JP2016108247A - Bis(silylamideaminoalkane) manganese compound and method for producing manganese-containing film using the manganese compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially suitable manganese compound and a method for producing a manganese-containing film using the manganese compound.SOLUTION: The present invention provides a bis(silylamideaminoalkane) manganese compound represented by formula (1).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a novel bis (silylamidoaminoalkane) manganese compound and the manganese compound, and a chemical vapor deposition method (hereinafter referred to as a CVD method) or an atomic layer deposition method (Atomic Layer Deposition). The present invention relates to a method for producing a manganese-containing film on an object to be formed by a method; Bis (silylamidoaminoalkane) manganese compounds are useful compounds, for example, as materials for producing manganese-containing films, catalysts, raw materials for producing pharmaceuticals, agricultural chemicals, and the like.

In recent years, many researches and developments have been made on manganese-containing films as materials in the fields of semiconductors and electronic components.
Examples of manganese compounds for producing manganese-containing films that have been proposed so far include, for example, bis (dipivaloylmethanato) manganese (see, for example, Patent Document 1) and bis (ethylcyclopentadienyl) manganese (for example, patents). References 1 and 2), bis (N, N′-diisopropylacetamidinato) manganese (for example, see Patent Document 3), bis (amidoaminoalkane) manganese (for example, see Patent Documents 4 and 5), and the like. It is done.

  On the other hand, as a manganese compound for producing a manganese-containing film containing a silicon atom in the structure, bis (hexamethyldisilazane) manganese (see, for example, Patent Document 6 and Non-Patent Document 1) and specific examples of film formation However, bis (N, N′-di (t-butyl) -1,1-dimethylsilylamino) manganese (for example, see Patent Document 7) has been proposed.

  As the use of the manganese-containing film, for example, as a material for a barrier metal film of copper wiring, a metal manganese film, a manganese oxide film, a manganese nitride film, a manganese silicide film, a manganese silicate film (for example, Patent Documents 8 to 11) Browse) is available.

  Further, a manganese silicide film (for example, see Patent Document 12) can be used as a thermoelectric conversion material. Further, a manganese nitride film can be used as the wear resistant coating (see, for example, Patent Document 13).

International Publication No. 2010/116889 International Publication No. 2011/037090 JP 2010-156058 A International Publication No. 2012/060428 JP 2014-141739 A International Publication No. 2013/155436 Japanese Patent No. 4388021 Japanese Patent No. 4946008 JP 2014-62312 A International Publication No. 2013/19165 Japanese Patent No. 5608350 JP 2011-210845A JP 2002-356766 A

Chem. Vap. Deposition 1, No. 2, 49-51 (1995)

  However, conventional manganese compounds are not necessarily optimal in the production of manganese-containing films because of their physical properties such as vapor pressure, thermal stability, and reactivity during film formation. What are sufficient manganese compounds for producing manganese-containing films? It was hard to say.

Therefore, a manganese compound that satisfies all physical properties such as vapor pressure, thermal stability, and reactivity during film formation has been demanded.
Here, the thermal stability refers to the stability against heat required since the manganese compound is not deposited in a pipe or the like until the manganese compound is transported from the raw material tank onto the substrate.
The reactivity at the time of film formation refers to the fact that the film formation speed is a practical speed from the viewpoint of productivity when manufacturing (depositing) a manganese-containing thin film, and the film formation apparatus member and the film formation substrate. In order to produce a high-quality film (for example, a low-resistance film in the case of a conductive film) that reacts at a lower temperature from the viewpoint of the heat-resistant temperature, etc. It is a reaction characteristic at the time of film formation of a necessary manganese compound.

  An object of the present invention is to solve the above-mentioned problems and produce a manganese-containing film on a film-forming target by a simple method, and an industrially suitable manganese compound and a manganese-containing film using the manganese compound. A manufacturing method is provided.

  The subject of this invention is general formula (1).

(In formula, R < ¹ >, R < ² > and R < ³ > may be same or different, and show a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group.
R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms. R ⁴ and R ⁵ may be bonded to each other to form a ring.
Z represents a linear or branched alkylene group having 1 to 5 carbon atoms. )
This is solved by a bis (silylamidoaminoalkane) manganese compound represented by:

  The subject of this invention is also general formula (2).

(In the formula, R ⁶ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and M represents an alkali metal atom.)
An alkylalkali metal compound represented by formula (3):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Z are as defined above.)
Is reacted with a silylaminoaminoalkane compound represented by the general formula (4):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Z and M have the same meanings as described above).
A (silylamidoaminoalkane) alkyl metal compound represented by the formula (5) is obtained.

(In the formula, X represents a halogen atom.)
It can also be solved by a method for producing a bis (silylamidoaminoalkane) manganese compound in which a dihalogenomanganese compound represented by formula (1) is reacted.

  Another object of the present invention is to provide a method for producing a manganese-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using a bis (silylaminoamidoalkane) manganese compound as a manganese source. Is also resolved.

  According to the present invention, a bis (silylamidoaminoalkane) manganese compound suitable for producing a manganese-containing film by a CVD method or an ALD method can be provided, and a method for producing a manganese-containing film using the manganese compound is provided. be able to.

It is a figure which shows the structure of the vapor deposition apparatus which manufactures a manganese containing film | membrane using the bis (silyl amide amino alkane) manganese compound of this invention.

