KR100936490B1 - Organic metal precursors compound for deposition of metal oxide, metal nitride and pure metal thin films and, method for preparing the same and, deposition process of the thin films using the same - Google Patents

Abstract

PURPOSE: An organic metal precursor compound for depositing metal oxide, metal nitride, and metal thin film is provided to ensure high thermal stability and volatility. CONSTITUTION: An organic metal precursor compound for depositing metal oxide film, metal nitride film and pure metal thin film is denoted by chemical formula 1. A method for producing the organic metal precursor compound comprises: a step of adding 3LiNR3R4 in (R1CCR2)M(NR3R4)3 compound solution under the presence of organic solvent such as benzene, hexane, or toluene at low temperature; and a step of stirring, filtering and purifying. The metal oxide film, metal nitride film or meal thin film is formed on a substrate using the organic metal precursor compound through metal organic chemical vapor deposition(MOCVD) or atomic layer deposition(ALD). The deposition temperature is 200~1000°C.

Description

Organic metal precursors compound for deposition of metal oxide, metal nitride and pure metal thin films and, method for preparing the same and, deposition process of the thin films using the same}

The present invention relates to an organic metal precursor compound for depositing a metal oxide film, a metal nitride film and a pure metal thin film applied to a semiconductor device, and more particularly, to an organic metal chemical vapor deposition (MOCVD) or atomic layer deposition method. (Atomic Layer Deposition, ALD) relates to an organic metal precursor compound for metal oxide film, metal nitride film and pure metal thin film deposition, a method for producing the same, and a thin film deposition method using the compound.

In recent years, semiconductor devices have been studied as copper wiring materials that can replace conventional aluminum alloy wirings to improve the performance of semiconductor devices by realizing ultra high integration and ultra high speed of Ultra Large Scale Integration (ULSI). It is the situation that is being put to practical use. This copper has a relatively low resistivity (1.67 μΩcm) compared to aluminum (2.67 μΩcm) and excellent resistance to electrical migration (electromigration) has been actively studied as a next-generation semiconductor wiring material, but still resolved There are some problems that must be addressed.

One of them is that copper diffuses through silicon or dielectric film and damages the electrical characteristics of the device. To prevent this, a diffusion barrier is used. As the diffusion barrier, refractory metal materials such as titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), tungsten (W), and tungsten nitride (WN) are used in the copper wiring material process. It is known to be an effective material (GSChen. Et al., Thin Solid Films, 353 , 264, 1999; AZ Moshfegh et al., Thin Solid Films, 370 , 10,2000; K. Hinode. Et al., J. Vac. Sci. Tech.A. , 15, 2017,1997; including F.-H.Lu., Thin Solid Films, 375, 123,2000).

In general, metal nitride thin films have properties such as excellent hardness, high melting point, and resistance to organic solvents or acids. In particular, titanium nitride (TiN), tantalum nitride (TaN), and tantalum silicon nitride (TaSiN) prevent aluminum (Al) and copper (Cu), which are used for interconnects in the semiconductor industry, from spreading into silicon substrates. Is used as a diffusion barrier.

In addition, a titanium thin film and a tantalum thin film, which are metal thin films, are used as a glue layer between a silicon substrate and an electrode, a wiring material, or a diffusion barrier. These titanium and tantalum metal thin films form titanium silicide (TiSi) and tantalum silicide (TaSi) by reaction with a silicon layer when deposited on a silicon substrate, and are inferior in adhesion to silicon substrates and other metals (Al, Cu, TiN, etc.). Used as a thin film to improve adhesion to).

Thin films such as metal nitrides and pure metals have been mainly deposited by physical vapor deposition such as sputtering using an electron beam (e-beam) in a semiconductor manufacturing process. This physical vapor deposition method is a method of forming a thin film on a silicon substrate by activating the metal or ceramic particles protruding from the target by supplying an electron beam in a high vacuum state to a solidified ceramic material called a high purity target.

However, in the manufacture of nano-class semiconductor devices such as more than 256 mega (M: mega), 1 g (G: Giga), 4G, the circuit line width is 0.25㎛. As it is rapidly miniaturized to 0.11 μm and 0.09 μm, the sputtering physical vapor deposition method, which has less step coverage, which is used under 256M Dynamic Random Access Memory (DRAM), has a high fineness ratio. Applications are limited, for example, in filling processes such as contacts or via holes.

In contrast, chemical vapor deposition and atomic layer deposition, which are used to deposit thin films such as pure metal or metal nitride on a substrate, show high step coverage to overcome the disadvantages of conventional physical vapor deposition. Therefore, the application of these thin film deposition processes using chemical vapor deposition and atomic layer deposition processes to nanoscale memory semiconductor manufacturing processes is further expanded.

In particular, in order to realize miniaturization and high integration in nanoscale semiconductor processes, the chip structure is a multi-layer wiring structure. In the chemical vapor deposition method and atomic layer deposition method for depositing these thin films, different precursors are used. Complexity is increasing. Accordingly, in order to realize nanoscale semiconductor processes, development of excellent multi-purpose precursors that can be used for chemical vapor deposition and atomic layer deposition is required.

In the semiconductor industry, metal nitride and silicon nitride thin films are used as a diffusion barrier of wiring materials. Among them, tantalum (Ta) is a high melting point refractory material and has a lower resistance value than other materials. It has been reported to maintain a relatively stable interface without the reaction of and tantalum (K. Holloway. Et al., J. Appl. Phys. 71 , 5433, 1992), and stable thermal stability up to 650 ° C. In particular, the properties of tantalum nitride (TaN) and tantalum silicon nitride (TaSiN) thin films show better suitability as diffusion barriers.

This is because the tantalum nitride thin film produced by chemical vapor deposition and atomic layer deposition has a disoredred grain boundary structure, which effectively prevents aluminum or copper from diffusing into the silicon substrate, and tantalum does not react with copper to ensure stability. Because it is excellent. In addition, since the three-element material such as Ta-Si-N thin film has an amorphous structure, there is no grain boundary, thereby effectively suppressing copper diffusion.

