JP6855191B2 - Manufacturing method of metal thin film by atomic layer deposition method - Google Patents

Description

The present invention relates to a method for producing a metal molybdenum thin film, a metal vanadium thin film, a metal cobalt thin film, a metal nickel thin film, a metal copper thin film, or a metal chromium thin film by an atomic layer deposition method.

Metal molybdenum thin film, metallic vanadium thin film, metallic cobalt thin film, metallic nickel thin film, metallic copper thin film and metallic chromium thin film can be used for electronic materials, display materials, coating materials, heat resistant materials, superalloys, aircraft members, etc. It has been known.

Examples of the method for producing the above thin film include a sputtering method, an ion plating method, a MOD method such as a coating thermal decomposition method and a solgel method, a CVD method, and an atomic layer deposition method (hereinafter, may be referred to as an ALD method). The CVD method and the ALD method are mainly used because the quality of the obtained thin film is good.

Non-Patent Document _{1, Mo (NR) 2 (} NR '2) 2 a method for producing molybdenum nitride thin films by the ALD method is disclosed which uses, in Patent Document _{1, Mo (NR) 2 (} NHR' ) ₂ is disclosed as a method for producing a thin film containing molybdenum by the ALD method. When a metal molybdenum thin film is produced by directly reacting an organic molybdenum complex with a reducing agent as in the methods disclosed in Non-Patent Document 1 and Patent Document 1, a carbon component remains in the thin film, resulting in quality. It is not possible to produce a good metallic molybdenum thin film. Patent Document ^{_{2, Cp (R 1) m}} V (NR 2 2) 2 (= NR 3) manufacturing method of a thin film of vanadium by the ALD method using are disclosed. When a metal vanadium thin film is produced by directly reacting an organic vanadium complex with a reducing agent as in the method disclosed in Patent Document 2, a carbon component remains in the thin film, and a high-quality metal vanadium thin film is produced. Could not be manufactured. As described above, when a metal thin film is produced by directly reacting a raw material for the ALD method, which has been conventionally known as a metal supply source for the ALD method, with a reducing agent, a residual carbon component remains in the thin film. It was difficult to produce a high quality metal thin film from.

_{In Patent Document 3, MoCl 5} gas and reduction gas as molybdenum raw materials are simultaneously supplied or alternately supplied with a purge in the processing container into a processing container having a reduced pressure atmosphere in which the substrate to be processed is arranged, and the substrate to be processed is provided. A method of forming a molybdenum film by reacting _{MoCl 5} gas and a reducing gas on a substrate to be treated while heating the molybdenum film is disclosed. However, since MoCl ₅ is a melting point of 190 to 200 ° C., poor transportability it is necessary to heat to a very high temperature in order to transport a liquid state, the metallic molybdenum thin film using MoCl ₅ The problem with manufacturing was that it was extremely poorly productive. Further, since MoCl ₅ has a boiling point of 270 ° C., when MoCl ₅ is vaporized in the raw material container and MoCl ₅ gas is supplied to the processing container, it is difficult to uniformly heat _{MoCl 5} in the raw material container, _{and MoCl 5} The problem was that it was not possible to vaporize the film in a stable manner, and it was difficult to obtain a film having a uniform thickness.

Special Table 2016-516892 Special Table 2012-505177 Japanese Unexamined Patent Publication No. 2016-098406

MIIKKULAINEN, CHEM. VAP. DEPOSITION (2008) 14,71-77

It has been difficult to produce a metal molybdenum thin film, a metal vanadium thin film, a metal cobalt thin film, a metal nickel thin film, a metal copper thin film, and a metal chromium thin film with a small amount of residual carbon and good quality by conventionally known methods.

As a result of repeated studies, the present inventors have found that a method for producing a metal thin film by an atomic layer deposition method having a specific step can solve the above problems, and have arrived at the present invention.

