KR100897495B1 - Novel gallium amino-alkoxide complexes and process for preparing thereof - Google Patents

Abstract

The present invention relates to a novel gallium aminoalkoxide compound represented by the following formula (1) and a preparation method thereof.

[Formula 1]

[In Formula 1, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group.]

The gallium compound according to the present invention is a precursor of gallium or gallium oxide, which is present in the solid state at room temperature and sublimes at low temperature, and thus is useful as a gallium raw material for thin film deposition or preparation of various alloys of gallium-containing materials. Can be used.

Gallium, gallium oxide precursors, gallium oxide, thin films, organometallic chemical vapor deposition (MOCVD), atomic layer deposition (ALD)

Description

Novel gallium amino-alkoxide compound and method for preparing the same

The present invention relates to a novel gallium trivalent aminoalkoxide compound, and more particularly, to a gallium aminoalkoxide compound useful as a precursor for preparing a material containing gallium and a method for producing the same.

Gallium oxide (Ga ₂ O ₃ ) is attracting attention as a new material for gas sensors, transparent conductors, phosphors, etc., and as a wide band gap compound (4.8 eV) In the state where oxygen is slightly deficient by addition of another compound, it becomes an n-type semiconductor. Ga ₂ O ₃ is an electrical insulator at room temperature and a semiconductor at temperatures above 500 ° C. having a chemically and thermally stable monoclinic form. Above 900 ° C, since the electrical conductivity changes depending on the concentration of oxygen, the oxygen concentration can be detected. Below 900 ° C it acts as a surface-control-type sensor to reduce gases such as ethanol. Therefore, it can be used as a gas sensor according to temperature. . (JS Kim, SB Lee, JH Bahng, JC Choi, HL Park, SI Mho, TW Kim, YH Whang, GC Kim, Phys Stat Sol, 2001, 187, 569;.. S. Basharat, CJ Carmalt, SJ King , ES Peters, DA Tocher, Dalton Trans . , 2004 , 3475; R. Binions, CJ Carmalt, IP Parkin, KFE Pratt, GA Shaw, Chem . Mater . , 2004 , 16, 2489). In addition, β-Ga ₂ O ₃ and amorphous Ga ₂ O ₃ are being concentrated as new phosphor host materials in thin-film electroluminescent (TFEL) devices. In addition, Ga ₂ O ₃ : Mn, Ga ₂ O ₃ : Cr, Ga ₂ O ₃ : Eu is a high emission multicolor emission in a thin-film emitting layer and a thick ceramic insulating layer luminescence multicolor emissions) were observed. (T. Miyata, T. Nakatani, T. Minami, Thin Solid Films , 2000 , 373, 145; T. Minami, H. Yamada, Y. Kubota, T. Miyata, Jpn. J. Appl . Phys . , 1997 , 31, L1191; T. Xiao, AH Kitai, G. Liu, A. Nakua, J. Barbier, Appl . Phys . Lett . , 1998 , 72, 3356) In addition, the use of ultraviolet light for the purposes of lithography, surface modification, anion generation, sterilization, etc., is increasing. The importance of materials that are compatible with each other is also increasing. In this respect, the tin-doped β-Ga ₂ O ₃ film is a unique oxide film that transmits a wide range of ultraviolet light and exhibits electrical conductivity. (M. Orita, H. Hiramatsu, H. Ohta, M. Hirano, H. Hosono, Thin Solid Films , 2002 , 411, 134; M. Orita, H. Hirano, H. Hosono, Appl . Phys . Lett . , 2000 , 77, 4166).

Precursors used for gallium oxide deposition include compounds containing fluorine such as [Ga (hfac)] ₃ (hfac = hexafluoroacetoacetonate), [Ga (OCH (CF ₃ ) ₂ ) ₃ (HNMe ₂ )], and the like. Gallium alkoxides such as [Ga (OBu ^t ) ₃ ] ₂ , [Ga (OPr ⁱ ) ₃ ] ₄ , and [Ga (OCMe ₂ Et) ₃ ] ₂ are known. However, the above-mentioned compounds have a disadvantage in that gallium fluoride (GaF ₃ ) is formed by fluorine when the thin film is deposited to contaminate the thin film, and the alkoxide type compound is not a unit, and thus has a poor volatility. (GA Battiston, R. Gerbasi, M. Porchia, R. Bertoncello, F. Caccavale, Thin Solid Films , 1996 , 279, 115; L. Miinea, S. Suh, SG Bott, J.-R. Liu, W.-K. Chu, DM Hoffmam, J. Mater . Chem . , 1999 , 9, 929; M. Valet, DM Hoffman, Chem . mater . , 2001 , 13, 2135)

