KR20130136445A - Magnesium bis(dialkylamide)compound, and process for production of magnesium-containing thin film using the magnesium compound - Google Patents

Abstract

(식 중, R¹ 은 이소프로필기, 또는 탄소 원자수 4 ∼ 6 의 분기형의 알킬기를 나타내고, R² 는 탄소 원자수 1 ∼ 5 의 직사슬형 또는 분기형의 알킬기를 나타낸다. 단, R¹ 및 R² 가 모두 이소프로필기인 경우, R¹ 및 R² 가 모두 이소부틸기인 경우, 및, R¹ 이 이소프로필기이고 R² 가 메틸기인 경우를 제외한다) 로 나타내는 마그네슘비스(디알킬아미드) 화합물, 및 당해 마그네슘 화합물을 사용하는 마그네슘 함유 박막의 제조 방법에 관한 것이다.The present invention is formula (1)

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. If ¹ and R ² are both caused isopropyl, R ¹ and R ² If both the isobutyl group, and, R ¹ is an isopropyl group and magnesium bis (dialkylamide represented by exclusive of) a case where R ² is a methyl group ) And a method for producing a magnesium-containing thin film using the magnesium compound.

Description

MAGNESIUM BIS (DIALKYLAMIDE) COMPOND, AND PROCESS FOR PRODUCTION OF MAGNESIUM-CONTAINING THIN FILM USING THE MAGNESIUM COMPOUND}

The present invention relates to a novel magnesium bis (dialkylamide) compound and a method for producing a magnesium-containing thin film by chemical vapor deposition (hereinafter referred to as CVD method) using the magnesium compound. .

Conventionally, as a magnesium compound for magnesium containing thin film manufacture, various kinds of magnesium compounds, such as alkylmagnesium, magnesium alkoxide, and magnesium diketonate, are examined (for example, refer patent documents 1-2). Especially, bis (cyclopentadienyl) magnesium and its flexible compound are mainly used.

On the other hand, as a raw material for forming other metal containing thin films, such as a titanium containing thin film, a zirconium containing thin film, a hafnium containing thin film, and an aluminum containing thin film, the compound which has a dialkylamide ligand is proposed (refer patent document 3).

In addition, magnesium bis (dialkylamide) compounds are also known, and are used, for example, as raw materials for production of catalysts for polymerization, medicines and pesticides (see Non-Patent Document 1 and Patent Document 4, for example).

Japanese Unexamined Patent Publication No. 2002-170993 Japanese Laid-Open Patent Publication 2005-298874 Japanese Unexamined Patent Publication No. 2007-153869 European Patent Application No. 1031581

 J. Org. Chem., Vol. 43, No. 8, pp. 1564-1566 (1978)

However, the conventional magnesium compound is not necessarily optimal in the production of magnesium-containing thin film properties such as vapor pressure, thermal stability, reactivity, even the most adopted bis (cyclopentadienyl) magnesium, to prepare a magnesium-containing thin film It was difficult to say enough magnesium compounds. Therefore, there has been a demand for a magnesium compound that satisfies any physical properties such as vapor pressure, thermal stability, and reactivity.

An object of the present invention is to solve the above problems, and to manufacture a magnesium-containing thin film by a simple method, an industrially preferable magnesium compound, more specifically magnesium suitable for the production of a magnesium-containing thin film by the CVD method. To provide a compound. Another object of the present invention is to provide a method for producing a magnesium-containing thin film using the magnesium compound.

The present invention relates to the following matters.

General formula (1)

[Formula 1]

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. ^{When 1} and R ² are both isopropyl groups, except when R ¹ and R ² are both isobutyl groups, and when R ¹ is isopropyl group and R ² is methyl group)

Magnesium bis (dialkylamide) compound represented by.

2. General formula (2)

(2)

(In formula, R <^3> and R <^4> may be same or different, and each independently shows the C1-C10 linear or branched alkyl group.)

Dialkyl magnesium compound represented by general formula (3)

(3)

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. ^{When 1} and R ² are both isopropyl groups, except when R ¹ and R ² are both isobutyl groups, and when R ¹ is isopropyl group and R ² is methyl group)

A method for producing a magnesium bis (dialkylamide) compound represented by the general formula (1), comprising the step of reacting a dialkylamine represented by the formula (1).