The present invention contains one kind of metal atom selected from the group consisting of (A) molybdenum atom, vanadium atom, cobalt atom, nickel atom, copper atom and chromium atom in a method for producing a metal thin film by an atomic layer deposition method. A step of vaporizing an organometallic compound, introducing it into a reaction chamber in which a substrate is installed, and depositing the organometallic compound on the substrate (hereinafter, may be abbreviated as step (A)), (B) hydrogen chloride, hydrogen bromide. , Hydrogen iodide, monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, boron trichloride, boron tribromide, methyl iodide and at least one first reactive gas selected from the group consisting of methyl bromide. A step of introducing into the reaction chamber and reacting with the organometallic compound (hereinafter, may be abbreviated as step (B)), and (C) at least one second reaction selected from hydrogen, monosilane, disilane and diboran. The present invention provides a method for producing a metal thin film, which comprises a step of introducing a sex gas into a reaction chamber and further reacting with the reaction product obtained in (B) above (hereinafter, may be abbreviated as step (C)). ..

According to the present invention, it is possible to produce a metal molybdenum thin film, a metal vanadium thin film, a metal cobalt thin film, a metallic nickel thin film, a metallic copper thin film and a metallic chromium thin film with less residual carbon and good quality.

FIG. 1 is a schematic view showing an example of an ALD method apparatus used in the method for producing a metal thin film according to the present invention. FIG. 2 is a schematic view showing another example of the ALD method apparatus used in the method for producing a metal thin film according to the present invention. FIG. 3 is a schematic view showing another example of the ALD method apparatus used in the method for producing a metal thin film according to the present invention. FIG. 4 is a schematic view showing another example of the ALD method apparatus used in the method for producing a metal thin film according to the present invention.

The method for producing a metal thin film by the atomic layer deposition method of the present invention can use the same procedure as the well-known general atomic layer deposition method, but it is a feature of the present invention that the step (B) described later is essential. is there.

In the step (A) of the production method of the present invention, an organic metal compound containing one kind of metal atom selected from the group consisting of molybdenum atom, vanadium atom, cobalt atom, nickel atom, copper atom and chromium atom is vaporized. This is a step of introducing this into a reaction chamber in which a substrate is installed and depositing it on the substrate. The production method of the present invention may include a step of installing the substrate in the reaction chamber before the step (A). The method for installing the substrate in the reaction chamber is not particularly limited, and the substrate may be installed in the reaction chamber by a well-known general method. Examples of the material of the substrate include silicon; indium arsenic, indium gallium arsenic, silicon oxide, silicon nitride, silicon carbide, titanium nitride, tantalum oxide, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, and hafnium oxide. , Ceramics such as lanthanum oxide and gallium nitride; glass; metals such as platinum ruthenium, aluminum, copper, nickel, cobalt, tungsten and molybdenum. Examples of the shape of the substrate include plate-like, spherical, fibrous, and scaly shapes. The surface of the substrate may be flat or may have a three-dimensional structure such as a trench structure.

The organic metal compound containing one kind of metal atom selected from the group consisting of molybdenum atom, vanadium atom, cobalt atom, nickel atom, copper atom and chromium atom is not particularly limited, and the desired metal thin film can be used. Any organic metal compound having a metal atom in its structure may be used. Examples of the organic metal compound containing one metal atom selected from the group consisting of molybdenum atom, vanadium atom, cobalt atom, nickel atom, copper atom and chromium atom include alkyl, alkoxy, cycloalkyl, aryl and alkoxyl. Alkoxy imino, amino, dialkylaminoalkyl, monoalkylamino, dialkylamino, diamine, di (silyl-alkyl) amino, di (alkyl-silyl) amino, disilylamino, alkoxy, alkoxyalkyl, hydrazide, phosphide, nitrile, dialkylaminoalkoxy , Alkoxyalkyldialkylamino, syroxy, diketonate, cyclopentadienyl, silyl, pyrazolate, guanidineate, phosphoguanidineate, amidinate, phosphoamidinate, ketoiminate, diketiminate, carbonyl and phosphoamidinate as ligands. Metal compounds can be mentioned. Since it has good reactivity with the first reactive gas used in the step (B) described later and can form a high-quality metal thin film, it is composed of the group consisting of alkylimino, monoalkylamino and dialkylamino. It is preferably an organometallic compound having at least one ligand of choice.

In the production method of the present invention, when producing a metal molybdenum thin film or a metal vanadium thin film, at least selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). When one kind of compound is used, it is preferable because a high quality metal thin film can be produced.

