WO2022169232A1

WO2022169232A1 - Group 4 transition metal compound, method for manufacturing same, and method for forming thin film using same

Info

Publication number: WO2022169232A1
Application number: PCT/KR2022/001606
Authority: WO
Inventors: 정택모; 박보근; 이가연; 김창균; 김건환; 엄태용
Original assignee: 한국화학연구원
Priority date: 2021-02-05
Filing date: 2022-01-28
Publication date: 2022-08-11
Also published as: KR102567107B1; KR20220113029A

Abstract

The present invention relates to a Group 4 transition metal compound, a method for manufacturing same, and a method for forming a thin film using same. The Group 4 transition metal compound according to the present invention is thermally stable, and has excellent volatility and high storage stability. Accordingly, by using same as a precursor, a Group 4 transition metal-containing thin film of high density and high purity and a method for manufacturing same can be provided.

Description

Group 4 transition metal compound, manufacturing method thereof, and method of forming thin film using the same

The present invention relates to a Group 4 transition metal compound, a method for preparing the same, and a method for forming a thin film using the same.

In the semiconductor process, silicon oxide (SiO ₂ ) has been mainly used as a gate dielectric because the manufacturing process is relatively simple. Although the manufacturing process of the silicon oxide is simple, since it has a relatively low dielectric constant (k), when the thickness is thin, there is a problem in that a gate-to-channel leakage current occurs.

In order to solve this problem, research on materials and process technologies for high dielectric thin films having excellent insulating properties and high dielectric constants is being actively conducted.

On the other hand, as the semiconductor structure becomes more direct and miniaturized, it is applied to various processes (eg, atomic layer deposition (ALD), chemical vapor deposition (CVD)) with excellent step coverage even in fine patterns. As a high-k thin film material capable of this, there is an increasing demand for a precursor compound having high thermal stability.

As an example of such a high-k thin film material, a Group 4 transition metal compound has been proposed. Specifically, the Group 4 transition metal compound may include a titanium precursor, a zirconium precursor, a hafnium precursor, and the like, and the preparation of the Group 4 transition metal oxide thin film through an atomic layer deposition method or a chemical vapor deposition method using the same depends on the ligand structure of these precursors. developed in various ways.

As an example, group 4 transition metal inorganic salts such as ZrCl ₄ , ZrI ₄ , and ZrF ₄ are known. In the zirconium oxide thin film using the atomic layer deposition method or the chemical vapor deposition method using this, inorganic salts (Cl ^- , F ^- , I ^- ) remain inside the thin film, so that the electrical properties of the thin film are deteriorated and an aggromeration phase of the thin film occurs. I had an easy problem. In addition, the roughness of the zirconium oxide film cannot be arbitrarily adjusted, and it is difficult to adjust the thickness of the zirconium oxide film.

For example, in Non-Patent Document 1, a zirconium alkoxide precursor and a zirconium oxide thin film using the same are known. However, the zirconium alkoxide precursor has a very short shelf life because it has a very high reactivity, so it is very difficult to handle in a thin film manufacturing process, and it causes a catalytic hydrolytic decomposition reaction even with a trace amount of moisture.

For example, in Non-Patent Document 2, a zirconium compound to which an amido ligand is coordinated and a zirconium oxide thin film using the same as a precursor are known. However, all of the precursors represented by the zirconium compound (eg, Zr(NMeEt) ₄ or Zr(NEt ₂ ) ₄ ) exist in a liquid state with low viscosity at room temperature, have a very high vapor pressure, and an amido ligand by ozone and water vapor It is easy to remove the zirconium oxide thin film through the atomic layer deposition method. However, the zirconium compound is very reactive, so long-term storage is not easy, and in particular, it has low thermal stability, so it is decomposed during vaporization to cause deterioration of the quality of the thin film.

In order to solve the problems of the prior art, Patent Document 1 discloses a zirconium precursor having a cyclopentadiene group as a ligand, but has not yet obtained satisfactory results.

Therefore, there is still a need for research on a precursor compound having superior properties compared to the precursor compound used as a conventional high-k thin film material.

An object of the present invention is to provide a novel Group 4 transition metal compound useful as a precursor for thin film deposition due to its thermal stability, high volatility and excellent cohesion, and a method for preparing the same.

