfluoropropyl. Group, perfluorobutyl group, perfluorohexyl group, and pentafluorophenyl group.

In the general formula (1), ^{R 5} is a divalent hydrocarbon group or a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, having 1 to 12 carbon atoms.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a divalent linear or branched hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, A bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms is exemplified.

The divalent linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a divalent linear or branched hydrocarbon group having 1 to 8 carbon atoms.
Examples of the hydrocarbon group in the divalent linear or branched hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an alkylene group, an alkenylene group, and an alkynylene group.
Specific examples of the alkylene group include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.
Preferable specific examples of the alkenylene group include vinylene group, propenylene group, butadienylene group and the like.
Preferable specific examples of the alkynylene group include ethynylene group, propynylene group, butynylene group and the like.

The divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.
Specific examples of the “alicyclic hydrocarbon group” in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group and the like. A cycloalkylene group; a cycloalkenylene group such as a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, and the like. The binding site of the alicyclic hydrocarbon group may be on any carbon atom on the alicyclic ring.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include arylene groups such as a phenylene group, a biphenylene group, and a naphthylene group.
Specific examples of the “divalent hydrocarbon group having 1 to 12 carbon atoms” include alkenylene groups and arylene groups. Among these, a vinylene group and a phenylene group are particularly preferable.

In addition, as the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms represented by R ⁵ , a part or all of the hydrogen atoms in the above divalent hydrocarbon group having 1 to 12 carbon atoms are halogen atoms. Examples include substituted groups.
Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.

一般式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、上記一般式（１）中と同義である。
また、上記一般式（２）で表わされる化合物は、下記の一般式（３）で表わされる化合物と、下記の一般式（４）で表わされる化合物とを反応させて得ることができる。

一般式（３）中、Ｘ^１はハロゲン原子であり、Ｒ^５は上記一般式（１）中と同義である。
Ｘ^１で表されるハロゲン原子の例としては、塩素、臭素、ヨウ素が挙げられる。中でも、反応性及びコストの観点から臭素が好ましい。

一般式（４）中、Ｘ²はハロゲン原子であり、Ｒ^１、Ｒ^２は上記一般式（１）中と同義である。
Ｘ²で表されるハロゲン原子の例としては、塩素、臭素、ヨウ素が挙げられる。中でも、反応性及びコストの観点から塩素が好ましい。The method for synthesizing the compound represented by the general formula (1) can be obtained, for example, by reacting dodecacarbonyl triruthenium with a compound represented by the following general formula (2).

In general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as in general formula (1).
The compound represented by the general formula (2) can be obtained by reacting a compound represented by the following general formula (3) with a compound represented by the following general formula (4).

In General Formula (3), X ¹ is a halogen atom, and R ⁵ has the same meaning as in General Formula (1).
Examples of the halogen atom represented by X ¹ include chlorine, bromine and iodine. Among these, bromine is preferable from the viewpoint of reactivity and cost.

In General Formula (4), X ² is a halogen atom, and R ¹ and R ² have the same meaning as in General Formula (1).
Examples of the halogen atom represented by X ² include chlorine, bromine and iodine. Among these, chlorine is preferable from the viewpoint of reactivity and cost.

  Specific examples of the compound represented by the general formula (1) include 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d ] [2,1,3] rutenadicylol, 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] rutenadicylol 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] rutenadisilole, 1,1,3 Mention may be made of 3-tetramethyl-2,2,2,2-tetracarbonyl.

  These compounds can be used alone or in combination of two or more as a material for forming a ruthenium film. It is preferable to use one kind of compound alone as a material for forming a ruthenium film.