(In the formula, R ^{1 to} R ³ independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, M represents a molybdenum atom or a vanadium atom, y represents 0 or 2, and x represents 0 or 2. When y is 0, it is 4, and when y is 2, it is 2, and a plurality of R ^{1 to} R ³ existing may be the same or different.)

(In the formula, R ⁴ independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, and L is a linear or branched alkyl group having 1 to 5 carbon atoms, a trimethylsilyl group, or a dimethylisopropylsilyl. represents a group or dimethyl tertiary butylsilyl group, M represents a molybdenum atom or vanadium atom, each L and R ⁴ there exist a plurality may be the same or different.)

The linear or branched alkyl group having 1 to 5 carbon atoms represented by ^{R 1} , R ² , R ³ , R ⁴ and L in the above general formulas (1) and (2) includes a methyl group and an ethyl group. Examples thereof include a group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, a pentyl group, an isopentyl group, a second pentyl group, and a third pentyl group.

Specific examples of the organic molybdenum compound represented by the general formula (1) include the following compound No. 1 to 81 can be mentioned. However, the present invention is not limited to the following exemplary compounds. The organic vanadium compound is the following compound No. Examples thereof include those in which the molybdenum atom in 1 to 81 is replaced with a vanadium atom.

Specific examples of the organic molybdenum compound represented by the general formula (2) include the following compound No. 82 to 89 can be mentioned. However, the present invention is not limited to the following exemplary compounds. The organic vanadium compound is the following compound No. Examples thereof include those in which the molybdenum atom in 82 to 89 is replaced with a vanadium atom.

Among these, compound No. 2, 9, 37 and 38 are particularly preferable because they have a low melting point, a high vapor pressure, and very little residual carbon in the metal thin film obtained when applied to the production method of the present invention.

In the production method of the present invention, when a metallic nickel thin film is produced, it is preferable to use a compound represented by the following general formula (3) because a high quality metallic nickel thin film can be produced.

(In the formula, R ⁵ represents a linear or branched alkyl group having 2 to 4 carbon atoms, and R ⁶ and R ⁷ represent a linear or branched alkyl group having 1 to 4 carbon atoms.)

Examples of the straight-chain or branched alkyl group having 2 to 4 carbon atoms represented by R ⁵ in the general formula (3), an ethyl group, a propyl group, an isopropyl group, butyl group, secondary butyl group, tertiary butyl Groups and isobutyl groups can be mentioned.

^{Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 6} and R ⁷ of the general formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a second group. Examples thereof include a butyl group, a tertiary butyl group, and an isobutyl group.

Specific examples of the organic nickel compound represented by the general formula (3) include the following compound No. 90 to 95 can be mentioned. However, the present invention is not limited to the following exemplary compounds.

Among these, compound No. 90, 92 and 94 are particularly preferable because they have a low melting point, a high vapor pressure, and very little residual carbon in the metal thin film obtained when applied to the production method of the present invention.

The method for vaporizing the organometallic compound in the step (A) is not particularly limited, and the method for vaporizing the organometallic compound used in a well-known general atomic layer deposition method can be used. For example, it can be vaporized by heating or reducing the pressure in the raw material container. The temperature at the time of heating is preferably in the range of 20 ° C. to 200 ° C. Further, in the step (A), the temperature of the substrate when the vaporized organometallic compound is deposited on the substrate is preferably in the range of 20 to 600 ° C, more preferably 100 to 450 ° C.

The step (B) in the production method of the present invention includes hydrogen chloride, hydrogen bromide, hydrogen iodide, monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, boron tribromide, boron tribromide, methyl iodide and bromide. This is a step of introducing at least one first reactive gas selected from the group consisting of methyl into the reaction chamber and reacting it with the organic metal compound deposited in step (A). The first method for introducing the reactive gas is not particularly limited, and can be introduced in the same manner as the method for introducing the reactive gas used in the well-known general atomic layer deposition method. The temperature of the substrate during the step (B) is preferably in the range of 20 to 600 ° C, more preferably 100 to 450 ° C. Among the first reactive gases, when hydrogen chloride is used, it is particularly preferable because the residual carbon in the obtained metal thin film can be significantly reduced.

