KR102567107B1 - Group iv transition metal compounds, preparation method thereof and process for the formation of thin films using the same - Google Patents

Abstract

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. The Group 4 transition metal compound according to the present invention is thermally stable, has excellent volatility, and has high storage stability, It is possible to provide a high-density and high-purity Group 4 transition metal-containing thin film and a method for manufacturing the same.

Description

Group 4 transition metal compound, method for preparing the same, and method for forming a 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 semiconductor processing, silicon oxide (SiO ₂ ) has been mainly used as a gate dielectric because of its relatively simple manufacturing process. The manufacturing process of the silicon oxide is simple, but has a problem in that a gate-to-channel leakage current occurs when the thickness is thin because it has a relatively low dielectric constant (k).

In order to solve these problems, research on materials and process technologies for high dielectric thin films with excellent insulation and high dielectric constant is being actively conducted.

On the other hand, as the semiconductor structure becomes more direct and refined, it is applied to various processes (e.g., atomic layer deposition (ALD), chemical vapor deposition (CVD)) that have excellent step coverage even in fine patterns. As a high dielectric thin film material that can achieve this, the demand for a precursor compound having high thermal stability is increasing.

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 a Group 4 transition metal oxide thin film through an atomic layer deposition method or a chemical vapor deposition method using these compounds depends on the ligand structure of these precursors. have developed in various ways.

For example, Group 4 transition metal inorganic salts such as ZrCl ₄ , ZrI ₄ , and ZrF ₄ are known. In zirconium oxide thin films using atomic layer deposition or chemical vapor deposition using this, inorganic salts (Cl ^- , F ^- , I ^- ) remain inside the thin film, resulting in deterioration of the electrical properties of the thin film and the occurrence of agglomeration phase of the thin film. 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 thin film.

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

For example, non-patent document 2 discloses a zirconium compound coordinated with an amido ligand and a zirconium oxide thin film using the same as a precursor. However, all of the precursors represented by the zirconium compounds (eg, Zr(NMeEt) ₄ or Zr(NEt ₂ ) ₄ ) exist in a liquid state with low viscosity at room temperature, have very high vapor pressure, and form amido ligands by ozone and water vapor. It is easy to remove and it is possible to manufacture a zirconium oxide thin film through an atomic layer deposition method. However, the zirconium compound has problems such as being very reactive and not easy to store for a long period of time, and being decomposed during vaporization due to low thermal stability, causing deterioration in the quality of the thin film.

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

Therefore, compared to the precursor compound used as a conventional high-k thin film material, research on a precursor compound having more excellent properties is still required.

KR 10-2007-0121281 A

J. Mater. Chem., 1994, 4, 1815-1819 Chem. Mater. 14, 10, 4350-4358

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, an object of the present invention is to provide a composition for thin film deposition containing a Group 4 transition metal containing the Group 4 transition metal compound of the present invention.

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

In order to achieve the above object, the present invention provides a Group 4 transition metal compound represented by Formula 1 below.

[Formula 1]

[In Chemical 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 to 4.]

In Formula 1 according to an embodiment of the present invention, M is titanium, zirconium or hafnium; 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 identically C ₁ -C ₄ alkyl; The R ³ to R ⁵ may each independently be C ₁ -C ₄ alkyl.

In Formula 1 according to an embodiment of the present invention, R ¹ and R ² are identically methyl or ethyl; At least one of R ³ to R ⁵ may be ethyl, propyl or butyl, and the others may be methyl, ethyl, propyl or butyl.

In the present invention, a method for preparing a Group 4 transition metal compound represented by Formula 1 below by reacting Formula A with Formula B is provided.

[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 to 4.]

In addition, in the present invention, a composition for depositing a thin film containing a Group 4 transition metal containing a Group 4 transition metal compound represented by Chemical Formula 1 is provided.

In the composition for thin film deposition containing a Group 4 transition metal 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 manufacturing 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 for a Group 4 transition metal-containing thin film and can be applied to various thin film deposition methods. Furthermore, since the adsorption to the substrate is excellent, it is possible to manufacture a high-quality thin film containing a Group 4 transition metal.

In addition, the Group 4 transition metal compound according to the present invention does not decompose 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-k 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, has a fast and easy deposition rate due to high volatility, and has excellent cohesion and excellent step coverage, so that high dielectric thin films can be applied to various types of substrates It can be formed with a uniform thickness on the top. Thus, 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 a semiconductor manufacturing process.

