KR102215341B1 - Metal precursor and metal containing thin film prepared by using the same - Google Patents

Abstract

상기 식에서, M, R, X_a 내지 X_c 및 m은 명세서 중에서 정의한 바와 같다.In the present invention, it has excellent thermal stability, which is advantageous for high-temperature processes, thereby solving problems arising in the micronization process with high productivity, and being in a liquid state, it has high volatility and sufficient vapor pressure, so that chemical vapor deposition, especially organometallics The metal precursor of the following Formula 1 and a metal-containing thin film manufactured using the same, useful for forming a thin film for next-generation DRAM through a chemical vapor deposition (MOCVD; metal-organic chemical vapor deposition) or atomic layer deposition (ALD) process Provided:
[Formula 1]

In the above formula, M, R, X _a to X _c and m are as defined in the specification.

Description

A metal precursor and a metal-containing thin film prepared by using the same {METAL PRECURSOR AND METAL CONTAINING THIN FILM PREPARED BY USING THE SAME}

The present invention relates to a metal precursor and a metal-containing thin film prepared using the same.

In recent years, dynamic random access memory (DRAM) memory devices have a smaller cell size according to a miniaturization process. In particular, as the half pitch of the capacitor decreases, the process is in progress with a structure in which the aspect ratio increases in order to secure capacitance. Therefore, a high- k film on the capacitor by using a conventional metal-organic chemical vapor deposition (MOCVD) method or an atomic layer deposition (ALD) method using a conventional organometallic precursor. In the case of evaporation, void formation and defects occur due to low step-coverage. Therefore, it is necessary to develop a new high-dielectric material film or a thermally stable precursor required for a high-temperature process to improve step coverage.

US Patent No. 6100414 (2000.08.08 registered)

It is an object of the present invention to have excellent thermal stability, which is advantageous for high-temperature processes, thereby solving problems arising in the micronization process and high productivity, and is present in a liquid state, resulting in high volatility and sufficient vapor pressure. It is to provide a new metal precursor useful for forming a thin film for next-generation DRAM through a metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) process.

Another object of the present invention is to provide a method of forming a metal-containing thin film using the metal precursor.

Another object of the present invention is to provide a metal-containing thin film manufactured using the metal precursor and a semiconductor device including the same.

In order to achieve the above object, according to an embodiment of the present invention, a metal precursor of the following formula 1 is provided:

[Formula 1]

In Formula 1,

M is selected from the group consisting of Zr, Hf and Ti,

X _a and X _b are each independently NR _a R _b or -OR _c ,

X _c is -(NR _d )- or -O-,

R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,

R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, and

m is an integer from 0 to 4.

The metal precursor for forming a metal-containing thin film is selected from the group consisting of Zr, Hf and Ti in Formula 1, X _a and X _b are each independently -NR _a R _b , and X _c is- (NR _d )- or -O-, and R _a , R _b and R _d are each independently selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a tert-butyl group And, it may be a compound in which m is an integer of 0.

In addition, the metal precursor for forming the metal-containing thin film is (methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) zirconium (Cp(CH ₂ ) ₃ NMeZr(NMe ₂ ) ₂ ), (methyl-3-cyclo Pentadienylpropylamino) bis(dimethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi(NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(diethylamino) zirconium (Cp(CH ₂ ) ₃ NMeZr(NEt ₂ ) ₂ ), (methyl-3-cyclo Pentadienylpropylamino) bis(diethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi (NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis (ethylmethylamino) zirconium (Cp (CH ₂ ) ₃ NMeZr (NEtMe) ₂ ), (methyl-3-cyclo Pentadienylpropylamino) bis(ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NEtMe) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(ethylmethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi(NEtMe) ₂ ), 3-cyclopentadienylpropoxy)bis(dimethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy) Bis(dimethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy)bis(diethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy)bis(diethylamino) Hafnium (Cp(CH ₂ ) ₃ OHf(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy) bis(diethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NEt ₂ ) ₂ ), (3 -Cyclopentadienylph Lopoxy)bis(ethylmethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NEtMe) ₂ ), ((3-cyclopentadienylpropoxy)bis (ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ OHf (NEtMe) ₂ ) and (3-cyclopentadienylpropoxy) bis(ethylmethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NEtMe) ₂ ) may be selected from the group consisting of.

According to another embodiment of the present invention, the compound of Formula 3 is reacted with the compound of Formula 2 including a metal (M) selected from the group consisting of Zr, Hf and Ti; Alternatively, the preparation of a metal precursor for forming a metal-containing thin film of formula 1 comprising the step of reacting a compound of formula 3 with a compound of formula 4 to prepare a compound of formula 6 and reacting it with a compound of formula 5 Methods are provided:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 2 to 6,

M is selected from the group consisting of Zr, Hf and Ti,

M'is Li or Na,

X is -NR _a R _b or -OR _c ,

X _c is -(NR _d )- or -O-,

Y, Y _a and Y _b are each independently selected from the group consisting of Cl, Br and I,

R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,

R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,

R'is a hydrogen atom or a C ₁ to C ₅ alkyl group, and

m is an integer from 0 to 4.

According to another embodiment of the present invention, the metal precursor of Formula 1, or the metal precursor of Formula 1 and silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb) , Depositing a mixture of a second metal precursor containing at least one metal (M") selected from barium (Ba), hafnium (Hf), tantalum (Ta) and lanthanide atoms on a substrate for forming a metal-containing thin film A method of manufacturing a thin film containing metal is provided.

In the above manufacturing method, the deposition may be carried out using an organic metal chemical vapor deposition method or an atomic layer deposition method.

In addition, in the deposition, supplying a metal precursor of the following Formula 1 or a mixture of the metal precursor of Formula 1 and the second metal precursor on a substrate for forming a metal thin film located in the reactor, and supplying a reactive gas into the reactor After that, in the presence of a reactive gas, it may be carried out by performing any one treatment step selected from the group consisting of heat treatment, plasma treatment, and light irradiation.

In addition, the reactive gas may be selected from the group consisting of steam, oxygen, ozone, hydrogen, ammonia, hydrazine, and silane.

In addition, the metal-containing thin film may include a compound represented by Formula 7:

[Formula 7]

(M _1-a M" _a )O _b

In the above formula,

a is 0 ≤ a <1,

b is 0 <b ≤ 2,

M is selected from the group consisting of Zr, Hf and Ti, and

M" is selected from silicon, titanium, germanium, strontium, niobium, barium, hafnium, tantalum and lanthanide atoms.

According to another embodiment of the present invention, the metal precursor of Formula 1, or the metal precursor of Formula 1 and silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb) , Barium (Ba), hafnium (Hf), tantalum (Ta), and a mixture of a second metal precursor containing at least one metal (M") selected from lanthanide atoms is deposited on a substrate for forming a metal-containing thin film. A metal-containing thin film is provided:

The metal-containing thin film may include a compound represented by the following formula (7):

[Formula 7]

(M _1-a M" _a )O _b

In the above formula,

a is 0 ≤ a <1,

b is 0 <b ≤ 2,

M is selected from the group consisting of Zr, Hf and Ti, and

M" is selected from silicon, titanium, germanium, strontium, niobium, barium, hafnium, tantalum and lanthanide atoms.

According to another embodiment of the present invention, the metal precursor of Formula 1, or the metal precursor of Formula 1 and silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb) , Barium (Ba), hafnium (Hf), tantalum (Ta), and a mixture of a second metal precursor containing at least one metal (M") selected from lanthanide atoms is deposited on a substrate for forming a metal-containing thin film. A semiconductor device comprising a metal-containing thin film is provided.

The semiconductor device described above may include a metal insulator metal (MIM) for a random access memory (RAM).

Other specifics of the embodiments of the present invention are included in the detailed description below.

It is an object of the present invention to have excellent thermal stability, which is advantageous for high-temperature processes, thereby solving problems arising from the micronization process and expecting high productivity, and is present in a liquid state, so that it has high volatility and sufficient vapor pressure, so that MOCVD or ALD processes can be performed. It is to provide a new metal precursor useful for forming a thin film for next-generation DRAM.