In general, the synthesis of compounds having high volatility is the most important problem for designing and synthesizing precursors for thin films or nanomaterials, and a method of saturating the coordination sites of metals using a bidentate ligand instead of a simple alkoxide ligand is known. Among the bidentate ligands, aminoalkoxide strains are known to be more useful than alkoxyalkoxides (LG Hubert-Pfalzgraf, H. Guillon, Appl . Organomet. Chem ., 1998 , 12 , 221).

As described above, the gallium trivalent compound known in the art has problems such as insufficient volatility and fluorine contamination generated in the manufactured film. Therefore, for the easy synthesis of gallium trivalent compounds and nanomaterials having high volatility without containing fluorine in the compound itself as a precursor for the production of gallium oxide thin film, it is well soluble in organic solvents and can be decomposed at low temperatures. The development of gallium trivalent compounds is quite significant.

The present invention has been made to solve the above-mentioned problems, the object of the present invention is a thermally stable, highly volatile and capable of producing pure gallium oxide at low temperature, it does not contain fluorine or chlorine-containing amino alkoxide It is to provide a gallium compound and a method for producing the same.

The present invention relates to a novel gallium aminoalkoxide compound which is thermally stable, highly volatile and capable of producing pure gallium oxide at low temperature, and provides a gallium aminoalkoxide compound represented by the following Chemical Formula 1.

[Formula 1]

[In Formula 1, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group.]

More specifically, the gallium aminoalkoxide compound of Formula 1 includes a gallium aminoalkoxide compound represented by Formula 2 below.

[Formula 2]

[In Formula 2, R ¹ , R ² , R ⁴ and R ⁵ are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group; m is an integer of 1 to 3.]

More preferably, a gallium aminoalkoxide compound having m of 1 or 2 in Formula 2 is preferable, and specifically, in Formula 2, R ¹ , R ² , R ^4, and R ⁵ are each independently hydrogen, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , R ³ is CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ , C (CH ₃ ) ₃ , Si (CH _{3) ) 3, Si (C 2 H} 5) 3 or Si (CH ₃₎ a gallium alkoxide amino compound selected from ₂ (C ₂ H ₅₎ and the like.

Hereinafter, the present invention will be described in more detail.

The gallium amino alkoxide compound represented by Formula 1 according to the present invention is a gallium compound represented by the following formula (3) and the alkali metal salt represented by the formula (4) as a starting material to obtain a compound represented by the formula (5) by reacting in an organic solvent, The obtained compound of formula (5) and the alkali salt of dialkylamide or bistrialkylsilylamide of formula (6) can be prepared by reflux in an organic solvent, the reaction scheme for preparing a gallium amino alkoxide compound of formula (1) is shown in Scheme 1 Can be represented.

[Formula 1]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[In Formula 1, Formulas 3 to 6, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group; M is Li, Na or K; X is Cl, Br or I.]

Scheme 1

를 제조하는 다른 방법으로 하기 화학식 7로 표시되는 갈륨 아미드 화합물과 화학식 8로 표시되는 아미노알코올 화합물 2 당량을 반응시키는 방법이 있다. 이에 대한 반응식을 하기 반응식 2로 나타낼 수 있다.Gallium Compounds of the Invention

As another method of preparing a method, there is a method of reacting a gallium amide compound represented by Formula 7 with 2 equivalents of an aminoalcohol compound represented by Formula 8. Scheme for this can be represented by the following scheme 2.

[Formula 1]

[Formula 7]

[Formula 8]

[In Formula 1, 7 and 8, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group.]

