KR101785594B1 - Precusor compositions and Method for forming a thin film using thereof - Google Patents

Abstract

상기 <화학식 1>의 M은 주기율표상에서 4A족 또는 4B족에 속하는 금속 원소 중에서 선택된 어느 하나이며, m은 1 내지 5의 정수 중에서 선택된 어느 하나이고, L은 C₁-C₅의 알콕사이드기, C₁-C₅의 아미노기 또는 C₁-C₅의 다이알킬아미노기 중에서 선택된 어느 하나이다.The precursor composition for film formation according to an embodiment of the present invention includes a compound represented by the following formula (1).
&Lt; Formula 1 >

Wherein M is any one selected from the group consisting of 4A and 4B metal elements on the periodic table, m is any one selected from integers from 1 to 5, L is a C ₁ -C ₅ alkoxide group, C any one selected from the group consisting of ₁ -C ₅ group of an amino group or a dialkyl amino group of the C ₁ -C _5.

Description

TECHNICAL FIELD The present invention relates to a precursor composition for forming a thin film,

The present invention relates to a film forming precursor composition and a thin film forming method using the same, and more particularly, to a film forming precursor composition containing an organic metal compound and a thin film forming method using the same.

BACKGROUND ART [0002] As electronic technology has developed, demands for miniaturization and weight reduction of electronic devices used in various electronic devices have increased rapidly. A variety of physical and chemical deposition methods have been proposed to form fine electronic devices. Various thin film deposition methods are available for manufacturing various electronic devices such as a metal thin film, a metal oxide thin film, or a metal nitride thin film by such a deposition method.

In order to manufacture a miniaturized electronic device so as to meet the trend of miniaturization, low power consumption and high capacity due to development of electronic technology, miniaturization of various electronic devices including metal oxide semiconductor (MOC) devices is required.

A precursor containing a Group 4A or Group 4B metal element has been spotlighted for thin film deposition as a precursor having excellent stability and conductivity. Particularly, precursors including metal elements of group 4A or group 4B have been utilized in metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) processes. In order to ensure the thin film properties to be deposited in the MOCVD or ALD process, the precursor containing the 4A or 4B metal element to be supplied must be thermally stable and have a high vapor pressure at low temperatures.

Korean Patent Publication No. 10-2009-0115145 (published on April 4, 2009)

An object of the present invention is to provide a precursor composition for film formation that is excellent in thermal stability, and to provide a thin film deposition method for depositing a thin film using the precursor composition.

Other objects of the present invention will become more apparent from the following detailed description and drawings.

The precursor composition for film formation according to one embodiment of the present invention includes a compound represented by the following formula (1).

Wherein M is any one selected from the group consisting of 4A and 4B metal elements on the periodic table, m is any one selected from integers from 1 to 5, L is a C ₁ -C ₅ alkoxide group, C any one selected from the group consisting of ₁ -C ₅ group of an amino group or a dialkyl amino group of the C ₁ -C _5.

M in Formula 1 may be any one selected from Ti, Zr, and Hf.

The compound contained in the film forming precursor composition may be represented by the following formula (2).

The compound contained in the film forming precursor composition may be characterized by being represented by the following formula (3).

The R in the formula 3 may be any one selected from the group consisting of C ₁ -C ₅ alkyl groups.

The compound contained in the film forming precursor compound may be represented by the following formula (4).

The compound contained in the film forming precursor composition may be represented by the following formula (5).

The compound contained in the film forming precursor composition may be represented by the following formula (6).

R ₁ to R ₆ in Formula 6 may each independently be selected from C ₁ -C ₅ alkyl groups.

R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ in the formula 6 are connected to each other to form a C ₃ -C ₆ cyclic amine group together with the nitrogen atom to which they are bonded .

Wherein the precursor composition for film formation comprises 1 to 10 mol of a compound represented by the general formula (6); And an amine compound represented by the following formula (15), an alicyclic unsaturated compound represented by the following formula (16), or an aromatic compound represented by the following formula (17): can do.

In the formula 15, R ' ₁ to R' ₃ may be the same or different from each other and are an alkyl group having 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R " ₁ to R" ₈ may be the same or different from each other and are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, and R ' ₁ to R '"' ₆ may be the same or different from each other and are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, m 'and n 'May be independently selected from integers of 0 to 10.

The compound of formula (15) may be characterized in that it is triethylamine.

The compound of formula (16) may be characterized by being cycloheptatriene.

The compound of formula (17) may be characterized as being xylene.

Wherein the precursor composition for film formation comprises 1 to 5 mol of a compound represented by the formula (6); And 1 to 5 moles of triethylamine, cycloheptatriene or xylene, and the compound represented by the formula (6) is a mixture of tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium IV). &Lt; / RTI >

The compound contained in the film forming precursor composition may be represented by the following formula (7).

The compound contained in the film forming precursor composition may be represented by the following formula (8).

R in the formula 8 may be any one selected from the group consisting of C ₁ -C ₅ alkyl groups.

The compound contained in the film forming precursor composition may be represented by the following formula (9).

The compound contained in the film forming precursor composition may be represented by the following formula (10).

The compound contained in the film forming precursor composition may be represented by the following formula (11).

Each of R ₁ to R ₆ in the formula (11) may be independently selected from C ₁ -C ₅ alkyl groups.

R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ in the formula (11) are connected to each other to form a C ₃ -C ₆ cyclic amine group together with the nitrogen atom to which they are bonded .

The compound contained in the film forming precursor composition may be represented by the following formula (12).

The compound contained in the film forming precursor composition may be represented by the following formula (13).

R in the above formula (13) may be any one selected from a C ₁ -C ₅ alkyl group.

The compound contained in the film forming precursor composition may be represented by the following formula (14).

A thin film deposition method according to an embodiment of the present invention is a method of depositing a thin film on a substrate by supplying the precursor composition for film formation and atomic layer deposition (ALD) or chemical vapor deposition (CVD) Lt; / RTI &gt;

The thin film may be deposited at a temperature ranging from 50 to 700 ° C.

The precursor composition for film formation may be a bubbling method, a vapor phase mass flow controller (MFC) method, a direct gas injection (DGI) method, a direct liquid injection (DLI) Or an organic solution supplying method in which the precursor composition for film formation is dissolved in an organic solvent and transferred onto the substrate.

The precursor composition for film formation is moved onto the substrate by the bubbling method or the direct gas injection method together with a carrier gas, and the carrier gas may be argon (Ar), nitrogen (N ₂ ), helium And hydrogen (H ₂ ).

The thin film is any one of a titanium oxide film, a zirconium oxide film, and a hafnium oxide film. The thin film is composed of water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), and hydrogen peroxide (H ₂ O ₂ ) It is possible to supply at least one kind of reaction gas selected from the group.

The thin film is any one of a titanium nitride film, a zirconium nitride film, and a hafnium nitride film. The thin film is composed of ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), nitrogen dioxide (NO ₂ ), and nitrogen (N ₂ ) Can be supplied.

Effects of the precursor composition for film formation and the thin film formed using the precursor composition according to an embodiment of the present invention will be described below.