1 shows Example 1-1 and Comparative Example It is a thermogravimetric analysis graph for the metal precursors prepared in 1 and 2.
2 shows Example 1-1 and Comparative Example Differential scanning calorimetry graphs for the metal precursors prepared in steps 1 and 2.
3 is an observation of a change in deposition rate depending on temperature when forming a metal-containing thin film according to the atomic layer deposition method (ALD) using the metal precursors prepared in Example 1-1 and Comparative Examples 1 and 2 in Test Example 3, respectively. It is a graph.
Figure 4a is a case of forming a metal-containing thin film according to the atomic layer deposition method using the metal precursors prepared in Example 1-1 and Comparative Example 1 in Test Example 4, respectively. It is a graph of the deposition rate change according to the injection time of the metal precursor, and FIG. 4B is a graph of the deposition rate change according to the ozone injection time.
5 is a graph of AES (Auger Electron Spectroscopy) analysis of a metal-containing thin film formed using the metal precursor of Example 1-1 in Test Example 5. FIG.
6A and 6B are XPS (X-ray photoelectron spectroscopy) analysis graphs of a metal-containing thin film formed using each of the metal precursors of Example 1-1 in Test Example 5, FIG. 6A is a Zr3d scan, and FIG. 6B is Each of the O1s scans is shown.
7A to 7C are SIMS (Secondary ion Mass spectroscopy) analysis graphs of a metal-containing thin film formed using the metal precursors of Example 1-1 and Comparative Examples 1 and 2 in Test Example 5, respectively.
8 is an HR-TEM (High-Resolution Transmission Electron Microscopy) analysis photograph of a metal-containing thin film formed by ALD deposition of the precursor of Example 1-1.

The present invention is intended to illustrate specific embodiments and to be described in detail in the detailed description, since various transformations may be applied and various embodiments may be provided. However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present invention, terms such as'comprise' or'have' are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance the possibility.

In the present specification, unless otherwise specified, an'alkyl group' refers to a linear or branched alkyl group having 1 to 5 carbon atoms, and the alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, A hexyl group, an isohexyl group, and the like, but are not limited thereto.

The present invention has excellent thermal stability and is advantageous for high-temperature processes, thereby solving problems occurring in the micronization process and expecting high productivity. Since it exists in a liquid state, it has high volatility and sufficient vapor pressure, so that DRAM through MOCVD or ALD process It is characterized by providing a novel metal precursor useful for forming a thin film.

That is, the metal precursor for forming a metal-containing thin film according to an embodiment of the present invention may be a compound having a structure represented by the following Formula 1:

[Formula 1]

In Formula 1,

M is selected from the group consisting of Zr, Hf and Ti,

X _a and X _b are each independently -NR _a R _b or -OR _c ,

X _c is -(NR _d )- or -O-,

R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, preferably a hydrogen atom (H), a methyl group (-CH ₃ ), an ethyl group (-CH ₂ CH ₃ ), a propyl group (- (CH ₂ ) ₂ CH ₃ ), isopropyl group (-CH(CH ₃ ) ₂ ), n-butyl group (-(CH ₂ ) ₃ CH ₃ ) and tert-butyl group (-C(CH ₃ ) ₃ ) It may be selected from the group consisting of,

Each R is independently a hydrogen atom or a C ₁ to C ₅ alkyl group, and preferably may be selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a tert-butyl group, and

m is an integer from 0 to 4.

Specifically, the metal precursor is (methyl-3-cyclopentadienylpropylamino) bis (dimethylamino) zirconium (Cp (CH ₂ ) ₃ NMeZr (NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropyl Amino) bis (dimethylamino) hafnium (Cp (CH ₂ ) ₃ NMeHf (NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis (dimethylamino) titanium (Cp (CH ₂ ) ₃ NMeTi ( NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(diethylamino) zirconium (Cp(CH ₂ ) ₃ NMeZr(NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropyl Amino) bis (diethylamino) hafnium (Cp (CH ₂ ) ₃ NMeHf (NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis (dimethylamino) titanium (Cp (CH ₂ ) ₃ NMeTi (NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(ethylmethylamino) zirconium (Cp(CH ₂ ) ₃ NMeZr(NEtMe) ₂ ), (methyl-3-cyclopentadienylpropyl Amino) bis (ethylmethylamino) hafnium (Cp (CH ₂ ) ₃ NMeHf (NEtMe) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis (ethylmethylamino) titanium (Cp (CH ₂ ) ₃ NMeTi (NEtMe) ₂ ), 3-cyclopentadienylpropoxy)bis(dimethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy)bis(dimethylamino ) Hafnium (Cp(CH ₂ ) ₃ OHf(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NMe ₂ ) ₂ ), (3 -Cyclopentadienylpropoxy)bis(diethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy)bis(diethylamino) hafnium (Cp( CH ₂ ) ₃ OHf(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy) bis(diethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NEt ₂ ) ₂ ), (3-cyclopentadie Nylpropoxy)bis(ethylmethylamino) Leconium (Cp(CH ₂ ) ₃ OZr(NEtMe) ₂ ), ((3-cyclopentadienylpropoxy) bis(ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NEtMe) ₂ ) or (3 -Cyclopentadienylpropoxy)bis(ethylmethylamino)titanium (Cp(CH ₂ ) ₃ OTi(NEtMe) ₂ ) and the like.

Among them, in Formula 1, M is selected from the group consisting of Zr, Hf, and Ti, and X _a and X _b are each independently -NR _a R _b , and X _c is -(NR _d )- or -O -And R _a , R _b and R _d are each independently a hydrogen atom (H), a methyl group (-CH ₃ ), an ethyl group (-CH ₂ CH ₃ ), a propyl group (-(CH ₂ ) ₂ CH ₃ ), It is selected from the group consisting of isopropyl group (-CH(CH ₃ ) ₂ ), n-butyl group (-(CH ₂ ) ₃ CH ₃ ) and tert-butyl group (-C(CH ₃ ) ₃ ), and m The compound which is this integer of 0 may be more preferable.

The metal precursor having the above structure is a step of reacting a compound of the following formula (2) containing a metal (M) selected from the group consisting of Zr, Hf and Ti and a compound of the following formula (3) containing a cyclopentadienyl group It can be prepared by a manufacturing method comprising:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, M, X _c , R and m are the same as defined above,

X is -NR _a R _b or -OR _c , wherein R _a to R _c are the same as previously defined, and

R'is a hydrogen atom or a C ₁ to C ₅ alkyl group.

A method of preparing a metal precursor according to the present invention will be described in more detail with reference to the reaction equations presented below. The presented reaction schemes are only examples for explaining the present invention, and the present invention is not limited thereto.

The metal precursor according to the present invention is a compound of the following formula (3) including a compound of the following formula (2) and a cyclopentadienyl group containing a metal (M) selected from the group consisting of Zr, Hf and Ti as shown in Scheme 1 below. It can be prepared by the reaction of:

[Scheme 1]

In Scheme 1, M, R, R', X, X _a to X _c and m are the same as defined above.

The compound of Formula 2 is a raw material for providing a metal (M) to the metal precursor compound, and the compound of Formula 4 including a metal (M) selected from the group consisting of Zr, Hf and Ti as shown in Scheme 2 below. Can be prepared by reacting with a compound of formula (5):

[Scheme 2]

In Scheme 2, M and X are the same as defined above, M'is Li or Na, and Y is selected from the group consisting of Cl, Br and I.

The compound of Formula 4 may be a chloride containing Zr, Hf, or Ti, and specific examples include ZrCl ₄ , HfCl ₄ or TiCl ₄ , but are not limited thereto.

In addition, the compound of Formula 5 may be selected from the group consisting of an amide compound and an alkoxide compound including a metal (M'). Specific examples may include LiNMe ₂ , LiNEt ₂ , LiNEtMe, LiOMe or NaOMe, but are not limited thereto. In addition, in the functional groups, Me means a methyl group and Et means an ethyl group.

For example, when LiNMe ₂ is used as the compound of Formula 4, a compound of M(NMe ₂ ) ₄ may be prepared as a result of reaction with a metal raw material.

The reaction between the compound of Formula 4 and the compound of Formula 5 is preferably carried out under low temperature conditions, and the amount of each compound may be determined stoichiometrically.

In addition, specific examples of the compound of Formula 3 including the cyclopentadiene group used in the preparation of the metal precursor according to the present invention include Cp(CH ₂ ) ₃ NHCH ₃ or Cp(CH ₂ ) ₃ OH, etc. However, it is not limited thereto.

The compound of Formula 3 may be commercially obtained and used, or may be prepared according to various manufacturing methods.

For example, in the case of a compound in Formula 3 wherein X _c is -(NR _d )-, R _d and R'are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, according to the reaction as in Scheme 3 below Can be manufactured.

