KR100308916B1 - β-ketoester or amide Type Precursors for Ferroelectric BST thin films - Google Patents

Abstract

PURPOSE: Precursors for producing a monomer structured beta-diketonated BST(BaxSr1-xTIO3) thin layer using beta-keto ester or amide ligand are provided, which compounds have improved volatilization and stability in atmosphere. CONSTITUTION: A precursor for producing a monomer structured beta-diketonated BST(BaxSr1-xTIO3) thin layer using beta-keto ester is represented by the formula(I): £M(RC(O)CHC(O)OR')2|3, wherein M is Ba or Sr; R is C1-C4 alkyl; and R' is C3-C4 alkyl. A precursor for producing a monomer structured beta-diketonated BST(BaxSr1-xTIO3) thin layer using beta-keto ester and a N, O-electron donor ligand(L) is represented by the formula(V): M(RC(O)CHC(O)OR')2L, wherein M is Ba or Sr; R and R' are C1-C4 alkyl; and L is amine of (CL3)N(CH2CH2N)n(CH3) when n is 1 to 4 and glycol ether of CH3O(CH2CH2O)nCH3 when n is 1 to 4. A precursor for producing a monomer structured beta-diketonated BST(BaxSr1-xTIO3) thin layer prepared by reacting beta-keto ester and Ti(OiPr)4 is represented by the formula(IX): Ti(OiPr)2(RC(O)CHC(O)OR')2, wherein R and R' are C1-C4 alkyl.

Description

Precursor for producing ferroelectric BST thin film using β-keto ester or amide ligand {β-ketoester or amide Type Precursors for Ferroelectric BST thin films}

The present invention relates to a precursor for manufacturing Ba _x Sr _1-x TiO ₃ (BST) thin film, which is a ferroelectric used in the manufacture of a capacitor of a giga-class dynamic random access memory (DRAM) using high dielectric constant characteristics. In more detail, the present invention provides a variety of N, O-electron donor ligands for β-keto esters and amides, and β-diketo esters and amides to Ba, Sr metals. The present invention relates to a Ti precursor obtained by synthesizing Ba and Sr precursors by reacting with and reacting β-keto ester and amide and β-diketo ester and amide with Ti (O ⁱ Pr) ₄ .

Ferroelectrics having high dielectric constants include PbTiO ₃ (PTO), PbZr _1-x TixO ₃ (PZT), Ba _1-x Sr _x TiO ₃ (BST), and LiNbO ₃ , all of which are perovskite structures. Have Thin films manufactured using such ferroelectrics have been put to practical use in a wide range of fields, such as piezoelectric elements, electro-optical elements, infrared detection elements, and ceramic capacitors, based on the characteristics of dielectric, insulating, piezoelectric, and superconducting properties. In particular, ferroelectrics used in the fabrication of capacitors of giga-class dynamic random access memory (DRAM) using high dielectric constants have high dielectric constants, low dielectric losses, and do not disperse dielectric constants up to high frequencies (> 100 MHz) in the practical temperature range. BST thin films are known to be the most suitable.

The preparation of BST thin films has been studied mainly with the sputtering method and the sol-gel method. However, the sputtering method has the disadvantages of damaging the thin film due to high energy ion collision during deposition, poor step coverage and difficult composition control, and the sol-gel method is well matched with the existing semiconductor manufacturing process. It is known that it is difficult to manufacture high quality thin film due to relatively incomplete thin film (Q. Linker, O. Meyer, Appl. Phys. Lett. 1989, 54, 2367). MOCVD (Metal-Organic Chemical Vapor Deposition) method using an organometallic compound as a precursor has attracted attention. This method has been accepted as the most suitable deposition method because of its excellent step coverage, adjustable composition, and high productivity (R. Sato, K. Takahashi, M. Yoshino, H. Kato, S. Ohshima, Jpn. J.). Appl. Phys. 1993, 32, 1590). Therefore, the selection or development of precursors is essential for developing a good thin film.

Precursors suitable for thin film production by MOCVD method must first maintain high vapor pressure even at low temperatures, secondly, the difference between the vaporization temperature and the decomposition temperature must be large, third liquid state, and fourth organic material of precursor material It should not be left in the air, it should be stable in the fifth air, it should be non-toxic sixth, and so on.

In the recently announced precursors for ferroelectric BST thin films, M (RC (O) CHC (O) R ') ₂ compounds with β-diketonide ligands are known to be most suitable. Examples are compounds in the form of M (tmhd) ₂ (tmhd: R = R ′ = ^t Bu) and show a relatively high vapor pressure (AA Drozdov, SI Trojanov, Polyhedron 1992, 11, 2877). Ba (tmhd) ₂ is a compound having a nucleophilic crystal structure, which is hydrolyzed when placed in air, and has a problem in terms of stability. When Ba (tmhd) ₂ is used as a precursor, a vaporization temperature of 200 ° C. or higher is required. The entire apparatus shall be maintained at 250 ° C as a whole. At this time, since the precursor itself is decomposed, non-volatile materials are generated and the Ba concentration of the thin film is reduced (RE Sievers, Inorg. Chem. 1991, 30, 1164).