In addition, it is an object of the present invention to provide a composition for depositing a thin film containing a Group 4 transition metal comprising the Group 4 transition metal compound of the present invention.

Another object of the present invention is to provide a method for manufacturing a thin film containing a Group 4 transition metal of high density and high purity prepared by using the Group 4 transition metal compound of the present invention.

In order to achieve the above object, in the present invention, there is provided a Group 4 transition metal compound represented by the following formula (1).

[Formula 1]

[In Formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁵ are each independently C ₁ -C ₁₀ alkyl;

n is an integer independently selected from 1-4.]

In Formula 1 according to an embodiment of the present invention, M is titanium, zirconium, or hafnium; wherein R ¹ to R ⁵ are each independently C ₁ -C ₇ alkyl; The n may be an integer selected from 1 to 3.

In Formula 1 according to an embodiment of the present invention, R ¹ and R ² are the same as each other C ₁ -C ₄ alkyl; The R ³ to R ⁵ may be each independently C ₁ -C ₄ alkyl.

In Formula 1 according to an embodiment of the present invention, R ¹ and R ² are methyl or ethyl in the same manner as each other; At least one of R ³ to R ⁵ may be ethyl, propyl, or butyl, and the rest may be methyl, ethyl, propyl, or butyl.

In the present invention, there is provided a method for preparing a Group 4 transition metal compound represented by the following Chemical Formula 1 by reacting the following Chemical Formulas A and B.

[Formula A]

M(NR ¹ R ² ) ₄

[Formula B]

[Formula 1]

[In Formula A, Formula B and Formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁵ are each independently C ₁ -C ₁₀ alkyl;

n is an integer independently selected from 1-4.]

In addition, the present invention provides a composition for depositing a thin film containing a Group 4 transition metal comprising the Group 4 transition metal compound represented by Formula 1 above.

In the composition for depositing a Group 4 transition metal-containing thin film according to an embodiment of the present invention, the Group 4 transition metal of the Group 4 transition metal compound may be titanium, zirconium, or hafnium.

In addition, the present invention provides a method for producing a Group 4 transition metal-containing thin film using the Group 4 transition metal compound. In this case, the manufacturing method may be performed by a chemical vapor deposition method or an atomic layer deposition method.

The Group 4 transition metal compound according to the present invention has high thermal stability and excellent volatility, so it is very useful as a precursor of a Group 4 transition metal-containing thin film and can be applied to various thin film deposition methods. Furthermore, it is possible to prepare a thin film containing a group 4 transition metal of good quality due to its excellent adsorption to the substrate.

In addition, the Group 4 transition metal compound according to the present invention is not decomposed even at a high process temperature, and has excellent storage stability.

In addition, when the Group 4 transition metal compound according to the present invention is employed, it is possible to manufacture a high dielectric thin film having high density and purity and excellent physical and electrical properties.

With these characteristics, the Group 4 transition metal compound according to the present invention can be applied to various thin film deposition methods, and the deposition rate is fast and easy with high volatility. It can be formed with a uniform thickness on the top. Accordingly, according to the present invention, it is possible to provide a method for manufacturing a thin film containing a Group 4 transition metal that can satisfy all of the stability, efficiency and reliability of the semiconductor manufacturing process.

1 shows a TGA graph of Example 1 according to the present invention,

Figure 2 shows the TGA graph of Example 2 according to the present invention,

3 shows a TGA graph of Example 3 according to the present invention.

Advantages and features of the present invention, and methods for achieving them, will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be embodied in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Hereinafter, the Group 4 transition metal compound according to the present invention, a method for preparing the same, and a method for forming a thin film using the same will be described in detail.

As used herein, the term “alkyl” is a monovalent substituent and includes both linear and branched forms.

In addition, the term "comprising" as used herein is an open-ended description having an equivalent meaning to expressions such as "comprises", "contains", "has" or "characterized by", and is not listed further. It does not exclude elements, materials or processes that are not

In addition, the term "substantially the same" as used herein refers to a range that does not cause changes in the state and structure of the compound before and after the specified treatment, that is, the compound before and after the specified treatment can fall within the scope of identity. means there is

Also, the singular form used herein may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio.