3. General formula (3)

[Formula 4]

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. ^{When 1} and R ² are both isopropyl groups, except when R ¹ and R ² are both isobutyl groups, and when R ¹ is isopropyl group and R ² is methyl group)

The dialkyl amine represented by the reaction with alkyllithium is reacted with general formula (4)

[Chemical Formula 5]

(Wherein R ¹ and R ² have the same meaning as above)

Synthesizing a lithium dialkylamide compound represented by

Lithium dialkylamide compound represented by the said General formula (4), and General formula (5)

[Chemical Formula 6]

(Wherein X represents a halogen atom)

A process for producing a magnesium bis (dialkylamide) compound represented by the general formula (1), comprising the step of reacting dihalogeno magnesium represented by

4. A method for producing a magnesium-containing thin film by chemical vapor deposition using a magnesium bis (dialkylamide) compound represented by the general formula (1) as a magnesium source.

5. A raw material for forming a magnesium-containing thin film containing a magnesium bis (dialkylamide) compound represented by the general formula (1).

According to the present invention, it is possible to provide novel magnesium bis (dialkylamide) compounds which are particularly suitable for film formation by the CVD method. Using this magnesium compound, a magnesium-containing thin film can be produced with good film forming characteristics by the CVD method.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the structure of the vapor deposition apparatus for manufacturing a magnesium containing thin film using the magnesium bis (dialkylamide) compound used in the Example.

The magnesium bis (dialkylamide) compound of this invention is represented by said General formula (1).

In the general formula (1), R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms such as t-butyl group, t-pentyl group and neopentyl group, and R ² is a methyl group And a linear or branched alkyl group having 1 to 5 carbon atoms such as ethyl group, isopropyl group, t-butyl group, t-pentyl group and neopentyl group. However, when R ¹ and R ² are both isopropyl group, when R ¹ and R ² are both an isobutyl group, and, R ¹ is an isopropyl group and excluding the case where R ² is a methyl group.

Since the two R ¹ are different, and also, two R ² can be different, but also, the two R ¹ are the same and the two R ² The same compound is synthesized relatively easily, which is preferable.

In a preferred embodiment of the present invention, R ¹ is a branched alkyl group having 4 to 5 carbon atoms, and R ² is a linear or branched alkyl group having 1 to 5 carbon atoms. As R ¹ , a t-butyl group, a t-pentyl group and a neopentyl group are particularly preferable. As R ² , a methyl group, an ethyl group, isopropyl group, t-butyl group, t-pentyl group and neopentyl group are particularly preferable. R ¹ is a t-butyl group, a t-pentyl group, more preferably a t-butyl group, R ² is a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, It is preferable that they are an ethyl group, isopropyl group, t-butyl group, t-pentyl group, and neopentyl group.

As a magnesium bis (dialkylamide) compound of this invention, the compound represented by the following formula (6)-(20) is mentioned, for example.

[Formula 7]

The synthesis of the magnesium bis (dialkylamide) compound of the present invention can be carried out by a method represented by the following (A) or (B) (hereinafter sometimes referred to as the reaction of the present invention).

[Formula 8]

(In formula, R <^1> and R <^2> is synonymous with the above, R <^3> and R <^4> represents the C1-C10 linear or branched alkyl group. Moreover, R <^3> and R <^4> is the same or Or X may represent a halogen atom)

[Method (A)]

Method (A) is a method of synthesizing a magnesium bis (dialkylamide) compound by reacting a dialkyl magnesium compound with a dialkylamine.

The dialkyl magnesium compound used in reaction (A) of this invention is represented by said general formula (2). In the general formula (2), R ³ and R ⁴ are a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, t-pen The C1-C10 linear or branched alkyl group, such as a methyl group, a neopentyl group, and n-decyl group, is shown. In addition, R <^3> and R <^4> may be the same or different.

