KR20200082778A - 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 enhanced storage stability, and thus can be used as a precursor to provide a high-density and high-purity group 4 transition metal-containing thin film. The present invention can also provide a method for preparing the group 4 transition metal compound.

Description

Group 4 transition metal compound, manufacturing method thereof, and method of forming thin film using the same{GROUP IV TRANSITION METAL COMPOUNDS, PREPARATION METHOD THEREOF AND PROCESS FOR THE FORMATION OF THIN FILMS USING THE SAME}

The present invention relates to a Group 4 transition metal compound, a method of manufacturing the same, and a method of 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. The manufacturing process of the silicon oxide is simple, but has a low dielectric constant (k), so that when the thickness is thin, a gate-to-channel leakage current occurs from the gate to the channel.

In order to solve these problems, studies on high dielectric thin film materials and process technologies having excellent insulation properties and high dielectric constants have been actively conducted.

On the other hand, as the semiconductor structure is directly 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 possible high dielectric thin film material, there is an increasing demand for a precursor compound having high thermal stability.

As an example of such a high dielectric 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, etc., and the preparation of a Group 4 transition metal oxide thin film through atomic layer deposition or chemical vapor deposition using the ligand structure of these precursors It has been developed in various ways.

As an example, Group 4 transition metal inorganic salts such as ZrCl ₄ , ZrI ₄ and ZrF ₄ are known. Zirconium oxide thin film by atomic layer deposition or chemical vapor deposition method using the same, the inorganic salt in the inner films ^{(Cl -, F -, I} -) is to remain in the electric characteristics of the thin film degradation and aggregation (aggromeration) of the thin film differs generated Had an easy problem. In addition, the roughness of the zirconium oxide film cannot be arbitrarily adjusted, and it is also difficult to adjust the thin film thickness.

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 has a very high reactivity and is very difficult to handle in a thin film manufacturing process and causes a catalytic hydrolytic decomposition reaction even in a small amount of moisture.

As an example, a non-patent document 2 discloses a zirconium compound in which an amido ligand is coordinated and a zirconium oxide thin film using the same as a precursor. However, the zirconium compound (eg, Zr(NMeEt) ₄ )  Alternatively, all of the precursors represented by Zr(NEt ₂ ) ₄ ) exist in a liquid state with low viscosity at room temperature, and the zirconium oxide thin film through atomic layer deposition is easy because the vapor pressure is very high and the amido ligand is easily removed by ozone and water vapor. It is possible to manufacture. However, the zirconium compound has a problem such as high reactivity, so long-term storage is not easy, and in particular, thermal stability is low, so that it decomposes during vaporization to cause deterioration 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 yet to obtain satisfactory results.

Therefore, there is still a need to study a precursor compound having superior properties compared to a precursor compound used as a conventional high dielectric thin film material.

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 and a method for producing the same, which are thermally stable, have high volatility, and have excellent cohesiveness and can be used as precursors for thin film deposition.

Another object of the present invention is to provide a composition for depositing a group 4 transition metal-containing thin film containing the group 4 transition metal compound of the present invention.

Another object of the present invention is to provide a method for producing 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, a new Group 4 transition metal compound represented by Formula 1 is provided.

[Formula 1]

[In the formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;

n is each independently 0 to 5.]

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

Group 4 transition metal compound according to an embodiment of the present invention, in Formula 1, wherein R ¹ , R ² and R ⁴ to R ⁷ are each independently C ₁ -C ₇ linear or branched alkyl; R ³ may be C ₃ -C ₇ branched alkyl.

In the Group 4 transition metal compound according to an embodiment of the present invention, in Chemical Formula 1, R ¹ , R ² and R ⁴ to R ⁷ are each independently methyl or ethyl; Each of R ³ may be independently t-butyl or t-amyl.

The present invention provides a manufacturing method comprising the step of preparing a Group 4 transition metal compound represented by the following Chemical Formula 1 by reacting a compound of the following Chemical Formula A with a compound of the following Chemical Formula B.

[Formula A]

M(X ¹ ) ₂ (NR ⁴ R ⁵ )(NR ⁶ R ⁷ )

[Formula B]

[Formula 1]

[In the above formula A, formula B and formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;

n is each independently 0 to 5;

X ¹ is halogen.]

