KR102043296B1 - method of manufacturing an organic metal amine compound - Google Patents

Abstract

The present invention relates to a method for preparing an organometallic amine compound, which is a Group 13 organometallic thin film precursor applied to a transistor oxide semiconductor thin film and the like in a semiconductor and a display. It is a very efficient method for preparing organometallic amine compounds in high yield.

Description

Method of manufacturing an organic metal amine compound

The present invention relates to a method for producing an organometallic amine compound, and more particularly, to a method for producing an amine compound containing a Group 13 organometallic compound.

 "Oxide" is an important base material in semiconductors, displays, etc., attracting attention in various fields such as semiconductor devices, light emitting diodes, solar cells.

In particular, in order to realize high resolution in a display field, a transistor thin film material having high charge-carrier mobility is required for a channel.

The channel region of a conventional thin film transistor is mainly composed of amorphous silicon (a-Si). However, amorphous silicon (a-Si) has a low charge mobility of 0.5 cm ² / Vs or less, and requires a high manufacturing process temperature of 350 ° C. or higher, and thus there is a limit in implementing a high quality display.

Accordingly, in order to realize high quality displays, various efforts have been made to develop new materials to replace amorphous silicon (a-Si) applied to the channel region of the thin film transistor.

Accordingly, a thin film transistor using a zinc oxide (ZnO) -based amorphous oxide semiconductor, which has been recently studied, is known to have high uniformity in high charge mobility and electrical and optical characteristics. However, since the zinc oxide thin film is very easily crystallized during the deposition process, it is not easy to obtain an amorphous phase suitable for large area orientation, and there is a high possibility that the mobility of the device and the threshold voltage distribution problem may occur due to the presence of grain boundaries.

Recently, a thin film transistor using an indium-gallium-zinc oxide (hereinafter referred to as IGZO) in an amorphous state as an active layer has been proposed.

Since the active layer made of IGZO has a high mobility of about 10 cm 2 / Vs, device characteristics can be improved [K. Nomura et al., Nature (London) 432, 488 (2004) and H. Yabuta et al., Appl. Phys. Lett. 89, 112123 (2006).

Generally, sputtering using an IGZO target is mainly used to manufacture an IGZO thin film, but there is a problem in that the control of the thin film composition is not easy.

Recently, a method of preparing an IGZO thin film using an atomic layer deposition (ALD) or chemical vapor deposition (CVD) process using a precursor has emerged.

The composition of the IGZO thin film can be easily controlled when the thin film is manufactured using the ALD or CVD process, and there is an advantage that the electrical properties of the transistor device can be sufficiently represented through the uniform film quality.

Precursors used in the preparation of the IGZO thin film through the ALD or CVD process are typically trimethylindium (hereinafter referred to as TMI), trimethylgallium (hereinafter referred to as TMG), and diethylzinc (hereinafter referred to as DEZ).

Among these, precursors such as TMG and DEZ are liquid at room temperature, and thin film can be deposited by uniform composition control through uniform precursor supply when manufacturing thin film using ALD or CVD through high vapor pressure. However, since it exists as a solid at room temperature, there is a disadvantage in that particle production and uniform precursor supply are relatively difficult when manufacturing a thin film through a process.

Therefore, liquid indium and other Group 13 organometallic precursors that are liquid at room temperature required in ALD and CVD processes and which can suppress spontaneous flammability in water or air are required.

For this reason, [(3-dimethylamino) propyl] dimethylindium (hereinafter DADI) has recently emerged as a liquid indium precursor. DADI precursors are liquid at room temperature, have a relatively high vapor pressure, and unlike alkyl organometallic precursors (TMG, TMI, DEZ, etc.), which are mainly used for IGZO thin film deposition, they also suppress spontaneous ignition in water or air, and thus, It has the advantage of safe handling.

HERBERT SCHUMANN et al., Polyhedron Vol. 9, No. 2/3, pp. 353, 1990 are known methods for the preparation of DADI compounds.

