JPH09199445A - Manufacture of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate the errosion of silicon by a method wherein a tungsten nitride film, which is used as a part of an electrode wiring, is formed by a chemical vapor deposition method using mixed gas containing an organic compound of tungsten, ammonia and carrier gas. SOLUTION: The second layer wiring is formed on a tungsten film 15 by successively depositing a titanium nitride film 17 using a sputtering method. A three-layer interlayer insulating film 18 is formed on the second layer wiring, and a tungsten nitride film 19, to be used as a part of an electrode wiring, is formed on the whole surface of substrate of the three-layer interlayer insulating film 18 by a chemical vapor phase growth method using the mixed gas containing an organic compound of tungsten such as hexakisditungsten and bistungstendiehydride, ammonia and carrier gas. As a result, the errosion of silicon can be eliminated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor device, and more particularly to a method of manufacturing electrodes and wirings of the semiconductor device.

[0002]

2. Description of the Related Art In a multilayer wiring technique for semiconductor devices, tungsten nitride has been studied as an adhesive layer for tungsten wiring and a barrier layer for aluminum-based laminated wiring. The use of the chemical vapor deposition method (CVD method) is indispensable for forming an adhesion layer or a barrier layer of tungsten nitride in a fine and high aspect ratio contact hole of a highly integrated semiconductor device. The tungsten nitride film is formed by the CVD method by thermal CVD method in Journal of the Electrochemical Society, Vol. 134, pages 3175-3178, and by plasma CVD method in Applied Physics Letters, vol. 62. Reported on pages 3312-3314.

[0003]

The tungsten hexafluoride and ammonia used as raw materials in the above-mentioned prior art are difficult to react with each other. Therefore, in order to react both, 6
A high temperature of about 00 ° C. (thermal CVD method) and plasma energy (plasma CVD method) are required. However, thermal CVD
Since the temperature is high in the method, problems such as silicon erosion due to the reaction between the raw material tungsten hexafluoride and silicon on the substrate and heat resistance of aluminum wiring occur, and cannot be applied to the wiring process of semiconductor devices. Further, the plasma CVD method has problems that the substrate is damaged by plasma, the step coverage of the film is low, and the apparatus is complicated and expensive. Therefore, none of the above conventional techniques can be applied to the manufacturing process of a fine semiconductor device.

An object of the present invention is to provide a W ₂ N film CVD method applicable to a wiring process of a semiconductor device.

[0005]

In order to achieve the above object, the present invention is achieved by using an organic compound of tungsten and ammonia as raw materials. Further, when an organic compound of tungsten having a functional group containing nitrogen such as an amino group is used as a raw material, the above object can be achieved without using ammonia.

The organic compound of tungsten is 250-40
Pyrolyzes at a low temperature of about 0 ° C. to produce tungsten.
Therefore, by adding ammonia to the raw material, the tungsten nitride film can be formed at a low temperature of about 250 to 400 ° C. without using plasma. Also, since the organic compound of tungsten does not react with the silicon substrate,
Silicon erosion does not occur during film formation, and since plasma is not used, plasma damage does not occur.

When a tungsten organic compound containing nitrogen is used as a raw material, a tungsten nitride film is formed without using ammonia by appropriately selecting reaction conditions so that nitrogen in the raw material is contained in the film. can do. Even in this case, 250-4 without using plasma
The film can be formed at 00 ° C, and silicon erosion does not occur. Tungsten organic compounds containing nitrogen include, for example, hexakis (dimethylamino) ditungsten (III) (molecular formula
W ₂ [N (CH ₃ ) ₂ ] ₆ ).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

(Embodiment 1) In the embodiment of the present invention, a tungsten nitride (hereinafter abbreviated as W ₂ N) film according to the present invention is used as a first layer of tungsten (hereinafter abbreviated as W) wiring adhesive layer and second and third layers. An example of using a layered aluminum alloy (hereinafter abbreviated as Al) wiring laminated film will be described.

FIG. 1 is a cross-sectional view of a semiconductor device manufactured according to an embodiment of the present invention, and FIGS. 2 to 4 are cross-sectional views showing a forming process according to the embodiment of the present invention.

As shown in FIG. 2A, p-type (100)
A 20 nm thick pad oxide film and a 120 nm thick silicon nitride film were formed on a silicon (hereinafter abbreviated as Si) substrate 1. Then, the silicon nitride film other than on the diffusion layer formation planned region was removed by the photolithography technique and the dry etching technique. Further, it was oxidized in a wet oxygen atmosphere at 1000 ° C. to form a device-isolated silicon oxide (hereinafter abbreviated as SiO ₂ ) film 2 having a thickness of 400 nm.