As a dialkyl magnesium compound used in reaction (A) of this invention, a commercial item can be used and can be manufactured from metal magnesium by a well-known method. In reaction (A) of this invention, Preferably di (n-butyl) magnesium, n-butyl ethyl magnesium, etc. are used.

The dialkylamine used in reaction (A) of this invention is represented by said general formula (3). In the general formula (3), R ¹ and R ² correspond to R ¹ and R ² in the formula (1), respectively, and have the same meaning as described above.

Therefore, as dialkylamine used in reaction (A) of this invention, t-butylmethylamine, t-butylethylamine, t-butylisopropylamine, di-t-butylamine, t-butyl-t -Pentylamine, di-t-pentylamine and the like are preferable.

The usage-amount of the said dialkylamine becomes like this. Preferably it is 1.5-3.0 mol with respect to 1 mol of dialkyl magnesium, More preferably, it is 1.8-2.2 mol.

It is preferable to perform reaction (A) of this invention in an organic solvent. Although it will not specifically limit, if it is a thing which does not inhibit reaction as an organic solvent used, For example, Ether, such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane; Aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane and ethylcyclohexane; Although aromatic hydrocarbons, such as toluene and xylene, are mentioned, Preferably, the mixed solvent of ethers, aliphatic hydrocarbons, ethers, and aliphatic hydrocarbons is used. In addition, you may use these organic solvents individually or in mixture of 2 or more types.

The usage-amount of the said organic solvent is 1-100 g, More preferably, it is 1-10 g with respect to 1 g of dialkyl magnesium.

Reaction (A) of this invention is performed by the method of, for example, mixing a dialkyl magnesium compound, a dialkylamine, and an organic solvent, making it react, stirring. The reaction temperature at that time becomes like this. Preferably it is -20-120 degreeC, More preferably, it is 0-100 degreeC, and reaction pressure is not specifically limited.

[Method (B)]

Method (B) is a method for synthesizing a magnesium bis (dialkylamide) compound by reacting lithium dialkylamide synthesized with dialkylamine and alkyllithium and dihalogeno magnesium.

The dialkylamine used in reaction (B) of this invention is represented by said general formula (3). In the said General formula (3), R <^1> and R <^2> respectively correspond to R <^1> and R <^2> in Formula (1), and are the same meaning as the above.

Although the alkyl lithium used in reaction (B) of this invention is not specifically limited, For example, methyl lithium, ethyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, etc. are mentioned, It is preferable. N-butyllithium is preferably used.

The amount of the alkyllithium used is preferably 0.8 to 1.2 moles, more preferably 0.9 to 1.1 moles, per 1 mole of dialkylamine.

In reaction (B) of this invention, lithium dialkylamide is synthesize | combined with dialkylamine and alkyl lithium, and this lithium dialkylamide and dihalogeno magnesium are made to react.

Dihalogeno magnesium used in reaction (B) of this invention is represented by said 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, but is preferably a chlorine atom.

The usage-amount of the said dihalogeno magnesium is 0.3-0.6 mol preferably with respect to 1 mol of dialkylamines, More preferably, it is 0.45-0.55 mol. When lithium dialkylamide is isolated, the usage-amount of lithium dialkylamide is 1.5-3.0 mol with respect to 1 mol of dihalogeno magnesium, More preferably, it is 1.8-2.2 mol.

It is preferable to perform reaction (B) of this invention in an organic solvent. Although it will not specifically limit, if it is a thing which does not inhibit reaction as an organic solvent used, For example, Ether, such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane; Aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane and ethylcyclohexane; Aromatic hydrocarbons, such as toluene and xylene, are mentioned, Preferably, a mixed solvent of ethers, aliphatic hydrocarbons, ethers and aliphatic hydrocarbons is used. In addition, you may use these organic solvents individually or in mixture of 2 or more types.

The usage-amount of the said organic solvent is 1-100 g with respect to 1 g of dialkylamines, More preferably, it is 1-10 g. When lithium dialkylamide is isolated, the usage-amount of the organic solvent at the time of making lithium dialkylamide and dihalogeno magnesium react is 1-100 g with respect to 1 g of dihalogeno magnesium, More preferably, 1-10 g.