[Scheme 3]

In Scheme 3, R, R', m are the same as previously defined, and Z is selected from the group consisting of Cl, Br and I.

Specifically, preparing a compound of Formula 3b by reacting the 3-aminopropanol of Formula 3a with an alkyl formate-based compound such as ethyl formate with an amide; Reducing the compound of Formula 3b using a reducing agent such as LiAlH ₄ to prepare a compound of Formula 3c; Preparing a compound of Formula 3d by refluxing the compound of Formula 3c with a hydrogen halide such as hydrogen bromide (HBr); And the compound of Formula 3 may be prepared by a manufacturing method comprising the step of reacting the compound of Formula 3d with the metal cyclopentadiene of Formula 3e.

Alternatively, as in Scheme 4 below, reacting 1,3-dihalogenated alkyl of Formula 3f with metal cyclopentadiene of Formula 3e to prepare a compound of Formula 3g; In addition, the compound of Formula 3 may be prepared by a method comprising reacting the compound of Formula 3g with the amine compound of Formula 3h.

[Scheme 4]

In Scheme 4, M', R, R', Z and m are the same as defined above.

As another method, as in Scheme 5 below, reacting an amino-3-halogenated alkyl halide of Formula 3h with a metal cyclopentadiene of Formula 3e to prepare a compound of Formula 3i, and a compound of Formula 3i The compound of Formula 3 may be prepared by a method comprising the step of reacting the aldehyde-based compound of Formula 3j with a reductive amination reaction:

[Scheme 5]

In Scheme 5, M', R, R', Z and m are the same as previously defined.

The reaction between the compound of Formula 2 and the compound of Formula 3 is preferably carried out under low temperature conditions, and the amount of each compound may be determined stoichiometrically.

The metal precursor of Formula 1 is prepared by the reaction of the compound of Formula 2 and the compound of Formula 3 as described above.

In another method, the metal precursor of Formula 1 according to the present invention comprises the steps of preparing a compound of Formula 6 by reacting a compound of Formula 3 with a compound of Formula 4 as shown in Scheme 6 below; And it may be prepared by a manufacturing method comprising the step of reacting the compound of formula 6 with the compound of formula 5:

[Scheme 6]

In Scheme 6, M, M', R, X _a to X _c , and m are the same as previously defined, and Y, Y _a and Y _b are each independently selected from the group consisting of Cl, Br and I.

The metal precursor of Formula 1 prepared by the above manufacturing method is an asymmetric quadruple compound containing a cyclopentadienyl group (Cp) forming an intramolecular ring, and is a suitable distribution (physical state at a distribution temperature, Thermal stability), precursors used to form a high dielectric film (zirconium oxide film) of a conventional DRAM capacitor with a wide range of self-limiting atomic layer deposition (ALD), for example, TEMAZr, CpZr having the following structures It is more thermally stable than (NMe ₂ ) ₃ , or Cp(CH ₂ ) ₂ NMeZr(NMe ₂ ) ₂ , and is more advantageous in MOCVD and ALD processes. Therefore, the metal precursor according to the present invention can be applied to a high-dielectric film for a capacitor of a DRAM, and the application range is not limited thereto.

TEMAZr CpZr(NMe ₂ ) ₃ Cp(CH ₂ ) ₂ NMeZr(NMe ₂ ) ₂

According to another embodiment of the present invention, a method for manufacturing a metal-containing thin film using the metal precursor of Formula 1 is provided.

The manufacturing method may be carried out according to a conventional method of manufacturing a metal thin film by vapor deposition, except that the compound of Formula 1 is used as a metal precursor, and specifically, chemical vapor deposition (CVD) or atomic layer deposition method. (atomic layer deposition, ALD), or the like.

Specifically, the step of supplying the metal precursor of Formula 1 onto the substrate for forming a metal thin film existing in the reactor, and supplying a reactive gas into the reactor, and one selected from the group consisting of heat treatment, plasma treatment, and light irradiation. It can be manufactured by a manufacturing method comprising the step of performing a treatment process of.

Hereinafter, each step will be described in detail, first, a metal precursor of Formula 1 is supplied onto a substrate for forming a metal thin film.

At this time, the substrate for forming a metal thin film may be used without particular limitation as long as it is used for semiconductor manufacturing, which needs to be coated with a metal thin film due to a technical action. Specifically, silicon substrate (Si), silica substrate (SiO ₂ ), silicon nitride substrate (SiN), silicon oxynitride substrate (SiON), titanium nitride substrate (TiN), tantalum nitride substrate (TaN), tungsten substrate (W) or a noble metal substrate, for example, a platinum substrate (Pt), a palladium substrate (Pd), a rhodium substrate (Rh), a gold substrate (Au), or the like may be used.

In addition, the supply of the metal precursor of Formula 1 may be a method of transporting a volatilized gas, a direct liquid injection method, or a liquid transport method of dissolving and transporting the metal precursor in an organic solvent. Specifically, the method of transferring the metal precursor to the volatilized gas is to evaporate the metal precursor by bubbling with an inert gas such as helium, neon, argon, krypton, xenon or nitrogen after placing a container containing the metal precursor in a thermostat. Then, it may be transferred onto a substrate for forming a metal thin film, or a liquid metal precursor is converted into a gas phase through a vaporizer using a liquid delivery system (LDS) and transferred onto a substrate for forming a metal thin film.

When the metal precursor of Formula 1 is supplied, silicon (Si), titanium (Ti), germanium (Ge), and strontium are used as second metal precursors to further improve electrical properties, that is, capacitance, in the metal thin film that is finally formed. Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and a metal precursor containing at least one metal (M") selected from a lanthanide atom may be optionally further supplied.

Specifically, the second metal precursor may be an alkylamide compound or an alkoxy compound including the above metal. For example, when the metal is Si, SiH(N(CH ₃ ) ₂ ) ₃ , Si(N(C ₂ H ₅ ) ₂ ) ₄ , Si(N(C ₂ H ₅ )(CH ₃ ) as the second metal precursor ) ₄ , Si(N(CH ₃ ) ₂ ) ₄ Si(OC ₄ H ₉ ) ₄ , Si(OC ₂ H ₅ ) ₄ , Si(OCH ₃ ) ₄ , Si(OC(CH ₃ ) ₃ ) ₄ etc. It may be used, but is not limited thereto.

The supply of the second metal precursor may be performed in the same manner as the method of supplying the metal precursor of Formula 1, and the second metal precursor may be supplied together with the metal precursor of Formula 1 onto the substrate for thin film formation, or It may be sequentially supplied after the supply of the precursor is completed.

The metal precursor of Formula 1 and optionally the second metal precursor as described above are preferably maintained at a temperature of 150 to 600° C. before being supplied into the reaction chamber to contact the substrate for forming the metal thin film, and more preferably 150 It is good to maintain the temperature of to 450 ℃.

In addition, after the supplying step of the metal precursor, prior to supplying the reactive gas, the metal precursor of Formula 1 and optionally the second metal precursor are assisted to move onto the substrate, or the inside of the reactor is made to have an appropriate pressure for deposition. In order to discharge existing impurities to the outside, a process of purging an inert gas such as argon (Ar), nitrogen (N ₂ ), or helium (He) in the reactor may be performed. At this time, purging of the inert gas may be preferably carried out so that the pressure in the reactor is 1 to 5 Torr.

After the supply of the metal precursors is completed, a reactive gas is supplied into the reactor, and in the presence of the reactive gas, one type of treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation is performed.

As the reactive gas, water vapor (H ₂ O), oxygen, ozone (O ₃ ), hydrogen, ammonia, hydrazine, and silane may be used. At this time, when conducted in the presence of oxidizing gases such as water vapor, oxygen, ozone, etc., a metal oxide thin film may be formed, and when conducted in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a metal alone or a thin film of metal nitride is formed. Can be.

The heat treatment, plasma treatment, or light irradiation treatment process is to provide thermal energy for depositing a metal precursor, and may be performed according to a conventional method. Preferably, in order to produce a metal thin film having a desired physical state and composition at a sufficient growth rate, it is preferable to perform the above treatment so that the temperature of the substrate in the reactor is 100 to 1000°C, preferably 300 to 500°C. Do.

In addition, during the treatment process, argon in the reactor helps to move the reactive gas onto the substrate as before, or to have a pressure suitable for deposition in the reactor, and to release impurities or by-products present in the reactor to the outside. A process of purging an inert gas such as (Ar), nitrogen (N ₂ ), or helium (He) may be performed.