The precursor composition for film formation according to an embodiment of the present invention effectively increases thermal stability.

Since the precursor composition for film formation according to an embodiment of the present invention has excellent thermal stability, the precursor composition for film formation may increase the deposition temperature of the thin film on the substrate.

Since the precursor composition for film formation according to an embodiment of the present invention has excellent thermal stability, a single atomic layer can be deposited stably in an atomic layer deposition (ALD) process, and the window range of an ALD process can be extended.

The precursor composition for film formation according to one embodiment of the present invention effectively reduces the amount of residue in the deposition process.

Since the precursor composition for film formation according to an embodiment of the present invention effectively reduces the amount of the residue, the storage stability of the precursor compound for deposition is secured and the temperature of the vaporizer can be increased during the deposition process.

When a thin film is deposited on a substrate using the precursor composition for film formation according to an embodiment of the present invention, the quality of the thin film deposited on the substrate is improved.

1 is a graph showing FID analysis results of CpCp according to an embodiment of the present invention.
2 is a graph showing NMR analysis results of CpCpTi (O-Ipr) ₃ according to an embodiment of the present invention.
FIG. 3 is a graph showing NMR analysis performed after a thermal test of CpCpTi (O-Ipr) ₃ according to an embodiment of the present invention.
4 is a graph showing a TGA / DSC analysis result of CpCpTi (O-Ipr) ₃ according to an embodiment of the present invention.
5 is a graph showing NMR analysis results of a CpCpTDMAZ compound according to an embodiment of the present invention.
6 is a graph showing NMR analysis results of each of the composition (CT), the composition (CX), and the composition (CH) according to one embodiment of the present invention.
7 is a graph showing the results of NMR analysis performed after a thermal test of a CpCpTDMAZ compound, a composition (CT), a composition (CX), and a composition (CH) according to an embodiment of the present invention.
8 is a graph showing the DSC thermal curve and the TGA thermal curve of the CpCpTDMAZ compound, the composition (CT), the composition (CX), and the composition (CH) according to an embodiment of the present invention.

The present invention relates to a film forming precursor composition and a thin film forming method using the same, and the embodiments of the present invention will be described with reference to the following formulas and graphs. The embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below.

BACKGROUND ART [0002] With the development of electronic technology, demands for miniaturization, low power consumption, and high capacity of electronic devices used in various electronic devices are increasing rapidly. In order to manufacture a miniaturized electrochemical cleaner, miniaturization of a metal oxide semiconductor (MOS) or metal oxide semiconductor (MOS) device is required.

In order to miniaturize electronic devices including MOS devices, it is necessary to reduce the area or the thickness of the gate dielectric film of the MOS transistor or the oxide which is the gate dielectric material forming the dielectric film of the capacitor. However, reducing the area of the gate dielectric film reduces the gate charge capacity. Also, if the thickness of the gate dielectric film is reduced, the charging capacity is increased, but the leakage current is also increased and the performance of the electronic device is deteriorated.

In the past, silicon dioxide (SiO ₂ ) was generally used as a MOS device. Silicon dioxide has a limitation of the physical thickness at which direct quantum mechanical tunneling occurs, and its physical thickness limit is about 1.5 to 2 mm. There has been a limit to reducing the dielectric film thickness of MOS devices using silicon dioxide because silicon dioxide has a problem of leakage current due to the tunneling effect at thicknesses below the physical thickness limit. Therefore, there is a growing interest in a high dielectric constant material that forms an oxide film that is electrically equivalent to silicon dioxide, and at the same time does not cause physical tunneling and can form a relatively thin dielectric film compared to silicon dioxide. Particularly, TiO ₂ Metal oxides such as ZrO ₂ , HfO ₂ , STO (SrTiO ₃ ), BST ((Ba, Sr) TiO ₃ ), HfSiO _x and ZrSiO _x are attracting attention as the next generation high-permittivity materials.

Titanium (Ti) is used in various fields of semiconductor devices. Titania (TiO ₂ ) thin films are single films and thin films with the highest dielectric constant, and can be used as various insulating layers of dynamic random access memory (DRAM). The titanium nitride (TiN) thin film may be used as a lower electrode of a high-density DRAM, and may also be used as an interconnection metal such as an adhesion layer for depositing Cu and the like.

Zirconium (Zr) is also used in various fields of semiconductor devices. A zirconia (ZrO ₂ ) thin film has a dielectric constant of about 25, a band gap of about 5 eV, a large refractive index (greater than about 2), an excellent reactivity , And is chemically stable. Since the zirconium oxide thin film is thermally stable when it is in contact with the Si interface, it is used as a gate dielectric or a dielectric of a capacitor in manufacturing a semiconductor device such as a DRAM.

Hafnium (Hf) is also used in various fields of semiconductor devices, and hafnium oxide (HfO ₂ ) has properties similar to zirconium oxide (ZrO ₂ ).

Generally, when forming a titanium-containing film, a zirconium-containing film, and a hafnium-containing film, a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method typified by metalorganic chemical vapor deposition (MOCVD) ), And the like are deposited through a chemical vapor deposition process. The MOCVD deposition method can form a high-quality titanium-containing film, a zirconium-containing film-containing hafnium-containing film through chemical vapor deposition, and the ALD deposition method produces a titanium-containing film, a zirconium- It is possible to adjust to the atomic unit.

In order to form and deposit the desired titanium, zirconium or hafnium containing film through MOCVD or ALD processes, a titanium precursor, zirconium precursor or hafnium precursor suitable for each process must be used. Typically, in the MOCVD process, a ligand of a titanium precursor for film formation, a zirconium precursor for film formation, or a hafnium precursor for film formation is thermally decomposed to remove titanium oxide, zirconium oxide or hafnium oxide at a temperature of 250 to 500 ° C It must be disassembled. On the other hand, in the ALD process, the ligand present in the titanium precursor for film formation, the zirconium precursor for film formation or the hafnium precursor for film formation must be completely decomposed and removed by ozone (O ₃ ) or water (H ₂ O) .

The conditions of the titanium precursor for film formation, the zirconium precursor for film formation and the hafnium precursor for film formation suitable for MOCVD or ALD processes must have a high vapor pressure at a low temperature (approximately 100 ° C or less), have sufficient thermal stability, Material.

The present invention provides a precursor material capable of depositing a thin film at a high temperature with an excellent thermal stability, improving the step coverage of the formed thin film, and capable of stable atomic layer deposition, thereby securing an extensive ALD window. I want to.

The precursor composition for film formation according to one embodiment of the present invention includes an organometallic compound represented by the following Chemical Formula 1.

&Lt; Formula 1 >

In Formula 1, M is a metal element belonging to Group 4A or 4B on the periodic table and may be any one selected from Ti, Zr, and Hf. <Formula 1> and m is 1, represents any one of integers of 1 to 5, L is any one selected from a dialkyl amino group of the C ₁ -C ₅ alkoxide group, C ₁ -C ₅ amino group or a C ₁ -C ₅ of the Lt; / RTI &gt;

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (2). In Formula 2, m represents any one of integers from 1 to 5, and L may be any one selected from the group consisting of C ₁ -C ₅ alkoxide groups. L may be an isopropoxy group.