(Bis (silylamidoaminoalkane) manganese compound)
The bis (silylamidoaminoalkane) manganese compound of the present invention is represented by the general formula (1). In the general formula (1), R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

  Examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, t-butyl group, cyclobutyl group, t -A pentyl group, a neopentyl group, etc. are mentioned, Preferably they are a methyl group, an ethyl group, More preferably, it is a methyl group.

R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms.
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group, preferably a methyl group, an ethyl group, and more preferably a methyl group. It is a group.
R ⁴ and R ⁵ may be bonded to each other to form a ring.

Z represents a linear or branched alkylene group having 1 to 5 carbon atoms.
Examples of the linear or branched alkylene group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetraethylene group, and a 2-methyltrimethylene group. A methylene group, an ethylene group, and a trimethylene group are preferable, and an ethylene group is more preferable.

In a preferred embodiment of the present invention, R ¹ , R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are an alkyl group having 1 to 2 carbon atoms, and Z is It is an alkylene group having 1 to 3 carbon atoms.

(Production of bis (silylamidoaminoalkane) manganese compound)
The bis (silylamidoaminoalkane) manganese compound (1) of the present invention is synthesized by the following method. Specifically, an alkylalkali metal compound (2) and a silylaminoaminoalkane compound (3) are synthesized. By reacting (silylamidoaminoalkane) to obtain an alkali metal compound (4) (hereinafter sometimes referred to as reaction (A)), this is then reacted with a dihalogenomanganese compound (5) (hereinafter referred to as reaction ( B) is sometimes synthesized.
In addition, reaction (A) and reaction (B) are collectively called reaction of this invention.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , M, X and Z are as defined above).

(Reaction (A); Synthesis of (silylamidoaminoalkane) alkali metal compound (4))
The alkyl alkali metal compound used in the reaction (A) of the present invention is represented by the general formula (2). In the general formula (2), R ⁶ represents a linear or branched alkyl group having 1 to 10 carbon atoms.
Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t- Examples thereof include a butyl group, an n-pentyl group, a t-pentyl group, a neopentyl group, and an n-decyl group, but preferably a methyl group, an ethyl group, an n-butyl group, an s-butyl group, a t-butyl group, A methyl group and an n-butyl group are preferable.

M represents an alkali metal.
Examples of the alkali metal include a lithium atom, a sodium atom, a potassium atom, and the like, preferably a lithium atom, a sodium atom, and more preferably a lithium atom.

Examples of the alkyl alkali metal compound include methyl lithium, ethyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, and the like. Preferably, methyl lithium and n-butyl lithium are used. .
In addition, you may use these alkyl alkali metal compounds individually or in mixture of 2 or more types.

(Silylaminoaminoalkane compound)
The silylaminoaminoalkane compound used in the reaction (A) of the present invention is represented by the general formula (3), and in the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Z are as defined above.

Examples of the silylaminoaminoalkane compound include 1-trimethylsilylamino-2-dimethylaminoethane, 1-dimethylsilylamino-2-dimethylaminoethane, 1-methylsilylamino-2-dimethylaminoethane, and 1-silylamino-2. -Dimethylaminoethane, 1-ethylsilylamino-2-dimethylaminoethane, 1- (ethyldimethylsilyl) amino-2-dimethylaminoethane, and the like, preferably 1-trimethylsilylamino-2-dimethylaminoethane, 1-dimethylsilylamino-2-dimethylaminoethane, more preferably 1-trimethylsilylamino-2-dimethylaminoethane is used.
In addition, you may use these silylamino amino alkane compounds individually or in mixture of 2 or more types.

  The silylaminoaminoalkane compound used in the reaction (A) of the present invention can be produced by combining a commercially available product or a known method. For example, an aminodialkylaminoalkane and an alkylalkali metal compound are reacted, (Amidodialkylamine) A method in which an alkali metal compound is synthesized and reacted with a corresponding halogenated silane compound, or a method in which an aminodialkylaminoalkane and a corresponding alkyldisilazane are reacted in a concentrated sulfuric acid catalyst is suitably employed. The

The amount of the silylaminoaminoalkane compound used is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 1 mol of the alkyl alkali metal compound.
By setting it as this range, an alkali metal compound (silylamidoaminoalkane) can be produced with good yield from a silylaminoaminoalkane compound and an alkylalkali metal compound.

(Organic solvent)
The reaction (A) of the present invention is preferably carried out in an organic solvent, and the organic solvent used is not particularly limited as long as it does not inhibit the reaction. For example, diethyl ether, dibutyl ether, cyclopentyl methyl ether, methyl -Ethers such as t-butyl ether, ethyl t-butyl ether, tetrahydrofuran, dimethoxyethane, dioxane; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane; aromatics such as toluene, xylene Although hydrocarbons are mentioned, Ethers, aliphatic hydrocarbons, and mixed solvents of ethers and aliphatic hydrocarbons are preferably used.
In addition, you may use these organic solvents individually or in mixture of 2 or more types.

The amount of the organic solvent to be used is preferably 1 to 100 g, more preferably 1 to 20 g, relative to 1 g of the alkyl alkali metal compound.
By setting it as this range, agitation property improves and reaction advances smoothly.

