KR20230014552A - Novel 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 novel group 4 transition metal compound, a manufacturing method thereof and a method for forming a thin film using the same, wherein the group 4 transition metal compound according to the present invention is thermally stable, has excellent volatility, and has high storage stability, and thus, by using the group 4 transition metal compound as a precursor, it is possible to provide a high-density and high-purity group 4 transition metal-containing thin film and a manufacturing method thereof.

Description

Novel 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 novel 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 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. Accordingly, research on suitable alternative thin-film materials and process technologies for providing very thin, reliable, and low-defect gate dielectrics to improve device performance is actively progressing.

In order to solve these problems, studies on high-k metal oxide materials are being actively conducted as a high-k metal oxide material having excellent insulating properties, high permittivity, and low dielectric loss.

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-permittivity thin film material, Group 4 transition metal precursors have been proposed, and specifically, titanium-containing, zirconium-containing, and hafnium-containing precursors may be mentioned, and atomic layer deposition or chemical vapor deposition using the same may be used. The preparation of Group 4 transition metal oxide thin films has been developed in various ways according to the ligand structure of these precursors.

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 oxide thin film using a zirconium alkoxide precursor, and Zr(OtBu) ₄ is used as the precursor. However, Zr(OtBu) ₄ is very reactive, so it is very difficult to handle in a thin film manufacturing process and has a short shelf life because it causes a catalytic hydrolytic decomposition reaction even in a small amount of moisture.

For example, in Non-Patent Document 2, a zirconium oxide thin film formed by using a zirconium compound coordinated with an amido ligand as a precursor is known. Zirconium amido compounds represented by Zr(NMeEt) ₄ or Zr(NEt ₂ ) ₄ all exist in a low-viscosity liquid state at room temperature, have very high vapor pressure, and are easy to remove amido ligands by ozone and water vapor. It is most widely used as a precursor for manufacturing ZrO ₂ thin films using a layer deposition process. However, these zirconium amido compounds are known to have problems such as being very reactive and not easy to store for a long period of time, and in particular, having low thermal stability and decomposing during vaporization to cause deterioration in the quality of thin films.

In addition, group 4 transition metal precursors according to US 8471049 are not thermally stable at high temperatures, and thus have low deposition rates and low deposition rates during chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes. There was a downside to having a growth rate.

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.

US 8471049

J. Mater. Chem., 1994, 4, 1815-1819 Chem. Mater., 2002, 14, 4350-4358

An object of the present invention is to provide a novel Group 4 transition metal compound that is thermally stable, has high volatility and excellent cohesion and is useful as a precursor for thin film deposition.

In addition, the present invention provides a method for preparing the Group 4 transition metal compound.

In addition, an 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 using the Group 4 transition metal compound.

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

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

R ¹ to R ³ are each independently C1-C10 alkyl.

In Formula 1 according to an embodiment of the present invention, M is titanium, zirconium or hafnium; R ¹ to R ³ may each independently be C1-C7 alkyl.

In Chemical Formula 1 according to an embodiment of the present invention, M is zirconium or hafnium; R ¹ is C1-C4 alkyl; R ² and R ³ may be C1-C4 alkyl identically to each other.

In Formula 1 according to an embodiment of the present invention, R ¹ is methyl, ethyl, propyl or butyl; R ² and R ³ may equally be methyl or ethyl.

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 zirconium or hafnium.

In addition, the present invention provides a method for preparing a Group 4 transition metal compound of Formula 1 by reacting a compound of Formula 2 with a compound of Formula 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

M is a Group 4 transition metal;

R ¹ to R ⁵ are each independently C1-C10 alkyl.

In addition, the present invention provides a method for preparing a thin film containing a Group 4 transition metal using the Group 4 transition metal compound of Formula 1. 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 of the present invention has a novel structure including an acetimidamide-modified ligand, that is, an acetamidoxime ligand, and has good thermal stability and excellent volatility, making it very useful as a precursor for a Group 4 transition metal-containing thin film. Furthermore, since the adsorption to the substrate is excellent, a higher quality group 4 transition metal-containing thin film, in particular, a group 4 transition metal oxide thin film can be manufactured.