In order for the precursor to have a high vapor pressure, the β-diketonate compounds of Ba and Sr are generally unsaturated in the coordination number of 4 to form a bulk compound so that the coordination number satisfies 8 to 12 (Simon. R. Drake, Michael B. Hursthouse, KM Abdul Malik, and David J. Otway, J. Chem. Soc. Dalton Trans. 1993, 2883). In order to make a monomer, it is possible to achieve the objective by satisfying the coordination number by forming a complex with another ligand of the electron donor (G. Malandrino, DS Richeson, Tobin J. Marks, DC Degroot, CR Kannewurf, Appl. Phys. Lett. 1991, 58, 182). Alternatively, larger ligands, such as butyl ( ^t Bu) groups instead of methyl (Me) groups, can be used to effectively screen central metal ions, preventing the aggregation of compounds and increasing vapor pressure (GS Hammond, DC Nonhebel, Inorg.Chem. 1963, 2, 73). In addition, fluorinated β-diketonate ligands can obtain high vapor pressure by reducing intermolecular attraction due to the repulsive force of fluorine, which has a high electronegativity (H. Sato, S. Sugawara, Inorg. Chem. 1993, 32, 1941).

First, when complexed with electron donor ligands, agglomerates such as tetranuclide or trinuclear body can be separated into monomers. NH ₃ , NMe ₃ , NEt ₃ , pyridine, NH ₂ CH ₂ CH ₂ NH ₂ , Me ₂ NCH ₂ CH ₂ NMe ₂ , THF, CH ₃ O (CH ₂ CH ₂ O) _n CH ₃ (n = 1 ~ 4) The complexes of N, 0-electron donor ligands and Ba (tmhd) ₂ as Ba precursors help to improve thermal stability and volatility and obtain a constant high vapor pressure even at low vaporization temperatures. (DW Gardiner, Brown and PS Kirlin, Chem. Mater. 1991, 3, 1053).

Fluorinated β-diketonate is known as M (hfac) ₂ (R = R '= CF ₃ ) or M (hfod) ₂ (R' = C ₃ F ₇ ; R "= ^t Bu) and shows high vapor pressure (JA Belot, DA Neumayer, CJ Reedy, DB Strudebaker, BJ Hinds, Tobin J. Marks, Chem. Mater. 1997, 9, 1638. These compounds usually sublimate under conditions of 200 ° C. at 0.1 Torr. It is known to form a bulk compound structure such as a tetranuclear body, and an example of synthesizing a thermally stable monomer compound using a polyether has also been reported (JA Norman, GP Pez, J. Chem. Soc. Chem. Common. 1991). these forms are _{Ba (hfac) 2 .L, Sr} (hfac) 2 .L (L = triglyme, tetraglyme, hexaglyme, 18-crown-6) is known as Ba and Sr highest volatility of the precursor material so far However, fluorine contamination of the thin film becomes a problem and post annealing is required.

In the case of Ti compounds, Ti alkoxide is known as the best precursor. Among them, Ti (O ⁱ Pr) ₄ is a liquid and has a wide range of physical properties such as vapor pressure and stability, so it is widely used as Ti precursor (WR Russo, WH Nelson, J. Am. Chem. Soc. 1970, 92, 1521). However, since Ti (O ⁱ Pr) ₄ showed a higher vapor pressure change than Ba and Sr precursors, the difficulty of quantitative control in manufacturing BST thin films became a problem. Therefore, Ti (O ⁱ Pr) ₂ (tmhd) ₂ precursors have been recently reported to control vapor pressure changes to a similar degree to Ba and Sr precursors. (RC Fay, AF Lindmark, J. Am. Chem. Soc. 1983, 10, 5, 2118) Also, US Pat. No. 5,248,787 discloses β-diketonate ligands and O-electrons which are currently the most studied precursors for the preparation of BST thin films. Ba and Sr precursors have been synthesized using donor ligands.

The technical problem of the present invention is the synthesis of a compound of β-diketonated BST precursor of monomer structure which is free of fluorine, stable in air, and has a high vapor pressure even at low temperature.

This can be achieved by using β-diketo ester substituted with alkoxy or β-diketo amide substituted with amine with various electron donor ligands instead of alkyl.

To achieve the object of the present invention, BST precursors were synthesized by reacting β-keto ester and amide and β-diketo ester and amide with various N, O-electron donor ligands with Ba and Sr metals. Ti precursors were synthesized by reacting β-keto ester and amide, β-diketo ester and amide ligand with Ti (O ⁱ Pr) ₄ (IV).

In the present invention, β-keto ester and amide and N, O-electron donor ligands (triamine, triglyme, tetramine, tetraglyme) were used to synthesize a new type of precursor for BST thin film. β-Diketo ester is similar to the structure of β-diketonate, the ligand that has the best condition among known precursors. In other words, β-diketonate has two carbonyl groups at the β-position, alkoxy group is substituted for alkyl, β-diketo amide is amine substituted for alkyl, alkoxy and amine are carbonyl groups By increasing the electron density of the oxygen to bond with the metal can stabilize the compound. In addition, since the N, O-electron donor ligand satisfies the coordination number of Ba and Sr metal ions, the aggregation of compounds can be reduced. Synthesis of compounds was carried out using the general method of synthesis of ML ₂ (M = Sr, Ba) (Formula (1)) (AA Drozdov, SI Trojanov, Polyhedron 1992, 11, 2877), and all compounds were purified using recrystallization. A precursor was obtained.

The invention is explained in more detail in the following examples. However, the scope of the present invention is not limited by these Examples.