(2)

The precursor composition for film formation according to one embodiment of the present invention may include an organometallic compound represented by the following formula (3). R in formula (3) may be any one selected from the group consisting of C ₁ -C ₅ alkyl groups.

(3)

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (4). An organic metal compound represented by the following <Formula 4> is tris (isopropoxy) (cyclopentyl-cyclopentadienyl) titanium (Tris (isopropoxy) (cyclopenthylcyclopentadienyl) titanium, ((η-C 5 H 5) C 5 H 9 ) is _{Ti (OCH (CH 3) 2} ) 3, CpCpTi (O-Ipr) 3).

&Lt; Formula 4 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (5). M in the following formula (5) is the same as m in the formula (1).

&Lt; Formula 5 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (6). R ₁ to R ₆ in the following formula (6) may be the same or different from each other and may be selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 13 carbon atoms , Preferably a C ₁ -C ₅ alkyl group. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ in the following formula (6) are connected to each other to form a cyclic amine group having 3 to 10 carbon atoms together with the nitrogen atom to which they are bonded, Preferably a C ₃ -C ₆ cyclic amine group.

(6)

The formula 6 may be any one of compounds represented by the following formulas.

Specific examples of the cyclopentadienyl zirconium (IV) compound in which the cycloalkyl group is substituted with the above-mentioned formula 6 include tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium (IV) (((nC ₅ H ₅ ) C ₅ H ₉ ) Zr (N (CH ₃ ) ₂ ) ₃ : CpCpTDAMZ), tris (dimethylamino) (cyclopropylcyclopentadienyl) zirconium (IV), tris Zirconium (IV), tris (dimethylamino) (cyclohexylcyclopentadienyl) zirconium (IV) and tris (dimethylamino) (cycloheptylcyclopentadienyl) zirconium (IV).

The precursor composition for forming a zirconium-containing film according to an embodiment of the present invention comprises 1 to 10 moles of a cyclopentadienyl zirconium (IV) compound substituted with a cycloalkyl group represented by the formula 6, , An alicyclic unsaturated compound represented by the following formula (16) or an aromatic compound represented by the following formula (17): Preferably, the cyclopetazienyl zirconium (IV) based compound in which the cycloalkyl group is substituted with the formula 6 is an amine compound represented by the formula 15, an alicyclic unsaturated The ratio of the number of moles of the compound or the aromatic compound represented by the formula (17) is preferably 1 to 6: 1 to 6 in terms of convenience in the vapor deposition process, thermal stability, storage stability, And more preferably from 1: 5: 1 to 5: 1 to 3: 1 to 3.

&Lt; Formula 15 >

&Lt; Formula 16 >

&Lt; Formula 17 >

In Formula 15, R ' ₁ to R' ₃ may be the same or different from each other, and may be an alkyl group having 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R '' ₁ to R '' ₈ in the above Formula 16 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms &Lt; / RTI &gt; R ''' ₁ to R''' ₆ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 7 to 13 carbon atoms Aralkyl group, and m 'and n' may be independently selected from integers of 0 to 10.

Specific examples of the amine compound represented by the formula (15) include triethylamine, trimethylamine, tripropylamine, tributylamine, and the like. The compound of formula (15) does not cause a chemical reaction with the compound of formula (6), and a stable mixture of the compound of formula (6) and the compound of formula From the viewpoint of increasing the temperature, the above-mentioned formula (15) is preferably trienylamine.

Specific examples of the alicyclic unsaturated compound represented by the formula (16) include cycloheptatriene, cyclooctatriene, cyclononetetraene, and cyclooctadiene. The compound of formula (16) does not cause a chemical reaction with the compound of formula (6), and a stable mixture of the compound of formula (6) and the compound of formula From the viewpoint of increasing the decomposition temperature, the above-mentioned formula (16) is preferably cycloheptatriene.

Specific examples of the aromatic compound represented by the formula (17) include benzene, toluene, o-, m-, or p-xylene. The compound of the formula (17) can be obtained without causing a chemical reaction with the compound of the formula (6), and the storage stability of the compound of the formula In order to increase the decomposition temperature, it is preferable that the formula (17) is o-, m- or p-xylene.

The zirconium-containing film-forming precursor composition of the present invention comprises 1 to 5 mol of tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium (IV) and 1 to 5 mol of triethylamine, cycloheptatriene or xylene . &Lt; / RTI &gt;

The zirconium-containing film-forming precursor composition of the present invention is a composition in which the above-mentioned two compounds are stably mixed at a constant molar ratio, but each precursor compound does not react with each other during deposition and is sprayed from one nozzle to form zirconium Containing film can be formed.

The cyclopentadienyl zirconium (IV) based compound in which the cycloalkyl group is substituted with the formula 6 may be prepared by reacting an amine compound represented by the formula 15, an alicyclic unsaturated compound represented by the formula 16, The volatile composition exhibiting a high vapor pressure at a temperature including room temperature while being in a stable and uniformly mixed state with each other in a liquid state without reacting with the aromatic compound represented by the formula (17) can be formed. This composition is also excellent in storage stability and thermal stability and has less decomposition residue. Therefore, by using the zirconium-containing film-forming precursor composition according to the present invention, it is possible to easily and efficiently form a zirconium-containing film having excellent film characteristics, thickness uniformity and step coverage in the semiconductor manufacturing process.

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following general formula (7).

&Lt; Formula 7 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (8), and R in formula (8) may be any one selected from a C ₁ -C ₅ alkyl group have.

(8)

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (9).

&Lt; Formula 9 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following general formula (10). M in the following formula (10) is the same as m in the formula (1).

&Lt; Formula 10 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (11). R ₁ to R ₆ in the following formula (11) may be the same or different from each other and may be selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 13 carbon atoms , Preferably a C ₁ -C ₅ alkyl group. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ in the following formula (11) are connected to each other to form a cyclic amine group having 3 to 10 carbon atoms together with the nitrogen atom to which they are bonded, Preferably a C ₃ -C ₆ cyclic amine group.

&Lt; Formula 11 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (12).

&Lt; Formula 12 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (13), wherein R in the following formula (13) is any one selected from a C ₁ -C ₅ alkyl group .

&Lt; Formula 13 >

The precursor composition for film formation according to an embodiment of the present invention may include an organometallic compound represented by the following formula (14).

&Lt; Formula 14 >

A thin film deposition method according to an embodiment of the present invention includes depositing a thin film on a substrate using a precursor composition containing an organometallic compound represented by Chemical Formulas 1 to 14.

In the thin film deposition method according to an embodiment of the present invention, the deposition process for forming the thin film is not particularly limited. Chemical vapor deposition and other physical vapor deposition (PVD) may be used and preferably include chemical vapor deposition (CVD) such as metal organic chemical vapor deposition (MOCVD), low pressure CVD (LPCVD), plasma enhanced chemical vapor deposition (PECVD), pulsed PECVD, atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PE-ALD), and combinations thereof.