In addition, as used herein, the term "Group 4 transition metal compound" may be represented by Formula 1, and has an equivalent meaning to expressions such as "precursor" or "precursor compound".

In addition, as used herein, the term "thermal stability" may mean that physical properties do not change even during a continuous heating process or a high temperature process, and specifically, it means that the structure does not change even when exposed for a long time under the harsh conditions described above. do.

When a thin film is formed by performing an atomic layer deposition process or a chemical vapor deposition process, a precursor is introduced into the chamber by using a precursor introduction device such as a bubbling system or an injection system. For example, in the bubbling system, the precursor is vaporized by bubbling a precursor in a liquid state with a carrier gas, or a precursor in a solid state is vaporized to introduce the precursor in a vapor state into the chamber together with the carrier gas. That is, the precursors, which are liquid or solid at room temperature, are heated and converted to a vapor state before being provided into the chamber. As such, energy is applied to the precursor while the precursor is introduced into the chamber, and the chamber in which the atomic layer deposition process or the chemical vapor deposition process is performed also maintains a high temperature state. Therefore, the precursors used to form the thin film are required to have excellent thermal stability. If the precursors are thermally unstable and easily decomposed by heat, it is difficult to control process conditions, it is difficult to form a thin film having a uniform thickness, and it is difficult to control the electrical characteristics of the semiconductor device.

Accordingly, the present inventors have devised a novel Group 4 transition metal compound that can solve the problems by paying attention to the above-described problems. The Group 4 transition metal compound of the present invention is a heteroleptic compound to which two kinds of ligands having different reactivity are bound.

The Group 4 transition metal compound of the present invention having such structural characteristics has high thermal stability that does not change physical properties even during a continuous heating process or a high temperature process, and can provide a high-quality and reliable thin film containing a Group 4 transition metal with excellent volatility. There is, the present invention is proposed.

Hereinafter, the Group 4 transition metal compound according to the present invention will be described.

The Group 4 transition metal compound according to an embodiment of the present invention is a novel compound, and exhibits improved thermal stability and excellent volatility. In addition, it has high reactivity and when a thin film is manufactured using it, the growth rate of the thin film is excellent and a good quality thin film can be manufactured even at a relatively low temperature, so it is useful as a precursor for manufacturing a thin film containing a group 4 transition metal. can do.

Specifically, the Group 4 transition metal compound according to the present invention is represented by the following formula (1).

[Formula 1]

[In Formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁵ are each independently C ₁ -C ₁₀ alkyl;

n is an integer independently selected from 1-4.]

As described above, the Group 4 transition metal compound according to an embodiment of the present invention has a structure including an alkoxyimideamide ligand. Accordingly, the Group 4 transition metal compound effectively provides electrons to the central metal and exhibits improved stability due to intermolecular bonding. In addition, the thermal stability is very excellent, so that it is not decomposed even in a continuous heating process, so that a thin film of good quality can be manufactured.

In addition, the Group 4 transition metal compound according to an embodiment of the present invention forms a highly crystalline structure by implementing excellent cohesion as well as implementing excellent volatility, so that the growth rate of the thin film is excellent and good quality even at a relatively low temperature. A thin film may be provided. In addition, since the Group 4 transition metal compound of the present invention has excellent thermal stability, volatility and reactivity, it can be deposited by various deposition methods, and a high-density, high-purity Group 4 transition metal-containing thin film can be manufactured at a high deposition rate.

In the Group 4 transition metal compound according to an embodiment of the present invention, in order to implement improved volatility, specifically, in Formula 1, M is titanium, zirconium, or hafnium; wherein R ¹ to R ⁵ are each independently C ₁ -C ₇ alkyl; The n may be an integer selected from 1 to 3.

In the aspect that the Group 4 transition metal compound according to an embodiment of the present invention is not easily decomposed by heat before forming a chemical bond on the substrate surface or after vaporization when forming a thin film, specifically, in Formula 1, M is titanium; zirconium or hafnium; wherein R ¹ and R ² are the same as each other C ₁ -C ₄ alkyl; The R ³ to R ⁵ may be each independently C ₁ -C ₄ alkyl.