The reaction (A) of the present invention is carried out, for example, by a method in which a mixture of a silylaminoaminoalkane compound and an organic solvent is stirred and an organic solvent solution of an alkyl alkali metal compound is added and reacted. The reaction temperature at that time is preferably −78 to 120 ° C., more preferably −20 to 60 ° C., and the reaction pressure is not particularly limited.
By setting it as this range, the production | generation of a by-product can be reduced and the target (silyl amide amino alkane) alkyl metal compound can be obtained with a sufficient yield.

(Reaction (B); synthesis of bis (silylamidoaminoalkane) manganese compound (1))
The dihalogenomanganese compound used in the reaction (B) of the present invention is represented by the general formula (5). In the general formula (5), X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

(Dihalogenomanganese compound)
Examples of the dihalogenomanganese compound include manganese (II) chloride, manganese (II) bromide, manganese (II) iodide, and preferably manganese chloride is used.
In addition, you may use these dihalogeno manganese compounds individually or in mixture of 2 or more types.

The amount of the dihalogenomanganese compound used is preferably 0.25 to 0.75 mol, more preferably 0.4 to 0.6 mol, relative to 1 mol of the (silylamidoaminoalkane) alkali metal compound.
By setting it within this range, the production of by-products is reduced from the (silylamidoaminoalkane) alkyl metal compound and the dihalogenomanganese compound, and the bis (silylamidoaminoalkane) manganese compound is produced in a desired yield. can do.

(Organic solvent)
The reaction (B) of the present invention is preferably carried out in an organic solvent, and the organic solvent used is not particularly limited as long as it does not inhibit the reaction. For example, diethyl ether, dibutyl ether, cyclopentyl methyl ether, methyl -Ethers such as t-butyl ether, ethyl t-butyl ether, tetrahydrofuran, dimethoxyethane, dioxane; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane; aromatics such as toluene, xylene Although hydrocarbons are mentioned, Ethers, aliphatic hydrocarbons, and mixed solvents of ethers and aliphatic hydrocarbons are preferably used.
In addition, you may use these organic solvents individually or in mixture of 2 or more types.

The amount of the organic solvent used is preferably 1 to 100 g, more preferably 1 to 20 g, per 1 g of (silylamidoaminoalkane) alkali metal compound.
By setting it as this range, agitation property improves and reaction advances smoothly.

In the reaction (B) of the present invention, for example, an organic solvent solution of the (silylamidoaminoalkane) alkali metal compound obtained in the reaction (A) is added while stirring a mixture of a dihalogenomanganese compound and an organic solvent. It is performed by the method of making it react. The reaction temperature at that time is preferably −78 to 120 ° C., more preferably −20 to 60 ° C., and the reaction pressure is not particularly limited.
By setting it as this range, the production | generation of a by-product can be reduced and the target bis (silyl amide amino alkane) manganese compound can be obtained with the target yield.

  The target bis (silylamidoaminoalkane) manganese compound can be obtained by the reaction (B) of the present invention. After completion of the reaction, for example, extraction, filtration, concentration, distillation, sublimation, recrystallization, column chromatography, etc. It is isolated and purified by a known method.

  When performing the reaction (A) and the reaction (B) in the present invention, for example, using the same solvent or substituting with another solvent having a higher boiling point, the resultant (silylamide) is obtained. The aminoalkane) alkali metal compound (4) can also be synthesized continuously without isolation and purification.

  The target product, bis (silylamidoaminoalkane) manganese compound, its starting material, alkylalkali metal compound and synthetic intermediate, (silylamidoaminoalkane) alkylmetal compound, are effective against moisture and oxygen in the atmosphere. Therefore, it is desirable to perform a reaction operation or a post-treatment of the reaction solution under anhydrous conditions or in an inert gas atmosphere. Moreover, it is desirable to dehydrate or dry the starting materials and solvents before use.

  Examples of the bis (silylamidoaminoalkane) manganese compound produced by the reaction of the present invention include compounds represented by the following formulas (6) to (26).

(Vapor deposition method (film formation method))
As a method for depositing a manganese-containing film on a film formation target, a known CVD method or ALD method can be used. For example, vapor of a bis (silylamidoaminoalkane) manganese compound under normal pressure or reduced pressure. Or hydrogen source / reducing gas (for example, hydrogen, ammonia, etc.), nitrogen source (for example, nitrogen, ammonia, etc.) or oxygen source (for example, oxidizing gas such as oxygen, ozone, etc.); water; methanol, Contains reaction gas (including single or mixed gas) including reaction gas such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol), etc. A method of depositing a film can be used.
Note that these gases (including vaporized liquids) may be diluted with an inert gas or the like. At this time, the reaction gas may be supplied in a plasma state or an activated state in which radical species are generated by irradiation with electromagnetic waves or the like or a hot wire method.
Alternatively, a manganese-containing film may be deposited by reacting a (silylamidoaminoalkane) manganese compound vapor alone or mixed with a reaction gas and reacting in a plasma state in the vicinity of the substrate. Further, a manganese-containing film can be deposited by an ALD method in which a vapor of a bis (silylamidoaminoalkane) manganese compound, the above-described reaction gas and an activated reaction gas are alternately supplied to form a film. . Further, an intermediate pulse CVD method between the CVD method and the ALD method can also be used.