A composition for depositing a thin film containing a Group 4 transition metal comprising a Group 4 transition metal compound represented by Formula 1 below is provided.

[Formula 1]

[In the formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;

n is each independently 0 to 5.]

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.

The present invention provides a method for manufacturing a Group 4 transition metal-containing thin film using the Group 4 transition metal compound of the present invention described above.

The method of manufacturing a Group 4 transition metal-containing thin film according to an embodiment of the present invention may be performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

The novel Group 4 transition metal compound according to the present invention has high volatility and excellent cohesiveness despite being a solid, and can be usefully used as a precursor for a Group 4 transition metal-containing thin film. In addition, the novel Group 4 transition metal compound according to the present invention has high thermal stability. Accordingly, the vaporized precursor can be uniformly diffused on various types of substrates without decomposition even at a high process temperature. In addition, the novel Group 4 transition metal compound according to the present invention is very excellent in storage stability.

With such characteristics, the Group 4 transition metal compound according to the present invention can be applied to various thin film deposition methods. In addition, the high volatility makes the deposition rate quick and easy, and it is possible to deposit thin films having excellent cohesion and excellent step coverage, so that thin films with uniform thickness can be easily formed on various types of substrates.

Thus, according to the present invention, it is possible to provide a thin film capable of satisfying both stability, efficiency and reliability of a semiconductor manufacturing process.

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

Advantages and features of the present invention, and methods for achieving them will be clarified with reference to embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the present 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 completely inform the person having 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 of manufacturing the same, and a method of 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 “includes” in the present specification is an open-ended description having a meaning equivalent to expressions such as “have”, “contains”, “has” or “makes a feature”, and is not further listed. It does not rule out elements, materials or processes that are not.

In addition, the term "substantially the same" in the present specification is a range that does not cause changes in the state and structure of the compound before and after the specified treatment, that is, each of the compounds before and after the specified treatment can be included in the category of identity. It means that there is.

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

In addition, the units used in this specification without specific mention are based on weight, and for example, units of% or ratio mean weight percent or weight ratio.

In addition, the term "group 4 transition metal compound" may be represented by the formula (1), and has the same meaning as the expression "precursor" or "precursor compound".

In addition, the term "thermal stability" in the present specification may mean that the physical properties are not changed even during a continuous heating process or a high temperature process, and specifically, does not cause a structural change even when exposed for a long period of time under the above-mentioned harsh conditions. do.

In the case of forming a thin film by performing an atomic layer deposition process or a chemical vapor deposition process, a precursor is introduced into a chamber using a precursor inflow device such as a bubbling system and an injection system. For example, in a 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 to introduce a vapor precursor 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 provided into the chamber. As described above, energy is applied to the precursor while introducing the precursor 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 are 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 properties of the semiconductor device.

Accordingly, the present inventor has devised a novel Group 4 transition metal compound capable of solving the above-mentioned problems by focusing on the above-described problems. The Group 4 transition metal compound of the present invention is a heteroleptic compound in which two ligands having different reactivity are bound. Specifically, the Group 4 transition metal compound according to the present invention has a dimer structure including an aminoalkoxide ligand and an amide ligand at the same time.

The Group 4 transition metal compound of the present invention having such a structural characteristic has a high thermal stability that does not change physical properties during a continuous heating process or a high temperature process, and can provide a high quality Group 4 transition metal-containing thin film with high volatility and reliability. 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, when a thin film is produced by using it with high reactivity, the growth rate of the thin film is excellent and a high-quality thin film can be produced even at a relatively low temperature, which is useful as a precursor for manufacturing a group 4 transition metal-containing thin film. can do.

Specifically, the Group 4 transition metal compound according to the present invention is represented by Formula 1 below.

[Formula 1]

[In the formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;

n is each independently 0 to 5.]

As described above, the Group 4 transition metal compound according to an embodiment of the present invention has a dimer structure including an aminoalkoxide ligand and an amide ligand at the same time. Thus, the Group 4 transition metal compound effectively provides electrons to the central metal and exhibits improved stability through intermolecular bonding. Thus, the Group 4 transition metal compound according to an embodiment of the present invention can realize high thermal stability.