Scheme 2

는 안정한 착화합물이고, 금속과 결합하는 알콕사이드의 산소에 대하여 α-탄소 위치에 비극성 알킬기가 결합해 있어 유기 용매에 대한 친화성이 높고, 중심 금속이 이웃한 리간드의 산소와 분자간 상호 작용을 일으키지 못하도록 입체 장애를 주기 때문에 단위체로 존재할 수 있다. 이러한 구조적 특성으로 인하여 상기 화학식 1의 갈륨 산화물용 선구 물질은 상온에서 안정한 고체로서 유기 용매, 예를 들면 벤젠, 테트라하이드로퓨란, 톨루엔, 클로로포름 등에 대한 용해도가 높고, 휘발성이 뛰어날 뿐만 아니라, 할로겐 원소를 포함하지 않기 때문에, 이들을 사용하여 질이 더 좋은 갈륨 산화물 박막을 얻을 수 있다.Gallium aminoalkoxide compound that is a novel gallium oxide precursor of Formula 1

Is a stable complex, has a non-polar alkyl group bonded to the α -carbon position with respect to the oxygen of the alkoxide which binds to the metal, and thus has high affinity for the organic solvent, and is steric such that the central metal does not cause intermolecular interaction with the oxygen of the neighboring ligand. It can be present as a monomer because of its disability. Due to these structural characteristics, the precursor for gallium oxide of Formula 1 is a stable solid at room temperature, has high solubility in organic solvents such as benzene, tetrahydrofuran, toluene, chloroform, and the like, and is highly volatile. Since it does not contain, a gallium oxide thin film of higher quality can be obtained by using these.

The thermal stability, volatility and decomposition temperature of the gallium aminoalkoxide compounds synthesized in the present invention were investigated using thermogravimetric analysis / differential thermal analysis (TGA / DTA). As shown in Figure 4 it was confirmed that a sharp weight loss occurs in the vicinity of 220 ℃ -295 ℃. It also shows a single step and the residual amount is 4.05%.

As a result, the gallium amino alkoxide compound (Formula 1), which is a gallium oxide precursor synthesized in the present invention, exhibits sufficient volatility before decomposition temperature and has high solubility in organic solvents. It is preferably applicable to a vapor deposition method (MOCVD) process or an atomic layer deposition method (ALD).

The gallium oxide precursor according to the present invention binds to an oxygen atom ligand to favor the preparation of gallium oxide, and has an excellent thermal stability and volatility as well as an excellent storage stability due to the combination of an alkylamide which improves volatility. It can be usefully used as a gallium precursor having a novel ligand for organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), which requires the production of an excellent oxide film.

The invention is better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

[ Example ]

All experiments were performed in an inert argon or nitrogen atmosphere using a glove box or Schlenk line. The structure of the reaction product is characterized by proton nuclear magnetic resonance spectroscopy ( ¹ H NMR), carbon atom nuclear magnetic resonance spectroscopy ( ¹³ C NMR), Fourier transform infrared spectroscopy (FT-IR) analysis and elemental analysis (EA) and thermal weight Analyzes were performed using thermogravimetric analysis / differential thermal analysis (TGA / DTA).

[ Example  1] {bis [1-dimethylamino-2- methyl -2- Propoxy ] [ Vis ( Trimethylsilyl ) Amido]} Gallium [Ga ( dmamp ) ₂ (btsa)] Synthesis I

2.8 g (20 mmol) of Na (dmamp) was added to a 125 mL Schlenk flask containing hexane (50 mL), and 1.76 g (10 mmol) of GaCl ₃ was added to hexane (30 mL). This mixed solution was refluxed for one day, the solution was filtered and the solvent was removed under reduced pressure. The obtained solid was sublimed (74 ° C./10 ⁻² torr) to obtain a gallium compound in which two alkoxides and one halide were bonded to each other, as represented by the formula (5). 2 g (5.92 mmol) of compound Ga (dmamp) ₂ Cl (5.92 mmol) and 1 g (5.92 mmol) of Li (btsa) (btsa = bis (trimethylsilyl) amide) were added to a 125 mL Schlenk flask and toluene (100 mL) was added. To reflux for 24 hours. The mixture was filtered, the solvent was removed under reduced pressure, and then sublimed (64 ° C./10 ⁻² torr) to give the title compound Ga (dmamp) ₂ (btsa) as a white solid (2.27 g, yield 83%).

¹ H NMR (C ₆ D ₆ , 300.13 MHz): 0.47, (s, 18H, Si (C H ₃ ) ₃ ), 1.23, 1.27 (d, 12H, C (C H ₃ ) ₂ ), 2.02, 1.98 ( d, 2H, C H ₂ ), 2.29 (s, 12H, N (C H ₃ ) ₂ ), 2.25 (d, 2H, C H ₂ ).

