Precursor metal-silicon containing thin film, deposition method of thin film using the same, and semiconductor device comprising the same

Abstract

This invention relates to a precursor for forming a metal-silicon thin film, a thin film deposition method using the precursor, and a semiconductor device including the thin film. The precursor contains an organometallic compound with a novel chemical structure represented by Formula 1, which has high volatility, is liquid at room temperature, and has high thermal stability. This allows for the formation of excellent metal-silicon thin films through thin film formation processes such as chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

Description

Precursors for Forming Metal-Silicon Thin Films, Thin Film Deposition Methods Using the Precursors, and Semiconductor Devices Comprising the Thin Films The present invention relates to a precursor for forming a metal-silicon thin film, a thin film deposition method using the precursor, and a semiconductor device comprising the thin film, and more particularly to a novel precursor for forming a thin film, a thin film deposition method using the precursor, and a semiconductor device comprising the thin film, the novel precursor containing a group 4 transition metal compound containing a silylamino group and capable of forming a thin film containing a group 4 metal and silicon. With the miniaturization and high integration of thin films used in semiconductor devices, in order to suppress leakage current and ensure a high dielectric constant, a precursor having a high dielectric constant containing a group 4 transition metal compound is used in the thin film formation process. At this time, it has been known that in order to suppress leakage current, compared with a group 4 transition metal oxide film formed using a precursor containing a group 4 transition metal oxide, applying a metal-selenate (e.g., HfSiO x and ZrSiO x ) can obtain more favorable effects. A thin film in which a group 4 transition metal is in direct contact with silicon can be manufactured, but when a group 4 transition metal oxide is in direct contact with silicon, an increase in leakage current may occur due to a decrease in thermal stability. On the contrary, a metal-selenate film doped with silicon, as a high dielectric constant film, exhibits characteristics of suppressing leakage current and having less mobility degradation. In order to form a metal-selenate film, a metal oxide film forming precursor and a silicon oxide film forming precursor can be used respectively to form a metal-silicon oxide film. However, when applying the above method, it is difficult to set the process temperature due to the difference in volatility and decomposition temperature between the two precursors, making it difficult to form a thin film with a uniform composition ratio, and there is also a problem of difficulty in ensuring step coverage. As a method for improving the above problems, a technique of forming a thin film using a precursor compound containing silicon as a ligand in the molecule of the precursor compound has been developed. For example, Korean Registered Patent Publication No. 10-1216068 reports that when a group 4 transition metal compound having a high volatility, being liquid at room temperature, and having excellent thermal stability, in which an amine group and a silylamino group are bonded to a central metal atom, is used as a precursor, excellent thin film characteristics, thickness, and step coverage can be ensured by metalorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD). In addition, a technique of forming a metal selenate gate dielectric film using a group 4 transition metal compound containing siloxane such as Zr bis(trimethylsilyloxy)bis(thd), tetrakis(trimethylsilyloxy)zirconium, tetrakis(trimethylsilyloxy)hafnium, and Hf bis(trimethylsilyloxy)bis(thd) is disclosed in Korean Registered Patent Publication No. 10-0779468. [Prior Art Documents] [Patent Documents] Korean Registered Patent Publication No. 10-1216068 Korean Registered Patent Publication No. 10-0779468 The present invention aims to solve the problems existing in the prior art as described above, and its object is to provide a precursor for forming a thin film, which is a novel chemical structure compound containing a carbosilyl group-bonded cyclopentadienyl ligand in a central metal atom, has a relatively high volatility, is in a liquid state at room temperature, and has a relatively high thermal stability. In addition, an object of the present invention is to provide a precursor for forming a thin film that can form an excellent metal-silicon-containing thin film through a thin film formation process such as metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). In addition, an