KR101359518B1 - Magnesium oxide precursors, preparation method thereof and process for the formation of thin films using the same - Google Patents

Abstract

The present invention relates to a magnesium oxide precursor represented by the following formula (1), the magnesium oxide precursor is thermally stable and good volatility can form a thin film containing a high quality magnesium oxide.
[Chemical Formula 1]

Description

MAGNESIUM OXIDE PRECURSORS, PREPARATION METHOD THEREOF AND PROCESS FOR THE FORMATION OF THIN FILMS USING THE SAME}

The present invention relates to a novel magnesium oxide precursor, and more particularly, to a magnesium oxide precursor and a method for preparing the magnesium oxide precursor, which are capable of producing a thin film including high quality magnesium oxide at low temperature, with improved thermal stability and volatility. It relates to a method of manufacturing a thin film containing magnesium.

Magnesium oxide has very wide band gap (7.2eV), excellent thermal stability (melting point = 2900 ° C), low dielectric constant (9.8), and low refractive index. Therefore, the present invention is applied to various fields such as a thin film buffer layer, a plasma display panel protective layer, and optical materials (Wang, L .; Yang, Y .; Ni, J .; Stern, CL; Marks, TJ Chem. Mater. 2005, 17, 5697; Renault, O. Ph.D. Thesis; Institut National Polytechnique de Grenoble, Grenoble, France, 1998; Andoh, S .; Murase, K .; Umeda , S .; Nakayama, N. IEEE Trans.Electron Devices 1976, 23, 319; Hinds, BJ; McNeely, RJ; Chen, J .; Dias, C .; Studebaker, DL; Marks, TJ; Hogan, TP; Schindler , JL; Kannewurf, CRJ Alloys Compd. 1997, 251, 328; Musolf, J .; Boeke, E .; Waffenschmidt, E .; He, X .; Heuken, M .; Heime, KJ Alloys Compd. 1993, 195, 295; Tonouchi, M .; Sakaguchi, Y .; Kobayashi, TJ Appl. Phys. 1987, 62, 961; Nashimoto, K .; Fork, DK; Geballe, TH Appl. Phys. Lett. 1992, 60, 1199; Basit, NA; Kim, HK; Blachere, J. Appl. Phys. Lett. 1998, 73, 3941; Yoon, J.-G .; Kim, K. Appl. Phys. Lett. 1996, 68, 2523). In addition, sol-gel, sputtering, pulsed laser ablation (CVD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD) and atomic Various methods such as layer deposition are used (Lee, JH; Eun, JH; Park, SY; Kim, SG; Kim, HJ Thin). Solid Films 2003 , 435 , 95-101; Ho, IC; Xu, YH; Chakrabarti, S .; Ganguli, D .; Chaudhuri, S. Mater . Lett . 2003 , 57 , 4483-4492; Babcock, JR; Benson, DD; Wang, AC; Edleman, NL; Belot, JA; Metz, MV; Marks, TJ Chem . Vapor Deposition 2000 , 6 , 180-183; Burton, BB; Goldstein, DN; George, SMJ Phys. Chem. C 2009, 113, 1939; Davies, HO; Jones, AC; Leedham, TJ; Crosbie, MJ; Wright, PJ; Boag, NM; Thompson, JR Chem. Vap. Deposition 2000, 6, 71). Known and widely used magnesium oxide precursors for CVD include diethylmagnesium and bis (2,2,6,6-tetramethyl-3,5-heptanedionate) magnesium (bis (2, 2,6,6-tetramethyl-3,5-heptanedionatomagnesium), bis (acetylacetonato) magnesium (bis (accetylacetonato) magnesium), magnesium acetate, magnesium 2-ethylhexanoate -ethylhexanoate) and bis (cyclopentadienyl) magnesium, but most of them except for diethylmagnesium are volatilized at a high temperature of 100 ° C or higher and H ₂ O or O ₂ and It has the disadvantage of providing the same oxygen source. Alkyl, alkoxide, carboxylates, carbamates, cyclopentadienyls, and β-diketonates to synthesize such precursors Various ligands such as) are used. Among them, the compound using β-diketonate has the advantage of excellent thermal stability and volatility, and thus, magnesium β-diketonate and magnesium β- Research is being actively conducted on compounds such as magnesium β-diketonatatoalkoxide, and magnesium β-ketoiminate (Davies, HO; Jones, AC; Leedham, TJ; Crosbie, MJ; Wright, PJ; Boag, NM;.. Thompson, JR Chem Vap Deposition 2000, 6 , 71; Matthews, JS; Just, O .; Obi-Johnson, B .; Rees, Jr., W. S; Chem . Vap . Deposition 2000, 6 , 129; Babcock, JR; Benson, DD; Wang, A .; Edleman, NL; Belot, JA; Metz, MV; Marks, TJ Chem . Vap . Deposition 2000, 6 , 180; Hill, MR; Jones, AW; Russel, JR; Roberts, NK; Lamb, RNJ Mater. Chem. 2004, 14, 3198; Carta, G .; El Habra, N .; Crociani, L .; Rossetto, G .; Zanella, P .; Zanella, A .; Paolucci, G .; Barreca, D .; Tondello, E. Chem. Vap. Deposition 2007, 13, 185; Jones, ACJ Mater. Chem. 2002, 12, 2576). Korean Patent Laid-Open Publication No. 2001-0027037 discloses a method of forming a thin film by chemical vapor deposition using an organic magnesium compound such as magnesium acetate or magnesium acetylacetonate, but the organic magnesium compound is not sufficiently volatile and thermally stable. There is a problem that the thin film is not easy to manufacture and the physical properties of the manufactured thin film are not sufficient.

