KR101221861B1 - Metal precursor and metal containing thin film prepared using same - Google Patents

Abstract

PURPOSE: A metal precursor and a metal-containing thin film fabricated using the same are provided to ensure storage stability, and to fabricate an In-Sb-Te(IST) thin film for a PRAM and InGaN film of an LED. CONSTITUTION: A metal precursor has a structure of chemical formula 1. In chemical formula 1: M is In; R1-R4 are independently a C1-C6 alkyl group; X is -NR5R6; R1 and R2 are independently a methyl group or ethyl group; and X is dimethylamino, ethylmethylamino, diethylamino, ethylmethylamino, diethylamino, dipropylamino, or diisopropylamino. A method for forming a metal-containing thin film comprises: a step of supplying the metal precursor of chemical formula 1 on a substrate for forming a metal thin film; and a step of thermally treating, treating with plasma, or irradiating light under the presence of reactive gas. The reactive gas is steam, ozone, hydrogen, ammonium, hydrazine, or silane.

Description

Metal precursor and metal-containing thin film manufactured using the same {METAL PRECURSOR AND METAL CONTAINING THIN FILM PREPARED USING SAME}

The present invention relates to a metal precursor and a metal-containing thin film produced using the metal precursor.

Semiconductor memory devices are classified into dynamic random access memory (DRAM), which is a volatile memory device, and non-volatile random access memory (NVRAM), a nonvolatile memory device. DRAM has a large market, but since the stored information is volatile, the same information needs to be stored again in a very short cycle, which consumes a lot of power. On the other hand, in the face of technical limitations due to the miniaturization process, non-volatile memory has emerged as a next-generation low-cost memory having a storage density of DRAM and an operating speed of static RAM (SRAM). In addition, research on the next generation nonvolatile memory is being actively conducted at home and abroad, and among them, phase change random access memory (PRAM) is attracting the most attention.

The phase change memory uses a chalcogenide material that exhibits optical and electrical switching phenomena between an amorphous and crystalline state, and is a memory in which information is recorded / erased / reproduced due to a difference in electrical resistance. Phase change memory is very excellent in terms of performance such as fast operation speed and high integration, and can be manufactured at low process cost because of simple device structure and manufacturing process.

Currently, Ge / Sb / Te (hereinafter referred to as 'GST') is widely used as a phase change memory device material, but GST material has significantly higher step coverage due to lower crystallization temperature than precursors used for depositing trench structures. There is a problem that voids occur.

In addition, an indium precursor is used as a phase change memory device material. Indium precursors have a problem in that process conditions are difficult and reproducibility is low because most of them are solid. In addition, due to low thermal stability, decomposition is promoted when heat is applied, and when exposed to air, there are various problems such as spontaneous ignition.

U.S. Pat.No.7,960,205 (registered June 14, 2011) Korea Patent Publication No. 2011-0088607 (2011.08.04 published)

It is an object of the present invention to have excellent thermal stability and to exist in a liquid state without fear of decomposition at room temperature and as a result shows excellent storage stability, less reactivity with moisture, there is no fear of spontaneous ignition, easy handling, high volatility and Sufficient vapor pressure is provided to provide novel metal precursors useful for the fabrication of In-Sb-Te (IST) thin films for next-generation phase change memory (PRAM) and InGaN films for light emitting diodes (LEDs) through the deposition process.

Another object of the present invention is to provide a metal-containing thin film prepared using the metal precursor.

According to an embodiment of the present invention, a metal precursor having a structure of Formula 1 is provided:

In Formula 1,

M is selected from the group consisting of B, Al, Ga, In and Tl,

R ¹ to R ⁴ are each independently an alkyl group of C ₁ to C ₆ ,

X is C ₁ to C ₆ alkyl group or -NR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently C ₁ to C ₆ alkyl group.

Preferably, R ¹ and R ² are each independently a methyl group or a methyl group.

Preferably, X is a methyl group (ethyl), ethyl group (ethyl), isopropyl group (isopropyl), dimethylamino group (dimethylamino), ethylmethylamino group (ethylmethylamino), diethylamino group, dipropylamino group, dipropylamino group, And it may be selected from the group consisting of diisopropylamino group (diisopropylamino).