More specifically, in the Group 4 transition metal compound, in Formula 1, M is titanium, zirconium, or hafnium; wherein R ¹ and R ² are the same as methyl or ethyl; At least one of R ³ to R ⁵ may be ethyl, propyl, or butyl, and the rest may be methyl, ethyl, propyl, or butyl. In addition, in Formula 1, n may be an integer of 1 or 2.

For example, in the Group 4 transition metal compound, in Formula 1, M is titanium; wherein R ¹ and R ² are the same as methyl or ethyl; at least one of R ³ to R ⁵ is ethyl, propyl or butyl, and the other is methyl or ethyl; n is an integer of 1, or in Formula 1, M is zirconium or hafnium; wherein R ¹ and R ² are the same as methyl or ethyl; at least one of R ³ to R ⁵ is ethyl, propyl or butyl, and the other is methyl or ethyl; The n may be an integer of 2.

For example, at least one of R ³ to R ⁵ may be ethyl, n -propyl, i -propyl, n -butyl, s -butyl or t -butyl, and the rest may be methyl or ethyl.

In the Group 4 transition metal compound according to an embodiment of the present invention, when the substituent substituted for the ligand satisfies 1 to 4 carbon atoms, the stability to heat is extremely improved so that it is not decomposed at a high temperature for a long time. Accordingly, it is possible to prevent the deposition of solid impurities generated during the decomposition of the precursor during the formation of the thin film or the filling of holes or the like on the substrate. In addition, the vaporized precursor is uniformly supplied on the substrate, so that excellent step coverage can be imparted.

In addition, the Group 4 transition metal compound according to an embodiment of the present invention may have a molecular weight of 1,500 or less. The molecular weight of the Group 4 transition metal compound may be, specifically, 400 to 1,000, and more specifically, 500 to 800.

Most specifically, the Group 4 transition metal compound according to an embodiment of the present invention may be selected from the following structure, but is not limited thereto.

[In the above structure,

M is titanium, zirconium or hafnium.]

The Group 4 transition metal compound represented by the following Chemical Formula 1 according to an embodiment of the present invention may be prepared through various synthesis methods, and specifically, it may be prepared by reacting the following Chemical Formulas A and B.

[Formula A]

M(NR ¹ R ² ) ₄

[Formula B]

[Formula 1]

[In Formula A, Formula B and Formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁵ are each independently C ₁ -C ₁₀ alkyl;

n is an integer independently selected from 1-4.]

The reaction according to an embodiment of the present invention may be carried out under an organic solvent, and the usable organic solvent is not limited, but an organic solvent having high solubility for the reactants may be used, and specifically, hexane (Hexane) ), one or more mixed organic solvents selected from diethylether, toluene, tetrahydrofuran (THF), etc. may be used.

In addition, of course, the reactants may be appropriately changed and used in a stoichiometric equivalent ratio according to a desired ligand ratio.

For example, Formula B may be used in an amount of 1 to 5 moles, or 1 to 4 moles, or 1 to 3 moles, based on 1 mole of Formula A.

In addition, the reaction may be performed under an inert gas atmosphere such as nitrogen or argon.

For example, in the reaction, in hexane, diethyl ether, toluene, tetrahydrofuran or a mixed organic solvent thereof, the compound of Formula A and the compound of Formula B are reacted at 10 to 35° C. for 5 to 30 hours, The Group 4 transition metal compound of Formula 1 can be obtained in high yield (70% or more). At this time, after the reaction, if necessary, the purification may be performed by recrystallization, column chromatography, sublimation, or the like.

In addition, the present invention provides a composition for depositing a Group 4 transition metal-containing thin film comprising the Group 4 transition metal compound represented by Formula 1 of the present invention and a Group 4 transition metal-containing thin film prepared using the Group 4 transition metal compound. A manufacturing method will be described.

The composition for depositing a Group 4 transition metal-containing thin film according to an embodiment of the present invention includes the Group 4 transition metal compound of Formula 1, and the amount of the Group 4 transition metal compound used in the composition of the present invention depends on the film formation conditions of the thin film or Of course, it may be included within the range recognized by those skilled in the art in consideration of the thickness and characteristics of the thin film.