Example 1

Abbreviations of the materials used in the examples are as follows.

HEBAc: (CH ₃ ) ₂ CHCOCH ₂ COOC ₂ H ₅ , Ethylisobutyrylacetate

EBAc: (CH ₃ ) ₂ CHCOCHCOOC ₂ H ₅ , Ethylisobutylacetate anion

HBAAc: CH ₃ COCH ₂ COOC (CH ₃ ) ₃ , tert-Buthylacetoacetate

Triamine is 1,1,4,7,7-pentamethyldiethylenetriamine represented by (CH ₃ ) ₂ NCH ₂ CH ₂ N (CH ₃ ) CH ₂ CH ₂ N (CH ₃ ) ₂ ,

tetramine is 1,1,4,7,10,10- represented by (CH ₃ ) ₂ NCH ₂ CH ₂ N (CH ₃ ) CH ₂ CH ₂ N (CH ₃ ) CH ₂ CH ₂ N (CH ₃ ) ₂ Hexamethyl triethylene tetramine,

triglyme is triethylene glycol dimethyl ether represented by CH ₃ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ ,

tetraglyme is tetraethylene glycol dimethyl ether represented by CH ₃ 0CH ₂ CH ₂ 0CH ₂ CH ₂ 0CH ₂ CH ₂ 0CH ₂ CH ₂ 0CH ₃ ,

In addition, BAAc is used as a tert-Buthylacetoacetate anion meaning CH ₃ COCHCOOC (CH ₃ ) ₃ from which one hydrogen is removed from the HBAAc.

Synthesis of [Ba (EBAc) ₂ ] ₃

HEBAc (1.805 g, 11.40 mmol) was slowly added to a toluene (20.0 mL) solution of Ba (0.783 g, 5.70 mmol) and reacted at room temperature for 24 hours. As the reaction proceeds, Ba metal gradually melts, producing a gas expected to be H ₂ . After the reaction was completed, the solution was filtered, and the solvent was removed in vacuo and recrystallized from toluene / hexane (4 ° C.) to obtain 0.925 g (72%) of colorless crystals of [Ba (EBAc) ₂ ] ₃ . The analysis results are shown below. However, the trimer structure can be confirmed through X-ray single crystal structure analysis.

IR (KBr, cm ^-1 ) 2955 s, 2932 w, 2907 w, 2870 w, 1639 w, 1613 s, 1510 vs, 1459 s, 1382 w, 1359 w, 1319 m, 1222 vs, 1171 s, 1095 m, 1042 s, 981 w, 946 s, 836 m, 789 s, 743 w, 500 w; ¹ H NMR (Acetone-d ₆ , 25 ° C) δ 0.99 (d, 6H, -CH (CH ₃ ) ₂ ), 1.11 (t, 3H, -CH ₂ CH ₃ ), 2.22 (m, 1H, -CH ( CH ₃ ) ₂ ), 3.95 (q, 2H, CH ₂ CH ₃ ), 4.55 (s, 1H, CH); ¹³ C NMR (Acetone-d ₆ , 25 ° C) δ 15.1 (-CH ₂ CH ₃ ), 21.3 (-CH (CH ₃ ) ₂ ), 39.6 (-CH (CH ₃ ) ₂ ), 58.1 (-CH ₂ CH ₃ ), 80,8 (CH), 172.4 (CO), 194.6 (COO).

Example 2

Synthesis of Ba (EBAc) ₂ (triamine)

Triamine (0.988 g, 5.70 mmol) was added to a toluene (20.0 mL) solution of Ba (0.980 g, 5.70 mmol) at room temperature, and HEBAC (1.805 g, 11.40 mmol) was added slowly to react at room temperature for 48 hours. As the reaction proceeds, Ba metal is gradually melted to generate a gas that is thought to be H ₂ , and a white solid precipitates after 2 to 3 hours after the reaction. After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized in pentane to give 2.46 g (69%) of colorless crystals Ba (EBAc) ₂ (triamine).

IR (KBr, cm ^-1 ) 2962 s, 2864 m, 2826 m, 2782 w, 1635 vs, 1662 s, 1507 vs, 1460 s, 1316 m, 1203 vs, 1156 vs, 1083 s, 1050 s, 940 s, 830 m, 785 s, 748 m, 431 w;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.93 (d, 6H, -CH (CH ₃ ) ₂ ), 1.14 (t, 3H, -CH ₂ CH ₃ ), 2.09 (s, 3H, -N (CH) ₃ )-), 2.27 (s, 12H, N (CH ₃ ) ₂ ), 2.40 (br, 8H, -NCH ₂ CH ₂ N-), 3.90 (q, 2H, -CH ₂ H ₃ ), 4.56 (s , 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ14.8 (-CH ₂ CH ₃ ), 20.5 (-CH (CH ₃ ) ₂ ), 38.7 (-CH (CH ₃ ) ₂ ), 41.5 (-N (CH ₃ )-), 44.5 (-N (CH ₃ ) ₂ ), 56.1 (-CH ₂ CH ₃ ), 56,7 (NCH ₂ CH ₃ N-), 79.1 (CH), 170.9 (CO), 194.9 (COO )

Example 3

Synthesis of Ba (EBAc) ₂ (tetramine)

After adding tramine (1.314 g, 5.70 mmol) to a toluene (20.0 mL) solution of Ba (0.783 g, 5.70 mmol) at room temperature, HEBAc (1.805 g, 11.40 mmol) was slowly added and reacted at room temperature for 72 hours. As the reaction proceeds, Ba metal is gradually melted to generate a gas thought to be H ₂ . After completion of the reaction, the solution was filtered and the solvent was removed in vacuo and recrystallized from pentane (4 ° C.) to obtain 2.066 g (53%) of colorless crystals Ba (EBAc) ₂ (tetramine).