Preferably, the metal precursor is dimethyl amidinate indium or dimethyl guadinate indium.

According to another embodiment of the present invention, there is provided a method of preparing a metal precursor of Chemical Formula 1, comprising reacting a compound of Chemical Formula 2 with an alkali metal-containing amidinate or guadiate:

In Formula 2,

M is selected from the group consisting of B, Al, Ga, In and Tl,

R ¹ and R ² are each independently a C ₁ to C ₆ alkyl group,

Y is a halogen atom.

The compound of Formula 2 may be prepared by reacting a trialkyl compound of a Group 13 metal with a Group 13 metal trihalide.

The trialkyl compound of the Group 13 metal may be selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, trimethyl aluminum, and mixtures thereof. .

The Group 13 metal trihalide may be selected from the group consisting of trichloro indium, trichloro gallium, trichloro aluminum, and mixtures thereof.

According to another embodiment of the present invention, a method of forming a metal-containing thin film comprising the step of supplying a metal precursor of the formula (1) on a substrate for forming a metal thin film, followed by heat treatment, plasma treatment or light irradiation in the presence of a reactive gas To provide.

The reactive gas may be selected from the group consisting of water vapor, oxygen, ozone, hydrogen, ammonia, hydrazine, and silane.

According to another embodiment of the present invention, the metal precursor of Formula 1 is supplied onto a substrate for forming a metal thin film, and then a metal-containing thin film prepared by heat treatment, plasma treatment or light irradiation in the presence of a reactive gas is provided.

Other specific details of embodiments of the present invention are included in the following detailed description.

The metal precursor according to the present invention has excellent thermal stability and is present in a liquid state without fear of decomposition at room temperature. As a result, it exhibits excellent storage stability. Its volatility makes it possible to carry out processes at low temperatures, and its sufficient vapor pressure makes it useful for the fabrication of next-generation In-Sb-Te (IST) thin films for PRAM and InGaN films for LEDs.

1 is a graph showing the results of thermogravimetric measurement using a thermo-gravimetric analyzer (TGA) for the metal precursors prepared in Examples 1, 2, and 4 to 6;

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise specified herein, 'halo' or 'halogen atom' means any one selected from the group consisting of fluorine, chlorine, bromine and iodine.

Unless otherwise specified herein, an 'alkyl group' refers to a linear or crushed alkyl group having 1 to 6 carbon atoms, and the alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, Hexyl group, and isohexyl group, but is not limited thereto.

The present invention has excellent thermal stability compared to the precursor material for forming a metal-containing thin film, and thus exists in a liquid state at room temperature without fear of decomposition, and as a result, shows excellent storage stability, and has low reactivity with moisture, which may cause spontaneous ignition. It is characterized by providing a novel metal precursor useful for the manufacture of next generation PRAM thin film for IST thin film and InGaN film for LED through the deposition process, easy to handle, high volatility and sufficient vapor pressure.

That is, the metal precursor according to the embodiment of the present invention may be a compound having the structure of Formula 1 below:

[Formula 1]

In Formula 1,

M is selected from the group consisting of B, Al, Ga, In and Tl,

R ¹ to R ⁴ are each independently an alkyl group of C ₁ to C ₆ ,

X is C ₁ to C ₆ alkyl group or -NR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently C ₁ to C ₆ alkyl group.

Specifically, in Chemical Formula 1, R ¹ to R ⁴ are each independently a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group , Neopentyl group, tert-pentyl group, hexyl group and isohexyl group may be selected, preferably R ¹ and R ² may be each independently a methyl group or an ethyl group, R ³ and R ⁴ is It may be an isopropyl group.

In addition, X may be selected from the group consisting of methyl group, ethyl group, isopropyl group, dimethylamino group, ethylmethylamino group, diethylamino group, dipropylamino group, and diisopropylamino group, preferably methyl group or dimethylamino group. have.

Specifically, the metal precursor of Chemical Formula 1 is dimethyl amidinate indium or dimethyl guadinate indium.

