KR20080101040A - Organometallic precursors for deposition of metal or ceramic thin films, and deposition process of the thin films - Google Patents

Abstract

An organometallic precursors for deposition of metal or ceramic thin films, and deposition process of the thin films in which volatility is high and existing as the liquid state in the room temperature and is stabilized are provided. Moreover, the metallic foil or the ceramic thin film can be formed through the metal organic chemical vapor deposition or the method for atomic layer deposition by using the organometallic precursor compound. A metallic foil or the ceramic thin film deposition organometallic precursor compound in which the organometallic precursor compound that is used to deposit the ceramic thin film like the metallic foil or the metal oxide or the metal-nitride (Metal nitride) is defined as below chemical formula 1. In the chemical formula 1, M is selected between 4A family or the metal element belonging to 4B family and M on the periodic table, the trial kill silyl which R1 or R4 is independently expressed as the alkyl group of 4 through the hydrogen or the carbon number 1, and -SiR6R7R8 (trialkylsilyl).

Description

Organometallic precursors for deposition of metal or ceramic thin films, and deposition process of the thin films}

FIG. 1 shows Examples 1 ( ^Me CpHf (NEtMe) ₃ ), Example 2 ( ^Et CpHf (NEtMe) ₃ ), Example 7 ( ^Me CpHf (O ⁱ Pr) ₃ ), Example 8 ( ^Et CpHf) TG graphs of hafnium precursor compounds prepared in (O ⁱ Pr) ₃ ) and TEMAHf (Hf (NEtMe) ₄ ) for comparison with them are shown.

FIG. 2 shows Examples 3 ( ^Me CpZr (NEtMe) ₃ ), Example 4 ( ^Et CpZr (NEtMe) ₃ ), Example 9 ( ^Me CpZr (O ⁱ Pr) ₃ ), Example 10 ( ^Et CpZr ^{) of the present} invention. TG graphs of zirconium precursor compounds prepared in (O ⁱ Pr) ₃ ) and TEMAZr (Zr (NEtMe) ₄ ) for comparison with them are shown.

FIG. 3 shows Examples 5 ( ^Me CpTi (NEtMe) ₃ ), Example 6 ( ^Et CpTi (NEtMe) ₃ ), Example 11 ( ^Me CpTi (O ⁱ Pr) ₃ ), Example 12 ( ^Et CpTi) TG graphs of titanium precursor compounds prepared in (O ⁱ Pr) ₃ ), Example 15 ( ^Me CpTi (OEt) ₃ ) and TEMATi (Ti (NEtMe) ₄ ) for comparison with them.

4 is a graph showing the change in thickness of the thin film according to the number of ALD cycles when hafnium oxide thin film deposition using the ALD process performed by Experimental Example 2.

FIG. 5 shows the results of Auger analysis of hafnium oxide having 50 ALD cycles performed by Experimental Example 2 and the temperature of the substrate deposited at 430 ° C. FIG.

6 is a zirconium oxide thin film electron scanning microscope (SEM) analysis deposited at 300 ° C carried out by Experimental Example 3.

7 is a zirconium oxide thin film electron scanning microscope (SEM) analysis deposited at 400 ° C carried out by Experimental Example 3.

8 is a zirconium oxide thin film electron scanning microscope (SEM) photograph deposited at 500 ° C carried out by Experimental Example 3.

9 is a graph showing the zirconium oxide thin film X-ray diffraction (XRD) analysis results deposited at 300 ° C, 400 ° C and 500 ° C carried out by Experimental Example 3.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic metal precursor compound for depositing a metal thin film applied to a semiconductor device or a ceramic thin film such as metal oxide or metal nitride, and more particularly, Atomic Layer Deposition (ALD) or organic metal chemical vapor deposition. The present invention relates to an organic metal precursor compound used to deposit a metal thin film or a ceramic thin film through Metal Organic Chemical Vapor Deposition (MOCVD) and a method of depositing a thin film using the same.

In recent years, remarkable developments in electronic products such as computers, digital TVs, wireless mobile communications, and the like have been made through super integration, miniaturization, low power, high capacity, and high performance of electronic devices. The technological development of these electronic devices is centered on the continuous miniaturization of metal-oxide-semiconductor devices based on metal-oxide-semiconductor field effect transistors (MOSFETs). Miniaturization of MOS devices is accompanied by a reduction in the area and thickness of the oxide, the gate dielectric material. The decrease in the area of the gate dielectric layer causes a decrease in the gate capacitance, and the decrease in thickness increases the charge capacity, but at the same time increases the leakage current, causing device degradation and reducing power consumption. Increase.

The gate dielectric material of the MOS device uses SiO ₂ and has been continuously reduced at 100 nm thickness 30 years ago. In general, however, the physical thickness limit of SiO ₂ in which direct quantum mechanical tunneling occurs is known to be 1.5 to 2 nm, and below this, the leakage current due to the tunneling effect causes further decrease in the dielectric film thickness of the MOS device. It becomes impossible. In addition, the high concentration of boron on the gate electrode poly-Si (poly-Si) is diffused to the gate channel doped with a low concentration of boron at a dielectric film thickness of 2 nm or less, thereby reducing the reliability of the device. Cause. Therefore, attention has been focused on high-k materials that can realize thicker dielectric thin films having an equivalent oxide thickness (EOT) electrically but without physically tunneling. As next-generation high-k materials, attention is focused on metal oxides such as TiO ₂ , ZrO ₂ , HfO ₂ , STO (SrTiO ₃ ), BST ((Ba, Sr) TiO ₃ ), and HfSiO _x , ZrSiO _x .

Metal nitride films, on the other hand, have interesting properties such as excellent hardness, high melting point, and resistance to organic solvents or acids. In particular, titanium nitride (TiN) is used as a diffusion barrier to prevent the diffusion of metal aluminum (Al) and copper (copper) into the silicon substrate used in the semiconductor industry. Recently, research as a diffusion barrier for tri-element nitrides such as zirconium nitride (ZrN), hafnium nitride (HfN) and TaSiN has been conducted.

In order to apply these metal oxides and metal nitrides as thin films of next-generation electronic devices that are extremely miniaturized, they are excellent in a structure having a high step ratio of contacts or vias that constitute a dynamic random access memory (DRAM). Application of organometallic chemical vapor deposition or atomic layer deposition, which can realize step coverage, becomes essential. Accordingly, researches for developing precursors suitable for each deposition process have been intensively conducted.

As a precursor for depositing metal thin films or ceramic thin films such as metal oxides and metal nitrides by organometallic chemical vapor deposition or atomic layer deposition, the most representative of them is metal tetrachloride (MCl ₄ ), a metal halide-based compound. Ti, Zr, Hf)). Although TiCl ₄ , a chemical vapor deposition precursor of a typical titanium nitride (TiN) thin film, is a liquid compound having a high vapor pressure at room temperature, it is reported that there is a problem of chloride contamination in the deposited thin film. In addition, ZrCl ₄ and HfCl ₄ are compounds with low vapor pressure at room temperature, which are difficult to apply to semiconductor mass production process due to low thin film deposition rate, and also have problems with chloride contamination.

A study of depositing a thin film using an organometallic chemical vapor deposition method using a precursor compound having a beta dichitonate (β-diketonate) as a ligand (M (β-diketonate) ₄ ; M = Ti, Zr, Hf)) as another precursor compound Has been going on. However, these compounds are also known to be low vapor pressure solid precursors at room temperature and serious carbon contamination in the final oxide thin film. In addition, tfac (1,1,1-trifluoropentane-2,4-dionate) and hfac (hexafluoropentane-2,4) in which a hydrogen portion of the beta dichitonate ligand is substituted with a fluorine group to improve the low volatility of the beta dichitonate compounds. Although thin films were deposited using precursors incorporating -dione) as ligands, they are all known to cause fluorine contamination in the thin films.

In addition, Anthony C. Jones et al. Modified the alkoxide ligand in US Patent Application Publication No. US 2005/0008781 to introduce a ligand of the OCR ¹ (R ² ) CH ₂ X (X = OR, NR ₂ ) form at room temperature M (OCR ¹ (R ² ) CH ₂ X) ₄ (M = Ti, Zr, Hf) and M (OR) ₂ (OCR ¹ (R ² ) CH ₂ X) ₂ (M = Ti, Zr, Hf) form precursors have been reported. In addition, Timothy J. Leedham et al. Reported a precursor synthesis in the form of Zr (OR) _x (b-diketonate) _y in which alkoxide ligand and beta diketonate ligand were mixed in US Pat. No. 6,383,669. Hyun-Kook Shin of KP Chemical reported the deposition of Ti precursor in Ti (β-diketonate) ₂ (O (CHR ¹ ) _l (CR ⁴ R ⁵ ) _m -OR ⁶ ) ₂ form and oxide thin film deposition using Korean Patent No. 38188. . However, these modified alkoxides or beta-dikytonate precursors have excellent thermal stability but low volatility, which is difficult to apply by direct vaporization, and is expected to be used in liquid delivery, which is a method of transporting and depositing dissolved in a solvent. Have

On the other hand, unlike the aforementioned compound, a metal in the form of M (NR ¹ R ² ) ₄ (M = Ti, Zr, Hf; R ¹ and R ² = methyl or ethyl group) having a dialkylamino group as a ligand- Metal oxide or metal nitride thin film deposition using amide as a precursor is most widely used. The metal-amide precursor may be a high vapor pressure liquid compound (M (NEt ₂ ) ₄ , M (NEtMe) ₄ ) or a low melting point volatile solid compound (Zr (NMe ₂ ) ₄ , mp: 57-60 ° C .; Hf ( NMe ₂ ) ₄ , mp: 26 ~ 29 ℃), and very reactive to ammonia used as a reaction gas for metal nitride thin film deposition as well as water vapor, oxygen, ozone used as a reaction gas for metal oxide thin film deposition. Fast metal oxides (MO ₂ ; M = Ti, Zr, Hf), composite metal oxides (MSiOx; M = Zr, Hf) and metal nitrides (MN; M = Ti, Zr, Hf) It is attracting attention as a precursor for thin film deposition.