object of the present invention is to provide a method for forming a metal-silicon-containing thin film using the precursor for forming a thin film. In addition, an object is to provide a semiconductor device including the thin film. In order to achieve the above object, the precursor for forming a thin film of the present invention is characterized in that it is used for forming a metal-silicon-containing thin film and includes an organometallic compound represented by the following Chemical Formula 1. [Chemical Formula 1] In Chemical Formula 1, M is one of group 4 transition metals, and R 1 to R 4 are each independently a hydrogen atom or a linear, branched, or cyclic alkyl or alkenyl group of C 1 ~C 5 ; R 5 to R 6 are each independently a hydrogen atom or a linear or branched alkyl or alkenyl group of C 1 ~C 3 ; and R 7 to R 8 are each independently a C 1 ~C 5 The linear, branched or cyclic alkyl or alkenyl group of R 9 to R 11 are each independently C 1 ~C 5 The linear, branched or cyclic alkyl or alkenyl group or C 1 ~C 5 Aminoalkyl or alkoxyalkyl. At this time, in the Chemical Formula 1, R 1 to R 4 One or more of them may be a hydrogen atom. In addition, in the Chemical Formula 1, the R 5 and R 6 At least one or more of them may be methyl (Me). In addition, in the Chemical Formula 1, the R 7 and R 8 may each independently be C 1 ~C 2 Linear alkyl. In addition, the organometallic compound represented by the Chemical Formula 1 may be an organometallic compound represented by the following Chemical Formula 2. [Chemical Formula 2] In the Chemical Formula 2, M and R 1 to R 11 Have the same definitions as in the Chemical Formula 1, and R 12 to R 17 are each independently C 1 ~C 5 The linear, branched or cyclic alkyl or alkenyl group. At this time, in the Chemical Formula 2, the R 12 to R 17One or more of them may be methyl. At this time, in Chemical Formula 2, the R 12 to R 17 One or more of them may all be the same. In addition, the precursor for film formation may further include a solvent, and as the solvent, C 1 ~C 16 One or more of saturated or unsaturated hydrocarbons, ketones, ethers, ethylene glycol dimethyl ether, esters, tetrahydrofuran, and tertiary amines may be used. The solvent may be included in an amount of 1 to 99% by weight based on the total weight of the precursor for film formation. The film formation method of the present invention may include a process of forming a film on a substrate using the precursor for film formation. At this time, the process of forming a film on the substrate may include a process of forming a precursor film by depositing the precursor for film formation on the surface of the substrate, and a process of reacting the precursor film with a reactive gas. At this time, the reactive gas may be nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), ozone (O 3 ), hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ), or one or more of them. In addition, the process of forming the precursor film may include a process of vaporizing the precursor for film formation and transferring it into the chamber, or may include a process of transferring the precursor for film formation into the chamber by direct liquid injection (DLI). In addition, the deposition may be performed by one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma - chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced atomic layer deposition (PEALD) process. In addition, the process of forming a film on a substrate may include: a step of forming a film by supplying the precursor for film formation onto the substrate and applying plasma. In addition, the semiconductor device of the present invention is characterized in that: it includes a film manufactured by the film formation method. The precursor for film formation according to the present invention contains a compound having a novel chemical structure in which a cyclopentadienyl ligand containing an aminosilyl group is bonded to a central metal atom, and exhibits physical properties of relatively high volatility, being in a liquid state at room temperature, and relatively high thermal stability. In addition, by performing a film formation process such as a metalorganic chemical vapor deposition (MOCVD) method or an atomic layer deposition (ALD) method using the precursor for film formation, an excellent metal-silicon-containing film can be formed. In particular, films such as metal monomers, oxides, and nitrides containing group 4 transition metal-silicon can be formed. In addition, high-quality semiconductor devices can be manufactured using the film. Next, the present invention will be described in more detail. The terms or words used in the specification and the claims of the invention should not be construed as being limited to the general or dictionary