On the other hand, TaN thin films using chemical vapor deposition or atomic layer deposition is _{TaF 5, TaCl 5, TaBr 5} , but a method using an inorganic compound such as TaI _5, it is difficult to obtain a sufficient vapor pressure (vapor pressure) as a solid compound In addition, fluorine (F) or chlorine (Cl), which is a fatal impurity in the operation of the semiconductor device in the deposited thin film, may be penetrated. In addition, there is a disadvantage that the deposition temperature for depositing a thin film is high.

In order to overcome this disadvantage, it is possible to form a thin film at a somewhat low temperature, and has a relatively high vapor pressure characteristic under the deposition conditions, and the tantalum amide compound and the tantalum imido compound precursor, which are liquid organometallic compounds containing no halogen, are widely used. It is becoming.

The tantalum amide compound has a disadvantage that some compounds are already converted into compounds even when heated to obtain a high vapor pressure, and Ta ₃ N _{5, which} is an insulator, is mainly deposited rather than conductor TaN.

The tantalum imido compound is a stable liquid compound even when heated above 100 ℃ to increase the vapor pressure, and due to the strong imido double bond between Ta and N, it is advantageous to generate a TaN phase as a conductor compared to Ta ₃ N ₅ as an insulator. . However, the disadvantage is that it is difficult to configure the device because it heats more than 100 ℃, carbon pollution occurs a lot in the TaN thin film.

That is, a preferred conductor used as a metal-to-metal diffusion barrier is TaN, but in most cases, an insulator Ta ₃ N ₅ thin film which is advantageous for Ta oxide water is deposited. Therefore, since precursors are generally used in Ta (V) oxidation, Ta ₃ N ₅ thin films are often produced during chemical vapor deposition or atomic layer deposition, especially in low temperature processes. It is not easy to obtain TaN thin film.

The present invention is to solve the above problems,

+3 oxidized state of the central metal, which is highly volatile to ensure excellent thin film properties, thickness, composition, and step coverage by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) and is in a liquid state at room temperature An object is to provide an organometallic precursor compound for phosphorus metal oxide film, metal nitride film and pure metal thin film deposition.

In addition, another object is to provide a method for preparing the aforementioned organometallic precursor compound.

In addition, another object of the present invention is to provide a thin film deposition method for forming a metal oxide film, a metal nitride film and a pure metal thin film using an organometallic chemical vapor deposition method or an atomic layer deposition method using the above-described organometallic precursor compound.

The present invention to achieve the above object,

The organometallic precursor compound for depositing the metal oxide film, the metal nitride film, and the pure metal thin film, wherein the organometallic precursor compound used to deposit the metal oxide film, the metal nitride film, and the pure metal thin film is an organometallic precursor compound defined by Formula 1 below. To provide.

<Formula 1>

In Formula 1, M is one selected from Group 5B on the periodic table, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkyl group, a perfluoroalkyl group, an alkylaminoalkyl group, an alkoxyalkyl group, a silyl An alkyl group, an alkoxysilylalkyl group, a cycloalkyl group, a benzyl group, an allyl group, an alkylsilyl group having 1 to 4 carbon atoms, an alkoxysilyl group, an alkoxyalkylsilyl group or an aminoalkylsilyl group is selected, and each of R ₃ and R ₄ is independent of each other It is selected from an alkyl group or an alkylsilyl group having 1 to 4 carbon atoms.

In addition, in order to prepare the aforementioned organometallic precursor compound, (R ₁ CCR ₂ ) M (NR ₃ R ₄ ) in an organic solvent such as benzene, hexane, toluene, and the like as in Scheme 1 below. ₃ after the stirring followed by the addition of 3LiNR ₃ R ₄ in the low-temperature reaction to the compound solution, wearing a manufacturing method of an organometallic precursor compound was filtered and purified metal oxide film, characterized in that produced by the metal nitride film and the pure metal thin film increases to provide.

M and R ₁ , R ₂ , R ₃ and R ₄ in Scheme 1 are the same as defined in Chemical Formula 1.

In addition, by using an organic metal precursor compound (Metal Organic Chemical Vapor Deposition (MOCVD) or Atomic Layer Deposition (ALD) method of forming a metal oxide film, a metal nitride film or a metal thin film on the substrate of the thin film) In the vapor deposition method,

Provided is a thin film deposition method using the above-described organometallic precursor compound as the organometallic precursor compound.

 As described above, it was confirmed experimentally that the organometallic precursor compound according to the present invention is suitable for depositing a metal oxide film, a metal nitride film, and a pure metal thin film. Semiconductors that deposit metal oxides, metal nitrides, and metal thin films using organometallic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) by having high vapor pressures with high thermal stability that properties of precursors do not deteriorate under constant heating. The effect is that it can be usefully applied to the manufacturing process.

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

The present invention provides an organometallic precursor compound defined by Formula 1 as an organometallic precursor compound used for depositing a metal oxide film, a metal nitride film and a pure metal thin film applied to a semiconductor device.

In Formula 1, M is one selected from Group 5B on the periodic table, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkyl group, a perfluoroalkyl group, an alkylaminoalkyl group, an alkoxyalkyl group, a silyl An alkyl group, an alkoxysilylalkyl group, a cycloalkyl group, a benzyl group, an allyl group, an alkylsilyl group having 1 to 4 carbon atoms, an alkoxysilyl group, an alkoxyalkylsilyl group, an aminoalkylsilyl group, and each of R ₃ and R ₄ are independent of each other And an alkyl group having 1 to 4 carbon atoms or an alkylsilyl group.

More preferably, R ₁ and R ₂ in the compound represented by Formula 1 are each independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms, an alkoxysilyl group or an alkylsilyl group having 1 to 4 carbon atoms. , More preferably, in the compound represented by Formula 1, R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t -Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i -Pr, t -Bu, sec -Bu or CH ₃ CH ₂ CH ₂ CH ₂ is preferably selected from among (CH ₃ ) ₃ Si, C ₂ H ₅ , is a CH ₃ CH ₂ CH ₂ are more preferred.

In addition, in the compound represented by Formula 1, R ₃ and R ₄ are more preferably different from each other CH ₃ , C ₂ H ₅ .

