KR100627631B1 - Volatile indium amino-alkoxide complexes and process for preparing thereof - Google Patents

Abstract

The invention relates to an indium amino alkoxide compound represented by the following formula (1).

[Formula 1]

In [OCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴ ] ₃

In Chemical Formula 1, m is an integer ranging from 1 to 3, and R ¹ to R ⁴ are each independently hydrogen or a linear or branched alkyl group of C ₁ -C ₅ .

The indium amino alkoxide compound according to the present invention is an indium precursor, which is in a liquid state at room temperature and has a high vapor pressure, and thus may be usefully used as an indium raw material for depositing thin films of various materials including indium or depositing various alloys.

Indium Amino Alkoxide Compound

Description

Volatile indium amino-alkoxide compound and method for preparing the same

1 is a ¹ H NMR analysis of the In (dmamp) ₃ compound prepared in Example 1,

2 is a ¹³ C NMR spectrum of the In (dmamp) ₃ compound prepared in Example 1,

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

4 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the In (dmamp) ₃ compound prepared in Example 1,

FIG. 5 is a ¹ H NMR analysis result of In (dmampe) ₃ compound prepared in Example 2,

6 is a ¹³ C NMR spectrum of an In (dmampe) ₃ compound prepared in Example 2,

7 is a result of FT-IR analysis of the In (dmampe) ₃ compound prepared in Example 2,

8 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the In (dmampe) ₃ compound prepared in Example 2.

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-indium oxide 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 material 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, and trialkylindium (III) such as Me ₃ In or Et ₃ In It has good volatility but has the 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 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, amino alkoxide strains are known to be 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, the development of the indium trivalent compound as a precursor that can be used in the manufacture of indium oxide thin film having high volatility can be said to have a significant meaning.

The present invention has been made to solve the above-mentioned conventional problems, the object of the present invention is thermally stable and highly volatile and indium amino alkoxide compound containing no fluorine or chlorine, which is capable of producing pure indium oxide at low temperature and The manufacturing method is provided.

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

[Formula 1]

In [OCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴ ] ₃

In Formula 1, m is an integer ranging from 1 to 3, R ¹ to R ⁴ are independently of each other hydrogen, or a linear or branched alkyl group of C ₁ -C ₅ , preferably m is 1 or 2, R ¹ to R ⁴ are each independently a compound which is methyl, ethyl, n-propyl, i-propyl, or t-butyl.

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

The indium compound of the compound of formula 1 according to the present invention may be prepared by refluxing an indium amide compound of formula 2 and three equivalents of an amino alcohol of formula 3 in an organic solvent such as toluene.

[Formula 2]

In [N (R ⁵ ) ₂ ] ₃

[Formula 3]

HOCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴

In Formula 2 and Formula 3, R ⁵ is CH ₃ , C ₂ H ₅ or Si (CH ₃ ) ₃ , m and R ¹ to R ⁴ are corresponding substituents of Formula 1, m is an integer ranging from 1 to 3 , R ¹ to R ⁴ are each independently hydrogen or a C ₁ -C ₅ linear or branched alkyl group.

Indium compounds of the compound of formula 1 according to the present invention can be prepared by ligand substitution reaction by refluxing in an organic solvent such as indium halide compound of formula 4 and 3 equivalents of alkali metal salt amino alkoxide compound of formula 5 and toluene.

[Formula 4]

InX ₃

[Formula 5]

MOCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴

In Formulas 4 and 5, X is Cl, Br or I, M is Li, Na or K, m and R ¹ to R ⁴ are corresponding substituents of Formula 1, m is an integer ranging from 1 to 3, R ¹ to R ⁴ are independently of each other hydrogen or a C ₁ -C ₅ linear or branched alkyl group.

The preparation of the alkali metal salt amino alkoxide compound and the indium halide compound of formula (4) can be used by converting amino alcohol, Na and the like into an alkoxide in a conventional manner such as adding an alkali metal in an organic solvent, the reaction conditions are The reaction proceeds under conditions similar to those of the compound of formula 3.

The reaction product, which is an indium compound according to the present invention, is characterized by proton nuclear magnetic resonance spectroscopy ( ¹ H NMR), carbon atom nuclear magnetic resonance ( ¹³ C NMR), Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA) It was confirmed using.

Hereinafter, one example will be described in more detail with reference to the embodiments of the present invention, but the present invention is not limited thereto.

All experiments were performed in an inert argon or nitrogen atmosphere using a glove box or Schlenk line as follows.

Example 1

Tris (1-dimethylamino-2-methyl-2-propoxy) indium (III) [(CH ₃ ) ₂ NCH ₂ C (CH ₃ ) ₂ O] ₃ In, In (dmamp) ₃ Manufacture of

In [N (SiMe ₃ ) ₂ ] ₃ (5.96 g, 0.01 mol) was dissolved in toluene (50 mL) in a 125 mL Schlenk flask and 1- (dimethylamino) -2-methylpropan-2-ol ((CH ₃ ) After slowly adding ₂ NCH ₂ C (CH ₃ ) ₂ OH, dmampH, 4.69 g, 0.04 mol), the cooling tube was connected and refluxed for about 72 hours under a nitrogen atmosphere. After the solvent was removed to give a dark brown liquid compound, the liquid compound was again distilled under reduced pressure to give the title compound as a pure colorless liquid (distillation temperature 126 ° C., 10 ⁻² Torr .; yield 4.30 g, 93%) .

¹ H NMR (C ₆ D ₆ , 300.13 MHz): 1.24, 1.30 (s, 18H, C (C H ₃ ) ₂ ), 1.96-2.34 (m, N (C H ₃ ) ₂ , C H ₂ ).

