KR20180056949A - Group 13 metal precursor, composition for depositing thin film comprising the same, and a process for producing the thin film using the composition - Google Patents

Abstract

The present invention provides: a group 13 metal precursor; a manufacturing method thereof; and a method for producing a thin film using the same, wherein the group 13 metal precursor of the present invention presents as a liquid at room temperature to be easily handled, and has high volatile properties and thermal stability, thereby providing the thin film containing high quality group 13 metal easily by using the method.

Description

[0001] The present invention relates to a Group 13 metal precursor, a thin film deposition composition containing the same, and a method for manufacturing the thin film using the thin film deposition composition,

The present invention relates to a Group 13 metal precursor, a thin film deposition composition comprising the Group 13 metal precursor, and a method of preparing the thin film using the same. More particularly, the present invention relates to a Group 13 metal precursor useful as a precursor for thin film deposition containing a Group 13 metal, And a method of manufacturing a thin film using the same.

2. Description of the Related Art Recently, as demand for electronic devices such as liquid crystal display devices and thin film type displays such as organic light emitting diodes has increased, demands for high quality electronic devices have increased rapidly.

Silicon is the most widely used display driving element, but research is underway to replace silicon with the appearance of oxide semiconductors.

For example, oxide semiconductors are a new thin-film transistor material with a wide energy band gap and excellent light transmittance. Therefore, the oxide semiconductors have attracted a great deal of attention as a channel layer of an active region in a thin film transistor. Much research is under way as a material for future improvement.

Group 13 metal oxides can be used as transparent oxide semiconductor materials and can be applied to electrodes and conductive coating materials.

In particular, indium among the Group 13 metals is useful because of its excellent resistance to abrasion in the field of indium plating through electroplating and its low resistance in contact with aluminum wires. As a precursor used for indium oxide deposition, Me ₃ In is widely used.

However, InCl ₃ has a disadvantage in that chlorine contamination may occur during thin film deposition and oxygen source is required from the outside. Trialkylindium (III) such as Me ₃ In or Et ₃ In is highly volatile, There is a drawback that it is sensitive and solid.

Accordingly, in Korean Patent No. 10-1629696, an indium precursor which does not contain halogen and can prevent contamination is provided in order to solve the above-mentioned disadvantages.

However, studies on Group 13 metal precursors that are still volatile and thermally stable and applicable to various thin films are required.

Korean Patent No. 10-1629696

The present invention provides a Group 13 metal precursor which is highly volatile and thermally stable and can be used as a precursor of high quality Group 13 metal thin films.

The present invention also provides a composition for thin film deposition comprising a Group 13 metal precursor of the present invention.

The present invention also provides a method for preparing a thin film using the thin film deposition composition of the present invention and a thin film prepared using the Group 13 metal precursor of the present invention.

The present invention provides a Group 13 metal precursor useful for depositing a Group 13 metal thin film, wherein the Group 13 metal precursor is represented by the following Formula 1:

[Chemical Formula 1]

(In the formula 1,

M is a Group 13 metal;

R ¹ and R ² are independently C1 to C4 linear or branched alkyl, and R ³ to R ⁷ are independently of each other C 1 to C 10 linear or branched alkyl;

A is - (CR ¹¹ R ¹² ) _n -, and R ¹¹ and R < ¹² > independently from each other are hydrogen or (C1-C5) alkyl;

and n is an integer of 0 to 5.]

Preferably, in Formula 1 of the present invention, M may be aluminum, indium or gallium.

In the present invention, R ¹ and R ² are each independently (C 1 -C 4) alkyl, R ³ to R ⁷ are each independently (C 1 -C 10) alkyl, and R ¹¹ and R ¹² can be hydrogen; Preferably, R ¹ to R ⁷ independently of one another are (C 1 -C 4) alkyl, and R ¹¹ and R ¹² is hydrogen and n can be 1; More preferably, R ¹ to R ⁴ are methyl, R ⁵ to R ⁷ are (C 1 -C 3) alkyl, and R ¹¹ and R ¹² is hydrogen and n can be 1.