However, the method for preparing a DADI compound described in the above literature requires an additional step to obtain a starting material, which is inefficient and inefficient, and also requires a study on a more efficient method for preparing a DADI compound.

Nature (London) 432, 488 (2004) Phys. Lett. 89, 112123 (2006) Polyhedron Vol. 9, No. 2/3, pp. 353, 1990

The present invention provides a method for preparing a Group 13 organometallic amine compound that can be used as a precursor of an organometallic thin film because it has a liquid or low melting point and high vapor pressure at room temperature.

The present invention provides an efficient method for producing a Group 13 organometallic amine compound, and the method for producing an organometallic amine compound of the present invention,

And reacting the organometallic compound represented by the following Chemical Formula 2 and the amine compound represented by the following Chemical Formula 3 in the presence of an alkali metal or an alkaline earth metal to prepare the organometallic amine represented by the following Chemical Formula 1.

[Formula 1]

 [Formula 2]

[Formula 3]

(In Chemical Formulas 1 to 3,

M is a Group 13 metal;

R ₁ to R ₃ and R ₁₁ to R ₁₂ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 3 -C 12) cycloalkyl or (C 3 -C 12) heterocycloalkyl;

X and X ₁ are independently of each other halogen;

n is an integer from 1 to 9;

Alkyl, alkoxy, cycloalkyl and heterocycloalkyl of R ₁ to R ₃ and R ₁₁ to R ₁₂ may be further substituted with one or more substituents selected from halogen, trifluoromethyl, amino, cyano and hydroxy. )

Preferably R ₁ to R ₃ and R ₁₁ to R ₁₂ in the general formula 1 according to an embodiment of the method for producing an organometallic amine compound of the present invention independently of each other hydrogen or (C1-C10) alkyl; n is an integer from 1 to 5; Alkyl of R ₁ to R ₃ and R ₁₁ to R ₁₂ may be further substituted with one or more substituents selected from halogen, trifluoromethyl, amino, cyano and hydroxy.

Preferably in the formula 1 according to an embodiment of the method for producing an organometallic amine compound of the present invention M may be boron, aluminum, gallium or indium.

More preferably, in Formula 1 according to an embodiment of the present invention, R ₁ to R ₃ and R ₁₁ to R ₁₂ are each independently hydrogen or (C 1 -C 3) alkyl, n may be an integer of 1 to 3.

Specifically, Formula 1 according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

[Wherein M is a Group 13 metal]

The alkali metal or alkaline earth metal according to an embodiment of the present invention may be used in 2.0 to 2.5 moles with respect to 1 mole of the organometallic compound represented by Formula 2, the alkali metal may be preferably lithium, sodium or potassium, The alkaline earth metal can be calcium or magnesium.

The amine compound represented by Chemical Formula 3 according to an embodiment of the present invention may be used in an amount of 1.0 to 1.5 mol based on 1 mol of the organometallic compound represented by Chemical Formula 2.

The reaction according to an embodiment of the present invention may be carried out for 8 to 24 hours at 0 to 60 ℃, aliphatic hydrocarbon solvent, alicyclic hydrocarbon solvent, aromatic hydrocarbon solvent, ketone solvent, aliphatic hydrocarbon chloride system It may be carried out in one or two or more mixed solvents selected from ether solvents and amide solvents.

The method for preparing the organometallic amine compound of the present invention is very economical and efficient because it proceeds to a simple process in a one-pot reaction.

In addition, the method for preparing the organometallic amine compound of the present invention is a very efficient method to obtain the organometallic amine compound in high yield and purity under mild reaction conditions.

The organometallic amine compound prepared according to the present invention can produce a very uniform and highly pure metal-containing thin film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) as a precursor of a metal thin film.

1 is a graph showing the vapor pressure of [3- (dimethylamino) propyl] dimethylindium prepared in Example 1. FIG.
FIG. 2 is a ¹ H-NMR graph of [3- (dimethylamino) propyl] dimethylindium prepared in Example 1. FIG.

The present invention provides a method for producing a Group 13 organometallic amine compound in high yield and purity under mild conditions in a single step process rather than a multi-step process.