The organometallic precursor compound of the present invention represented by Chemical Formula 1 has a high thermal stability that does not deteriorate even under continuous heating because the alkyne ligand having a triple bond among the ligands bound to the central metal strongly forms a π-bond with the central metal. In the thin film used as a diffusion barrier, since the core metal is in an oxidation state of +3, the use of the organometallic precursor compound of the present invention having an oxidation number of +3 compared to the existing organometallic precursor compound having an oxidation number of +5 is diffusion. In addition to the formation of the barrier film, a dialkyl amino ligand capable of causing a high vapor pressure is combined with the central metal to exhibit a high vapor pressure.

In particular, it is more preferable to use Ta and Nb as the central metals in the TaN or NbN thin film used as the anti-magnification film, and the organic metal of the present invention having Ta and Nb as the central metal as the central metal as described above. By using the metal precursor compound, it is possible to more advantageously form a diffusion barrier film of TaN or NbN.

In addition, in the organometallic precursor compound represented by Formula 1, R ₃ and R ₄ are both CH ₃ so as to have high volatility in order to easily apply to chemical vapor deposition or atomic layer deposition without contamination of impurities in the final thin film. The organometallic precursor compound represented by is preferable.

In Formula 2, M is one selected from Group 5B on the periodic table, and R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t -Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i- Pr, t- Bu, sec- Bu or CH ₃ CH ₂ CH ₂ CH ₂ .

In addition, among the organometallic precursor compounds represented by Formula 2, an organometallic precursor compound represented by the following Formula 3, wherein R ₁ and R ₂ are both C ₂ H ₅ , is preferable.

In Formula 3, M is one selected from Group 5B on the periodic table.

In addition, in the organometallic precursor compound represented by Formula 3, an organic compound represented by Formula 4, in which M is Ta, is more preferable as the organometallic precursor compound used to deposit a metal oxide film, a metal nitride film, and a pure metal thin film.

In addition, in the organometallic precursor compound represented by Formula 3, an organic compound represented by Formula 5, in which M is Nb, is more preferable as the organometallic precursor compound used to deposit a metal oxide film, a metal nitride film, and a pure metal thin film.

Also, among the organometallic precursor compounds represented by Chemical Formula 1, R ₃ and R ₄ are preferably CH ₃ and C ₂ H ₅ which are different from each other, and an organometallic precursor compound represented by the following Chemical Formula 6 is preferable.

In Formula 6, M is one selected from Group 5B on the periodic table, and R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t -Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i- Pr, t- Bu, sec- Bu or CH ₃ CH ₂ CH ₂ CH ₂ .

In addition, among the organometallic precursor compounds represented by Chemical Formula 6, R ₁ and R ₂ are preferably C ₂ H ₅ , and the organometallic precursor compounds represented by the following Chemical Formula 7 are preferable.

M in Formula 7 is one selected from Group 5B on the periodic table.

In addition, in the organometallic precursor compound represented by Formula 7, an organic compound represented by Formula 8, in which M is Ta, is more preferable as the organometallic precursor compound used to deposit a metal oxide film, a metal nitride film, and a pure metal thin film.

In addition, in the organometallic precursor compound represented by Formula 7, the organic compound represented by Formula 9, wherein M is Nb, is more preferable as the organometallic precursor compound used to deposit a metal oxide film, a metal nitride film, and a pure metal thin film.

In addition, among the organometallic precursor compounds represented by the general formula (1), compounds represented by the following general formula (10) in which R ₃ and R ₄ are both C ₂ H ₅ are preferable.

In Formula 10, M is one selected from Group 5B on the periodic table, and R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t -Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i- Pr, t- Bu, sec- Bu or CH ₃ CH ₂ CH ₂ CH ₂ .

In addition, among the organometallic precursor compounds represented by Chemical Formula 10, R ₁ and R ₂ are preferably C ₂ H ₅ , and the organometallic precursor compounds represented by the following Chemical Formula 11 are preferable.

In Formula 11, M is one selected from Group 5B on the periodic table.

In addition, in the organometallic precursor compound represented by Formula 11, an organic compound represented by Formula 12, in which M is Ta, is more preferable as the organometallic precursor compound used to deposit a metal oxide film, a metal nitride film, and a pure metal thin film.

In addition, in the organometallic precursor compound represented by Formula 11, an organic compound represented by Formula 13, in which M is Nb, is more preferable as the organometallic precursor compound used to deposit a metal oxide film, a metal nitride film, and a pure metal thin film.

As described above, the organometallic precursor compound represented by Chemical Formula 1 may be prepared by various methods, but in the present invention, as shown in Scheme 1, (R ₁ CCR ₂ ) M (NR ₃ R ₄ ) under an organic solvent. ) after which the reaction was stirred and then the mixture 3LiNR ₃ R ₄ in the compound ₃ in the low-temperature solution, can be easily obtained by filtration and purified. Herein, hexane, benzene or toluene may be used as the organic solvent.

Scheme 1

M and R ₁ , R ₂ , R ₃ and R ₄ in Scheme 1 are the same as defined in Chemical Formula 1.

The organometallic precursor compound defined by Chemical Formula 1 prepared by the present invention may be usefully used as a precursor for depositing a metal oxide film, a metal nitride film, and a pure metal thin film. In particular, the compounds represented by the formulas (4), (5), (8), (9), (12), and (13) may be more usefully applied.

Among these, the tantalum (Ta) organometallic precursor compound represented by the formulas (4), (8), and (12) is a metal oxide film such as a tantalum oxide (Ta ₂ O ₅ ) thin film, a composite metal oxide film such as a TaSiO _x , TaAlO _x thin film, TaN, Ta _It can be suitably used as a precursor for the deposition of metal nitride films such as 3N ₅ thin films, composite metal nitride films such as TaCN, tantalum silicon nitride (TaSiN) thin films, or metal silicide thin films such as tantalum silicide (TaSi) thin films. .

In addition, the niobium (Nb) organometallic precursor compounds represented by the formulas (5), (9) and (13) may be metal oxide films such as niobium oxide (Nb ₂ O ₅ ) thin films, composite metal oxide films such as NbSiO _x , NbAlO _x thin films, NbN, Nb _It can be suitably used as a precursor for the deposition of metal nitride films such as 3N ₅ thin films, composite metal nitride films such as NbCN and NbSiN thin films, and metal silicide thin films such as niobium silicide (NbSi) thin films.