meanings, but should be construed in accordance with the meanings and concepts that conform to the technical idea of the present invention, based on the principle that the inventor can appropriately define the concept of the term in order to best explain his invention. The precursor for thin film formation according to the present invention is used for forming a metal-silicon thin film and contains an organometallic compound containing a silyl group and having a Group 4 transition metal as a central metal atom, represented by the following Chemical Formula 1. [Chemical Formula 1] In Chemical Formula 1, M is one of the Group 4 transition metals, and R 1 to R 4 are each independently a hydrogen atom or a linear, branched, or cyclic alkyl or alkenyl group of C 1 ~C 5 ; R 5 to R 6 are each independently a hydrogen atom or a linear or branched alkyl or alkenyl group of C 1 ~C 3 ; R 7 to R 8 are each independently a linear, branched, or cyclic alkyl or alkenyl group of C 1 ~C 5 ; R 9 to R 11 are each independently a linear, branched, or cyclic alkyl or alkenyl group of C 1 ~C 5 or an aminoalkyl or alkoxyalkyl group of C 1 ~C 5 . By applying the precursor for thin film formation to a thin film formation process, particularly a thin film formation process such as metalorganic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), an excellent metal-silicon thin film can be formed. In addition, in order to be used in the thin film formation process as described above, the precursor for thin film formation is a compound containing a silyl group in a chemical structure with high volatility, existing in a liquid state at room temperature, and having thermal stability. The compound represented by Chemical Formula 1 may include various chemical structures. According to one embodiment, in Chemical Formula 1, R 1 to R 4 One or more of them may be a hydrogen atom. In addition, in the Chemical Formula 1, the R 5 and R 6 At least one or more of them may be a methyl group (Me). In addition, in the Chemical Formula 1, the R 7 and R 8 may each independently be a linear alkyl group of C 1 ~C 2 . The compound of the exemplary chemical structure as described above exists in a liquid state at room temperature and is thus suitable for use in a film forming process. In addition, the organometallic compound represented by Chemical Formula 1 may be an organometallic compound represented by the following Chemical Formula 2. [Chemical Formula 2] In the Chemical Formula 2, M and R1 to R11 have the same definitions as in Chemical Formula 1. R 12 to R 17 each independently is a linear, branched or cyclic alkyl or alkenyl group of C 1 ~C 5 . In the compound represented by Chemical Formula 2 as described above, one or more of the R 12 to R 17 may be a methyl group, and in the Chemical Formula 2, the R 12 to R 17 may all exemplarily contain the same chemical structure. In addition, the precursor for film formation may additionally contain a solvent. The solvent may be one or more of a saturated or unsaturated hydrocarbon, a ketone, an ether, ethylene glycol dimethyl ether, an ester, tetrahydrofuran, and a tertiary amine of C 1 ~C 16 , and the solvent may be contained in an amount of 1 to 99% by weight based on the total weight of the precursor for film formation. Precursors with or without solvents can be vaporized and the deposition process can be carried out by supplying them into the interior of the chamber. Soluble solvents can also be appropriately selected and added for use according to the nature of the organometallic compound. That is, depending on the type of organometallic compound, when it is in a liquid state at room temperature, the deposition process can be carried out without a separate solvent. The method for forming a thin film according to the present invention is characterized by including a process of forming a thin film on a substrate using the precursor for thin film formation. At this time, the precursor for thin film formation can additionally contain the solvent as described above, and the solvent can be contained in an amount of 1 to 99% by weight based on the total weight of the precursor for thin film formation. The method for forming a metal-containing silicon thin film using a precursor for thin film formation containing the organometallic compound represented by Chemical Formula 1, except for containing the organometallic compound represented by Chemical Formula 1 or Chemical Formula 2 as a precursor for thin film formation, can be carried out according to a general method for manufacturing a thin film using a deposition process. Specifically, the deposition can be carried out by one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma - chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced atomic layer deposition (PEALD) process. That is, the process of forming a thin film on the substrate can include a process of forming a precursor thin film by depositing the precursor for thin film formation on the surface of the substrate using the above-described process, and a process of reacting the precursor thin film with a reactive gas. At this time, nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), ozone (O 3 ), hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ), or one or more of them. Specifically, when implemented in the presence of oxidizing gases such as water vapor, oxygen, and ozone, metal-silicon oxides can be formed, and when implemented in the presence of reducing gases such as hydrogen, ammonia, hydrazine, and silane, various films such as metal-silicon films or metal nitride-silicon films can be formed. In addition, the process of forming the precursor film may include a process of vaporizing the precursor for film formation and transferring it into the chamber. At this time, the volatility, structure, and thermal stability of the precursor for film formation will be the main factors determining the deposition efficiency on the substrate inside the chamber. In addition, after supplying the reactive gas to the reactor, a processing process selected from the group consisting of heat treatment, plasma treatment, and light irradiation may be implemented. Specifically, the process of forming a film on the substrate may include: a step of forming a film by supplying the precursor for film formation to the substrate and applying plasma. In addition, as the substrate for film formation, any substrate used in semiconductor manufacturing that needs to be coated with a metal film due to its technical function can be used without limitation. Specifically, substrates such as silicon substrates (Si), silicon oxide substrates (SiO 2 ), silicon nitride substrates (SiN), silicon oxynitride substrates (SiON), titanium nitride substrates (TiN), tantalum nitride substrates (TaN), tungsten substrates (W), or noble metal substrates such as platinum substrates (Pt), palladium substrates (Pd), rhodium substrates (Rh), or gold substrates (Au) can be used. In the process of transferring the film-forming precursor into the interior of the chamber, it is possible to use transfer by volatile gas, or a liquid transfer method such as direct liquid injection (DLI) or dissolving the organometallic compound in an organic solvent for transfer. The method of transferring the precursor by volatile gas can be carried out by bubbling with an inert gas such as helium, neon, argon, krypton, xenon or nitrogen after putting the container containing the precursor into a constant temperature bath, so that after the precursor evaporates, it is transferred onto the substrate for forming a metal film, or by using a liquid delivery system (LDS) to convert the liquid precursor into other forms through a vaporizer and then transfer it onto the film-forming substrate. For the liquid transfer method of dissolving the precursor in an organic solvent for transfer, a composition in the form of a combination of the organometallic compound represented by Chemical Formula 1 or Chemical Formula 2 and a solvent as described above can be used. When it is difficult to be fully vaporized in the vaporizer of the liquid transfer method due to the high viscosity of the organometallic compound, the deposition process can be effectively carried out by using a composition containing a solvent. The solvent as described above should be a solvent that has the property of dissolving substances in solid form, or can dissolve and disperse substances in liquid form. In addition, it is preferably selected considering the boiling point, density and vapor pressure conditions of the solvent to improve the annual reduction effect and volatility improvement effect of the film-forming composition, and thereby form a film with improved uniformity and step coverage characteristics of the deposited film. In addition, when supplying the film-forming precursor into the interior of the chamber, in order to further improve the electrical characteristics, i.e., capacitance, of the finally formed metal film, a metal precursor containing one or more metals (M") selected from silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta) and lanthanide elements can be selectively further supplied as a second metal precursor. The second metal precursor can be an alkylamide compound or an alkoxy compound containing the metal. The supply of the second metal precursor can be carried out in the same manner as the supply method of the film-forming precursor, and the second metal precursor can be supplied onto the film-forming substrate together with the film-forming precursor, or can be supplied sequentially after the supply of