JP4277195B2 - Chemical vapor deposition material and method for producing metal tungsten film - Google Patents

Description

The present invention relates to a tungsten compound as a chemical vapor deposition material and a method for producing metallic tungsten by chemical vapor deposition using the same.

  At present, the advancement of technology in the field of electronic devices is remarkable, and in order to further improve the signal processing speed, device miniaturization is progressing, and in particular, miniaturization of a conductor (wiring) portion is required. However, since the electrical resistance is inevitably increased when the wiring is made thinner, a material having a lower resistance has been demanded as a material for forming the wiring.

  And the current mainstream wiring material is aluminum, and copper is considered the mainstream as the next generation material.

  However, it is known that when aluminum is used as a wiring material for an electric device, when the wiring surface comes into contact with air, the vicinity of the surface is easily oxidized, and the signal transmission / reception speed decreases. In particular, when aluminum or copper is used as the wiring material of a thin layer transistor (TFT), aluminum atoms or copper atoms forming the wiring diffuse into the silicon from the portion in contact with silicon as the substrate material, and the TFT It is known that performance may be impaired.

  Therefore, a so-called contact plug layer for preventing oxidation is provided at a signal transmitting / receiving portion in the aluminum wiring, and a barrier layer for preventing diffusion between aluminum or copper as a wiring material and a silicon substrate. It has been studied to provide (see Patent Documents 1 and 2). Patent Documents 1 and 2 also describe that tungsten is suitable as such a contact plug material and barrier material.

As a method for forming a tungsten film, a sputtering method has been conventionally known (see Patent Document 3), but in recent years, a chemical vapor deposition method (CVD method) has been proposed in order to cope with a more miniaturized film structure and mass productivity. (See Non-Patent Document 1 and Patent Document 4). Non-Patent Document 1 discloses that a tungsten film can be deposited on a substrate by performing chemical vapor deposition using W (CO) ₆ as a chemical vapor deposition material. However, W (CO) _{6 as} a raw material has poor stability in the air, and has a problem in handling because of low solubility in a normal organic solvent.

Patent Document 1 discloses a method of forming a tungsten film by chemical vapor deposition using WF ₆ and hydrogen as raw materials. This method is used when a tungsten film is formed on titanium nitride. This relates to the improvement of adhesion, and no investigation has been made on the adhesion to silicon, aluminum or copper, which is the object of the present invention.
Japanese Patent Laid-Open No. 2001-7204 Japanese Unexamined Patent Publication No. 7-135186 JP 2003-171760 A JP-T-2001-524261 J. et al. Electrochem. Soc. , 117, 693 (1970)

The present invention has been made in view of the above problems, and its object is to obtain a good-quality film-like metallic tungsten by a safe process, and for chemical vapor deposition that can be easily handled in air. It is to provide a chemical vapor deposition material .

Another object of the present invention is to provide a method for producing a metal tungsten film using the chemical vapor deposition material .

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
W (RCN) _n (CO) _6-n (1)
Here, R is a C1-C10 hydrocarbon group or a C1-C10 halogenated hydrocarbon group, and n is an integer of 0-6. However, when n is an integer of 2-6, several R may mutually be same or different.
It is achieved by a chemical vapor deposition material comprising a compound represented by

In addition, according to the present invention, the above objects and advantages of the present invention are secondly achieved by a method for producing a metal tungsten film from the chemical vapor deposition material of the present invention by chemical vapor deposition .

According to the present invention, a high-quality film-like metallic tungsten can be obtained, and a chemical vapor deposition material for chemical vapor deposition that is more stable in air and chemical vapor deposition using the same. A method is provided.

  Hereinafter, the present invention will be described in detail.

(Chemical Vapor Deposition Material)
The tungsten compound as the chemical vapor deposition material of the present invention is represented by the above formula (1).

  In said formula (1), R is a C1-C10 hydrocarbon group or a C1-C10 halogenated hydrocarbon group. Preferably it is a C1-C8 hydrocarbon group or a C1-C6 halogenated hydrocarbon group, More preferably, it is a C1-C8 linear or branched alkyl group and C1-C6. A haloalkyl group. Examples of such groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, phenyl, trifluoromethyl, 1,1,1 -A trifluoroethyl group, a trichloromethyl group, and a 1,1,1-trichloroethyl group can be mentioned.