And reacting the organometallic compound represented by the following Chemical Formula 2 and the amine compound represented by the following Chemical Formula 3 in the presence of an alkali metal or an alkaline earth metal to prepare an organometallic amine represented by the following Chemical Formula 1.

[Formula 1]

 [Formula 2]

[Formula 3]

(In Chemical Formulas 1 to 3,

M is a Group 13 metal;

R ₁ to R ₃ and R ₁₁ to R ₁₂ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 3 -C 12) cycloalkyl or (C 3 -C 12) heterocycloalkyl;

X and X ₁ are independently of each other halogen;

n is an integer from 1 to 9;

Alkyl, alkoxy, cycloalkyl and heterocycloalkyl of R ₁ to R ₃ and R ₁₁ to R ₁₂ may be further substituted with one or more substituents selected from halogen, trifluoromethyl, amino, cyano and hydroxy. )

The organometallic amine compound of the present invention is a compound having low spontaneous ignition in water and air, being present as a liquid at room temperature or as a solid having a low melting point, which is easy to handle, and has a high vapor pressure to facilitate thin film deposition.

Among these organometallic amine compounds, a method for preparing [(3-dimethylamino) propyl] dimethylindium (hereinafter referred to as DADI) is described in Polyhedron Vol. 9, No. 2/3, pp. 353, 1990. Polyhedron Vol. 9, No. According to the method known from 2/3, pp. 353, 1990, DADI is prepared by the following scheme 1.

Scheme 1

)는 하기 반응식 2에 의해 제조하였다.However, as described in the literature, dimethyl indium chloride (

) Was prepared by the following Scheme 2.

Scheme 2

)은 하기 반응식 3으로부터 제조하였다.3-dimethylaminopropyllithium (

) Was prepared from Scheme 3 below.

Scheme 3

Thus, Polyhedron Vol. 9, No. The method described in 2/3, pp. 353, 1990 proceeds in three stages of multi-step reactions, which is time consuming and costly, economically inefficient, and has a low yield of product.

The present inventors have completed the present invention in search of a method for obtaining an organometallic amine compound with a high yield by a simple process that proceeds in one step as a result of endless efforts to improve these disadvantages.

Unlike the conventional method, the organometallic amine compound of the present invention can prepare the organometallic amine in one step, and can produce the organometallic amine in high yield under mild conditions, which is very efficient.

Preferably R ₁ to R ₃ and R ₁₁ to R ₁₂ in formula 1 according to an embodiment of the present invention are independently of each other hydrogen or (C1-C10) alkyl; n is an integer from 1 to 5; Alkyl of R ₁ to R ₃ and R ₁₁ to R ₁₂ may be further substituted with one or more substituents selected from halogen, trifluoromethyl, amino, cyano and hydroxy.

More preferably, R ₁ to R ₃ may be independently of each other (C1-C10) alkyl, and R ₁₁ to R ₁₂ may be independently of each other hydrogen or (C1-C10) alkyl.

More preferably in Formula 1 R ₁ to R ₃ and R ₁₁ to R ₁₂ may be independently of each other hydrogen or (C1-C5) alkyl, more preferably hydrogen or (C1-C3) alkyl.

Specifically, R ₁ to R ₃ of the present invention are preferably methyl, ethyl, normal propyl, isopropyl, butyl and tertbutyl, most preferably methyl or ethyl.

Preferably n in the formula 1 according to an embodiment of the present invention may be an integer of 1 to 5, preferably 1 to 3, may be more preferably 3.

In terms of the reaction efficiency in the formula 1 according to an embodiment of the present invention preferably R ₁ to R ₃ and R ₁₁ to R ₁₂ are independently of each other hydrogen or (C1-C3) alkyl, n is 1 to 3 of It may be an integer.

The organometallic amine compound represented by Chemical Formula 1 according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

[Wherein M is a Group 13 metal, preferably indium.]

Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all linear or pulverized forms, preferably 1 to 10 carbon atoms, preferably 1 to 5, more preferably 1 It has a carbon atom of 3 to.

