WO2021085810A2 - Group 4 transition metal compound, preparation method therefor, and composition, comprising same, for depositing thin film - Google Patents

Abstract

The present invention relates to a Group 4 transition metal compound, a preparation method therefor, and a method for forming a thin film by using same. The Group 4 transition metal compound according to the present invention shows excellent volatility and is thermally stable, and can be used as a precursor to prepare a high-density and high-purity Group 4 transition metal-containing thin film.

Description

Group 4 transition metal compound, preparation method thereof, and composition for thin film deposition comprising the same

The present invention relates to a group 4 transition metal compound, a method for preparing the same, and a composition for thin film deposition including the same, and more particularly, a group 4 transition metal compound useful as a group 4 transition metal thin film precursor, a method for preparing the same, and a thin film comprising the same It relates to a vapor deposition composition and a method of manufacturing a 　 group 4 transition metal-containing thin film using the same.

With the development of electronic technology, demands for miniaturization and weight reduction of electronic devices used in various electronic devices are increasing rapidly. Various physical and chemical vapor deposition methods have been proposed in order to form a fine electronic device, and various thin films for manufacturing various electronic devices such as a metal thin film, a metal oxide thin film, or a metal nitride thin film are possible by such a deposition method.

In general, the deposition process of a thin film is classified into a physical deposition method and a chemical deposition method. In order to manufacture a high-quality thin film by chemical vapor deposition, not only the thin film itself, that is, the chemical properties of the compound forming the thin film must be excellent, but also the thin film forming compound can be easily introduced into the deposition chamber of the thin film manufacturing equipment. , Physical properties such as thermal stability and vapor pressure of the compound for forming a thin film must be excellent. As a method of introducing the compound for thin film formation into the deposition chamber, a method of directly transferring the compound for thin film formation by using its own vapor pressure, a method using an inert gas as a transfer gas, etc. have been used. A method of directly transferring and spraying into the deposition chamber using an injector (Liquid delivery system) is being used.

In the process of transporting and vaporizing the liquid compound for forming a thin film, the compound for forming a thin film is continuously heated and exposed to heat. In this process, if the compound for forming a thin film is decomposed or the viscosity of the compound for forming a thin film is excessively decreased, the transport of the compound for forming a thin film is difficult or spraying into the chamber is not smoothly performed, so that the thickness of the formed thin film is reduced. There is a problem that it becomes uneven and the quality is deteriorated.

On the other hand, as the semiconductor structure is directly refined 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 capable of this, there is a growing 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, and a hafnium precursor, 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 the same depends on the ligand structure of these precursors. It has developed in various ways.

For 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, it is not possible to arbitrarily adjust the roughness of the zirconium oxide film, and it is difficult to adjust the thickness of the thin film.

For example, Chem. Mater., 2002, 14, 4350 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 precursors represented by the zirconium compound (e.g., Zr(NMeEt) ₄ or Zr(NEt ₂ ) ₄ ) all exist in a liquid state with low viscosity at room temperature, and the vapor pressure is very high, and the amido ligand is caused by ozone and water vapor. It is easy to remove the zirconium oxide thin film through the atomic layer deposition method. However, since the zirconium compound is very reactive, it is not easy to store for a long period of time. In particular, the zirconium compound is decomposed during evaporation due to low thermal stability, resulting in deterioration of the quality of the thin film.

Therefore, there is still a need for research on a precursor compound having better properties as a high dielectric thin film material.

The present invention provides a novel Group 4 transition metal compound and a method for preparing the same.

In addition, the present invention provides a composition for depositing a thin film containing a group 4 transition metal comprising the group 4 transition metal compound of the present invention and a method for manufacturing a thin film containing a group 4 transition metal using the same.

The present invention provides a Group 4 transition metal compound which is very useful as a precursor for thin film deposition due to its excellent thermal stability and volatility, and the Group 4 transition metal compound of the present invention is represented by the following formula (1).

[Formula 1]

(In Chemical Formula 1,

M is a Group 4 transition metal;

R ₁ to R ₆ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl.)