A composition for depositing a Group 4 transition metal-containing thin film according to an embodiment of the present invention includes a linear, branched or cyclic alkane compound having 5 to 10 carbon atoms; aromatic hydrocarbon compounds having 6 to 12 carbon atoms; an alkylamine compound having 2 to 10 carbon atoms; and heterocycloalkyl compounds containing oxygen, nitrogen, and the like; It may further include one solvent or a mixed solvent of two or more selected from the like.

For example, the alkane compound may include hexane, heptane, octane, cyclohexane, and neopentane, the aromatic hydrocarbon compound may include benzene, toluene, and xylene, and the alkylamine compound may include dimethylamine, di Ethylamine, ethylmethylamine, triethylamine, tributylamine, tetramethylethylenediamine, etc. are mentioned.

For example, the heterocycloalkyl compound may include tetrahydrofuran, pyridine, and the like.

In addition, the composition for depositing a Group 4 transition metal-containing thin film may contain 0.1 to 10 moles, or 0.2 to 5 moles, or 0.5 to 3 moles of the solvent based on 1 mole of the Group 4 transition metal compound.

For example, the group 4 transition metal-containing composition for thin film deposition may be used for thin film deposition through a conventional solution process.

For example, when the group 4 transition metal-containing composition for thin film deposition is a mixture of the group 4 transition metal compound and the solvent in a 1:1 molar ratio, the viscosity (Viscosity, Cp, measured at 28.3 ° C.) is 1 to 50 Cp. may be, specifically 1 to 30Cp, more specifically 1 to 20Cp.

When the composition for depositing a Group 4 transition metal-containing thin film according to an embodiment of the present invention or the Group 4 transition metal compound of the present invention is employed, it is possible to provide a thin film containing a Group 4 transition metal of high purity with high volatility and reactivity. In addition, the group 4 transition metal-containing thin film prepared therefrom is useful as a high-density, high-k thin film material.

In addition, the present invention provides a method for producing a Group 4 transition metal-containing thin film comprising; preparing a Group 4 transition metal-containing thin film using the Group 4 transition metal compound of the present invention described above.

The method for manufacturing a Group 4 transition metal-containing thin film according to an embodiment of the present invention may provide a Group 4 transition metal-containing thin film on a substrate through a known deposition method. Specifically, the deposition method may be chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), low pressure vapor deposition, plasma enhanced atomic layer deposition, etc. .

The Group 4 transition metal compound according to an embodiment of the present invention has excellent volatility and is not easily decomposed even at a high temperature, and can maintain a stable vapor state even after vaporization, so it can be effective in the deposition method described above.

For example, in the case of a method for producing a Group 4 transition metal-containing thin film through chemical vapor deposition using the Group 4 transition metal compound, the alkoxyimideamide ligand bound to the Group 4 transition metal compound is introduced onto the substrate and then the It may be chemically bonded to the substrate to form a thin film. In addition, after the ligand is introduced on the substrate, one or more reactive gases selected from oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), carbon dioxide (CO ₂ ), etc. may include more.

For example, in the case of a method for producing a Group 4 transition metal-containing thin film through atomic layer deposition using the Group 4 transition metal compound, the alkoxyimideamide ligand bound to the Group 4 transition metal compound is chemically adsorbed on the substrate. After that, a thin film may be formed on the substrate. In this case, of course, it may further include a step of substituting with the above-described reaction gas.

The Group 4 transition metal-containing thin film prepared through the deposition method may include a titanium thin film, a zirconium thin film, and a hafnium thin film; titanium oxide thin film, zirconium oxide thin film, hafnium oxide thin film; titanium oxynitride thin film, zirconium oxynitride thin film, hafnium oxynitride thin film; or a group 4 transition metal-containing composite oxynitride thin film; etc.

The substrate is not limited as long as it is a conventional substrate, and non-limiting examples thereof include a substrate including at least one semiconductor material of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP, a silicon on insulator (SOI). ) a rigid substrate, such as a substrate, a quartz substrate, or a glass substrate for a display, or polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethyl methacrylate (PMMA, Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyether sulfone (PES), may be a flexible plastic substrate such as polyester (Polyester).

Specifically, the method for manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention includes the first step of maintaining the temperature of the substrate mounted in the chamber at 80 to 400 ℃; and a second step of supplying energy to the substrate.

For example, the step of supplying the energy is to activate a reaction for deposition, and may be a step of supplying energy by plasma, light, heat, voltage, or the like.