the film-forming precursor is completed. The precursor for thin film formation and the optional second metal precursor as described above are preferably maintained at a temperature of 100 to 200 °C, more preferably 130 to 180 °C, before being supplied into the reaction chamber for contact with the thin film formation substrate. In addition, before supplying the reactive gas after the supply step of the thin film formation precursor, a process of purging an inert gas such as argon (Ar), nitrogen (N 2 ) or helium (He) into the reactor can be implemented to assist the movement of the thin film formation precursor and the optional second metal precursor onto the substrate or to make the pressure inside the reactor suitable for deposition, and to discharge impurities and the like present inside the chamber to the outside. At this time, the purging of the inert gas is preferably implemented in such a way that the pressure inside the reactor reaches 1 to 5 Torr. After completing the supply of the precursor, the reactive gas is supplied into the reactor in the manner described above, and a treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation is implemented in the presence of the reactive gas. In addition, the purpose of the heat treatment, plasma treatment, or light irradiation treatment process is to provide thermal energy for depositing the metal precursor, and it can be implemented according to a general method. Preferably, in order to manufacture a metal thin film having the required physical state and composition at a sufficient growth rate, the treatment process is preferably implemented in such a way that the substrate temperature inside the reactor reaches 100 to 1,000 °C, preferably 300 to 500 °C. In addition, when implementing the treatment process, as described above, a process of purging an inert gas such as argon (Ar), nitrogen (N 2 ) or helium (He) into the reactor can be implemented to assist the movement of the reactive gas onto the substrate or to make the pressure inside the reactor suitable for deposition, and to discharge impurities or by-products and the like present inside the chamber to the outside. A metal-containing thin film can be formed by taking the processes of inputting the precursor, inputting the reactive gas, and inputting the inert gas as described above as one cycle and implementing more than one cycle. Specifically, when an oxidizing gas is used as the reactive gas, the manufactured thin film may contain a metal oxide of the following Chemical Formula 3 as the second metal precursor. [Chemical Formula 3] (M 1-a M" a )O b In Chemical Formula 3, 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 (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and lanthanide elements. The method for forming a metal-silicon-containing thin film as described above can perform a deposition process at a temperature higher than in the past during the deposition process by using a precursor with excellent thermal stability, and can form a high-purity thin film such as a metal-silicon, metal oxide, silicon, or metal nitride-silicon thin film without dust contamination or impurity contamination such as carbon caused by thermal decomposition of the precursor. Accordingly, the thin film formed by the thin film forming method of the present invention can be effectively applied to high-k dielectric thin films in semiconductor devices, such as gate dielectric films of metal-oxide semiconductor field effect transistors (MOS) and gate dielectric films of capacitors or non-volatile memory devices. As another embodiment, a metal-silicon-containing thin film formed by the thin film forming method and a semiconductor device including the thin film are provided. As an example, 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 has the same configuration as a general semiconductor device except that it includes a thin film according to the present invention as a dielectric film requiring high-k dielectric characteristics within the device. Therefore, detailed descriptions related to the configuration of the semiconductor device will be omitted in this specification. Next, the effects of the present invention will be described with reference to examples. [Synthesis Example 1] Cp-Si(Me) 2 Manufacture of DEA Compound Under a nitrogen atmosphere, 20 g of dimethyldichlorosilane (0.155 mol) and 300 ml of n-pentane were added to a 500 ml Schlenk flask, and 22.5 g of diethylamine (0.307 mol) was slowly added dropwise at -30°C, followed by stirring at room temperature for 14 hours. After completion of the reaction, the reaction solution was filtered, and then the solvent and volatile side reaction products were removed by reducing the pressure of the obtained solution. 