  Moreover, n is an integer of 1-6 in the said Formula (1). When n is an integer of 2 to 6, a plurality of R may be the same or different. N is preferably 2 to 4, particularly preferably 3.

  The tungsten compound is a D.I. P. Tate, W.W. R. Knipple and J.M. M.M. Augl, Inorganic. Chem. , Vol. 1, No. 1 2 (1962) 433, W.W. Strohmeir and G.M. Schonauer, Chem. Ber. , Vol. 94, (1961) 1346.

  Examples of the tungsten compound represented by the above formula (1) include hexa (acetonitrile) tungsten, penta (acetonitrile) carbonyltungsten, tetra (acetonitrile) dicarbonyltungsten, tri (acetonitrile) tricarbonyltungsten, di (acetonitrile) tetracarbonyl. Tungsten, (acetonitrile) pentacarbonyltungsten, hexa (propionitrile) tungsten, penta (propionitrile) carbonyltungsten, tetra (propionitrile) dicarbonyltungsten, tri (propionitrile) tricarbonyltungsten, di (propio) Nitrile) tetracarbonyltungsten, (propionitrile) pentacarbonyltungsten, hexa (butyronitrile) tongue Ten, penta (butyronitrile) carbonyltungsten, tetra (butyronitrile) dicarbonyltungsten, tri (butyronitrile) tricarbonyltungsten, di (butyronitrile) tetracarbonyltungsten, (butyronitrile) pentacarbonyltungsten, hexa (isobutyronitrile) tungsten, penta (Isobutyronitrile) carbonyltungsten, tetra (isobutyronitrile) dicarbonyltungsten, tri (isobutyronitrile) tricarbonyltungsten, di (isobutyronitrile) tetracarbonyltungsten, (isobutyronitrile) pentacarbonyl Tungsten, hexa (valeronitrile) tungsten, penta (valeronitrile) carbonyl tungsten, tetra (valeronite) Lu) dicarbonyltungsten, tri (valeronitrile) tricarbonyltungsten, di (valeronitrile) tetracarbonyltungsten, (valeronitrile) pentacarbonyltungsten, hexa (valeronitrile) tungsten, penta (valeronitrile) carbonyltungsten, tetra (valero) Nitrile) dicarbonyltungsten, tri (valeronitrile) tricarbonyltungsten, di (valeronitrile) tetracarbonyltungsten, (valeronitrile) pentacarbonyltungsten, hexa (trimethylacetonitrile) tungsten, penta (trimethylacetonitrile) carbonyltungsten, tetra (trimethyl) Acetonitrile) dicarbonyltungsten, tri (trimethylacetonitrile) trica Rubonyl tungsten, di (trimethylacetonitrile) tetracarbonyltungsten, (trimethylacetonitrile) pentacarbonyltungsten, hexa (benzonitrile) tungsten, penta (benzonitrile) carbonyltungsten, tetra (benzonitrile) dicarbonyltungsten, tri (benzonitrile) tri Carbonyl tungsten, di (benzonitrile) tetracarbonyl tungsten, (benzonitrile) pentacarbonyl tungsten, hexa (trichloroacetonitrile) tungsten, penta (trichloroacetonitrile) carbonyl tungsten, tetra (trichloroacetonitrile) dicarbonyl tungsten, tri (trichloroacetonitrile) tri Carbonyl tungsten, di (trichloroa Tonitoriru) tetracarbonyl tungsten, may be mentioned as being preferred and (trichloroacetonitrile) pentacarbonyl tungsten.

  Of these, tetra (acetonitrile) dicarbonyltungsten, tri (acetonitrile) tricarbonyltungsten, di (acetonitrile) tetracarbonyltungsten, tetra (propionitrile) dicarbonyltungsten, tri (propionitrile) tricarbonyltungsten , Di (propionitrile) tetracarbonyltungsten, tetra (valeronitrile) dicarbonyltungsten, tri (valeronitrile) tricarbonyltungsten, di (valeronitrile) tetracarbonyltungsten, tetra (trimethylacetonitrile) dicarbonyltungsten, tri (trimethyl) Acetonitrile) tricarbonyltungsten and di (trimethylacetonitrile) tetracarbonyltungsten It is.