Moreover, the ruthenium film-forming material of the present invention can be used by dissolving in a solvent. The solvent is not particularly limited as long as it dissolves the compound represented by the general formula (1). Examples of the solvent include hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, and the like.
Examples of the hydrocarbon solvent include n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, decane, cyclodecane, dicyclopentadiene hydride, benzene, and toluene. 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, 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 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, Examples include 1.3-butanediol, propylene glycol, cyclopentanol, cyclohexanol, phenol, and 3-chloro-1-propanol.
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, a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent, or a mixed solvent composed of two or more selected from these solvents from the viewpoint of solubility and stability of the resulting composition solution. It is preferable to use it.
Preferable examples of the hydrocarbon solvent include cyclohexane, n-heptane, cycloheptane, n-octane, benzene, toluene and xylene. Preferred examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, anisole, 2-methylanisole, 3-methylanisole, and 4-methylanisole. , Fentol, veratrol, 2-ethoxyanisole or 1,4-dimethoxybenzene. A preferred example of the ester solvent is ethyl acetate. Preferable examples of the ketone solvent include acetone, methyl ethyl ketone, and acetylacetone.
The ratio of the total mass of the components excluding the solvent in the ruthenium film forming material of the present invention to the total mass of the composition (hereinafter referred to as “solid content concentration”) is preferably 0.1 to 70% by mass. More preferably, it is 20-50 mass%.
The ruthenium film-forming material of the present invention can contain other ruthenium compounds in addition to the compound represented by the above formula (1). Other ruthenium compounds include ruthenium dodecacarbonyl, (2,3-dimethyl-1,3-butadiene) tricarbonyl ruthenium, (1,3-butadiene) tricarbonyl ruthenium, (1,3-cyclohexadiene) tricarbonyl ruthenium. , (1,4-cyclohexadiene) tricarbonylruthenium, (1,5-cyclooctadiene) tricarbonylruthenium, and the like.
The ratio of the compound represented by the general formula (1) in the total amount of the components excluding the solvent of the ruthenium film forming material of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass. More preferably, it is 70-100 mass%, More preferably, it is 80-100 mass%, Most preferably, it is 90-100 mass%.

The ruthenium film forming method of the present invention uses the above-mentioned ruthenium film forming material.
The ruthenium film forming method of the present invention may be a method known per se, except that the above-described ruthenium film forming material is used. For example, the following method (a) or (b) can be used. .

(A) Method by Chemical Vapor Deposition Method In this method, the ruthenium film forming material of the present invention is supplied onto a substrate (for example, a substrate), and then the ruthenium film forming material supplied onto the substrate is thermally decomposed. Thus, a ruthenium film is formed on the substrate.
(B) Method by coating In this method, the ruthenium film-forming material of the present invention is coated on a substrate (for example, a substrate), and then the ruthenium film-forming material coated on the substrate is subjected to heat treatment and / or light. In this method, a ruthenium film is formed on the substrate by treatment.

As a base material that can be used in the ruthenium film forming method of the present invention, for example, an appropriate material such as glass, silicon semiconductor, quartz, metal, metal oxide, and synthetic resin can be used, but a process of thermally decomposing a ruthenium compound. It is preferable that the material can withstand this temperature.
Examples of the substrate include metal films such as Ta, Ti, Zr, Hf, Pt, Ir, Cu, Au, and Al, metal nitride films such as TaN, TiN, ZrN, and AlN, and insulating films.
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 an acceleration 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 an acceleration condition.

Examples of the insulating film having a low dielectric constant include an organic SOG, a hydrogen-containing SOG, a low dielectric constant material made of an organic polymer, a SiOF low dielectric constant material, or a SiOC low dielectric constant material. Can do. Here, “SOG” is an abbreviation for “Spin On Glass”, and means an insulating film material formed by 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. An insulating film made of organic SOG can be obtained by applying a precursor containing, for example, a mixture of tetraethoxysilane and methyltrimethoxysilane on a substrate and then performing a heat treatment or the like.
The hydrogen-containing SOG is composed of a silicon oxide containing a silicon-hydrogen bond. The insulating film made of hydrogen-containing SOG can be obtained by applying a precursor containing, for example, triethoxysilane on the substrate and then performing a 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 insulating film made of the material can be obtained by applying a precursor containing, for example, polyarylene or the like on the substrate and then performing a heat treatment or the like.
The SiOF-based low dielectric constant material is composed of silicon oxide containing fluorine atoms. The insulating film made of the material can be obtained, for example, by adding (doping) fluorine to a film made of silicon oxide obtained by chemical vapor deposition.
The SiOC-based low dielectric constant material is composed of silicon oxide containing carbon atoms. The insulating film made of the material can be obtained by, for example, chemical vapor deposition using a mixture of silicon tetrachloride and carbon monoxide as a raw material.
Among those described above, the low dielectric constant material composed of organic SOG, hydrogen-containing SOG, and organic polymer may have fine pores (pores) in the formed film.