  In the CVD method and the ALD method, it is necessary to vaporize a bis (silylamidoaminoalkane) manganese compound for forming a manganese-containing film, but a method of vaporizing the bis (silylamidoaminoalkane) manganese compound used in the present invention. For example, not only a method of vaporizing the bis (silylamidoaminoalkane) manganese compound itself by filling or transporting it into the vaporizing chamber, but also a bis (silylamidoaminoalkane) manganese compound in an appropriate solvent (for example, hexane, cyclohexane). Aliphatic hydrocarbons such as methylcyclohexane, ethylcyclohexane, heptane and octane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene, tetralin and 1-methylnaphthalene; glyme, diglyme, triglyme, dioxane, te Ethers such as Rahidorofuran like. Diluted solution to) methods for vaporizing introduced into the vaporizing chamber in liquid conveying pump (solution process) may be used.

When the manganese-containing film is deposited by the CVD method or the ALD method using the bis (silylamidoaminoalkane) manganese compound of the present invention, as the deposition conditions, for example, the pressure in the reaction system is preferably 1 Pa to 200 kPa, The film formation target temperature is preferably 50 to 900 ° C., more preferably 100 to 600 ° C., and the temperature for vaporizing the bis (silylamidoaminoalkane) manganese compound is preferably 0 to 250 ° C., more preferably 30 to 200. ° C.
By setting it as this range, a manganese containing film | membrane can be efficiently vapor-deposited (formed) on a film-forming target object.

  It should be noted that a hydrogen source / reducing gas (for example, hydrogen gas or ammonia gas, or a mixed gas thereof), an oxygen source (for example, oxidizing gas, water vapor or alcohol vapor) with respect to the total gas amount when depositing the manganese-containing film, Or a mixed gas thereof) and a nitrogen source (for example, nitrogen gas, ammonia gas or a mixed gas thereof) are preferably 0.1 to 99.9% by volume, more preferably 1 to 99% by volume. is there.

  In the ALD method, the manganese compound and the reaction gas are alternately supplied in pulses. In order to repeat the process of alternately supplying the manganese compound and the reactive gas in a pulsed manner until the required film thickness is achieved, valve opening / closing control can be automated by a PLC (Programmable Logic Controller) or the like.

  In the ALD method, from the principle, the temperature of the film formation target is desirably lower than the thermal decomposition temperature of the manganese compound. The temperature allowable range of the film formation target in the ALD method is generally called an ALD window (ALD Window), and indicates a temperature range between the temperature at which the manganese compound is vaporized and the thermal decomposition temperature of the manganese compound. In general, a wider ALD window (a wider allowable temperature range) is desirable because the degree of freedom of the temperature of the film formation object is higher.

The manganese-containing film using the bis (silylamidoaminoalkane) manganese compound of the present invention can be used, for example, as a barrier film for copper wiring. Specifically, a manganese silicate film can be formed, or a manganese silicate film. A metal manganese film, a manganese oxide film, a manganese silicide film, a manganese nitride film, or the like can be formed as a pre-stage film for forming the film.
Further, a manganese nitride film may be used as the barrier film, or a manganese silicate film containing nitrogen may be formed.
Further, a manganese silicide film may be manufactured for a thermoelectric conversion element.

  A substrate on which both the CVD method and the ALD method are deposited can be cleaned in advance with hydrofluoric acid or ozone. Further, when it is desired to remove moisture adsorbed on the substrate surface, the substrate can be heated in the film forming apparatus or exposed to a reaction gas at an arbitrary temperature.

  Improve the physical properties of the film by reducing the impurities in the film by flowing the reaction gas again at an arbitrary temperature or heating the manganese-containing film deposited by both CVD and ALD methods, or the metal and alloy contained in the substrate (For example, silicidation or silicate formation) is also possible. At that time, it is possible to use a reaction gas converted into plasma as a reaction gas, or to convert it into a plasma near the substrate for reaction.

(Manufacturing equipment for manganese-containing films)
In the production of the manganese-containing film of the present invention,
A deposition target is provided,
A reaction chamber having a heating section that can be set to a predetermined temperature;
Bis (silylaminoamidoalkane) manganese compound supply means in the reaction chamber;
A gas (for example, ammonia gas, oxygen gas, water vapor gas, hydrogen gas, etc.) supplying means required for film formation in the reaction chamber;
An exhaust pipe connected to the reaction chamber, and exhaust means capable of exhausting the gas in the reaction chamber from the exhaust pipe and setting the reaction chamber to a predetermined pressure;
Supplying the bis (silylaminoamidoalkane) manganese compound in a state where the heating chamber is controlled to set the reaction chamber to a predetermined temperature, and the exhaust means is controlled to set the reaction chamber to a predetermined pressure. And a control unit for controlling the means to supply the bis (silylaminoamidoalkane) manganese compound into the reaction chamber and forming a manganese-containing film on the film formation target, and using a manufacturing apparatus for a manganese-containing film. be able to.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Reference Example 1 (Synthesis of 1-trimethylsilylamino-2-dimethylaminoethane)

