TWI896184B - Precursor metal-silicon containing thin film, deposition method of thin film using the same, and semiconductor device comprising the same - Google Patents

Abstract

The present invention relates to a thin film forming precursor for forming a metal-silicon containing thin film, a thin film deposition method using the precursor, and a semiconductor device including the thin film. The precursor comprises an organometallic compound having a novel chemical structure represented by Chemical Formula 1, which is highly volatile, liquid at room temperature, and highly thermally stable. This allows the formation of excellent metal-silicon containing thin film formation processes such as metal vapor deposition (MOCVD) or atomic layer deposition (ALD).

Description

Precursor for forming metal-silicon containing thin film, thin film deposition method using the precursor, and semiconductor device containing the thin film

The present invention relates to a precursor for forming a metal-silicon containing thin film, a thin film deposition method using the precursor, and a semiconductor device including the thin film. In particular, it relates to a novel thin film formation precursor for forming a thin film containing Group 4 metals and silicon, a thin film deposition method using the precursor, and a semiconductor device including the thin film.

With the miniaturization and high integration of thin films used in semiconductor devices, high-k dielectric precursors containing Group IV transition metal compounds are being used in thin film formation processes to suppress leakage current and ensure a high dielectric constant. It has been shown that the use of metal selenates (e.g., _HfSiOx and _ZrSiOx ) in Group IV transition metal oxide thin films, compared to those formed using precursors containing Group IV transition metal oxides, can achieve more advantageous results in suppressing leakage current.

While it's possible to create films with Group IV transition metals in direct contact with silicon, direct contact between Group IV transition metal oxides and silicon can lead to increased leakage current due to decreased thermal stability. In contrast, silicon-doped metal-selenate films, as high-k films, exhibit reduced leakage current and exhibit minimal mobility degradation.

To form a metal-selenate thin film, a metal oxide thin film-forming precursor and a silicon oxide thin film-forming precursor can be used separately to form a metal-silicon oxide thin film. However, when applying this method, the differences in volatility and decomposition temperature between the two precursors make it difficult to set the process temperature, making it difficult to form a thin film with a uniform composition ratio. Furthermore, it is difficult to ensure coverage of step differences.

As a method for improving the above-mentioned problems, a technology has been developed to form a thin film using a precursor compound containing silicon as a ligand within the precursor compound molecule.

For example, Korean Registered Patent Publication No. 10-1216068 reports that using a Group 4 transition metal compound with amino and silylamine groups bonded to the central metal atom, which is highly volatile, liquid at room temperature, and has excellent thermal stability, as a precursor, can ensure excellent thin film properties, thickness, and step coverage through metalorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD).

Furthermore, Korean Registered Patent Publication No. 10-0779468 discloses a technology for forming a metal selenate gate dielectric film using a Group 4 transition metal compound containing siloxane, such as Zrbis(trimethylsiloxy)bis(thd), tetrakis(trimethylsiloxy)zirconium, tetrakis(trimethylsiloxy)eum, and Hfbis(trimethylsiloxy)bis(thd).

Prior Art Literature Patent Literature

Korean Registered Patent No. 10-1216068

Korean Registered Patent No. 10-0779468

The present invention aims to solve the problems existing in the prior art as described above. Its purpose is to provide a thin film forming precursor comprising a novel chemical structure compound having a silyl-containing cyclopentadienyl ligand bonded to a central metal atom, which has high volatility, is liquid at room temperature, and has high thermal stability.

Furthermore, the present invention aims to provide a thin film forming precursor that can be used to form excellent metal-silicon containing thin films through thin film forming processes such as metal vapor deposition (MOCVD) or atomic layer deposition (ALD).

Furthermore, the present invention aims to provide a method for forming a metal-silicon containing thin film using the thin film forming precursor.

Furthermore, the present invention aims to provide a semiconductor device comprising the thin film.

To achieve the above-mentioned purpose, the thin film forming precursor of the present invention, which is used to form a metal-silicon thin film, contains an organometallic compound represented by the following chemical formula 1.