However, these metal-amide compound precursors are reported to cause decomposition and to cause particle contamination during the process due to poor thermal stability during long time heating for vaporization of the compound in the thin film deposition process conditions. In addition, since the thermal stability of the compound is weak, the deposition process temperature is narrow (up to 280 ° C.), which makes it difficult to deposit a high-density oxide film. In addition, carbon contamination has been reported to be somewhat higher, especially during metal-nitride deposition, due to poor thermal stability (Journal of Materials Chemistry, 2004, 14, 3101-3112). In particular, in order to be applied as a gate dielectric material in the flash memory field as well as a DRAM process of 50 nm or less, a higher dielectric constant and a higher density oxide thin film are required to minimize leakage current, and thus a wider process. There is a need for a metal thin film by atomic layer deposition or a precursor capable of depositing a ceramic thin film such as a metal oxide or a metal nitride at a temperature (250 to 450 ° C.).

Accordingly, an object of the present invention is to solve the problems of the precursors mentioned in the prior art, to provide an organic metal precursor compound for depositing a metal thin film or ceramic thin film that is thermally stable, high in volatility, and exists in a liquid state at room temperature. There is this.

In addition, another object of the present invention is to provide a thin film deposition method for forming a metal thin film or a ceramic thin film using an organometallic chemical vapor deposition method or an atomic layer deposition method using the above-described organometallic precursor compound.

In order to achieve the above object, the present invention is defined by the following Chemical Formula 1 as an organometallic precursor compound used to deposit a metal thin film or a ceramic thin film such as metal oxide or metal nitride applied to a semiconductor device. It provides an organometallic compound.

In Formula 1, M is selected from metal elements belonging to group 4A or 4B on the periodic table, and R ¹ to R ⁴ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, -SiR ⁶ R ⁷ R ⁸ It is selected from trialkylsilyl represented by (trialkylsilyl), an alkoxy group (alkoxy) represented by -OR ⁶ , a dialkylamino group represented by -NR ⁶ R ⁷ , R ⁵ is an alkyl group having 1 to 4 carbon atoms ( alkyl), a trialkylsilyl group represented by -SiR ⁶ R ⁷ R ⁸ , an alkoxy group represented by -OR ^6, and a dialkylamino group represented by -NR ⁶ R ⁷ . . In addition, L ¹ to L ³ are each independently alkoxy represented by -OR ⁶ , trialkylsiloxy represented by -OSiR ⁶ R ⁷ R ⁸ , and die represented by -NR ⁶ R ⁷ . Bis (trialkylsilyl) amino group represented by dialkylamino, -N (SiR ⁶ R ⁷ R ⁸ ) ₂ , bis (trialkylsilyl) amino group, represented by -N (SiR ⁶ R ⁷ R ⁸ ) R ⁹ N, N-alkyl, trialkylsilylamino group (N, N-alkyl, trialkylsilylamino) is selected from. R ⁶ to R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms.

Furthermore, the present invention is a thin film deposition method characterized in that the thin film is formed by atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD) using the precursor compound of the present invention described above. To provide.

Hereinafter, the organometallic precursor compound for depositing the metal thin film or the ceramic thin film and the deposition method using the same according to the present invention will be described in more detail.

The present invention provides an organometallic compound defined by Chemical Formula 1 as an organometallic precursor compound used for depositing a metal thin film applied to a semiconductor device or a ceramic thin film such as metal oxide or metal nitride. .

<Formula 1>

In Formula 1, M is selected from metal elements belonging to group 4A or 4B on the periodic table, and R ¹ to R ⁴ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, -SiR ⁶ R ⁷ R ⁸ It is selected from trialkylsilyl represented by (trialkylsilyl), an alkoxy group (alkoxy) represented by -OR ⁶ , a dialkylamino group represented by -NR ⁶ R ⁷ , R ⁵ is an alkyl group having 1 to 4 carbon atoms ( alkyl), a trialkylsilyl group represented by -SiR ⁶ R ⁷ R ⁸ , an alkoxy group represented by -OR ^6, and a dialkylamino group represented by -NR ⁶ R ⁷ . . L ¹ to L ³ are each independently alkoxy represented by -OR ⁶ , trialkylsiloxy represented by -OSiR ⁶ R ⁷ R ⁸ , and die represented by -NR ⁶ R ⁷ . Bis (trialkylsilyl) amino group represented by dialkylamino, -N (SiR ⁶ R ⁷ R ⁸ ) ₂ , bis (trialkylsilyl) amino group, represented by -N (SiR ⁶ R ⁷ R ⁸ ) R ⁹ N, N-alkyl, trialkylsilylamino group (N, N-alkyl, trialkylsilylamino) is selected from. R ⁶ to R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms.

The organometallic precursor compound of the present invention represented by Chemical Formula 1 is an ideal chemical vapor deposition or primary layer that can improve the thermal stability by introducing a cyclopentadienyl-based ligand that can be strongly bonded to the metal ion to solve the problems of the prior art It is a precursor for vapor deposition.

Among the organometallic precursor compounds represented by Chemical Formula 1, L ¹ , L ² , and L ³ which are combined with metal M in order to have high volatility in order to easily apply a metal thin film or a ceramic thin film to chemical vapor deposition without impurity contamination, respectively Preference is given to organometallic precursor compounds represented by the formula (2) below -NR ⁶ R ⁷ .

In Formula 2, M and R ¹ to R ⁵ are as defined in Formula 1, and R ⁶ and R ⁷ each represent an alkyl group having 1 to 4 carbon atoms.

Among the organometallic precursor compounds of Formula 2, M is selected from Hf, Zr or Ti, and more preferably an organometallic precursor compound of Formula 3 below wherein R ¹ to R ⁵ are each represented by R ¹⁰ to R ¹⁴ .

In Formula 3, M 'is selected from Hf, Zr or Ti, R ⁶ and R ⁷ are the same as or different from each other, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ to R ¹³ are the same as or different from each other hydrogen or An alkyl group having 1 to 4 carbon atoms, and R ¹⁴ is an alkyl group having 1 to 4 carbon atoms.

Among the organometallic precursor compounds of Formula 3, R ¹⁰ to R ¹³ are hydrogen, and organometallic precursor compounds represented by the following Formula 4 are preferable.

In Formula 4, M 'is selected from Hf, Zr or Ti, R ⁶ and R ⁷ are the same as or different from each other, an alkyl group having 1 to 4 carbon atoms, R ¹⁴ is an alkyl group having 1 to 4 carbon atoms.

Among the organometallic precursor compounds of Formula 4, an organometallic precursor compound represented by the following Formula 5 wherein R ¹⁴ is a methyl group is preferable.

In Formula 5, M 'is selected from Hf, Zr or Ti, and R ⁶ and R ⁷ are each an alkyl group having 1 to 4 carbon atoms.

Among the organometallic precursor compounds of Formula 5, R ⁶ and R ⁷ are more preferably organometallic precursor compounds represented by the following Formula 6 selected from methyl or ethyl groups.

In Formula 6, M ′ is selected from Hf, Zr, or Ti, and R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

In the organometallic precursor compound of Formula 6, M 'is hafnium, an organometallic precursor compound represented by Formula 7 below, M' is zirconium, an organometallic precursor compound represented by Formula 8 below, or M 'is titanium The organometallic precursor compound represented by is preferable.

In Formula 7, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

R ¹⁵ and R ¹⁶ in Formula 8 are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

In Formula 9, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

More preferably, compounds represented by the following Chemical Formulas 10 to 12 in which the R ¹⁵ and R ¹⁶ are methyl groups and ethyl groups in the organometallic precursor compounds of Formulas 7 to 9 are preferable.

In addition, an organometallic precursor compound represented by the following Chemical Formula 14, wherein R ¹⁴ is an ethyl group, is preferable.

In Formula 13, M 'is selected from Hf, Zr or Ti, and R ⁶ and R ⁷ are each an alkyl group having 1 to 4 carbon atoms.

Among the organometallic precursor compounds of Formula 13, R ⁶ and R ⁷ are more preferably organometallic precursor compounds represented by the following Formula 14 selected from methyl or ethyl groups.

In Formula 14, M ′ is selected from Hf, Zr, or Ti, and R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

In the organometallic precursor compound of Formula 14, M 'is hafnium, an organometallic precursor compound represented by Formula 15, M' is zirconium, an organometallic precursor compound represented by Formula 16, or M 'is titanium. The organometallic precursor compound represented by is preferable.

In Formula 15, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

In Formula 16, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

In Formula 17, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ).