Korean Laid-Open Patent Publication 2001-0027037 Korean Laid-Open Patent Publication 2008-0046485 Korean Laid-Open Patent Publication 2010-0071463

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems, and to provide a novel magnesium oxide precursor capable of producing a thin film containing high quality magnesium oxide at low temperature with improved thermal stability and volatility.

It is also an object of the present invention to provide a novel method for producing the magnesium oxide precursor, to provide a method for producing a thin film comprising magnesium oxide using the same and a thin film comprising magnesium oxide prepared therefrom.

In order to achieve the above object, the present invention provides a magnesium oxide precursor represented by the following formula (1).

 [Formula 1]

Wherein m is an integer ranging from 1 to 3, R1, R2, R3 and R4 are each independently a linear or branched alkyl group of C1-C10, and R5 and R6 are each independently linear or branched of C1-C10 An alkyl group or a C1-C10 linear or branched alkyl group substituted with fluorine or a C1-C10 alkoxy group . )

In another aspect, the present invention provides a method for producing a magnesium oxide precursor of the formula (1).

In another aspect, the present invention provides a method for growing a thin film including magnesium oxide using the magnesium oxide precursor of Formula 1 and a thin film comprising magnesium oxide prepared therefrom.

The magnesium oxide precursor represented by Formula 1 of the present invention is a compound having two different ligands, and has excellent thermal stability and high volatility, thereby making it easy to prepare a thin film including high quality magnesium oxide.

1 is a ¹ H-NMR spectrum for Mg (dmamp) (tmhd).
Figure 2 is a ¹³ C-NMR spectrum for Mg (dmamp) (tmhd).
3 is the FT-IR spectrum for Mg (dmamp) (tmhd).
4 is a ¹ H-NMR spectrum for Mg (dmamp) (acac).
5 is ¹³ C-NMR spectrum for Mg (dmamp) (acac).
6 is an FT-IR spectrum for Mg (dmamp) (acac).
7 is a ¹ H-NMR spectrum for Mg (dmamp) (hfac).
8 is ¹³ C-NMR spectrum for Mg (dmamp) (hfac).
9 is an FT-IR spectrum for Mg (dmamp) (hfac).
10 is a ¹ H-NMR spectrum for Mg (dmamp) (tfac).
Figure 11 is a ¹³ C-NMR spectrum for Mg (dmamp) (tfac).
12 is the FT-IR spectrum for Mg (dmamp) (tfac).
13 is TG / DTA data for Mg (dmamp) (tmhd).
14 is TG / DTA data for Mg (dmamp) (hfac).