1 shows a TGA graph of Example 1 according to the present invention,
Figure 2 shows a 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 how to achieve them, will become clear with reference to the detailed description of the following embodiments. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various forms different from each other, only these embodiments make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to completely inform the person who has the scope of the invention, and the present invention is only defined by the scope of the claims. Hereinafter, a 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" in this specification is an open description having the same meaning as the expression "includes", "includes", "has" or "characterized by", and is not further listed. It does not exclude any element, material or process that is not

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

Also, the singular form used in this specification may be intended to include the plural form as well, unless otherwise indicated in the context.

In addition, units used in the present specification are based on weight without particular mention, and as an example, the unit of % or ratio means weight% or weight ratio.

In addition, the term "Group 4 transition metal compound" in the present specification may be represented by Chemical Formula 1 and has the same meaning as the expression "precursor" or "precursor compound".

In addition, the term "thermal stability" as used herein may mean that physical properties are not changed even during a continuous warming process or a high temperature process, and specifically means that no structural change occurs even when exposed to the above-mentioned harsh conditions for a long time. 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 using a precursor introduction device such as a bubbling system or an injection system. For example, in the bubbling system, a precursor in a liquid state is bubbled with a carrier gas to vaporize the precursor, or a precursor in a solid state is vaporized and the precursor in a vapor state is introduced into the chamber together with the carrier gas. That is, the precursors, which are liquid or solid at room temperature, are heated and converted into a vapor state before being supplied into the chamber. As such, while introducing the precursor into the chamber, energy is applied to the precursor, and the chamber in which the atomic layer deposition process or the chemical vapor deposition process is performed is also maintained at a high temperature. Therefore, precursors used to form thin films are required to have excellent thermal stability. If the precursors are thermally unstable and are easily decomposed by heat, it is difficult to control process conditions and it is difficult to form a thin film having a uniform thickness and to control electrical characteristics of the semiconductor device.

Accordingly, the present inventors focused on the above-mentioned problems and devised a novel Group 4 transition metal compound capable of solving the problems. The Group 4 transition metal compound of the present invention is a heteroleptic compound in which two 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 its physical properties even during a continuous warming process or a high temperature process, and has excellent volatility. Yes, we propose the present invention.

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

A 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, so 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 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 Formula 1 below.

[Formula 1]

[In Chemical 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 to 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, since it has excellent thermal stability, it does not decompose even in a continuous heating process, so that a high-quality thin film can be manufactured.

In addition, the Group 4 transition metal compound according to an embodiment of the present invention forms a high crystalline structure by realizing excellent volatility as well as excellent cohesion, so that the growth rate of the thin film is excellent, and even at a relatively low temperature, high quality A thin film can be provided. In addition, the Group 4 transition metal compound of the present invention has excellent thermal stability, volatility and reactivity, so that 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.

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

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; R ¹ and R ² are identically C ₁ -C ₄ alkyl; The R ³ to R ⁵ may each independently represent C ₁ -C ₄ alkyl.

More specifically, the Group 4 transition metal compound, wherein M in Formula 1 is titanium, zirconium or hafnium; R ¹ and R ² are identically methyl or ethyl; At least one of R ³ to R ⁵ may be ethyl, propyl or butyl, and the others 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 Chemical Formula 1, M is titanium; R ¹ and R ² are identically methyl or ethyl; at least one of R ³ to R ⁵ is ethyl, propyl or butyl and the others are methyl or ethyl; n is an integer of 1, or in Formula 1, M is zirconium or hafnium; R ¹ and R ² are identically methyl or ethyl; at least one of R ³ to R ⁵ is ethyl, propyl or butyl and the others are 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 others 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, stability against heat is greatly improved so as not to decompose at high temperature for a long time. Accordingly, it is possible to prevent a phenomenon in which solid impurities generated during the decomposition of the precursor are deposited on the substrate or fill holes during thin film formation. In addition, it is good that the vaporized precursor can be uniformly supplied on the substrate to provide excellent step coverage.

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, 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 structures, but is not limited thereto.

[In the above structure,

M is titanium, zirconium or hafnium.]

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

[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 to 4.]

The reaction according to an embodiment of the present invention may be carried out in 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 ), diethylether, toluene, tetrahydrofuran (THF), or the like, or a mixed organic solvent of two or more may be used.