For example, the temperature of the substrate may be specifically 100 to 350 °C, more specifically 200 to 325 °C range.

In the first step, a deposition source in which the Group 4 transition metal compound is vaporized may be provided. As described above, in the first step, an additional reaction gas may be further provided. In this case, the reaction gas may be provided simultaneously with the deposition source or may be provided subsequently. Also, the deposition source may be moved through a transport gas that does not react therewith.

For example, the reaction gas may be one or a mixture of two or more selected from oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), carbon dioxide (CO ₂ ), and the like.

For example, the reaction gas may be provided at a flow rate of 1 to 1,000 sccm, specifically 100 to 500 sccm, more specifically 150 to 400 sccm. In addition, the transport gas may be provided at a flow rate of 1 to 200 sccm, but is not limited thereto.

In addition, each step may further include a purge step.

For example, the purge gas in the purge step is not limited as long as it does not react with the Group 4 transition metal compound of the present invention, and non-limiting examples thereof include helium, neon, argon, krypton, xenon, radon, etc. It may be one or two or more mixed gases.

For example, the purge gas may be provided at a flow rate of 1 sccm to 3,000 sccm, specifically 100 sccm to 1,500 sccm, more specifically 300 to 1,300 sccm.

For example, the pressure in the chamber may be 0.1 to 10 torr, specifically 0.1 to 5 torr, more specifically 0.5 to 3 torr.

In addition, an additional heat treatment step may be further performed on the Group 4 transition metal-containing thin film obtained through the method for manufacturing the Group 4 transition metal-containing thin film according to an embodiment of the present invention.

The group 4 transition metal-containing thin film prepared according to the method for manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention is a high-density high-k thin film material. That is, according to the method for manufacturing a Group 4 transition metal-containing thin film according to the present invention, a desired high-density high-k thin film material is easily supplied through an ALD process or a CVD process, so that wiring of semiconductor devices, gate insulating films of transistors, It can be used in various ways, such as forming a dielectric film of a capacitor or a coating film of an electronic component.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

Examples of the Group 4 transition metal compound according to the present invention were carried out in an inert argon or nitrogen atmosphere using a glove box or a Schlenk line, and the structural analysis of the obtained title compound was performed by ¹ H NMR and ¹³ C NMR It was measured through a spectrum (Bruker Advance 400 NMR). In addition, in order to measure the thermal stability, volatility, and decomposition temperature of the Group 4 transition metal compound, a thermogravimetric analysis (TGA) method was used. The TGA method was measured under nitrogen gas injection at a pressure of 1.5 bar/min while warming the obtained title compound to 800°C at a rate of 5°C/min. In addition, in order to confirm the thermal stability of the Group 4 transition metal compound, ¹ H NMR spectra measured using the same sample left at room temperature and 130° C. for 4 days were compared.

In addition, the thickness of the Group 4 transition metal thin film prepared using the Group 4 transition metal compound according to the present invention was measured using an ellipsometer.

(Example 1)

Preparation of compound 1

After dissolving tetrakis(dimethylamido)titanium (Tetrakis(dimethylamido)titanium, 1.00 g, 4.46 mmol) in hexane (50 ml), (Z)-N'-ethoxy-N-methylacetimidamide ( (Z)-N'-ethoxy-N-methylacetimidamide, NNOH, 0.52 g, 4.46 mmol) was added dropwise. After stirring at room temperature (25° C.) for 12 hours, the pressure was reduced to remove hexane. Then, it was purified by distillation (150° C./0.5 torr) to obtain 1.00 g of an orange liquid (76 %).

¹ H NMR (25° C., C ₆ D ₆ , 400 MHz): δ 1.28 (t, 3H, CH ₃ ), 1.78 (s, 3H, NCCH ₃ ), 2.94 (s, 3H, NCH ₃ ), 3.18 (s) , 18H, 6NCH ₃ ), 4.06-4.12 (q, 2H, CH ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 13.5, 15.0, 38.6, 45.8, 71.3, 162.4.

After standing at 130° C. for 4 days, the ¹ H NMR spectrum of Compound 1 also showed substantially the same state as the ¹ H NMR spectrum (25° C.) described above. From these results, it was confirmed that Compound 1 did not decompose even during a high process temperature and had excellent thermal stability.