In Chemical Formula 1, M is a Group 4 transition metal, ^R1 to ^R4 are each independently a hydrogen atom or a _C1 - _C5 linear, branched, or cyclic alkyl or alkenyl group, ^R5 is a _C1 - _C3 linear or branched alkyl group, ^R6 to ^R8 are each independently a hydrogen atom or a C1-C5 linear, branched, or cyclic alkyl or alkenyl group, and ^R9 to _R11 are each independently _{a C1} -C5 linear, branched, or cyclic alkyl or alkenyl group, or _{a C1} - _C5 aminoalkyl or alkoxyalkyl ^group .

At this time, in the chemical formula 1, one or more of R ₁ to R ₄ may be a hydrogen atom.

In addition, in the chemical formula 1, the R ₅ may be a methyl group (Me).

In addition, in Chemical Formula 1, at least one of R ₆ to R ₈ may be a methyl group, and all of R ₆ to R ₈ may be the same.

In addition, the organic metal compound represented by Chemical Formula 1 may be an organic metal compound represented by the following Chemical Formula 2.

In Chemical Formula 2, M and _R1 to _R11 are the same as defined in Chemical Formula 1, and _R12 to _R17 are each independently a _C1 - _C5 linear, branched, or cyclic alkyl or alkenyl group.

In addition, in Chemical Formula 2, at least one of R ₁₂ to R ₁₇ may be a methyl group, and all of R ₁₂ to R ₁₇ may be the same.

In addition, the thin film-forming precursor may further include a solvent. As the solvent, one or more of _C1 - _C16 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 wt % relative to the total weight of the thin film-forming precursor.

The thin film forming method of the present invention may include a step of forming a thin film on a substrate using the thin film forming precursor.

In this case, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.

At this time, the reactive gas may be one or more of 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 ).

Furthermore, the step of forming the precursor film may include vaporizing the thin film forming precursor and transferring it into the chamber, or may include transferring the thin film forming precursor into the chamber using direct liquid injection (DLI).

Furthermore, the deposition can be performed by any 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.

Furthermore, the process of forming a thin film on a substrate may include the step of supplying the thin film forming precursor onto the substrate and loading plasma to form the thin film.

In addition, the semiconductor device of the present invention includes a thin film manufactured by the thin film formation method.

The thin film forming precursor of the present invention comprises a compound having a novel chemical structure in which a cyclopentadienyl ligand containing a silyl group is bonded to a central metal atom. It exhibits high volatility, is liquid at room temperature, and has high thermal stability.

Furthermore, by using the thin film forming precursor to perform thin film formation processes such as metal vapor deposition (MOCVD) or atomic layer deposition (ALD), excellent metal-silicon-containing thin films can be formed, particularly thin films of metal monomers, oxides, and nitrides containing Group 4 transition metal-silicon.

Furthermore, high-quality semiconductor devices can be manufactured using the thin film.

FIG1 shows the hydrogen nuclear magnetic resonance ( ¹ H-NMR) analysis results of the organometallic compound according to Example 1.

Figure 2 shows the analysis results of the organometallic compound according to Example 1 using a thermogravimetric analyzer (TGA) (a) and a differential scanning calorimeter (DSC) (b).

FIG3 shows the hydrogen nuclear magnetic resonance ( ¹ H-NMR) analysis results of the organometallic compound according to Example 2.

Figure 4 shows the analysis results of the organometallic compound according to Example 2 using a thermogravimetric analyzer (TGA) (a) and a differential scanning calorimeter (DSC) (b).

Next, we will provide a more detailed description of the present invention. Terms and phrases used in the specification and patent application should not be construed solely based on their general or dictionary meanings. Instead, they should be interpreted based on the principle that the inventor can appropriately define the concepts of the terms to best describe their invention, and should be interpreted in a manner consistent with the meaning and concepts of the present invention's technical concepts.