Preferably, in Formula 1 according to an embodiment of the present invention, M is titanium, zirconium or hafnium, R ₁ to R ₆ are independently of each other C ₁ -C ₇ alkyl, and R ₁₁ to R ₁₅ are independently hydrogen or It _{may be C 1} -C ₇ alkyl, more preferably M is zirconium or hafnium, R ₁ to R ₃ are the same as each other C ₁ -C ₄ alkyl, R ₄ to R ₆ are the same as each other C _1- It may be _{C 4 alkyl.}

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 structural formula, M is titanium, zirconium, or hafnium.)

In addition, the present invention provides a method for preparing a Group 4 transition metal compound of the present invention. The method for preparing a Group 4 transition metal compound of the present invention is represented by the following Chemical Formula 2 by reacting a compound of Chemical Formula 3 with a compound of Chemical Formula 4. And preparing a Group 4 transition metal compound.

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4,

M is a Group 4 transition metal;

R ₁ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl;

R ₂₁ to R ₂₆ are each independently C ₁ -C ₁₀ alkyl.)

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

Preferably, in Formula 1 according to an embodiment of the present invention, M is titanium, zirconium or hafnium, R ₁ to R ₆ are independently of each other C ₁ -C ₇ alkyl, and R ₁₁ to R ₁₅ are independently hydrogen or C _It may be 1 -C ₇ alkyl, more preferably M is zirconium or hafnium, R ₁ to R ₃ are the same as each other C ₁ -C ₄ alkyl, R ₄ to R ₆ are the same as each other C ₁ -C ₄ may be alkyl.

In addition, the present invention provides a method of manufacturing a group 4 transition metal-containing thin film using the composition for depositing a transition metal-containing thin film of the present invention.

The novel Group 4 transition metal compound of 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. Manufacturing is possible.

In addition, the novel Group 4 transition metal compound of the present invention is very easy to handle as a liquid at room temperature, has excellent thermal stability and volatility, and thus can be applied to various thin film deposition methods, and has the advantage of producing a high-quality thin film with a fast deposition rate. Have.

In addition, since the composition for depositing a group 4 transition metal thin film of the present invention includes the novel group 4 transition metal compound of the present invention, it is possible to manufacture a thin film having high density and purity of the thin film and very excellent physical and electrical properties.

1 shows a TGA graph _{of Zr(cp)(edpa) 3} prepared in Example 1 according to the present invention.

2 shows a TGA graph _{of Hf(cp)(edpa) 3} prepared in Example 2 according to the present invention.

Figure 3 is a graph showing the change in the growth rate of the thin film according to the supply time using the Hf (cp) (edpa) ₃ precursor of the present invention and the reaction gas H _{2 O gas.}

4 is a graph showing a change in thickness according to a deposition cycle of a hafnium oxide thin film prepared in Example 4 of the present invention.

5 is a graph showing the XPS analysis results of the hafnium oxide thin film prepared in Example 4 of the present invention.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only the present embodiments are intended to complete the disclosure of the present invention, and common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims.

Hereinafter, a novel Group 4 transition metal compound of the present invention, a preparation method thereof, a composition for depositing a Group 4 transition metal thin film including the same, and a method of forming a Group 4 transition metal thin film using the same will be described in detail.

In the present specification, the term "alkyl" includes both straight-chain or branched-chain forms, and may have 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 4 carbon atoms.

As used herein, the term "cycloalkyl" is a substituent derived by the removal of one hydrogen from a fully saturated or partially unsaturated hydrocarbon ring, and as a specific example, cyclopentyl, cyclohexyl, cycloheptyl, 　cyclooctyl, cyclopentenyl , Cyclohexenyl, cycloheptenyl, cyclopentadiene, cyclohexadiene, cycloheptadiene, 　bicycloheptyl or 　bicycloheptenyl, and the like, but is not limited thereto.

The present invention provides a group 4 transition metal compound that is very useful as a precursor of a high-k thin film, and the group 4 transition metal compound of the present invention is represented by the following formula (1).

[Formula 1]

(In Chemical Formula 1,

M is a Group 4 transition metal;

R ₁ to R ₆ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl.)

The Group 4 transition metal compound of Formula 1 according to an embodiment of the present invention exists as a liquid at room temperature, so it is easy to handle and has excellent thermal stability, so that it is not decomposed even in a continuous heating process, so that a high quality thin film can be manufactured.