As described above, the introduction of the metal precursor, the addition of the reactive gas, and the implementation of the treatment process under the introduction of an inert gas were carried out in one cycle. A metal-containing thin film can be formed by repeating one or more cycles.

Specifically, when an oxidizing gas is used as the reactive gas, the metal-containing thin film prepared may include a metal oxide represented by the following Formula 7:

[Formula 7]

(M _1-a M" _a )O _b

In Chemical Formula 7,

a is 0 ≤ a <1,

b is 0 <b ≤ 2,

M is selected from the group consisting of Zr, Hf and Ti, and

M" is derived from a second metal precursor and is selected from silicon, titanium, germanium, strontium, niobium, barium, hafnium, tantalum and lanthanide atoms.

In the method of manufacturing a metal-containing thin film as described above, by using a metal precursor with excellent thermal stability, it is possible to perform the deposition process at a higher temperature than the conventional one during the deposition process, and contamination of particles or impurities such as carbon due to thermal decomposition of the precursor. Without it, a high-purity metal, metal oxide or metal nitride thin film can be formed. Accordingly, the metal-containing thin film formed according to the manufacturing method of the present invention is useful as a high-k material film in a semiconductor device, especially a DRAM, CMOS, etc. in a semiconductor memory device.

Accordingly, according to another embodiment of the present invention, a metal-containing thin film formed by the method for forming the metal-containing thin film, and a semiconductor device including the thin film are provided. Specifically, the semiconductor device may be a semiconductor device including a metal insulator metal (MIM) for a random access memory (RAM).

In addition, the semiconductor device is the same as the configuration of a conventional semiconductor device, except that the metal-containing thin film according to the present invention is included in a material film requiring high dielectric properties such as DRAM in the device. Detailed descriptions of these are omitted.

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

Preparation Example 1-1. 3- N -Synthesis of formylamino-1-propanol

Ethyl formate (222g, 3mol, 3eq.) was added to a 1L round bottom flask, cooled to 0°C, and 3-aminopropanol (75g, 1mol, 1eq.) was slowly added dropwise. After the addition was completed, the temperature of the mixed solution was heated to room temperature and stirred for 12 hours. After the reaction was completed, the resulting solution was distilled under reduced pressure to remove excess ethyl formate. A colorless liquid 3- N -formylamino-1-propanol (103g, 100%) was obtained as the target compound without a separate purification process.

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.18 (s, 1H), 6.42 (br, 1H), 3.68 (t, 2H), 3.46 (q, 2H), 3.08 (s, 1H), 1.72 (m, 2H)

Preparation Example 1-2. N -Synthesis of methylamino-1-propanol

LiAlH ₄ (100g, 2.6mol, 1.2eq) was added to a 3ℓ round bottom flask, and 1.3ℓ of THF was added, followed by stirring. The resulting reaction solution was cooled to 0°C, and then 3- N -formylamino-1-propanol (223g, 2.1mol, 1eq.) prepared in Preparation Example 1-1 was diluted in 190ml THF to prepare it. One solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at reflux temperature for 3 hours. After the reaction was completed, the temperature of the resulting reaction solution was cooled to 0° C., and 97.2 ml of distilled water was slowly added dropwise, 220 ml of 10% w/w NaOH aqueous solution was slowly added, and 97.2 ml of distilled water was slowly added thereto. After completion of the addition, the resulting solid was filtered, and the filtrate was concentrated and fractionated to obtain a colorless liquid N -methylamino-1-propanol (160 g, 83%) as the target compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.45 (t, 2H), 3.3-2.8 (br, 1H), 2.50 (t, 2H), 2.16 (s, 3H), 1.44 (m, 2H)

Preparation Example 1-3. N -3-Bromopropyl- N -Synthesis of methylamine bromate

47-49% bromic acid (970g, 5.3mol, 3eq.) was added to a 1 ℓ round bottom flask, cooled to 0°C, and then N -methylamino-1-propanol (160g) prepared in Preparation Example 1-2 , 1.8 mol, 1 eq.) was slowly added dropwise. After the addition was completed, the mixture was stirred at reflux for 6 hours. The resulting reactant was distilled under reduced pressure to remove excess water, and recrystallized using acetone. The resulting solid was filtered and washed with acetone to obtain a white solid N- 3-bromopropyl- N -methylamine bromate (292g, 70%) as the target compound.

¹ H NMR (300 MHz, D ₂ O) δ 3.35 (t, 2H), 3.02 (t, 2H), 2.55 (s, 3H), 2.07 (m, 2H)

Preparation Example 1-4. Methyl-3-cyclopentadienylpropylamine (Cp(CH ₂ ) ₃ NHMe) synthesis

In a 3 liter reactor, N- 3-bromopropyl- N -methylamine bromate (232 g, 1 mol, 1 eq.) prepared in Preparation Example 1-3 was dissolved in 1.3 liter of THF and then cooled to 0°C. 2M sodium cyclopentadiene solution (1ℓ, 2mol, 2eq.) was slowly added dropwise to the resulting solution, and after the addition was completed, the mixture was heated to room temperature and stirred for 12 hours. After the reaction was completed, the resulting solid was filtered, and the filtrate was concentrated and fractionated to obtain methyl-3-cyclopentadienylpropylamine (89g, 65%) as a light yellow liquid as the target compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 6.02-6.43 (m, 3H), 2.89-2.95 (m, 2H) 2.59 (m, 2H), 2.35-2.43 (m, 5H), 1.75 (m, 2H) , 1.26 (br s, 1H).

Preparation Example 1-5. 3-cyclopentadienylpropyl alcohol (Cp(CH ₂ ) ₃ OH) synthesis

In a 3 liter reactor, 3-bromopropanol (139g, 1 mol, 1eq.) was dissolved in 1.3 liter of THF and then cooled to 0°C. 2M sodium cyclopentadiene solution (0.5ℓ, 1mol, 2eq.) was slowly added dropwise to the resulting solution, and after the addition was completed, the mixture was heated to room temperature and stirred for 12 hours. After the reaction was completed, the resulting solid was filtered, and the filtrate was concentrated and fractionated to obtain 3-cyclopentadienylpropyl alcohol (62 g, 50%) as a light yellow liquid as the target compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 6.01-6.23 (m, 3H), 3.89-3.92 (m, 2H) 2.59 (m, 2H), 2.31-2.35 (m, 2H), 1.85 (m, 2H) .

Preparation Example 2-1. Tetrakis (dimethylamino) zirconium (IV) (Zr(NMe ₂ ) ₄ ) Of manufacture

After dissolving 242 g of LiNMe _{2 in 2} L of toluene, it was cooled to -20°C. After adding 233 g of ZrCl ₄ to the cooling solution, it was reacted at reflux for 6 hours to prepare Zr(NMe ₂ ) ₄ .

Preparation Example 2-2. Tetrakis (diethylamino) zirconium (IV) (Zr(NEt ₂ ) ₄ ) Of manufacture

Conducted in the same manner as in Preparation Example 2-1 except for using, instead of ₂ LiNEt LiNMe ₂ in Preparation Example 2-1 to prepare a Zr (NEt _{2) 4.}

Preparation Example 2-3. Tetrakis(ethylmethylamino)zirconium(IV) (Zr(NEtMe) ₄ ) Of manufacture

Zr(NEtMe) ₄ was prepared in the same manner as in Preparation Example 2-1, except that LiNEtMe was used instead of LiNMe ₂ in Preparation Example 2-1.

Preparation Example 2-4. Tetrakis(dimethylamino)hafnium(IV) (Hf(NMe ₂ ) ₄ ) Of manufacture

Hf(NMe ₂ ) ₄ was prepared in the same manner as in Preparation Example 2-1, except that HfCl ₄ was used instead of ZrCl ₄ in Preparation Example 2-1.

Preparation Example 2-5. Tetrakis(diethylamino)hafnium(IV) (Hf(NEt ₂ ) ₄ ) Of manufacture

Hf(NEt ₂ ) ₄ was prepared in the same manner as in Preparation Example 2-2, except that HfCl ₄ was used instead of ZrCl ₄ in Preparation Example 2-2.

Preparation Example 2-6. Tetrakis(ethylmethylamino)hafnium(IV) (Hf(NEtMe) ₄ ) Of manufacture

Hf(NEtMe) ₄ was prepared in the same manner as in Preparation Example 2-3, except that HfCl ₄ was used instead of ZrCl ₄ in Preparation Example 2-3.

