KR20100024558A - Novel indium amino-alkoxide complexes and process for preparing thereof - Google Patents

Abstract

PURPOSE: A novel indium amino alkoxide compound is provided to prepare thin film deposition or various alloys. CONSTITUTION: An indium amino alkoxide compound is denoted by chemical formula 1, (In[O-A-NR^1R^2]2[NR^3_2]). In chemical formula 1, A is C2-C5 alkylene; R^1 and R^2 are dependently hydrogen or C1-C5 linear or branched alkyl group; and R^3 is C1-C5 linear or branched alkyl group or tri(C1-C5)alkylsilyl group. A method for preparing an indium amino alkoxide compound comprises: a step of reacting alkali metal salt of chemical formula 4(MO-A-NR^1R^2) with an indium compound of chemical formula 2(InX3) to obtain a compound of chemical formula 5(In[O-A-NR^1R^2]2X); and a step of reacting the compound of chemical formula 5 with alkali metal salt of chemical formula 6(MNR^3_2). A thin film and nanomaterial containing indium are prepared using the compound of chemical formula 1 as a precursor. The thin film containing the indium is formed through chemical vapor deposition(MOCVD) or atomic layer deposition(ALD).

Description

Novel indium amino-alkoxide complexes and process for preparing novel

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

Indium is useful because of its high resistance to abrasion in electroplating and low resistance to contact with aluminum wires.Indium coating of sodium vapor lamp in Europe Indium oxide may be used as a material.

Indium oxide and tin oxide-indium films are also used in conductive coating materials and electroluminescent pannels in glass and ceramics.

Indium oxide can also be used as a heat insulator and in the solar cell or semiconductor industry (M. Veith, S. Hill, V. Huch, Eur. J. Inorg. Chem. , 1999 , 1343). .

It can also be used for photoelectrode materials, liquid crystal displays, photovoltaic devices, etc. (CR Patra, A. Gedanken, New. J. Chem. , 2004 , 28 , 1060 ).

InCl ₃ is a precursor that has been used for the deposition of indium oxide, which may have chlorine contamination during thin film deposition and requires an oxygen source from the outside. Me ₃ In or Et ₃ In Trialkylindium (III), such as the like, is highly volatile but has a disadvantage of being very sensitive to oxygen and moisture (C. Xu, TH Baum, I. Guzei, AL Rheingold, Inorg. Chem. , 2000, 39 , 2008).

Indium alkoxides such as [In (OC ₂ H ₄ OMe) ₃ ] _m and [In (OC ₂ H ₄ NMe ₂ ) ₃ ] _m are known to be difficult to use due to their low volatility (S. Daniele, D). Tchebou, LG Hubert-Pfalzgraf, S. Lecocq, Inorg.Chem . Comm. , 2002 , 5 , 347).

Another precursor is beta such as In (thd) ₃ (where thd is 2,2,6,6-tetramethyl-3,5-heptadionate) and In (acac) ₃ (where acac is acetylacetonate) Compounds using diketonate ligands (P. Lobinger, HS Park, H. Hohmeister, HW Roesky, Chem. Vap. Deposition , 2001 , 7 , 105).

However, when a material containing indium is made using a compound using these beta diketonate ligands, there is a disadvantage in that the properties of the film are deteriorated due to contamination of oxygen and carbon.

In general, the synthesis of a compound having high volatility is the most important problem to design and synthesize precursors for thin films or nanomaterials. A method of saturating the coordination sites of metals by using a double-site ligand instead of a simple alkoxide ligand Among the bidentate ligands, amino alkoxide strains are known and more useful than alkoxy alkoxides (LG Hubert-Pfalzgraf, H. Guillon, Appl. Organomet. Chem., 1998 , 12 , 221).

As described above, indium trivalent compounds known in the art have problems such as insufficient volatility, supply of oxygen from the outside, contamination of carbon and chlorine generated in the prepared film, and the like.