  More preferably, tetra (acetonitrile) dicarbonyltungsten, tri (acetonitrile) tricarbonyltungsten, di (acetonitrile) tetracarbonyltungsten, tri (propionitrile) tricarbonyltungsten, tetra (valeronitrile) dicarbonyltungsten, tri (valero) Nitrile) tricarbonyltungsten and di (valeronitrile) tetracarbonyltungsten are used.

  Furthermore, particularly preferably, tri (acetonitrile) tricarbonyltungsten, tri (propionitrile) tricarbonyltungsten, tetra (valeronitrile) dicarbonyltungsten, tri (valeronitrile) tricarbonyltungsten are used.

  These compounds can be used alone or as a mixture of two or more chemical vapor deposition materials. One chemical vapor deposition material is preferably used alone.

  In addition, the chemical vapor phase material of the present invention vaporizes and heats the material itself and introduces it into the reaction vessel. However, since the tungsten compound of the present invention has high solubility in a solvent, it can be uniformly dissolved in a solvent. The solution may be introduced into the reactor, vaporized, or heated.

  The solvent used is not particularly limited as long as it dissolves these chemical vapor deposition materials and does not react with the solvent. For example, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, decane, cyclodecane, dicyclopentadiene hydride, benzene, toluene, xylene, durene, indene, tetrahydro Hydrocarbon solvents such as naphthalene, decahydronaphthalene, squalane; 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, anisole, 2-methylanisole, ether solvents such as 4-methylanisole; nitriles such as acetonitrile, propionitrile, benzonitrile; propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, Polar solvents such as dimethylformamide, dimethyl sulfoxide, methylene chloride, chloroform; and methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, decanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether Examples thereof include alcohols such as tellurium, propylene glycol monoethyl ether, glycerol, glycerol monomethyl ether, glycerol dimethyl ether, glycerol monoethyl ether, and glycerol diethyl ether; esters having a hydroxyl group such as methyl lactate and ethyl lactate. Of these, hydrocarbon solvents, ether solvents, nitriles, or mixed solvents of these solvents are preferred in terms of the solubility of the chemical vapor deposition material and the stability of the solution. Particularly preferably, n-pentane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, decane, cyclodecane, benzene, toluene, xylene, diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, Examples include tetrahydropyran, p-dioxane, anisole, 2-methylanisole, 4-methylanisole, acetonitrile, propionitrile, and benzonitrile. These solvents can be used singly or as a mixture of two or more.

(Chemical vapor deposition method)
The chemical vapor deposition method of the present invention is characterized by using the above chemical vapor deposition material.

  As the chemical vapor deposition method of the present invention, a method known per se can be used except that the chemical vapor deposition material of the present invention is used. For example, it can be carried out as follows.

  (A) The chemical vapor deposition material of the present invention is vaporized, and then (B) the gas is heated to thermally decompose the chemical vapor deposition material to deposit tungsten on the substrate.

  As 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, but materials that can withstand the process temperature for thermally decomposing chemical vapor deposition materials are used. Preferably it is.

  In the step (A), the temperature for vaporizing the chemical vapor deposition material is preferably 80 to 400 ° C, more preferably 100 to 300 ° C.

  In the said process (B), as temperature which makes a chemical vapor deposition material thermally decompose, it becomes like this. Preferably it is 80-600 degreeC, More preferably, it is 200-500 degreeC. This thermal decomposition temperature can be realized by preheating the substrate.

  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 and 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, argon, helium, and the like. Examples of the reducing gas include hydrogen and ammonia.

Further, the chemical vapor deposition method of the present invention can be carried out under any conditions under pressure, normal pressure, and reduced pressure, but is preferably carried out under normal pressure or reduced pressure, and 15,000 Pa or less. More preferably, it is carried out under the following pressure.
The tungsten film obtained as described above has high purity and electrical conductivity, as will be apparent from examples described later. For example, a multilayer wiring material, a plug material for a fine contact hole, a barrier film for preventing copper diffusion, etc. Can be suitably used. Further, as will be apparent from the examples described later, it is stable in the air and can be stably used in the chemical vapor deposition method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.