According to FIG. 1 below, as the three amide ligands are decomposed from room temperature, a decrease of about 45% is shown, and a decrease in mass that appears to finally remain TiO ₂ (27%) is confirmed, but since the compound 1 is substantially distilled, the thermal stability of It should not be construed as deterioration.

(Example 2)

Preparation of compound 2

After dissolving tetrakis (dimethylamido) zirconium (Tetrakis (dimethylamido) zirconium, 0.50 g, 1.87 mmol) in hexane (50 ml) (Z) -N'-ethoxy-N-methylacetimidamide ( (Z)-N'-ethoxy-N-methylacetimidamide, NNOH, 0.43 g, 3.74 mmol) was added dropwise. After stirring at room temperature (25° C.) for 12 hours, the pressure was reduced to remove hexane. Then, it was purified by sublimation (65° C./0.5 torr) to obtain 0.65 g of a white solid (85 %).

¹ H NMR (25° C., C ₆ D ₆ , 400 MHz): δ 1.28 (t, 6H, CH ₃ ), 1.73 (s, 6H, NCCH ₃ ), 2.89 (s, 6H, NCH ₃ ), 3.10 (s) , 12H, 2NCH ₃ ), 4.09 (b, 4H, CH ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 13.5, 14.9, 36.0, 43.5, 71.4, 161.9.

In addition, in order to confirm the thermal stability of the obtained compound 2, ¹ H NMR spectra of samples left at 130° C. for 4 days were compared. As a result, after standing at 130° C. for 4 days, the ¹ H NMR spectrum of Compound 2 also showed substantially the same state as the ¹ H NMR spectrum (25° C.) described above.

(Example 3)

Compound 3 was obtained by using the starting materials shown in Table 1 below in a similar manner to Example 2 above.

In order to confirm the thermal stability of the obtained compound 3, ¹ H NMR spectra of samples left for 4 days at room temperature and 130° C. were compared. As a result, after standing at 130° C. for 4 days, the ¹ H NMR spectrum of Compound 3 also showed substantially the same state as the ¹ H NMR spectrum (25° C.) described above.

	구조rescue	반응물reactant
		¹H-NMR ¹ H-NMR
실시예3Example 3		Tetrakis(dimethylamido)hafnium / NNOH =(1/1, 몰비)Tetrakis(dimethylamido)hafnium / NNOH = (1/1, molar ratio)
		화합물3 ¹H NMR (25℃, C₆D₆, 400 MHz): δ 1.27 (t, 6H, CH₃), 1.72 (s, 6H, NCCH₃), 2.90 (s, 6H, NCH₃), 3.16 (s, 12H, 2NCH₃), 4.00-4.16 (b, 4H, CH₂). ¹³C NMR (C₆D₆, 100 MHz): δ 13.3, 14.8, 35.8, 43.3, 71.6, 162.8.compound 3 ¹ H NMR (25° C., C ₆ D ₆ , 400 MHz): δ 1.27 (t, 6H, CH ₃ ), 1.72 (s, 6H, NCCH ₃ ), 2.90 (s, 6H, NCH ₃ ), 3.16 (s) , 12H, 2NCH ₃ ), 4.00-4.16 (b, 4H, CH ₂ ). ¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 13.3, 14.8, 35.8, 43.3, 71.6, 162.8.

According to Figures 2 and 3 below, in Compound 2, one amide ligand is decomposed and decreased by about 11% from room temperature, and then one alkoxyimimidamide ligand and the remaining amide ligand are decomposed and the weight is reduced by about 50%. looks like Compound 3 also shows a decrease of about 9% by decomposition of one amide ligand from room temperature, followed by a reduction in weight by about 49% as one alkoxy imidamide ligand and amide ligand are decomposed. However, since Compound 2 and Compound 3 are substantially sublimated or distilled, it should not be interpreted as deterioration of thermal stability.

(Example 4)

Production of Ti Oxide Thin Film

A thin film was deposited through atomic layer deposition.