As shown in FIG. 2B, a SiO ₂ film 3 having a thickness of 4 nm is formed by thermal oxidation, and then a 200 nm-thick n-type polycrystalline Si film 4 containing phosphorus is formed by a low pressure CVD method. Formed. Then, the n-type polycrystalline Si film 4 was processed into a shape of a gate electrode having a gate length of 200 nm by an electron beam lithography technique and a dry etching technique. Next, using the gate electrode as a mask, the first ion implantation was performed on the diffusion layer formation planned region 5. Here, 4 nm thick S
Arsenic ions of 1 × 10 ¹⁴ cm ⁻² were implanted at ¹⁵ keV through the iO ₂ film.

As shown in FIG. 2C, high temperature (750 ° C.) using monosilane gas and nitrous oxide gas as source gases
After forming the SiO ₂ film 6 of 130nm thickness by the thermal CVD method, to process the SiO ₂ film 6 to the shape of the gate sidewall spacers by a dry etching technique. Then, using the gate electrode and the gate sidewall spacer as a mask, a second ion implantation was performed on the diffusion layer formation planned region 5. Here 5
Arsenic ions of 5 × 10 ¹⁵ cm ⁻² were implanted at 0 keV. Then, heat treatment was performed in a nitrogen atmosphere at 800 ° C. to form the diffusion layer 7. The junction depth was 50 nm and 100 nm in the lower portion of the gate electrode and the diffusion layer portion other than that, respectively.

As shown in FIG. 2D, plasma CVD
The phosphorus-doped SiO ₂ (hereinafter abbreviated as PSG) film 8 by
After forming, the contact hole 9 was opened by the electron beam lithography technique and the dry etching technique.

As shown in FIG. 2E, a W ₂ N film 10 having a thickness of 50 nm is formed on the entire surface of the substrate by a CVD method using hexakis (dimethylamino) ditungsten (III) and ammonia (hereinafter abbreviated as NH ₃ ) as raw materials. Deposited by. here,
Since hexakis (dimethylamino) ditungsten (III) is a solid, it is made into a 0.1 mol / l toluene solution, the flow rate is controlled by a liquid mass flow controller, and then vaporized to form argon (hereinafter abbreviated as Ar) as a carrier gas. It was introduced into the membrane chamber. The CVD conditions for the W ₂ N film are: substrate temperature of 400 ° C., toluene solution flow rate of 5 ml / min, NH
The flow rates of ₃ and Ar were 100 and 200 sccm, respectively, and the film forming pressure was 100 Pa.

Here, when the cross section of the contact hole 9 was observed with a scanning electron microscope, the silicon substrate 1 and W ₂ N
It was confirmed that the interface of the film 10 was smooth and no silicon erosion occurred.

The CVD conditions for forming the W ₂ N film are not limited to the above conditions. The concentration of the toluene solution is 0.
It may be 01 mol / l or more and 0.123 mol / l (saturation concentration) or less, more preferably 0.04 mol / l or more and 0.11 m.
It may be ol / l (90% of saturation concentration) or less. If the substrate temperature is in the range of 250 ° C. or higher and 500 ° C. or lower, a practical deposition rate can be obtained. The flow rate of the toluene solution is
From the viewpoint of obtaining a practical deposition rate and effective use of the raw material, it may be 0.5 ml / min or more and 50 ml / min or less.

The flow rate of the toluene solution is 5 ml / min.
In this case, if the flow rate of NH ₃ is in the range of 10 sccm or more and 2000 sccm or less and the flow rate of Ar is in the range of 50 sccm or more and 5000 sccm or less, a WN ₂ film with good film quality can be formed. When the flow rate of the toluene solution is not 5 ml / min, the flow rates of NH ₃ and Ar may be increased / decreased so that the ratio becomes the same. When the film forming pressure is 1 Pa or more and 1000 Pa or less, a W ₂ N film having good film quality can be formed.

Under the CVD condition, the raw material gas is 50 sccm or more 5
The W ₂ N film can be formed even by adding hydrogen gas (hereinafter abbreviated as H ₂ ) of 000 sccm or less. In this case, there is an advantage that the resistivity of the W ₂ N film is lowered by about 10%. Hexakis (dimethylamino) ditungsten (II
Since the structure I) has a structure in which nitrogen atoms are bonded to tungsten atoms, a W ₂ N film can be formed without using NH ₃ . Further, in the embodiment of the present invention, Ar
Was used as the carrier gas, but nitrogen gas can also be used as the carrier gas.