"Cycloalkyl" described in the present invention means a non-aromatic monocyclic or polycyclic ring system having 3 to 12 carbon atoms, and the monocyclic ring is, without limitation, cyclopropyl, cyclobutyl , Cyclopentyl and cyclohexyl. Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Bridged polycyclic cycloalkyl groups include adamantyl, norbornyl, and the like.

"Heterocycloalkyl" described in the present invention means a substituted or unsubstituted non-aromatic 3 to 12 membered ring radical composed of carbon atoms and 1 to 5 heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur, and heterocycloalkyl The radical may be a monocyclic, bicyclic or tricyclic ring system which may be fused, bridged or comprise a spiro ring system and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in the heterocyclic ring radicals may May be oxidized in some cases. In addition, the nitrogen atom may be quaternized in some cases.

In Formula 1 according to an embodiment of the present invention, M may be any group 13 metal, preferably boron, aluminum, gallium or indium, preferably indium or gallium.

In Formula 1 according to an embodiment of the present invention X and X ₁ are independently of each other halogen, for example F, Cl, Br and I, and may be preferably Cl or Br.

Alkali metal or alkaline earth metal according to an embodiment of the present invention can be any one of the range recognized by those skilled in the art, for example, may include Na, Li, K, Ca, Mg, but there is a limitation It is not.

Preferably, the alkali metal according to an embodiment of the present invention may be lithium.

Alkali metal or alkaline earth metal according to an embodiment of the present invention may be used in 2.0 to 2.5 moles, preferably 2.1 to 2.3 moles with respect to 1 mole of the organometallic compound represented by the formula (2).

The amine compound represented by Chemical Formula 3 according to an embodiment of the present invention may be used in an amount of 1.0 to 1.5 mol, preferably 1.1 to 1.3 mol, based on 1 mol of the organometallic compound represented by Chemical Formula 2.

 One or more mixed solvents selected from aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, aliphatic hydrocarbon chlorides, ether solvents, and amide solvents according to one embodiment of the present invention It may be carried out in, it may be preferably an ether solvent in terms of reaction efficiency.

Specifically, the solvent in one embodiment of the present invention is an aliphatic hydrocarbon solvent such as n-pentane, i-pentane, n-hexane, i-hexane or 2,2,4-trimethylpentane; Alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethyl benzene, ethyl benzene or methyl ethyl benzene; Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, diethyl ketone, cyclohexanone, methylcyclohexanone or acetylacetone; Aliphatic chloride hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene and tetrachloroethylene; Tetrahydrofuran, 2-methyl tetrahydrofuran, diethyl ether, n-propyl ether, diisopropyl ether, diglyme, dioxin, dimethyl dioxin, dimethoxymethane, dimethoxyethane, dimethoxypropane, diethoxymethane Ether solvents such as diethoxyethane or diethoxypropane; Ester solvents such as diethyl carbonate, methyl acetate or ethyl acetate; And amide solvents such as N-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylacetamide, or N, N-diethylacetamide. It is possible to use more than one species, and may be preferably an ether solvent in terms of reaction efficiency, and may be diethyl ether, n-propyl ether or diisopropyl ether in the ether solvent, more preferably diethyl ether It is effective to use.

The manufacturing method of the Group 13 organometallic compound of the present invention is very effective and economical because it is possible to produce a high purity Group 13 organometallic compound with a high yield in a very simple process.

The reaction according to an embodiment of the present invention may be performed for 8 to 24 hours at 0 to 60 ℃, preferably from 8 to 16 hours at 10 to 40 ℃ in terms of reaction efficiency.

The present invention will be described in more detail with reference to the following examples. Prior to this, terms or words used in the present specification and claims should not be construed as being limited to the common or dictionary meanings, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, these can be replaced at the time of the present application It should be understood that there are various equivalents and variations.