The thin film forming precursor according to the present invention is used to form a metal-silicon containing thin film and comprises an organometallic compound represented by the following chemical formula 1, which contains a silyl group and includes a Group 4 transition metal as the central metal atom.

In Chemical Formula 1, M is a Group 4 transition metal, ^R1 to ^R4 are each independently a hydrogen atom or a _C1 - _C5 linear, branched, or cyclic alkyl or alkenyl group, ^R5 is a _C1 - _C3 linear or branched alkyl group, ^R6 to ^R8 are each independently a hydrogen atom or a C1-C5 linear, branched, or cyclic alkyl or alkenyl group, and ^R9 to _R11 are each independently _{a C1} -C5 linear, branched, or cyclic alkyl or alkenyl group, or _{a C1} - _C5 aminoalkyl or alkoxyalkyl ^group .

By applying the thin film forming precursor to a thin film forming process, particularly a thin film forming process such as metal vapor deposition (MOCVD) or atomic layer deposition (ALD), a superior metal-silicon containing thin film can be formed. Furthermore, to be usable in such thin film forming processes, the thin film forming precursor is a highly volatile compound containing a silyl group in its chemical structure that exists in a liquid state at room temperature and is thermally stable.

The compound represented by Chemical Formula 1 may include various chemical structures.

According to one embodiment, in Chemical Formula 1, at least one of _R1 to _R4 may be a hydrogen atom. In addition, in Chemical Formula 1, _R5 may be a methyl group (Me). In addition, in Chemical Formula 1, at least one of _R6 to _R8 may be a methyl group, and all of _R6 to _R8 may be the same.

The compound having the exemplary chemical structure described above exists in a liquid state at room temperature and is therefore suitable for use in thin film formation processes.

In addition, the organic metal compound represented by Chemical Formula 1 may be an organic metal compound represented by the following Chemical Formula 2.

In Chemical Formula 2, M and _R1 to _R11 are the same as defined in Chemical Formula 1, and _R12 to _R17 are each independently a _C1 - _C5 linear, branched, or cyclic alkyl or alkenyl group.

In the compound represented by Chemical Formula 2 as described above, at least one of R ₁₂ to R ₁₇ may be a methyl group, and all of R ₁₂ to R ₁₇ may illustratively have the same chemical structure.

The thin-film-forming precursor may further include a solvent. The solvent may be one or more of a C1-C16 saturated or unsaturated hydrocarbon, a ketone, an ether, ethylene glycol dimethyl ether, an ester, tetrahydrofuran, and a tertiary amine. The solvent may be present in an amount of 1 to 99% by weight relative to the total weight of the thin-film-forming precursor.

Precursors containing or not containing a solvent can be vaporized and supplied to the chamber for deposition. Alternatively, a solvent suitable for dissolving the organometallic compound can be appropriately selected and added depending on the properties of the organometallic compound. In other words, depending on the type of organometallic compound, deposition can be performed without a separate solvent when the compound is liquid at room temperature.

The thin film forming method of the present invention is characterized by comprising a step of forming a thin film on a substrate using the thin film forming precursor.

In this case, the thin film forming precursor may further contain the solvent described above, and the solvent may be contained in an amount of 1 to 99 wt % relative to the total weight of the thin film forming precursor.

The method for forming a metal-silicon containing thin film using a thin film forming precursor containing the organometallic compound represented by Chemical Formula 1 can be implemented according to a general thin film manufacturing method using a deposition process, except that the thin film forming precursor contains the organometallic compound represented by Chemical Formula 1 or Chemical Formula 2. Specifically, the deposition can be performed through one of the following processes: spin-on dielectric (SOD) process, low temperature plasma (LTP) process, chemical vapor deposition (CVD) process, plasma enhanced chemical vapor deposition (PECVD) process, high density plasma-chemical vapor deposition (HDPCVD) process, atomic layer deposition (ALD) process, or plasma-enhanced atomic layer deposition (PEALD) process.