21.2 g of a transparent liquid compound, 1-chloro-N,N-diethyl-1,1-dimethylsilanamine (yield: 70%), was obtained by purifying the remaining liquid at 40°C (6.6 Torr). Under a nitrogen atmosphere, 3.0 g of sodium hydride (NaH, 60%) (0.076 mol) and 100 ml of tetrahydrofuran (THF) were added to a 1000 ml Schlenk flask, and 5.0 g of cyclopentadiene (0.0923 mol) was slowly added dropwise at room temperature, followed by stirring at room temperature for 5 hours. After the reaction was completed at room temperature, 12.6 g of the synthesized 1-chloro-N,N-diethyl-1,1-dimethylsilylamine (0.076 mol) was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 14 hours. After the reaction was completed, the reaction solution was filtered, and then the solvent and volatile side reaction products were removed by reducing the pressure of the obtained solution. 5.3 g of a transparent liquid compound 1 (yield 35.8%) was obtained by purifying the remaining liquid at 58.5 °C (560 mTorr). [Compound 1] 1 H-NMR(400MHz, CDCl 3 , 25℃): Mixture, δ 6.607(br, 3H, C 5 H 5 -Si), δ 2.954, (br, 1H, C 5 H 5 -Si), δ 2.853-2.818, 2.797-2.744, 2.717-2.664 (q, 4H, Si(CH 3 ) 2 N(CH 2 CH 3 ) 2 )), δ 0.974-0.942, 0.929-0.894(t, 6H, Si(CH 3 ) 2 N(CH 2 CH 3 ) 2 )), δ 0.250, -0.048(s, 6H, Si(CH 3 )) 2 N(CH 2 CH 3 )) 2 )) [Synthesis Example 2] Cp-Si(Me) 2 Manufacture of EMA Compound Under a nitrogen atmosphere, 20 g of dimethyldichlorosilane (0.155 mol) and 300 ml of n-pentane were placed in a 500 ml Schlenk flask, and 18.1 g of N-ethylmethylamine (0.307 mol) was slowly added dropwise at -30 °C. Then, the mixture was stirred at room temperature for 14 hours. After completion of the reaction, the reaction solution was filtered, and then the solvent and volatile side reaction products were removed by reducing the pressure of the obtained solution. 15.3 g of a transparent liquid compound, 1-chloro-N-ethyl-N,1,1-trimethylsilanamine (yield: 65.1%), was obtained by purifying the remaining liquid at 35.2 °C (6.6 Torr). Under a nitrogen atmosphere, 3.7 g of sodium hydride (NaH, 60%) (0.0923 mol) and 100 ml of tetrahydrofuran (THF) were placed in a 1000 ml Schlenk flask, and 6.1 g of cyclopentadiene (0.0923 mol) was slowly added dropwise at room temperature. Then, the mixture was stirred at room temperature for 5 hours. To the reaction solution obtained after completion of the reaction at room temperature, 14 g of the synthesized 1-chloro-N-ethyl-N,1,1-trimethylsilanamine (0.0923 mol) was added dropwise, and the mixture was stirred at room temperature for 14 hours. After completion of the reaction, the reaction solution was filtered, and then the solvent and volatile side reaction products were removed by reducing the pressure of the obtained solution. 10.0 g of a transparent liquid compound 2 (yield: 60.0%) was obtained by purifying the remaining liquid at 50.4 °C (630 mToor). [Compound 2] 1 H-NMR(400MHz, CDCl 3 , 25 °C): Mixture, δ 6.602(br, 3H, C 5 H 5-Si), δ 2.957, (br, 1H, C 5 H 5 -Si), δ 2.814-2.757, 2.623-2.588 (q, 4H, Si(CH 3 ) 2 N(CH 3 )(CH 2 CH 3 )), δ 2.468, 2.454 (s, 3H, Si(CH 3 ) 2 N(CH 3 )(CH 2 CH 3 )), δ 1.123-1.087, 1.040-0.987(t, 3H, Si(CH 3 ) 2 N(CH 3 )(CH 2 CH 3 )), δ 0.203, -0.043(s, 6H, Si(CH 3 ) 2 N(CH 2 CH 3 ) 2 )) [Example 1] (Cp-Si(Me) 2 DEA)Hf(DMA) 3 Preparation of Compounds In a 100 ml Schlenk flask under nitrogen atmosphere, 3.3 g of tetrakis(dimethylamino)arbium [Hf(NMe 2 ) 4 (9.3 mmol) and 50 mL of n - hexane. Next, 1.9 g of Compound 1 produced through Synthesis Example 1 (9.8 mmol) was taken and slowly added dropwise at - 40 °C, and then stirred at room temperature for 14 hours. After completion of the reaction, the solvent and volatile side - reaction products were removed by reducing the pressure of the obtained reaction solution. 2.7 g of a transparent liquid Compound 3 (yield: 57.4%) was obtained by purification at 101.5 °C (5.6 mTorr). The nuclear magnetic resonance spectrum (NMR) analysis data of the produced compound are shown in Figure 1, and it can be confirmed that it has the chemical structure as shown in Compound 3 below. In addition, the thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) analysis results are shown in Figure 2. [Compound 3] 1 H - NMR(400MHz, C 6 D 6 , 25℃): δ 6.361 - 6.272(m, 4H,C 5 H 4 -Si), δ 2.995(s, 18H,Hf-(N(CH 3 ) 2 ) 3 ), δ 2.812 - 2.759 (q, 4H, Si(CH 3 ) 2 N(CH 2 CH 3 ) 2 )), δ 0.971 - 0.936 (t, 6H, Si(CH 3 ) 2 N(CH 2 CH 3 ) 2))), δ 0.396 (s, 6H, Si(CH 3 ) 2 N(CH 2 CH 3 ) 2 )) [Example 2] (Cp-Si(Me) 2 EMA)Hf(DMA) 3 Synthesis of Compound Under a nitrogen atmosphere, 5.0 g of hafnium tetrakis(dimethylamino) [Hf(NMe 2 ) 4 (0.0141 mol) and 60 ml of n-hexane were placed in a 250 ml Schlenk flask. Next, 2.2 g of Compound 2 (0.0148 mol) prepared in Synthesis Example 2 was taken and slowly added dropwise at -40 °C, followed by stirring at room temperature for 14 hours. After completion of the reaction, the solvent and volatile side reaction products were removed by reducing the pressure of the obtained reaction solution. 