More preferably, in the organometallic precursor compounds of Formula 15 to Formula 17, compounds represented by the following Formulas 18 to 20, wherein R ¹⁵ and R ¹⁶ are methyl groups and ethyl groups, respectively, are preferable.

According to the present invention, a highly volatile metal thin film or a ceramic thin film such as metal oxide or metal nitride among the organometallic precursor compounds represented by Chemical Formula 1 can be easily applied to chemical vapor deposition without impurity contamination. The organometallic precursor compound represented by the following general formula (21) in which L ¹ , L ² , and L ³ bonded to the metal M are each -OR ⁶ in order to have a moiety is preferable.

M and R ¹ to R ⁵ in Chemical Formula 21 are as defined in Chemical Formula 1, and R ⁶ is an alkyl group having 1 to 4 carbon atoms.

Among the organometallic precursor compounds of Formula 21, M is selected from Hf, Zr or Ti, and R ¹ to R ⁵ are each preferably represented by R ¹⁰ to R ¹⁴ , preferably the organometallic precursor compound of Formula 22.

In Formula 22, M 'is selected from Hf, Zr or Ti, R ⁶ is an alkyl group having 1 to 4 carbon atoms, R ¹⁰ to R ¹³ are each independently hydrogen (H) or an alkyl group having 1 to 4 carbon atoms, R ¹⁴ is a C1-C4 alkyl group.

Among the organometallic precursor compounds of Formula 22, a precursor compound represented by the following Formula 23 wherein R ¹⁰ to R ¹³ is hydrogen is preferable.

In Formula 23, M 'is selected from Hf, Zr or Ti, and R ⁶ and R ¹⁴ are the same as or different from each other, and represent an alkyl group having 1 to 4 carbon atoms.

Preferably, the organometallic precursor compound represented by the following Chemical Formula 24, wherein R ¹⁴ is a methyl group, is preferable.

In Formula 24, M 'is selected from Hf, Zr or Ti, and R ⁶ represents an alkyl group having 1 to 4 carbon atoms.

Preferably, the organometallic precursor compound represented by the following Chemical Formula 25, wherein M 'is hafnium, is preferable.

In Formula 25, R ⁶ represents an alkyl group having 1 to 4 carbon atoms.

More preferably expression is to the R ⁶ is a methyl group in the organometallic precursor compound of the formula 25 to the compounds, R ⁶ is represented by the formula 26 group compound represented by the formula 27, R ⁶ in the formula 28 due isopropyl The compound which becomes is good.

In addition, the organometallic precursor compound represented by the following Chemical Formula 29 wherein M 'is zirconium in the organometallic precursor compound of Chemical Formula 24 is preferable.

In Formula 29, R ⁶ represents an alkyl group having 1 to 4 carbon atoms.

And more preferably represent this in the R ⁶ group in the organometallic precursor compound of the formula (29) compound represented by the general formula 30, a compound that R ⁶ is represented by the following general formula 31 group, R ⁶ in the general formula 32 have originated isopropyl The compound which becomes is good.

In addition, the organometallic precursor compound represented by the following Chemical Formula 33 in which M 'is titanium in the organometallic precursor compound of Chemical Formula 24 is preferable.

In Formula 33, R ⁶ represents an alkyl group having 1 to 4 carbon atoms.

More preferably, in the organometallic precursor compound of Formula 33, a compound represented by the following Formula 34 wherein R ⁶ is a methyl group, a compound represented by the following Formula 35 wherein R ⁶ is an ethyl group, and R ⁶ is an isopropyl group represented by the following Formula 36: The compound which becomes is good.

In addition, the organometallic precursor compound represented by the following Chemical Formula 37 wherein R ¹⁴ is an ethyl group among the organometallic precursor compounds represented by Chemical Formula 23 is preferable.

In Formula 37, M 'is selected from Hf, Zr or Ti, and R ⁶ represents an alkyl group having 1 to 4 carbon atoms.

Preferably, the organometallic precursor compound represented by the following Chemical Formula 38, wherein M 'is hafnium, is preferable.

R ⁶ in Formula 38 represents an alkyl group having 1 to 4 carbon atoms.

More preferably, in the organometallic precursor compound of Formula 38, a compound represented by the following Formula 39 wherein R ⁶ is a methyl group, a compound represented by the following Formula 40 wherein R ⁶ is an ethyl group, and R ⁶ is an isopropyl group represented by the following Formula 41: The compound which becomes is good.

In addition, the organometallic precursor compound represented by the following Chemical Formula 42 wherein M 'is zirconium in the organometallic precursor compound of Chemical Formula 37 is preferable.

R ⁶ in Formula 42 represents an alkyl group having 1 to 4 carbon atoms.

And more preferably represent this in the R ⁶ group in the organometallic precursor compound of the formula 42 compound represented by General Formula 43, a compound that R ⁶ is represented by the following general formula 44 group, R ⁶ in the formula 45 due isopropyl The compound which becomes is good.

In addition, in the organometallic precursor compound of Formula 37, an organometallic precursor compound represented by the following Formula 46, wherein M 'is titanium, is preferable.

R ⁶ in Formula 46 represents an alkyl group having 1 to 4 carbon atoms.

More preferably, in the organometallic precursor compound of Formula 46, a compound represented by the following Formula 47 wherein R ⁶ is a methyl group, a compound represented by the following Formula 48 wherein R ⁶ is an ethyl group, and R ⁶ is an isopropyl group represented by the following Formula 49: The compound which becomes is good.

The above-described organometallic precursor compound for metal thin film or ceramic thin film deposition represented by Chemical Formula 1 according to the present invention may be prepared by various methods.

First, as shown in the following Scheme 1, the cyclopentadiene-based compound is added to the tetraligand metal compound at a low temperature in a non-polar solvent at low temperature, and then subjected to reflux exchange reaction, followed by easy distillation under reduced pressure.

In Scheme 1, M and R ¹ to R ⁵ , L ¹ to L ³ are the same as defined in Formula 1, and L ⁴ is the alkoxy represented by -OR ⁶ , represented by -OSiR ⁶ R ⁷ R ⁸ . Trialkylsiloxy, a dialkylamino group represented by -NR ⁶ R ⁷ , and a bis (trialkylsilyl) amino group represented by -N (SiR ⁶ R ⁷ R ⁸ ) ₂ N, N-alkyl, trialkylsilylamino group (N, N-alkyl, trialkylsilylamino) represented by amino) or -N (SiR ⁶ R ⁷ R ⁸ ) R ⁹ .

In addition, as shown in Scheme 2, tetrachloride metal (MCl ₄ ) can be easily prepared in a solvent as a starting material. As the solvent, diethyl ether, tetrahydrofuran or toluene having weak polarity may be used.

In Reaction Scheme 2, M and R ¹ to R ⁵ , L ¹ to L ³ are as defined in Formula 1, and AM means lithium (Li) or sodium (Na) metal cation.

More specifically, the manufacturing method of the organic metal precursor compound for metal thin film or ceramic thin film deposition according to the present invention is as follows.

The precursor compound of Formula 3 described above is a cyclopentadiene compound (R ¹⁰ R ¹¹ R) in a tetrakis (dialkylamino) metal (M (NR ⁶ R ⁷ ) ₄ ) compound solution in a non-polar solvent as shown in Scheme 3 below. ¹² R ¹³ C ¹⁴ C ₅ ) It can be obtained by the distillation under reduced pressure after the reflux stirring reaction after addition at low temperature. In this case, benzene, hexane, toluene, or the like may be used as the nonpolar solvent. At this time, in order to effectively remove the secondary amine HNR ⁶ R ⁷ which is a product during the reflux reaction and to inhibit the decomposition reaction by moisture or oxygen during the reaction, the reaction is carried out under nitrogen (N ₂ ) or argon (Ar) stream. desirable.

In Scheme 3, M 'is selected from Hf, Zr or Ti, R ⁶ and R ⁷ are the same as or different from each other, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ to R ¹³ are the same as or different from each other hydrogen or An alkyl group having 1 to 4 carbon atoms, and R ¹⁴ is an alkyl group having 1 to 4 carbon atoms.

The precursor compound of Chemical Formula 3 described above may be prepared by using a metal-tetrachloride compound as a starting material, as shown in Scheme 4, in addition to the preparation method according to Scheme 3.

M 'in Scheme 4 is selected from Hf, Zr or Ti, R ⁶ And R ⁷ are the same as or different from each other, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ to R ¹³ are the same as or different from each other, hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ is an alkyl group having 1 to 4 carbon atoms .

In Scheme 4, AM means lithium (Li) or sodium (Na) metal cation, and AM (R ¹⁰ R ¹¹ R ¹² R ¹³ C ¹⁴ C ₅ ) and AM (NR ² R ³ ) are each normal butyllithium (n use alkyllithium such as butyllithium or methyllithium, metal hydrides such as lithium hydride (LiH) or sodium hydride (NaH), or metals such as lithium (Li) or sodium (Na) By reacting with weakly polar diethylether, tetrahydrofuran or toluene solvents in HR ¹⁰ R ¹¹ R ¹² R ¹³ C ¹⁴ C ₅ or secondary amine HNR ⁶ R ⁷ You can get it.

Likewise, in order to prepare the precursor compound of Chemical Formula 22, a metal-tetrachloride compound may be prepared as a starting material as in Scheme 5 below.