Therefore, as a precursor for the manufacture of thin films and nanomaterials containing indium, it has high volatility without containing halogen elements in the compound itself and has good solubility in organic solvents for easy synthesis of nanomaterials and decomposes at low temperatures. The development of an indium trivalent compound that can be said that the meaning is quite significant.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to include a halogen element, which is thermally stable, highly volatile, and capable of producing a material containing pure indium or indium at low temperature. It is to provide a novel indium compound having amino alkoxide and amide as a ligand and a method for producing the same.

The present invention relates to a novel indium amino alkoxide compound which is thermally stable and highly volatile and capable of preparing a material including pure indium and indium at low temperature, and provides an indium amino alkoxide compound represented by the following Chemical Formula 1.

[Formula 1]

In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ]

In Formula 1, A is C ₂ -C ₅ alkylene, A may be further substituted with one or more C ₁ -C ₅ linear or branched alkyl group, R ¹ and R ² is a silyl group each independently a linear or branched alkyl group of hydrogen or C ₁ -C _5, and R ³ is a linear or branched alkyl group or a tree of _{C 1 -C 5 (C 1 -C} 5) alkyl.

More specifically, the indium aminoalkoxide compound of Formula 1 includes an indium aminoalkoxide compound represented by the following formula (2).

[Formula 2]

In [O-CR ⁴ R ⁵ (CH ₂ ) _m -NR ¹ R ² ] ₂ [NR ³ 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, indium aminoalkoxide compounds in which m is 1 or 2 in Formula 2 are preferable. Specifically, in Formula 2, R ¹ , R ² , R ⁴ and R ⁵ are independently of each other 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₎ Indium aminoalkoxide compounds selected from Si ₃ , Si (C ₂ H ₅ ) ₃ or Si (CH ₃ ) (C ₂ H ₅ ) ₂ are exemplified.

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

Indium amino alkoxide compound represented by the formula (1) according to the present invention is a starting material to react with an indium compound represented by the formula (3) and an alkali metal salt represented by the formula (4) in an organic solvent to obtain a compound represented by the formula (5), 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 the indium amino alkoxide compound of formula 1 is represented by the following scheme Can be represented.

[Formula 1]

In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ]

[Formula 3]

InX ₃

[Formula 4]

MO-A-NR ¹ R ²

[Formula 5]

In [OA-NR ¹ R ² ] ₂ X

[Formula 6]

MNR ³ ₂

[In Chemical Formula 1, Chemical Formulas 3 to 6, A is alkylene of C ₂ -C ₅ ; 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

As another method for preparing an indium compound In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ] of the present invention, a method of reacting an indium amide compound represented by the following formula (7) with 2 equivalents of an aminoalcohol compound represented by the formula (8) There is this. Scheme for this can be represented by the following scheme 2.

[Formula 1]

In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ]

[Formula 7]

In [NR ³ ₂ ] ₃

[Formula 8]

HO-A-NR ¹ R ²

[In Formula 1, Formula 7 and Formula 8, A is alkylene of C ₂ -C ₅ ; 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

Indium aminoalkoxide compound In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ], which is a novel indium precursor of Formula 1, is a stable complex compound and has a nonpolar alkyl group at the α -carbon position relative to the oxygen of the alkoxide bound to the metal. May be present as a monomer because of its high affinity for organic solvents and a steric hindrance that prevents the central metal from causing intermolecular interactions with oxygen of neighboring ligands.

Due to these structural characteristics, the indium precursor of Chemical Formula 1 is a stable solid at room temperature, has high solubility in organic solvents such as benzene, tetrahydrofuran, toluene, chloroform, etc. As a result, they can be used to obtain thin films and nanomaterials containing higher quality indium.

The thermal stability, volatility and decomposition temperature of the indium aminoalkoxide compounds synthesized in the present invention were investigated using thermogravimetric analysis / differential thermal analysis (TGA / DTA).

As shown in Figure 2 it was confirmed that a sharp weight loss occurs in the vicinity of 100-200 ℃. It shows almost a single step and the residual amount is 20.9%.