Manufacturing Example 2-7. Tetrakis (dimethylamino) titanium (IV) (Ti (NMe ₂ ) ₄ ) Of manufacture

Ti(NMe ₂ ) ₄ was prepared in the same manner as in Preparation Example 2-1, except that TiCl ₄ was used instead of ZrCl ₄ in Preparation Example 2-1.

Manufacturing Example 2-8. Tetrakis (diethylamino) titanium (IV) (Ti (NEt ₂ ) ₄ ) Of manufacture

Ti(NEt ₂ ) ₄ was prepared in the same manner as in Preparation Example 2-2, except that TiCl ₄ was used instead of ZrCl ₄ in Preparation Example 2-2.

Manufacturing Example 2-9. Tetrakis (ethylmethylamino) titanium (IV) (Ti (NEtMe) ₄ ) Of manufacture

Ti(NEtMe) ₄ was prepared in the same manner as in Preparation Example 2-3, except that TiCl ₄ was used instead of ZrCl ₄ in Preparation Example 2-3.

Example 1-1. (Methyl-3-cyclopentadienepropylamido)bis(dimethylamido)zirconium (Cp(CH ₂ ) ₃ NMeZr (NMe ₂ ) ₂ ) synthesis

Zr(NMe ₂ ) ₄ (15.6g, 58.4mmol, 1eq) prepared in Preparation Example 2-1 was added to a 250 ml flame-dried Schrank flask, and 25 ml of toluene was added to dissolve. After the resulting solution was cooled to -20°C, Cp(CH ₂ ) ₃ NHMe (8.02g, 58.4mmol, 1eq.) prepared in Preparation Example 1-4 was slowly added dropwise. After the dropwise addition was completed, the resulting reaction solution was heated to room temperature and stirred at 40°C for 15 minutes. The resulting reaction solution was distilled under reduced pressure to remove the toluene solvent, and subjected to fractional distillation to form Cp(CH ₂ ) ₃ NMeZr(NMe ₂ ) ₂ (17.38g, 90%) i) was obtained as a colorless liquid.

(1a)

(1a)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.95 (t, 2H), 5.76 (t, 2H), 3.21 (s, 3H), 2.91 (s, 12H), 2.76 (m, 2H), 2.50 ( m, 2H), 1.79 (m, 2H).

Example 1-2. (Methyl-3-cyclopentadienylpropylamino) bis(diethylamino) zirconium (Cp(CH ₂ ) ₃ NMeZr(NEt ₂ ) ₂ ) Synthesis

Except for using Zr(NEt ₂ ) ₄ prepared in Preparation Example 2-2 instead of Zr(NMe ₂ ) ₄ in Example 1-1, the following was carried out in the same manner as in Example 1-1. The structural formula Cp(CH ₂ ) ₃ NMeZr(NEt ₂ ) ₂ was obtained.

(1b)

(1b)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.98 (t, 2H), 5.79 (t, 2H), 3.35 (q, 8H), 3.20 (s, 3H), 2.77 (t, 2H), 2.50 ( m, 2H), 1.79 (m, 2H), 1.01 (t, 12H).

Example 1-3. (Methyl-3-cyclopentadienylpropylamino) bis(ethylmethylamino) zirconium (Cp(CH ₂ ) ₃ NMeZr(NEtMe) ₂ ) Synthesis

Except for using Zr (NEtMe) ₄ prepared in Preparation Example 2-3 instead of Zr (NMe ₂ ) ₄ in Example 1-1, the following was carried out in the same manner as in Example 1-1. The structural formula of Cp(CH ₂ ) ₃ NMeZr(NEtMe) ₂ was obtained.

(1c)

(1c)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.96 (t, 2H), 5.78 (t, 2H), 3.21 (t, 4H), 2.98 (s, 3H), 2.86 (s, 6H), 2.76 ( t, 2H), 2.50 (m, 2H), 1.79 (m, 2H), 1.05 (t, 6H).

Example 1-4. (3-cyclopentadienylpropoxy)bis(dimethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NMe ₂ ) ₂ ) Synthesis

Examples 1-1 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is subjected to the in the same manner as in Example 1-1, except that the Structural Formula ₃ OH (CH _{2) 3} OZr(NMe ₂ ) ₂ was obtained.

(1d)

(1d)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.94 (t, 2H), 5.72 (t, 2H), 2.90 (s, 12H), 2.71 (m, 2H), 2.49 (m, 2H), 1.77 ( m, 2H).

Example 1-5. (3-cyclopentadienylpropoxy)bis(diethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NEt ₂ ) ₂ ) Synthesis

Example 1-2 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is of a structure to conducted in the same manner as in Example 1-2 but using ₃ OH (CH _{2) 3} OZr(NEt ₂ ) ₂ was obtained.

(1e)

(1e)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.96 (t, 2H), 5.71 (t, 2H), 3.31 (q, 8H), 2.69 (t, 2H), 2.48 (m, 2H), 1.71 ( m, 2H), 1.11 (t, 12H).

Example 1-6. (3-cyclopentadienylpropoxy) bis(ethylmethylamino) zirconium (Cp(CH ₂ ) ₃ OZr(NEtMe) ₂ ) Synthesis

Examples 1-3 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is of a structure to conducted in the same manner as in Example 1-3 but using ₃ OH (CH _{2) 3} OZr(NEtMe) ₂ was obtained.

(1f)

(1f)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.91 (t, 2H), 5.71 (t, 2H), 3.20 (t, 4H), 2.83 (s, 6H), 2.71 (t, 2H), 2.42 ( m, 2H), 1.70 (m, 2H), 1.15 (t, 6H).

Example 1-7. (Methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf (NMe ₂ ) ₂ ) Synthesis

Except for using Hf (NMe ₂ ) ₄ prepared in Preparation Example 2-4 instead of Zr (NMe ₂ ) ₄ in Example 1-1, the following was carried out in the same manner as in Example 1-1. The structural formula of Cp(CH ₂ ) ₃ NMeHf(NMe ₂ ) ₂ was obtained.

(1g)

(1g)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.91 (t, 2H), 5.75 (t, 2H), 3.20 (s, 3H), 2.96-2.98 (m, 14H), 2.47 (m, 2H), 1.74 (m, 2H).

Example 1-8. (Methyl-3-cyclopentadienylpropylamino) bis(diethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NEt ₂ ) ₂ ) Synthesis

Except for using Hf(NEt ₂ ) ₄ prepared in Preparation Example 2-5 instead of Zr(NMe ₂ ) ₄ in Example 1-1, the following was carried out in the same manner as in Example 1-1. The structural formula of Cp(CH ₂ ) ₃ NMeHf(NEt ₂ ) ₂ was obtained.

(1h)

(1h)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.95 (t, 2H), 5.78 (t, 2H), 3.37 (q, 8H), 3.19 (s, 3H), 2.93 (t, 2H), 2.49 ( m, 2H), 1.76 (m, 2H), 1.15 (t, 12H).

Example 1-9. (Methyl-3-cyclopentadienylpropylamino) bis(ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf (NEtMe) ₂ ) Synthesis

Except for using Hf (NEtMe) ₄ prepared in Preparation Example 2-6 instead of Zr (NMe ₂ ) ₄ in Example 1-1, the following structural formula was carried out in the same manner as in Example 1-1 Cp(CH ₂ ) _{3 of} NMeHf(NEtMe) ₂ was obtained.

(1i)

(1i)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.93 (t, 2H), 5.77 (t, 2H), 3.21 (t, 4H), 3.14 (t, 2H), 3.04 (s, 3H), 2.91 ( s, 6H), 2.48 (t, 2H), 1.75 (m, 2H), 1.05 (t, 6H).

Example 1-10. (3-cyclopentadienylpropoxy)bis(dimethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NMe ₂ ) ₂ ) Synthesis

Example 1-7 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is, in the embodiment to the embodiment in the same manner as in Example 1-7, except that the Structural Formula ₃ OH (CH ₂ ) ₃ OHf (NMe ₂ ) ₂ was obtained.

(1j)

(1j)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.90 (t, 2H), 5.72 (t, 2H), 2.94-2.91 (m, 14H), 2.43 (m, 2H), 1.71 (m, 2H).