Reaction (B) of this invention mixes dialkylamine, alkyllithium, and an organic solvent, for example, is made to react, stirring, and it synthesize | combines a lithium dialkylamide compound, and then adds dihalogeno magnesium, and further stirs The reaction is carried out while isolating or isolating the synthesized lithium dialkylamide, and then the obtained lithium dialkylamide, dihalogeno magnesium and an organic solvent are mixed and reacted while stirring. The reaction temperature at that time becomes like this. Preferably it is -20-100 degreeC, More preferably, it is 0-50 degreeC, and reaction pressure is not specifically limited. In addition, a lithium dialkylamide compound may be isolated once before reaction with dihalogeno magnesium, may be used as it is, without isolation, and may change, remove, and / or add an organic solvent suitably. .

By reaction (A) or (B) of the present invention, a magnesium bis (dialkylamide) compound as a target product is obtained. The synthesized magnesium bis (dialkylamide) compound is isolated and purified by a known method such as extraction, filtration, concentration, distillation, sublimation, recrystallization, column chromatography after completion of the reaction.

In addition, the magnesium bis (dialkylamide) compound which is the object of the present invention, and the dialkyl magnesium used for the production thereof are often unstable with respect to moisture and oxygen in the air, and therefore, the reaction operation is performed under anhydrous conditions or inert gas conditions. Or post-treatment of the reaction solution is preferable.

Using the magnesium bis (dialkylamide) compound of the present invention, a magnesium-containing thin film can be formed into a film with good film forming properties, for example, by the CVD method.

As a method for depositing a magnesium-containing thin film onto a film forming object, it can be carried out by a known CVD method or an atomic layer deposition method (ALD method). For example, magnesium bis (dialkylamide) under normal pressure or reduced pressure Compound vapor may be converted into an oxygen source (e.g., oxidizing gas such as oxygen, ozone; water; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol) or reducing gas (e.g., hydrogen Gas or ammonia gas, or a mixed gas thereof) can be used to deposit a magnesium-containing thin film by sending it onto a heated film forming object. In addition, these gases (including vaporized liquid) may be diluted with an inert gas or the like. Moreover, by the same raw material supply, a magnesium containing thin film can also be deposited by plasma CVD method.

In the CVD method, it is necessary to vaporize the magnesium bis (dialkylamide) compound in order to form a thin film, but as a method of vaporizing the magnesium bis (dialkylamide) compound used in the present invention, for example, magnesium bis In addition to the method of vaporizing the (dialkylamide) compound itself in the vaporization chamber by vaporization, the magnesium bis (dialkylamide) compound may be used in a suitable solvent (for example, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, Aliphatic hydrocarbons such as heptane and octane; aromatic hydrocarbons such as toluene, ethylbenzene and xylene; ethers such as glim, diglyme, triglyme, dioxane, tetrahydrofuran and the like); The method (solution method) which introduce | transduces into a vaporization chamber and vaporizes with a liquid conveying pump can also be used.

When depositing a magnesium containing thin film using the magnesium bis (dialkylamide) compound of this invention, as the vapor deposition conditions, the pressure in a reaction system, for example, Preferably it is 1 kPa-200 kPa, More preferably, The temperature at which the film-forming object temperature is 10 kPa to 110 kPa, preferably 50 to 900C, more preferably 100 to 600C, and the magnesium bis (dialkylamide) compound is preferably 30 to 250C, More preferably, it is 60-200 degreeC.

In addition, an oxygen source (e.g., an oxidizing gas, water vapor or alcohol vapor, or a mixed gas thereof) or a reducing gas (e.g., hydrogen gas or ammonia gas) relative to the total amount of gas when the magnesium-containing thin film is deposited As a content rate of these mixed gas), Preferably it is 3-99 volume%, More preferably, it is 5-98 volume%.

Example

Next, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited to these.