The present invention relates to a magnesium oxide precursor represented by the following formula (1).

[Formula 1]

Wherein m is an integer ranging from 1 to 3, R1, R2, R3 and R4 are each independently a linear or branched alkyl group of C1-C10, and R5 and R6 are each independently linear or branched of C1-C10 An alkyl group, or a C1-C10 linear or branched alkyl group substituted with fluorine or a C1-C10 alkoxy group.)

The novel magnesium oxide precursor represented by the formula (1) is a magnesium compound having two different ligands, i.e., a -diketonate and an aminoalkoxide ligand, and are thermally stable and have good volatility. The magnesium oxide precursor may be a white or yellow solid.

The magnesium oxide precursor of the present invention can be prepared by various methods.

Preferably, the compound of Formula 1 of the present invention may be obtained by reacting a magnesium compound of Formula 2 with an aminoalkoxy alkali metal compound of Formula 3 and a diketone compound of Formula 4 below.

(2)

R7-MgX

(3)

[Chemical Formula 4]

Wherein m is an integer ranging from 1 to 3, R 1, R 2, R 3 and R 4 are each independently a linear or branched alkyl group of C 1 -C 10, and R 5 and R 6 are each independently linear or minute of C 1 -C 10 A topographic alkyl group, or a fluorine or a C1-C10 linear or branched alkyl group substituted with a C1-C10 alkoxy group, R7 is a C1-C10 linear or branched alkyl group, or a fluorine-substituted C1-C10 linear or branched alkyl group Alkyl group, M is Li or Na, and X is F, Cl or Br.)

Toluene, tetrahydrofuran, hexane, diethyl ether, etc. can be used as a solvent of the said reaction, Preferably tetrahydrofuran can be used.

The reaction may be preferably carried out at room temperature for 12 hours to 24 hours to obtain a compound of Formula 1, which is a white or pale yellow solid compound.

Specifically showing the preparation method is shown in Scheme 1 below.

[Reaction Scheme 1]

[화학식 2] [화학식 3] [화학식 4] [화학식 1]

[Formula 2] [Formula 3] [Formula 4] [Formula 1]

Wherein m is an integer ranging from 1 to 3, R 1, R 2, R 3 and R 4 are each independently a linear or branched alkyl group of C 1 -C 10, and R 5 and R 6 are each independently linear or minute of C 1 -C 10 A topographic alkyl group, or a fluorine or a C1-C10 linear or branched alkyl group substituted with a C1-C10 alkoxy group, R7 is a C1-C10 linear or branched alkyl group, or a fluorine-substituted C1-C10 linear or branched alkyl group Alkyl group, M is Li or Na, and X is F, Cl or Br.)

The novel magnesium oxide precursor of the present invention is a precursor for manufacturing a thin film including magnesium oxide, and can be preferably applied to a process using chemical vapor deposition (CVD) or atomic layer deposition (ALD), which is widely used in manufacturing magnesium oxide thin film. have.

For example, when chemical vapor deposition is used, a thin film including magnesium oxide may be formed on various substrates by supplying a reactant including the magnesium oxide precursor of the present invention and an oxygen-containing gas or organic material to a reactor. Because of its thermal stability and high volatility, it is possible to manufacture thin films under various conditions and to produce high quality thin films.

In addition, using the magnesium oxide precursor of the present invention can be prepared a thin film containing magnesium oxide by the ALD process, the reactant containing the magnesium oxide precursor of the present invention in the ALD process is supplied to the deposition chamber in the form of a pulse and the pulse is It produces chemical reactions with the wafer surface and achieves precise monolayer film growth. Since the magnesium oxide precursor of the present invention has thermal stability and high volatility, a thin film including high quality magnesium oxide can be easily produced by an ALD process.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Synthesis of Magnesium Oxide Precursor Material

Example  1: (1-dimethylamino-2- methyl -2- Propoxy ) ( Tetramethylheptanedione )magnesium( II ) Preparation of [Mg (dmamp) (tmhd)]

In a 125 mL Schlenk flask, Na (dmamp) [1-dimethylamino-2-methyl-2-propoxy sodium, (1 g, 7.18 mmol, 1 eq)] was dissolved in THF, followed by MeMgBr (3.0 M). in Et ₂ O) [2.39 mL, 7.18 mmol, 1 eq] was added slowly and stirred at room temperature for 12 hours. To the mixed solution, tmhd ( tetramethylheptanedione , 1.32 g, 7.18 mmol, 1 eq) was slowly added and stirred at room temperature for 12 hours. The mixture was filtered and the solvent was removed under reduced pressure to obtain a white solid compound (1.4 g, 60.9%).