IR (KBr, cm ^-1 ) 2967 s, 2865 m, 2827 m, 2814 m, 2798 m, 1635 vs, 1498 vs, 1457 vs, 1352 m, 1315 m, 1225 m, 1204 s, 1151 vs, 1096 m, 1083 m, 1047 s, 938 m, 901 w, 829 m, 786 s, 740 w, 720 w, 433 w;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.96 (s, 6H, -CH (CH ₃ ) ₂ ), 1.17 (t, 3H, -CH ₂ CH ₃ ), 2.16 (s, 12H, -N (CH ₃ ) ₂ ), 2.18 (m, 1H, CH (CH ₃ ) ₂ ), 2.22 (s, 6H, -N (CH ₃ )-), 2.75 (br, 12H, -NCH ₂ CH ₂ N-), 3.93 (q, 2H, CH ₂ CH ₃ ), 4.57 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ14.8 (-CH ₂ CH ₃ ), 20.5 (-CH (CH ₃ ) ₂ ), 38.8 (-CH (CH ₃ ) ₂ ), 40.2 (-N (CH ₃ )-), 45.2 (-N (CH ₃ ) ₂ ), 56.8 (-CH ₂ CH ₃ ), 56.9 (NCH ₂ CH ₂ N (CH ₃ ) CH _2- ), 78.3 (CH), 170.1 (CO) , 194.1 (COO)

Example 4

Synthesis of Ba (EBAc) ₂ (triglyme)

Triglyme (1.016 g, 5.70 mmol) was added to a toluene (20.0 mL) solution of Ba (0.783 g, 5.70 mmol) at room temperature, followed by slow addition of HEBAc (1.805 g, 11.40 mmol) for 20 hours at room temperature. As the reaction proceeds, the Ba metal gradually melts, generating a gas that is thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized in pentane to give Ba (EBAc) ₂ (triglyme) as a colorless crystals quantitatively.

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.96 (d, 6H, —CH (CH ₃ ) ₂ ), 1.15 (t, 3H, —CH ₂ CH ₃ ), 2.15 (m, 1H, —CH ( CH ₃ )-), 3.33 (s, 6H, -OCH ₃ ), 3.53 (m, 4H, -CH ₂ CH ₂ O-), 3.65 (m, 4H, -OCH ₂ CH ₂ O-), 3.66 (s , -OCH ₂ CH ₂ O-), 3.91 (q, 2H, CH ₂ CH ₃ ), 4.57 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ14.8 (-CH ₂ CH ₃ ), 20.8 (-CH (CH ₃ ) ₂ ), 39.1 (-CH (CH ₃ ) ₂ ), 57.5 (-CH ₂ CH ₃ ), 58.9 (-OCH ₃ ), 70.2 (-OCH ₂ CH ₂ O-), 71.5 (-OCH ₂ CH ₂ O-), 78.9 (CH), 170.9 (CO), 194.8 (COO)

Example 5

Synthesis of Ba (EBAc) ₂ (tetraglyme)

Tetraglyme (1.266 g, 5.70 mmol) was added to a solution of toluene (20.0 mL) of Ba (0.783 g, 5.70 mmol) at room temperature, and HEBAc (1.805 g, 11.40 mmol) was added slowly to react at room temperature for 72 hours. As the reaction proceeds, Ba metal is gradually melted to generate a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized in pentane (-25 ℃) to give 3.740 g (96%) of colorless crystals Ba (EBAc) ₂ (tetraglyme).

mp 83-84 ° C .;

IR (KBr, cm ^-1 ) 2975 m, 2965 m, 2930 m, 1646 vs, 1500 vs, 1357 w, 1321 m, 1204 s, 1150 s, 1095 s, 1084 s, 1047 m, 945 m, 831 w, 786 m, 742 w;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.97 (d, 6H, —CH (CH ₃ ) ₂ ), 1.16 (t, 3H, —CH ₂ CH ₃ ), 2.15 (m, 1H, —CH ( CH ₃ ) ₂ ), 3.36 (s, 6H, -OCH ₃ ), 3.49 (m, 4H, -OCH ₂ CH ₂ O-), 3.59 (m, 4H, -OCH ₂ CH ₂ O-), 3.67 (m , 4H, -OCH ₂ CH ₂ O-), 3.75 (m, 4H, -OCH ₂ CH ₂ O-), 3.93 (d, 2H, CH ₂ CH ₃ ), 4.54 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ 14.9 (-CH ₂ CH ₃ ), 20.8 (-CH (CH ₃ ) ₂ ), 39.1 (-CH (CH ₃ ) ₂ ), 57.0 (-CH ₂ CH ₃ ), 58.9 (-OCH ₃ ), 70.0 (-OCH ₂ CH ₂ O-), 70.1 (-OCH ₂ CH ₂ O-), 70.2 (-OCH ₂ CH ₂ O-), 71.1 (-OCH ₂ CH ₂ O-), 78.2 (CH), 170.3 (CO), 194.4 (COO)

Example 6

Synthesis of Ba (BAAc) ₂ (triglyme)

Triglyme (1.016 g, 5.70 mmol) was added to a toluene (20.0 mL) solution of Ba (0.783 g, 5.70 mmol) at room temperature, and HBAAc (1.805 g, 11.40 mmol) was slowly added to react at room temperature for 48 hours. As the reaction proceeds, Ba metal is gradually melted to generate a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and yellow oil Ba (BAAc) ₂ (triglyme) was obtained quantitatively.