In the step (C) of the production method of the present invention, at least one second reactive gas selected from hydrogen, monosilane, disilane and diborane is introduced into the reaction chamber, and the reaction product obtained in the step (B) is used. This is a step of further reacting. The second method for introducing the reactive gas is not particularly limited, and can be introduced in the same manner as the method for introducing the reactive gas used in the well-known general atomic layer deposition method. The temperature of the substrate during the step (C) is preferably in the range of 20 to 600 ° C, more preferably 100 to 450 ° C. Among the second reactive gases, when hydrogen is used, it is particularly preferable because the residual carbon in the obtained metal thin film can be significantly reduced.

For example, when producing a metal molybdenum thin film on a silicon substrate by the production method of the present invention, first, the silicon substrate is placed in a reaction chamber, the organic molybdenum compound is vaporized in a raw material container, and this is introduced into the reaction chamber. , It is deposited on a silicon substrate heated to 100 ° C. to 600 ° C. (step (A)).

Next, the organic molybdenum compound that has not been deposited on the silicon substrate is exhausted from the reaction chamber (exhaust step 1). Ideally, the organic molybdenum compound that has not been deposited (adsorbed) on the silicon substrate is completely exhausted from the reaction chamber, but it does not necessarily have to be completely exhausted. Examples of the exhaust method include a method of purging the inside of the system with an inert gas such as helium and argon, a method of exhausting by depressurizing the inside of the system, and a method of combining these. When the pressure is reduced, the degree of pressure reduction is preferably 0.01 to 300 Pa, more preferably 0.1 to 100 Pa.

Next, hydrogen chloride is introduced into the reaction chamber as the first reactive gas and reacted with the organic molybdenum compound deposited on the silicon substrate (step (B)). The temperature at which heat is applied in this step is preferably 20 ° C to 600 ° C, more preferably 100 to 450 ° C.

Next, unreacted hydrogen chloride and by-produced gas are exhausted from the reaction chamber (exhaust step 2). Ideally, unreacted hydrogen chloride and by-produced gas are completely exhausted from the reaction chamber, but not necessarily completely. Examples of the exhaust method include a method of purging the inside of the system with an inert gas such as helium and argon, a method of exhausting by depressurizing the inside of the system, and a method of combining these. When the pressure is reduced, the degree of pressure reduction is preferably 0.01 to 300 Pa, more preferably 0.1 to 100 Pa.

Next, hydrogen is introduced into the reaction chamber as the second reactive gas, and the reaction product of the organic molybdenum compound deposited on the silicon substrate and the first reactive gas is further reacted (step (C)). The temperature at which heat is applied in this step is preferably 20 ° C to 600 ° C, more preferably 100 to 450 ° C.

Next, unreacted hydrogen and by-produced gas are exhausted from the reaction chamber (exhaust step 3). Ideally, unreacted hydrogen and by-produced gas are completely exhausted from the reaction chamber, but not necessarily completely. Examples of the exhaust method include a method of purging the inside of the system with an inert gas such as helium and argon, a method of exhausting by depressurizing the inside of the system, and a method of combining these. When the pressure is reduced, the degree of pressure reduction is preferably 0.01 to 300 Pa, more preferably 0.1 to 100 Pa.

The thin film deposition by a series of operations including the above steps (A), exhaust step 1, (B), exhaust step 2, (C) and exhaust step 3 is regarded as one cycle, and this cycle is defined as a metal having a required thickness. It may be repeated a plurality of times until a thin film is obtained.

Further, energy such as plasma, light, and voltage may be applied to the production method of the present invention. The timing of applying these energies is not particularly limited, and for example, when introducing the organometallic compound gas in the step (A), when heating in the step (B) or step (C), and exhaust in the system in the exhaust step. It may be timely or during each of the above steps.

In the production method of the present invention, after thin film deposition, annealing treatment may be performed in an inert atmosphere or a reducing gas atmosphere in order to obtain better film quality, and if step embedding is required, reflow A process may be provided. The temperature in this case is 400 to 1200 ° C, preferably 500 to 800 ° C.