Since the precursor composition for film formation according to an embodiment of the present invention is excellent in thermal stability, a thin film of good quality can be formed in a high temperature deposition process such as metalorganic chemical vapor deposition (MOCVD) as well as low temperature. It is also possible to uniformly grow a single atomic layer according to a self-limiting reaction in an atomic layer deposition (ALD) process. In addition, since the precursor composition for forming a film according to an embodiment of the present invention has almost no residue even at a high temperature of about 500 ° C or more, the temperature of the evaporator can be increased during the thin film deposition process.

In the thin film deposition method according to an embodiment of the present invention, the temperature range of the deposition temperature for depositing the precursor composition for forming a substrate according to an embodiment of the present invention may be 50 to 700 ° C. The temperature range of the deposition temperature may preferably be 50 to 500 占 폚. In addition, the internal pressure of the process chamber in which the deposition reaction is performed can be maintained at 0.2 to 10 torr.

In the thin film deposition method according to an embodiment of the present invention, a thermal deposition method using thermal energy or a plasma enhanced chemical vapor deposition (PECVD) Or a method of applying an appropriate electrical bias on a substrate may be used. In the method using plasma, a direct or remote plasma source may be used.

In the thin film deposition method according to an embodiment of the present invention, if necessary for the process, a step of transferring the precursor composition for film formation onto a substrate before deposition may be preceded. As a method of transferring the precursor composition for film formation onto a substrate, a bubbling method, a vapor phase MFC (mass flow controller), a direct gas injection method (DGI), a direct liquid injection method DLI, Direct Liquid Injection) or an organic solution supplying method in which the precursor composition for film formation is dissolved in an appropriate organic solvent and transferred.

The precursor composition for film formation may be transferred to an upper portion of the substrate together with a suitable carrier gas and a gas which does not react with the precursor composition for film formation according to an embodiment of the present invention may be used as the carrier gas. The carrier gas may comprise a gas comprised of argon (Ar), nitrogen (N ₂ ), helium (He), hydrogen (H ₂ ), and combinations thereof.

In the thin film deposition method according to an embodiment of the present invention, a pure metal thin film such as a titanium thin film, as well as a thin film of a titanium oxide film and a titanium nitride film can be formed by using the precursor composition for film formation of the present invention as a source material. The titanium oxide layer may have a chemical structure of TiOx as an example, and the titanium nitride film may have a chemical structure of TiNx as an example.

(H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), and hydrogen peroxide (H ₂ O) as a separate oxygen supply source in addition to the precursor compound for film formation of the present invention as a titanium source material, O) may be used as the reaction gas.

(NH ₃ ), hydrazine (N ₂ H ₄ ), and nitrogen (N ₂ ) as a separate nitrogen supply source in addition to the precursor compound for film formation of the present invention as a titanium source material in the case of forming a titanium nitride film May be used.

The thin film deposition method according to an embodiment of the present invention can form a thin metal film such as a zirconium oxide film and a zirconium nitride film as well as a pure metal thin film such as a zirconium thin film by using the precursor composition for film formation of the present invention as a source material. The zirconium oxide film may have a chemical structure of ZrOx, for example, and the zirconium nitride film may have a chemical structure of ZrNx, for example.

(H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), and hydrogen peroxide (H ₂ O) as a separate oxygen supply source in addition to the precursor composition for film formation of the present invention as a zirconium oxide material, O) may be used as the reaction gas.

(NH ₃ ), hydrazine (N ₂ H ₄ ), and nitrogen (N ₂ ) as a separate nitrogen supply source in addition to the precursor composition for film formation of the present invention as a zirconium source material in order to form a zirconium nitride film May be used.

The thin film deposition method according to an embodiment of the present invention can form a thin film of a hafnium oxide film and a hafnium nitride film as well as a pure metal thin film such as a hafnium thin film by using the precursor composition for film formation of the present invention as a source material . The hafnium oxide film may illustratively have the chemical structure of HfOx, and the hafnium nitride film may illustratively have the chemical structure of HfNx.

(H ₂ O), oxygen (O ₂ ), ozone (O ₃ ) and hydrogen peroxide (H ₂ O) as a separate oxygen supply source in addition to the precursor composition for film formation of the present invention as a hafnium source material, O) may be used as the reaction gas.

(NH ₃ ), hydrazine (N ₂ H ₄ ), and nitrogen (N ₂ ) as a separate source of nitrogen supply, in addition to the precursor composition for film formation according to one embodiment of the present invention as a hafnium source material, May be used as the reaction gas.

The precursor composition for film formation of the present invention used as a metal source to form an oxide film (titanium oxide film, zirconium oxide film, hafnium oxide film) or nitride film (titanium nitride film, zirconium nitride film or hafnium nitride film) , Or sequentially (ALD process). When the oxide film and the nitride film are deposited through the ALD process, the precursor composition for film formation of the present invention, which is a source material, and the above-mentioned reaction gas can be alternately transferred to the substrate.

The reaction gas, which is provided as an oxygen source or a nitrogen source, can be decomposed into a radical form by plasma treatment. Plasma can be generated at a power in the range of 50 to 500 W for the plasma treatment of the reaction gas.

A specific method for performing ALD deposition using the thin film deposition method according to an embodiment of the present invention, particularly the precursor composition for film formation of the present invention, is as follows. I) transferring the precursor composition for film formation to a chamber, ii) adsorbing the transferred precursor composition for film formation onto a substrate to form a precursor layer on the substrate, iii) injecting a first purge gas into the chamber, Removing the precursor, iv) injecting a reactive gas into the chamber to form an oxide film or nitride film, and v) injecting a second purge gas into the chamber to remove excess reactive gas and byproducts in one cycle , 10 to 1000 times, preferably 100 to 600 times can be repeated. As the first purge gas and the second purge gas, an inert gas such as argon may be used.

The following examples are provided to more clearly illustrate the precursor composition for film formation of the present invention, and the scope of the present invention is not construed as being limited to the following examples.

Experimental conditions

In the present invention, a standard vacuum line Schlenk technique was used as a technique for synthesizing an organometallic compound, and synthesis for all materials was performed in a nitrogen gas atmosphere. In the experiments, the dicyclopentadiene (DCPD), NaH, ZrCl ₄ , dimethylamine (DMA), triethylamine (TEA), cycloheptatriene, chlorotriisopropoxy titanium (chlorotriisopropoxytitanium, ClTi (O-Ipr) ₃ ), n-BuLi, bromocycloprntane (BCP), hexane, tetrahydrofurane (THF) and p- will be. All the solvents were stirred with CaH ₂ for one day before use to completely remove the residual water, followed by fractional purification. NaH was washed with hexane and then filtered under reduced pressure to completely remove the oil present in NaOH and stored in a glove box. Substance fraction of material proceeded in glove box.

The structure of the compound was analyzed by JEOL JNM-ECS 400 MHz NMR spectrometer ( ¹ H-NMR 400 Mhz). Benzene- d ₆ in NMR solvent was stirred with CaH ₂ for one day to remove residual water completely before use. The purity of the compound was analyzed using Agilent 7890A, and the sample injection amount was 0.6 μl. The thermal stability and decomposition temperature of the compound were analyzed using a TA-Q 600 product, and a sample amount of 10 mg was used.