¹ H-NMR (COCl ₃ , 25 ° C) δ 1.35 (d, 9H, -C (CH ₃ ) ₃ ), 1.73 (s, 3H, CH ₃ (CO)), 3.30 (s, 6H, -OCH ₃ ), 3.50 (m, 4H, -OCH ₂ CH ₂ O-), 3.62 (m, 4H, -OCH ₂ CH ₂ O-), 3.65 (s, -OCH ₂ CH ₂ O-), 4.48 (s, 1H , CH);

¹³ C-NMR (CDCl ₃ , 25 ° C) δ 27.6 (CH ₃ (CO)), 28.8 (-C (CH ₃ ) ₃ ), 58.1 (-OCH ₃ ), 70.1 (-OCH ₂ CH ₂ O-) , 71.2 (-OCH ₂ CH ₂ O-), 85.5 (CH), 170.7 (CO), 184.8 (COO)

Example 7

Synthesis of Ba (BAAc) ₂ (tetramine)

After adding tramine (1.314 g, 5.70 mmol) to a solution of toluene (20.0 mL) of Ba (0.783 g, 5.70 mmol) at room temperature, HBAAc (1.805 g, 11.40 mmol) was slowly added and reacted at room temperature for 48 hours. As the reaction proceeds, Ba metal is gradually melted to generate a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized in pentane to give 2.944 g (76%) of colorless crystals Ba (BAAc) ₂ (tetramine).

IR (KBr, cm ^-1 ) 2977 m, 2923 w, 2830 m, 2777 w, 1643 vs, 1508 s, 1488 m, 1421 m, 1382 w, 1360 w, 1312 w, 1294 w, 1237 s, 1190 w, 1144 vs, 1103 w, 1044 w, 974 s, 787 w, 771 w, 742 w, 727 w, 456 w;

¹ H-NMR (Acetone-d ₆ , 25 ° C) δ 1.36 (s, 9H, -C (CH ₃ ) ₃ ), 1.67 (s, 3H, -CH ₃ ), 2.19 (s, 12H, -N ( CH ₃ ) ₂ ), 2.25 (s, 6H, -N (CH ₃ )-), 2.40 (m, 4H, -NCH ₂ CH ₂ N-), 2.53 (m, 4H, -NCH ₂ CH ₂ N-) , 2.56 (s, 4H, -NCH ₂ CH ₂ N-), 4.40 (s, 1H, CH);

¹³ C-NMR (Acetone-d ₆ , 25 ° C.) δ28.2 (CH ₃ ), 29.2 (-C (CH ₃ ) ₃ ), 41.7 (-N (CH ₃ ) ₂ ), 57.1 (-NCH ₂ CH ₂ N-), 57.3 (-NCH ₂ CH ₂ N-), 57.8 (-NCH ₂ CH ₂ N-), 75.9 (C (CH ₃ ) ₃ ), 171.4 (CO), 195.0 (COO)

Example 8

Synthesis of [Sr (EBAc) ₂ ] ₃

HEBAc (1.805 g, 11.40 mmol) was slowly added to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) and reacted at room temperature for 24 hours. As the reaction proceeds, the Sr metal gradually melts, generating a gas thought to be H ₂ . After completion of the reaction, the solution was filtered and the solvent was removed in vacuo and recrystallized from toluene / hexane to give 1.601 g (69%) of colorless crystals [Sr (EBAc) ₂ ] ₃ . However, the trimer structure can be confirmed through X-ray single crystal structure analysis.

IR (KBr, cm ^-1 ) 2961 s, 2950 m, 2917 s, 2956 s, 1644 vs, 1614 vs, 1514 br, 1466 s, 1382 m, 1361 w, 1322 m, 1226 vs, 1174 vs, 1098 m, 1039 s, 986 w, 947 s, 837 m, 791 s, 742 m, 504 w;

^I H-NMR (Acetone-d ₆ , 25 ° C) δ1.00 (d, 6H, -CH (CH ₃ ) ₂ ), 1.12 (t, 3H, -CH ₂ CH ₃ ), 2.26 (m, 1H,- CH (CH ₃ ) ₂ ), 3.94 (q, 2H, -CH ₂ CH ₃ ), 4.55 (s, 1H, CH);

¹³ C-NMR (Acetone-d ₆ , 25 ° C.) δ15.1 (-CH ₂ CH ₃ ), 21.5 (-CH (CH ₃ ) ₂ ), 39.8 (-CH (CH ₃ ) ₂ ), 58.1 (-CH ₂ CH ₃ ), 80.8 (CH), 172.5 (CO), 194.9 (COO)

Example 9

Synthesis of Sr (EBAc) ₂ (triamine)

Trianine (0.998 g, 5.70 mmol) was added to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) at room temperature, followed by slow addition of HEBAc (1.805 g, 11.40 mmol) at room temperature for 24 hours. As the reaction proceeds, the Sr metal gradually melts, generating a gas thought to be H ₂ . After completion of the reaction, the solution was filtered and the solvent was removed in vacuo and recrystallized in pentane to give 2.160 g (78%) of colorless crystals, Sr (EBAc) ₂ (triamine).