In addition, it goes without saying that the reactants may be appropriately changed and used in a stoichiometric equivalent ratio according to the 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 carried out under an inert gas atmosphere such as nitrogen or argon.

For example, in the reaction, the compound of formula A and the compound of formula B are reacted at 10 to 35 ° C. for 5 to 30 hours in the presence of hexane, diethyl ether, toluene, tetrahydrofuran or a mixed organic solvent thereof, The Group 4 transition metal compound of Formula 1 can be obtained in high yield (more than 70%). At this time, you may refine|purify by recrystallization, column chromatography, or "sublimation" as needed after the said reaction.

In addition, the present invention relates to a composition for depositing a Group 4 transition metal-containing thin film comprising the Group 4 transition metal compound represented by Formula 1 and a Group 4 transition metal-containing thin film prepared using the Group 4 transition metal compound of the present invention. The manufacturing method is explained.

The composition for depositing a thin film containing a Group 4 transition metal according to an embodiment of the present invention includes the Group 4 transition metal compound of Chemical Formula 1, and the amount of the Group 4 transition metal compound in the composition of the present invention is determined according to film formation conditions 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 thin film deposition containing a Group 4 transition metal 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; Alkylamine compounds 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, neopentane, etc., the aromatic hydrocarbon compound may include benzene, toluene, xylene, etc., and the alkylamine compound may include dimethylamine, diethyl Amine, ethylmethylamine, triethylamine, tributylamine, tetramethylethylenediamine, etc. are mentioned.

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

Also, the composition for thin film deposition containing the Group 4 transition metal may include 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 composition for thin film deposition containing a Group 4 transition metal 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 a solvent in a 1:1 molar ratio, its viscosity (Viscosity, Cp, measured at 28.3 °C) is 1 to 50 cp. It may be, specifically, 1 to 30cp, more specifically, it may be 1 to 20cp.

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

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

The manufacturing method of 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, and the like. .

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

For example, in the case of a method for manufacturing a thin film containing a Group 4 transition metal through a chemical vapor deposition method using the Group 4 transition metal compound, after an alkoxyimideamide ligand bonded to the Group 4 transition metal compound is introduced onto a substrate, the It is chemically bonded on a substrate to form a thin film. In addition, after the ligand is introduced onto the substrate, a step of replacing it with one or two or more reaction gases selected from oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), carbon dioxide (CO ₂ ), and the like can include more.

For example, in the case of a method for manufacturing a thin film containing a Group 4 transition metal through atomic layer deposition using the Group 4 transition metal compound, an alkoxyimideamide ligand bonded to the Group 4 transition metal compound is chemically adsorbed on the substrate. After that, a thin film may be formed on the substrate. At this time, it is of course possible to further include the step of replacing the reaction gas described above.

The group 4 transition metal-containing thin film manufactured through the above deposition method includes a titanium thin film, a zirconium thin film, and a hafnium thin film; a titanium oxide thin film, a zirconium oxide thin film, and a hafnium oxide thin film; titanium oxynitride thin film, zirconium oxynitride thin film, hafnium oxynitride thin film; or a complex oxynitride thin film containing a Group 4 transition metal; etc.

The substrate is not limited as long as it is a conventional substrate, and a non-limiting example thereof is a substrate including one or more semiconductor materials of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, SOI (Silicon On Insulator ) Rigid substrates such as substrates, quartz substrates or display glass substrates, or polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethyl methacrylate (PMMA, It may be a flexible plastic substrate such as Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), or polyester.

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

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

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

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. At this time, the reaction gas may be provided simultaneously with the deposition source or provided subsequently. In addition, 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), and carbon dioxide (CO ₂ ).

For example, the reaction gas may be provided at a flow rate of 1 to 1,000 sccm, specifically 100 to 500 sccm, and more specifically 150 to 400 sccm. In addition, the transfer 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 are selected from helium, neon, argon, krypton, xenon, radon, etc. It may be one or a mixture of two or more 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, and 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 a group 4 transition metal-containing thin film according to an embodiment of the present invention.

A group 4 transition metal-containing thin film manufactured according to the manufacturing method of a group 4 transition metal-containing thin film according to an embodiment of the present invention is a high-density, high-permittivity thin film material. That is, according to the method for manufacturing a thin film containing a Group 4 transition metal according to the present invention, wiring of a semiconductor device, gate insulating film of a transistor, 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 skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Examples of Group 4 transition metal compounds according to the present invention were carried out under an inert argon or nitrogen atmosphere using a glove box or a Schlenk line, and structural analysis of the obtained title compound was performed using 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 heating 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 (1.00 g, 4.46 mmol) in hexane (50 ml), (Z)-N'-ethoxy-N-methylacetimideamide ( (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, hexane was removed under reduced pressure. Thereafter, 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 being allowed to stand 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 the compound 1 did not decompose even at a high process temperature and had excellent thermal stability.