 Example 1 Preparation of [3- (dimethylamino) propyl] dimethylindium ([3- (dimethylamino) propyl] dimethylindium)

60.2 g (0.38 mol, 1.1 equiv) of 3-dimethylamino-1-propyl chloride hydrochloride was added to a flame dried 1000 mL Schlenk flask. After cooling the reaction solution to about 10 ℃ 300ml diethyl ether (Et2O) was injected. After the completion of the injection, 55.38 g (0.34 mol, 1 equivalent) of trimethylindium (InMe3) was slowly injected over about 90 minutes. At this time, the reaction temperature was not to exceed 30 ℃. After completion of the injection, the reaction solution was cooled again to about 10 ° C., and then slowly injected with 4.8 g of lithium (0.69 mol, 2 equivalents) being careful not to exceed the reaction temperature of 30 ° C. After completion of the injection, the temperature was raised to 35 ° C. and stirred under reflux for 12 hours. After completion of the reaction, lithium chloride (LiCl) was separated through filtration under reduced pressure, and the filtrate was removed by distillation under reduced pressure. Distillation under reduced pressure (44 ° C./2.2 Torr) to increase purity yielded 56 g (70% yield) of the title compound as a liquid.

¹ H-NMR (C ₆ D ₆ ): δ -0.20 (s, 6H), 0.60 (t, 2H), 1.71 (tt, 2H), 1.77 (s, 6H), 1.83 (t, 2H)

Claims (10)

Organic containing an organometallic compound represented by the following formula (2) and an amine compound represented by the following formula (3) in the presence of an alkali metal or alkaline earth metal reacted in one step to produce an organometallic amine compound represented by the formula (1) Method for producing a metal amine compound.
[Formula 1]

[Formula 2]

[Formula 3]

(In Chemical Formulas 1 to 3,
M is a Group 13 metal;
R ₁ to R ₃ and R ₁₁ to R ₁₂ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 3 -C 12) cycloalkyl or (C 3 -C 12) heterocycloalkyl;
X and X ₁ are independently of each other halogen;
n is an integer from 1 to 9;
Alkyl, alkoxy, cycloalkyl and heterocycloalkyl of R ₁ to R ₃ and R ₁₁ to R ₁₂ may be further substituted with one or more substituents selected from halogen, trifluoromethyl, amino, cyano and hydroxy. ) The method of claim 1,
R ₁ to R ₃ and R ₁₁ to R ₁₂ in Formula 1 are each independently hydrogen or (C 1 -C 10) alkyl;
n is an integer from 1 to 5;
Alkyl of R ₁ to R ₃ and R ₁₁ to R ₁₂ may be further substituted with one or more substituents selected from halogen, trifluoromethyl, amino, cyano and hydroxy. The method of claim 1,
M in the formula (1) is a method for producing an organometallic amine compound is boron, aluminum, gallium or indium. The method of claim 1,
In Formula 1, in Formula 1, R ₁ to R ₃ and R ₁₁ to R ₁₂ are each independently hydrogen or (C 1 -C 3) alkyl, n is an integer of 1 to 3 method for producing an organometallic amine compound. The method of claim 1,
The organometallic amine compound represented by Chemical Formula 1 may be selected from the following structures.

[Wherein M is a Group 13 metal] The method of claim 1,
The alkali metal or alkaline earth metal is a method for producing an organometallic amine compound which is lithium, sodium, potassium, calcium, magnesium. The method of claim 1,
The alkali metal or alkaline earth metal is a method for producing an organometallic amine compound is used in 2.0 to 2.5 moles with respect to 1 mole of the organometallic compound represented by the formula (2). The method of claim 1,
The amine compound represented by the formula (3) is a method for producing an organometallic amine compound is used in 1.0 to 1.5 moles with respect to 1 mole of the organometallic compound represented by the formula (2). The method of claim 1,
The reaction is carried out at 0 to 60 ℃ for 8 to 24 hours to prepare an organometallic amine compound. The method of claim 1,
The reaction is carried out in one or two or more mixed solvents selected from aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, aliphatic chloride hydrocarbons, ether solvents, and amide solvents. Method for producing an amine compound.

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