The organometallic precursor compound defined by Chemical Formula 1 prepared by the present invention is a compound having high thermal stability and high vapor pressure even under continuous heating, and may be formed using a metal oxide film, a metal nitride film, and a metal thin film using an organic metal chemical vapor deposition method or an atomic layer deposition method. It can be usefully applied to the deposition.

When the thin film is deposited on the substrate using the organometallic precursor compound defined by Chemical Formula 1 according to the present invention, the deposition temperature may be between 200 and 1000 ° C. In this case, in order to vaporize the organometallic precursor compound, it may be bubbled with argon (Ar) or nitrogen (N ₂ ) gas, thermal energy or plasma, or a bias may be applied to the substrate. In addition, the delivery method for supplying the organometallic precursor compound according to the present invention to a process may include a bubbling method, a vapor phase mass flow controller (MFC), a direct liquid injection (DLI), or a precursor compound. Various feeding methods may be applied, including a liquid transfer method for dissolving and dissolving it in an organic solvent.

One or more mixtures of argon (Ar), nitrogen (N ₂ ), helium (He), or hydrogen (H ₂ ) may be used as a carrier gas or a diluent gas for supplying the precursor to the process. Reaction gas for depositing metal oxide thin films (Ta ₂ O _5, Nb ₂ O ₅ ) or composite metal oxide thin films (TaSiOx, NbSiOx, TaAlOx, NbAlOx) by organometallic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) One or two or more mixtures selected from steam (H ₂ O), oxygen (O ₂ ) or ozone (O ₃ ) may be used.

More specifically, in order to deposit a tantalum oxide (Ta ₂ O ₅ ) thin film, TaSiO _x , TaAlO _x thin film, etc., water vapor, oxygen, or ozone is used as a reaction gas, and the organic metal precursor compound is represented by Chemical Formula 4, 8, or 12. It is preferable to use a tantalum (Ta) organometallic precursor compound represented, and in order to deposit a niobium oxide (Nb ₂ O ₅ ) thin film, NbSiO _x , NbAlO _x thin film, etc., steam, oxygen or ozone is used as a reaction gas. It is preferable to use a niobium (Nb) organometallic precursor compound represented by the formula (5), (9) or (13) as the organometallic precursor compound.

In addition, a metal nitride thin film (TaN, NbN, Ta ₃ N _5, Nb ₃ N ₅ ) or a metal composite nitride thin film (TaCN, NbCN, TaSiN, NbSiN) by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) In order to deposit the reaction gas, ammonia (NH ₃ ) or hydrazine (N ₂ H ₄ ) may be used.

More specifically, in order to deposit TaN, Ta ₃ N ₅ , TaCN, and tantalum nitride (TaSiN) thin films, ammonia or hydrazine is used as a reaction gas, and tantalum represented by Chemical Formula 4, 8, or 12 as an organometallic precursor compound ( Ta) It is preferable to use an organometallic precursor compound, and in order to deposit NbN, Nb ₃ N ₅ thin films, NbCN, NbSiN thin films, niobium silicide (NbSi) thin films, and the like, ammonia or hydrazine is used as the reaction gas. It is preferable to use a niobium (Nb) organometallic precursor compound represented by the formula (5), (9), or (13) as the precursor compound.

Hereinafter, the metal oxide film, the metal nitride film, and the organic metal precursor compound for pure metal thin film deposition according to the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention. This is not limited to the following examples.

<Example 1>

Preparation of (3-Hexyne) Ta (NMe ₂ ) ₃ of Formula 4

47.8 g (175 mmol) of n-BuLi 2.55M sol in Hexane was quantified in a 500 mL flask, diluted in 250 mL of hexane, and stirred at a low temperature (-10 to 0 ° C.) of dimethylamine (Dimethylamine, HNMe ₂ ). 7.9 g (175 mmol) was bubbled into the flask and allowed to react, followed by stirring at room temperature for 2 to 3 hours. 27 g (58 mmol) of (3-Hexyne) TaCl ₃ (DME) was dissolved in 100 mL of toluene, and then slowly added at low temperature (-5˜0 ° C.) using cannula, and then 30-40. The reaction is stirred at 15 ° C. for 15 hours. After completion of the reaction, the resulting solution was filtered under reduced pressure to remove the solvent, and the remaining dark yellow liquid was purified under reduced pressure to obtain 17.6 g of a yellow viscous liquid (3-Hexyne) Ta (NMe ₂ ) ₃ (yield: 76.8%).

Anal. Calcd for C ₁₂ H ₂₈ N ₃ Ta: C, 36.46; H, 7. 14; N, 10.63. Find: C, 35.92; H, 7. 16; N, 11.42.

b.p: 76 ° C. at 0.188 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.34 (C H ₃ CH ₂ CCCH ₂ C H ₃ , t, 6H)

δ 3.18 (Ta- [N (C H ₃ ) ₂ ] ₃ ), s, 18H)

δ 3.25 (CH ₃ C H ₂ CC CH ₂ CH ₃ , q, 4H)

¹³ C-NMR (C ₆ D ₆ ): δ 15.17 ( C H ₃ CH ₂ CCCH ₂ C H ₃ )

δ 28.59 (CH ₃ C H ₂ CC C H ₂ CH ₃ )

δ 43.92 (Ta- [N ( C H ₃ ) ₂ ] ₃ )

δ 215.65 (CH ₃ CH ₂ CC CH ₂ CH ₃ )

<Example 2>

Preparation of (3-Hexyne) Nb (NMe ₂ ) ₃ of Formula 5

40.8 g (150 mmol) of n-BuLi 2.55M sol in hexane was quantified in a 500 mL flask, diluted with 250 mL of hexane, and stirred at low temperature (-10 to 0 ° C.) 6.8 g of dimethylamine (HNMe ₂ ). (150 mmol) is bubbled to react, and the temperature is raised to room temperature and stirred for about 2 hours. 18.6 g (50 mmol) of (3-Hexyne) NbCl ₃ (DME) was dissolved in 100 mL of toluene, and then slowly added at low temperature (0-5 ° C) using cannula, followed by 30 The reaction is completed by stirring at ˜40 ° C. for 14 hours. Filter through a frit filter to obtain a brown solution, and remove the solvent under reduced pressure to distill the remaining dark brown liquid under reduced pressure to give a viscous brown liquid compound (3-Hexyne) Nb (NMe ₂ ) ₃ 6.5 g (Yield 42.5%) is obtained.