In an argon atmosphere equipped with a stirrer, a thermometer and a dropping funnel, 7.1 g (81 mmol) of N, N-dimethylethylenediamine and 20 ml of hexane were added in an argon atmosphere. Next, while maintaining the liquid temperature at 0 ° C., 50 mL (80 mmol) of a 1.6 mol / L n-butyllithium hexane solution was slowly added dropwise and stirred at the same temperature for 30 minutes and at 20 ° C. for 2 hours. Reacted.
After completion of the reaction, the reaction solution was concentrated under reduced pressure, and then the concentrate was dried under vacuum to obtain (1-amido-2-dimethylaminoethane) lithium. 50 mL of tetrahydrofuran was added to make (1-amido-2-dimethylaminoethane) lithium suspended, and then 30 mL of a tetrahydrofuran solution of 8.7 g (80 mmol) of trimethylchlorosilane was gently added while maintaining the liquid temperature at 0 ° C. The solution was added dropwise and reacted at the same temperature for 30 minutes and at 20 ° C. for 3 hours while stirring.
After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 80 ml of hexane was added to the concentrate and stirred. After filtration, the filtrate obtained was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (74 ° C., 6.3 kPa) to give 7.8 g of 1-trimethylsilylamino-2-dimethylaminoethane as a colorless transparent liquid. (Isolated yield; 61%).

Example 1 (Synthesis of bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6)))

In an argon atmosphere, 3.2 g (20 mmol) of 1-trimethylsilylamino-2-dimethylaminoethane and 10 mL of hexane were added to a 50-mL flask equipped with a stirrer, a thermometer, and a dropping funnel. Then, while maintaining the liquid temperature at 0 ° C., 10 mL (16 mmol) of a 1.6 mol / L n-butyllithium hexane solution was gently added dropwise and stirred at the same temperature for 30 minutes and at 20 ° C. for 2 hours. Reacted. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and then the concentrate was dried under vacuum to obtain (1-trimethylsilylamido-2-dimethylaminoethane) lithium.
In a 50-mL flask equipped with a stirrer, thermometer, and dropping funnel separately prepared, 1.0 g (8.0 mmol) of manganese (II) chloride (anhydrolyzed in advance) and tetrahydrofuran in an argon atmosphere 20 mL was mixed and allowed to stir for 2 hours. Next, while maintaining the liquid temperature at 0 ° C., 10 mL of the tetrahydrofuran solution of the total amount of (1-trimethylsilylamido-2-dimethylaminoethane) lithium synthesized earlier was slowly dropped. Then, it was made to react at 20 degreeC for 6 hours, stirring.
After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 40 mL of hexane was added to the concentrate and stirred. After filtration, the filtrate obtained was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (80 ° C., 13 Pa) to obtain (bis (1-trimethylsilylamido-2-dimethylaminoethane-N) as a pale green solid. , N ′) 2.6 g of manganese (II) was obtained (isolation yield; 88%).
In addition, (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) was a novel compound represented by the following physical property values.

Melting point: 66-68 ° C
Manganese content by inductively coupled plasma (ICP) analysis; 14.9% by mass, silicon content; 15.3% by mass (calculated value; manganese; 14.7% by mass, silicon; 15.0% by mass)
In addition, the lithium used for the raw material which may be contained as an impurity was a concentration below the limit of quantification.

Comparative Example 1 (Synthesis of bis (hexamethyldisilazane) manganese (II))
In an argon atmosphere, 3.2 g (20 mmol) of hexamethyldisilazane and 10 ml of hexane were added to a flask having an internal volume of 50 mL equipped with a stirrer, a thermometer and a dropping funnel. Then, while maintaining the liquid temperature at 0 ° C., 10 mL (16 mmol) of a 1.6 mol / L n-butyllithium hexane solution was gently added dropwise and stirred at the same temperature for 30 minutes and at 20 ° C. for 2 hours. Reacted.
After completion of the reaction, the reaction solution was concentrated under reduced pressure, and then the concentrate was dried under vacuum to obtain hexamethyldisilazane lithium.
In a 50-ml flask equipped with a stirrer, a thermometer, and a dropping funnel separately prepared, 1.0 g (8.0 mmol) of manganese (II) chloride (anhydrolyzed in advance) and tetrahydrofuran in an argon atmosphere 20 mL was mixed and allowed to stir for 2 hours. Next, while maintaining the liquid temperature at 0 ° C., 10 mL of the tetrahydrofuran solution of the total amount of hexamethyldisilazane lithium synthesized previously was slowly dropped.
Then, it was made to react at 20 degreeC for 6 hours, stirring. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 40 mL of hexane was added to the concentrate and stirred. After filtration, the obtained filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (70 ° C., 13 Pa) to obtain a light brown solid.
Next, recrystallization was performed using hexane as a solvent to remove tetrahydrofuran coordinated to bis (hexamethyldisilazane) manganese. The obtained crystals were dissolved by heating and again distilled under reduced pressure (70 ° C., 13 Pa) to obtain 1.0 g of bis (hexamethyldisilazane) manganese (II) as a light brown solid (isolated yield; 33 %).

  The synthesized bis (hexamethyldisilazane) manganese (II) was confirmed to have the following physical property values.

Melting point: 57-60 ° C
Manganese content by inductively coupled plasma (ICP) analysis; 14.3% by mass, silicon content; 30.1% by mass (calculated value; manganese; 14.6% by mass, silicon; 29.9% by mass)
In addition, the lithium used for the raw material which may be contained as an impurity was a concentration below the limit of quantification.