In addition, the Group 4 transition metal compound according to the present invention exists as a solid at room temperature and has good handling properties.

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.

That is, the Group 4 transition metal compound according to the present invention is a precursor for a Group 4 transition metal-containing thin film, such as a Group 4 transition metal oxide thin film, and a nano-sized Group 4 transition metal-containing particle, such as a Group 4 transition metal oxide. useful as a precursor.

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 Zr(mdao) ₄ prepared in Example 1 according to the present invention.
2 shows a TGA graph of Zr(tdao) ₄ prepared in Example 2 according to the present invention.
3 shows a TGA graph of Hf(mdao) ₄ prepared in Example 3 according to the present invention.
4 shows a TGA graph of Hf(tdao) ₄ prepared in Example 4 according to the present invention.

Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical terms and scientific terms used at this time, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and will unnecessarily obscure the gist of the present invention in the following description. Descriptions of possible known functions and configurations are omitted.

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

In addition, the term "includes" 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 the compound before and after the specified treatment, that is, the compounds before and after the 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 expressions such as "precursor" or "precursor compound".

In addition, the term "thermal stability" in the present specification may mean that physical properties do not change 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.

The present invention relates to a novel Group 4 transition metal compound that can be used as a precursor for preparing a Group 4 transition metal-containing thin film, a Group 4 transition metal-containing nanoparticle, and a nanomaterial containing a Group 4 transition metal. More specifically, the following It relates to a Group 4 transition metal compound represented by Formula 1.

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

R ¹ to R ³ are each independently C1-C10 alkyl.

The Group 4 transition metal compound of the present invention is a compound having a novel structure including an acetimidamide-modified ligand, that is, an acetamidoxime ligand, and includes a Group 4 transition metal-containing thin film, a Group 4 transition metal-containing nanoparticle, and a Group 4 transition metal. It can be usefully used as a precursor for the production of nanomaterials including. In particular, the Group 4 transition metal compound of Formula 1 is a precursor for preparing a Group 4 transition metal-containing thin film, and has high solubility in organic solvents widely used in semiconductor manufacturing processes, such as benzene, tetrahydrofuran, toluene, chloroform, etc. Therefore, a high-quality thin film containing a Group 4 transition metal can be manufactured using a known thin film manufacturing method.

Furthermore, the Group 4 transition metal compound of the present invention has good thermal stability and does not decompose even in a continuous heating process, so that a high-quality thin film can be produced.

In addition, the Group 4 transition metal compound of the present invention can be deposited by various deposition methods due to its good thermal stability and excellent reactivity, and it is possible to manufacture a high-density, high-purity Group 4 transition metal-containing thin film at a high deposition rate.

A Group 4 transition metal compound according to an embodiment may include all structural isomeric forms of a ligand including a cis-trans form and an E-Z form.

In Formula 1 according to an embodiment, M is preferably titanium, zirconium or hafnium; R ¹ to R ³ may each independently be C1-C7 alkyl.

From the viewpoint of having a high crystalline structure due to thermal stability and excellent cohesion, M is zirconium or hafnium in Formula 1 according to an embodiment of the present invention; R ¹ is C1-C4 alkyl; R ² and R ³ may be C1-C4 alkyl identically to each other.

In Formula 1 according to one embodiment, R ¹ is methyl, ethyl, propyl or butyl; R ² and R ³ may equally be methyl or ethyl.

In Formula 1 according to one embodiment, R ¹ is methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, s -butyl or t -butyl; R ² and R ³ may equally be methyl or ethyl.

A Group 4 transition metal compound according to an embodiment may be selected from the following structures, but is not limited thereto.

In the above structure, M is zirconium or hafnium.

In addition, the present invention provides a method for preparing the Group 4 transition metal compound of Formula 1.

The Group 4 transition metal compound of Chemical Formula 1 may be prepared by reacting a compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

M is a Group 4 transition metal;

R ¹ to R ⁵ are each independently C1-C10 alkyl.