The substrate on which the ruthenium film is formed may have a trench. The trench is formed on a base made of the above-described material 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 When the value obtained by dividing the above by the minimum distance of the surface opening of the trench 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, more preferably 30 to 200 nm. The aspect ratio of the trench is preferably 3 to 40, more preferably 5 to 25.

(A) Method by Chemical Vapor Deposition Method An example of this method is as follows: (1) The ruthenium film-forming material of the present invention is vaporized or evaporated under reduced pressure and heat, and the vaporized product or evaporated product is converted into a substrate (for example, And (2) after the step (1), the obtained deposit is heated and thermally decomposed to form a ruthenium film on the substrate.
In addition, even if it decomposes | disassembles the ruthenium film forming material of this invention in the said process (1), the effect of this invention is not weakened.
In the said process (1), the temperature which vaporizes or evaporates a ruthenium compound becomes like this. Preferably it is 100-350 degreeC, More preferably, it is 120-300 degreeC, Most preferably, it is 150-250 degreeC.
In the above step (2), the temperature for thermally decomposing the ruthenium compound is preferably 100 to 800 ° C, more preferably 100 to 600 ° C, still more preferably 180 to 450 ° C, still more preferably 200 to 420 ° C, and particularly preferably. 250-410 ° C.

The chemical vapor deposition method of the present invention can be carried out under any conditions 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 chemical vapor deposition 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 ruthenium 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 ratio of the oxidizing gas in the atmosphere is preferably 10 mol% or less, more preferably 1 mol% or less, and particularly 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.

(B) Method by coating In this method, the ruthenium film-forming material is coated on a substrate, then heat-treated and / or light-treated to convert the compound represented by the general formula (1) onto the ruthenium film on the substrate. By converting, a ruthenium film is formed.

When applying the above-mentioned ruthenium 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 material for forming a ruthenium film reaches every corner of the substrate depending on the shape and size of the substrate. For example, when the spin coating method is adopted as the coating method, the spinner rotation speed is preferably 300 to 2,500 rpm, more preferably 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 applied ruthenium film forming material. The heating temperature and time vary depending on the type of solvent used, the boiling point (vapor pressure), etc., but preferably 100 to 350 ° C. for 5 to 90 minutes, more preferably 100 to 250 ° C. for 10 to 60 minutes. is there. At this time, the solvent can be removed at a lower temperature by reducing the pressure of the entire system.

Then, the ruthenium film is formed on the substrate by subjecting the coating film formed as described above to heat treatment and / or light treatment.
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 irradiation include a mercury lamp, deuterium lamp, rare gas discharge light, YAG laser, argon laser, carbon dioxide laser, rare gas halogen excimer laser, and the like. 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. In addition, the use of laser light is particularly preferable from the viewpoint of the film quality of the formed ruthenium film. In addition, plasma oxidation can be performed in an oxidizing gas atmosphere for the purpose of forming a better ruthenium film. 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 introduction gas, the remainder is argon gas, and introduction pressure of introduction gas is 0.05 to 0.2 Torr. And the plasma oxidation time can be 10 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 (light irradiation) 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 ruthenium film, plasma oxidation may be performed separately from the heat treatment and / or the light treatment step.

The ruthenium film-forming material of the present invention hardly deteriorates due to oxidation or the like with respect to storage in the air, and is excellent in storage stability. For example, when the ruthenium film-forming material of the present invention is placed in a commercially available sealed container for experiments and kept in a cool and dark place, the deterioration of the material will not occur for about 15 days even if the atmosphere in the container is not made an inert atmosphere. Does not occur.
The ruthenium 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.

    EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.

[Synthesis Example 1] Synthesis of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] rutenadisilol Magnesium (5.10 g), chlorodimethylsilane (19.86 g), and tetrahydrofuran (15 mL) were placed in a three-necked flask, and a solution of 1,2-dibromobenzene (12 mL) and tetrahydrofuran (100 mL) was slowly added dropwise over 1 hour. After completion of dropping, the mixture was heated to reflux for 1 hour. The solution was cooled to room temperature and then filtered and distilled (10 Torr, 93 ° C.) to obtain 6.73 g of 1,2-bis (dimethylsilyl) benzene as a colorless transparent liquid. 2.91 g of this 1,2-bis (dimethylsilyl) benzene, 3.20 g of dodecacarbonyltriruthenium (0), and 80 mL of hexane were placed in a three-necked flask purged with nitrogen, and heated to reflux for 9 hours. After completion of the reflux, filtration is performed, and concentration and drying are performed under reduced pressure. 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3 represented by the following formula (5) -6.04 g of dihydro-benzo [d] [2,1,3] rutenazicilol was obtained as a black-red-brown liquid. The yield was 35% by mass.