Anal. Calcd for C ₁₂ H ₂₈ N ₃ Nb: C, 46.91; H, 9. 18; N, 13.67. Find: C, 46.39; H, 8.87; N, 14.05.

b.p: 76 ° C. at 0.188 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.36 (C H ₃ CH ₂ CCCH ₂ C H ₃ , t, 6H)

δ 3.14 (Nb— [N (C H ₃ ) ₂ ] ₃ ), s, 18H)

δ 3.18 (CH ₃ C H ₂ CC CH ₂ CH ₃ , q, 4H)

¹³ C-NMR (C ₆ D ₆ ): δ 14.86 ( C H ₃ CH ₂ CCCH ₂ C H ₃ )

δ 26.78 (CH ₃ C H ₂ CC C H ₂ CH ₃ )

δ 44.38 (Nb- [N ( C H ₃ ) ₂ ] ₃ )

δ 200.16 (CH ₃ CH ₂ CC CH ₂ CH ₃ )

<Example 3>

Preparation of (3-Hexyne) Ta (NMeEt) ₃ of Formula 8

47.8 g (175 mmol) of n-BuLi 2.55M sol in hexane was quantified in a 500 mL flask, diluted in 250 mL of Hexane, and added dropwise with a dropping funnel at low temperature (-10 to 0 ° C.) to ethylmethylamine (HNEtMe). Slowly drop 10.4 g (175 mmol) and stir 2 to 3 hours at room temperature. 27 g (58 mmol) of (3-Hexyne) TaCl ₃ (DME) was dissolved in 100 mL of toluene, and then slowly added at low temperature (-5˜0 ° C.) using cannula, and then 30-40. The reaction is stirred at 15 ° C. for 15 hours. The reaction was completed and filtered to give a yellow solution, the solvent was removed under reduced pressure, and the remaining thick yellow liquid was purified under reduced pressure to give 21.2 g of (3-Hexyne) Ta (NMeEt) _{3 as} a viscous yellow liquid compound (yield: 83.8% Get)

Anal. Calcd for C ₁₅ H ₃₄ N ₃ Ta: C, 41.19; H, 7.83; N, 9.61. Find: C, 40.69; H, 7.80; N, 10.06.

b.p: 90 ° C. at 0.238 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.04 (Ta- [NMeCH ₂ C H ₃ ] ₃ , t, 9H)

δ 1.35 (C H ₃ CH ₂ CCCH ₂ C H ₃ ), t, 6H)

δ 3.16 (Ta- [NC H ₃ Et] ₃ , s, 9H)

δ 3.25 (CH ₃ C H ₂ CCC H ₂ CH ₃ , q, 4H)

δ 3.47 (Ta- [NMeC H ₂ CH ₃ Et] ₃ , q, 6H)

¹³ C-NMR (C ₆ D ₆ ): δ 15.15 ( C H ₃ CH ₂ CCCH ₂ C H ₃ )

δ 15.91 (Ta- [NMeCH ₂ C H ₃ ] ₃ )

δ 28.61 (CH ₃ C H ₂ CC C H ₂ CH ₃ )

δ 39.40 (Ta- [N C H ₃ Et] ₃ )

δ 50.24 (Ta- [NMe C H ₂ CH ₃ ] ₃ )

δ 215.15 (CH ₃ CH ₂ CC CH ₂ CH ₃ )

<Example 4>

Preparation of (3-Hexyne) Nb (NMeEt) ₃ of Formula 9

Quantify n-BuLi 2.55M sol in hexane 39 g (143 mmol) in a 500 mL flask, add 250 mL of hexane (Hexane), and dilute. Ethylmethylamine using a dropping funnel at low temperature (-10 ~ 0 ℃). , HNEtMe) 8.5 g (143 mmol) was added dropwise slowly to the reaction and stirred at room temperature for about 2-3 hours. 17.8 g (47 mmol) of (3-Hexyne) NbCl ₃ (DME) was dissolved in 100 mL of toluene, and then slowly added at low temperature (0-5 ° C.) using cannula, followed by about 30 The reaction is completed by stirring at ˜40 ° C. for 14 hours. The brown solution obtained by filtration was removed under reduced pressure to remove the solvent, and the remaining dark brown liquid was distilled under reduced pressure to obtain 9.9 g (yield: 60.4%) of a viscous brown liquid compound (3-Hexyne) Nb (NMeEt) ₃ .

Anal. Calcd for C ₁₅ H ₃₄ N ₃ Nb: C, 51.57; H, 9.81; N, 12.03. Find: C, 51.24; H, 9.58; N, 12.69.

b.p: 82 ° C. at 0.46 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.04 (Nb- [NMeCH ₂ C H ₃ ] ₃ , t, 9H)

δ 1.35 (C H ₃ CH ₂ CCCH ₂ C H ₃ ), t, 6H)

δ 3.12 (Nb— [NC H ₃ Et] ₃ , s, 9H)

δ 3.18 (CH ₃ C H ₂ CCC H ₂ CH ₃ , q, 4H)

δ 3.43 (Nb— [NMeC H ₂ CH ₃ Et] ₃ , q, 6H)

¹³ C-NMR (C ₆ D ₆ ): δ 14.85 ( C H ₃ CH ₂ CCCH ₂ C H ₃ )

δ 15.64 (Nb- [NMeCH ₂ C H ₃ ] ₃ )

δ 26.87 (CH ₃ C H ₂ CC C H ₂ CH ₃ )

δ 39.99 (Nb- [N C H ₃ Et] ₃ )

δ 50.60 (Nb- [NMe C H ₂ CH ₃ ] ₃ )

δ 200.04 (CH ₃ CH ₂ CC CH ₂ CH ₃ )

Example 5

Preparation of (3-Hexyne) Ta (NEt ₂ ) ₃ of Formula 12

47.8 g (175 mmol) of n-BuLi 2.55M sol in hexane was quantified in a 500 mL flask, diluted in 250 mL of hexane, and dimethylamine (Diethylamine, 12.8 g (175 mmol) of HNEt ₂ ) are slowly added dropwise and stirred at room temperature for 2 to 3 hours. 27 g (58 mmol) of (3-Hexyne) TaCl ₃ (DME) was dissolved in 100 mL of toluene, and then slowly added to a low temperature (-5˜0 ° C.) using cannula. Thereafter, the mixture was stirred at 30-40 ° C. for 15 hours to complete the reaction, filtered to obtain a yellow solution, and the solvent was removed under reduced pressure. The remaining liquid was purified under reduced pressure to give a viscous yellow liquid compound (3-Hexyne) Ta (NEt ₂ ) ₃ 23.1 g (yield: 83.39%) are obtained.