As shown in FIG. 3A, 300 n was formed by a CVD method using H ₂ and WF ₆ as raw materials (H ₂ reduction W-CVD method).
m W film 11 and then W film 11 and W ₂ N film 1
0 was processed by the lithography technique and the dry etching technique to form the wiring of the first layer. Subsequently, a three-layer interlayer insulating film 12 was formed as an interlayer insulating film by sandwiching a coating type silicon oxide film above and below with a PSG film formed by a plasma CVD method and then performing a planarization process. After that, the connection hole 13 was opened by the photolithography technique and the dry etching technique.

When the cross section of the contact hole 9 was observed with a scanning electron microscope, no silicon erosion was observed at the bottom of the contact hole. From this, it is understood that the W ₂ N film formed by the present invention has a sufficient barrier property against WF ₆ .

As shown in FIG. 3B, a thickness of 5 is formed on the entire surface of the substrate.
A 0 nm W ₂ N film 14 is formed with bis (cyclopentadienyl)
Using tungsten die hydride and NH ₃ as raw materials, C
It was deposited by the VD method. Here, since bis (cyclopentadienyl) tungsten dihydride is a solid,
A 0.15 mol / l tetrahydrofuran (hereinafter abbreviated as THF) solution was prepared and the flow rate was controlled by a liquid mass flow controller, and then vaporized and Ar was introduced into the film forming chamber as a carrier gas. The CVD conditions for the W ₂ N film are: substrate temperature of 350 ° C., THF solution flow rate of 3 ml / min, NH ₃ ,
The flow rates of Ar were 200 and 150 sccm, respectively, and the film forming pressure was 50 Pa.

Then, as shown in FIG. 4A, the W film 1
5 is formed by the H ₂ reduction W-CVD method, and then the entire surface is etched back to form the W film 15 and the W ₂ film only in the connection hole 13.
A W plug structure was formed while leaving the N 2 film 14. Then, titanium nitride (hereinafter abbreviated as TiN) is formed by sputtering.
The film 16 and the Al film 17 were sequentially deposited and then processed by the photolithography technique and the dry etching technique to form the second layer wiring.

Thereafter, as shown in FIG. 4B, a three-layer interlayer insulating film 18 was formed, and a contact hole was opened by the photolithography technique and the dry etching technique. Then hexakis (dimethylamino) ditungsten (III)
A W ₂ N film 19 having a thickness of 50 nm was formed on the entire surface of the substrate by the CVD method using a 1 mol / l THF solution and NH ₃ as raw materials. As for the CVD conditions, the substrate temperature is 400 ° C., the flow rate of the THF solution is 5 ml / min, the flow rates of NH ₃ , Ar and H ₂ are 100, 200 and 500 sccm, respectively, and the film forming pressure is 100 Pa.
Met.

After that, an Al film 20 was formed by a sputtering method, and the Al film 20 was subjected to a reflow treatment to fill the inside of the connection hole. Then, the Al film 20 and the W ₂ N film 19 are processed by the photolithography technique and the dry etching technique to form a third-layer wiring, and then heat treatment is performed in an H ₂ atmosphere at 450 ° C. to obtain the semiconductor shown in FIG. The device was made.

Since the semiconductor device formed as described above has no silicon corrosion, it has a small leak current at the junction and high reliability. Since the formation temperature of the W ₂ N film is low, the W ₂ N film can be formed by the CVD method even after the Al wiring of the second layer is formed. Further, Al and W ₂ N do not react with each other even when H ₂ heat treatment or reflow treatment is performed, and therefore there is an advantage that the resistance of the second and third layer wirings is low.

In the embodiment of the present invention, toluene or THF was used to dissolve the raw material tungsten organic compound, but another organic solvent, if the raw material can be dissolved,
For example, alcohols such as ethanol and isopropanol, ethers such as dibutyl ether and diethyl ether, hydrocarbons such as n-hexane and decane, aromatic compounds such as n-butylbenzene and benzene, amines such as diethylamine, diisopropylethylamine, triethylamine and triallylamine. Classes and the like can also be used. At this time, the concentration of the solution is 0.01 mol / l or more and the saturation concentration or less, preferably 0.04 mol / l or more and the saturation concentration of 9 or more.
It should be 0% or less. Further, in the embodiment of the present invention, the method of dissolving the solid raw material in the organic solvent and vaporizing it is adopted, but the raw material can be sublimated in the heating container and introduced into the film forming chamber by the carrier gas. Further, even if a tungsten organic compound other than the one used in the embodiment of the present invention, for example, bis (isopropylcyclopentadienyl) tungsten dihydride is used as a raw material, W ₂ N
A film can be formed.