The metal precursor includes an alkyl group as substituents (R ¹ and R ² ) for the metal, and thus exhibits excellent stability compared to the metal precursor including an amide group as a substituent of the conventional metal, and enables low temperature deposition.

According to another embodiment of the present invention, a method of preparing a metal precursor of Chemical Formula 1 is provided by reacting a compound of Chemical Formula 2 with an alkali metal-containing amidinate or guadiate:

[Formula 2]

In Formula 2,

M is selected from the group consisting of B, Al, Ga, In, and Tl,

R ¹ and R ² are each independently a C ₁ to C ₆ alkyl group,

Y is a halogen atom, Preferably it is a chloro group.

In preparing the metal precursor compound of Chemical Formula 1, the compound prepared by Chemical Formula 2 may be prepared by the reaction of a trialkyl compound of Group 13 metal with a trihalide of Group 13 metal.

In this case, as the trialkyl compound of the Group 13 metal, a Group 13 metal-containing tri (C ₁ to C ₆ alkyl) compound may be used. Specifically, trimethyl indium, triethyl indium, trimethyl gallium, or trimethyl aluminum may be used, but is not limited thereto, and one or a mixture of two or more thereof may be used.

In addition, as the trihalide of the Group 13 metal, trichloroindium, trichlorogallium, or trichloroaluminum may be used, but is not limited thereto, and one or a mixture of two or more of them may be used.

Since the trialkyl compound of the Group 13 metal and the Group 13 metal trihalide react stoichiometrically, the amount of the trialkyl compound of the Group 13 metal and the Group 13 metal trihalide can be appropriately determined according to the stoichiometric reaction ratio. have. Specifically, the trialkyl compound of the Group 13 metal is preferably used in 1.5 to 2.5 moles with respect to 1 mole of the Group 13 metal trihalide.

The reaction of the trialkyl compound of the Group 13 metal and the trihalide of the Group 13 metal is carried out at -20 ° C to room temperature in a hydrocarbon-based organic solvent such as hexane, heptane, octane, benzene, toluene, ethylbenzene, and xylene. It is preferable.

Specifically, chlorodimethylindium, chlorodiethylindium, chlorodimethylgallium, or chlorodimethylaluminum may be used as the compound of Formula 2, but is not limited thereto, and one or a mixture of two or more of them may be used. Can be used.

In addition, in the preparation of the metal precursor compound of Formula 1, as the alkali metal-containing amidate or guadiate, one prepared by reacting alkyl lithium or lithium-alkylamine with alkylcarbodiimide may be used.

As the alkyl lithium or lithium-alkylamine, methyl lithium, ethyl lithium, propyl lithium, lithium dimethyl amine, lithium ethyl methyl amine, lithium diethyl amine, etc. may be used. As the alkyl carbodiimide, diisopropyl carboy may be used. Mead etc. may be used.

The reaction of the alkyllithium or lithium-alkylamine with alkylcarbodiimide may be carried out at an ethereal organic solvent such as diethyl ether at a temperature of -40 to 0 ° C, wherein the alkyllithium or alkyl-lithium The reaction ratio of the amine and the alkylcarbodiimide may be appropriately determined according to the stoichiometric ratio. Specifically, the alkyl carimide may be used in an amount of 0.9 to 1.1 mol based on 1 mol of alkyl lithium or alkyl-lithium amine.

The reaction of the compound of Formula 2 with an alkali metal-containing amidinate or guadiate includes hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene, ethyl benzene and xylene; Or in an organic solvent such as ethers such as diethyl ether, diisopropyl ether, glyme, dioxane, tetrahydrofuran and cyclopentylmethyl ether.

In the reaction of the compound of Formula 2 with an alkali metal-containing amidinate or guadiate, it is preferable that the compound of Formula 2 is used in an amount of 0.9 to 1.1 moles per 1 mole of alkali metal-containing amidinate or guadiate. . If the content of the compound of Formula 2 is less than 0.9 mole, the content of impurities may increase, and if it exceeds 1.1 mole, the yield may be lowered, which is not preferable.