Example 1 (Method (A); Synthesis of Magnesium Bis (t-Butylmethylamide) (Compound (6)))

To a flask of 100 ml of internal volume equipped with a stirring device, a thermometer and a dropping funnel, 5.5 g (0.23 mol) of metal magnesium and 20 ml of diethyl ether were added in an argon atmosphere, followed by 3.0 g (21 mmol) of bromobutane. ) Was slowly added dropwise. Subsequently, 180 ml of diethyl ether and 25 g (0.18 mol) of bromobutane were slowly added dropwise and reacted at 40 ° C for 2 hours while stirring, and at 40 ° C while 55 g (0.62 mol) of dioxane was added and stirred. The reaction was carried out for 2 hours. After the reaction was completed, the reaction solution was filtered in an argon atmosphere, and the filtrate was concentrated under reduced pressure. The concentrate was dried in vacuo while heating to give 22 g of dibutylmagnesium (isolation yield: 80%).

Subsequently, in an argon atmosphere, 7.0 g (50 mmol) of dibutylmagnesium obtained first and 70 mL of heptane were added to a 200 mL flask equipped with a stirring device, a thermometer, and a dropping funnel, and the liquid temperature was brought to about 25 ° C. 10 g (0.11 mol) of t-butylmethylamines were dripped slowly, and it was made to react at 25 degreeC for 3 hours, stirring. After completion | finish of reaction, after concentrating a reaction liquid, it sublimed under reduced pressure (140 degreeC, 20 kPa), and obtained 6.4 g of magnesium bis (t-butylmethylamide) as a white solid (isolation yield: 66%).

Magnesium bis (t-butylmethylamide) was a novel compound represented by the following physical properties.

¹ H-NMR (tetrahydrofuran-d ₈ , δ (ppm)); 2.58 (3H, s), 1.03 (9H, s)

Melting point; 140-141 degreeC.

Example 2 (Method (A); Synthesis of Magnesium Bis (t-butylethylamide) (Compound (7)))

In Example 1, reaction was performed similarly to Example 1 except having changed the dialkylamine into 11 g (0.11 mol) of t-butylethylamine. As a result, 5.8 g of magnesium bis (t-butylethylamide) was obtained as a white solid (isolation yield: 52%).

In addition, magnesium bis (t-butylethylamide) was a novel compound represented by the following physical properties.

¹ H-NMR (tetrahydrofuran-d ₈ , δ (ppm)); 2.90 (2H, q, 6.8 Hz), 1.07 (9 H, s), 0.97 (3 H, t, 6.8 Hz)

Melting point; 75 to 78 deg.

Example 3 (Method (B); Synthesis of Magnesium Bis (t-butylisopropylamide) (Compound (8)))

 1.8 g (16 mmol) of t-butylisopropylamine and 30 mL of heptane were added to the flask of 100 mL of internal volume provided with the stirring apparatus, the thermometer, and the dropping funnel. Subsequently, 10 ml (16 mmol) of 1.6 mol / L n-butyllithium hexane solution was slowly added dropwise while maintaining the liquid temperature at around 25 ° C, and reacted at 25 ° C for 2 hours while stirring. After the completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 1.7 g of lithium-t-butylisopropylamide (isolation yield: 88%).

Subsequently, 0.40 g (4.2 mmol) of magnesium chloride and 10 mL of tetrahydrofuran were added to a 50 mL flask equipped with a stirring device, a thermometer, and a dropping funnel. Subsequently, 10 mL of 1.0 g (8.3 mmol) of tetrahydrofuran solutions of lithium-t-butylisopropylamide were dripped slowly, maintaining liquid temperature near 25 degreeC, and it was made to react at 25 degreeC for 8 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 20 ml of hexane was added to the concentrate, followed by stirring, followed by filtration. The filtrate was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (120 ° C., 5.7 kPa) to obtain 0.53 g of magnesium bis (t-butylisopropylamide) as a pale yellow liquid (isolation yield: 50%).

Magnesium bis (t-butylisopropylamide) was a novel compound represented by the following physical properties.