Examples 2 to 7 (deposition experiment; production of manganese-containing thin film)
Using the manganese compound of the present invention (the compound obtained in Example 1), vapor deposition experiments were conducted by the CVD method and the ALD method, and the film formation characteristics were evaluated. The apparatus shown in FIG. 1 was used for the vapor deposition experiment. The apparatus shown in FIG. 1 has the following structure.
The manganese compound in the manganese raw material container (vaporizer) 7 maintained at a constant temperature by the thermostat 8 is heated and vaporized, and leaves the raw material container 7 along with the helium gas introduced through the mass flow controller 4. The gas exiting the raw material container 7 is introduced into the reactor 9. On the other hand, various reaction gases (hydrogen, ammonia, oxygen, etc.) are introduced into the reactor 9 via the mass flow controller 6. The water vapor was supplied by flowing helium gas from the mass flow controller 6 and passing water in the water container 24 maintained at a constant temperature by the thermostat 24. Various reaction gases are diluted to an arbitrary concentration with helium gas introduced through the mass flow controller 5 and then introduced into the reactor 9. The pressure in the reaction system is monitored by the pressure gauge 12 and is controlled to a predetermined pressure by opening and closing the valve 22. The central part of the reactor 9 has a structure that can be heated by the heater 11. The manganese compound introduced into the reactor 9 is set at the center in the reactor and reacts on the surface of the substrate 10 heated to a predetermined temperature by the heater 11 to form a manganese-containing thin film on the substrate 10. The The gas exiting the reactor 9 passes through a trap 13 and a vacuum pump 14, passes through a detoxifying device such as a scrubber, and is then exhausted to the atmosphere.
In the vapor deposition experiment by the ALD method, the gas of the manganese compound is supplied in a pulsed manner by operating the valves 19, 20, and 21, and then the various reactive gases are supplied in a pulsed manner by operating the valves 16, 17, 18. After reacting, exhausting, supplying manganese compound gas in pulses again, exhausting, reacting by supplying various reaction gases in pulses, and then evacuating until the desired film thickness is reached It was. Other operations were performed according to the CVD method.
Deposition conditions and film characteristics were as follows.

The deposition conditions and deposition results (film characteristics) are shown in Table 1. Note that a 6 mm × 20 mm rectangular substrate was used as the deposition substrate. As the SiO ₂ substrate, a Si wafer provided with a 300 nm SiO ₂ thermal oxide film was used.

Example 2 (Vapor deposition experiment; Manufacture of manganese-containing film)
(Bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6)) of the present invention, and existing bis (hexamethyldisilazane) manganese (II) (Patent Literature) 6, compounds described in Non-Patent Document 1) and (bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II) (compounds described in Patent Documents 4 and 5) The vapor deposition experiment by the CVD method was conducted to evaluate the film formation characteristics, and the vapor deposition conditions and film characteristics were as follows.

(Deposition condition 1A; Manganese silicide film produced by thermal decomposition)
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 450 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, SEM, XPS-depth measurement and sheet resistance value by four probe method))
Appearance: Silver metallic gloss film thickness: 100 nm
XPS analysis; manganese silicide film sheet resistance; 49Ω / □

Comparative Example 2A (deposition experiment; production of manganese-containing film)
(Deposition condition 1B: Manganese silicide film produced by thermal decomposition)
Manganese raw material; bis (hexamethyldisilazane) manganese (II)
Evaporation temperature: 60 ° C
Carrier helium flow rate: 10 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 450 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, sheet resistance value by four-probe method))
Appearance: No film formation, sheet resistance; not measurable

Comparative Example 2B (deposition experiment; production of manganese-containing film)
(Deposition condition 1C; Manganese silicide film produced by thermal decomposition)
Manganese raw material; bis (hexamethyldisilazane) manganese (II)
Evaporation temperature: 60 ° C
Carrier helium flow rate: 10 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 550 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement and sheet resistance value by four probe method))
Appearance; Silver metallic glossy film XPS analysis; Manganese silicide film sheet resistance; 251Ω / □

Reference Example 2 (Vapor deposition experiment; Manufacture of manganese-containing film)
(Vapor deposition condition 1D: Manufacture of metal manganese containing film by thermal decomposition)
Manganese raw material; (bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II) (compounds described in Patent Documents 4 and 5)
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 300 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, as measured by XPS-depth))
Appearance; Glossy metallic glossy film XPS analysis; Manganese film (silicon is not detected)
(Analysis is in the range from the surface to 50 nm, the film thickness of the Mn-containing film is 50 nm or more (about 100 nm), and since the manganese raw material does not contain silicon, the diffusion of Si from the substrate is in the range of 50 nm from the surface. (Not below the detection limit)

  From the above, it was found that a manganese silicide film having low resistance and low resistance can be produced using the manganese compound (6) of the present invention.

Example 3 (Vapor deposition experiment; Manufacture of manganese-containing film)
(Deposition condition 2A: Manganese nitride film produced under ammonia atmosphere)
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Ammonia flow rate; 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 200 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, SEM, XPS-depth measurement and sheet resistance value by four probe method))
Appearance; Silver metallic gloss film thickness: 300nm
XPS analysis; manganese nitride film sheet resistance; 57Ω / □

Comparative Example 3 (deposition experiment; production of manganese-containing film)
(Deposition condition 2B: Manganese nitride film production under ammonia atmosphere)
Manganese raw material; bis (hexamethyldisilazane) manganese (II)
Evaporation temperature: 60 ° C
Carrier helium flow rate: 10 sccm
Ammonia flow rate; 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 200 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement and sheet resistance value by four probe method))
Appearance; Silver metallic glossy film XPS analysis; Manganese nitride film sheet resistance; 105Ω / □

Comparative Example 4 (deposition experiment; production of manganese-containing film)
(Vapor deposition condition 2C; Manganese nitride film produced under ammonia atmosphere)
Manganese raw material; (bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II)
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Ammonia flow rate; 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 200 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement and sheet resistance value by four probe method))
Appearance; Silver metallic glossy film XPS analysis; Manganese nitride film sheet resistance; 83Ω / □

  From the above, it was found that a low resistance manganese nitride film can be produced using the manganese compound (6) of the present invention.