Synthesis Example 2 Synthesis of 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol Magnesium (5.10 g), trichlorosilane (28.44 g), and tetrahydrofuran (15 mL) were placed in a three-necked flask, and a solution of 1,2-dibromobenzene (12 mL) and tetrahydrofuran (100 mL) was slowly added dropwise over 1 hour. After completion of dropping, the mixture was heated to reflux for 1 hour. The solution was cooled to room temperature and then filtered and distilled (10 Torr, 93 ° C.) to obtain 11.32 g of 1,2-bis (dichlorosilyl) benzene as a colorless transparent liquid. This 1,2-bis (dichlorosilyl) benzene (4.14 g), dodecacarbonyltriruthenium (0) (3.20 g), and hexane (80 mL) were placed in a three-necked flask purged with nitrogen, and heated to reflux for 9 hours. After completion of the reflux, filtration is performed, and the filtrate is concentrated and dried under reduced pressure. 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3 represented by the following formula (6) -7.37 g of dihydro-benzo [d] [2,1,3] rutenazicilol was obtained as a black-red-brown liquid. The yield was 41% by mass.

Synthesis Example 3 Synthesis of 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadicillol Magnesium (5.10 g), chlorobis (trifluoromethyl) silane (42.53 g), and tetrahydrofuran (15 mL) were placed in the substituted three-necked flask, and a solution of 1,2-dibromobenzene (12 mL) and tetrahydrofuran (100 mL) was slowly added dropwise over 1 hour. After completion of dropping, the mixture was heated to reflux for 1 hour. The solution was cooled to room temperature and then filtered and distilled (10 Torr, 93 ° C.) to obtain 19.28 g of 1,2-bis (bistrifluoromethylsilyl) benzene as a colorless transparent liquid. 6.15 g of this 1,2-bis (bistrifluoromethylsilyl) benzene, 3.20 g of dodecacarbonyltriruthenium (0) and 80 mL of hexane were placed in a three-necked flask purged with nitrogen, and heated to reflux for 9 hours. After completion of the reflux, filtration is performed, and the filtrate is concentrated and dried under reduced pressure. 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1 represented by the following formula (7) , 3-dihydro-benzo [d] [2,1,3] rutenazicilol 9.38 g was obtained as a black-red liquid. The yield was 47% by mass.

[Synthesis Example 4] Synthesis of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene In a nitrogen-substituted three-necked flask, 5.10 g of magnesium, chloro 19.86 g of dimethylsilane and 15 mL of tetrahydrofuran were added, and a solution of 18.59 g of 1,2-dibromoethylene and 100 mL of tetrahydrofuran was slowly added dropwise over 1 hour. After completion of dropping, the mixture was heated to reflux for 1 hour. The solution was cooled to room temperature and then filtered and distilled (10 Torr, 93 ° C.) to obtain 4.48 g of 1,2-bis (dimethylsilyl) ethylene as a colorless transparent liquid.
The 1,2-bis (dimethylsilyl) ethylene (2.17 g), dodecacarbonyltriruthenium (0) (3.20 g), and hexane (80 mL) were placed in a three-necked flask purged with nitrogen, and heated to reflux for 9 hours. After completion of the reflux, filtration is performed, and concentration and drying are performed under reduced pressure. 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1 represented by the following formula (8) , 3-disilartenolene (5.99 g) was obtained as a black-brown liquid. The yield was 31% by mass.

  In the following examples, the specific resistance was measured with a probe resistivity meter (model: RT-80 / RG-80) manufactured by Napson. The film thickness and film density were measured with an oblique incidence X-ray analyzer (type: X'Pert MRD) manufactured by Philips. The ESCA spectrum was measured with a device manufactured by JEOL Ltd. (form: JPS80). The evaluation of adhesion was based on a cross-cut tape method in accordance with JIS K-5400.