The metal precursor of Chemical Formula 1 prepared by the above method not only exists in a liquid state at room temperature but also has excellent storage stability, and trimethylindium decomposes at 101 ° C. or higher as compared to trimethylindium used as a precursor for forming a metal thin film. On the contrary, since the metal precursor of Chemical Formula 1 decomposes at 230 ° C. or higher, it has excellent thermal stability. In addition, due to the excellent volatility, the process can be carried out at low temperatures when forming a thin film can reduce the process cost. In addition, the metal precursor of Chemical Formula 1 has little reactivity with water, so there is no fear of spontaneous ignition and is easy to handle, and has a high vapor pressure, which is useful for forming a thin film through a deposition process such as chemical vapor deposition or atomic layer deposition.

Accordingly, according to another embodiment of the present invention, a method of manufacturing a metal-containing thin film using the metal precursor is provided.

The manufacturing method is carried out by a conventional method for producing a metal thin film, for example, chemical vapor deposition (CVD) or atomic layer deposition (ALD), except that the compound of Formula 1 is used as the metal precursor. Can be.

Specifically, the metal thin film may be formed by gasifying the metal precursor of Chemical Formula 1 and supplying it onto a substrate, for example, TiN, SiO ₂ , Si ₃ N ₄ , to form a metal thin film layer, and then decomposing the metal precursor. have.

In this case, as the gasification method of the metal precursor, a method of gasifying the metal precursor as it is, or gasifying or putting the metal precursor in a thermostat, and then gasified by supplying an inert gas such as helium, neon, argon, krypton, xenon or nitrogen. Can be used.

The decomposition of the metal precursor may be performed by a method such as heat treatment, plasma treatment or light irradiation, and at this time, may be performed in the presence of a reactive gas such as water vapor, oxygen, ozone, hydrogen, ammonia, hydrazine, silane, or the like. When the decomposition process of the metal precursor is performed in the presence of a reactive gas such as water vapor, oxygen, ozone, etc., a metal oxide thin film may be formed, and the decomposition process of the metal precursor is performed in the presence of a reactive gas such as hydrogen, ammonia, hydrazine, or silane. If so, a metal thin film can be formed.

In addition, when the metal precursor is decomposed by heat treatment, the process may be performed at 100 to 1000 ° C.

The method for manufacturing a metal-containing thin film according to the present invention as described above, by using a metal precursor excellent in thermal stability, the deposition process can be carried out at a lower temperature than in the conventional deposition process, particle contamination or carbon due to thermal decomposition of the precursor It is possible to form a high purity metal, metal oxide, or metal nitride thin film without impurity contamination.

Thus, according to another embodiment of the present invention provides a metal-containing thin film prepared by the process of forming the metal-containing thin film described above.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Manufacturing example  One

To a solution prepared by adding 10 g (62.5 mmol) of anhydrous trimethylindium and 200 ml of toluene to a 250 ml Schlenk flask and cooling to -20 ° C, 6.91 g (31.3 mmol) of trichloroindium was slowly added dropwise and stirred for 30 minutes, and then gradually It was raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to give 16.9g (93.7mmol) of chlorodimethylindium (1-1) having the following structure as a white solid.

(1-1)

(1-1)

¹ H-NMR (C ₆ D ₆ , 25 ° C): 0.185 (s, 6H)

Manufacturing example  2

To a solution prepared by adding 10 g (49.5 mmol) of anhydrous triethylindium and 200 ml of toluene to a 250 ml Schlenk flask and cooling to -20 ° C, 5.47 g (24.8 mmol) of trichloroindium was slowly added dropwise and stirred for 30 minutes. The temperature was gradually raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to give 15.4 g (73.9 mmol) of chlorodiethylindium (1-2) having the following structure as a white solid.

(1-2)

(1-2)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): 0.195 (q, 4H), 0.91 (t, 6H)

Manufacturing example  3

To a solution prepared by adding 10 g (87.1 mmol) of anhydrous trimethylgallium and 200 ml of hexane to a 250 ml Schlenk flask, slowly adding dropwise addition of 7.67 g (43.6 mmol) of trichlorogallium to the solution prepared by cooling to -20 ° C, and then slowly stirring the temperature. Raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to give 17.6 g (130.1 mmol) of chlorodimethylgallium (1-3) having a structure as follows as a white solid.