  In the following examples, elemental analysis was performed by a model “JM10” manufactured by J-Science Lab. The specific resistance was measured by a probe resistivity measuring device manufactured by Napson, model “RT-80 / RG-80”. The film thickness was measured by an oblique X-ray analyzer manufactured by Philips Co., Ltd., model “X′Pert MRD”. The ESCA spectrum was measured by JEOL Co., Ltd. model “JPS80”.

Synthesis example 1
In a 200 mL flask purged with nitrogen, 5 g of hexacarbonyltungsten (W (CO) ₆ ) was weighed and placed under reduced pressure at 25 ° C. for 30 minutes. Next, dry nitrogen was introduced into the flask, and the pressure was brought to normal pressure. Then, 100 mL of well-dried acetonitrile was added. The mixture was heated under a nitrogen stream under acetonitrile reflux and stirred for 40 hours. During the heating and stirring, hexacarbonyltungsten was dissolved in the solvent. After completion of stirring and heating, the reaction solution was returned to room temperature, and the solution was collected by filtration using Teflon filter paper manufactured by Advantech Toyo Co., Ltd., model “PF040”, and the solution was cooled to 0 ° C. under nitrogen. A yellow precipitate was deposited in the flask. The precipitated solid was collected by filtration using the same filter paper as described above under nitrogen, transferred to a 100 mL flask, and placed under reduced pressure at 25 ° C. for 2 hours. Next, dried nitrogen was introduced into the flask to obtain 4.5 g of tri (acetonitrile) tricarbonyltungsten as a light yellow solid under normal pressure (yield 81%).

  When elemental analysis of the solid obtained above was performed, C: 27.6%, H: (relative to calculated values C: 27.64%, H: 2.32%, N: 10.75%). 2.2%, N: 10.5%, and confirmed to be tri (acetonitrile) tricarbonyltungsten.

Synthesis example 2
In a 200 mL flask purged with nitrogen, 5 g of hexacarbonyltungsten (W (CO) ₆ ) was weighed and placed under reduced pressure at 25 ° C. for 30 minutes. Next, after introducing dry nitrogen into the flask to bring it to normal pressure, 100 mL of well-dried valeronitrile was added. It heated at 120 degreeC under nitrogen stream, and stirred for 40 hours. During the heating and stirring, hexacarbonyltungsten was dissolved in the solvent. After completion of stirring and heating, the reaction solution was returned to room temperature, and the solution was collected by filtration using Teflon filter paper manufactured by Advantech Toyo Co., Ltd., model “PF040”, and the solution was cooled to 0 ° C. under nitrogen. A white precipitate was deposited in the flask. The precipitated solid was collected by filtration using the same filter paper as described above under nitrogen, transferred to a 100 mL flask, and placed under reduced pressure at 25 ° C. for 2 hours. Next, dried nitrogen was introduced into the flask to obtain 3.9 g of tri (valeronitrile) tricarbonyltungsten as a white solid at normal pressure (yield 53%).

  When elemental analysis of the solid obtained above was performed, C: 41.5%, H: (relative to calculated values C: 41.80%, H: 5.26%, N: 8.12%) It was 5.1%, N: 8.4%, and confirmed to be tri (valeronitrile) tricarbonyltungsten.

Example 1
0.05 g of tri (acetonitrile) tricarbonyltungsten obtained in Synthesis Example 1 was weighed in a quartz boat-type vessel in nitrogen gas and set in a quartz reaction vessel. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added to the reaction vessel at 100 mL / min. Then, the inside of the system was set to 1,333 Pa, and the reaction vessel was heated at 150 ° 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 was completed, the decompression was stopped and a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added at 500 mL / min. When the reaction vessel was raised to 400 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 400 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. Moreover, when the specific resistance of the metal tungsten film was measured by the four-terminal method, it was 13.3 μΩcm.

Example 2
0.05 g of tri (acetonitrile) tricarbonyltungsten obtained in Synthesis Example 1 was weighed in a quartz boat-type vessel in nitrogen gas and set in a quartz reaction vessel. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, nitrogen gas was introduced into the reaction vessel at 100 mL / min. Then, the system was 667 kPa, and the reaction vessel was heated at 200 ° 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 was completed, the decompression was stopped and nitrogen gas was supplied at 500 mL / min. When the reaction vessel was raised to 450 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 430 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. Moreover, when the specific resistance of the metal tungsten film was measured by the four-terminal method, it was 14.1 μΩcm.