IR (KBr, cm ^-1 ) 2975 s, 2867 m, 2831 m, 2804 w, 1633 vs, 1577 w, 1504 w, 1455 vs, 1382 w, 1355 m, 1323 s, 1216 vs, 1151 vs, 1085 s, 1050 vs, 985 m, 945 s, 931 m, 788 vs, 746 m;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.95 (d, 6H, —CH (CH ₃ ) ₂ ), 1.14 (t, 3H, —CH ₂ CH ₃ ), 2.14 (s, 3H, —N ( CH ₃ )-), 3.92 (q, 2H, -CH ₂ CH ₃ ), 4.59 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ14.0 (-CH ₂ CH ₃ ), 19.8 (-CH (CH ₃ ) ₂ ), 37.8 (-CH (CH ₃ ) ₂ ), 42.5 (-N (CH ₃ )-), 44.2 (-N (CH ₃ ) ₂ ) 54.6 (-CH ₂ CH ₃ ), 56.2 (-NCH ₂ CH ₂ N-), 78.3 (CH), 170.5 (CO), 194.9 (COO)

Example 10

Synthesis of Sr (EBAc) ₂ (tetramine)

After adding tetramine (1.314 g, 5.70 mmol) to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) at room temperature, HEBAc (1.805 g, 11.40 mmol) was slowly added and reacted at room temperature for 72 hours. As the reaction proceeds, the Sr metal gradually melts, generating a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized in pentane (4 ℃) to give 2.523 g (70%) of colorless crystals Sr (EBAc) ₂ (tetramine).

IR (KBr, cm ^-1 ) 2965 s, 2865 m, 2824 m, 2796 m, 1638 vs, 1501 vs, 1455 s, 1356 w, 1312 w, 1228 s, 1290 s, 1163 s, 1153 s, 1097 m, 1084 w, 1036 s, 937 m, 830 w, 738 w, 719 w, 433 w;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.95 (d, 6H, —CH (CH ₃ ) ₂ ), 1.14 (t, 3H, —CH ₂ CH ₃ ), 2.09 (s, 12H, —N ( CH ₃ ) ₂ ), 2.16 (m, 1H, -CH (CH ₃ ) ₂ ), 2.19 (s, 6H, -N (CH ₃ )-), 2.50 (br, 12H, -NCH ₂ CH ₂ N-) , 3.93 (q, 2H, -CH ₂ CH ₃ ), 4.58 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ15.0 (-CH ₂ CH ₃ ), 20.6 (-CH (CH ₃ ) ₂ ), 38.8 (-CH (CH ₃ ) ₂ ), 41.7 (-N (CH ₃ )-), 46.4 (-N (CH ₃ ) ₂ ) 57.0 (-CH ₂ CH ₃ ), 57.4 (-NCH ₂ CH ₂ N-), 78.3 (CH), 170.6 (CO), 194.9 (COO)

Example 11

Synthesis of Sr (EBAc) ₂ (triglyme)

Triglyme (1.016 g, 5.70 mmol) was added to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) at room temperature, followed by slow addition of HEBAc (1.805 g, 11.40 mmol) at room temperature for 10 hours. As the reaction proceeds, the Sr metal gradually melts, generating a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized in pentane to give 2.07 g (63%) of Sr (EBAc) ₂ (triglyme) as a white solid compound.

IR (KBr, cm ^-1 ) 2956 m, 2930 m, 2840 m, 1641 vs, 1500 vs, 1458 s, 1333 w, 1316 m, 1220 s, 1206 s, 1161 s, 1146 s, 1097 s, 1049 s, 947 s, 869 w, 833 m, 786 s, 722 w;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 0.96 (d, 6H, —CH (CH ₃ ) ₂ ), 1.15 (t, 3H, —CH ₂ CH ₃ ), 2.18 (m, 1H, —CH ( CH ₃ ) ₂ ), 3.30 (s, 6H, -OCH ₃ ), 3.51 (m, 4H, -OCH ₂ CH ₂ O-), 3.66 (m, 4H, -OCH ₂ CH ₂ O-), 3.74 (s , 4H, -OCH ₂ CH ₂ O-), 3.93 (q, 2H, -CH ₂ CH ₃ ), 4.56 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ14.8 (-CH ₂ CH ₃ ), 20.7 (-CH (CH ₃ ) ₂ ), 38.9 (-CH (CH ₃ ) ₂ ), 57.2 (-CH ₂ CH ₃ ), 59.0 (-OCH ₃ ) 69.7 (-OCH ₂ CH ₂ O-), 69.9 (-OCH ₂ CH ₂ O-), 71.2 (-OCH ₂ CH ₂ O-), 78.5 (CH), 171.0 (CO ), 195.0 (COO)

Example 12

Synthesis of Sr (EBAc) ₂ (tetraglyme)