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 realizing excellent cohesion, so the growth rate of the thin film is excellent, and it is of good quality even at a relatively low temperature. A thin film can be provided.

For example, the Group 4 transition metal compound of Formula 1 may be in a solid state at room temperature, and has high volatility and high reactivity, resulting in a fast deposition rate.

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

The Group 4 transition metal compound according to an embodiment of the present invention is not easily decomposed by heat after forming a chemical bond on the substrate surface or vaporizing after forming a thin film, specifically, M is titanium, zirconium or hafnium ; R ¹ , R ² and R ⁴ to R ⁷ are each independently C ₁ -C ₇ linear or branched alkyl; R ³ may be C ₃ -C ₇ branched alkyl.

More specifically, in the Group 4 transition metal compound, M is zirconium or hafnium; R ¹ , R ² and R ⁴ to R ⁷ are each independently methyl, ethyl, n -propyl, n -butyl, n -pentyl, n -hexyl or n -heptyl; The R ³ may be i -propyl, i -butyl, s -butyl, t -butyl, i -pentyl, s -pentyl, t-amyl, i -hexyl or s -hexyl.

Most specifically, in the Group 4 transition metal compound, the M is zirconium or hafnium; R ¹ , R ² and R ⁴ to R ⁷ are each independently methyl or ethyl; R ³ may be t -butyl or t-amyl.

The group 4 transition metal compound of the present invention comprising a branched alkyl substituted with 4 to 5 carbon atoms and an amide ligand substituted with linear alkyl having 1 to 2 carbons is stable to heat so as not to decompose for a long time at a high temperature. This can be extremely improved. Accordingly, when the thin film is formed, solid impurities generated during decomposition of the precursor may be prevented from being deposited on the substrate or filling holes or the like. In addition, the vaporized precursor is uniformly supplied on the substrate, so that it is possible to impart 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.

The Group 4 transition metal compound according to an embodiment of the present invention may be prepared through various synthetic methods, and specifically, when prepared from Reaction Scheme 1 below, a high reaction yield may be realized.

[Scheme 1]

[In the above reaction formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;

n is each independently 0 to 5;

X ¹ is halogen.]

In Reaction Scheme 1, the reaction may be performed under an organic solvent, and the usable organic solvent is not limited, but an organic solvent having high solubility with respect to the reactants may be used, and specifically, hexane (Hexane). , Diethylether, toluene, tetrahydrofuran (THF), or the like, or one or more mixed organic solvents.

In Reaction Scheme 1, the reactants may be used in stoichiometric equivalent ratios.

Specifically, according to Reaction Scheme 1, under hexane, diethyl ether, toluene, tetrahydrofuran or a mixed organic solvent thereof, the compound of Formula A and the compound of Formula B are at room temperature (25° C.) for 5 to 30 hours. By reacting, 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, purification may be performed by recrystallization, column chromatography or sublimation.

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

Hereinafter, a composition for depositing a group 4 transition metal-containing thin film containing a group 4 transition metal compound according to the present invention and a method for manufacturing a group 4 transition metal-containing thin film using the group 4 transition metal compound will be described.

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

[Formula 1]

[In the formula 1,

M is a Group 4 transition metal;

R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;

n is each independently 0 to 5.]

For example, the group 4 transition metal-containing thin film deposition composition may include the group 4 transition metal compound at a molar concentration of 0.01 to 2 M. At this time, the composition for thin film deposition containing a Group 4 transition metal is pentane, hexane, heptane, octane, decane, dodecane, ethylcyclohexane, propylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, Hydrocarbon-based solvents such as ethyl toluene; Alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; "Ether-based" solvents such as diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether and tetrahydrofuran; Ester-based solvents such as methyl butylate, ethyl butylate, and propyl propionate; may include one or more mixed organic solvent selected from.

In addition, the viscosity (Viscosity, Cp, measured at 28.3 °C) of the group 4 transition metal-containing thin film deposition composition may be 1 to 50 Cp, specifically 1 to 30 Cp, and more specifically 1 to 20 Cp.