As a result, the indium aminoalkoxide compound (Formula 1), an indium precursor synthesized in the present invention, exhibits sufficient volatility before decomposition temperature and has high solubility in organic solvents. Or the atomic layer deposition method (ALD).

Indium precursor according to the present invention is not only excellent in thermal stability and volatility because it is combined with the oxygen atom ligand to improve the production of thin films and nanomaterials including indium, and the alkylamide to improve the volatility, It is advantageous to be used as an indium precursor having a novel ligand for organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). Useful compounds.

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] [bis (trimethylsilyl) amido]} indium [In (dmamp) ₂ (btsa)] Synthesis I

5.60 g (40 mmol) of Na (dmamp) was added to a 250 mL Schlenk flask containing toluene (100 mL), and 4.42 g (20 mmol) of InCl ₃ was added to toluene (50 mL).

This mixed solution was refluxed for 24 hours, the solution was filtered and the solvent was removed under reduced pressure. The obtained solid was sublimed (95 ° C./10 ⁻² torr) to obtain an indium compound in which two alkoxides and one halide were bonded to each other as shown in Formula 5, to obtain a white solid.

4.52 g (11.8 mmol) of the obtained compound In (dmamp) ₂ Cl and 2.00 g (11 mmol) of Li (btsa) (btsa = bis (trimethylsilyl) amide) were added to a 250 mL Schlenk flask, and toluene (150 mL) was added thereto. Reflux for 24 hours.

The mixture was filtered, the solvent was removed under reduced pressure, and then sublimed (70 ° C./10 ⁻² torr) to give the title compound In (dmamp) ₂ (btsa) as a white solid (4.61 g, yield 77%).

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 0.44 (s, 18H, Si (C H ₃ ) ₃ ), 1.28-1.30 (m, C (C H ₃ ) ₂ , 1.98-2.18 (dd, 2H , C H ₂ ), 2.21 (s, 8H, C H ₂ + N (C H ₃ ) ₂ ), 2.40 (s, 6H, N (C H ₃ ) ₂ ).

Example 2

{Bis [1-dimethylamino-2-methyl-2-propoxy] [bis (trimethylsilyl) amido]} indium [In (dmamp) ₂ (btsa)] II

Dissolve 9.48 g (14.8 mmol) of In [N (SiMe ₃ ) ₂ ] ₃ in toluene (100 mL) in a 250 mL Schlenk flask and 4.10 g of dmampH (1-dimethylamino-2-methyl-2-propanol) at low temperature (35.2 mmol) is added. After stirring for 12 hours, the solvent was removed under reduced pressure and sublimed at 70 ° C. (10 ⁻² torr) to obtain 6.09 g (yield 81%) of In (dmamp) ₂ [N (SiMe ₃ ) ₂ ] as a white solid.

Example 3

{Bis [1-dimethylamino-2-ethyl-2-butoxy] [bis (trimethylsilyl) amido]} indium [In (dmaeb) ₂ (btsa)]

2.98 g (4.6 mmol) of a 125 mL Schlenk flask In [N (SiMe ₃ ) ₂ ] ₃ was dissolved in toluene (50 mL) and slowly dmaebH (1-dimethylamino-2-ethyl-2-butanol) (1.52 g, 13 mmol) is added dropwise. After stirring at room temperature for 12 hours, the solvent was removed under reduced pressure and sublimed at 100 ° C. (10 ⁻² torr) to obtain 1.50 g (yield 58%) of the title compound In (dmaeb) ₂ (btsa) as a pure white solid.

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 0.44 (s, 18H, Si (C H ₃ ) ₃ ), 0.88-0.97 (m, 12H, CH ₂ C H ₃ ), 1.51-1.55 (m, 8H, C H ₂ CH ₃ ), 2.03-2.22 (dd, 2H, C H ₂ ), 2.24 (s, 8H, C H ₂ + N (C H ₃ ) ₂ ), 2.40 (s, 6H, N (C H ₃ ) ₂ ).