Example 1: Synthesis of cyclopentadiene, C ₅ H ₆ , Cp)

6.3 g (0.048 mol) of dicyclopentadiene (DCPD) was added to a 500 ml round-bottomed round flask as shown in the following Reaction Scheme 1, the temperature was raised to 160 ° C and the mixture was subjected to simple distillation to obtain a colorless cyclopentadiene C ₅ H ₆ , Cp) (yield: 95%).

_{^{1 H-NMR (C 6 D}} 6): δ 2.7, 6.3, 6.5 [(C 5 H 6), m, 6H]

<Reaction Scheme 1>

Example 2: Synthesis of cyclopentylcyclopentadiene, ((C ₅ H ₅ ) C ₅ H ₉ , CpCp)

Cyclopentylcyclopentadiene (C ₅ H ₅ ) C ₅ H ₉ , CpCp) was synthesized using the Cp obtained in Example 1, as shown in Reaction Scheme 2 below. To a 500 ml round trip flask were added 2 g (0.081 mol) of NaOH and 100 ml of tetrahydrofuran (THF). After cooling the reactor temperature to -10 ° C, 6 g (0.09 mol) of Cp was added very slowly using a dropping funnel. When Cp was completely added, the reactor temperature was raised to 20 < 0 > C and stirred for 4 hours. When the violet solution was made after stirring for 4 hours, the reactor temperature was again cooled to -10 DEG C and 12.1 g (0.09 mol) of bromocyclopentane (BCP) was added very slowly. When the BCP was completely added, the reactor temperature was raised to 20 &lt; 0 &gt; C and stirred for 4 hours. After stirring for 4 hours, the salt was completely removed by filtration under reduced pressure to obtain 5.47 g of yellow CpCp (yield: 60%, purity: 99% or more) through reduced pressure purification.

Boiling point (b.p): 30 ° C at 0.8 torr

<Reaction Scheme 2>

FIG. 1 shows the result of analyzing the CpCp with a flame ionization detector (FID). As shown in FIG. 1, as a result of FID analysis for CpCp, a single peak is formed, which indicates that CpCp has a high purity as a single substance.

Example 3: Synthesis of tri (isopropoxy) (cyclopentylcyclopentadienyl) titanium, ((η-C (cyclopentylcyclopentadienyl) ₅ H ₅ ) C ₅ H ₉ ) Ti (OCH (CH ₃ ) ₂ ) ₃ , CpCpTi (O-Ipr) ₃ ) Synthesis of

(Isopropoxy) (cyclopentylcyclopentadienyl) titanium, ((η-C ₅ (cyclopentylcyclopentadienyl)) titanium was obtained by using CpCp obtained in Example 2, H ₅ ) C ₅ H ₉ ) Ti (OCH (CH ₃ ) ₂ ) ₃ and CpCpTi (O-Ipr) ₃ ) were synthesized. To a 500 ml eggplant flask was added 250 ml of THF and 16.11 ml (0.04 mol) of 2.5 M-BuLi was added. Cooling the reactor temperature to -10 ℃ and chlorotrifluoroethylene-isopropoxy titanium (chlorotriisopropoxytitanium, ClTi (O-Ipr ) 3 10.62 g (0.04 mol) was added. When the reactor temperature 20 was added to completely ClTi (O-Ipr) ₃ After stirring for 12 hours, the salt was completely removed by filtration under reduced pressure, and 8.67 g (yield: 60%) of yellow CpCpTi (O-Ipr) ₃ was obtained through vacuum purification.

Boiling point (b.p): 130 ° C at 0.5 torr

_{^{1 H-NMR (C 6 D}} 6): δ 1.22 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, m, 18H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.68 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, br, 4H)

_{^{1 H-NMR (C 6 D}} 6): δ 2.06 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, br, 4H)

_{^{1 H-NMR (C 6 D}} 6): δ 3.18 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, m, 1H)

_{^{1 H-NMR (C 6 D}} 6): δ 4.55 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, m, 3H)

_{^{1 H-NMR (C 6 D}} 6): δ 6.05 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, m, 2H)

_{^{1 H-NMR (C 6 D}} 6): δ 6.10 (((η-C 5 H 4) C 5 H 9) Ti (OCH (CH 3) 2) 3, m, 2H)

<Reaction Scheme 3>

Example 4: CpCpTi (O-Ipr) ₃ Thermal Stability Experiment

2 shows NMR analysis results of CpCpTi (O-Ipr) ₃ synthesized in Example 3 above. Fig. 3 shows the results of NMR analysis after CpCpTi (O-Ipr) ₃ synthesized in Example 3 was subjected to a thermal stability test at 200 ° C for 16 hours. As shown in FIGS. 2 and 3, it was observed that the same peak was formed. As a result, the decomposition of CpCpTi (O-Ipr) ₃ did not occur even though the thermal stability test was conducted at 200 ° C. for 16 hours. Therefore, it can be seen that CpCpTi (O-Ipr) ₃ according to one embodiment of the present invention has excellent thermal stability.

Example 5: CpCpTi (O-Ipr) ₃ Thermal analysis of

Thermogravimetric analysis (TGA) / differential scanning calorimetry (DSC) analysis was performed to investigate the thermal properties of CpCpTi (O-Ipr) ₃ synthesized in Example 3 above. The results of TGA / DSC analysis according to this embodiment are shown in FIG. In Figure 4, the green curve shows the TGA analysis of the CpCpTi (O-Ipr) _3, the blue curve represents the DSC analysis of the CpCpTi (O-Ipr) _3. As shown in FIG. 4, the decomposition temperature of CpCpTi (O-Ipr) ₃ was 238.87 ° C, and T (1/2) was 218.99 ° C. In addition, the temperature was raised to 500 ° C and the residue was confirmed to be 4.86%. Therefore, it can be seen that the thermal stability of CpCpTi (O-Ipr) ₃ of the present invention is excellent and the residue is small.

Example 6: Synthesis of tetrakis (dimethylamino) zirconium, Zr (N (CH ₃ ) ₂ ) ₄ , TDMAZ)

250 ml of hexane was added to a 500 ml eggplant-shaped flask, and then 64.42 ml (0.16 mol) of 2.5 M n-BuLi was added as shown in Reaction Scheme 4 below. The reactor temperature was cooled to -10 DEG C and 7.35 g (0.16 mol) of dimethylamine (DMA) gas was slowly added. When the DMA gas introduction was completed, the temperature of the reactor was raised to 20 占 폚 and stirred for 4 hours. After 4 hours, the reactor temperature was cooled to 0 ° C and 9.5 g (0.04 mol) of ZrCl ₄ was added. When the addition of ZrCl ₄ was complete, the reactor temperature was raised to 20 ° C and further stirred for 4 hours. After 4 hours, the salt was completely removed by filtration under reduced pressure, and 10.9 g of colorless tetrakis (dimethylamino) zirconium, Zr (N (CH ₃ ) ₂ ) ₄ , TDMAZ 95%).