That is, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor 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, the reactive gas may be _one or more of 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 )} . Specifically, when the process is carried out in the presence of oxidizing gases such as water vapor, oxygen, and ozone, _a metal-silicon oxide can be formed. When the process is carried out in the presence of reducing gases such as hydrogen, ammonia, hydrazine, and silane, various thin films such as a metal-silicon thin film or a metal nitride-silicon thin film can be formed.

Furthermore, the process of forming a precursor film may include vaporizing the film-forming precursor and transferring it into the chamber. In this case, the volatility, structure, and thermal stability of the film-forming precursor will be the primary factors determining the deposition efficiency on the substrate within the chamber.

Furthermore, after supplying the reactive gas into the reactor, a treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation may be performed. Specifically, the process of forming a thin film on the substrate may include supplying the thin film forming precursor onto the substrate and applying plasma to form the thin film.

Furthermore, any substrate used in semiconductor manufacturing that requires coating with a metal thin film due to its technical function can be used as the thin film-forming substrate without limitation. Specifically, substrates such as silicon (Si), silicon oxide ( _SiO2 ), silicon nitride (SiN), silicon oxynitride (SiON), titanium nitride (TiN), tank nitride (TaN), tungsten (W), or precious metal substrates such as platinum (Pt), palladium (Pd), rhodium (Rh), or gold (Au) can be used.

The thin film forming precursor can be transferred into the chamber using volatile gas, direct liquid injection (DLI), or a liquid transfer method in which the organometallic compound is dissolved in an organic solvent. The volatile gas method can be used to transfer the precursor by placing a container containing the precursor in a constant temperature bath and bubbling it with an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen to evaporate the precursor before transferring it to the metal thin film forming substrate. Alternatively, a liquid delivery system (LDS) can be used to convert the liquid precursor into another gas via a vaporizer before transferring it to the thin film forming substrate.

For liquid transfer methods that transfer a precursor by dissolving it in an organic solvent, a composition comprising an organometallic compound represented by Chemical Formula 1 or Chemical Formula 2 and a solvent, as described above, can be employed. When the organometallic compound's high viscosity makes it difficult to fully vaporize it in a vaporizer used in liquid transfer methods, utilizing this composition containing a solvent allows for efficient deposition.

The solvent described above should be capable of dissolving solid substances or dissolving and dispersing liquid substances. Furthermore, it is preferable to select a solvent that enhances the annual reduction and volatility improvement effects of the thin film-forming composition, taking into account the solvent's boiling point, density, and vapor pressure, thereby achieving a deposited film with improved uniformity and step coverage.

Furthermore, when supplying the thin film forming precursor into the chamber, a metal precursor containing one or more metals (M") selected from silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), niobium (Hf), tantalum (Ta), and ytterbium elements may be selectively supplied as a second metal precursor to further improve the electrical properties, i.e., the electrostatic capacitance, of the ultimately formed metal thin film. This second metal precursor may be an alkylamide compound or an alkoxy compound containing the metal.

The second metal precursor can be supplied in the same manner as the thin film-forming precursor. The second metal precursor can be supplied to the thin film-forming substrate together with the thin film-forming precursor, or can be supplied sequentially after the thin film-forming precursor is supplied.

The thin film forming precursor and the optional second metal precursor 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 to come into contact with the thin film forming substrate.

Furthermore, after supplying the thin film-forming precursor and before supplying the reactive gas, the reactor interior may be purged with an inert gas such as argon (Ar), nitrogen ( _N2 ), or helium (He). This facilitates movement of the thin film-forming precursor and, optionally, the second metal precursor, toward the substrate, maintains a pressure within the reactor suitable for deposition, and discharges impurities within the chamber. The inert gas purge is preferably performed to achieve an internal pressure of 1 to 5 Torr.

After the precursor is supplied, a reactive gas is supplied into the reactor as described above, and a treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation is performed in the presence of the reactive gas.