¹³ C NMR (C ₆ D ₆ , 75.47 MHz): 6.67, 32.6, 33.5, 49.1, 67.1, 68.8, 72.1

FT-IR (cm ^-1 , KBr pellet): υ (Ga-O) 643

Elemental Analysis C ₁₈ H ₄₆ N ₃ O ₂ Si ₂ Ga {Calcd. (Found)}: C, 46.75 (46.13); H, 10.03 (10.66); N, 9.01 (9.09).

[ Example  2] {bis [1-dimethylamino-2- methyl -2- Propoxy ] [ Vis ( Trimethylsilyl ) Amido]} Gallium [ Ga ( dmamp ) ₂ (btsa)] II

Add 11.02 g (20 mmol) of Ga (btsa) ₃ to a 250 mL Schlenk flask containing toluene (100 mL). Lower the reaction solution to 0 ° C. and slowly add 4.69 g (40 mmol) of dmampH (1-dimethylamino-2-methyl-2-propanol) using a syringe. The reaction was raised to room temperature and stirred for 24 hours. The mixture was filtered, and then the volatiles of the solution were removed under reduced pressure and then sublimed (64 ° C./10 ⁻² torr) to give compound Ga (dmamp) ₂ (btsa) as a white solid (7.60 g, Yield 75%).

Proton nuclear magnetic resonance spectroscopy ( ¹ H NMR) analysis results of the gallium oxide precursor synthesized in Example 1 shown in Figure 1, carbon atom nuclear magnetic resonance spectroscopy ( ¹³ C NMR) analysis results in Figure 2, Fourier transform Infrared spectroscopy (FT-IR) analysis results are shown in FIG. 3, and thermogravimetric analysis (TGA) and differential thermal analysis (DTA) results are shown in FIG. 4.

1 is a result of ¹ H NMR analysis of the Ga (dmamp) ₂ (btsa) compound prepared in Example 1,

FIG. 2 is Ga (dmamp) ₂ (btsa) prepared in Example 1. FIG. ¹³ C NMR spectrum of a compound,

3 is a Fourier transform FT-IR analysis result of the Ga (dmamp) ₂ (btsa) compound prepared in Example 1,

Figure 4 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of Ga (dmamp) ₂ (btsa) compound prepared in Example 1.

Claims (8)

Gallium aminoalkoxide compound represented by the following formula (1). [Formula 1]

[In Formula 1, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group.] The method of claim 1, Gallium aminoalkoxide compound represented by the following formula (2). [Formula 2]

[In Formula 2, R ¹ , R ² , R ⁴ and R ⁵ are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group; m is an integer of 1 to 3.] The method of claim 2, The gallium amino alkoxide compound, wherein m is 1 or 2. The method of claim 2, R ¹ , R ² , R ⁴ and R ⁵ are independently selected from hydrogen, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and R ³ is CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ , C (CH ₃ ) ₃ , Si (CH ₃ ) ₃ , Si (C ₂ H ₅ ) ₃ or Si (CH ₃ ) ₂ (C ₂ H ₅ ) Gallium aminoalkoxide compound characterized by the above-mentioned. To prepare a gallium amino alkoxide compound of formula (1) characterized by reacting the compound represented by the formula (5) and the alkali metal salt of the formula (6) obtained by reacting the gallium compound represented by the formula (3) and the alkali metal salt represented by the formula (4) Way. [Formula 1]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[In Formula 1, Formulas 3 to 6, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group; M is Li, Na or K; X is Cl, Br or I.] A method for producing a gallium aminoalkoxide compound of formula (1) characterized by reacting a gallium amide compound represented by the formula (7) and an aminoalcohol compound represented by the formula (8). [Formula 1]

[Formula 7]

[Formula 8]

[In Formula 1, 7 and 8, A is alkylene of C ₂ -C ₅ , wherein A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl groups; R ¹ and R ² are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group; R ³ is a C ₁ -C ₅ linear or branched alkyl group or a tri (C ₁ -C ₅ ) alkylsilyl group.] A method of growing gallium oxide using the gallium aminoalkoxide compound according to any one of claims 1 to 4 as a precursor. The method of claim 6, Gallium oxide is formed by chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

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