Example 4 (Vapor deposition experiment; Production of manganese-containing film)
(Deposition condition 3A; Manganese silicate film produced under oxygen atmosphere)
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Oxygen flow rate: 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 200 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement)
Appearance; Light brown film XPS analysis; Manganese silicate film

Comparative Example 5A (deposition experiment; production of manganese-containing film)
(Vapor deposition condition 3B; Manganese silicate film produced under oxygen atmosphere)
Manganese raw material; bis (hexamethyldisilazane) manganese (II)
Evaporation temperature: 60 ° C
Carrier helium flow rate: 10 sccm
Oxygen flow rate: 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 200 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance))
Appearance: No film formation

Comparative Example 5B (deposition experiment; production of manganese-containing film)
(Deposition condition 3C; Manganese silicate film produced in oxygen atmosphere)
Manganese raw material; bis (hexamethyldisilazane) manganese (II)
Evaporation temperature: 60 ° C
Carrier helium flow rate: 10 sccm
Oxygen flow rate: 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 250 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement)
Appearance; Light brown film XPS analysis; Manganese silicate film

Reference Example 3 (Vapor deposition experiment; Manufacture of manganese-containing film)
(Vapor deposition condition 3D; Manganese silicate film produced under oxygen atmosphere)
Manganese raw material; (bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II)
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Oxygen flow rate: 2.0 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 200 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement)
Appearance; Light brown film XPS analysis; Manganese oxide film (silicon is not detected)
(Analysis is in the range from the surface to 50 nm, the film thickness of the Mn-containing film is 50 nm or more (about 100 nm), and since the manganese raw material does not contain silicon, the diffusion of Si from the substrate is in the range of 50 nm from the surface. (Not below the detection limit)

  From the above, it was found that a manganese silicate film can be produced at a lower temperature using the manganese compound (6) of the present invention.

Example 5 (Vapor deposition experiment; Production of manganese-containing film)
(Vapor deposition condition 4A; Manganese silicate film produced under water vapor atmosphere)
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Water vapor flow rate: 0.5 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 100 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement))
Appearance; Light brown film XPS analysis; Manganese silicate film

Comparative Example 6 (Vapor deposition experiment; Manufacture of manganese-containing film)
(Vapor deposition condition 4B; Manganese silicate film produced under water vapor atmosphere)
Manganese raw material; bis (hexamethyldisilazane) manganese (II)
Evaporation temperature: 60 ° C
Carrier helium flow rate: 10 sccm
Water vapor flow rate: 0.5 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO2
Substrate temperature: 100 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement and sheet resistance value by four probe method))
Appearance; Light brown film XPS analysis; Manganese oxide film (silicon is not detected)

Reference Example 4 (Vapor Deposition Experiment; Manufacture of Manganese-Containing Film)
(Deposition condition 4C; Manganese silicate film produced under water vapor atmosphere)
Manganese raw material; (bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II)
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Water vapor flow rate: 0.5 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 100 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement))
Appearance; Light brown film XPS analysis; Manganese oxide film (silicon is not detected)
(Analysis is in the range from the surface to 50 nm, the film thickness of the Mn-containing film is 50 nm or more (about 100 nm), and since the manganese raw material does not contain silicon, the diffusion of Si from the substrate is in the range of 50 nm from the surface. (Not below the detection limit)

  From the above, it was found that a manganese silicate film can be produced using the manganese compound (6) of the present invention.

Example 6 (Vapor deposition experiment; Manufacture of manganese-containing film)
(Vapor deposition condition 5: Production of manganese metal film under hydrogen atmosphere)
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Hydrogen flow rate: 10 sccm
Diluted helium flow rate: 10 sccm
Substrate material: SiO ₂
Substrate temperature: 450 ° C
Reaction system pressure: 1.33 kPa
Deposition time: 20 minutes

(Membrane properties (appearance, XPS-depth measurement, sheet resistance value by four probe method))
Appearance; Silver metallic glossy film XPS analysis; Metal manganese film sheet resistance value: 42Ω / □

  From the above, it was found that a low-resistance metal manganese film can be produced using the manganese compound (6) of the present invention.