In one embodiment, M is titanium, zirconium or hafnium; R ¹ to R ⁵ may each independently be C1-C7 alkyl.

In one embodiment, M is zirconium or hafnium; R ¹ is C1-C4 alkyl; R ² and R ³ are identically C1-C4 alkyl; R ⁴ and R ⁵ may be C1-C4 alkyl identically to each other.

In one embodiment, R ¹ is methyl, ethyl, propyl or butyl; R ² and R ³ are identically methyl or ethyl; R ⁴ and R ⁵ may equally be methyl or ethyl.

In one embodiment, R ¹ is methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, s -butyl or t -butyl; R ² and R ³ are identically methyl or ethyl; R ⁴ and R ⁵ may equally be methyl or ethyl.

According to one embodiment, the reaction may be carried out for 8 hours to 24 hours at 10 to 35 ℃.

According to one embodiment, the compound of Formula 3 may be used in an amount of 4 to 6 moles, preferably 4 to 4.5 moles, based on 1 mole of the compound of Formula 2.

According to one embodiment, the reaction 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, specifically hexane, One or two or more mixed organic solvents selected from ethyl ether, toluene, tetrahydrofuran, and the like may be used.

According to one embodiment, the reaction may be performed under an inert gas atmosphere such as nitrogen or argon.

In one embodiment, the reaction is performed by reacting the compound of Formula 2 and the compound of Formula 3 at 10 to 35 ° C. for 8 to 24 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 of 80% or more. At this time, you may refine|purify by recrystallization, column chromatography, or "sublimation" as needed after the said reaction.

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 of Formula 1 or the Group 4 transition metal-containing film deposition composition containing the same.

According to an embodiment, the composition for depositing a thin film containing a Group 4 transition metal includes a 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 depends on the film formation conditions of the thin film or the thin film. Of course, it can be included within the range recognized by those skilled in the art in consideration of the thickness and characteristics of the.

According to one embodiment, the composition for thin film deposition containing a Group 4 transition metal may include 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.

According to one embodiment, the composition for thin film deposition containing the Group 4 transition metal contains 0.1 to 10 moles, specifically 0.2 to 5 moles, more specifically 0.5 to 3 moles of the solvent based on 1 mole of the Group 4 transition metal compound. may contain moles.

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 at a molar ratio of 1:1, its viscosity (Viscosity, Cp, measured at 28.3 ° C.) is 1 to 50 Cp. It may be, specifically, 1 to 30 Cp, more specifically, it may be 1 to 20 Cp.

According to one embodiment, when the Group 4 transition metal-containing composition for thin film deposition 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 reactivity can be provided.

According to an embodiment, the method for manufacturing a group 4 transition metal-containing thin film may provide a group 4 transition metal-containing thin film on a substrate through a known deposition method. Specifically, the deposition method may be a solution process or vacuum deposition, and the vacuum deposition is specifically chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (atomic layer deposition, ALD), low pressure vapor deposition, plasma enhanced atomic layer deposition, and the like.

For example, the group 4 transition metal-containing thin film manufactured through the deposition method may be a group 4 transition metal oxide thin film or a group 4 transition metal nitride thin film.

For example, in one embodiment of the present invention, the substrate used for the Group 4 transition metal-containing thin film is not limited as long as it is a conventional substrate, and non-limiting examples thereof include Ru, TiN, Si, Ge, SiGe, GaP, GaAs, A substrate containing one or more semiconductor materials of SiC, SiGeC, InAs, and InP, a rigid substrate such as a silicon on insulator (SOI) substrate, a quartz substrate, or a display glass substrate, or a substrate made of polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), Polyethylene Naphthalate (PEN), Poly Methyl Methacrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyethersulfone (PES), Polyester, etc. It may be a plastic substrate.

According to an embodiment, the method of manufacturing a group 4 transition metal-containing thin film using the group 4 transition metal-containing thin film deposition composition may be performed by, for example, chemical vapor deposition (CVD) or atomic layer deposition (ALD). there is.

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.