The present invention also provides a method for growing a Group 13 metal-containing thin film using the thin film deposition composition comprising the Group 13 metal precursor of the present invention and the Group 13 metal precursor of the present invention and a thin film containing the Group 13 produced therefrom .

The Group 13 metal precursor of the present invention exists as a liquid at room temperature, and is easy to store and handle, and has excellent thermal stability and volatility, so that a thin film of good quality can be produced.

In addition, the Group 13 metal precursor of the present invention can produce various thin films, a Group 13 metal oxide thin film, and especially a Group 13 metal nitride thin film in a uniform and high-purity thin film.

Therefore, the thin film deposition composition containing the Group 13 metal precursor of the present invention can easily produce a thin film of good quality by using the Group 13 metal precursor of the present invention.

1 is a graph showing the TG analysis results of the aluminum precursor prepared in Example 2 of the present invention.

The present invention provides a Group 13 metal precursor useful as a precursor for the deposition of various Group 13 metal thin films due to its high thermal stability and volatility. The Group 13 metal precursor of the present invention is represented by the following Chemical Formula 1.

[Chemical Formula 1]

(In the formula 1,

M is a Group 13 metal;

R ¹ and R ² are independently C1 to C4 linear or branched alkyl, and R ³ to R ⁷ are independently of each other C 1 to C 10 linear or branched alkyl;

A is - (CR ¹¹ R ¹² ) _n -, and R ¹¹ and R < ¹² > independently from each other are hydrogen or (C1-C5) alkyl;

and n is an integer of 0 to 5.]

In the general formula (1) of the present invention, M is a Group 13 metal, and examples thereof include boron, aluminum, gallium, indium, tallium or naphthyl And preferably aluminum, indium or gallium.

In the present invention, R ¹ and R ² are each independently (C 1 -C 4) alkyl, R ³ to R ⁷ are each independently (C 1 -C 10) alkyl, and R ¹¹ and R ¹² can be hydrogen; Preferably, R ¹ to R ⁷ independently of one another are (C 1 -C 4) alkyl, and R ¹¹ and R ¹² is hydrogen and n can be 1; More preferably, R ¹ to R ⁴ are methyl, R ⁵ to R ⁷ are (C 1 -C 3) alkyl, and R ¹¹ and R ¹² is hydrogen and n can be 1.

The term "alkyl" as used in the present invention includes both straight chain and branched chain.

Preferably, R ¹ to R ⁷ in the formula (1) of the present invention are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, isobutyl iso-butyl or tert-butyl.

The Group 13 metal precursor of the present invention can be prepared by reacting, for example, the following Chemical Formula 2 with Chemical Formula 3 or Chemical Formula 4, but any method that can be recognized by those skilled in the art is possible.

(2)

M (R ¹ ) (R ² ) (R ^a )

(3)

[Chemical Formula 4]

(Wherein M, R ¹ to R ⁷ , A are as defined in the above formula (1), R ^a is the same as defined in the above-mentioned formula (R ¹⁾ and R ² , and M ₁ is an alkali metal.

In the method of preparing the compound of Formula 1 according to an embodiment of the present invention, the reaction may be performed under nitrogen or an inert gas, and may be performed at room temperature (10 to 35 ° C) for 8 to 24 hours.

The present invention also provides a thin film deposition composition of the present invention and a method of preparing a thin film using the Group 13 metal precursor of the present invention.

The Group 13 metal thin film of the present invention can be manufactured by a conventional method, and examples thereof include MOCVD, ALD, LPCVD, PECVD, Or plasma enhanced atomic layer deposition (PEALD).

The Group 13 metal thin film of the present invention is manufactured using the Group 13 metal precursor of the present invention and is not limited thereto. For example, the Group 13 metal nitride film, the Group 13 metal oxide film, the Group 13 metal carbon nitride film, And preferably a Group 13 metal nitride film.