In the embodiment of the present invention, the contact hole 9
Was directly formed W ₂ N film 10 within, it is also possible to form a W ₂ N film after forming a titanium film by sputtering. In this case, there is an advantage that the contact resistance between the silicon substrate and the first layer wiring becomes low. Further, in the embodiment of the present invention, H ₂ reduction W− is used to form the W film 11.
Although the CVD method was used, instead of this, a CVD method using silane difluoride (molecular formula SiH ₂ F ₂ ) and WF ₆ as raw materials (Si
The W film can also be formed by H ₂ F ₂ reduction W-CVD method).

(Second Embodiment) FIGS. 5 to 14 show a manufacturing process for forming a charge storage electrode of a semiconductor memory device according to a second embodiment of the present invention.

Si for element isolation is formed on the p-type (100) Si substrate 101 (FIG. 5) in the same manner as in the first embodiment of the invention.
After forming the O ₂ film 102, a gate SiO ₂ film 103 having a thickness of 5 nm was formed on the substrate surface (FIG. 6).

For the gate electrode, a 70 nm-thick n-type polycrystalline Si film 104 doped with 1 × 10 ²⁰ cm ^{-3 of} phosphorus was formed, and further a 100 nm-thick SiO ₂ film 105 was formed (FIG. 7). . Next, the SiO ₂ film 105 and the n-type polycrystalline Si film 1 are formed by using the lithography technique and the dry etching technique.
04 was processed and the gate electrode 104 was formed. afterwards,
Using the gate electrode as a mask, arsenic ion implantation is performed under the conditions of an acceleration energy of 25 keV and a dose of 2 × 10 ¹⁵ cm ⁻² , and heat treatment is performed in a nitrogen atmosphere at 750 ° C. for 30 minutes to perform n-type impurity region 107. Was formed (FIG. 8).

Then, a SiO ₂ film 106 for a gate side wall spacer having a thickness of 50 nm was formed, and then a Si ₃ N ₄ film 108 having a thickness of 200 nm was formed to etch back the entire surface (FIG. 9).

After a contact hole was formed in a predetermined portion of Si ₃ N ₄ on the n-type impurity layer by using a lithography technique and a dry etching technique, phosphorus was doped at 1 × 10 ²⁰ cm ^-3 to a thickness of 200 nm. An n-type polycrystalline Si film is formed, and the entire surface is etched back to form n-type polycrystalline Si in the contact hole.
109 was embedded (FIG. 10).

[0033] Next, an Si ₃ N ₄ film 121 having a thickness of 30 nm, after forming the SiO ₂ film 122 of the further thickness 200 nm, SiO ₂ film 122 of the charge storage electrode region 123
And the Si ₃ N ₄ film 121 were etched by using a lithography technique. After that, a W ₂ N film 124 having a thickness of 50 nm is formed on the film by using hexakis (dimethylamino) ditungsten (III) and NH 3.
_It was formed by a CVD method using ₃ as a raw material. Here, hexakis (dimethylamino) ditungsten (III) was used as a normal butylbenzene solution having a concentration of 0.04 mol / l. Other conditions are vaporizer temperature = 180 ° C., raw material solution flow rate = 10 ml / min, NH ₃ flow rate = 100 scc
m, Ar flow rate = 500 sccm, H ₂ flow rate = 200 sccm, substrate temperature = 300 ° C., film formation pressure = 200 Pa. Then, after forming a SiO ₂ film 125 having a thickness of 200 nm, the SiO ₂ film 125 and the W ₂ N film 124 on the surface were etched back to form the lower electrode 124 of the charge storage capacitor (FIG. 11).

The SiO ₂ film 125 and the SiO ₂ film 122 are set to H
CV using penta (ethoxy) tantalum (molecular formula Ta (OH ₅ C ₂ ) ₅ ) and O ₂ as raw materials after removal with an aqueous solution of F
A Ta ₂ O ₅ film 126 having a thickness of 10 nm was formed by the D method. Then, a TiN film 127 having a thickness of 50 nm was formed by the CVD method. The TiN film 127 is formed under the following conditions: titanium tetrachloride flow rate is 5 sccm, NH ₃ flow rate is 70 sccm, and substrate temperature is 5 sccm.
The film forming pressure was 00 ° C., the film forming pressure was 40 Pa, and the film forming time was 5 min. Then, an opening 128 in the bit line contact region was formed by dry etching (FIG. 12).