Tetraglyme (1.266 g, 5.70 mmol) was added to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) at room temperature, and HEBAc (1.805 g, 11.40 mmol) was added slowly to react at room temperature for 48 hours. As the reaction proceeds, a gas that is thought to be H ₂ is generated while the Sr metal gradually melts. After completion of the reaction, the solution was filtered and the solvent was removed in vacuo and recrystallized from pentane / toluene to give 2.330 g (65%) of colorless crystals, Sr (EBAc) ₂ (tetraglyme).

mp 57-59 ° C .;

IR (KBr, cm ^-1 ) 2953 m, 2925 m, 2868 s, 2828 w, 1645 vs, 1509 vs, 1491 vs, 1458 s, 1385 w, 1355 w, 1342 w, 1317 m, 1204 s, 1119 s, 1097 s, 1081 s. 1052 s, 979 w, 948 s, 854 w, 829 m, 785 s, 740 w, 721 w;

¹ H-NMR (CDCl ₃ , 25 ° C) δ 0.97 (d, 6H, -OCH ₃ ), 3.48 (m, 4H, -OCH ₂ CH ₂ O-), 3.60 (m, 4H, -OCH ₂ CH ₂ O-), 3.71 (m, 4H, -OCH ₂ CH ₂ O-), 3.78 (m, 4H, -OCH ₂ CH ₂ O-), 3.96 (q, 2H, -CH ₂ CH ₃ ), 4.58 (s , 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ 14.9 (-CH ₂ CH ₃ ), 20.9 (-CH (CH ₃ ) ₂ ), 39.0 (-CH (CH ₃ ) ₂ ), 57.2 (-CH ₂ CH ₃ ), 59.0 (-OCH ₃ ) 70.0 (-OCH ₂ CH ₂ O-), 70.1 (-OCH ₂ CH ₂ O-), 71.5 (-OCH ₂ CH ₂ O-), 170.9 (CO), 194.8 (COO )

Example 13

Synthesis of Sr (BAAc) ₂ (triglyme)

Tetraglyme (1.016 g, 5.70 mmol) was added to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) at room temperature, and HBBAc (1.805 g, 11.40 mmol) was added slowly to react at room temperature for 30 hours. As the reaction proceeds, the Sr metal gradually melts, generating a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, the solvent was removed in vacuo and recrystallized from toluene to give 2.07 g (63%) of a white solid compound Sr (BBAc) ₂ (triglyme).

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 1.36 (d, 9H, —C (CH ₃ ) ₃ ), 1.71 (s, 3H, CH ₃ (CO)), 3.32 (s, 6H, —OCH ₃ ), 3.49 (m, 4H, -OCH ₂ CH ₂ O-), 3.52 (m, 4H, -OCH ₂ CH ₂ O-), 3.66 (s, -OCH ₂ CH ₂ O-), 4.50 (s, 1H , CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ27.6 (-CH ₃ (CO)), 28.7 (-C (CH ₃ ) ₃ ), 58.6 (-OCH ₃ ) 70.1 (-OCH ₂ CH ₂ O-) , 70.2 (-OCH ₂ CH ₂ O-), 86.2 (CH), 170.7 (CO), 183.9 (COO)

Example 14

Synthesis of Sr (BAAc) ₂ (tetramine)

After adding tetraglyme (1.314 g, 5.70 mmol) to a solution of toluene (20.0 mL) of Sr (0.500 g, 5.70 mmol) at room temperature, HBAAc (1.805 g, 11.40 mmol) was slowly added and reacted at room temperature for 48 hours. As the reaction proceeds, the Sr metal gradually melts, generating a gas thought to be H ₂ . After the reaction was completed, the solution was filtered, and the solvent was removed in vacuo and recrystallized from hexane to obtain 2.330 g (65%) of colorless crystals, Sr (BAAc) ₂ (tetramine).

IR (KBr, cm ^-1 ) 2963 m, 2925 m, 2868 s, 2828 w, 1645 vs, 1509 vs, 1491 vs, 1458 s, 1385 w, 1355 w, 1342 w, 1317 m, 1204 s, 1119 s, 1097 s, 1081 s, 1052 s, 979 w, 948 s, 854 w, 829 m, 785 s, 740 w, 721 w;

¹ H-NMR (Acetone-d ₆ , 25 ° C) δ 1.37 (s, 9H, -C (CH ₃ ) ₃ ), 1.73 (br, 3H, -CH ₃ ), 2.15 (s, 12H, -N ( CH ₃ ) ₂ ), 2.21 (s, 4H, -NCH ₂ CH ₂ N-), 2.33 (t, 4H, -NCH ₂ CH ₂ N-), 2.49 m, 4H, -NCH ₂ CH ₂ N-) 2.50 (m, 4H, -NCH ₂ CH ₂ N-), 4.45 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ27.9 (-CH ₃ ), 28.9 (-C (CH ₃ ) ₃ ), 41.8 (-N (CH ₃ )-), 46.3 (-N (CH ₃ ) ₂ ), 56.0 (-NCH ₂ CH ₂ N-) 57.4 (-NCH ₂ CH ₂ N-) 75.3 (-C (CH ₃ ) ₃ ), 82.8 (CH), 171.0 (CO), 185.7 (COO)

Example 15

Synthesis of Ti (O ⁱ Pr) ₂ (EBAc) ₂

HEBAc (1.113 g, 7.03 mmol) was slowly added to a pentane (2.0 mL) solution of Ti (O ⁱ Pr) ₄ (1.000 g 3.51 mmol) at room temperature, followed by reaction for 2 hours. The solvent is removed in vacuo from the clear solution to form an orange liquid compound. The liquid compound was vacuum distilled (70 占 폚, 10 ^-3 Torr) to obtain 0.823 g (49%) of Ti (O ⁱ Pr) ₂ (EBAc) ₂ as a pale yellow liquid compound.