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

(Example 2)

Preparation of Compound 2

After dissolving tetrakis(dimethylamido) zirconium (0.50 g, 1.87 mmol) in hexane (hexane, 50 ml), (Z)-N'-ethoxy-N-methylacetimideamide ( (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, hexane was removed under reduced pressure. 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 being allowed to stand at 130 ° C for 4 days, ^{the 1} H NMR spectrum of the compound 2 also showed substantially the same state as the above-described ¹ H NMR spectrum (25 ° C).

(Example 3)

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

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

According to FIGS. 2 and 3, the Compound 2 exhibits a decrease of about 11% as one amide ligand is decomposed from room temperature, followed by a decomposition of one alkoxy imidamide ligand and the remaining amide ligand, and weight reduction by about 50% show Compound 3 also shows a weight loss of about 9% due to decomposition of one amide ligand from room temperature, followed by decomposition of one alkoxy imideamide ligand and amide ligand, resulting in a weight loss of up to about 49%. However, since the compounds 2 and 3 are substantially sublimated or distilled, it should not be interpreted as deterioration of thermal stability.

(Example 4)

Manufacture 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 container was supplied to a silicon substrate using argon gas (50 sccm) as a transfer 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, the H ₂ O reaction gas was supplied by increasing the supply time from 1 second to 5 seconds, and the thin film deposition rate according to the supply time was measured.

In the case of the compound 1, it was confirmed that the thin film deposition rate was maintained constant even when the supply time of the precursor (compound 1) increased after 5 seconds. Thus, 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 above results, the supply time of the compound 1 was 5 seconds, and the supply time of H ₂ O was supplied at 3 seconds, and then reaction by-products and residual reaction gas were removed using argon gas (1000 sccm) for about 10 seconds. A titanium oxide thin film (Ti oxide thin film) was formed by repeating 100 cycles with the above process as one cycle.

Likewise, 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 titanium oxide thin film produced 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 manufacturing 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 those skilled in the art that various substitutions, modifications, and changes are possible within a range that does not deviate from the technical spirit of the present invention will be clear to

Claims (10)

A Group 4 transition metal compound represented by Formula 1:
[Formula 1]

In Formula 1,
M is a Group 4 transition metal;
R ¹ and R ² are identically C ₁ -C ₄ alkyl;
R ³ to R ⁵ are each independently C ₁ -C ₄ alkyl;
n is 1 or 2; According to claim 1,
In Formula 1,
Wherein M is titanium, zirconium or hafnium, a Group 4 transition metal compound. delete According to claim 1,
In Formula 1,
R ¹ and R ² are identically methyl or ethyl;
At least one of R ³ to R ⁵ is ethyl, propyl or butyl, and the others are methyl, ethyl, propyl or butyl, Group 4 transition metal compound. According to claim 1,
A Group 4 transition metal compound selected from the following structures:




In the above structure,
M is titanium, zirconium or hafnium. A method for preparing a Group 4 transition metal compound represented by Formula 1 below by reacting Formula A with Formula 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 and R ² are identically C ₁ -C ₄ alkyl;
R ³ to R ⁵ are each independently C ₁ -C ₄ alkyl;
n is 1 or 2; A composition for thin film deposition containing a Group 4 transition metal comprising a Group 4 transition metal compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
M is a Group 4 transition metal;
R ¹ and R ² are identically C ₁ -C ₄ alkyl;
R ³ to R ⁵ are each independently C ₁ -C ₄ alkyl;
n is 1 or 2; According to claim 7,
The Group 4 transition metal of the Group 4 transition metal compound,
A composition for thin film deposition containing a Group 4 transition metal, which is titanium, zirconium or hafnium. Using a Group 4 transition metal compound selected from any one of claims 1, 2, 4, and 5, preparing a Group 4 transition metal-containing thin film; comprising a Group 4 transition metal-containing thin film. Manufacturing method of. According to claim 9,
A method for producing a thin film containing a Group 4 transition metal, which is performed by chemical vapor deposition or atomic layer deposition.