Then, a SiO ₂ (BPSG) film 113 containing boron and phosphorus having a thickness of 500 nm was formed, annealed at 750 ° C. for 10 minutes to fluidize and flatten, and then a bit line contact hole was opened. Next, CVD using bis (cyclopentadienyl) tungsten and NH ₃ as raw materials
Method and SiH ₂ F ₂ reduction method to obtain W ₂ N having a thickness of 50 nm.
A film 114 and a W film 115 having a thickness of 100 nm were successively formed, and then processed by a lithography technique and a dry etching technique to form a data line (FIG. 13).

Here, the concentration of 0.1 mol is used for forming the W ₂ N film.
/ L toluene solution, vaporizer temperature 150 ° C, raw material solution flow rate 3 ml / min, NH ₃ flow rate 100 sccm,
The Ar flow rate was 500 sccm, the H ₂ flow rate was 1000 sccm, the substrate temperature was 300 ° C., and the film forming pressure was 200 Pa. The film formation conditions for the W film by the SiH ₂ F ₂ reduction method are WF ₆
Flow rate is 100 sccm, SiH ₂ F ₂ flow rate is 400 sccm, Ar
Flow rate is 300sccm, substrate temperature is 400 ℃, deposition pressure is 7
It was 0 Pa.

Then, a thickness of 3 is formed by a plasma CVD method.
After forming the SiO ₂ film 129 having a thickness of 00 nm, the connection hole was opened by the lithography technique and the dry etching technique. Then, using hexakis (dimethylamino) ditungsten (III) as a raw material, a thickness of 70 nm was obtained by a CVD method.
Of W ₂ N film 130 was formed. Here, hexakis (dimethylamino) ditungsten (III) was used after being sublimated at 180 ° C. Carrier gas Ar flow rate is 150scc
m, the substrate temperature was 400 ° C., the film forming pressure was 100 Pa, and NH ₃ was not used. Then, after forming an Al film 131 having a thickness of 300 nm by a sputtering method, the Al film 1 is formed.
31 and the W ₂ N film 130 were processed to form Al / W ₂ N laminated wiring. In this way, a semiconductor memory device can be formed (FIG. 14).

In the embodiment of the present invention, the lower electrode 124 is used.
Is W ₂ N, the electrode surface is less likely to be oxidized when the Ta ₂ O ₅ film 126 is formed, and the capacitance of the capacitor is larger than that when the lower electrode is W.

Although the lower electrode of the charge storage capacitor is formed of the W ₂ N film in the embodiment of the present invention, the upper electrode is also made of Ti.
Instead of the N film 127, a W ₂ N film can be formed.
Further, although the Ta ₂ O ₅ film 126 is used as the capacitor insulating film, instead of this, a high dielectric constant film such as lead zirconate titanate (PZT), strontium barium titanate (BST) or strontium titanate (STO) is used. Can also be used for the capacitor insulating film. In this case, the lower electrode must be made of platinum, but the upper electrode must be made of W ₂
An N 2 film can be used.

In the embodiment of the present invention, the Al / W ₂ N laminated wiring is used for the wiring of the second layer, but instead of this, Cu /
It is also possible to use a laminated wiring of W ₂ N for the wiring of the second layer.

[0041]

According to the present invention, it is possible to form a W ₂ N film at a low temperature of about 250 ° C. -400 ° C., no silicon erosion, can form a W ₂ N film also on the Al wiring. Further, since plasma is not used, it is not necessary to use a complicated and expensive device, which is effective in reducing the manufacturing cost of the semiconductor device.

[Brief description of drawings]

FIG. 1 is a sectional view showing the structure of a first embodiment of the present invention.

FIG. 2 is an explanatory view showing a first manufacturing process of the first embodiment of the present invention.

FIG. 3 is an explanatory view showing a second manufacturing step of the first embodiment of the present invention.

FIG. 4 is an explanatory view showing a third manufacturing process of the first embodiment of the present invention.

FIG. 5 is an explanatory view showing a fourth manufacturing step of the first embodiment of the present invention.

FIG. 6 is an explanatory view showing the first manufacturing process of the second embodiment of the present invention.

FIG. 7 is an explanatory diagram showing a second manufacturing step of the second embodiment of the present invention.

FIG. 8 is an explanatory view showing a third manufacturing step of the second embodiment of the present invention.