In Scheme 5, AM (R ¹⁰ R ¹¹ R ¹² R ¹³ C ¹⁴ C ₅ ) is as described above, and AM (OR ⁶ ) is alkyl lithium, such as normal butyllithium (n-butyllithium) or methyllithium (methyllithium), respectively. Diethyl ether, tetrahydrofuran or toluene solvents with weak polarity or metal hydrides such as lithium hydride (LiH) or sodium hydride (NaH), or metals such as lithium (Li) or sodium (Na) Under reaction with primary alcohol HOR ⁶ .

The precursor compound of Chemical Formula 22 may be prepared through the method according to Scheme 6, in addition to the method according to Scheme 5.

As shown in Scheme 6, under a non-polar solvent such as hexane, benzene, toluene, or the like under a nitrogen (N ₂ ) or argon (Ar) stream, or diethylether, tetrahydrofuran (tetrahydrofuran) ), A weakly acidic polar solvent such as dichloromethane, and the like of the above-described compound of Formula 3 and anhydrous alcohol (R ⁶ OH) in a weak polar solvent at room temperature after stirring to remove the solvent and distilled under reduced pressure Can be. At this time, it is preferable to proceed with the reaction under nitrogen or argon stream in order to effectively remove the HNR ⁶ R ⁷ product secondary amine and to decompose the reaction by moisture or oxygen.

The above-described organometallic precursor compound for depositing a metal thin film or ceramic thin film according to the present invention has excellent thermal stability, exists as a liquid at room temperature, and is a highly volatile organometallic compound which is used as a precursor of an organic metal chemical vapor deposition method or an atomic layer deposition method. It can be usefully used to deposit single metal oxides (SiO ₂ , TiO ₂ , ZrO ₂ , HfO ₂ ), composite metal oxides (ZrSiO _x , HfSiO _x ), and metal nitrides (TiN, ZrN, HfN). In particular, when M is Ti among the organometallic precursor compounds defined by Chemical Formula 1, ferroelectric oxide thin films such as BST ((Ba, Sr) TiO ₃ ) and STO (SrTiO ₃ ) are formed through organic metal chemical vapor deposition or atomic layer deposition. It can be usefully used as a Ti precursor.

When the thin film is deposited on the substrate using the organometallic precursor compound defined by Chemical Formula 1 according to the present invention, the deposition temperature may be between 200 and 700 ° C. In this case, in order to vaporize the organometallic precursor compound, it may be bubbled with argon (Ar) or nitrogen (N ₂ ) gas, thermal energy or plasma, or a bias may be applied to the substrate. In addition, the delivery method for supplying the organometallic precursor compound according to the present invention to a process may include a bubbling method, a vapor phase mass flow controller (MFC), a direct liquid injection (DLI), or a precursor compound. Various feeding methods may be applied, including a liquid transfer method for dissolving and dissolving it in an organic solvent.

One or more mixtures of argon (Ar), nitrogen (N ₂ ), helium (He), or hydrogen (H ₂ ) may be used as a carrier gas or a diluent gas for supplying the precursor to the process. In addition, metal oxide thin films (HfO ₂ , ZrO ₂ , TiO ₂ , SiO ₂ ) or composite metal oxide thin films (HfSiOx, ZrSiOx, TiSiOx) by atomic layer deposition (ALD) and chemical vapor deposition (CVD) To deposit HfAlOx, ZrAlOx, TiAlOx, water vapor (H ₂ O), oxygen (O ₂ ) and ozone (O ₃ ) can be used as reaction gases, atomic layer deposition (ALD) and chemical vapor deposition. Ammonia (NH ₃ ) or hydrazine (N ₂ H ₄ ) may be used as a reaction gas to deposit a metal nitride thin film by chemical vapor deposition (CVD).

Hereinafter, the organic metal precursor compound for depositing the metal thin film or the ceramic thin film according to the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention. It is not limited to.

<Example 1>

Preparation of ^Me CpHf (NEtMe) ₃ of Formula 10 wherein ^Me Cp is a methylcyclopentadienyl group in which one hydrogen is substituted with a methyl group in a cyclopentadienyl group, CH ₃ -C ₅ H ₄

After diluting 71 g (0.172 mol) of tetrakis (ethylmethylamino) hafnium (Hf (NEtMe) ₄ ) in 150 ml of hexane, 15 g (0.187 mol) of methylcyclopentadiene were added dropwise to this solution at 0 ° C. After slowly raising the mixed solution to room temperature while stirring, the reaction was refluxed for 8 hours using a reflux condenser. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a dark yellow liquid compound. This liquid compound was distilled off under reduced pressure to obtain 52 g (yield: 69.7%) of ^Me CpHf (NEtMe) _{3 as} a yellow liquid compound.

b.p: 94 ° C. at 0.25 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.055 (Hf- [N (CH ₂ C H ₃ ) (CH ₃ )] ₃ , t, 9H),

d 2.123 ([C H ₃ C ₅ H ₄ ] -Hf), s, 3H),

d 2.912 (Hf— [N (CH ₂ CH ₃ ) (C H ₃ )] ₃ ), s, 9H),

d 3.241, 3.264 (Hf— [N (C H ₂ CH ₃ ) (CH ₃ )] ₃ ), q, 6H),

d 5.856 and 5.954 ([CH ₃ C ₅ H ₄ ] -Hf), t, 4H)

<Example 2>

Preparation of ^Et CpHf (NEtMe) ₃ of Formula 18, wherein ^Et Cp is an ethylcyclopentadienyl group in which one hydrogen is substituted with an ethyl group in a cyclopentadienyl group, and C ₂ H ₅ -C ₅ H ₄ )

After diluting 419 g (1.02 mol) of tetrakis (ethylmethylamino) hafnium (Hf (NEtMe) ₄ ) in 300 ml of hexane, 107 g (1.14 mol) of ethylcyclopentadiene was added dropwise to this solution at 0 ° C. After slowly raising the mixed solution to room temperature while stirring, the reaction was refluxed for 8 hours using a reflux condenser. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a dark yellow liquid compound. This liquid compound was distilled under reduced pressure to obtain 329 g (yield: 69.5%) of ^Et CpHf (NEtMe) _{3 as} a yellow liquid compound.

b.p: 110 ° C. at 0.2 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.047 (Hf- [N (CH ₂ C H ₃ ) (CH ₃ )] ₃ , t, 9H),

d 1.133 ([C H ₃ CH ₂ C ₅ H ₄ ] -Hf), t, 3H),

d 2.504, 2.530 ([CH ₃ C H ₂ C ₅ H ₄ ] -Hf), q, 2H),

d 2.902 (Hf— [N (CH ₂ CH ₃ ) (C H ₃ )] ₃ ), s, 9H),

d 3.228, 3.251 (Hf— [N (C H ₂ CH ₃ ) (CH ₃ )] ₃ ), q, 6H),

d 5.888 and 5.965 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Hf), t, 4H)

<Example 3>

Preparation of ^Me CpZr (NEtMe) ₃ of Formula 11

After diluting 70 g (0.216 mol) of tetrakis (ethylmethylamino) zirconium (Zr (NEtMe) ₄ ) in 100 ml of hexane, 18.5 g (0.231 mol) of methylcyclopentadiene was added dropwise to this solution at 0 ° C. After slowly raising the mixed solution to room temperature while stirring, the reaction was refluxed for 8 hours using a reflux condenser. After completion of the reaction, the solvent and volatile side reactions are removed using a liquid nitrogen trap under reduced pressure to give a dark yellow liquid compound. This liquid compound was distilled under reduced pressure to obtain 48 g (yield: 64.5%) of ^Me CpZr (NEtMe) _{3 as} a yellow liquid compound.

b.p: 105-106 ℃ at 0.45torr,

¹ H-NMR (C ₆ D ₆ ):

d 1.050 (Zr— [N (CH ₂ C H ₃ ) (CH ₃ )] ₃ , t, 9H),

d 2.098 ([C H ₃ C ₅ H ₄ ] -Zr), s, 3H),

d 2.889 (Zr— [N (CH ₂ CH ₃ ) (C H ₃ )] ₃ ), s, 9H),

d 3.221, 3.244 (Zr— [N (C H ₂ CH ₃ ) (CH ₃ )] ₃ ), q, 6H),

d 5.881 and 5.983 ([CH ₃ C ₅ H ₄ ] -Zr), t, 4H)

<Example 4>

Preparation of ^Et CpZr (NEtMe) ₃ of Formula 19

After diluting 270 g (0.834 mol) of tetrakis (ethylmethylamino) zirconium (Zr (NEtMe) ₄ ) in 300 ml of hexane, 79 g (0.839 mol) of ethylcyclopentadiene were added dropwise to this solution. After slowly raising the mixed solution to room temperature while stirring, the reaction was refluxed for 8 hours using a reflux condenser. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a dark yellow liquid compound. This liquid compound was distilled off under reduced pressure to obtain 215 g (yield: 71.9%) of ^Et CpZr (NEtMe) _{3 as} a yellow liquid compound.

b.p: 113 ° C. at 0.6 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.057 (Zr- [N (CH ₂ C H ₃ ) (CH ₃ )] ₃ , t, 9H),

d 1.146 ([C H ₃ CH ₂ C ₅ H ₄ ] -Zr), t, 3H),

d 2.491, 2.515 ([CH ₃ C H ₂ C ₅ H ₄ ] -Zr), q, 2H),

d 2.893 (Zr— [N (CH ₂ CH ₃ ) (C H ₃ )] ₃ ), s, 9H),

d 3.223, 3.245 (Zr— [N (C H ₂ CH ₃ ) (CH ₃ )] ₃ ), q, 6H),

d 5.923 and 6.006 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Zr), t, 4H)