(1-3)

(1-3)

1 H-NMR (C ₆ D ₆ , 25 ° C.): 0.201 (s, 6H)

Manufacturing example  4

To a solution prepared by adding 10 g (138.7 mmol) of anhydrous trimethylaluminum and 200 ml of hexane to a 250 ml Schlenk flask, and slowly cooling to -20 ° C, 9.25 g (69.4 mmol) of trichloroaluminum was slowly added dropwise, followed by stirring for 30 minutes and then slowly It was raised and stirred at room temperature. After the completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain 19.2 g (207.6 mmol) of chlorodimethylaluminum (1-4) having a white solid as follows.

(1-4)

(1-4)

1 H-NMR (C ₆ D ₆ , 25 ° C.): -0.331 (s, 6H)

Example  One

300 mL of anhydrous diethyl ether was added to a 500 mL Schlenk flask, and 49.3 ml (78.9 mmol) of methyllithium (1.6 M in diethyl ether) solution was added while cooling to -40 ° C., followed by diisopropylcarmide at -40 ° C. 9.96 g (78.9 mmol) was slowly added dropwise, and the mixture was slowly raised to room temperature and stirred for 4 hours. The resulting solution was cooled to −40 ° C., and then 15 g (83.1 mmol) of chlorodimethylindium prepared in Preparation Example 1 was slowly added thereto. After the addition, the temperature of the resulting reaction was gradually raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain a pale yellow liquid. The liquid was distilled under vacuum to remove impurities to obtain a clear colorless liquid compound (1). Compound (1) did not ignite or decompose upon exposure to air.

(1)

(One)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): 0.148 (s, 6H), 0.92 (d, 12H), 1.436 (s, 3H), 3.38 (s, 2H)

¹³ C-NMR (C ₆ D ₆ , 25 ° C): -6.269 (s, 2C), 10.99 (s, 1C), 25.774 (s, 4C), 45.587 (s, 2C), 167.59 (s, 1C)

DSC: 230 ℃

Example  2

300 mL of anhydrous diethyl ether was added to a 500 mL Schlenk flask, and 4.03 g (78.95 mmol) of lithium dimethylamine was added while cooling to -40 ° C., and then 9.96 g (78.95 mmol) of diisopropylcarbide was slowly added at -40 ° C. The mixture was added dropwise and gradually raised to room temperature, followed by stirring for 4 hours. After cooling the resulting solution to -40 ℃, 15 g (83.1 mmol) of chlorodimethyl indium prepared in Preparation Example 1 was slowly added. After the addition, the temperature of the resulting reaction was gradually raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain a pale yellow liquid. The liquid was distilled under vacuum to remove impurities to obtain a clear colorless liquid compound (2). The prepared compound (2) did not ignite or decompose even when exposed to the atmosphere.

(2)

(2)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): 0.173 (s, 6H), 0.97 (d, 12H), 2.42 (s, 6H), 3.50 (s, 2H)

¹³ C-NMR (C ₆ D ₆ , 25 ° C.): -5.804 (s, 2C), 25.404 (s, 4C), 39.234 (s, 2C), 46.05 (s, 2C), 167.081 (s, 1C)

DSC: 250 ℃

Example  3

300 mL of anhydrous diethyl ether was added to a 500 mL Schlenk flask, and 3.49 g (68.4 mmol) of lithium dimethylamine was added while cooling to -40 ° C., followed by 8.63 g (68.4 mmol) of diisopropylcarbodiimide at -40 ° C. It was slowly added dropwise, and gradually raised to room temperature, followed by stirring for 4 hours. The resulting solution was cooled to −40 ° C., and then 15 g (72 mmol) of chlorodiethylindium prepared in Preparation Example 2 was slowly added thereto. After the addition, the temperature of the resulting reaction was gradually raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain a pale yellow liquid. The liquid was distilled under vacuum to remove impurities to obtain a clear colorless liquid compound (3). The prepared compound (3) did not ignite or decompose even when exposed to the atmosphere.