Anal. Calcd for C ₁₈ H ₄₀ N ₃ Ta: C, 45.09; H, 8.41; N, 8.76. Find: C, 44.31; H, 8. 35; N, 9.14

b.p: 102 ° C. at 0.158 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.04 (Ta- [N (CH ₂ C H ₃ ) ₂ ] ₃ , t, 18H)

δ 1.35 (C H ₃ CH ₂ CCCH ₂ C H ₃ ), t, 6H)

δ 3.24 (CH ₃ C H ₂ CCC H ₂ CH ₃ , q, 4H)

δ 3.50 (Ta- [N (C H ₂ CH ₃ ) ₂ ] ₃ , q, 12H)

¹³ C-NMR (C ₆ D ₆ ): δ 15.01 ( C H ₃ CH ₂ CCCH ₂ C H ₃ )

δ 16.22 (Ta- [N (CH ₂ C H ₃ ) ₂ ] ₃ )

δ 28.59 (CH ₃ C H ₂ CC C H ₂ CH ₃ )

δ 44.71 (Ta- [N ( C H ₂ CH ₃ ) ₂ ] ₃ )

δ 214.85 (CH ₃ CH ₂ CC CH ₂ CH ₃ )

<Example 6>

Preparation of (3-Hexyne) Nb (NEt ₂ ) ₃ of Formula 13

Quantify 40.8 g (150 mmol) of n-BuLi 2.55M sol in hexane in a 500 mL flask, dilute 250 mL of hexane, and dilute with diethylamine, using a dropping funnel at low temperature (-10 to 0 ° C). 11 g (150 mmol) of HNEt ₂ ) were slowly added dropwise and the temperature was raised to room temperature, followed by stirring for about 2 hours. 18.6 g (50 mmol) of (3-Hexyne) NbCl ₃ (DME) was dissolved in 100 mL of toluene, and then slowly added using Cannula at low temperature (0-5 ° C) and at 30-40 ° C. Stir for about 15 hours to complete the reaction. Thereafter, the mixture was filtered to give a brown solution, and the solvent was removed under reduced pressure, and the remaining dark brown liquid was distilled under reduced pressure to obtain 7.7 g (yield: 39.5%) of a viscous brown liquid compound (3-Hexyne) Nb (NEt ₂ ) ₃ . .

Anal. Calcd for C ₁₈ H ₄₀ N ₃ Nb: C, 55.23; H, 10. 30; N, 10.73. Find: C, 53.93; H, 9.88; N, 11.64.

b.p: 101 ° C. at 0.55 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.03 (Nb- [N (CH ₂ C H ₃ ) ₂ ] ₃ , t, 18H)

δ 1.36 (C H ₃ CH ₂ CCCH ₂ C H ₃ ), t, 6H)

δ 3.17 (CH ₃ C H ₂ CCC H ₂ CH ₃ , q, 4H)

δ 3.47 (Nb— [N (C H ₂ CH ₃ ) ₂ ] ₃ , q, 12H)

¹³ C-NMR (C ₆ D ₆ ): δ 14.74 ( C H ₃ CH ₂ CCCH ₂ C H ₃ )

δ 15.90 (Nb- [N (CH ₂ C H ₃ ) ₂ ] ₃ )

δ 226.91 (CH ₃ C H ₂ CC C H ₂ CH ₃ )

δ 45.24 (Nb- [N ( C H ₂ CH ₃ ) ₂ ] ₃ )

δ 199.81 (CH ₃ CH ₂ CC CH ₂ CH ₃ )

Experimental Example 1

Example 1 ((3-Hexyne) Ta (NMe ₂ ) ₃ ), Example 3 ((3-Hexyne) Ta (NMeEt) ₃ ), and Example 5 ((3-Hexyne) Ta (NEt ₂ ) TG analysis was performed for basic thermal characteristics analysis of the tantalum organometallic precursor compounds prepared in ₃ ). At this time, tertiary butylimidotrisethylmethylamino tantalum compound ( tert- BuNTa (NMeEt) ₃ , hereinafter referred to as 'TBITEMATa') was used, and each precursor compound sample weighed about 5 mg and placed in an alumina sample container. After the measurement to 300 ℃ at a temperature increase rate of 10 ℃ / min is shown in Figure 1 the results.

As can be seen in Figure 1 it can be seen that the novel tantalum organometallic precursor compounds of the present invention are more volatile than TBITEMATa used as a comparative example, the residual amount (residue) of the organic compounds of Examples 1, 3, 5 compared to TBITEMATa As the metal precursor compound appeared about 5% less, the organometallic precursor compounds of Examples 1, 3, and 5, which are novel compounds according to the present invention, can be judged to have much less decomposition in the vaporization process than the comparative example of TBITEMATa. . That is, it can be confirmed that the thermal stability is more excellent. Above all, it was confirmed that the volatility and thermal stability of the organometallic precursor compound of Example 3 was the most excellent.

Experimental Example 2

Example 2 [(3-Hexyne) Nb (NMe ₂ ) ₃ ] described above, Example 4 [(3-Hexyne) Nb (NMeEt) ₃ ] and Example 6 [(3-Hexyne) Nb (NEt ₂ ) ₃ TG analysis was performed to analyze basic thermal characteristics of the niobium organic precursor compounds prepared in the US. At this time, tertiarybutylimidotrisethylmethylaminoniobium compound ( tert- BuNNb (NMeEt) ₃ , hereinafter referred to as 'TBITEMANb') was used as a comparative example. After the measurement to 300 ℃ at a temperature increase rate of 10 ℃ / min is shown in Figure 2 the results.

As can be seen in Figure 2 it was confirmed that the novel niobium organometallic precursor compounds of the present invention have a higher volatility than TBITEMANb used as a comparative example.