¹ H-NMR (tetrahydrofuran-d ₈ , δ (ppm)); 2.99 (1H, sept, 6.6 Hz), 1.14 (9H, s), 0.99 (6H, d, 6.6 Hz)

Example 4 (Method (B); Synthesis of Magnesium Bis (t-butyl-t-pentylamide) (Compound (10)))

To an internal volume 100 ml flask equipped with a stirring device, a thermometer, and a dropping funnel, 1.1 g (8.0 mmol) of t-butyl-t-pentylamine and 15 ml of heptane were added in an argon atmosphere, and the liquid temperature was around 25 ° C. 5.0 ml (8.0 mmol) of 1.6 mol / L n-butyllithium hexane solution was dripped slowly, and it was made to react at 25 degreeC for 2 hours, stirring. After the reaction was completed, the reaction solution was concentrated under reduced pressure to obtain 1.1 g of lithium-t-butyl-t-pentylamide (isolation yield: 90%).

Subsequently, 0.16 g (1.7 mmol) of magnesium chloride and 10 ml of tetrahydrofuran were added to a 50 ml flask with an internal volume equipped with a stirring device, a thermometer, and a dropping funnel, while maintaining the liquid temperature at around 25 ° C. 10 ml of tetrahydrofuran solutions of 0.51 g (3.4 mmol) of butyl-t-pentylamides were dripped slowly, and it was made to react at 25 degreeC for 8 hours, stirring. After completion | finish of reaction, after concentrating a reaction liquid, 20 ml of hexane was added and stirred, and it filtered. The filtrate was concentrated under reduced pressure, and 0.31 g of magnesium bis (t-butyl-t-pentylamide) was obtained as a pale yellow solid (isolation yield: 60%).

In addition, magnesium bis (t-butyl-t-pentylamide) was a novel compound represented by the following physical properties.

¹ H-NMR (tetrahydrofuran-d ₈ , δ (ppm)); 1.44 (4H, q, 7.3 Hz), 1.20 (18 H, s), 1.12 (12 H, s), 0.85 (6 H, t, 7.3 Hz)

Melting point; More than 170 ℃

Example 5 (Deposition Experiment; Preparation of Magnesium-Containing Thin Film)

Using the magnesium bis (t-butylmethylamide) (compound (6)) obtained in Example 1, the vapor deposition experiment by CVD method was performed, and the film formation characteristic was evaluated. The apparatus shown in FIG. 1 was used for vapor deposition experiment. Deposition conditions and film characteristics were as follows.

(Deposition condition)

Magnesium raw material; Magnesium Bis (t-butylmethylamide) (Compound (6))

Vaporization temperature; 100 ℃

He carrier flow rate; 100 sccm

Oxygen flow rate; 10 sccm

Substrate material; SiO ₂ / Si

Substrate temperature; 300 ° C

Pressure in reaction system; 1.33 ㎪

Deposition time; 30 minutes

Membrane Properties (XPS-depth Measurement)

Film thickness; 50 nm or more

XPS analysis; Magnesium oxide film

Carbon content rate; Not detected

Nitrogen content rate; Not detected

The apparatus shown in FIG. 1 has the following structures. The magnesium compound in the magnesium raw material container (vaporizer) 7 maintained at a constant temperature by the thermostat 8 is heated and vaporized and accompanies the raw material container 7 with the helium gas introduced through the mass flow controller 4. Comes out. The gas exiting the raw material container 7 is introduced into the reactor 9 together with the helium gas introduced through the mass flow controller 5. On the other hand, oxygen gas which is a reaction gas is also introduced into the reactor 9 via the mass flow controller 6. The pressure in the reaction system is monitored by the pressure gauge 12 and controlled to a predetermined pressure by opening and closing the valve in front of the vacuum pump 14. The center part of the reactor 9 has a structure which can be heated by the heater 11. The magnesium compound introduced into the reactor 9 is set at the central part in the reactor and is oxidatively pyrolyzed on the surface of the substrate 10 heated to a predetermined temperature by the heater 11 so that a magnesium-containing thin film is formed on the substrate 10. Is formed. The gas exiting the reactor 9 is exhausted to the atmosphere via the trap 13 and the vacuum pump 14.

Comparative Example 1 (Deposition Experiment; Preparation of Magnesium-Containing Thin Film)

Using bis (cyclopentadienyl) magnesium, deposition experiments by the CVD method were carried out in the same manner as in Example 5 to evaluate the film formation characteristics. Deposition conditions and film characteristics were as follows. In addition, vapor deposition experiments were carried out by adjusting various conditions and matching the supply amounts of raw materials with those in Example 5.