[Example 1]
(1) Formation of Ruthenium Film 1,1,3,3-Tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2, obtained in Synthesis Example 1 0.05 g of 1,3] rutenazicilol was weighed into a quartz boat-type container in nitrogen gas and set in a quartz reaction container. 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 13 Pa, and the reaction vessel was heated at 200 ° 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, the pressure is returned, and then the nitrogen gas is allowed to flow at 101.3 kPa at a flow rate of 200 ml / min to raise the temperature of the reaction vessel to 400 ° C. When kept for 1 hour, a film having metallic luster was obtained on the substrate. The film thickness was 400 mm.
When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that it was metal ruthenium. Further, when the resistivity of this ruthenium film was measured by a four-terminal method, it was 82 μΩcm. The film density of this film was 11.8 g / cm ³ . About the ruthenium film | membrane formed here, when the adhesiveness with a board | substrate was evaluated by the cross cut tape method, peeling between a board | substrate and a ruthenium film | membrane was not seen at all. The results are shown in Table 1.
In Table 1, the case where the adhesion to the substrate was good was indicated as “◯”, and the case where it was defective was indicated as “x”.

(2) Storage stability test As a confirmation of storage stability, a deterioration test against air was conducted by a heating acceleration test. 1 g of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol in a 50 mL quartz three-necked flask The whole container was heated to 50 ° C., and then air was circulated at a flow rate of 3 L / min for 3 hours under normal pressure. In appearance, there was no change in 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol. Then, after returning a container to room temperature and replacing the inside of a container with dry nitrogen gas, when the film-forming was implemented in the same way as said (1), the film | membrane which has a metallic luster on the board | substrate was obtained. The film thickness was 400 mm.
When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that it was metal ruthenium. Further, when the resistivity of this ruthenium film was measured by a four-terminal method, it was 82 μΩcm. The film density of this film was 11.8 g / cm ³ . When the ruthenium film formed here was evaluated for adhesion to the substrate by the cross-cut tape method, no peeling between the substrate and the ruthenium film was observed, and deterioration of the ruthenium metal film quality by the air exposure heating test was observed. There wasn't. The results are shown in Table 1.