Experimental Example 3

Of (3-Hexyne) Ta (NMeEt) ₃ represented by Formula 8 prepared by Example 3 In order to evaluate thermal stability over time, ISO-Thermal TG analysis was performed at 70 ° C., 90 ° C., 120 ° C., and 150 ° C., and the results are shown in FIG. 2.

As can be seen in Figure 3 Example 3 did not show the deformation and thermal decomposition of the compound at a temperature of less than 120 ℃, it was confirmed that it has sufficient volatility.

Therefore, it is expected that the organometallic precursor compound according to the present invention may be used as a precursor useful in organometallic chemical vapor deposition and atomic layer deposition as precursor compounds which are excellent in thermal stability and liquid at room temperature and have high volatility.

Experimental Example 4

Film formation evaluation by CVD process was performed using the tantalum (III) organometallic precursor compound prepared in Examples 1, 3 and 5. At this time, the substrate used for deposition was a substrate coated with a SiO ₂ film 100nm on a Si substrate. The vessel used for deposition was closed with one end and a pyrex glass tube with an inner diameter of 3.5 cm and a length of 40 cm connected to a vacuum ( ^10-2 torr) pump. At this time, the Pyrex glass tube was maintained in a low vacuum (120 ~ 300 mtorr) state using a vacuum pump. In order to prevent condensation of the precursor onto the glass tube wall during deposition, the heating band was maintained at the same temperature as the precursor volatilization temperature. Deposition conditions and the results are shown in detail in Table 1 below.

Precursor Precursor temperature SiO ₂ substrate temperature (℃) Deposition Thickness (nm) Deposition rate (nm / min) Deposition time (min) (3-Hexyne) Ta (NMe ₂ ) ₃  55 ℃ 250 26.17 0.436     60 300 290.68 4.845 350 680 11.333 (3-Hexyne) Ta (NMeEt) ₃  70 ℃ 250 - - 300 237.77 3.963 350 369.81 6.164 (3-Hexyne) Ta (NEt ₂ ) ₃  80 ℃ 250 - - 300 408.42 6.807 350 930 15.5

As shown in Table 1, the organometallic precursor compounds prepared by Examples 1, 3, and 5 of the present invention were volatilized at relatively low temperatures of 55 ° C., 70 ° C., and 80 ° C., so that the wafer temperatures were 250 ° C. and 300, respectively. It was confirmed that the deposition at ℃, 300 ℃, the higher the temperature of the silicon oxide (SiO ₂ ) substrate was found that the thicker Ta film is deposited.

Experimental Example 5

The surface and cross section of the Ta thin film deposited on the silicon oxide (SiO ₂ ) substrate at 300 ° C. using (3-Hexyne) Ta (NMeEt) ₃ of Example 3 among the Ta thin films deposited according to the deposition conditions in Experimental Example 3. After the photographs were measured using an electron scanning microscope (SEM), the results are shown in FIG. 4, and carbon (C) and nitrogen (N) of the Ta thin film deposited using Auger electron Spectroscopy. , Oxygen (O) and tantanum (Ta) are shown in FIG. 5.

As shown in FIG. 4, it can be seen that the Ta thin film deposited using the precursor compound of Example 3 has a uniform surface and cross section, and through this, the organic metal precursor chemical according to the present invention has excellent step coverage. It can be seen that can be obtained.

In addition, it can be seen from FIG. 5 that the tantalum nitride (TaN) thin film to be deposited above is deposited on silicon oxide (SiO ₂ ).

FIG. 1 shows Example 1 [(3-Hexyne) Ta (NMe ₂ ) ₃ ], Example 3 [(3-Hexyne) Ta (NMeEt) ₃ ], and Example 5 [(3-Hexyne) Ta ( NEt ₂ ) ₃ ] TG graph for comparing the tantalum organic precursor compounds prepared in TBNEMATa ( tert -BuNTa (NMeEt) ₃ ).

FIG. 2 shows Example 2 [(3-Hexyne) Nb (NMe ₂ ) ₃ ], Example 4 [(3-Hexyne) Nb (NMeEt) ₃ ], and Example 6 [(3-Hexyne) Nb ( NEt ₂ ) ₃ ] TG graph for the comparison of niobium organic precursor compounds prepared in the TBITEMANb ( tert -BuNNb (NMeEt) ₃ ).

3 is a graph showing an ISO-Thermal TG analysis graph of [(3-Hexyne) Ta (NMeEt) ₃ ] prepared in Example 3. FIG.

4 is an electron scanning microscope (SEM) analysis result of a Ta thin film deposited at 300 ^° C. of an organic tantalum precursor prepared in Example 3 [(3-Hexyne) Ta (NMeEt) ₃ ].

FIG. 5 shows Auger analysis results of Ta films deposited with [(3-Hexyne) Ta (NMeEt) ₃ ] prepared at 300 ^° C. according to Example 3 of the present invention.

Claims (22)

An organometallic precursor compound used for depositing a metal oxide film, a metal nitride film, and a pure metal thin film is an organometallic precursor compound defined by Formula 1 below. <Formula 1>

In Formula 1, M is one selected from Ta or Nb, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkyl group, a perfluoroalkyl group, an alkylaminoalkyl group, an alkoxyalkyl group, or a silylalkyl group. , Alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group, alkylsilyl group having 1 to 4 carbon atoms, alkoxysilyl group, alkoxyalkylsilyl group or aminoalkylsilyl group, each of R ₃ and R ₄ are independently of each other It is selected from an alkyl group or an alkylsilyl group of 1 to 4 carbon atoms. In Chemical Formula 1, In the organometallic precursor compound represented by Formula 1, R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t -Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , For depositing metal oxide films, metal nitride films and pure metal thin films, which is an organometallic precursor compound selected from CH ₃ CH ₂ CH ₂ , i -Pr, t -Bu, sec -Bu or CH ₃ CH ₂ CH ₂ CH ₂ Organometallic precursor compounds. The method according to claim 2, In the organometallic precursor compound represented by Chemical Formula 1, both R ₃ and R ₄ are CH ₃ , which is an organometallic precursor compound represented by Chemical Formula 2 below, and the organic metal precursor for depositing a metal oxide film, a metal nitride film, and a pure metal thin film. compound. <Formula 2>