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 derived from the composition for depositing a thin film containing a Group 4 transition metal may be provided. At this time, the deposition source may be provided with an additional reaction gas. 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 is one or two or more selected from oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), carbon dioxide (CO ₂ ), water, oxygen plasma, ozone plasma, water plasma, and the like. It may be a mixed gas.

For example, the reaction gas may be provided at a flow rate of, but not limited to, 1 to 1,000 sccm, specifically 100 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 non-limiting examples thereof include nitrogen, helium, neon, argon, krypton, xenon, and radon. It may be one or a mixed gas of two or more selected from the like.

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

According to an embodiment, an additional heat treatment step may be further performed on the group 4 transition metal-containing thin film obtained through the method of manufacturing the group 4 transition metal-containing thin film.

According to one embodiment, the Group 4 transition metal-containing thin film manufactured according to the method for manufacturing a Group 4 transition metal-containing thin film is a high-k dielectric thin film material having a high density and a high dielectric constant. 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.

Hereinafter, the synthesis of the Group 4 transition metal compound according to the present invention was performed under an inert argon or nitrogen atmosphere using a glove box or a Schlenk line. The structure of the Group 4 transition metal compound obtained through ¹ H and ¹³ C NMR spectra (Bruker Advance 400 NMR) was analyzed. 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. In the TGA method, the obtained title compound was warmed up to 800°C at a rate of 10°C/min and measured under nitrogen gas injection at a pressure of 1.5 bar/min.

[Example 1] Preparation of Zr(mdao) ₄

After dissolving tetrakis(dimethylamido)zirconium (1.5 mmol) in 50 mL of hexane, N'-hydroxy-N,N-dimethylacetimideamide (N'-hydroxy-N,N- dimethylacetimidamide) (6 mmol) was added dropwise. After stirring at room temperature (25°C) for 12 hours, hexane was removed under reduced pressure, and recrystallization was performed in a mixed solvent of hexane and toluene to obtain the title compound Zr(mdao) ₄ as a solid (yield: 82%).

¹ H NMR (C ₆ D ₆ , 400 MHz): δ 2.03 (s, 3H, CH ₃ ), 2.57 (s, 6H, N(CH ₃ ) ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 14.0, 38.6, 153.5.

As shown in FIG. 1 , as a result of TG analysis of Zr(mdao) ₄ prepared in Example 1, mass reduction began to occur around 50° C. and 50% of the mass decreased at about 300° C. From this, it can be seen that the thermal stability of Zr(mdao) ₄ , which is the compound of Example 1 of the present invention, is high.

[Example 2] Preparation of Zr(tdao) ₄

Using N'-hydroxy-N,N-dimethylpivalimidamide (6 mmol) instead of N'-hydroxy-N,N-dimethylacetimidamide The title compound Zr(tdao) ₄ was obtained as a solid by reacting in the same manner as in Example 1 except for the above (yield: 81%).

¹ H NMR (C ₆ D ₆ , 400 MHz): δ 1.29 (s, 9H, 3CH ₃ ), 2.77 (s, 6H, N(CH ₃ ) ₂ ).

As shown in FIG. 2 , as a result of TG analysis of Zr(tdao) ₄ prepared in Example 2, mass reduction began to occur around 80° C., and a mass reduction of 50% occurred at about 300° C. From this, it can be seen that the thermal stability of Zr(tdao) ₄ , which is the compound of Example 2 of the present invention, is high.

[Example 3] Preparation of Hf(mdao) ₄

The title compound Hf (mdao ) ₄ was obtained as a solid (85% yield).

¹ H NMR (C ₆ D ₆ , 400 MHz): δ 2.06 (s, 3H, CH ₃ ), 2.56 (s, 6H, N(CH ₃ ) ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 14.1, 38.6, 153.4.

As shown in FIG. 3 , as a result of TG analysis of Hf(mdao) ₄ prepared in Example 3, mass loss started to occur around 70°C, and mass decreased by 50% at about 300°C. From this, it can be seen that the thermal stability of Hf(mdao) ₄ , which is the compound of Example 3 of the present invention, is high.