Example 3
0.05 g of tri (acetonitrile) tricarbonyltungsten obtained in Synthesis Example 1 was weighed in a quartz boat-type vessel in nitrogen gas and set in a quartz reaction vessel. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, nitrogen gas was introduced into the reaction vessel at 100 mL / min. The reaction vessel was further heated at 250 ° 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, nitrogen gas is added at 500 mL / min. When the reaction vessel was raised to 450 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 440 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. Moreover, when the specific resistance of the metal tungsten film was measured by the four-terminal method, it was 14.9 μΩcm.

Example 4
0.05 g of tri (valeronitrile) tricarbonyltungsten obtained in Synthesis Example 2 was weighed into a quartz boat-type vessel in nitrogen gas and set in a quartz reaction vessel. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added to the reaction vessel at 100 mL / min. Then, the inside of the system was set to 1,333 Pa, and the reaction vessel was heated at 180 ° 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 was completed, the decompression was stopped and a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added at 500 mL / min. When the reaction vessel was raised to 450 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 480 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. The specific resistance of the metal tungsten film measured by the four-terminal method was 20.1 μΩcm.

Example 5
0.05 g of tri (valeronitrile) tricarbonyltungsten obtained in Synthesis Example 2 and 2 mL of well-dried anisole were weighed and dissolved in a quartz boat-type container under a nitrogen stream, and then dissolved in a quartz reaction container. I set it. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added to the reaction vessel at 100 mL / min. The reaction system was heated to 200 ° 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 was completed, the decompression was stopped and a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added at 500 mL / min. When the reaction vessel was raised to 450 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 470 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. Further, when the specific resistance of the metal tungsten film was measured by the 4-terminal method, it was 22.4 μΩcm.

Example 7
0.05 g of tri (acetonitrile) tricarbonyltungsten obtained in Synthesis Example 1 was weighed in a quartz boat-type container in the air and left in a room kept at 25 ° C. for 2 days. There was no change in the appearance of the installed tri (acetonitrile) tricarbonyltungsten. The quartz boat was then set in a quartz reaction vessel under a nitrogen stream. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added to the reaction vessel at 100 mL / min. Then, the inside of the system was set to 1,333 Pa, and the reaction vessel was heated at 150 ° 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 was completed, the decompression was stopped and a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added at 500 mL / min. When the reaction vessel was raised to 400 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 400 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. Moreover, when the specific resistance of the metal tungsten film was measured by the four-terminal method, it was 13.5 μΩcm.

Comparative Example 1
Hexacarbonyltungsten (0.05 g) was weighed out in a quartz boat-type container in the air and left in a room kept at 25 ° C. for 2 days. Hexacarbonyltungsten darkened in appearance and turned light gray. The quartz boat was then set in a quartz reaction vessel under a nitrogen stream. A quartz substrate is placed near the airflow direction side in the reaction vessel, and nitrogen gas is supplied into the reaction vessel at 250 mL / min. For 30 minutes. Thereafter, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added to the reaction vessel at 100 mL / min. Then, the inside of the system was set to 1,333 Pa, and the reaction vessel was heated at 120 ° 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 was completed, the decompression was stopped and a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was added at 500 mL / min. When the reaction vessel was raised to 400 ° C. and held for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness was 400 mm. When the ESCA spectrum of this film was measured, a peak attributed to the W _{4f7 / 2} orbit was observed at 31.7 eV, and no peaks derived from other elements were observed, and it was found to be metallic tungsten. Further, when the specific resistance of the metal tungsten film was measured by the 4-terminal method, it was 28.0 μΩcm.

Claims (2)

Following formula (1)
W (RCN) _n (CO) _6-n (1)
Here, R is a C1-C10 hydrocarbon group or a C1-C10 halogenated hydrocarbon group, and n is an integer of 1-6. However, when n is an integer of 2-6, several R may mutually be same or different.
A chemical vapor deposition material comprising a compound represented by: A method for producing a metal tungsten film from the chemical vapor deposition material according to claim 1 by chemical vapor deposition .