Furthermore, the Group 4 transition metal compound of the present invention can produce a high-quality thin film having a high dielectric constant by simultaneously employing one cyclopentadienyl derivative and an alkoxyamide ligand.

In addition, since the Group 4 transition metal compound of the present invention has excellent thermal stability, volatility and reactivity, it can be deposited by various deposition methods, and a high density, high purity group 4 transition metal-containing thin film can be prepared at a high deposition rate.

Preferably, in Formula 1 according to an embodiment of the present invention, M is titanium, zirconium or hafnium, R ₁ to R ₆ are independently of each other C ₁ -C ₇ alkyl, and R ₁₁ to R ₁₅ are independently hydrogen or It may be a _{C 1} -C _{7 alkyl.}

In terms of having a high crystalline structure having thermal stability and excellent cohesion, M is more preferably zirconium or hafnium in Formula 1, R ₁ to R ₃ are the same as each other C ₁ -C ₄ alkyl, R ₄ to Like each other, _{R 6 may be C 1} -C ₄ alkyl.

Preferably, Formula 1 according to an embodiment of the present invention may be represented by the following Formula 2.

[Formula 2]

(In Chemical Formula 2,

M is a Group 4 transition metal;

R ₁ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl.)

Preferably in Formula 2 according to an embodiment of the present invention, M is zirconium or hafnium, R ₁ and R ₄ are independently of each other C ₁ -C ₄ alkyl, and R ₁₁ to R ₁₅ are independently hydrogen or C _It may be 1 -C _{4 alkyl.}

_{Preferably, R 1} and R ₄ in Formula 2 according to an embodiment of the present invention are independently of each other methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, s -butyl or t -butylyl I can.

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 structural formula, M is titanium, zirconium, or hafnium.)

In addition, the present invention provides a method for preparing a Group 4 transition metal compound. The method for preparing a Group 4 transition metal compound of the present invention comprises reacting a compound of Formula 3 with a compound of Formula 4, And preparing a group transition metal compound.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4,

M is a Group 4 transition metal;

R ₁ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl;

R ₂₁ to R ₂₆ are each independently C ₁ -C ₁₀ alkyl.

The reaction according to an embodiment of the present invention may be performed at room temperature (10 to 35°C) for 8 to 24 hours.

It may be used in an amount of 2 to 5 moles, preferably 2 to 4 moles, per 1 mole of the compound of Formula 3 according to an embodiment of the present invention.

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

In addition, the reaction according to an embodiment of the present invention may be carried out in an inert gas atmosphere such as nitrogen or argon.

It goes without saying that the Group 4 transition metal compound of Formula 1 according to an embodiment of the present invention can be prepared in a variety of ways possible within the range recognized by those skilled in the art.

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

[Formula 1]

(In Chemical Formula 1,

M is a Group 4 transition metal;

R ₁ to R ₆ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl.)

In one aspect, in Formula 1 according to an embodiment of the present invention, M is titanium, zirconium or hafnium; R ₁ to R ₆ are each independently C ₁ -C ₇ alkyl, and R ₁₁ to R ₁₅ may each independently be hydrogen or C ₁ -C ₇ alkyl.

In another embodiment, in Formula 1 according to an embodiment of the present invention, R ₁ to R ₃ are independently C ₃ -C ₇ alkyl, and R ₄ to R _{6 may be C 1} -C ₄ alkyl independently of each other. have.

In another embodiment, R ₁₁ to R ₁₅ in Formula 1 may be hydrogen independently of each other.

In another embodiment, R ₁ to R ₃ in Formula 1 may be C ₁ -C ₇ alkyl with the _{same substituent, and R 4} to R _{6 may be C 1} -C ₇ alkyl with the same substituent, preferably R ₁ To R ₃ may be C ₃ -C ₇ alkyl with the _{same substituent, and R 4} to R _{6 may be C 1} -C ₄ alkyl with the same substituent.

The composition for depositing a thin film containing a group 4 transition metal according to an embodiment of the present invention can produce a high-quality thin film by using the group 4 transition metal compound of the present invention having extremely improved thermal stability and volatility as a precursor.