Example 7 (Vapor deposition experiment; Production of manganese-containing film)
Using (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6)) of the present invention, a vapor deposition experiment by ALD method was performed to evaluate the film forming characteristics. The deposition conditions and film characteristics were as follows.
(Vapor deposition condition 6; Manganese nitride film produced under ammonia atmosphere (ALD))
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Ammonia flow rate; 2.0 sccm
Diluted helium flow rate: 10 sccm
Manganese compound supply time (pulse width); 2 seconds / 1 cycle manganese raw material vacuum exhaust time (purge time); 30 seconds / 1 cycle ammonia supply time (pulse width); 5 seconds / 1 cycle ammonia vacuum exhaust time (purge time) A substrate material that performs 100 cycles in a total of 50 seconds per cycle of 13 seconds / cycle; SiO ₂
Substrate temperature: 200 ° C
Base pressure in reaction system; 0.66 kPa

(Membrane properties (appearance))
Appearance: Silver metallic luster film (inferred that a manganese nitride film is formed)

Reference Example 5 (Vapor deposition experiment; Production of manganese-containing film)
Using (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6)) of the present invention, a vapor deposition experiment by ALD method was performed to evaluate the film forming characteristics. The deposition conditions and film characteristics were as follows.
(Vapor deposition condition 7; Manganese nitrite (MnN) film produced under ammonia atmosphere (ALD))
Manganese raw material; (bis (1-trimethylsilylamido-2-dimethylaminoethane-N, N ′) manganese (II) (compound (6))
Evaporation temperature: 70 ° C
Carrier helium flow rate: 10 sccm
Ammonia flow rate; 2.0 sccm
Diluted helium flow rate: 10 sccm
Manganese compound supply time (pulse width); 2 seconds / 1 cycle manganese raw material vacuum exhaust time (purge time); 30 seconds / 1 cycle ammonia supply time (pulse width); 5 seconds / 1 cycle ammonia vacuum exhaust time (purge time) A substrate material that performs 100 cycles in a total of 50 seconds per cycle of 13 seconds / cycle; SiO ₂
Substrate temperature: 170 ° C
Base pressure in reaction system; 0.66 kPa

(Membrane properties (appearance, XPS-depth measurement))
Appearance; Silver metallic glossy film XPS analysis; Manganese nitride film

  From the above, it has been found that the manganese-containing film can be produced not only by the CVD method but also by the ALD method using the manganese compound (6) of the present invention.

  In addition, it is possible to manufacture a manganese containing film | membrane with the same method by changing ammonia which is the reaction gas of (deposition condition 6) into oxygen and water vapor | steam.

  From the above results, the bis (silylamidoaminoalkane) manganese compound of the present invention can produce a manganese-containing film at a lower temperature than the existing compounds in the CVD method, and in the case of a conductive film, it has a high quality with low resistance. It has been found that it can be a raw material for producing manganese-containing films. It has also been found that the ALD method can be a raw material for producing a manganese-containing film.

The present invention relates to a novel bis (silylamidoaminoalkane) manganese compound and a method for producing a manganese-containing film on a film formation object by CVD or ALD using the manganese compound.
Bis (silylamidoaminoalkane) manganese compounds are useful compounds as raw materials for producing manganese-containing film production materials, polymerization catalysts, pharmaceuticals, agricultural chemicals, and the like.

1. Carrier gas (helium)
2. Dilution gas (Helium)
3. Reaction gas (hydrogen, ammonia, oxygen, helium / water vapor, etc.)
4). 4. Mass flow controller Mass flow controller 6. Mass flow controller 7. Manganese raw material container (vaporizer)
8). 8. Thermostatic bath Reactor 10. Substrate 11. Reactor heater 12. Pressure gauge 13. Trap 14. Vacuum pump 15. Valve 16. Valve 17. Valve 18. Valve 19. Valve 20. Valve 21. Valve 22. Valve 23. Water container 24. Temperature chamber

Claims (4)

General formula (1)

(In formula, R < ¹ >, R < ² > and R < ³ > may be same or different, and show a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group.
R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms. R ⁴ and R ⁵ may be bonded to each other to form a ring.
Z represents a linear or branched alkylene group having 1 to 5 carbon atoms. )
A bis (silylamidoaminoalkane) manganese compound represented by: General formula (2)

(In the formula, R ⁶ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and M represents an alkali metal atom.)
An alkylalkali metal compound represented by formula (3):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Z are as defined above.)
Is reacted with a silylaminoaminoalkane compound represented by the general formula (4):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Z and M have the same meanings as described above).
A (silylamidoaminoalkane) alkyl metal compound represented by the formula (5) is obtained.

(In the formula, X represents a halogen atom.)
The method for producing a bis (silylamidoaminoalkane) manganese compound according to claim 1, wherein the dihalogenomanganese compound represented by formula (1) is reacted.   A method for producing a manganese-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using the bis (silylaminoamidoalkane) manganese compound according to claim 1 as a manganese supply source. A deposition target is provided,
A reaction chamber having a heating section that can be set to a predetermined temperature;
Bis (silylaminoamidoalkane) manganese compound supply means in the reaction chamber;
A gas (for example, ammonia gas, oxygen gas, water vapor gas, hydrogen gas, etc.) supplying means required for film formation in the reaction chamber;
An exhaust pipe connected to the reaction chamber, and exhaust means capable of exhausting the gas in the reaction chamber from the exhaust pipe and setting the reaction chamber to a predetermined pressure;
Supplying the bis (silylaminoamidoalkane) manganese compound in a state where the heating chamber is controlled to set the reaction chamber to a predetermined temperature, and the exhaust means is controlled to set the reaction chamber to a predetermined pressure. An apparatus for producing a manganese-containing film, comprising: control means for controlling the means to supply the bis (silylaminoamidoalkane) manganese compound into the reaction chamber and forming a manganese-containing film on the film formation target.

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