4.0 g of a strong yellow liquid compound 4 (yield 58%) was obtained by purifying the remaining liquid at 93.0 °C (5.4 mToor). The nuclear magnetic resonance spectrum (NMR) analysis data of the synthesized compound is shown in Figure 3, and it can be confirmed that it has the chemical structure shown in Compound 4 below. In addition, the thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) analysis results are shown in Figure 4. [Compound 4] 1 H-NMR(400MHz, C 6 D 6 , 25℃): δ 6.338-6.267(m, 4H,C 5 H 4 -Si), δ 2.991(s, 18H,Hf-(N(CH 3 ) 2 ) 3), δ 2.781-2.729 (q, 2H, Si(CH 3 ) 2 N((CH 3 )(CH 2 CH 3 )), δ 2.426 (s, 3H, Si(CH 3 ) 2 N((CH 3 )(CH 2 CH 3 )), δ 0.984-0.950 (t, 3H, Si(CH 3 ) 2 N((CH 3 )(CH 2 CH 3 )), δ 0.370 (s, 6H, Si(CH 3 ) 2 N((CH 3 )(CH 2 CH 3 )) [Example 3] (Cp-Si(Me) 2 EMA)Zr(DMA) 3 Preparation of Compounds In a 100 ml Schlenk flask under nitrogen atmosphere, 5.0 g of tetrakis(dimethylamino)zirconium [Zr(NMe 2 ) 4(0.0187 mol) and 50 ml of n - hexane. Next, 3.5 g of compound 2 (0.0196 mol) produced through Synthesis Example 2 was taken and slowly added dropwise at - 40 °C, and then stirred at room temperature for 14 hours. After completion of the reaction, the solvent and volatile side - reaction products were removed by reducing the pressure of the obtained reaction solution. 5.6 g of a strong yellow liquid compound 5 (yield: 74.7%) was obtained by purifying the remaining liquid at 92.9 °C (14.5 mTorr). The nuclear magnetic resonance spectrum (NMR) analysis data of the produced compound is shown in Figure 5, and it can be confirmed that it has the chemical structure as shown in compound 5 below. In addition, the thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) analysis results are shown in Figure 6. [Compound 5] 1 H - NMR(400MHz, C 6 D 6 , 25℃): δ 6.350 - 6.291(m, 4H,C 5 H 4 - Si), δ 2.957(s, 18H,Zr-(N(CH 3 ) 2 ) 3 ), δ 2.792 - 2.740 (q, 2H, Si(CH 3 ) 2 N((CH 3 )(CH 2 CH 3 )), δ 2.438 (s, 3H, Si(CH 3 ) 2 N((CH 3 )(CH 2 CH 3 )), δ 0.993 - 0.958 (t, 3H, Si(CH 3 )) 2 N((CH 3 )(CH 2 CH 3 ))), δ 0.368 (s, 6H, Si(CH 3 )) 2 N((CH 3 )(CH 2 CH 3 )) The thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) analysis results of the synthesized compound are shown in Table 1 below. [Table 1] From the analysis results of the thermogravimetric analyzer (TGA) and differential scanning calorimeter (SDC), it can be confirmed that the synthesized compound has volatile and thermally stable physical properties suitable for use as a precursor for depositing Group 4 transition metal-silicon thin films. In addition, the results of analyzing the viscosity of the synthesized compound are shown in Table 2 below. [Table 2] When injecting a precursor in a liquid state into an atomic layer deposition (ALD) device or a chemical vapor deposition (CVD) device using a liquid delivery system (LDS) and vaporizing it using a flash evaporator, a precursor with a high viscosity is likely to cause clogging of the flash evaporator and it is difficult to achieve quantitative transfer. Considering the above problems, it can be judged that Compound 4 can be more easily used as a precursor for atomic layer deposition (ALD) or chemical vapor deposition (CVD) because of its low viscosity. In the above content, the present invention has been described with reference to preferred embodiments, but the present invention is not limited to the described embodiments, and those with ordinary knowledge in the technical field to which the present invention pertains can make various modifications and changes without departing from the gist of the present invention. The above-described modification examples and change examples should all be interpreted as being included within the present invention and the appended patent application scope of the invention. None Figure 1 is the nuclear magnetic resonance hydrogen spectrum of the organometallic compound according to Example 1 ( 1 1H-NMR) analysis results. Figure 2 shows the thermogravimetric analyzer (TGA) (a) and differential scanning calorimeter (DSC) (b) analysis results of the organometallic compound according to Example 1. Figure 3 shows the nuclear magnetic resonance hydrogen spectrum ( 1 1H-NMR) analysis results. Figure 4 shows the thermogravimetric analyzer (TGA) (a) and differential scanning calorimeter (DSC) (b) analysis results of the organometallic compound according to Example 2. Figure 5 shows the nuclear magnetic resonance hydrogen spectrum ( 1 1H-NMR) analysis results. Figure 6 shows the thermogravimetric analyzer (TGA) (a) and differential scanning calorimeter (DSC) (b) analysis results of the organometallic compound according to Example 3.