¹ H NMR, ¹³ C NMR and FT-IR for the obtained compound Mg (dmamp) (tmhd) are shown in FIGS. 1 to 3, respectively.

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 1.28 (s, 18H, ^t Bu), 1.31 (s, 6H, OC (C H ₃ ) ₂ ), 2.12 (s, 6 HN (C H ₃ ) ₂ ), 2.15 (s, 2H, CC H ₂ N), 5.82 (s, 1H, C H ₂ C═O).

¹³ C NMR (C ₆ D ₆ , 75.04 MHz): δ 28.8, 32.9, 41.1, 47.3, 66.9, 72.9, 89.8, 201.1.

Example  2: (1-dimethylamino-2- methyl -2- Propoxy (Acetylacetone) magnesium ( II ) Preparation of [Mg (dmamp) (acac)]

In a 125 mL Schlenk flask, Na (dmamp) [1-dimethylamino-2-methyl-2-propoxy sodium, (1 g, 7.18 mmol, 1 eq)] was dissolved in THF, followed by MeMgBr (3.0 M). in Et ₂ O) [2.39 mL, 7.18 mmol, 1 eq] was added slowly and stirred at room temperature for 12 hours. Acac (acetylacetone, 0.719 g, 7.18 mmol, 1 eq) was slowly added to the mixed solution and stirred at room temperature for 12 hours. After filtering the mixture, the solvent was removed under reduced pressure to obtain a white solid compound (1.4 g, 68.9%).

¹ H NMR, ¹³ C NMR and FT-IR for the obtained compound Mg (dmamp) (acac) are shown in FIGS. 4 to 6, respectively.

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 1.33 (s, 6H, OC (C H ₃ ) ₂ ), 1.90 (s, 6H, C H ₃ C═O), 2.10 (s, 6 HN ( C H ₃ ) ₂ ), 2.16 (s, 2H, CC H ₂ N), 5.37 (s, 1H, C H ₂ C═O).

¹³ C NMR (C ₆ D ₆ , 75.04 MHz): δ 28.1, 33.0, 47.2, 67.0, 72.8, 100.2, 191.5.

Example  3: (1-dimethylamino-2- methyl -2- Propoxy ) ( Hexafluoroacetylacetone )magnesium( II ) [Mg ( dmamp ) ( hfac )]

In a 125 mL Schlenk flask, Na (dmamp) [1-dimethylamino-2-methyl-2-propoxy sodium, (1 g, 7.18 mmol, 1 eq)] was dissolved in THF, followed by MeMgBr (3.0 M in Et ₂ O) [2.39 mL, 7.18 mmol, 1 eq] was added slowly and stirred at room temperature for 12 hours. To the mixed solution, hfac (hexafluoroacetylacetone, 1.49 g, 7.18 mmol, 1 eq) was slowly added and stirred at room temperature for 12 hours. The mixture was filtered and the solvent was removed under reduced pressure to give a viscous pale yellow solid compound. Was obtained (1.1 g, 44%).

¹ H-NMR, ¹³ C-NMR, and FT-IR for the obtained compound Mg (dmamp) (hfac) are shown in FIGS. 7 to 9, respectively.

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 1.05 (s, 6H, OC (C H ₃ ) ₂ ), 1.93 (s, 6 HN (C H ₃ ) ₂ ), 1.93 (s, 2H, CC H ₂ N), 6.30 (s, 1 H, C H ₂ C = O).

¹³ C NMR (C ₆ D ₆ , 75.04 MHz): δ 25.4, 47.6, 68.5, 89.9, 116.4, 120.2, 178.5.