(Deposition condition)

Magnesium raw material; Bis (cyclopentadienyl) magnesium

Vaporization temperature; 30 ℃

He carrier flow rate; 10 sccm

Dilute He flow rate; 90 sccm

Oxygen flow rate; 10 sccm

Substrate material; SiO ₂ / Si

Substrate temperature; 300 ° C

Pressure in reaction system; 10 Torr (about 1.33 ㎪)

Deposition time; 30 minutes

Membrane Properties (XPS-depth Measurement)

Film thickness; 50 nm or more

XPS analysis; Magnesium oxide film

Carbon content rate; 30% (in terms of carbon atoms)

Nitrogen content rate; Not detected (nitrogen atom is not present in original raw material)

From the above results, it was found that by using the magnesium bis (dialkylamide) compound of the present invention, a high-quality magnesium-containing thin film (magnesium oxide film) containing no impurities such as carbon atoms and nitrogen atoms can be produced.

Industrial availability

INDUSTRIAL APPLICABILITY According to the present invention, an industrially suitable and novel magnesium compound capable of producing a magnesium-containing thin film by a simple method, more specifically, a magnesium compound suitable for the production of a magnesium-containing thin film by the CVD method can be provided. . Moreover, the method of manufacturing a magnesium containing thin film on a film formation object can also be provided by the CVD method using the said magnesium compound. Magnesium bis (dialkylamide) compound is a compound useful as a manufacturing raw material, such as a magnesium containing thin film manufacturing material, a polymerization catalyst, a medicine, or an agricultural chemical.

1: carrier gas (He)
2: dilution gas (He)
3: reactive gas (O ₂ )
4: mass flow controller
5: mass flow controller
6: mass flow controller
7: magnesium raw material container (vaporizer)
8: thermostat
9: reactor
10: substrate
11: reactor heater
12: pressure gauge
13: trap
14: vacuum pump

Claims (5)

In general formula (1)
[Chemical Formula 1]

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. ^{When 1} and R ² are both isopropyl groups, except when R ¹ and R ² are both isobutyl groups, and when R ¹ is isopropyl group and R ² is methyl group)
Magnesium bis (dialkylamide) compound represented by. The method of claim 1,
In general formula (2)
(2)

(In formula, R <^3> and R <^4> may be same or different, and each independently shows the C1-C10 linear or branched alkyl group.)
Dialkyl magnesium compound represented by general formula (3)
(3)

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. ^{When 1} and R ² are both isopropyl groups, except when R ¹ and R ² are both isobutyl groups, and when R ¹ is isopropyl group and R ² is methyl group)
General formula (1) characterized by including the process of making dialkylamine represented by the following reaction.
[Chemical Formula 4]

(Wherein R ¹ and R ² have the same meaning as above)
The manufacturing method of the magnesium bis (dialkylamide) compound shown by The method of claim 1,
General formula (3)
[Chemical Formula 5]

In the formula, R ¹ represents an isopropyl group or a branched alkyl group having 4 to 6 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. ^{When 1} and R ² are both isopropyl groups, except when R ¹ and R ² are both isobutyl groups, and when R ¹ is isopropyl group and R ² is methyl group)
The dialkyl amine represented by the reaction with alkyllithium is reacted with general formula (4)
[Chemical Formula 6]

(Wherein R ¹ and R ² have the same meaning as above)
Synthesizing a lithium dialkylamide compound represented by
Lithium dialkylamide compound represented by the said General formula (4), and General formula (5)
(7)

(Wherein X represents a halogen atom)
General formula (1) characterized by including the process of making dihalogeno magnesium represented by
[Chemical Formula 8]

(Wherein R ¹ and R ² have the same meaning as above)
The manufacturing method of the magnesium bis (dialkylamide) compound shown by A method for producing a magnesium-containing thin film by chemical vapor deposition using the magnesium bis (dialkylamide) compound according to claim 1 as a magnesium source. The raw material for magnesium containing thin film formation containing the magnesium bis (dialkylamide) compound of Claim 1.

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