The composition for depositing a thin film 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; An alkylamine compound having 2 to 10 carbon atoms; Heterocycloalkyl compounds containing oxygen, nitrogen, and the like; It may further include one solvent selected from, or a mixed solvent of two or more.

As an example, the alkane compound may include hexane, heptane, octane cyclohexane, neopentane, and the like, and the aromatic hydrocarbon compound may include benzene, toluene, xylene, and the like, and the alkylamine compound is dimethylamine, diethyl Amine, ethylmethylamine, triethylamine, tributylamine, tetramethylethylenediamine, and the like.

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

In addition, the composition for depositing a thin film containing a Group 4 transition metal may include 0.1 to 10 moles of the solvent based on 1 mole of the Group 4 transition metal compound. The solvent may be specifically contained in an amount of 0.2 to 5 moles, more specifically 0.5 to 3 moles.

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

For example, when the composition for thin film deposition containing a group 4 transition metal 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.

In the group 4 transition metal-containing thin film deposition composition preferably mixed at the molar ratio described above, the R ₁ to R ₃ of the Group 4 transition metal compound are pulverized alkyl (for example, C 3-7 alkyl), more It is possible to implement a low viscosity, and it is possible to manufacture a high-density thin film having excellent step coverage and crystallinity.

In addition, the present invention provides a method of manufacturing a group 4 transition metal-containing thin film using the composition for depositing a group 4 transition metal-containing thin film of the present invention.

The Group 4 transition metal-containing thin film according to an embodiment of the present invention can be any known method that can be recognized by those skilled in the art, but examples include 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.

For example, the group 4 transition metal-containing thin film prepared by the above deposition method is a titanium oxide thin film, a zirconium oxide thin film, a hafnium oxide thin film, a titanium oxynitride thin film, a zirconium oxynitride thin film, a hafnium oxynitride thin film, or a group 4 transition metal-containing composite. It may be an oxynitride thin film.

As an example, the substrate used for the group 4 transition metal-containing thin film in one embodiment of the present invention is not limited as long as it is a conventional substrate, and non-limiting examples thereof include Ru, TiN, Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP, a substrate containing at least one semiconductor material, a silicon on insulator (SOI) substrate, a rigid substrate such as a quartz substrate or a glass substrate for a display, or a 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.

The method of manufacturing a group 4 transition metal-containing thin film through the composition for depositing a group 4 transition metal according to an embodiment of the present invention is specifically, performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). I can.

As a specific example, a method of manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention includes the steps of maintaining a temperature of a substrate mounted in a chamber at 80 to 400°C; And supplying energy to the substrate.

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

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

In the method of manufacturing a thin film containing a group 4 transition metal according to an embodiment of the present invention, a deposition source derived from the composition for depositing a thin film containing a group 4 transition metal at the temperature of the substrate may be provided. In this case, the deposition source may be provided with an additional reaction gas.

The reaction gases used in the method for manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention are oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), carbon dioxide (CO ₂ ), and water. , Oxygen plasma, ozone plasma, water plasma, and the like may be one or two or more mixed gases selected from.

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

In addition, each step of the method of manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention may further include a purge step.

For example, the purge gas in the purge step is not limited as long as it is a conventional one that 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 and the like.

For example, the deposition source and 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.

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

The group 4 transition metal-containing thin film manufactured according to the method of manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention is a high dielectric thin film material having a high density and 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, the high dielectric constant thin film material having a high density and high dielectric constant is easily supplied through an ALD process or a CVD process, and thus the wiring of a semiconductor device, It can be used in various ways to form a gate insulating film of a transistor, a dielectric film of a capacitor, or a coating film of an electronic component.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various 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 a Schlenk line, and the structural analysis of the obtained title compound was ¹ H and ¹³ C NMR. It was measured through spectrum (Bruker Advance 400 NMR) and elemental analysis (Thermo Scientific Flash 2000). 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 10°C/min.

[Example 1] Preparation of Zr(Cp)(edpa) ₃

Tris(dimethylamino)cyclopentadienylzirconium (0.50g, 1.73mmol) was dissolved in 100 mL of n-hexane, and then N-ethoxy-2,2-dimethylpropanamide (edpaH) (0.75 g, 5.20 mmol) was added dropwise. After stirring at room temperature for 12 hours, n-hexane was removed under reduced pressure. Purification by distillation (150° C./300 mtorr) gave about 0.75 g (74%) of the title compound as a pale yellow liquid.