Example 1-11. (3-cyclopentadienylpropoxy)bis(diethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NEt ₂ ) ₂ ) Synthesis

Example 1-8 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is, in the embodiment to the embodiment in the same manner as in Example 1-8, except that the Structural Formula ₃ OH (CH ₂ ) ₃ OHf (NEt ₂ ) ₂ was obtained.

(1k)

(1k)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.94 (t, 2H), 5.76 (t, 2H), 3.35 (q, 8H), 2.91 (t, 2H), 2.47 (m, 2H), 1.75 ( m, 2H), 1.13 (t, 12H).

Example 1-12. (3-cyclopentadienylpropoxy) bis(ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NEtMe) ₂ ) Synthesis

Example 1-9 In the Cp (CH _{2) 3} Cp instead NHMe (CH _{2) 3} and has, in the embodiment 1-9 to the embodiment in the same way as with the structural formula Cp but using OH (CH ₂ ) ₃ OHf (NEtMe) ₂ was obtained.

(1l)

(1l)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.92 (t, 2H), 5.78 (t, 2H), 3.22 (t, 4H), 3.13 (t, 2H), 2.92 (s, 6H), 2.46 ( t, 2H), 1.74 (m, 2H), 1.06 (t, 6H).

Example 1-13. (Methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi (NMe ₂ ) ₂ ) Synthesis

Except for using the Ti (NMe ₂ ) ₄ prepared in Preparation Example 2-7 instead of Zr (NMe ₂ ) ₄ in Example 1-1, the following was carried out in the same manner as in Example 1-1. The structural formula of Cp(CH ₂ ) ₃ NMeTi(NMe ₂ ) ₂ was obtained.

(1m)

(1m)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.81 (t, 2H), 5.65 (t, 2H), 3.47 (s, 3H), 3.11 (s, 12H), 2.78 (t, 2H), 2.44 ( m, 2H), 1.69 (m, 2H).

Example 1-14. (Methyl-3-cyclopentadienylpropylamino) bis(diethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi(NEt ₂ ) ₂ ) Synthesis

Except for using the Ti(NEt ₂ ) ₄ prepared in Preparation Example 2-8 instead of Zr(NMe ₂ ) ₄ in Example 1-1, the following was carried out in the same manner as in Example 1-1. The structural formula of Cp(CH ₂ ) ₃ NMeTi(NEt ₂ ) ₂ was obtained.

(1n)

(1n)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.96 (t, 2H), 5.79 (t, 2H), 3.36 (q, 8H), 3.20 (s, 3H), 2.92 (m, 2H), 2.49 ( m, 2H), 1.76 (m, 2H), 1.15 (t, 12H).

Example 1-15. (Methyl-3-cyclopentadienylpropylamino) bis(ethylmethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi (NEtMe) ₂ ) Synthesis

In Example 1-1, the following was carried out in the same manner as in Example 1-1, except that Ti(NEtMe ₂ ) ₄ prepared in Preparation Example 2-9 was used instead of Zr(NMe ₂ ) ₄ The structural formula of Cp(CH ₂ ) ₃ NMeTi(NEtMe) ₂ was obtained.

(1o)

(1o)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.92 (t, 2H), 5.76 (t, 2H), 3.20 (t, 4H), 3.13 (t, 2H), 3.01 (s, 3H), 2.90 ( s, 6H), 2.45 (t, 2H), 1.72 (m, 2H), 1.02 (t, 6H).

Example 1-16. (3-cyclopentadienylpropoxy)bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ OTi (NMe ₂ ) ₂ ) Synthesis

Examples 1-13 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is, in the embodiment to the embodiment in the same manner as in Example 1-13, except that the Structural Formula ₃ OH (CH ₂ ) ₃ OTi(NMe ₂ ) ₂ was obtained.

(1p)

(1p)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.82 (t, 2H), 5.64 (t, 2H), 3.13 (s, 12H), 2.76 (t, 2H), 2.47 (m, 2H), 1.65 ( m, 2H).

Example 1-17. (3-cyclopentadienylpropoxy)bis(diethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NEt ₂ ) ₂ ) Synthesis

Examples 1 to 14 in Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is, in the embodiment to the embodiment in the same manner as in Example 1-14, except that the Structural Formula ₃ OH (CH ₂ ) ₃ OTi(NEt ₂ ) ₂ was obtained.

(1q)

(1q)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.97 (t, 2H), 5.77 (t, 2H), 3.38 (q, 8H), 2.90 (m, 2H), 2.51 (m, 2H), 1.75 ( m, 2H), 1.17 (t, 12H).

Example 1-18. (3-cyclopentadienylpropoxy) bis(ethylmethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NEtMe) ₂ ) Synthesis

Example 15 In the Cp (CH _{2) 3} Cp instead NHMe (CH ₂₎ Cp, and is, in the embodiment to the embodiment in the same manner as in Example 1-15, except that the Structural Formula ₃ OH (CH ₂ ) ₃ OTi(NEtMe) ₂ was obtained.

(1r)

(1r)

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 5.90 (t, 2H), 5.78 (t, 2H), 3.21 (t, 4H), 3.11 (t, 2H), 2.87 (s, 6H), 2.42 ( t, 2H), 1.71 (m, 2H), 1.03 (t, 6H).

Comparative Example 1.(Cyclopentadienyl)tris(dimethylamino)zirconium (CpZr(NMe ₂ ) ₃ ) Synthesis

Zr (NMe ₂ ) ₄ prepared in Preparation Example 2-1 was cooled to -20°C, Cp 137g was added dropwise, heated to room temperature, and stirred under reflux for 6 hours. After the reaction was completed, the resulting reaction product was purified by distillation to obtain 202 g of CpZr(NMe ₂ ) ₃ of the following structural formula.

(8)

(8)

Comparative Example 2.(Methyl-2-cyclopentadieneethylamido)bis(dimethylamido)zirconium (Cp(CH ₂ ) ₂ NMeZr (NMe ₂ ) ₂ ) Synthesis

In a 250 ml flame-dried Schrank flask, 38 g of Zr(NMe ₂ ) ₄ prepared in Preparation Example 2-1 was added, and 100 ml of toluene was added to dissolve it. After the resulting solution was cooled to -20°C, (2-cyclopentadienyl-ethyl)methylamine (Cp(CH ₂ ) ₂ NHMe) 13.5 g was slowly added over 30 minutes. After the addition was completed, the resulting reaction solution was heated at room temperature and stirred for 12 hours. After completion of the reaction, the solvent was completely removed under reduced pressure, and the resulting liquid was distilled under reduced pressure to obtain 29.5 g of Cp(CH ₂ ) ₂ NMeZr(NMe ₂ ) ₂ of the following structural formula as a yellow liquid.

(9)

(9)

Test Example 1. Comparison of thermal behavior

Thermogravimetric analysis was performed to evaluate the thermal behavior of the metal precursors prepared in Example 1-1 and Comparative Examples 1 and 2.

Specifically, a thermal gravimetric analyzer (Universal V4.1D TA Instruments) was stored in an argon glove box with a moisture and oxygen content of less than 0.1 ppm, and the metals in Example 1-1 and Comparative Examples 1 and 2 10 mg of a sample containing each of the precursors was placed in an aluminum crucible and heated from 25°C to 500°C at a temperature gradient of 10°C/minute. Mass loss was monitored as a function of crucible temperature. The results are shown in FIG. 1.

As shown in FIG. 1, the metal precursor of Example 1-1 exhibited excellent thermal stability compared to the metal precursors of Comparative Examples 1 and 2.

Test Example 2. Comparison of calorific behavior

Differential scanning calorimetry was performed to evaluate the caloric behavior of the metal precursors prepared in Example 1-1 and Comparative Examples 1 and 2.

Specifically, 10 mg of a sample containing each of the metal precursors prepared in Example 1-1 and Comparative Examples 1 and 2 was put in a sealed aluminum crucible in a differential scanning calorimetry device, and 10° C./from 40° C. to 500° C. Heated to a minute temperature gradient. Caloric change was monitored as a function of crucible temperature. The results are shown in FIG. 2.

From the results shown in FIG. 2, it can be seen that the metal precursor of Example 1-1 has a higher thermal decomposition temperature than the metal precursors of Comparative Examples 1 and 2.