Example 5

Preparation of ^Me CpTi (NEtMe) ₃ of Formula 12

After diluting 100 g (0.357 mol) of tetrakis (ethylmethylamino) titanium (Ti (NEtMe) ₄ ) in 150 ml of hexane, 30.5 g (0.381 mol) of methylcyclopentadienyl was added dropwise to this solution at 0 ° C. Thereafter, the mixed solution was gradually raised to room temperature while stirring, and reflux reaction was performed for 8 hours using a reflux condenser. After completion of the reaction, the solvent and volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a dark red liquid compound. This liquid compound was distilled off under reduced pressure to obtain 67 g of a dark red liquid compound, ^Me CpTi (NEtMe) ₃ (yield: 62.3%).

b.p: 96-98 ℃ at 0.35torr,

¹ H-NMR (C ₆ D ₆ ):

d 1.033 (Ti- [N (CH ₂ C H ₃ ) (CH ₃ )] ₃ , t, 9H),

d 2.105 ([C H ₃ C ₅ H ₄ ] -Ti), s, 3H),

d 3.061 (Ti- [N (CH ₂ CH ₃ ) (C H ₃ )] ₃ ), s, 9H),

d 3.464, 3.482 (Ti— [N (C H ₂ CH ₃ ) (CH ₃ )] ₃ ), q, 6H),

d 5.774 and 5.883 ([CH ₃ C ₅ H ₄ ] -Ti), t, 4H)

<Example 6>

Preparation of ^Et CpTi (NEtMe) ₃ of Formula 20

After diluting 30 g (0.107 mol) of tetrakis (ethylmethylamino) titanium (Ti (NEtMe) ₄ ) in 80 ml of hexane, 11.2 g (0.119 mol) of ethylcyclopentadiene was added dropwise to this solution at 0 ° C. After slowly raising the mixed solution to room temperature while stirring, the reaction was refluxed for 8 hours using a reflux condenser. After completion of the reaction, the solvent and volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a dark red liquid compound. This liquid compound was distilled under reduced pressure to obtain 25 g (yield: 74.1%) of ^Et CpTi (NEtMe) _{3 as} a dark red liquid compound.

b.p: 100-102 ° C. at 0.34torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.039 (Ti- [N (CH ₂ C H ₃ ) (CH ₃ )] ₃ , t, 9H),

d 1.168 ([C H ₃ CH ₂ C ₅ H ₄ ] -Ti), t, 3H),

d 2.489, 2.507 ([CH ₃ C H ₂ C ₅ H ₄ ] -Ti), q, 2H),

d 3.062 (Ti- [N (CH ₂ CH ₃ ) (C H ₃ )] ₃ ), s, 9H),

d 3.469, 3.487 (Ti- [N (C H ₂ CH ₃ ) (CH ₃ )] ₃ ), q, 6H),

d 5.814 and 5.902 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Ti), t, 4H)

<Example 7>

Preparation of ^Me CpHf (O ⁱ Pr) ₃ of Formula 28

After diluting 11.4 g (0.0264 mol) of methylcyclopentadienyltris (ethylmethylamino) hafnium ( ^Me CpHf (NEtMe) ₃ ) in 50 ml of hexane, 4.75 g of 2-propanol (2-propanol) was added to this solution. 0.0790 mol) was added dropwise at 0 ° C., and then the mixed solution was gradually raised to room temperature while stirring, followed by stirring at room temperature for 3 hours. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled off under reduced pressure to obtain 8.7 g (yield 76.7%) of ^Me CpHf (O ⁱ Pr) _{3 as} a light yellow liquid compound.

b.p: 54 ° C. at 0.2 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.131, 1.146 (Hf— [OCH (C H ₃ ) ₂ ] ₃ , d, 18H),

d 2.182 ([C H ₃ C ₅ H ₄ ] -Hf), s, 3H),

d 4.305 (Hf— [OC H (CH ₃ ) ₂ ] ₃ ), h, 3H),

d 6.008 and 6.110 ([[CH ₃ C ₅ H ₄ ] -Hf), t, 4H)

<Example 8>

Preparation of ^Et CpHf (O ⁱ Pr) ₃ of Formula 41

27.1 g (0.0608 mol) of ethylcyclopentadienyltris (ethylmethylamino) hafnium ( ^Et CpHf (NEtMe) ₃ ) was diluted in 80 ml of hexane, and then 10.94 g of anhydrous 2-propanol was added to the solution. 0.18203 mol) was added dropwise at 0 ° C., and the mixed solution was gradually raised to room temperature while stirring, followed by stirring at room temperature for 3 hours. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled under reduced pressure to give 20.3 g (yield: 74.4%) of ^Et CpHf (O ⁱ Pr) _{3 as} a light yellow liquid compound.

b.p: 60-61 ° C. at 0.17 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.147, 1.162 (Hf— [OCH (C H ₃ ) ₂ ] ₃ , d, 18H),

d 1.199 ([C H ₃ CH ₂ C ₅ H ₄ ] -Hf), t, 3H),

d 2.620, 2.639 ([CH ₃ C H ₂ C ₅ H ₄ ] -Hf), q, 2H),

d 4.317 (Hf— [OC H (CH ₃ ) ₂ ] ₃ ), h, 3H),

d 6.094 and 6.145 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Hf), t, 4H)

Example 9

Preparation of ^Me CpZr (O ⁱ Pr) ₃ of Formula 32

After diluting 15 g (0.0435 mol) of methylcyclopentadienyltris (ethylmethylamino) zirconium ( ^Me CpZr (NEtMe) ₃ ) in 50 ml of hexane, the solution was diluted with 8.63 g of anhydrous 2-propanol (2-propanol). 0.1435 mol) was added dropwise at 0 ° C., and the mixed solution was gradually raised to room temperature while stirring, followed by stirring at room temperature for 4 hours. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled under reduced pressure to obtain 11.4 g (yield: 75.4%) of ^Me CpZr (O ⁱ Pr) _{3 as} a light yellow liquid compound.

b.p: 66 ° C. at 0.26 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.153, 1.172 (Zr— [OCH (C H ₃ ) ₂ ] ₃ , d, 18H),

d 2.188 ([C H ₃ C ₅ H ₄ ] -Zr), s, 3H),

d 4.260 (Zr— [OC H (CH ₃ ) ₂ ] ₃ ), h, 3H),

d 6.097 and 6.186 ([[CH ₃ C ₅ H ₄ ] -Zr), t, 4H)

<Example 10>

Preparation of ^Et CpZr (O ⁱ Pr) ₃ of Formula 45

20 g (0.0558 mol) of ethylcyclopentadienyltris (ethylmethylamino) zirconium ( ^Et CpZr (NEtMe) ₃ ) was diluted in 80 ml of hexane, and then 10.4 g of anhydrous 2-propanol (2-propanol) was added thereto. 0.173 mol) was added dropwise at 0 ° C., and the mixed solution was gradually raised to room temperature while stirring, followed by stirring at room temperature for 4 hours. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled off under reduced pressure to obtain 16.4 g (yield: 81.3%) of ^Et CpZr (O ⁱ Pr) _{3 as} a light yellow liquid compound.

b.p: 64-66 ° C. at 0.16torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.152, 1.167 (Zr— [OCH (C H ₃ ) ₂ ] ₃ , d, 18H),

d 1.212 ([C H ₃ CH ₂ C ₅ H ₄ ] -Zr), t, 3H),

d 2.610, 2.630 ([CH ₃ C H ₂ C ₅ H ₄ ] -Zr), q, 2H),

d 4.253 (Zr— [OC H (CH ₃ ) ₂ ] ₃ ), h, 3H),

d 6.153 and 6.195 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Zr), t, 4H)

<Example 11>

Preparation of ^Me CpTi (O ⁱ Pr) ₃ of Formula 36

10.0 g (0.0332 mol) of methylcyclopentadienyltris (ethylmethylamino) titanium ( ^Me CpTi (NEtMe) ₃ ) was diluted in 50 ml of hexane, and then 6.18 g (2-propanol) of anhydrous 2-propanol was added thereto. 0.1028 mol) was added dropwise at 0 ° C., and the mixed solution was gradually raised to room temperature while stirring, followed by stirring at room temperature for 3 hours. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled off under reduced pressure to obtain 9.14 g (yield 90.5%) of ^Me CpTi (O ⁱ Pr) _{3 as} a light yellow liquid compound.

b.p: 60-62 ° C. at 0.17 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.169, 1.184 (Ti- [OCH (C H ₃ ) ₂ ] ₃ , d, 18H),

d 2.190 ([C H ₃ C ₅ H ₄ ] -Ti), s, 3H),

d 4.542 (Ti- [OC H (CH ₃ ) ₂ ] ₃ ), h, 3H),

d 5.934 and 6.039 ([[CH ₃ C ₅ H ₄ ] -Ti), t, 4H)