¹ H-NMR (CDCl ₃ , 25 ° C.) δ1.02 to l.15 (m, 3H, -CH ₂ CH ₃ ; m, 6H, OCCH (CH ₃ ) ₂ ; m, 6H, OCH (CH ₃ ) ₂ ), 2.30 (m, 1H, OCCH (CH ₃ ) ₂ ), 3.95 (m. 2H, CH ₂ CH ₃ ), 4.67 (m, 1H, OCH (CH ₃ ) ₂ ), 4.87 (s, 1H, OCCHCOO) ;

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ14.4 (CH ₂ CH ₃ ), 20.0 (OCCH (CH ₃ ) ₂ ), 20.1 (OCCH (CH ₃ ) ₂ ), 24.9 (OCH (CH ₃ ) ₂ ) , 25.0 (OCH (CH ₃ ) ₂ ) 60.1 (CH ₂ CH ₃ ), 78.4 (OCH (CH ₃ ) ₂ ), 85.3 (COCHCOO), 172.9 (CO), 192.2 (COO)

Example 16

Synthesis of Ti (O ⁱ Pr) ₂ (BAAc) ₂

HBAAc (1.113 g, 7.03 mmol) was slowly added to a pentane (2.0 mL) solution of Ti (O ⁱ Pr) ₄ (1.000 g 3.51 mmol) at room temperature, followed by reaction for 2 hours. After the reaction, the solvent was removed in vacuo to obtain a white solid compound. Subsequently, the compound was sublimed (70 ° C., 10 ⁻³ Torr) to obtain Ti (O ⁱ Pr) ₂ (BAAc) ₂ as a white solid compound. g (65%) was obtained.

mp 103-106 ° C;

IR (KBr, cm ^-1 ) 1975 m, 2923 w, 2857 w, 1634 s, 1610 s, 1576 w, 1559 w, 1525 vs, 1458 w, 1367 w, 1292 vs, 1254 m, 1155 vs, 992 vs, 851 m, 788 m, 746 w, 621 w, 583 w, 479 m, 457 w, 436 w;

¹ H-NMR (CDCl ₃ , 25 ° C.) δ 1.14 (d, 3H, —CH (CH ₃ ) ₂ ), 1.19 (d, 3H, —CH (CH ₃ ) ₃ ), 1.36 (s, 9H, − C (CH ₃ ) ₃ ), 1.86 (s, 3H, CH ₃ ), 4.76 (m, 1H, —CH (CH ₃ ) ₂ ), 4.85 (s, 1H, CH);

¹³ C-NMR (CDCl ₃ , 25 ° C.) δ24.9 (-CH3), 25.1 (-CH (CH ₃ ) ₂ ), 28.5 (-C (CH ₃ ) ₃ ), 78.3 (CH (CH ₃ ) ₂ ) , 80.4 (-C (CH ₃ ) ₃ ) 98.8 (CH), 172.4 (CO), 183.6 (COO)

In the present invention, Ba, Sr precursors were synthesized by reacting β-keto ester and amide and β-diketo ester and amide with various N, O-electron donor ligands with Ba and Sr metals. In addition, Ti precursor was synthesized by reacting β-keto ester and amide and β-diketo ester and amide ligand with Ti (O ⁱ Pr) ₄ (IV). As described above, in the present invention, various types of precursors for manufacturing BST thin films capable of replacing the β-diketone compound used in the preparation of BST thin films by high-molecular metal chemical vapor deposition (MOCVD) have been recently synthesized. These compounds are not only highly volatile, but also stable and easy to handle in the air compared to the existing β-diketone compounds, and if the deposition of thin films using these precursors is established, it will make a significant contribution to the fabrication of the next generation Giga Gold DRAM. It is expected.

Claims (3)

Precursor for ferroelectric BST thin film represented by general formula [I] synthesized using β-keto ester [M (RC (O) CHC (O) OR ') ₂ ] ₃ . … … … … … [One] (In the formula, M is Ba or Sr, R is an alkyl group having 1 to 4 carbon atoms and R 'is an alkyl group having 3 to 4 carbon atoms.) A precursor for the production of ferroelectric BST thin films represented by general formula [V] synthesized using β-keto ester and N, O-electron donor ligand (L) M (RC (O) CHC (O) OR ') ₂ .L. … … … … … … [V] (Wherein M is Ba or Sr, R and R 'are alkyl groups of 1 to 4 carbon atoms and L is (CH ₃ ) N (CH ₂ CH ₂ N) n (CH ₃ ) ₂ n is 1 N having a structure of amine of 4 and CH ₃ O (CH ₂ CH ₂ O) nCH ₃ is 1-4 glycol ether.) β-keto A precursor for the production of ferroelectric BST thin films represented by the general formula [IX] synthesized by reacting an ester (β-keto ester) with Ti (O ⁱ Pr) ₄ Ti (0 ⁱ Pr) ₂ (RC (O) CHC (O) OR ') ₂ ... … … … … … … [IX] (In the formula, R and R 'is an alkyl group having 1 to 4 carbon atoms.)