The composition for thin film deposition containing a Group 4 transition metal according to an embodiment of the present invention may be used for thin film deposition through a conventional solution process.

The composition for depositing a group 4 transition metal-containing thin film according to an embodiment of the present invention may provide a high-density group 4 transition metal-containing thin film with high volatility and reactivity by including the group 4 transition metal compound of Chemical Formula 1. In addition, the Group 4 transition metal-containing thin film produced therefrom exhibits a low dielectric constant and is useful as a high dielectric thin film material.

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 of the present invention described above.

A method of 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 through a known deposition method on a substrate. 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, and thus may be effective in the above-described deposition method.

For example, in the case of a method of manufacturing a thin film containing a Group 4 transition metal by chemical vapor deposition using the Group 4 transition metal compound, two different ligands bound to the Group 4 transition metal compound, that is, an aminoalkoxide ligand and After the amide ligand is introduced onto the substrate, it can be chemically bonded onto the substrate to form a thin film. At this time, after the two different ligands are introduced onto the substrate, one or more reaction gases selected from oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), carbon dioxide (CO ₂ ), etc. And it may further include the step of being substituted.

For example, in the case of a method of manufacturing a thin film containing a Group 4 transition metal by atomic layer deposition using the Group 4 transition metal compound, two different ligands bound to the Group 4 transition metal compound are chemically deposited on the substrate. After being adsorbed, a thin film can be formed on the substrate. At this time, of course, may further include the step of being substituted with the reaction gas described above.

The group 4 transition metal-containing thin film prepared through the deposition method includes 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 include a substrate including one or more semiconductor materials of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, SOI (Silicon On Insulator) A rigid substrate such as a substrate, a quartz substrate, or a glass substrate for a display, or a polyimide, polyethylene terephthalate (PET), polyethylene phthalate (PEN), poly methyl methacrylate (PMMA, It may be a flexible plastic substrate such as Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyether sulfone (PES), 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 a temperature of a substrate mounted in a chamber at 80 to 400°C; And two steps of supplying energy to the substrate.

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

For example, the temperature of the substrate may be specifically 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 may be provided subsequently.

For example, the reaction gas may be one or more mixed gases 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 sccm to 1,000 sccm, specifically 100 sccm to 500 sccm, and more specifically 150 to 400 sccm.

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 one non-limiting example is selected from helium, neon, argon, krypton, xenon, radon, etc. It may be one or more of the mixed gas.

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, and more specifically 0.5 to 3 torr.

Depending on the purpose, an additional heat treatment step may be further performed on the Group 4 transition metal-containing thin film obtained by the above-described manufacturing method.

According to 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 having a uniform thickness can be provided on a substrate having a high step ratio and high aspect ratio. Further, the Group 4 transition metal-containing thin film prepared therefrom is a high-density high dielectric thin film material having a high density and high dielectric constant.

That is, according to the method for manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention, by supplying a high dielectric constant thin film material having a desired high density and high dielectric constant through an ALD process or a CVD process, etc. It can be used in various ways such as wiring of semiconductor devices, gate insulating films of transistors, dielectric films of capacitors or coating films of electronic parts.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

Hereinafter, examples of the Group 4 transition metal compound according to the present invention were performed under an inert argon or nitrogen atmosphere using a glove box or Schlenk line, and structural analysis of the obtained title compound was performed by ¹ H NMR spectrum (Bruker Advance 400 NMR). In addition, a thermogravimetric analysis (TGA) method was used to measure the thermal stability, volatility, and decomposition temperature of the Group 4 transition metal compound. 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 composition for group 4 transition metal-containing thin film deposition containing the Group 4 transition metal compound according to the present invention was measured using an ellipsometer.

(Example 1)

Preparation of compound 1

1-(t-butylamino)-2-methylpropan-2-ol (1-(tert-butylamino)-2-methylpropan-2-ol, 1.00 g, 6.88 mmol) was added to 50 mL of diethylether. After melting, n-BuLi (6.05 mL, 15.15 mmol) was added dropwise at 0°C. Thereafter, the temperature was raised to room temperature (25°C) and stirred for 2 hours. Zr(Cl) ₂ (NMe ₂ ) ₂ (THF) ₂ (2.71 g, 6.88 mmol) was dissolved in 100 mL of ether and then slowly added dropwise to the solution. Then, the mixture was stirred at room temperature for 12 hours.