¹³ C { ¹ H} NMR (C ₆ D ₆ , 75.47 MHz): 33.4, 33.8, 48.7, 49.3, 68.4, 69.3, 72.1, 73.1

Elemental Analysis {Calcd. (found)}: Calcd. For C ₁₈ H ₄₂ N ₃ O ₃ In: C, 46.66; H, 9. 14; N, 9.07. Found: C, 46.85; H, 9.51; N, 8.83.

FT-IR (cm ^-1 , KBr pellet): υ (In-O) 696, 614

Example 2

Preparation of tris (3-((dimethylamino) methyl) -3-pentoxy) indium (III) [(CH ₃ ) ₂ NCH ₂ C (CH ₂ CH ₃ ) ₂ O] ₃ In, In (dmampe) ₃ ]

In [N (SiMe ₃ ) ₂ ] ₃ (5.96 g, 0.01 mol) was dissolved in toluene (50 mL) in a 125 mL Schlenk flask and 3-((dimethylamino) methyl) pentan-3-ol (CH ₃ ) ₂ NCH ₂ C (CH ₂ CH ₃ ) ₂ OH, dmampeH, 5.81 g, 0.04 mol) was slowly added, refluxed in a nitrogen atmosphere for about 72 hours after connecting a cooling tube, and the reaction was terminated. Removal gave a dark brown liquid compound. The liquid compound obtained was again distilled under reduced pressure to give a pale yellow liquid as the title compound (distillation temperature 170 ° C., 10 ⁻² Torr .; yield 2.21 g, 40.4%).

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 0.87 (t, J = 7.50 Hz, 3H, CH ₂ C H ₃ ), 0.93 (t, J = 7.50 Hz, 3H, CH ₂ C H ₃ ), 1.03 (t, J = 7.20 Hz, 12H, CH ₂ C H ₃ ). 1.39-1.52 (m, 4H, C H ₂ CH ₃ ), 1.55-1.69 (m, 8H, C H ₂ CH ₃ ), 2.06 (s, 2H, NC H ₂ C), 2.10 (s, 3H, N ( C H ₃ )), 2.23 (s, 4H, NC H ₂ C), 2.31 (s, 3H, N (C H ₃ )), 2.35 (s, 12H, N (C H ₃ )).

¹³ C { ¹ H} NMR (CDCl ₃ 75.47 MHz): δ 8.7, 9.0, 33.8, 33.9, 49.6, 49.8, 68.4, 69.3, 71.3, 71.7.

Elemental Analysis Calcd. For C ₂₄ H ₅₄ N ₃ 0 ₃ In + 0.5H ₂ 0: C, 51.80; H, 9.96; N, 7.55. Found: C, 51.90; H, 10.46; N, 8.23.

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

The tris (aminoalkoxy) indium (III) compound, an organic indium trivalent compound prepared from the examples, was found to have very good solubility in organic solvents such as diethyl ether, tetrahydrofuran, toluene and hexane as liquids at room temperature. As such, the high volatility of the compounds of the present invention and the excellent solubility in organic solvents not only satisfy the coordination number of the indium ions by the three amino alkoxide ligands 5 coordination to the indium trivalent ions, but also the two at the alpha carbon position. This is due to the fact that the methyl group and the two alkyl groups substituted at the nitrogen atom of the amine effectively mask the oxygen and nitrogen, thereby reducing the intermolecular interaction and increasing the affinity for the organic solvent.

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

As shown in FIG. 4 and FIG. 8, all of the In (dmamp) ₃ and In (dmampe) ₃ compounds showed a rapid mass reduction between 150 and 250 ° C. The TG graph also shows that T _1/2 (the temperature at which _half the weight of the original sample is reached in weight-dependent weight loss) is 204 ° C and 250 ° C, respectively.

As described above, the indium (III) amino alkoxide compound according to the present invention has an advantage that it can be usefully used as an indium precursor in preparing a material containing volatility, thermal stability, high purity, and high quality indium. have.

Claims (4)

Indium amino alkoxide compound represented by the following formula (1). [Formula 1] In [OCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴ ] ₃ In Formula 1, m is 1 or 2, and R ¹ to R ⁴ are each independently methyl, ethyl, n-propyl, i-propyl, or t-butyl. delete A method of preparing an indium compound of Formula 1 according to claim 1 by reacting an indium amide compound of Formula 2 with an amino alcohol of Formula 3 below. [Formula 2] In [NR ⁵ ₂ ] ₃ [Formula 3] HOCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴ In Formula 2 and Formula 3, R ⁵ is CH ₃ , C ₂ H ₅ or Si (CH ₃ ) ₃ , m and R ¹ to R ⁴ are the corresponding substituents of Formula 1, m is 1 or 2, R ¹ To R ⁴ are independently of each other methyl, ethyl, n-propyl, i-propyl, or t-butyl. A method of preparing an indium compound of Chemical Formula 1 according to claim 1 by reacting an indium halide compound of Chemical Formula 4 with an alkali metal salt amino alkoxide compound of Chemical Formula 5. [Formula 4] InX ₃ [Formula 5] MOCR ¹ R ² (CH ₂ ) _m NR ³ R ⁴ In Formulas 4 and 5, X is Cl, Br or I, M is Li, Na or K, m and R ¹ to R ⁴ are corresponding substituents of Formula 1, m is 1 or 2, and R ¹ to R ⁴ is independently of each other methyl, ethyl, n-propyl, i-propyl, or t-butyl.

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