In Formula 2, M is one selected from Ta or Nb, and R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t -Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i- Pr, t- Bu, sec- Bu or CH ₃ CH ₂ CH ₂ CH ₂ . delete The method according to claim 3, In the organometallic precursor compound represented by Chemical Formula 2, R ₁ and R ₂ are both C ₂ H ₅ and M is Ta, which is an organic metal precursor compound represented by Chemical Formula 4, wherein the metal oxide film, metal nitride film, and pure water Organic metal precursor compound for metal thin film deposition. <Formula 4>

The method according to claim 3, In the organometallic precursor compound represented by Formula 2, R ₁ and R ₂ are both C ₂ H ₅ , M is Nb, and the metal oxide film, the metal nitride film, and the pure water, characterized in that the organic metal precursor compound represented by the following Formula 5 Organic metal precursor compound for metal thin film deposition. <Formula 5>

The method according to claim 2, R ₃ and R ₄ are different CH ₃ and C ₂ H ₅ in the formula 6, the organometallic precursor compound is a metal oxide film, metal nitride film, characterized in that, which is represented by and the pure metal in the organometallic precursor compound represented by the formula (1) Organic metal precursor compound for thin film deposition. <Formula 6>

In Formula 6, M is one selected from Ta or Nb, and R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t- Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i- Pr, t- Bu, sec- Bu or CH ₃ CH ₂ CH ₂ CH ₂ . delete The method according to claim 7, In the organometallic precursor compound represented by Chemical Formula 6, R ₁ and R ₂ are both C ₂ H ₅ and M is Ta, which is an organometallic precursor compound represented by Chemical Formula 8, wherein the metal oxide film, metal nitride film, and pure water Organic metal precursor compound for metal thin film deposition. <Formula 8>

The method according to claim 7, In the organometallic precursor compound represented by Chemical Formula 6, R ₁ and R ₂ are both C ₂ H ₅ , and M is Nb. The metal oxide film, metal nitride film, and pure water may be an organic metal precursor compound represented by Chemical Formula 9 below. Organic metal precursor compound for metal thin film deposition. <Formula 9>

The method according to claim 2, In the organometallic precursor compound represented by Chemical Formula 1, both R ₃ and R ₄ are C ₂ H ₅ , and the organic metal precursor compound represented by the following Chemical Formula 10 is organic for metal oxide film, metal nitride film and pure metal thin film deposition. Metal precursor compounds. <Formula 10>

In Formula 10, M is one selected from Ta or Nb, and R ₁ and R ₂ are each independently of each other (CH ₃ ) ₃ Si, t- Bu ₃ Si, (CH ₃ O) ₃ Si, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , i- Pr, t- Bu, sec- Bu or CH ₃ CH ₂ CH ₂ CH ₂ . delete The method according to claim 11, In the organometallic precursor compound represented by Chemical Formula 10, R ₁ and R ₂ are both C ₂ H ₅ and M is Ta, which is an organic metal precursor compound represented by Chemical Formula 12, wherein the metal oxide film, metal nitride film, and pure water Organic metal precursor compound for metal thin film deposition. <Formula 12>

The method according to claim 11, In the organometallic precursor compound represented by Chemical Formula 10, R ₁ and R ₂ are both C ₂ H ₅ , M is Nb, and the metal oxide film, the metal nitride film, and the pure water, characterized in that the organic metal precursor compound represented by the following Chemical Formula 13 Organic metal precursor compound for metal thin film deposition. <Formula 13>

In order to prepare the organometallic precursor compound of any one of claims 1 to 3, 5 to 7, 9 to 11, 13 or 14, benzene, hexane as shown in Scheme 1 below 3LiNR ₃ R ₄ was added to a (R ₁ CCR ₂ ) M (NR ₃ R ₄ ) ₃ compound solution at a low temperature under one organic solvent selected from (hexane) and toluene, followed by stirring. A method for producing an organometallic precursor compound for metal oxide film, metal nitride film and pure metal thin film deposition, which is prepared by filtration and purification. Scheme 1

M and R ₁ , R ₂ , R ₃ and R ₄ in Scheme 1 are the same as defined in Chemical Formula 1. Method of depositing a thin film to form a metal oxide film, metal nitride film or metal thin film on a substrate by using an organic metal precursor compound (Metal Organic Chemical Vapor Deposition, MOCVD) or atomic layer deposition (ALD) To Thin film deposition method using any one of the organometallic precursor compound selected from claim 1 to 3, 5 to 7, 9 to 11, 13 or 14 as the organometallic precursor compound. . The method according to claim 16, Thin film deposition method characterized in that the deposition temperature is 200 ~ 1000 ℃ when depositing on the substrate using the organometallic precursor compound. The method according to claim 16, The organometallic precursor compound using a thermal energy or plasma when the deposition on the substrate, or a thin film deposition method characterized in that applying a bias on the substrate. The method according to claim 16, The transfer method for transferring the organometallic precursor compound onto a substrate may include a bubbling method, a vapor phase mass flow controller (MFC), a direct liquid injection (DLI), or a precursor compound in an organic solvent. Thin film deposition method characterized in that used in the liquid transport method to melt and transfer to. The method according to claim 16, Using one or more mixtures selected from argon (Ar), nitrogen (N ₂ ), helium (He), or hydrogen (H ₂ ) as a transporting or diluting gas to transfer the organometallic precursor compound onto the substrate. Thin film deposition method characterized in that. The method according to claim 16, In order to deposit a metal oxide thin film (Ta ₂ O ₅ , Nb ₂ O ₅ ) or a composite metal oxide thin film (TaSiO _x , NbSiO _x , TaAlO _x , NbAlO _x ) on the substrate, an underwater gas (H ₂ O) as a reaction gas. Thin film deposition method characterized by using one or more mixtures selected from oxygen (O ₂ ), and ozone (O ₃ ). The method according to claim 16, Ammonia (NH ₃ ) or hydrazine as a reaction gas for depositing metal nitride thin films (TaN, NbN, Ta ₃ N _5, Nb ₃ N ₅ ) or composite metal nitride thin films (TaCN, NbCN, TaSiN, NbSiN) on the substrate Thin film deposition method characterized by using (N ₂ H ₄ ).

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