The silicon substrate was maintained at 300 °C, and the compound 1 obtained in Example 1 was filled in a stainless steel bubbler container and maintained at 110 °C. First, compound 1 vaporized in a stainless steel bubbler vessel was supplied to a silicon substrate using argon gas (50 sccm) as a transport gas, but the deposition rate of the thin film was measured as the supply time was increased from 1 second to 7 seconds. In addition, H ₂ O reaction gas was supplied by increasing the supply time from 1 second to 5 seconds to measure the thin film deposition rate according to the supply time.

In the case of Compound 1, it was confirmed that the thin film deposition rate was maintained constant even when the supply time of the precursor (Compound 1) was increased after 5 seconds. Accordingly, it can be seen that the precursor is included in the substrate after 5 seconds, and the H ₂ O reaction gas is saturated after 3 seconds with a constant thickness of the thin film after 3 seconds. From this, the supply time of the precursor was set to 5 seconds, and the supply time of H ₂ O was set to 3 seconds.

From the results, the supply time of the compound 1 was 5 seconds, the supply time of H ₂ O was 3 seconds, and then the reaction by-products and residual reaction gas were removed for about 10 seconds using argon gas (1000 sccm). A titanium oxide thin film (Ti oxide thin film) was formed by repeating 100 cycles of the above process as one cycle.

Similarly, an additional 300 cycles were repeated to form a titanium oxide thin film. As a result, it was confirmed that the thickness of the thin film increased linearly as the deposition cycle increased, and the deposition rate was about 1.0 Å/cycle.

In addition, XPS and XRF analysis of the titanium oxide thin film was performed. As a result, since there is no peak in C1s, it can be seen that the purity of the prepared titanium oxide thin film is excellent because there is almost no carbon as an impurity in the titanium oxide thin film.

In addition, as a result of checking a transmission electron microscope (TEM) image of the thin film (thickness: 40 Å) obtained by the above preparation method, it was confirmed that a high-density thin film having high step coverage and crystallinity was obtained.

The present invention is not limited by the above-described embodiments, and it is those of ordinary skill in the art to which the present invention pertains that various substitutions, modifications and changes are possible without departing from the technical spirit of the present invention. will be clear to

Claims

A group 4 transition metal compound represented by the following formula (1):

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

R 1 to R 5 are each independently C 1 -C 10 alkyl;

n is an integer independently selected from 1-4.
The method of claim 1,

In Formula 1,

M is titanium, zirconium or hafnium;

wherein R 1 to R 5 are each independently C 1 -C 7 alkyl;

Wherein n is an integer selected from 1 to 3, Group 4 transition metal compound.
The method of claim 1,

In Formula 1,

wherein R 1 and R 2 are the same as each other C 1 -C 4 alkyl;

The R 3 To R 5 Are each independently C 1 -C 4 Alkyl, Group 4 transition metal compound.
The method of claim 1,

In Formula 1,

wherein R 1 and R 2 are the same as methyl or ethyl;

At least one of R 3 to R 5 is ethyl, propyl or butyl, and the rest is methyl, ethyl, propyl or butyl, a Group 4 transition metal compound.
The method of claim 1,

A Group 4 transition metal compound, which is selected from the following structure:

In the above structure,

M is titanium, zirconium or hafnium.
A method for preparing a Group 4 transition metal compound represented by the following Chemical Formula 1 by reacting the following Chemical Formulas A and B:

[Formula A]

M(NR 1 R 2 ) 4

[Formula B]

[Formula 1]

In Formula A, Formula B and Formula 1,

M is a Group 4 transition metal;

R 1 to R 5 are each independently C 1 -C 10 alkyl;

n is an integer independently selected from 1-4.
A composition for depositing a group 4 transition metal-containing thin film comprising a group 4 transition metal compound represented by the following formula (1):

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

R 1 to R 5 are each independently C 1 -C 10 alkyl;

n is an integer independently selected from 1-4.
8. The method of claim 7,

The Group 4 transition metal of the Group 4 transition metal compound is,

Titanium, zirconium or hafnium, a composition for thin film deposition containing a Group 4 transition metal.
Using the Group 4 transition metal compound of any one of claims 1 to 5, preparing a Group 4 transition metal-containing thin film; A method of manufacturing a Group 4 transition metal-containing thin film comprising a.
10. The method of claim 9,

A method for producing a thin film containing a Group 4 transition metal, which is performed by a chemical vapor deposition method or an atomic layer deposition method.