¹³ C { ¹ H} NMR (C ₆ D ₆ , 75.47 MHz): δ 8.8, 8.9, 33.6, 34.1, 49.2, 49.8, 69.2, 72.6.

Elemental analysis Calcd. For C ₂₂ H ₅₄ InN ₃ O ₂ Si ₂ : C, 46.88; H, 9. 66; N, 7.45. Found: C, 45.49; H, 9.35; N, 7.43.

FT-IR (cm ⁻¹ , KBr pellet): υ (In-O) 635.

[Test Example 1]

(In (dmaeb) ₂ (btsa)] pyrolysis

1 g of [In (dmaeb) ₂ (btsa)] prepared in Example 3 was added to a 125 mL Schlenk flask, and the temperature was decomposed by heating at 250 ° C. for 2 hours.

The remaining material was analyzed for components by X-ray diffraction (XRD). As shown in Figure 5 it can be seen that the indium precursor developed in the present invention is pyrolyzed to be reduced to indium metal.

¹ H NMR analysis of the In (dmamp) ₂ (btsa) compound prepared in Example 1 is shown in Figure 1, In (dmamp) ₂ (btsa) prepared in Example 1 Thermogravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) of the compounds are shown in FIG. 2, and ¹ H NMR analysis results of the In (dmaeb) ₂ (btsa) compound prepared in Example 3 are shown in FIG. ¹³ C NMR analysis of the In (dmaeb) ₂ (btsa) compound prepared in Figure 4, XRD analysis of the material remaining after the thermal decomposition of the In (dmaeb) ₂ (btsa) compound in Example 3 is shown in Figure 5 Indicated.

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

2 is In (dmamp) ₂ (btsa) prepared in Example 1 A graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the compound,

3 is a result of ¹ H NMR analysis of the In (dmaeb) ₂ (btsa) compound prepared in Example 3,

4 is a ¹³ C NMR analysis result of In (dmaeb) ₂ (btsa) compound prepared in Example 3,

5 is an XRD analysis result of a material remaining after pyrolyzing In (dmaeb) ₂ (btsa) compound in Example 3. FIG.

Claims (8)

Indium amino alkoxide compound represented by the following formula (1). [Formula 1] In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ] [In Formula 1, A is alkylene of C ₂ -C ₅ ; 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, Indium amino alkoxide compound represented by the following formula (2). [Formula 2] In [O-CR ⁴ R ⁵ (CH ₂ ) _m -NR ¹ R ² ] ₂ [NR ³ 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, Indium amino alkoxide compound, characterized in that 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 ) Indium aminoalkoxide compound characterized by the above-mentioned. A method for preparing an indium aminoalkoxide compound of formula (1) characterized by reacting a compound represented by formula (5) and an alkali metal salt of formula (6) obtained by reacting an indium compound represented by formula (3) with an alkali metal salt represented by formula (4) . [Formula 1] In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ] [Formula 3] InX ₃ [Formula 4] MO-A-NR ¹ R ² [Formula 5] In [OA-NR ¹ R ² ] ₂ X [Formula 6] MNR ³ ₂ [In Chemical Formula 1, Chemical Formulas 3 to 6, A is alkylene of C ₂ -C ₅ ; 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 an indium aminoalkoxide compound of formula (1) comprising reacting an indium amide compound represented by formula (7) with an aminoalcohol compound represented by formula (8). [Formula 1] In [OA-NR ¹ R ² ] ₂ [NR ³ ₂ ] [Formula 7] In [NR ³ ₂ ] ₃ [Formula 8] HO-A-NR ¹ R ² [In Formula 1, Formula 7 and Formula 8, A is alkylene of C ₂ -C ₅ ; 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 preparing a thin film and a nanomaterial comprising indium using an indium aminoalkoxide compound according to any one of claims 1 to 4 as a precursor. The method of claim 6, A thin film comprising indium is formed by chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

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