Boiling point (b.p): 65 ° C at 0.8 torr

¹ H-NMR (C ₆ D ₆ ):? 2.97 ((N (C H ₃ ) ₂ ) ₄ Zr, s, 24H)

<Reaction Scheme 4>

Example 7 Tris (dimethylamino) (cyclopentyl-cyclopentadienyl) zirconium (Tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium, ((η-C 5 H 5) C 5 H 9) Zr (N (CH 3) 2 ) ₃ , CpCpTDMAZ)

(1) Reaction 1

As shown in Reaction Scheme 5, 250 ml of hexane was added to a 500 ml branched flask, 10.9 g (0.04 mol) of TDMAZ was added, and the reactor temperature was maintained at 20 占 폚. Then, 5.48 g (0.04 mol) of CpCp was added slowly and stirred for 4 hours. After 4 hours, 10 g of yellow CpCpTDMAZ (yield: 75%) was obtained through reduced pressure purification.

Boiling point (b.p): 130 ° C at 0.5 torr

_{^{1 H-NMR (C 6 D}} 6): δ 6.5, 6.2 (((η-C 5 H 5) C 5 H 9) Zr (N (CH 3) 2) 3, m, 5H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.5, 1.6, 1.9 (((η-C 5 H 5) C 5 H 9) Zr (N (CH 3) 2) 3, m, 9H)

_{^{1 H-NMR (C 6 D}} 6): δ 2.9 (((η-C 5 H 5) C 5 H 9) Zr (N (C H 3) 2) 3, s, 18H)

<Reaction Scheme 5>

(2) Reaction 2

To a 500 ml eggplant flask was added 250 ml of hexane and 64.42 ml (0.16 mol) of 2.5 M n-BuLi was added. After the reactor temperature was cooled to -10 ° C, 7.35 g (0.16 mol) of DMA gas was slowly added. When the DMA gas was fully charged, the reactor temperature was raised to 20 &lt; 0 &gt; C and further stirred for 4 hours. After 4 hours, the reactor temperature was cooled to 0 ° C and 9.5 g (0.04 mol) of ZrCl ₄ was added. When ZrCl ₄ is completely added, the reactor temperature raised to 20 ℃ and was stirred for 8 hours. After an 8 hour cure, 5.48 g (0.04 mol) of CpCp was further added and stirred for a further 4 hours. After stirring for 4 hours, the salt was removed by filtration under reduced pressure, and 10 g of yellow CpCpTDMAZ (yield: 75%) was obtained through purification under reduced pressure.

Boiling point (b.p): 130 ° C at 0.5 torr

_{^{1 H-NMR (C 6 D}} 6): δ 6.5, 6.2 (((η-C 5 H 5) C 5 H 9) Zr (N (CH 3) 2) 3, m, 5H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.5, 1.6, 1.9 (((η-C 5 H 5) C 5 H 9) Zr (N (CH 3) 2) 3, m, 9H)

_{^{1 H-NMR (C 6 D}} 6): δ 2.9 (((η-C 5 H 5) C 5 H 9) Zr (N (C H 3) 2) 3, s, 18H)

Example 8: Preparation of tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium-triethylamine (CpCpTDMAZ-TEA, C-T) composition

50 g (0.140 ml) of CpCpTDMAZ was added to a 500 ml round bottomed flask in a room temperature glove box and 2.83 g (0.028 mol) of triethylamine (TEA) was slowly added thereto after the temperature was lowered to 0 ° C. Thereafter, the temperature of the mixture was gradually raised to room temperature to obtain a CpCpTDMAZ-TEA (C-T) composition.

Example 9: Preparation of tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium-xylene (CpCpTDMAZ-xylene, C-X) composition

In a room temperature glovebox, 45 g (0.126 mol) of CpCpTDMAZ was added to a 500 ml round-bottomed flask, the temperature was lowered to 0 ° C, and 6.69 g (0.063 mol) of xylene was slowly added. Thereafter, the temperature of the mixture was gradually raised to room temperature to obtain a CpCpTDMAZ-xylene (C-X) composition.

Example 10: Preparation of tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium-cycloheptatriene (C-H) composition

48 g (0.13 mol) of CpCpTDMAZ was added to a 500 ml round bottom flask in a room temperature glove box, the temperature was lowered to 0 ° C, and then 6.20 g (0.067 mol) of cycloheptatriene was added slowly. Thereafter, the temperature of the mixture was gradually raised to room temperature to obtain a CpCpTDMAZ-cycloheptatriene (C-H) composition.

Example 11: Thermal stability test of CpCpTDMAZ, composition (C-T), composition (C-Z) and composition (C-H)

Composition (CX) and CpCpTDMAZ (CX) of the composition (CT), CpCpTDMAZ: p-xylene: p-xylene = 2: 1 molar ratio of CpCpTDMAZ compound obtained in Example 7 and CpCpTDMAZ: TEA = : Cycloheptatriene = 2: 1 molar ratio of the composition (CH).

FIG. 5 shows the NMR spectrum of the CpCpTDMAZ compound obtained in Example 5, and FIG. 6 shows the NMR spectra of the composition (C-T), the composition (C-X) and the composition (C-H) immediately after mixing as obtained in Examples 8 to 10.

As shown in Fig. 5, the CpCpTDMAZ according to the present invention was confirmed at proton peaks at 6.5 and 6.2 ppm of the CpCp cyclopentadienyl group and at 1.5, 1.6 and 1.9 ppm for the cyclopentyl group. Further, a proton peak derived from a dimethylamine group was confirmed at 2.9 ppm.

Referring to FIG. 6, peaks inherent to CpCpTDMAZ were retained in each of the composition (CT), the composition (CX) and the composition (CH), and the characteristics of TEA, xylene and cycloheptatriene mixed therewith It can be confirmed that it is maintained. Thus, it was confirmed that the CpCpTDMAZ compounds of the compositions prepared in Examples 8 to 10 did not cause any chemical reaction with TEA, p-xylene or cycloheptatriene, and that the respective compounds retained their properties have.

The composition (CX) of the CpCpTDMAZ compound and the composition (CT) of the CpCpTDMAZ: TEA = 5: 1 molar ratio, the composition (CX) and the composition CpCpTDMAZ: cycloheptatriene in a molar ratio of CpCpTDMAZ: p- CH) were heated and held at about 200 ° C for about 16 hours, and NMR spectroscopic analysis was performed thereon.

7 is an NMR spectrum obtained by performing NMR spectroscopic analysis tests on the CpCpTDMAZ compound and the composition (C-T), the composition (C-X) and the composition (C-H) after the above thermal stability test. Comparing FIG. 7 with FIG. 5 and FIG. 6, it can be seen that there is no difference between the NMR spectra of FIG. 7, FIG. 5, and FIG. Thus, it was found that heating the CpCpTDMAZ compound and the composition (CT), the composition (CX) and the composition (CH) at about 200 ° C for about 16 hours did not cause pyrolysis of the compound, It can be confirmed that no occurrence has occurred. It can be seen from these experiments that the CpCpTDMAZ compound and the composition (C-T), the composition (C-X) and the composition (C-H) according to the present invention are thermally and chemically very stable. As described above, the thermal stability of the CpCpTDMAZ compound and the composition (C-T), the composition (C-X), and the composition (C-H) is excellent. Therefore, the film characteristics are improved when the zirconium-containing film is deposited.