(3)

(3)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): 0.158 (q, 4H), 0.83 (t, 6H), 0.99 (d, 12H), 2.44 (s, 6H), 3.57 (s, 2H)

¹³ C-NMR (C ₆ D ₆ , 25 ° C.): 0.037 (s, 2H), 19.457 (s, 2C), 26.521 (s, 4C), 40.338 (s, 2C), 46.511 (s, 2C), 168.256 (s, 1C)

Example  4

300 ml of anhydrous diethyl ether was added to a 500 mL Schlenk flask, and 65.8 ml (105.4 mmol) of methyllithium (1.6 M in diethyl ether) solution was added while cooling to -40 ° C., followed by diisopropyl carboy at -40 ° C. 13.3 g (105.4 mmol) of meads was slowly added dropwise, and the mixture was slowly raised to room temperature and stirred for 4 hours. After cooling the resulting solution to -40 ℃, 15 g (110.9 mmol) of chlorodimethylgallium prepared in Preparation Example 3 was slowly added. After the addition, the temperature of the resulting reaction was gradually raised and stirred at room temperature. After the completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain a pale yellow liquid. The liquid was distilled under vacuum to remove impurities to obtain a clear colorless liquid compound (4). The prepared compound (4) did not ignite or decompose even when exposed to the atmosphere.

(4)

(4)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): 0.106 (s, 6H), 0.96 (d, 12H), 1.354 (s, 3H), 3.289 (s, 2H)

¹³ C-NMR (C ₆ D ₆ , 25 ° C): -5.544 (s, 2C), 9.957 (s, 1C), 25.115 (s, 4C), 45.356 (s, 2C), 167.63 (s, 1C)

DSC: 232 ℃

Example  5

300 mL of anhydrous diethyl ether was added to a 500 mL Schlenk flask, and 5.38 g (105.4 mmol) of lithium dimethylamine was added while cooling to -40 ° C., and then 13.3 g (105.4 mmol) of diisopropylcarbodiim was slowly added at -40 ° C. The mixture was added dropwise and gradually raised to room temperature, followed by stirring for 4 hours. After cooling the resulting solution to -40 ℃, 15 g (110.9 mmol) of chlorodimethylgallium prepared in Preparation Example 3 was slowly added. After the addition, the temperature of the resulting reaction was gradually raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain a pale yellow liquid. The liquid was distilled under vacuum to remove impurities to obtain a clear colorless liquid compound (5). The prepared compound (5) did not ignite or decompose even when exposed to the atmosphere.

(5)

(5)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): 0.147 (s, 6H), 1.025 (d, 12H), 2.341 (s, 6H), 3.404 (s, 2H)

¹³ C-NMR (C ₆ D ₆ , 25 ° C.): -4.580 (s, 2C), 24.348 (s, 4C), 38.534 (s, 2C), 45.523 (s, 2C), 165.843 (s, 1C)

DSC: 232 ℃

Example  6

300 ml of anhydrous diethyl ether was added to a 500 mL Schlenk flask, and 96.3 ml (154.1 mmol) of methyllithium (1.6 M in diethyl ether) solution was added while cooling to -40 ° C., followed by diisopropyl carboy at -40 ° C. 19.45 g (154.1 mmol) of meads were slowly added dropwise, and the mixture was slowly raised to room temperature and stirred for 4 hours. The resulting solution was cooled to −40 ° C., and then 15 g (162.2 mmol) of chlorodimethylaluminum prepared in Preparation Example 4 was slowly added thereto. After the addition, the temperature of the resulting reaction was gradually raised and stirred at room temperature. After completion of the reaction, the solvent was removed using a vacuum at room temperature to obtain a pale yellow liquid. The liquid was distilled under vacuum to remove impurities to obtain a clear colorless liquid compound (6). The prepared compound (6) did not ignite or decompose even when exposed to the atmosphere.