Example 2-1. ZrO by atomic layer deposition ₂ Thin film formation

The Cp(CH ₂ ) ₃ NMeZr(NMe ₂ ) ₂ prepared in Example 1-1 was put in a bubbler and heated at 130° C. for 5 seconds to be introduced into the reaction chamber. Ar purge was performed by supplying argon (Ar) as a carrier gas at a flow rate of 100 sccm for 10 seconds. At this time, the pressure in the reaction chamber was controlled to 1 Torr. Next, after introducing O ₃ as a reactive gas into the reaction chamber for 5 seconds, Ar purging was performed for 10 seconds. At this time, the substrate on which the metal thin film is to be formed was heated to 320°C. This process was repeated 200 times to obtain a ZrO ₂ thin film, which is a self-limiting atomic layer.

Example 2-2. ZrO by atomic layer deposition ₂ Thin film formation

A ZrO ₂ thin film was obtained in the same manner as in Example 2-1, except that H ₂ O was used as the oxygen source.

Example 2-3. HfO by atomic layer deposition ₂ Thin film formation

HfO, a self-limiting atomic layer, was carried out in the same manner as in Example 2-1, except that Cp(CH ₂ ) ₃ NMeHf(NMe ₂ ) ₂ synthesized in Example 1-7 was used as a metal precursor. _{2 A} thin film was formed.

Example 2-4. TiO by atomic layer deposition ₂ Thin film formation

A TiO ₂ thin film was formed in the same manner as in Example 2-1, except that the Cp(CH ₂ ) ₃ NMeTi(NMe ₂ ) ₂ synthesized in Example 1-13 was used as a metal precursor.

Example 3-1. ZrO by chemical vapor deposition ₂ Thin film formation

The metal precursor prepared in Example 1-1, Cp(CH ₂ ) ₃ NMeZr(NMe ₂ ) ₂ was put in a bubbler and heated at 130° C. for 5 seconds, and then introduced into a reaction chamber. Ar purge was performed by supplying argon (Ar) as a carrier gas at a flow rate of 50 sccm for 10 seconds. At this time, the pressure of the reaction vessel was controlled to 1 Torr. Next, Cp(CH ₂ ) ₃ NMeZr(NMe ₂ ) ₂ was mixed with an O ₃ /Ar gas mixture in a reaction chamber and heated from 300°C to 440°C to form a ZrO ₂ thin film. At this time, the pressure in the reaction chamber was controlled to 5 Torr.

Example 3-2. ZrO by chemical vapor deposition ₂ Thin film formation

A ZrO ₂ thin film was formed in the same manner as in Example 3-1, except that H ₂ O was used as the reactive gas.

Example 3-3. HfO by chemical vapor deposition ₂ Thin film formation

A HfO ₂ thin film was formed in the same manner as in Example 3-1, except that Cp(CH ₂ ) ₃ NMeHf(NMe ₂ ) ₂ synthesized in Example 1-7 was used as a metal precursor.

Example 3-4. TiO by chemical vapor deposition ₂ Thin film formation

A TiO ₂ thin film was formed in the same manner as in Example 3-1, except that Cp(CH ₂ ) ₃ NMeTi(NMe ₂ ) ₂ synthesized in Example 1-13 was used as a metal precursor.

Test Example 3. Evaluation of ALD growth characteristics according to temperature

In order to evaluate the ALD growth characteristics according to the substrate temperature, the metal precursors prepared in Example 1-1 and Comparative Examples 1 and 2 were used in a similar manner as in Example 2-1. However, for the metal precursor prepared in Example 1-1, the temperature of the precursor was set to 130°C, and for the metal precursor prepared in Comparative Examples 1 and 2, the temperature of the precursor was set to 105°C, respectively, and the precursor injection time and The ozone injection time was fixed at 5 seconds for both Examples and Comparative Examples, and then the deposition temperature was changed from 300°C to 460°C in Example 1-1, and from 300°C to 420°C in Comparative Example 1, and Comparative Example 1 In case 2, the deposition characteristics were evaluated by changing from 260°C to 420°C. The results are shown in FIG. 3.

As shown in FIG. 3, in the case of the metal precursor of Comparative Example 1, the deposition rate tended to increase as the temperature increased by the CVD reaction from 300° C. to 380° C., and the precursor of Comparative Example 2 was from 300° C. to 340 The ALD window was displayed in a short temperature range to °C, and the deposition rate decreased after 340 °C. On the other hand, in the case of the metal precursor of Example 1-1, a deposition rate of 1.2Å was exhibited at 300°C, and the temperature was increased, indicating a deposition rate of 1.25Å at a high temperature of 420°C. From these results, it can be seen that the metal precursor of Example 1-1 has excellent ALD growth characteristics even at high temperatures compared to Comparative Examples 1 and 2.

Test Example 4. Evaluation of ALD growth characteristics according to metal precursor and ozone injection time

In order to evaluate the ALD growth characteristics according to the metal precursor and ozone injection time, the metal precursor and the metal precursor prepared in Example 1-1 and Comparative Example 1 were used, except that the metal precursor and the ozone injection time were variously changed. It was carried out in a similar manner as in Example 2-1. At this time, for the metal precursor prepared in Example 1-1, the precursor temperature was set to 130°C, and for the metal precursor prepared in Comparative Example 1, the temperature of the precursor was set to 105°C. In the case of the substrate temperature, Example 1 The metal precursor of -1 was deposited at 320°C, and Comparative Example 1 was deposited at 300°C. In addition, the precursor injection time and the ozone injection time were 2 to 7 seconds/2 to 7 seconds in the case of Comparative Example 1, whereas the precursor injection time and ozone injection time were 2 to 7 seconds/2 in the case of Example 1-1. Changed to ~5 seconds. The experimental results are shown in FIGS. 4A and 4B.

FIG. 4A is a graph showing a result of observing a change in a deposition rate, that is, a growth characteristic for each metal precursor injection time, and FIG. 4B is a graph showing a result of observing a change in a deposition rate according to an ozone injection time.

As shown in FIG. 4A, as a result of evaluating the deposition characteristics for each precursor injection time, the precursors of Example 1-1 and Comparative Example 1 used in the deposition experiment showed a constant deposition rate at an injection time of 6 seconds or more. The precursor of Comparative Example 1 exhibited a constant deposition rate of 1.25 Å and that of Example 1-1 was 1.45 Å, from which it can be seen that each metal precursor was grown by ALD.

In addition, as shown in FIG. 4B, as a result of evaluating the deposition characteristics for each injection time of ozone, deposition was possible from 2 seconds in the injection time, but it was not a perfect ALD deposition. In detail, in the case of the metal precursor of Comparative Example 1, an average of 1.25 Å ALD deposition and growth were possible after 6 seconds injection, and in the case of the metal precursor of Example 1-1, a uniform ALD was grown with an average thickness of 1.45 Å after 4 seconds injection. Shown.

Test Example 5. Evaluation of metal-containing thin film

For the ZrO ₂ thin film formed by performing ALD deposition at 300°C using the metal precursor of Example 1-1 in Test Example 3, the silicon content and carbon and nitrogen in the film were measured using AES (Auger Electron Spectroscopy). The impurity content was analyzed (10 nm profile). The results are shown in Table 1 and FIG. 5.

Ingredient Atomic content (%) C 1.3 O 69.9 Zr 28.7 Si 0

As shown in Tables 1 and 5, the most important carbon ratio of the thin film was detected to be less than 1%, and the ratio of Zr and O of the deposited thin film was 1:2, indicating that the stoichiometric ratio was excellent. In particular, it can be seen that 1:2 of Zr and O are uniformly deposited during the depth profile.

In addition, XPS (X-ray photoelectron spectroscopy) analysis and SIMS on the metal-containing thin film formed by performing ALD deposition at 300°C using the precursors of Example 1-1 and Comparative Examples 1 and 2 in Test Example 3 (Secondary ion Mass spectroscopy) analysis was performed. The results are shown in Tables 2 and 3, and FIGS. 6a to 6b and 7a to 7c, respectively.

Table 2 and FIGS. 6A and 6B show the XPS analysis results, and FIG. 6A shows a Zr3d scan of a metal-containing thin film formed using the metal precursor of Example 1-1, and FIG. 6B shows an O1s scan.

In addition, the following Table 3 and Figures 7a to 7c show the SIMS analysis results, Figures 7a to 7c are SIMS analysis of the metal-containing thin film formed using the metal precursors of Example 1-1 and Comparative Examples 1 and 2, respectively It is a graph.