Example 12: Thermal analysis of CpCpTDMA, composition (C-T), composition (C-Z) and composition (C-H)

FIG. 8 shows the DSC heat curve and the TGA heat curve obtained in the experiment for the CpCpTDMAZ compound and the composition (C-T), the composition (C-X) and the composition (C-H), respectively, in one drawing. The heat curve indicated by (A) on the upper side of FIG. 8 is the result obtained by the DSC test, and the heat curve indicated by (B) on the lower side is the result obtained by the TGA test.

From FIG. 8, the composition (C-T), the composition (C-X) and the composition (C-H) as well as the CpCpTDMAZ compound all exhibit only one decomposition temperature. From these, it can be seen that the compositions act like one compound. From FIG. 8, it can be seen that the thermal decomposition temperature and residual amount of the CpCpTDMAZ compound and the composition (C-T), the composition (C-X) and the composition (C-H) are as shown in Table 1 below.

CpCpTDMAZ Composition (C-T) Composition (C-X) Composition (C-H) Decomposition temperature (℃) 257.36 251.02 252.06 253.83 T (1/2) (占 폚) 241.83 228.28 232.70 235.08 Residue Content (%) 10.17 11.27 11.00 11.16

Referring to Table 1, the decomposition temperatures of the CpCpTDMAZ compound and the composition (C-T), the composition (C-X) and the composition (C-H) were confirmed to be 257.36, 251.02, 252.06 and 253.83 ° C, respectively. Therefore, it can be confirmed that the CpCpTDMAZ compound and the composition (C-T), the composition (C-X) and the composition (C-H) according to an embodiment of the present invention have a high decomposition temperature and can be deposited at a high temperature.

The residual contents of the CpCpTDMAZ compound and the composition (CT), the composition (CX) and the composition (CH) were 10.17 wt%, 11.27 wt%, 11.00 wt%, respectively, And 11.16 wt%, respectively. Here, the residue content is a percentage based on the weight of the sample before heating. From this, it can be seen that the CpCpTDMAZ compound is decomposed rapidly into zirconium by the removal of the ligand without thermal decomposition. From these results, it can be seen that when a zirconium-containing film is deposited using the CpCpTDMAZ compound of the present invention and the composition (CT), the composition (CX) and the composition (CH) containing the same, the zirconium-containing film can be easily formed .

Example 13: Viscosity measurement of CpCpTDMAZ, composition (C-T), composition (C-Z) and composition (C-H)

The viscosity was measured for each of the CpCpTDMAZ compound and the composition (C-T), the composition (C-Z), and the composition (C-H). The viscosities of the CpCpTDMAZ compound, the composition (CT), the composition (CZ) and the composition (CH) were measured at a temperature of the inside of the glove box at about 13 ° C by using a viscometer (manufacturer: model: SV- Five times in total. Thereafter, a thermal stability test was conducted in which the CpCpTDMAZ compound and each of the composition (CT), the composition (CZ) and the composition (CH) were heated at about 200 ° C for about 2 hours, The viscosity was measured five times in total. The test results are shown in Table 2 below.

Viscosity (centipoise, before heating at 200 ° C) Viscosity (centipoise, after heating at 200 ° C) CpCpTDMAZ 17.4 15.8 Composition (C-T) 12.3 10.2 Composition (C-X) 11.9 9.9 Composition (C-H) 11.7 10.5

Referring to Table 2, it can be seen that the CpCpTDMAZ compound and the composition (C-T), the composition (C-Z) and the composition (C-H) have low viscosities both before and after heating. Therefore, it can be seen that the CpCpTDMAZ compound and the composition (C-T), the composition (C-Z), and the composition (C-H) according to an embodiment of the present invention are excellent in volatility due to low attraction between molecules. Therefore, it can be seen that the step coverage of the zirconium-containing film is improved.

Example 14: Synthesis of tris (dimethylamino) (cyclopentylcyclopentadienyl) hafnium (tris (dimethylamino) cyclopentylcyclopentadienyl) hafnium, ((? ₅ H ₅ ) C ₅ H ₉ ) Hf (NMe ₂ ) ₃ , CpCpTDMAHf)

250 ml of hexane was added to a 500 ml eggplant-like flask as shown in Reaction Scheme 6, and 64.42 ml (0.16 mol) of 2.6M n-BuLi was added. After the reactor temperature was cooled to -10 ° C, 7.25 g (0.16 mol) of DMA gas was slowly added. The DMA gas was fully charged and the reactor temperature was raised to 20 < 0 > C and stirred for an additional 4 hours. After 4 hours the reactor was cooled to 0 ℃ temperature and was added to the _{HfCl 4 12.81 g (0.04 mol)} . When HfCl ₄ was added completely, the reactor temperature was raised to 20 ° C and stirred for an additional 8 hours.

After a further 8 hours, 5.48 g (0.04 mol) of CpCp was further added and stirred for a further 4 hours. After stirring for 4 hours, the salt was removed by filtration under reduced pressure, and 13.2 g (yield: 75%) of CpCpTDMAHf as yellow was obtained through vacuum purification.

Boiling point (b.p): 130 ° C at 0.5 torr

_{^{1 H-NMR (C 6 D}} 6): δ 6.0, 5.95 (((η-C 5 H 4) C 5 H 9) Hf (N (CH 3) 2) 3, m, 4H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.5, 1.6, 1.9 (((η-C 5 H 4) C 5 H 9) Hf (N (CH 3) 2) 3, m, 9H)

_{^{1 H-NMR (C 6 D}} 6): δ 3.00 (((η-C 5 H 4) C 5 H 9) Hf (N (C H 3) 2) 3, s, 18H)

<Reaction Scheme 6>

Example 15: Synthesis of tris (tibutoxy) (cyclopentylcyclopentadienyl) hafnium (t-buthoxy) cyclopentylcyclopentadienyl hafnium, (((? ₅ H ₄ ) C ₅ H ₉ ) Hf (O (C (CH ₃ ))) ₃ , CpCpHf (O ^t -Bu) ₃ ) Synthesis of

250 ml of hexane was added to a 500 ml eggplant-like flask as shown in Reaction Scheme 7, and 10 g (0.025 mol) of CpCpTDMAHf was added. After the reactor temperature was cooled to -10 ° C, 5.02 g (0.068 mol) of t-butyl alcohol was slowly added. When the addition was completed, the temperature of the reactor was raised to 20 ° C and further stirred for 4 hours. After 4 hours _{CpCpHf (O (C (CH 3} ))) with a pressure-sensitive tablet ₃ to give the 8.96 g (75% yield).