(6)

(6)

¹ H-NMR (C ₆ D ₆ , 25 ° C.): -0.264 (s, 6H), 0.96 (d, 12H), 1.286 (s, 3H), 3.134 (s, 2H)

¹³ C-NMR (C ₆ D ₆ , 25 ° C.): -9.557 (s, 2C), 9.974 (s, 1C), 24.902 (s, 4C), 45.533 (s, 2C), 171.589 (s, 1C)

DSC: 235 ℃

Example  7

The metal precursor prepared in Example 1 was formed through an atomic layer deposition method to form an indium metal thin film. At this time, TiN was used as the substrate, and the substrate was heated to 200 to 350 ° C., and the metal precursor was vaporized by heating in a temperature range of 40 to 60 ° C. in a bubbler container made of stainless steel. At this time, the reaction gas was formed of a metal thin film through an ALD process using ammonia.

Test Example

In order to evaluate the volatility and thermal stability of the metal precursor according to the present invention, the thermogravimetric analysis (TGA) and the differential scanning calorimetry (DSC) were measured by the following method.

1) Thermogravimetric analysis (TGA) was performed up to 400 ° C. under a condition of an elevated temperature of 10 ° C./min in an atmosphere in which argon gas was flowed at 200 ml / min for the metal precursors prepared in Examples 1, 2, and 4 to 6 above. It was. For comparison, a known metal precursor for forming a metal thin film, (N, N'-diisopropylacetamidinato) bis (dimethylamido) gallium (Ga (dipma) (NMe) ₂ ) was used as Comparative Example 1. . The measurement results are shown in Table 1 and FIG. 1.

1 is a graph showing the results of TGA measurement for the metal precursor prepared in Examples 1, 2, and 4 to 6.

TGA (℃) Example 1 140 Example 2 170 Example 4 120 Example 5 156 Example 6 130 Comparative Example 1 185

As shown in Table 1 and FIG. 1, the metal precursors of Examples 1, 2, and 4 to 6 according to the present invention showed significantly improved volatility compared to Comparative Example 1.

2) Differential scanning calorimetry (DSC) was measured up to 400 ° C. under conditions of a temperature rising rate of 10 ° C./min in a sealed container for the metal precursors prepared in Examples 1, 2 and 4 to 6 above. For comparison, trimethylindium (TMIn), which is conventionally used as a precursor for forming a metal thin film, was used as Comparative Example 2. The measurement results are shown in Table 2 below.

DSC (占 폚) Example 1 230 Example 2 250 Example 4 232 Example 5 232 Example 6 235 Comparative Example 2 Decomposition above 101 ℃

As shown in Table 2, the trimethyl indium of Comparative Example 2 starts to decompose at 101 ° C or more, whereas the metal precursors of Examples 1, 2 and 4 to 6 have excellent thermal stability because they decompose at 230 ° C or more. You can check it.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (11)

A metal precursor having the structure of Formula 1
[Formula 1]

In Chemical Formula 1,
M is In,
R ¹ to R ⁴ are each independently an alkyl group of C ₁ to C ₆ ,
X is -NR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently an alkyl group of C ₁ to C ₆ . The method of claim 1,
Wherein R ¹ and R ² are each independently a methyl group or a methyl group. The method of claim 1,
X is a metal precursor selected from the group consisting of dimethylamino group (dimethylamino), ethylmethylamino group (ethylmethylamino), diethylamino group (diethylamino), dipropylamino group (dipropylamino), and diisopropylamino group (diisopropylamino). delete delete delete delete delete A method of forming a metal-containing thin film comprising supplying a metal precursor of Formula 1 to a substrate for forming a metal thin film and then performing heat treatment, plasma treatment, or light irradiation in the presence of a reactive gas:
[Formula 1]

In Chemical Formula 1,
M is In,
R ¹ to R ⁴ are each independently an alkyl group of C ₁ to C ₆ ,
X is -NR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently an alkyl group of C ₁ to C ₆ . 10. The method of claim 9,
And the reactive gas is selected from the group consisting of water vapor, oxygen, ozone, hydrogen, ammonia, hydrazine and silane. A metal-containing thin film prepared by supplying a metal precursor of Chemical Formula 1 onto a substrate for forming a metal thin film and then heat-treating, plasma treating or irradiating light in the presence of a reactive gas:
[Formula 1]

In Chemical Formula 1,
M is In,
R ¹ to R ⁴ are each independently an alkyl group of C ₁ to C ₆ ,
X is -NR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently an alkyl group of C ₁ to C ₆ .

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