<Example 12>

Preparation of ^Et CpTi (O ⁱ Pr) ₃ of Formula 49

16.19 g (0.0513 mol) of ethylcyclopentadienyltris (ethylmethylamino) titanium ( ^Et CpTi (NEtMe) ₃ ) was diluted in 50 mL of hexane, and then 9.57 g (2-propanol) anhydrous in this solution. 0.159 mol) was added dropwise at 0 ° C., and the mixed solution was gradually raised to room temperature while stirring, followed by stirring at room temperature for 3 hours. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled under reduced pressure to obtain 14.76 g (yield: 90.3%) of ^Et CpTi (O ⁱ Pr) _{3 as} a light yellow liquid compound.

b.p: 70-72 ° C at 0.22 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1. 159, 1.174 (Ti- [OCH (C H ₃ ) ₂ ] ₃ , d, 18H),

d 1.208 ([C H ₃ CH ₂ C ₅ H ₄ ] -Ti), t, 3H),

d 2.635, 2.654 ([CH ₃ C H ₂ C ₅ H ₄ ] -Ti), q, 2H),

d 4.536 (Ti- [OC H (CH ₃ ) ₂ ] ₃ ), h, 3H),

d 5.999 and 6.046 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Ti), t, 4H)

Example 13

Preparation of ^Me CpZr (OEt) ₃ of Formula 31

After diluting 15 g (0.0435 mol) of methylcyclopentadienyltris (ethylmethylamino) zirconium ( ^Me CpZr (NEtMe) ₃ ) in 50 ml of hexane, 6.21 g (0.1349 mol) of absolute ethanol was added to this solution. After dropwise addition at 0 ° C., the mixed solution was gradually raised to room temperature with stirring, followed by stirring for 4 hours at room temperature. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. The liquid compound was distilled off under reduced pressure to obtain 10 g (yield: 75.2%) of ^Me CpZr (OEt) _{3 as} a light yellow liquid compound.

b.p: 105-106 ° C. at 0.19 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.248 (Zr- [OCH ₂ C H ₃ ] ₃ , t, 9H),

d 2.199 ([C H ₃ C ₅ H ₄ ] -Zr), s, 3H),

d 4.136 (Zr— [OC H ₂ CH ₃ ] ₃ ), br, 6H),

d 5.982 and 6.139 ([[CH ₃ C ₅ H ₄ ] -Zr), t, 4H)

<Example 14>

Preparation of ^Et CpZr (OEt) ₃ of Formula 44

After diluting 20 g (0.0558 mol) of ethylcyclopentadienyltris (ethylmethylamino) zirconium ( ^Et CpZr (NEtMe) ₃ ) in 80 ml of hexane, 7.69 g (0.167 mol) of absolute ethanol was added to this solution. After dropwise addition at 0 ° C., the mixed solution was gradually raised to room temperature with stirring, followed by stirring for 4 hours at room temperature. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled off under reduced pressure to obtain 12.7 g (yield: 71.4%) of ^Et CpZr (OEt) _{3 as} a light yellow liquid compound.

b.p: 120 ° C. at 0.34 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1.211 ([C H ₃ CH ₂ C ₅ H ₄ ] -Zr), t, 3H),

d 1.264 (Zr- [OCH ₂ C H ₃ ] ₃ , t, 9H),

d 2.651, 2.670 ([CH ₃ C H ₂ C ₅ H ₄ ] -Zr), q, 2H),

d 3.96-4.20 (Zr— [OC H ₂ CH ₃ ] ₃ ), br., 6H),

d 6.055 and 6.184 ([[CH ₃ CH ₂ C ₅ H ₄ ] -Zr), t, 4H)

<Example 15>

Preparation of ^Me CpTi (OEt) ₃ of Formula 35

15 g (0.0498 mol) of methylcyclopentadienyltris (ethylmethylamino) titanium ( ^Me CpTi (NEtMe) ₃ ) was diluted in 50 ml of hexane, and then 7.1 g (0.154 mol) of absolute ethanol was added to the solution. After dropwise addition at 0 ° C., the mixed solution was gradually raised to room temperature with stirring, followed by stirring for 4 hours at room temperature. After completion of the reaction, the solvent and the volatile side reactions were removed using a liquid nitrogen trap under reduced pressure to give a pale yellow liquid compound. This liquid compound was distilled under reduced pressure to obtain 12.2 g (yield: 93.5%) of ^Me CpTi (OEt) _{3 as} a light yellow liquid compound.

b.p: 74-76 ° C. at 0.2 torr.

¹ H-NMR (C ₆ D ₆ ):

d 1. 145 (Ti- [OCH ₂ C H ₃ ] ₃ , t, 9H),

d 2.144 ([C H ₃ C ₅ H ₄ ] -Ti), s, 3H),

d 4.243, 4.260 (Ti- [OC H ₂ CH ₃ ] ₃ ), q, 6H),

d 5.896 and 5.995 ([[CH ₃ C ₅ H ₄ ] -Ti), t, 4H)

Experimental Example 1

Of the above embodiments, Example 1 ( ^Me CpHf (NEtMe) ₃ ), Example 2 ( ^Et CpHf (NEtMe) ₃ ), Example 7 ( ^Me CpHf (O ⁱ Pr) ₃ ), Example 8 ( ^Et CpHf TG graphs of the hafnium precursor compounds prepared in (O ⁱ Pr) ₃ ) and tetraethylmethylaminohafnium (Hf (NEtMe) ₄ ) for comparison with them are shown in FIG. 1, and Example 3 ( ^Me CpZr (NEtMe) ) ₃ ), zirconium precursor compounds prepared in Example 4 ( ^Et CpZr (NEtMe) ₃ ), Example 9 ( ^Me CpZr (O ⁱ Pr) ₃ ), Example 10 ( ^Et CpZr (O ⁱ Pr) ₃ ) And TG graphs of TEMAZr (Zr (NEtMe) ₄ ) for comparison with them are shown in FIG. 2, Example 5 ( ^Me CpTi (NEtMe) ₃ ), Example 6 ( ^Et CpTi (NEtMe) ₃ ), and Example Titanium precursor compounds prepared in 11 ( ^Me CpTi (O ⁱ Pr) ₃ ), Example 12 ( ^Et CpTi (O ⁱ Pr) ₃ ), Example 15 ( ^Me CpTi (OEt) ₃ ) and for comparison with these The TG graph of TEMATi (Ti (NEtMe) ₄ ) is shown in FIG. 3.

As can be seen from the TG graph, the novel organometallic precursors of the present invention all show sufficient volatility to be applied to chemical vapor deposition or atomic layer deposition. In addition, since the temperature of the weight decreases rapidly with the temperature, it can be seen that the decomposition of the precursor compound starts at a temperature that starts to gradually decrease, and thus the precursor compounds of the present invention have thermal stability equal to or higher than that of the conventional tetrakis (ethylmethyl) amidometal compounds. You can check that you have.

Experimental Example 2

Atomic layer deposition (ALD) experiments were performed using ethylcyclopentadienyltris (ethylmethylamino) hafnium compound prepared by the method of Example 2 and ozone (O ₃ ) as an oxygen source. First, sulfuric acid (H ₂ SO ₄ ) After dipping the silicon wafer for 10 minutes in a piranha solution mixed with hydrogen peroxide (H ₂ O ₂ ) 4: 1), and then immersing in dilute HF solution for 2 minutes to form a pure silicon surface. A hafnium oxide thin film was prepared by layer deposition (ALD). At this time, the temperature of the substrate was heated to 430 ℃ and the ^Et CpHf (NEtMe) ₃ used as a precursor is placed in a bubbler container made of stainless steel and heated at a temperature of 85 ± 5 ℃ while the flow rate of 100 sccm Argon (Ar) having a gas was used as a carrier gas of the precursor compound was bubbled to vaporize the vessel. At this time, the supply time of the precursor into the reactor was adjusted to 4 ± 1 seconds, the flow rate of oxygen-causing ozone gas was 100 sccm, the supply time was adjusted to 4 ± 1 seconds. Argon, a purge gas, was sent for 30 seconds after supplying precursor and ozone gas.

4 is a film thickness of the number of ALD cycles by measuring the thickness of the thin film obtained by maintaining the temperature of the substrate 430 ℃ and increasing the ALD process cycle 30, 50, 70, 100, 150, 200. As can be seen from FIG. 4, since the thickness of the thin film is primarily dependent on the ALD cycle, the thin film manufacturing process using ^Et CpHf (NEtMe) ₃ of the present invention as a precursor and ozone as an oxygen source exhibits ALD characteristics. It can be seen that it has an ALD deposition rate of about 0.73 dl / cycle.

In addition, the ALD cycle of FIG. 5 shows 50 results of OJ analysis of the thin film deposited at 430 ° C. As can be seen in Figure 5, the deposited thin film can be confirmed that the oxide film of HfO ₂ is hardly deposited such as carbon.

Experimental Example 3

Chemical vapor deposition experiments were carried out using an ethylcyclopentadienyltris (ethylmethylamino) zirconium compound prepared by the method of Example 4 and oxygen (O ₂ ) as the oxygen source. Argon (Ar) gas with a vacuum pressure of 1 x 10 ^-2 torr and a flow rate of 100 sccm while heating the vessel at a temperature between 85 ± 5 ° C in a bubbler vessel made of stainless steel Was used as a carrier gas of the precursor compound to vaporize the precursor compound by bubbling the vessel. The precursor compound vaporized from the vessel through bubbling was diluted in a carrier gas and introduced into a reactor in which a substrate for thin film deposition was placed through a stainless steel tube heated to 110 ± 10 ° C. At this time, the silicon substrate was heated between 300 ~ 500 ℃, the reaction gas oxygen was introduced into the reactor through a separate stainless steel tube at a flow rate of 50sccm, the deposition time was 60 minutes.