FIG. 9 is an explanatory view showing a fourth manufacturing step of the second embodiment of the present invention.

FIG. 10 is an explanatory diagram showing a fifth manufacturing step of the second embodiment of the present invention.

FIG. 11 is an explanatory view showing the sixth manufacturing step of the second embodiment of the present invention.

FIG. 12 is an explanatory view showing a seventh manufacturing step of the second embodiment of the present invention.

FIG. 13 is an explanatory view showing an eighth manufacturing step of the second embodiment of the present invention.

FIG. 14 is an explanatory view showing the ninth manufacturing step of the second embodiment of the present invention.

[Explanation of symbols]

19 ... W ₂ N film, 20 ... Al film.

Claims (17)

[Claims] 1. A method of manufacturing a semiconductor device having multi-layer wiring, wherein a tungsten nitride film used as a part of an electrode wiring is formed by a chemical vapor deposition method using a mixed gas containing an organic compound of tungsten, ammonia and a carrier gas. A method of manufacturing a semiconductor device, which comprises forming the semiconductor device. 2. A method of manufacturing a semiconductor device according to claim 1, wherein the mixed gas contains hydrogen gas. 3. A method for manufacturing a semiconductor device, wherein a tungsten film is formed on the tungsten nitride film according to claim 1 by chemical vapor deposition. 4. The tungsten film according to claim 3,
A method for manufacturing a semiconductor device, which is formed by a chemical vapor deposition method using a gas containing tungsten hexafluoride and hydrogen as a raw material. 5. The tungsten film according to claim 3,
A method for manufacturing a semiconductor device, which is formed by a chemical vapor deposition method using a gas containing tungsten hexafluoride and silane difluoride as a raw material. 6. The tungsten nitride film and the tungsten film according to claim 3 are formed on a semiconductor substrate having fine holes on the surface thereof, and then the tungsten nitride film and the tungsten film are dry-etched over the entire surface,
A method of manufacturing a semiconductor integrated circuit device, wherein the tungsten nitride film and the tungsten film are left only in the fine holes. 7. A method of manufacturing a semiconductor device, wherein the tungsten nitride film according to claim 1 or 2 and an aluminum alloy film are laminated. 8. A method of manufacturing a semiconductor device, comprising laminating the tungsten nitride film according to claim 1 and a copper or copper alloy film. 9. A method of manufacturing a semiconductor device, wherein the tungsten nitride film according to claim 1 or 2 is used as an electrode of a charge storage capacitor of a semiconductor memory device. 10. A semiconductor device using the tungsten nitride film according to claim 1 or 2 as an electrode of a charge storage capacitor of a semiconductor memory device. 11. The organic compound of tungsten according to claim 1 or 2, wherein the organic compound of tungsten is hexakis (dimethylamino) ditungsten, bis (cyclopentadienyl) tungsten dihydride or bis (isopropylcyclopentadienyl) tungsten dihydride. And a method for manufacturing a semiconductor device. 12. The organic compound of tungsten according to claim 1 or 2 is dissolved in an organic solvent to form a solution, and the solution whose flow rate is controlled by a liquid mass flow controller is vaporized by a vaporizer, and then a carrier gas is used. A method for manufacturing a semiconductor device in which a tungsten nitride film is formed by sending it to a film formation chamber. 13. The concentration of the solution according to claim 12,
A method for manufacturing a semiconductor device, wherein the concentration is not less than 0.04 mol / l and not more than the saturation concentration of the organic compound of tungsten with respect to the organic solvent. 14. The organic solvent according to claim 13 includes alcohols such as ethanol and isopropanol, ethers such as dibutyl ether and diethyl ether, hydrocarbons such as n-hexane and decane, toluene, n-butylbenzene, benzene and the like. A method for manufacturing a semiconductor device, which is an aromatic compound, an amine such as diethylamine, diisopropylethylamine, triethylamine, triallylamine, or tetrahydrofuran. 15. A method of manufacturing a semiconductor device having multi-layer wiring, wherein a tungsten nitride film used as a part of wiring is formed by a chemical vapor deposition method using a mixed gas containing an organic compound of tungsten containing nitrogen and a carrier gas. A method of manufacturing a semiconductor device, comprising: 16. A method of manufacturing a semiconductor device according to claim 15, wherein the mixed gas contains hydrogen gas. 17. A method of manufacturing a semiconductor device according to claim 15, wherein the organic compound of tungsten containing nitrogen is hexakis (dimethylamino) ditungsten.