[Example 4] Preparation of Hf(tdao) ₄

Tetrakis(dimethylamido)hafnium (1.5 mmol) was used instead of tetrakis(dimethylamido)zirconium, and N'-hydroxy-N, instead of N'-hydroxy-N,N-dimethylacetimidamide, The title compound Hf(tdao) ₄ was obtained as a solid (yield: 83%) in the same manner as in Example 1 except for using N-dimethylpivalimidamide (6 mmol).

¹ H NMR (C ₆ D ₆ , 400 MHz): δ 1.28 (s, 9H, 3CH ₃ ), 2.79 (s, 6H, N(CH ₃ ) ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 28.6, 41.5, 162.8.

As shown in FIG. 4 , as a result of TG analysis of Hf(tdao) ₄ prepared in Example 4, mass loss started to occur around 70°C, and mass decreased by more than 70% at about 300°C. From this, it can be seen that the thermal stability of Hf(tdao) ₄ , which is the compound of Example 4 of the present invention, is high.

[Example 5] Preparation of zirconium oxide thin film using Zr(mdao) ₄

A zirconium oxide thin film was prepared on a silicon substrate by atomic layer deposition. The silicon substrate was maintained at 300 °C, and Zr(mdao) ₄ synthesized in Example 1 was filled in a stainless steel bubbler container and maintained at 110 °C. First, Zr (mdao) ₄ vaporized in a stainless steel bubbler container is supplied to a silicon substrate using argon gas (50 sccm) as a transport gas, but the supply time is increased from 1 second to 7 seconds. Measure the deposition rate of the thin film did 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. As a result, when Zr(mdao) ₄ was used as the thin film deposition precursor, it was confirmed that the thin film deposition rate was kept constant even if the supply time of the precursor increased after ₅ seconds. It can be seen that this substrate is included. In addition, it can be seen that the H ₂ O reaction gas has a constant thickness of the thin film after 3 seconds and is saturated after 3 seconds. From this, the supply time of the precursor Zr(mdao) ₄ 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 precursor Zr(mdao) ₄ is 5 seconds, the supply time of H ₂ O is 3 seconds, and then the reaction by-products and residual reaction gases are removed using argon gas (1000 sccm) for about 10 seconds. did A zirconium oxide thin film was formed by repeating 100 cycles with the above process as one cycle. In addition, a zirconium oxide thin film was formed in the same manner as above, but 300 cycles were repeated to form a zirconium 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 0.6 Å/cycle.

In addition, as a result of XPS and XRF analysis of the zirconium oxide thin film, the binding energy of Zr-O was confirmed. In addition, since there is no peak in C1s, it can be seen that the purity of the zirconium oxide thin film produced is excellent because there is almost no carbon as an impurity in the zirconium oxide thin film.

As described above, the embodiments of the present invention have been described in detail, but those of ordinary skill in the art to which the present invention pertains, without departing from the spirit and scope of the present invention defined in the appended claims. It will be possible to implement the invention by modifying it in various ways. Therefore, changes in future embodiments of the present invention will not deviate from the technology of the present invention.

Claims (8)

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 to R ³ are each independently C1-C10 alkyl. According to claim 1,
M is titanium, zirconium or hafnium;
R ¹ to R ³ are each independently C1-C7alkyl, a Group 4 transition metal compound. According to claim 1,
M is zirconium or hafnium;
R ¹ is C1-C4 alkyl;
R ² and R ³ are C1-C4 alkyl identically to each other, a Group 4 transition metal compound. According to claim 1,
wherein R ¹ is methyl, ethyl, propyl or butyl;
R ² and R ³ are methyl or ethyl identically to each other, a 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 zirconium or hafnium. A method for preparing a Group 4 transition metal compound of Formula 1 below by reacting a compound of Formula 2 with a compound of Formula 3 below.
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
M is a Group 4 transition metal;
R ¹ to R ⁵ are each independently C1-C10 alkyl. A method for manufacturing a Group 4 transition metal-containing thin film using the Group 4 transition metal compound according to any one of claims 1 to 5. According to claim 7,
A 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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