6, 7, and 8 are photographic plane and cross-sectional photographs of thin films deposited at 300 ° C., 400 ° C. and 500 ° C., respectively, using an electron scanning microscope (SEM).

As can be seen in Figures 6,7 and 8 it was confirmed that the uniform zirconia thin film was deposited, and as the deposition temperature increases, the crystallinity of the deposited zirconia thin film was increased. In addition, when the thickness of the deposited thin film is 300 ℃ 70 ~ 80nm, 400 ℃ 100 ~ 110nm, 500 ℃ it can be seen that the deposition rate increases with increasing temperature to 300 ~ 310nm.

9 shows the results of X-ray diffraction analysis of the zirconia thin film deposited at 300 ° C, 400 ° C and 500 ° C.

As can be seen in Figure 9 it can be confirmed that the zirconia thin film deposited on the tetragonal (tetragonal) at a temperature below 400 ℃, it was confirmed that the zirconia thin film deposited on the monoclinic (monoclinic) at a deposition temperature of 500 ℃.

As described above, the organometallic precursor compounds according to the present invention were found to be suitable for depositing a metal thin film or a ceramic thin film such as metal oxide or metal nitride, and in particular, the precursor developed in the present invention. The compounds have a high vapor pressure with high thermal stability that does not deteriorate even under constant heating, making them useful for semiconductor manufacturing processes for depositing thin metal or ceramic thin films using organic metal chemical vapor deposition (MOCVD) and atomic layer deposition (ALD). It can be seen that it can be applied.

Claims (44)

An organic metal precursor compound used for depositing a metal thin film or a ceramic thin film such as metal oxide or metal nitride is an organic metal precursor for depositing a metal thin film or ceramic thin film, characterized in that compound. <Formula 1>

In Formula 1, M is selected from metal elements belonging to group 4A or 4B on the periodic table, and R ¹ to R ⁴ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, -SiR ⁶ R ⁷ R ⁸ It is selected from trialkylsilyl represented by (trialkylsilyl), an alkoxy group (alkoxy) represented by -OR ⁶ , a dialkylamino group represented by -NR ⁶ R ⁷ , R ⁵ is an alkyl group having 1 to 4 carbon atoms ( alkyl), a trialkylsilyl group represented by -SiR ⁶ R ⁷ R ⁸ , an alkoxy group represented by -OR ^6, and a dialkylamino group represented by -NR ⁶ R ⁷ . . In addition, L ¹ to L ³ are each independently alkoxy represented by -OR ⁶ , trialkylsiloxy represented by -OSiR ⁶ R ⁷ R ⁸ , and die represented by -NR ⁶ R ⁷ . Bis (trialkylsilyl) amino group represented by dialkylamino, -N (SiR ⁶ R ⁷ R ⁸ ) ₂ , bis (trialkylsilyl) amino group, represented by -N (SiR ⁶ R ⁷ R ⁸ ) R ⁹ N, N-alkyl, trialkylsilylamino group (N, N-alkyl, trialkylsilylamino) is selected from. R ⁶ to R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms. The method according to claim 1, In the organometallic precursor compound represented by Chemical Formula 1, L ¹ , L ² , and L ³ bonded to the metal M are each -NR ⁶ R ⁷ , a metal thin film, characterized in that the organometallic precursor compound represented by the following Chemical Formula 2 or Organic metal precursor compound for ceramic thin film deposition. <Formula 2>

In Formula 2, M is selected from metal elements belonging to group 4A or 4B on the periodic table, and R ¹ to R ⁴ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, -SiR ⁶ R ⁷ R ⁸ It is selected from trialkylsilyl represented by (trialkylsilyl), an alkoxy group (alkoxy) represented by -OR ⁶ , a dialkylamino group represented by -NR ⁶ R ⁷ , R ⁵ is an alkyl group having 1 to 4 carbon atoms ( alkyl), a trialkylsilyl group represented by -SiR ⁶ R ⁷ R ⁸ , an alkoxy group represented by -OR ^6, and a dialkylamino group represented by -NR ⁶ R ⁷ . And R ⁶ to R ⁸ each independently represent an alkyl group having 1 to 4 carbon atoms. The method according to claim 2, In the organometallic precursor compound of Formula 2, M is selected from Hf, Zr or Ti, and R ¹ to R ⁵ are each an organometallic precursor compound of Formula 3 represented by R ¹⁰ to R ¹⁴ , respectively. Or organometallic precursor compounds for ceramic thin film deposition. <Formula 3>

In Formula 3, M 'is selected from Hf, Zr or Ti, R ⁶ and R ⁷ are the same as or different from each other, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ to R ¹³ are the same as or different from each other hydrogen or An alkyl group having 1 to 4 carbon atoms, and R ¹⁴ is an alkyl group having 1 to 4 carbon atoms. The method according to claim 3, In the organometallic precursor compound of Formula 3, R ¹⁰ to R ¹³ is hydrogen, an organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that the organometallic precursor compound represented by the following formula (4). <Formula 4>

In Formula 4, M 'is selected from Hf, Zr or Ti, R ⁶ and R ⁷ are the same as or different from each other, an alkyl group having 1 to 4 carbon atoms, R ¹⁴ is an alkyl group having 1 to 4 carbon atoms. The method according to claim 4, In the organometallic precursor compound of Formula 4, R ¹⁴ is an organometallic precursor compound represented by the following formula (5) wherein the methyl group is an organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 5>

In Formula 5, M 'is selected from Hf, Zr or Ti, and R ⁶ and R ⁷ are each an alkyl group having 1 to 4 carbon atoms. The method according to claim 5, In the organometallic precursor compound of Chemical Formula 5, R ⁶ and R ⁷ are organometallic precursor compounds represented by the following Chemical Formula 6 selected from methyl or ethyl groups, respectively. <Formula 6>

In Formula 6, M ′ is selected from Hf, Zr, or Ti, and R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 6, The organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that the organometallic precursor compound of Formula 6 M 'is hafnium organometallic precursor compound represented by the following formula (7). <Formula 7>

In Formula 7, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 7, In the organometallic precursor compound of Formula 7 R ¹⁵ and R ¹⁶ is an organometallic precursor compound represented by the following formula 10 which is a methyl group and an ethyl group, respectively. <Formula 10>

The method according to claim 6, In the organometallic precursor compound of Formula 6, M 'is zirconium organometallic precursor compound represented by the following formula (8) characterized in that the organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 8>

R ¹⁵ and R ¹⁶ in Formula 8 are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 9, In the organometallic precursor compound of Formula 8, R ¹⁵ and R ¹⁶ are an organometallic precursor compound represented by the following formula (11), each of which is a methyl group and an ethyl group. <Formula 11>

The method according to claim 6, In the organometallic precursor compound of Formula 6, M 'is an organometallic precursor compound represented by the following formula (9) wherein titanium is an organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 9>

In Formula 9, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 11, In the organometallic precursor compound of Formula 9, R ¹⁵ and R ¹⁶ are an organometallic precursor compound represented by the following Formula 12, each of which is a methyl group and an ethyl group. <Formula 12>

The method according to claim 4, The organometallic precursor compound for metal thin film or ceramic thin film deposition, wherein R ¹⁴ is an organometallic precursor compound represented by the following Chemical Formula 13, wherein the organometallic precursor compound of Formula 4 is an ethyl group. <Formula 13>

In Formula 13, M 'is selected from Hf, Zr or Ti, and R ⁶ and R ⁷ are each an alkyl group having 1 to 4 carbon atoms. The method according to claim 13, In the organometallic precursor compound of Chemical Formula 13, R ⁶ and R ⁷ are organometallic precursor compounds represented by the following Chemical Formula 14 selected from methyl or ethyl groups, respectively. <Formula 14>

In Formula 14, M 'is selected from Hf, Zr, or Ti, and R ¹⁵ and R ¹⁶ are different or the same as each other, and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 14, The organometallic precursor compound for depositing a metal thin film or ceramic thin film, characterized in that the organometallic precursor compound of Formula 14 M 'is hafnium organometallic precursor compound represented by the following formula (15). <Formula 15>

In Formula 15, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 15, In the organometallic precursor compound of Formula 15, R ¹⁵ and R ¹⁶ is an organometallic precursor compound represented by the following formula (18) which is a methyl group and an ethyl group, respectively. <Formula 18>

The method according to claim 14, In the organometallic precursor compound of Formula 14, M 'is an organometallic precursor compound represented by the following formula (16) wherein zirconium is an organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 16>

In Formula 16, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 17, In the organometallic precursor compound of Formula 16, R ¹⁵ and R ¹⁶ are organometallic precursor compounds represented by the following Formula 19, wherein each of the methyl group and the ethyl group is an organometallic precursor compound for metal thin film or ceramic thin film deposition. <Formula 19>

The method according to claim 14, In the organometallic precursor compound of Formula 14, M 'is an organometallic precursor compound represented by the following formula (17) wherein titanium is an organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 17>