As the apparatus used for producing the metal thin film according to the present invention, a well-known ALD method apparatus can be used. Specific examples of the apparatus include an apparatus capable of bubbling and supplying a raw material for an atomic layer deposition method as shown in FIG. 1 and an apparatus having a vaporization chamber as shown in FIG. Further, as shown in FIGS. 3 and 4, an apparatus capable of performing plasma treatment on the reactive gas can be mentioned. Not limited to the single-wafer type apparatus as shown in FIGS. 1 to 4, an apparatus capable of simultaneously processing a large number of sheets using a batch furnace can also be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples and the like.

[Example 1] Production of metal molybdenum thin film Compound No. Using 2 as a raw material for the atomic layer deposition method, a metal molybdenum thin film was produced on a silicon wafer by the ALD method under the following conditions using the apparatus shown in FIG. When the film thickness of the obtained thin film was measured by the X-ray reflectivity method and the thin film composition was confirmed by the X-ray photoelectron spectroscopy, the film thickness was 2.0 nm, the film composition was metallic molybdenum, and carbon was contained. The amount was less than the lower limit of detection, 0.1 atom%. The film thickness obtained per cycle was 0.04 nm.

(conditions)
Reaction temperature (silicon wafer temperature); 380 ° C
First reactive gas: hydrogen chloride Second reactive gas: hydrogen (process)
A series of steps consisting of the following (1) to (6) was regarded as one cycle, and 50 cycles were repeated.
(1) The raw material for the atomic layer deposition method vaporized under the conditions of the raw material container temperature: 90 ° C. and the pressure inside the raw material container: 70 Pa is introduced into the film forming chamber and deposited at a system pressure of 100 Pa for 10 seconds.
(2) The raw material that has not been deposited is removed by argon purging for 15 seconds.
(3) The first reactive gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(4) The unreacted first reactive gas and by-product gas are removed by argon purging for 15 seconds.
(5) The second reactive gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(6) The unreacted second reactive gas and by-product gas are removed by argon purging for 15 seconds.

[Example 2] Production of metal molybdenum thin film Compound No. Using 2 as a raw material for the atomic layer deposition method, a metal molybdenum thin film was produced on a silicon wafer by the ALD method under the following conditions using the apparatus shown in FIG. When the film thickness of the obtained thin film was measured by the X-ray reflectivity method and the thin film composition was confirmed by the X-ray photoelectron spectroscopy, the film thickness was 1.5 nm, the film composition was metallic molybdenum, and carbon was contained. The amount was less than the lower limit of detection, 0.1 atom%. The film thickness obtained per cycle was 0.03 nm.

(conditions)
Reaction temperature (silicon wafer temperature); 400 ° C
First reactive gas: methyl iodide Second reactive gas: hydrogen (process)
A series of steps consisting of the following (1) to (6) was regarded as one cycle, and 50 cycles were repeated.
(1) The raw material for the atomic layer deposition method vaporized under the conditions of the raw material container temperature: 90 ° C. and the pressure inside the raw material container: 70 Pa is introduced into the film forming chamber and deposited at a system pressure of 100 Pa for 10 seconds.
(2) The raw material that has not been deposited is removed by argon purging for 15 seconds.
(3) The first reactive gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(4) The unreacted first reactive gas and by-product gas are removed by argon purging for 15 seconds.
(5) The second reactive gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(5) The unreacted second reactive gas and by-product gas are removed by argon purging for 15 seconds.

[Comparative Example 1] Production of Metal Molybdenum Thin Film Compound No. Using 2 as a raw material for the atomic layer deposition method, a metal molybdenum thin film was produced on a silicon wafer by the ALD method under the following conditions using the apparatus shown in FIG. When the film thickness of the obtained thin film was measured by the X-ray reflectivity method and the thin film composition was confirmed by the X-ray photoelectron spectroscopy, the film thickness was 1.5 nm, the film composition was metallic molybdenum, and carbon was contained. The amount was 5 atom%. The film thickness obtained per cycle was 0.03 nm.

(conditions)
Reaction temperature (silicon wafer temperature); 400 ° C
First reactive gas: None Second reactive gas: Hydrogen (process)
A series of steps consisting of the following (1) to (4) was regarded as one cycle, and 50 cycles were repeated.
(1) Atomic layer deposition method vaporized under the conditions of raw material container temperature: 90 ° C. and raw material container pressure: 70 Pa The raw material is introduced into the film forming chamber and deposited at a system pressure of 100 Pa for 10 seconds.
(2) The raw material that has not been deposited is removed by argon purging for 15 seconds.
(3) Hydrogen gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(4) Unreacted hydrogen gas and by-product gas are removed by argon purging for 15 seconds.