[Example 2]
(1) Formation of Ruthenium Film 1,1,3,3-Tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadicillol 0.05 g 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] obtained in Synthesis Example 2 A film having a metallic luster was obtained on the substrate in the same manner as in Example 1 except that 0.05 g of rutenazicilol was used. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Storage stability test As a confirmation of storage stability, a deterioration test against air was conducted by a heating acceleration test. Quartz three-necked flask with a volume of 50 mL of 1 g of 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol The whole container was heated to 50 ° C., and then air was circulated at a flow rate of 3 L / min for 3 hours under normal pressure. There was no change in the appearance of 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol. Then, after returning a container to room temperature and replacing the inside of a container with dry nitrogen gas, when the film-forming was implemented in the same way as said (1), the film | membrane which has a metallic luster on the board | substrate was obtained. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
(1) Formation of Ruthenium Film 1,1,3,3-Tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadicillol 0.05 g Instead of 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1, 3] A film having a metallic luster was obtained on the substrate in the same manner as in Example 1 except that 0.05 g of rutenadicirole was used. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Storage stability test As a confirmation of storage stability, a deterioration test against air was conducted by a heating acceleration test. 1 g of 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol The flask was placed in a three-necked flask, and the entire container was heated to 50 ° C., and then air was circulated at a flow rate of 3 L / min for 3 hours under normal pressure. There was no change in the appearance of 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilole . Then, after returning a container to room temperature and replacing the inside of a container with dry nitrogen gas, when it formed into a film like said (1), the film | membrane which has a metallic luster on the board | substrate was obtained. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
(1) Formation of Ruthenium Film 1,1,3,3-Tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadicillol 0.05 g Example 1 was used except that 0.05 g of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene obtained in Synthesis Example 4 was used instead of In the same manner as above, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Storage stability test As a confirmation of storage stability, a deterioration test against air was conducted by a heating acceleration test. 1 g of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene was placed in a 50 mL quartz three-necked flask, and the whole container was heated to 50 ° C., Thereafter, air was circulated at a flow rate of 3 L / min for 3 hours under normal pressure. In appearance, 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene was not changed. Then, after returning a container to room temperature and replacing the inside of a container with dry nitrogen, when it formed into a film like said (1), the film | membrane which has a metallic luster on the board | substrate was obtained. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
(1) Formation of ruthenium film The experiment was carried out in a glove box controlled in a dry nitrogen atmosphere. 1,1,3,3-Tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] rutenadisilole obtained in Synthesis Example 1 To 100 g, dry toluene was added to make a total amount of 2.00 g, and 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [d] [ A composition for forming a metal ruthenium film containing 33% by mass of [2,1,3] ruthena disilole was prepared.
1,1,3,3-Tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1 prepared by the above method by mounting a silicon substrate on a spin coater , 3] 2 mL of a composition for forming a metal ruthenium film containing 33% by mass of ruthenadicirole was dropped, and spinning was performed at a rotation speed of 500 rpm for 10 seconds. This substrate was heated on a hot plate at 150 ° 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 143 mm. When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that it was metal ruthenium. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Storage stability test As a confirmation of storage stability, a heat deterioration test was conducted. In a glove box at room temperature in a dry nitrogen atmosphere, 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-in a pressure-resistant stainless steel container with a capacity of 100 mL. 1 g of benzo [d] [2,1,3] rutenazicilol was accommodated and sealed. Then, the whole container was heated at 80 degreeC with the thermostat, and was stored for 1 month. Thereafter, the container was returned to room temperature, and the inside of the container was replaced with dry nitrogen gas, and then opened. As a result, the appearance was 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1 No change in, 3-dihydro-benzo [d] [2,1,3] ruthenadisilol was observed. Further, when a film was formed in the same manner as in the above (1), a film having a metallic luster was obtained on the substrate. The film thickness was 140 mm.
When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that it was metal ruthenium. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]
(1) Formation of Ruthenium Film 1,1,3,3-Tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2, obtained in Synthesis Example 2 1,3] rutenadicylol is added to 1.00 g of dried toluene to give a total amount of 4.00 g to 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3- A composition for forming a metal ruthenium film containing 25% by mass of dihydro-benzo [d] [2,1,3] ruthenadicillol was prepared.
Formation of a metal ruthenium film containing 33% by mass of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilole 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] prepared by the above method instead of the composition for use A film was formed in the same manner as (1) of Example 5 except that the composition for forming a metal ruthenium film containing 25% by mass of ruthena disilole was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Test of storage stability As confirmation of storage stability, 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2, 1,1,3,3-Tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2] obtained in Synthesis Example 2 instead of 1,3] rutenadicylol , 1, 3] A deterioration test against heat was carried out in the same manner as in (2) of Example 5 except that rutenazicilol was used. In appearance, no change of 1,1,3,3-tetrachloro-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol was observed . Further, when a film was formed in the same manner as in the above (1), a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 7]
(1) Formation of Ruthenium Film 1,1,3,3-Tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [d] obtained in Synthesis Example 3 2,1,3] rutenadisilole is added to 1.00 g of dried ethylene glycol diethyl ether to make a total amount of 5.00 g. 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2- A composition for forming a metal ruthenium film containing 20% by mass of tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol was prepared.
Formation of a metal ruthenium film containing 33% by mass of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilole 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1, 3] A film was formed in the same manner as (1) of Example 5 except that the composition for forming a metal ruthenium film containing 20% by mass of ruthenadicirole was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Test of storage stability As confirmation of storage stability, 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2, 1,1,3] 1,1,3,3-Tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] obtained in Synthesis Example 3 instead of 1,3] rutenadicylol A deterioration test against heat was carried out in the same manner as in (2) of Example 5 except that [2,1,3] rutenazicilol was used. In appearance, changes in 1,1,3,3-tetrakistrifluoromethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilol were observed. There wasn't. When the film was formed in the same manner as (1) above, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 8]
(1) Ruthenium film formation 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene obtained in Synthesis Example 4 was dried to 1.00 g. N-butanol was added to make the total amount 2.50 g, and 40% by mass of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disilalenolene was contained. A composition for forming a metal ruthenium film was prepared.
Formation of a metal ruthenium film containing 33% by mass of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2,1,3] ruthenadisilole Metal ruthenium film formation containing 40% by mass of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene prepared by the above method instead of the composition for use A film was formed in the same manner as (1) of Example 5 except that the composition for use was used. As a result, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Test of storage stability As confirmation of storage stability, 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-1,3-dihydro-benzo [d] [2, Except for using 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene obtained in Synthesis Example 4 instead of [1,3] rutenadicylol A deterioration test against heat was performed in the same manner as in Example 2 (2). On the appearance, no change of 1,1,3,3-tetramethyl-2,2,2,2-tetracarbonyl-2,1,3-disitalenolene was observed. When the film was formed in the same manner as (1) above, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
(1) Formation of Ruthenium Film 0.01 g of commercially available bis (ethylcyclopentadienyl) ruthenium was weighed into a quartz boat container in nitrogen gas and set in a quartz reaction vessel. A quartz substrate is placed near the downstream side of the air flow in the reaction vessel, and an oxygen / nitrogen mixed gas (oxygen content: 5% by volume) is allowed to flow in the reaction vessel at a flow rate of 250 mL / min for 60 minutes at room temperature. . Thereafter, an oxygen / nitrogen mixed gas (oxygen content: 5% by volume) was allowed to flow into the reaction vessel at a flow rate of 20 mL / min, the system was further set to 110 Pa, and the reaction vessel was heated to 350 ° C. for 30 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, the pressure is restored, and then nitrogen gas is flowed at 101.3 kPa at a flow rate of 200 mL / min. A glossy film was obtained. The film thickness was 850 mm.
When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that it was metal ruthenium. When the resistivity of this ruthenium film was measured by the four-terminal method, it was 25 μΩcm. The film density of this film was 12.1 g / cm ³ . When the ruthenium film formed here was evaluated for adhesion to the substrate by a cross-cut tape method, no peeling between the substrate and the ruthenium film was observed.