The process for preparing the Group 13 metal thin film of the present invention is excellent in physical, electrical and chemical properties of the Group 13 metal thin film produced by using the Group 13 metal precursor of the present invention having high volatility and high thermal stability.

In the process for preparing a Group 13 metal thin film of the present invention, the temperature of the Group 13 metal precursor may be in the range of 25 to 120 캜, and the Group 13 metal precursor may have a high volatility, The temperature may be between 100 and 450 캜, and the pressure inside the chamber may be between 0.1 and 10 torr.

The reaction gas used in the production process of a Group 13 metal thin film of the present invention include, but are not in limitation, hydrogen (H _2), hydrazine (N ₂ H _4), ozone (O _3), oxygen (O _2), water ( H ₂ O), ammonia (NH _3), nitrogen (N _2), silane (SiH _4), borane (BH _3), diborane (B ₂ H ₆₎ and one or one selected from the phosphine (PH ₃₎ Or more.

Hereinafter, the present invention will be described in more detail by way of examples. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It should be understood that there are numerous equivalents and variations.

Example 1 Synthesis of Al (CH ₃ ) ₂ (tmpda) (tmpda: N ² -methyl-N ¹ , N ¹ , 2-dimethylpropan-1,2-diamine)

Tromethaluminum (0.28 g, 3.83 mmol) was dissolved in toluene (20 mL) and then tmpda (0.50 g, 3.83 mmol) was added at low temperature (0 ° C.) and the mixture was stirred at room temperature for 12 hours . The reaction solution was filtered to remove by-products under reduced pressure to obtain the title compound (0.46 g, yield 64%) as a yellow liquid. (Purification temperature: 75 DEG C / 0.05 mmHg)

¹ H NMR (C ₆ D ₆ , 300 MHz):? - 0.55 (s, 6H), 1.05 (s, 6H), 1.84 (s, 6H), 2.11 (s, 2H), 2.69

Example 2 Synthesis of Al (CH ₃ ) ₂ (etmpda) (Etmpda: N ² -ethyl-N ¹ , N ¹ , 2-trimethylpropan-1,2-diamine)

 Tromethylaluminum (1.00 g, 13.8 mmol) was dissolved in toluene (50 mL) and the resulting solution was added with Etmpda (2.00 g, 13.8 mmol) at a low temperature (0 ° C.) and the temperature was raised to room temperature. . The reaction solution was filtered to remove the by-product under reduced pressure to obtain the title compound (2.13 g, yield 77%) as a yellow liquid. (Purification temperature: 70 DEG C / 0.05 mmHg)

^{_{1 H NMR (C 6 D 6}} , 300 MHz): δ -0.48 (s, 6H), 1.07 (s, 6H), 1.43 (t, 3H), 1.82 (s, 6H), 2.09 (s, 2H), 3.00 (q, 2H).

^{_{13 C NMR (C 6 D 6}} , 300 MHz): δ -7.6 (2C, Al (C H 3) 2), 19.0 (1C, N (CH 2 C H 3)), 28.9 (2C, C (C H _{3) 2), 38.0 (1C} , C (CH 3) 2), 47.1 (2C, CH 2 N (C H 3) 2), 54.5 (1C, N (C H 2 CH 3)), 73.6 (1C, C H ₂ N (CH ₃ ) ₂ ).

The results of the TG analysis of the aluminum precursor prepared in Example 2 are shown in FIG. 1. As shown in FIG. 1, the aluminum precursor of Example 2 starts mass reduction at about 80 ° C. and mass of not less than 87% at 242 ° C. It can be seen that the aluminum precursor produced has a high thermal stability.