After completion of the reaction, the mixture was concentrated under reduced pressure and hexane was further added. The solution was filtered to remove LiCl, and the filtrate was concentrated under reduced pressure. The concentrate was recrystallized from a mixed solution of hexane and toluene (7:3=wt:wt) to obtain white solid compound 1 (White solid, 2.1 g, yield 95%).

¹ H NMR (25°C, 400 MHz, C ₆ D ₆ ): δ 1.29 (s, 9H, 3CH ₃ ), 1.32 (s, 6H, 2OCCH ₃ ), 2.87 (s, 12H, 4NCH ₃ ), 3.16 (s , 2H, NCH ₂ ).

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 the compound 1 does not decompose even at a high process temperature, and has excellent thermal stability.

As shown in FIG. 1, it was confirmed that the compound 1 was able to form a thin film at an excellent deposition rate by volatilizing rapidly even at a lower process temperature due to excellent volatility. In addition, since the change in mass loss was not confirmed before 247°C, it was confirmed to have excellent thermal stability.

(Examples 2 to 4)

By reacting the reactants in a similar manner to Example 1 as shown in Table 1 below, each compound was obtained.

To confirm the thermal stability of each obtained compound, ¹ H NMR spectra of samples left at room temperature and 130° C. for 4 days were compared.

(Example 5)

The thin film was deposited through thermal atomic layer deposition.

The canister containing the Group 4 transition metal compound (Compound 1) obtained from Example 1 was set to about 60°C, and the temperature of the chamber was set to about 310°C. After the Group 4 transition metal compound (Compound 1) obtained from Example 1 was vaporized with a bubbling system, the Group 4 transition metal compound (Compound 1) obtained from Example 1 in the gaseous state was used by using a carrier gas. It was injected into the chamber. Specifically, reaction conditions are as follows.

a. Group 4 transition metal compound injection time: 10 sec

b. Carrier gas argon: 1,000 sccm/15 sec

c. Reaction gas_ ozone: 300 sccm/8sec

As a result of confirming 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 to which the present invention pertains are capable of various substitutions, modifications, and changes without departing from the technical spirit of the present invention. Will be obvious to you.

Claims (9)

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 ⁷ are each independently C ₁ -C ₁₀ alkyl;
n is each independently 0-5. According to claim 1,
In Chemical Formula 1,
M is titanium, zirconium or hafnium;
R ¹ to R ⁷ are each independently C ₁ -C ₇ alkyl;
The n is an integer of 1 to 3, Group 4 transition metal compound. According to claim 1,
In Chemical Formula 1,
R ¹ , R ² and R ⁴ to R ⁷ are each independently C ₁ -C ₇ linear or branched alkyl;
R ³ is a C ₃ -C ₇ branched alkyl, a Group 4 transition metal compound. According to claim 1,
In Chemical Formula 1,
R ¹ , R ² and R ⁴ to R ⁷ are each independently methyl or ethyl;
Each of R ³ is independently a t-butyl or t-amyl, a Group 4 transition metal compound. A method for preparing a Group 4 transition metal compound represented by Formula 1 by reacting Formula A and Formula B below:
[Formula A]
M(X ¹ ) ₂ (NR ⁴ R ⁵ )(NR ⁶ R ⁷ )
[Formula B]

[Formula 1]

In Chemical Formula A, Chemical Formula B and Chemical Formula 1,
M is a Group 4 transition metal;
R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;
n is each independently 0 to 5;
X ¹ is halogen. 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 Chemical Formula 1,
M is a Group 4 transition metal;
R ¹ to R ⁷ are each independently C ₁ -C ₁₀ alkyl;
n is each independently 0-5. The method of claim 6,
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. A method for producing a thin film containing a Group 4 transition metal using the Group 4 transition metal compound of any one of claims 1 to 4. The method of claim 8,
Method for producing a thin film containing a Group 4 transition metal, which is performed by chemical vapor deposition or atomic layer deposition.

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