¹ H NMR (C ₆ D ₆ , 400 MHz): δ 1.14 (t, 3H, C H ₃ ), 1.27 (s, 18H, 2CC H ₃ ), 1.29 (t, 6H, 2C H ₃ ), 1.30 (s , 9H, CC H ₃ ), 4.01-4.06 (q, 2H, C H ₂ ), 4.19-4.22 (m, 4H, 2C H ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 14.57, 14.98, 27.98, 28.15, 35.11, 35.31, 69.51, 70.28, 114.53, 171.07, 171.73

Anal. Calc. for C ₂₇ H ₅₀ N ₃ O ₆ Zr: C, 50.03; H, 8.04; N, 7.14%. Found: C, 52.79; H, 8.13; N, 7.00%.

In FIG. 1, as a result of TG analysis of Zr(Cp)(edpa) ₃ prepared in Example 1, a mass decrease began to occur around 120°C, and a mass of 95% or more decreased at about 240°C. From this, it can be seen that the thermal stability _{of Zr(Cp)(edpa) 3, which} is the compound of Example 1 of the present invention, is high.

[Example 2] Preparation of Hf(cp)(edpa) ₃

Tris(dimethylamino)cyclopentadienylhafnium (1.00 g, 2.66 mmol) was dissolved in 150 mL of hexane, and then N-ethoxy-2,2-dimethylpropanamide (edpaH) (1.16 g, 7.98 mmol) was added dropwise. After stirring at room temperature for 12 hours, hexane was removed under reduced pressure. Purification by distillation (180° C./300 mtorr) gave about 1.2 g (67 %) of the title compound as a pale yellow liquid.

¹ H NMR (C ₆ D ₆ , 400 MHz): δ 1.13 (t, 3H, C H ₃ ), 1.28 (s, 18H, 2CC H ₃ ), 1.28 (t, 6H, 2C H ₃ ), 1.30 (s , 9H, CC H ₃ ), 4.02-4.07 (q, 2H, C H ₂ ), 4.17-4.22 (m, 4H, 2C H ₂ ).

¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 14.49, 14.97, 27.92, 28.09, 35.13, 35.32, 69.52, 70.33, 112.84, 171.31, 171.72

Anal. Calc. for C ₂₇ H ₅₀ N ₃ O ₆ Hf: C, 46.92; H, 7.29; N, 6.08%. Found: C, 46.04; H, 7.09; N, 5.95%.

In FIG. 2, as a result of TG analysis of Hf(Cp)(edpa) ₃ prepared in Example 1, a mass decrease began to occur around 110°C, and a mass of 95% or more decreased at about 250°C. From this, it can be seen that the compound prepared in Example 2 of the present invention also has high thermal stability.

[Example 3] Preparation of Hf oxide thin film using Hf(cp)(edpa) ₃

A hafnium oxide thin film was prepared on a silicon substrate by atomic layer deposition. The silicon substrate was maintained at 300°C, and the Hf(cp)(edpa) ₃ precursor synthesized in Example 2 was filled in a stainless steel bubbler container and maintained at 110°C. First, the Hf(cp)(edpa) ₃ precursor vaporized in a stainless steel bubbler container is supplied to the silicon substrate using argon gas (50 sccm) as a transfer gas, but the supply time is increased from 1 second to 7 seconds. The deposition rate of was measured and shown in FIG. 3.

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 and shown in FIG. 3.

As shown in FIG. 3, in the case of the Hf(cp)(edpa) ₃ precursor, even if the supply time of the Hf(cp)(edpa) ₃ precursor increases after 5 seconds, the thin film deposition rate remains constant. After 5 seconds, the Hf It can be seen that the (cp)(edpa) ₃ precursor is included in the substrate, and the H ₂ O reaction gas is saturated after 3 seconds as the thickness of the thin film is constant after 3 seconds. From this, the supply time of the Hf(cp)(edpa) ₃ precursor was set to 5 seconds, and _{the supply time of H 2} O was set to 3 seconds.