[Example 3] Synthesis of Ga (CH ₃ ) ₂ (etmpda) (Etmpda: N ² -ethyl-N ¹ , N ¹ , 2-trimethylpropan-1,2-diamine)

 Trimethylaluminum (0.79 g, 6.93 mmol) was dissolved in toluene (50 mL) and the resulting solution was stirred at room temperature for 12 hours. . The reaction solution was filtered to remove by-products under reduced pressure to obtain 0.97 g (yield: 58%) of the title compound as a yellow liquid. (Purification temperature: 80 DEG C / 0.05 mmHg)

^{_{1 H NMR (C 6 D 6}} , 300 MHz): δ -0.14 (s, 6H), 1.11 (s, 6H), 1.36 (t, 3H), 1.80 (s, 6H), 2.08 (s, 2H), 3.07 (q, 2 H).

Example 4 Synthesis of In (CH ₃ ) ₂ (etmpda) (Etmpda: N ² -ethyl-N ¹ , N ¹ , 2-trimethylpropan-1,2-diamine)

Erlenmeyer flask was dissolved _{In (CH 3) 2 Cl (} 0.95g, 5.26 mmol) in THF (50) mL, Li ( etmpda) (0.79 g, 5.26 mmol) were put and stirred for 12 hours at room temperature. The reaction mixture was filtered to remove the byproducts under reduced pressure. The hexane was removed and the product was dried to obtain a pale yellow liquid compound (0.95 g, yield 63%). (Purification temperature: 75 DEG C / 0.05 mmHg)

^{_{1 H NMR (C 6 D 6}} , 300 MHz): δ -0.07 (s, 6H), 1.16 (s, 6H), 1.30 (t, 3H), 1.83 (s, 6H), 2.09 (s, 2H), 3.20 (q, 2H).

^{_{13 C NMR (C 6 D 6}} , 300 MHz): δ-5.9 (2C, In (C H 3) 2), 20.7 (1C, N (CH 2 C H 3)), 28.7 (2C, C (C H _{3) 2), 41.3 (1C} , N (C H 2 CH 3)), 48.9 (2C, CH 2 N (C H 3) 2), 57.9 (1C, C (CH 3) 2), 76.3 (1C, C H ₂ N (CH ₃ ) ₂ ).

Experimental Example 1. Analysis of manganese precursor material

Thermogravimetric analysis (TGA) was used to determine the thermal stability, volatility and decomposition temperature of Al (CH ₃ ) ₂ (etmpda) of Example 2 above. In the TGA method, argon gas was introduced at a pressure of 1.5 bar / min while heating the product to 900 ° C at a rate of 10 ° C / minute.

Al (CH ₃ ) ₂ (etmpda) of Example 2 began to show mass reduction at around 80 ° C and mass reduction of more than 87% at 200 ° C (FIG. 1).

It was also found from the TGA data that the degree of volatility of the compound of the present invention was good.

Claims (7)

A Group 13 metal precursor represented by the following formula (1).
[Chemical Formula 1]

(In the formula 1,
M is a Group 13 metal;
R ¹ and R ² are each independently C1 to C4 linear or branched alkyl,
R ³ to R ⁷ are each independently C1 to C10 linear or branched alkyl;
A is - (C (R ¹¹ R ¹² ) _n -, R ¹¹ and R < ¹² > independently from each other are hydrogen or (C1-C5) alkyl;
and n is an integer of 0 to 5.] The method according to claim 1,
R ¹ and R ² are independently (C 1 -C 4) alkyl, R ³ to R ⁷ are each independently (C 1 -C 4) alkyl, and R ¹¹ and R ¹² is hydrogen; and n is 1 to 2. 3. The method of claim 2,
R ¹ to R ⁷ are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl or tert-butyl tert-butyl) group 13 metal precursor.  A thin film deposition composition comprising a Group 13 metal precursor of any one of claims 1 to 3. A method of forming a Group 13 metal-containing thin film using a Group 13 metal precursor selected from any one of Claims 1 to 3. 6. The method of claim 5,
Wherein the thin film is grown by chemical vapor deposition (CVD) or atomic layer deposition (ALD). 13. A Group 13 metal-containing thin film prepared using the Group 13 metal precursor according to Claim 1.

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