Example  4: (1-dimethylamino-2- methyl -2- Propoxy ) ( Trifluoroacetylacetone )magnesium( II ) [Mg ( dmamp ) ( tfac )]

In a 125 mL Schlenk flask, Na (dmamp) [1-dimethylamino-2-methyl-2-propoxy sodium, (1 g, 7.18 mmol, 1 eq)] was dissolved in THF, followed by MeMgBr (3.0 M in Et ₂ O) [2.39 mL, 7.18 mmol, 1 eq] was added slowly and stirred at room temperature for 12 hours. Tfac (trifluoroacetylacetone, 1.10 g, 7.18 mmol, 1 eq) was slowly added to the mixed solution and stirred for 12 hours at room temperature. The mixture was filtered and the solvent was removed under reduced pressure to obtain a viscous yellow solid compound. Obtained (1.34 g, 54%).

¹ H-NMR, ¹³ C-NMR, and FT-IR for the obtained compound Mg (dmamp) (tfac) are shown in FIGS. 10 to 12, respectively.

¹ H NMR (C ₆ D ₆ , 300.13 MHz): δ 1.17 (s, 6H, OC (C H ₃ ) ₂ ), 1.73 (s, 3H, C H ₃ C═O), 2.01 (s, 6 HN ( C H ₃ ) ₂ ), 2.32 (s, 2H, CC H ₂ N), 5.78 (s, 1H, C H ₂ C═O).

¹³ C NMR (C ₆ D ₆ , 75.04 MHz): δ 25.7, 28.8, 47.1, 68.0, 95.6, 117.9, 121.7, 171.6, 199.6.

Experimental Example  1. Analysis of Magnesium Oxide Precursor Material

Thermogravimetric analysis (TGA) was used to measure the thermal stability, volatility and decomposition temperature of Mg (dmamp) (tmhd) of Example 1 and Mg (dmamp) (hfac) of Example 3. . In the TGA method, the product was heated to 900 DEG C at a rate of 10 DEG C / min while argon gas was introduced at a pressure of 1.5 bar / min. The TGA graph of the magnesium oxide precursor compound synthesized in Example 1 is shown in FIG. 13, and the TGA graph of the magnesium oxide precursor chemical synthesized in Example 3 is shown in FIG. 14. As can be seen in Figure 13, the magnesium compound of Example 1 mass loss occurred from 250 ℃ and the final residual amount was observed to 9.0% at 330 ℃.

In addition, as shown in FIG. 14, the magnesium compound obtained in Example 3 had a mass reduction from 180 ° C., a residual amount of 58.7% at 230 ° C., and a final residual amount of 12.9% at 340 ° C. were observed .

In addition, the TGA data shows that the degree of volatility of the compound of the present invention is good.

Claims (5)

Magnesium oxide precursor represented by the following formula (1):
[Chemical Formula 1]

Wherein m is an integer ranging from 1 to 3, R1, R2, R3 and R4 are each independently a linear or branched alkyl group of C1-C10, and R5 and R6 are each independently linear or branched of C1-C10 Alkyl or C1-C10 linear or branched alkyl group in which fluorine or C1-C10 alkoxy group is substituted.) A method for preparing a compound of Formula 1, comprising reacting a magnesium compound of Formula 2 with an aminoalkoxy alkali metal compound of Formula 3 and a diketone compound of Formula 4:
(2)
R7-MgX
(3)

[Chemical Formula 4]

[Chemical Formula 1]

Wherein m is an integer ranging from 1 to 3, R 1, R 2, R 3 and R 4 are each independently a linear or branched alkyl group of C 1 -C 10, and R 5 and R 6 are each independently linear or minute of C 1 -C 10 A topographic alkyl group, or a fluorine or a C1-C10 linear or branched alkyl group substituted with a C1-C10 alkoxy group, R7 is a C1-C10 linear or branched alkyl group, or a fluorine-substituted C1-C10 linear or branched alkyl group Alkyl group, M is Li or Na, and X is F, Cl or Br.) A method of growing a thin film containing magnesium oxide using the magnesium oxide precursor of claim 1. The method according to claim 3,
Wherein the thin film growth process is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). A thin film comprising magnesium oxide, which is prepared using the magnesium oxide precursor of claim 1.

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