(unit: %) Comparative Example 1 Comparative Example 2 Example 1-1 Etch. Time 0s 5s 0s 5s 0s 5s Zr 22.79 41.88 23.52 41.15 21.15 42.13 O 37.53 58.12 38.19 58.85 37.33 57.87 C 39.68 - 38.29 - 38.81 - N - - - - 2.71 -

(unit: %) Comparative Example 1 Comparative Example 2 Example 1-1 O 55.79 55.07 53.48 Zr 42.65 41.90 44.21 H 1.26 2.17 1.86 C 0.04 0.36 0.08 Si 0.21 0.44 0.33 N 0.04 0.07 0.04

As described above, the metal precursor according to the present invention has an appropriate distribution (physical state and thermal stability at the distribution temperature) and a wide self-limiting ALD range, enabling deposition of pure films by ALD and MOCVD. In particular, it is suitable for deposition of a group IV metal-containing thin film, which is advantageous for ALD or MOCVD processes compared to conventional TEMAZr, CpZr(NMe ₂ ) ₃ and Cp(CH ₂ ) ₂ Zr(NMe ₂ ) ₂ .

In addition, the thickness of the metal-containing thin film formed by performing ALD deposition at 300°C using the precursor of Example 1-1 in Test Example 3 was measured through an ellipsometer, and the HR-TEM was measured. The thickness was confirmed using. The results are shown in FIG. 8.

8 is an HR-TEM observation photograph of a metal-containing thin film formed by ALD deposition of the precursor of Example 1-1.

As a result, a ZrO2 thin film with excellent film quality was confirmed.

As described above, one embodiment of the present invention has been described, but those of ordinary skill in the relevant technical field add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. Various modifications and changes can be made to the present invention by means of the like, and this will also be said to be included within the scope of the present invention.

Claims (13)

Metal precursor of formula 1 below:
[Formula 1]

In Formula 1,
M is selected from the group consisting of Zr, Hf and Ti,
X _a and X _b are each independently NR _a R _b or -OR _c ,
X _c is -(NR _d )- or -O-,
R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,
R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, and
m is an integer from 0 to 4. The method of claim 1,
The M is selected from the group consisting of Zr, Hf and Ti,
X _a and X _b are each independently -NR _a R _b ,
X _c is -(NR _d )- or -O-,
R _a , R _b and R _d are each independently selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a tert-butyl group, and
A metal precursor in which m is an integer of 0. The method of claim 1,
The metal precursor is (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)zirconium (Cp(CH ₂ ) ₃ NMeZr(NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino)bis (Dimethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi(NMe ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino)bis(diethylamino)zirconium (Cp(CH ₂ ) ₃ NMeZr(NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino)bis (Diethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NEt ₂ ) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi(NEt ₂₎ ) ₂ ), (methyl-3-cyclopentadienylpropylamino)bis(ethylmethylamino)zirconium (Cp(CH ₂ ) ₃ NMeZr(NEtMe) ₂ ), (methyl-3-cyclopentadienylpropylamino)bis (Ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ NMeHf(NEtMe) ₂ ), (methyl-3-cyclopentadienylpropylamino) bis(ethylmethylamino) titanium (Cp(CH ₂ ) ₃ NMeTi(NEtMe) ₂ ), 3-cyclopentadienylpropoxy)bis(dimethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy)bis(dimethylamino)hafnium ( Cp(CH ₂ ) ₃ OHf(NMe ₂ ) ₂ ), (3-cyclopentadienylpropoxy) bis(dimethylamino) titanium (Cp(CH ₂ ) ₃ OTi(NMe ₂ ) ₂ ), (3-cyclopenta Dienylpropoxy)bis(diethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy) bis(diethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy)bis(diethylamino)titanium (Cp(CH ₂ ) ₃ OTi(NEt ₂ ) ₂ ), (3-cyclopentadienylpropoxy )Bis(ethylmethylamino)zirconium (Cp(CH ₂ ) ₃ OZr(NEtMe) ₂ ), ((3-cyclopentadienylpropoxy) bis(ethylmethylamino) hafnium (Cp(CH ₂ ) ₃ OHf(NEtMe) ₂ ) and (3-cyclopentadienylpro Foxy) bis (ethylmethylamino) titanium (Cp (CH ₂ ) ₃ OTi (NEtMe) ₂ ) The metal precursor that is selected from the group consisting of. Reacting the compound of the following formula (3) with a compound of the following formula (2) including a metal (M) selected from the group consisting of Zr, Hf, and Ti; Alternatively, a method of preparing a metal precursor of the following formula 1 comprising the step of reacting a compound of formula 3 with a compound of formula 4 to prepare a compound of formula 6, and reacting it with a compound of formula 5 below:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 1 to 6,
M is selected from the group consisting of Zr, Hf and Ti,
M'is Li or Na,
X is selected from the group consisting of -NR _a R _b and -OR _c ,
X is -NR _a R _b or -OR _c ,
X _c is -(NR _d )- or -O-,
Y, Y _a and Y _b are each independently selected from the group consisting of Cl, Br and I,
R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,
R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,
R'is a hydrogen atom or a C ₁ to C ₅ alkyl group, and
m is an integer from 0 to 4. The metal precursor of Formula 1 below, or the metal precursor of Formula 1 and silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), A method for producing a metal-containing thin film comprising depositing a mixture of a second metal precursor including tantalum (Ta) and at least one metal (M") selected from lanthanide atoms on a substrate for forming a metal-containing thin film:
[Formula 1]

In Formula 1,
M is selected from the group consisting of Zr, Hf and Ti,
X _a and X _b are each independently -NR _a R _b or -OR _c ,
X _c is -(NR _d )- or -O-,
R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,
R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, and
m is an integer from 0 to 4. The method of claim 5,
The deposition is carried out using an organic metal chemical vapor deposition method or an atomic layer deposition method. The method of claim 5,
The deposition is performed by supplying a metal precursor of the following formula (1) or a mixture of the metal precursor of the formula (1) and the second metal precursor onto a substrate for forming a metal thin film located in the reactor, and after supplying a reactive gas into the reactor. , In the presence of a reactive gas, the method for producing a metal-containing thin film is carried out by performing any one treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation. The method of claim 7,
The reactive gas is water vapor, oxygen, ozone, hydrogen, ammonia, hydrazine, and a method of manufacturing a metal-containing thin film selected from the group consisting of silane. The method of claim 5,
A method for producing a metal-containing thin film wherein the metal-containing thin film contains a compound of the following formula (7):
[Formula 7]
(M _1-a M" _a )O _b
In Chemical Formula 7,
a is 0 ≤ a <1,
b is 0 <b ≤ 2,
M is selected from the group consisting of Zr, Hf and Ti, and
M" is selected from silicon, titanium, germanium, strontium, niobium, barium, hafnium, tantalum and lanthanide atoms. The metal precursor of Formula 1 below, or the metal precursor of Formula 1 and silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), A metal-containing thin film prepared by depositing a mixture of a second metal precursor containing at least one metal (M") selected from tantalum (Ta) and a lanthanide atom on a substrate for forming a metal-containing thin film:
[Formula 1]

In Formula 1,
M is selected from the group consisting of Zr, Hf and Ti,
X _a and X _b are each independently -NR _a R _b or -OR _c ,
X _c is -(NR _d )- or -O-,
R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,
R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, and
m is an integer from 0 to 4. The method of claim 10,
A metal-containing thin film wherein the metal-containing thin film contains a compound of Formula 7 below:
[Formula 7]
(M _1-a M" _a )O _b
In Chemical Formula 7,
a is 0 ≤ a <1,
b is 0 <b ≤ 2,
M is selected from the group consisting of Zr, Hf and Ti, and
M" is selected from silicon, titanium, germanium, strontium, niobium, barium, hafnium, tantalum and lanthanide atoms. The metal precursor of Formula 1 below, or the metal precursor of Formula 1 and silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), A semiconductor device comprising a metal-containing thin film manufactured by depositing a mixture of a second metal precursor containing at least one metal (M") selected from tantalum (Ta) and a lanthanide atom on a substrate for forming a metal-containing thin film:
[Formula 1]

In Formula 1,
M is selected from the group consisting of Zr, Hf and Ti,
X _a and X _b are each independently -NR _a R _b or -OR _c ,
X _c is -(NR _d )- or -O-,
R _a to R _d are each independently a hydrogen atom or a C ₁ to C ₅ alkyl group,
R is each independently a hydrogen atom or a C ₁ to C ₅ alkyl group, and
m is an integer from 0 to 4. The method of claim 12,
Wherein the semiconductor device comprises a metal insulator metal for random access memory.

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