Claims

1. A method for forming a thin film, comprising: A process for forming a thin film on a substrate using a thin film forming precursor, wherein the thin film forming precursor is a thin film forming precursor for forming a metal-silicon thin film, comprising an organometallic compound represented by the following chemical formula 1: [Chemical Formula 1] In this chemical formula 1, M is one of Zr, Hf and Ti, R1 to R4 are each independently hydrogen atoms or C1 to C5 linear, branched or cyclic alkyl or alkenyl groups, R5 to R6 are each independently hydrogen atoms or C1 to C3 linear or branched alkyl or alkenyl groups, R7 to R8 are each independently C1 to C5 linear, branched or cyclic alkyl or alkenyl groups, and R9 to R11 are each independently C1 to C5 linear, branched or cyclic alkyl or alkenyl groups or C1 to C5 aminoalkyl or alkoxyalkyl groups.

2. The thin film forming method as claimed in claim 1, wherein in the chemical formula 1, one or more of R1 to R4 are hydrogen atoms.

3. The thin film forming method as claimed in claim 1, wherein in the chemical formula 1, at least one of R5 and R6 is a methyl group (Me).

4. The thin film forming method as claimed in claim 1, wherein in the chemical formula 1, R7 and R8 are each independently a C1-C2 straight-chain alkyl group.

5. The thin film forming method as described in claim 1, wherein the organometallic compound represented by the chemical formula 1 is an organometallic compound represented by the following chemical formula 2: [Chemical Formula 2] In this chemical formula 2, M and R1 to R11 are the same as defined in claim 1, and R12 to R17 are each independently a C1 to C5 linear, branched or cyclic alkyl or alkenyl group.

6. The thin film forming method as claimed in claim 5, wherein in the chemical formula 2, one or more of R12 to R17 is methyl.

7. The thin film forming method as described in claim 5, wherein in the chemical formula 2, all R12 to R17 are identical.

8. The thin film forming method as claimed in claim 1, wherein the precursor for thin film forming further comprises a solvent.

9. The thin film forming method as claimed in claim 8, wherein the solvent is any one or more of a C1-C16 saturated or unsaturated hydrocarbon, ketone, ether, and tertiary amine.

10. The thin film forming method as claimed in claim 8, wherein the solvent comprises 1 to 99% by weight relative to the total weight of the precursor for thin film forming.

11. The thin film forming method as described in claim 1, wherein the process of forming the thin film on the substrate includes: A precursor film is formed by depositing the precursor for film formation on the surface of the substrate. And the process by which the precursor film reacts with a reactive gas.

12. The thin film forming method as claimed in claim 11, wherein the reactive gas is any one or more selected from nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane, hydrogen (H2), and diborane (B2H6).

13. The thin film forming method as described in claim 11, wherein the process for forming the precursor thin film includes: The process of vaporizing the precursor for thin film formation and transferring it into the chamber.

14. The thin film forming method as described in claim 11, wherein the process for forming the precursor thin film includes: The process involves transferring the precursor for thin film formation into the chamber via direct liquid injection (DLI).

15. The thin film formation method as claimed in claim 11, wherein the deposition is performed by any one of the following processes: spin-on dielectric (SOD), low-temperature plasma (LTP), chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), high-density plasma-chemical vapor deposition (HDPCVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD).

16. The thin film forming method as described in claim 11, wherein the process of forming the thin film on the substrate includes: The step of supplying the precursor for thin film formation onto the substrate and forming a thin film by applying plasma.

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