(2) Storage stability test A commercial accelerated bis (ethylcyclopentadienyl) ruthenium was subjected to a heating acceleration test as a study on air deterioration as in (2) of Example 1. Bis (ethylcyclopentadienyl) ruthenium (1 g) was placed in a 50 mL quartz three-necked flask, the whole container was heated to 50 ° C., and then air was passed under normal pressure at a flow rate of 3 L / min for 3 hours. As a result, the appearance of bis (ethylcyclopentadienyl) ruthenium, which was originally a light yellow transparent liquid, changed to a yellow opaque liquid. Thereafter, the container was returned to room temperature, the inside of the container was replaced with dry nitrogen gas, and a film was formed in the same manner as in the above (1). As a result, a film having a slightly black metallic luster was obtained on the substrate. The film thickness was 300 mm.
When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that it was metal ruthenium. Further, when the resistivity of this ruthenium film was measured by the four-terminal method, it showed only a low conductivity of 78 μΩcm. The film density of this film was 12.1 g / cm ³ . The ruthenium film formed here was evaluated for adhesion to the substrate by a cross-cut tape method. As a result, 80 ruthenium films were peeled out of 100 cross-cut ruthenium films, and the quality of the ruthenium film was remarkably deteriorated. As described above, bis (ethylcyclopentadienyl) ruthenium has deteriorated ruthenium metal film quality formed by the air exposure heating test.

  From Table 1, it can be seen that the ruthenium film-forming materials of the present invention (Examples 1 to 8) are less susceptible to deterioration such as oxidation during storage in the air and are excellent in storage stability. It can also be seen that the ruthenium film formed using the ruthenium film-forming material of the present invention has excellent adhesion to the substrate. On the other hand, it can be seen that the ruthenium film-forming material (Comparative Example 1) not corresponding to the present invention is inferior in storage stability and adhesion after storage.

Claims (7)

A ruthenium film-forming material containing a compound represented by the following general formula (1).

(In General Formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group having 1 to 10 carbon atoms. , R ⁵ is a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms.)   The ruthenium film-forming material according to claim 1, which is used for chemical vapor deposition.   A ruthenium film forming method using the ruthenium film forming material according to claim 1.   A ruthenium film forming material supplying step for supplying the ruthenium film forming material according to claim 2 onto the substrate, and film formation for thermally decomposing the ruthenium film forming material to form a ruthenium film on the substrate And a ruthenium film forming method.   The ruthenium film forming method according to claim 4, wherein the thermal decomposition temperature in the film forming step is 100 ° C. to 800 ° C. 5.   The ruthenium film forming method according to claim 4 or 5, wherein the thermal decomposition in the film forming step is performed in an inert gas or a reducing gas.   A ruthenium film forming method comprising: forming a ruthenium film on the substrate by applying the ruthenium film-forming material according to claim 1 on the substrate and then performing heat treatment and / or light treatment.