In Formula 17, R ¹⁵ and R ¹⁶ are different from each other or are the same and are a methyl group (CH ₃ ) or an ethyl group (C ₂ H ₅ ). The method according to claim 19, In the organometallic precursor compound of Formula 17, R ¹⁵ and R ¹⁶ are each an organometallic precursor compound represented by the following Formula 20, which is a methyl group and an ethyl group, wherein the organometallic precursor compound for metal thin film or ceramic thin film deposition. <Formula 20>

The method according to claim 1, In the organometallic precursor compound represented by Chemical Formula 1, L ¹ , L ² , and L ³ bonded to the metal M are each an organic metal precursor compound represented by Chemical Formula 21, wherein -OR ⁶ is a metal thin film or ceramic thin film. Organometallic precursor compound for vapor deposition. <Formula 21>

In Formula 21, M is selected from metal elements belonging to group 4A or 4B on the periodic table, and R ¹ to R ⁴ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, -SiR ⁶ R ⁷ R Trialkylsilyl represented by ⁸ , alkoxy represented by -OR ⁶ , a dialkylamino represented by -NR ⁶ R ⁷ , and R ⁵ is an alkyl group having 1 to 4 carbon atoms. (alkyl), a trialkylsilyl group represented by -SiR ⁶ R ⁷ R ⁸ , an alkoxy group represented by -OR ^6, and a dialkylamino group represented by -NR ⁶ R ⁷ R ⁶ to R ⁸ each independently represent an alkyl group having 1 to 4 carbon atoms. The method according to claim 21, In the organometallic precursor compound of Formula 21, M is selected from Hf, Zr or Ti, and R ¹ to R ⁵ are each an organometallic precursor compound of Formula 22 represented by R ¹⁰ to R ¹⁴ . Or organometallic precursor compounds for ceramic thin film deposition. <Formula 22>

In Formula 22, M 'is selected from Hf, Zr or Ti, R ⁶ is an alkyl group having 1 to 4 carbon atoms, R ¹⁰ to R ¹³ are each independently hydrogen (H) or an alkyl group having 1 to 4 carbon atoms, R ¹⁴ is a C1-C4 alkyl group. The method according to claim 22, In the organometallic precursor compound of Chemical Formula 22, R ¹⁰ to R ¹³ are hydrogen, a precursor compound represented by Chemical Formula 23, wherein the organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 23>

In Formula 23, M 'is selected from Hf, Zr or Ti, and R ⁶ and R ¹⁴ are the same as or different from each other, and represent an alkyl group having 1 to 4 carbon atoms. The method according to claim 23, In the organometallic precursor compound of Formula 23, R ¹⁴ is an organometallic precursor compound represented by the following Formula 24, wherein the methyl group is an organometallic precursor compound for metal thin film or ceramic thin film deposition. <Formula 24>

In Formula 24, M 'is selected from Hf, Zr or Ti, and R ⁶ represents an alkyl group having 1 to 4 carbon atoms. The method of claim 24, The organometallic precursor compound for depositing a metal thin film or ceramic thin film, characterized in that the organometallic precursor compound represented by the formula (24) represented by the formula (25) wherein M 'is hafnium. <Formula 25>

In Formula 25, R ⁶ represents an alkyl group having 1 to 4 carbon atoms. The method according to claim 25, To which the R organometallic precursor compound of Formula 25 is ⁶ group to the organometallic precursor compounds, R ⁶ is an ethyl group in to an organometallic precursor compound, or R ⁶ is represented by the formula 27 is caused isopropyl represented by General Formula 26 Formula 28 An organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that selected from organometallic precursor compounds represented by. <Formula 26>

<Formula 27>

<Formula 28>

The method of claim 24, The organometallic precursor compound for depositing a metal thin film or ceramic thin film, characterized in that the organometallic precursor compound of Formula 24 M 'is zirconium organometallic precursor compound represented by the formula (29). <Formula 29>

In Formula 29, R ⁶ represents an alkyl group having 1 to 4 carbon atoms. The method of claim 27, To an organometallic precursor compound of Formula 29 is R ⁶ is a methyl group to the organometallic precursor compounds, R ⁶ is an ethyl group in to an organometallic precursor compound, or R ⁶ is represented by the formula 31 is a group of isopropyl, which is represented by Formula 30 Formula 32 An organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that selected from organometallic precursor compounds represented by. <Formula 30>

<Formula 31>

<Formula 32>

The method of claim 24, The organometallic precursor compound for depositing a metal thin film or ceramic thin film, characterized in that the organometallic precursor compound of formula 24 M 'is an organometallic precursor compound represented by the following formula 33 is titanium. <Formula 33>

In Formula 33, R ⁶ represents an alkyl group having 1 to 4 carbon atoms. The method of claim 29, An organometallic precursor compound of Formula 33 is R ⁶ is a methyl group in the formula 34, the organometallic precursor compound represented by, R ⁶ is an ethyl group in to an organometallic precursor compound, or R ⁶ is to due isopropyl formula 36 is represented by the formula 35 An organometallic precursor compound for depositing a metal thin film or ceramic thin film, characterized in that selected from organometallic precursor compounds represented by. <Formula 34>

<Formula 35>

<Formula 36>

The method according to claim 23, In the organometallic precursor compound of Formula 23, R ¹⁴ is an organometallic precursor compound represented by the following Formula 37, which is an ethyl group, an organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 37>

In Formula 37, M 'is selected from Hf, Zr or Ti, and R ⁶ represents an alkyl group having 1 to 4 carbon atoms. The method according to claim 31, The organometallic precursor compound for depositing a metal thin film or ceramic thin film, characterized in that the organometallic precursor compound represented by the formula (37) wherein M 'is hafnium. <Formula 38>

R ⁶ in Formula 38 represents an alkyl group having 1 to 4 carbon atoms. The method according to claim 32, The organometallic precursor compound of Formula 38 is an organometallic precursor compound represented by the following Formula 39 wherein R ⁶ is a methyl group, an organometallic precursor compound represented by the following Formula 40 wherein R ⁶ is an ethyl group or R ⁶ is an isopropyl group An organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that selected from organometallic precursor compounds represented by. <Formula 39>

<Formula 40>

<Formula 41>

The method according to claim 31, The organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that the organometallic precursor compound of formula 37 M 'is zirconium organometallic precursor compound represented by the following formula (42). <Formula 42>

R ⁶ in Formula 42 represents an alkyl group having 1 to 4 carbon atoms. The method of claim 34, wherein The organometallic precursor compound of Formula 42 may be an organometallic precursor compound represented by the following Formula 43 wherein R ⁶ is a methyl group, an organometallic precursor compound represented by the following Formula 44 wherein R ⁶ is an ethyl group, or R ⁶ is an isopropyl group An organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that selected from organometallic precursor compounds represented by. <Formula 43>

<Formula 44>

<Formula 45>

The method according to claim 31, In the organometallic precursor compound of Formula 37, M 'is an organometallic precursor compound represented by the formula (46) wherein titanium is an organic metal precursor compound for metal thin film or ceramic thin film deposition. <Formula 46>

R ⁶ in Formula 46 represents an alkyl group having 1 to 4 carbon atoms. The method of claim 36, The organometallic precursor compound of Formula 46 may be an organometallic precursor compound represented by the following Formula 47 wherein R ⁶ is a methyl group, an organometallic precursor compound represented by the following Formula 48 wherein R ⁶ is an ethyl group, or R ⁶ is an isopropyl group An organometallic precursor compound for metal thin film or ceramic thin film deposition, characterized in that selected from organometallic precursor compounds represented by. <Formula 47>

<Formula 48>

<Formula 49>

Metal thin film or metal oxide or metal nitride on the substrate by Atomic Layer Deposition (ALD) or Metal Organic Chemical Vapor Deposition (MOCVD) using organometallic precursor compounds A method of depositing a thin film to form a ceramic thin film as in claim 1, wherein the organometallic precursor compound of any one of claims 1 to 37 is used as the organometallic precursor compound. The method of claim 38, Thin film deposition method characterized in that the deposition temperature is 200 ~ 700 ℃ when depositing on the substrate using the organometallic precursor compound. The method of claim 39, The organometallic precursor compound using a thermal energy or plasma when the deposition on the substrate, or a thin film deposition method, characterized in that applying a bias on the substrate. The method of claim 40, The transfer method for moving the organometallic precursor compound onto a substrate may include a bubbling method, a vapor phase mass flow controller (MFC), a direct liquid injection (DLI), or a precursor compound in an organic solvent. Thin film deposition method characterized in that used in the liquid transport method to melt and transfer to. The method of claim 40, Using one or more mixtures selected from argon (Ar), nitrogen (N ₂ ), helium (He) or hydrogen (H ₂ ) as a transport gas or diluent gas for moving the organometallic precursor compound onto a substrate Thin film deposition method characterized in that. The method of claim 40, In order to deposit a metal oxide thin film (HfO ₂ , ZrO ₂ , TiO ₂ , SiO ₂ ) or a composite metal oxide thin film (HfSiOx, ZrSiOx, TiSiOx, HfAlOx, ZrAlOx, TiAlOx) on the substrate, steam (H ₂ O) is used as a reaction gas. ), Oxygen (O ₂ ) and ozone (O ₃ ) using a thin film deposition method. The method of claim 40, And depositing ammonia (NH ₃ ) or hydrazine (N ₂ H ₄ ) as a reaction gas to deposit a metal nitride thin film on the substrate.

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