Boiling point (bp): 110 ° C at 0.5 torr

_{^{1 H-NMR (C 6 D}} 6): δ 6.20, 6.21 (((η-C 5 H 4) C 5 H 9) Hf (O (C (CH 3))) 3, m, 4H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.70, 2.08, 3.20 (((η-C 5 H 4) C 5 H 9) Hf (O (C (CH 3))) 3, m, 9H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.28 (((η-C 5 H 4) C 5 H 9) Hf (O (C (C H 3))) 3, m, 9H)

<Reaction Scheme 7>

Example 16: Synthesis of tris (tibutoxy) (cyclopentylcyclopentanyl) zirconium (tris (t-buthoxy) cyclopentylcyclopentadienyl) zirconium, ₅ H ₄ ) C ₅ H ₉ ) Zr (O (C (CH ₃ ))) ₃ , CpCpZr (O ^t -Bu) ₃ ) Synthesis of

As shown in Reaction Scheme 8, 250 ml of hexane was added to a 500-ml branched flask, and 10 g (0.028 mol) of CpCpTDMAZr was added thereto. After the reactor temperature was cooled to -10 ° C, 6.25 g (0.084 mol) of t-butyl alcohol was slowly added. When the addition was completed, the temperature of the reactor was raised to 20 ° C and further stirred for 4 hours. After 4 hours _{CpCpZr (O (C (CH 3} ))) with a pressure-sensitive tablet ₃ to give the 9.34 g (75% yield).

Boiling point (bp): 110 ° C at 0.5 torr

_{^{1 H-NMR (C 6 D}} 6): δ 6.23, 6.26 (((η-C 5 H 4) C 5 H 9) Zr (O (C (CH 3))) 3, m, 4H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.17, 2.1, 3.17 (((η-C 5 H 4) C 5 H 9) Zr (O (C (CH 3))) 3, m, 9H)

_{^{1 H-NMR (C 6 D}} 6): δ 1.27 (((η-C 5 H 4) C 5 H 9) Hf (O (C (C H 3))) 3, m, 9H)

<Reaction Scheme 8>

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, Therefore, the technical idea and scope of the claims set forth below are not limited to the embodiments.

Claims (28)

A precursor composition for film formation comprising a compound represented by the following formula (1).
&Lt; Formula 1 >

M is any one selected from the group consisting of Ti, Zr and Hf, m is any one selected from integers from 3 to 5, L is a C ₁ -C ₅ alkoxide group, a C ₁ -C ₅ amino group Or a C ₁ -C ₅ dialkylamino group. delete delete The method according to claim 1,
The precursor composition for film formation according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (3).
(3)

Wherein any one selected from the group consisting of <Formula 3> R is an alkyl group of C ₁ -C ₅ a. 5. The method of claim 4,
The precursor composition for film formation is characterized in that the compound represented by the formula (3) is represented by the following formula (4).
&Lt; Formula 4 >

delete The method according to claim 1,
The precursor composition for film formation according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (6).
(6)

R ₁ to R ₆ in Formula 6 are each independently selected from C ₁ -C ₅ alkyl groups. 8. The method of claim 7,
R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ in the formula 6 are connected to each other to form a C ₃ -C ₆ cyclic amine group together with the nitrogen atom to which they are bonded By weight based on the total weight of the composition. 8. The method of claim 7,
The film forming precursor composition preferably contains,
1 to 10 moles of the compound represented by the formula (6); And
Is an admixture of an amine compound represented by the following formula (15), an alicyclic unsaturated compound represented by the following formula (16), or an aromatic compound represented by the following formula (17) , A film forming precursor composition.
&Lt; Formula 15 >

&Lt; Formula 16 >

&Lt; Formula 17 >

In the formula 15, R ' ₁ to R' ₃ may be the same or different from each other and are an alkyl group having 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R " ₁ to R" ₈ may be the same or different from each other and is selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, and R ' ₁ to R ''' ₆ may be the same or different from each other and are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, m' and n Are independently selected from integers of from 0 to 10. 10. The method of claim 9,
The precursor composition for film formation according to claim 15, wherein the compound of formula (15) is triethylamine. 10. The method of claim 9,
The precursor composition for film formation according to claim 16, wherein the compound of formula (16) is cycloheptatriene. 10. The method of claim 9,
The precursor composition for film formation, which is characterized in that the compound of formula (17) is xylene. 10. The method of claim 9,
The film forming precursor composition preferably contains,
1 to 5 moles of the compound represented by the formula (6); And
Triethylamine, cycloheptatriene or xylene at a ratio of 1 to 5 moles,
Wherein the compound represented by the formula (6) is tris (dimethylamino) (cyclopentylcyclopentadienyl) zirconium (IV). 8. The method of claim 7,
The precursor composition for film formation according to claim 6, wherein the compound represented by the formula (6) is represented by the following formula (7).
&Lt; Formula 7 >

The method according to claim 1,
The precursor composition for film formation according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (8).
(8)

R in the above formula (8) is any one selected from a C ₁ -C ₅ alkyl group. 16. The method of claim 15,
The compound represented by the formula (8) is represented by the following formula (9).
&Lt; Formula 9 >

delete The method according to claim 1,
The precursor composition for film formation according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (11).
&Lt; Formula 11 >

R ₁ to R ₆ in Formula 11 are each independently selected from C ₁ -C ₅ alkyl groups. 19. The method of claim 18,
R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ in the formula (11) are connected to each other to form a C ₃ -C ₆ cyclic amine group together with the nitrogen atom to which they are bonded By weight based on the total weight of the composition. 19. The method of claim 18,
Wherein the compound represented by the formula (11) is represented by the following formula (12).
&Lt; Formula 12 >

The method according to claim 1,
The precursor composition for film formation according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (13).
&Lt; Formula 13 >

R in the above formula (13) is any one selected from a C ₁ -C ₅ alkyl group. 22. The method of claim 21,
The precursor composition for film formation according to claim 13, wherein the compound represented by the formula (13) is represented by the following formula (14).
&Lt; Formula 14 >

A thin film deposition method for depositing a thin film on a substrate by supplying a precursor composition for film formation and atomic layer deposition (ALD) or chemical vapor deposition (CVD)
Wherein the precursor composition for film formation is the precursor composition for film formation according to any one of claims 1, 4, 5, 7 to 16, 18 to 22. 24. The method of claim 23,
Wherein the thin film is deposited at a temperature ranging from 50 to 700 占 폚. 24. The method of claim 23,
The precursor composition for film formation may be a bubbling method, a vapor phase mass flow controller (MFC) method, a direct gas injection (DGI) method, a direct liquid injection (DLI) Or an organic solution supplying method in which the film forming precursor composition is dissolved in an organic solvent and moved on the substrate. 26. The method of claim 25,
The precursor composition for film formation is moved onto the substrate by the bubbling method or the direct gas injection method together with the carrier gas,
The carrier gas,
Wherein the mixture is at least one selected from the group consisting of argon (Ar), nitrogen (N ₂ ), helium (He), and hydrogen (H ₂ ). 24. The method of claim 23,
Wherein the thin film is any one of a titanium oxide film, a zirconium oxide film, and a hafnium oxide film,
Wherein at least one reaction gas selected from the group consisting of water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ) and hydrogen peroxide (H ₂ O ₂ ) is supplied during the deposition of the thin film . 24. The method of claim 23,
The thin film is any one of a titanium nitride film, a zirconium nitride film, and a hafnium nitride film,
Wherein at least one reaction gas selected from the group consisting of ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), nitrogen dioxide (NO ₂ ), and nitrogen (N ₂ ) is supplied during deposition of the thin film.

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