[Example 4] Preparation of Hf oxide thin film using Hf(cp)(edpa) ₃

In Example 3, the supply time of the Hf(cp)(edpa) ₃ precursor was 5 seconds, and the supply time of H ₂ O was 3 seconds, and then reaction by-products and residual reaction gas were removed for about 10 seconds using argon gas (1000 sccm). Removed. Using the above process as one cycle, 100 cycles were repeated to form a hafnium oxide thin film, and the results are shown in FIG. 4.

Similarly, in the same manner as in Example 3, but repeated 300 cycles to form a hafnium oxide thin film, and the results are shown in FIG.

As shown in FIG. 4, it was confirmed that the thickness of the thin film linearly increased as the deposition cycle increased, and the deposition rate was about 0.9 Å/cycle.

In addition, XPS analysis results of the hafnium oxide thin film deposited in Example 4 are shown in FIG. 5. As a result of checking the peaks of Hf 4f _7/2 and 4f _5/2 of FIG. 5 and the peaks from O1s, it can be seen that the binding energy of Hf-O is shown in the hafnium oxide thin film. In addition, as there is no peak in C1s, it can be seen that the purity of the hafnium oxide thin film is excellent because there is almost no carbon as an impurity in the hafnium oxide thin film.

The hafnium oxide thin film deposited in Example 4 was analyzed by XRF. As a result, Hf was present in the thin film, indicating that a hafnium oxide thin film was prepared.

Those of ordinary skill in the art that the present invention is not limited by the above-described embodiments, and that various substitutions, modifications and changes are possible within the scope of the technical spirit of the present invention. It will be clear to you.

Claims (9)

1. Group 4 transition metal compound represented by the following formula (1):

   [Formula 1]

   

   In Formula 1,

   M is a Group 4 transition metal;

   R ₁ to R ₆ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

   R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl.
2. The method of claim 1,

   In Formula 1,

   M is titanium, zirconium or hafnium;

   R ₁ to R ₆ are each independently C ₁ -C ₇ alkyl;

   R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₇ alkyl.
3. The method of claim 2,

   M is zirconium or hafnium;

   R ₁ to R ₃ are the same as each other C ₁ -C ₄ alkyl;

   R ₄ to R ₆ are the same as each other C ₁ -C ₄ Alkyl Group 4 transition metal compound.
4. The method of claim 1,

   Group 4 transition metal compound selected from the following structures.

   

   

   

   

   (In the above structural formula, M is titanium, zirconium, or hafnium.)
5. A method for preparing a Group 4 transition metal compound comprising the step of preparing a Group 4 transition metal compound represented by the following Formula 2 by reacting the compound of Formula 3 and the compound of Formula 4 below.

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   In Formulas 2 to 4,

   M is a Group 4 transition metal;

   R ₁ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

   R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl;

   R ₂₁ to R ₂₆ are each independently C ₁ -C ₁₀ alkyl.
6. A composition for thin film deposition containing a Group 4 transition metal comprising a Group 4 transition metal compound represented by the following Formula 1:

   [Formula 1]

   

   In Formula 1,

   M is a Group 4 transition metal;

   R ₁ to R ₆ are independently of each other C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl;

   R ₁₁ to R ₁₅ are each independently hydrogen or C ₁ -C ₁₀ alkyl.
7. The method of claim 6,

   In Formula 1,

   M is titanium, zirconium or hafnium;

   R ₁ to R ₆ are each independently C ₁ -C ₇ alkyl;

   R ₁₁ to R ₁₅ are each independently hydrogen or a C ₁ -C ₇ alkyl group 4 transition metal-containing thin film deposition composition.
8. The method of claim 7,

   M is zirconium or hafnium;

   R ₁ to R ₃ are the same as each other C ₁ -C ₄ alkyl;

   R ₄ to R ₆ are the same as each other C ₁ -C ₄ Alkyl Group 4 transition metal-containing thin film deposition composition.
9. A method for producing a group 4 transition metal-containing thin film comprising the step of preparing a group 4 transition metal-containing thin film using the composition for depositing a group 4 transition metal-containing thin film according to any one of claims 6 to 8.

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