From the above results, in Comparative Example 1, a large amount of residual carbon component was mixed in the obtained metal molybdenum thin film, but in Examples 1 and 2, the obtained metal molybdenum thin film contained residual carbon. It was found that no components were detected and a high quality metal molybdenum thin film could be produced.

[Example 3] Production of metallic nickel thin film Compound No. Using 92 as a raw material for the atomic layer deposition method, a metallic nickel thin film was produced on a silicon wafer by the ALD method under the following conditions using the apparatus shown in FIG. When the film thickness of the obtained thin film was measured by the X-ray reflectivity method and the thin film composition was confirmed by the X-ray photoelectron spectroscopy, the film thickness was 2.0 nm, the film composition was metallic nickel, and carbon was contained. The amount was less than the lower limit of detection, 0.1 atom%. The film thickness obtained per cycle was 0.02 nm.

(conditions)
Reaction temperature (silicon wafer temperature); 250 ° C
First reactive gas: hydrogen chloride Second reactive gas: hydrogen (process)
A series of steps consisting of the following (1) to (6) was regarded as one cycle, and 100 cycles were repeated.
(1) Atomic layer deposition method vaporized under the conditions of raw material container temperature: 80 ° C. and raw material container pressure: 35 Pa The raw material is introduced into the film forming chamber and deposited at a system pressure of 100 Pa for 10 seconds.
(2) The raw material that has not been deposited is removed by argon purging for 15 seconds.
(3) The first reactive gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(4) The unreacted first reactive gas and by-product gas are removed by argon purging for 15 seconds.
(5) The second reactive gas is introduced into the film forming chamber and reacted at a system pressure of 100 Pa for 10 seconds.
(6) The unreacted second reactive gas and by-product gas are removed by argon purging for 15 seconds.

[Comparative Example 2] Production of Metallic Nickel Thin Film Using NiCl ₂ as a raw material for the atomic layer deposition method, a metallic nickel thin film is formed on a silicon wafer by the ALD method under the same conditions as in Example 3. _{Although an attempt was made to produce it, NiCl 2} did not vaporize even when the pressure inside the raw material container was raised to 133.3 Pa and the temperature of the raw material container was raised to 600 ° C., and a metallic nickel thin film could not be produced.

Claims (2)

In the method of manufacturing a metal thin film by the atomic layer deposition method,
(A) an organometallic compound represented by the following general formula (1), vaporizing organic metal compound represented by the organometallic compounds represented by the following general formula (2) or the following general formula (3), this A step of introducing a substrate into a reaction chamber in which the substrate is installed and depositing the substrate on the substrate.

(In the formula, R ^{1 to} R ³ independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, M represents a molybdenum atom or a vanadium atom, y represents 0 or 2, and x represents 0 or 2. When y is 0, it is 4, and when y is 2, it is 2, and a plurality of R ^{1 to} R ³ existing may be the same or different.)

(In the formula, R ⁴ independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, and L is a linear or branched alkyl group having 1 to 5 carbon atoms, a trimethylsilyl group, or a dimethylisopropylsilyl. represents a group or dimethyl tertiary butylsilyl group, M represents a molybdenum atom or vanadium atom, each L and R ⁴ there exist a plurality may be the same or different.)

(In the formula, R ⁵ represents a linear or branched alkyl group having 2 to 4 carbon atoms, and R ⁶ and R ⁷ represent a linear or branched alkyl group having 1 to 4 carbon atoms.)
(B) At least one selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, boron trichloride, boron tribromide, methyl iodide and methyl bromide. The step of introducing the first reactive gas of the species into the reaction chamber and reacting it with the organic metal compound, and (C) at least one second reactive gas selected from hydrogen, monosilane, disilane and diborane. A method for producing a metal thin film, which comprises a step of introducing into a reaction chamber and further reacting with the reaction product obtained in the step (B). The method for producing a metal thin film according to claim 1, wherein the first reactive gas is hydrogen chloride and the second reactive gas is hydrogen.

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