Furthermore, the heat treatment, plasma treatment, or light irradiation treatment is intended to provide thermal energy for depositing the metal precursor and can be performed according to conventional methods. Preferably, in order to produce a metal thin film with the desired physical state and composition at a sufficient growth rate, the treatment is performed such that the substrate temperature within the reactor reaches 100 to 1,000°C, preferably 300 to 500°C.

Furthermore, during the processing, as described above, an inert gas such as argon (Ar), nitrogen ( _N2 ), or helium (He) may be blown into the reactor to facilitate the movement of reactive gases onto the substrate, to create a pressure inside the reactor suitable for deposition, and to discharge impurities or byproducts within the chamber to the outside.

The metal-containing thin film can be formed by treating the aforementioned steps of introducing the precursor, introducing the reactive gas, and introducing the inert gas as one cycle and performing one or more cycles.

Specifically, when an oxidizing gas is used as the reactive gas, the produced thin film may contain the metal oxide represented by the following chemical formula 3 as the second metal precursor.

[Chemical formula 3](M1 _-aM " _a ) _Ob

In the 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 selected from silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), niobium (Hf), tantalum (Ta), and a tungsten group element.

The above-described method for forming a metal-silicon-containing thin film utilizes a precursor with excellent thermal stability, enabling deposition at higher temperatures than conventional methods. Furthermore, it can form high-purity thin films such as metal-silicon, metal oxide, silicon, or metal nitride-silicon, free from dust contamination or impurity contamination such as carbon caused by thermal decomposition of the precursor. Consequently, thin films formed using the thin film formation method of the present invention can be effectively applied to high-k films used in semiconductor devices, such as gate dielectric films for metal-oxide semiconductor field-effect transistors (MOS) and capacitors or nonvolatile memory devices.

As another embodiment, a metal-silicon containing thin film formed by the thin film formation 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 random access memory (RAM).

The semiconductor device described above has the same structure as a typical semiconductor device, except that it includes the thin film according to the present invention as a dielectric film requiring high dielectric constant characteristics. Therefore, detailed descriptions of the semiconductor device structure are omitted in this specification.

Next, the effects of the present invention will be described with reference to the embodiments.

[Synthesis Example 1] Preparation of Cp-CH ₂ Si(Me) ₃ Compound

Under a nitrogen atmosphere, 6 g of sodium hydroxide (NaH, 60%) (0.151 mol) and 150 ml of tetrahydrofuran (THF) were placed in a 1,000 ml Schlenk flask. 10 g of cyclopentadiene (0.151 mol) was slowly added dropwise at room temperature and stirred for 5 hours. To the resulting reaction solution, 18.6 g of (chloromethyl)trimethylsilane (0.151 mol) was added dropwise at room temperature. The reaction mixture was stirred at 80°C for 24 hours under convection. After the reaction was complete, the reaction solution was filtered, and the resulting solution was depressurized to remove the solvent and volatile side products. The remaining liquid was purified at 38.6°C (1.3 Torr) to obtain 8.1 g of Compound 1 as a clear liquid (yield: 35.2%).

¹ H-NMR (400MHz, CDCl ₃ , 25℃): Mixture, δ 6.421-5.801 (m, 3H, C ₅ H ₅ -CH ₂ ), δ 2.961-2.950, 2.862-2.852, (q, 2H, C ₅ H ₅ -CH ₂ ), δ 1.905-1.902,1.829-1.827(d,2H,C ₅ H ₅ -C H ₂ ),δ 0.011,0.000(s,9H,-CH ₂ -Si-(C H ₃ ) ₃ )

[Example 1] Preparation of (Cp-CH ₂ SiMe ₃ )Hf(DMA) ₃ Compound

Under a nitrogen atmosphere, 14.2 g of tetrakis(dimethylamino)arsenicum [Hf(NMe ₂ ) ₄ ] (0.040 mol) and 120 ml of n-hexane were placed in a 250 ml Schlenk flask. Next, 6.4 g of Compound 1 (0.042 mol), produced in Synthesis Example 1, was slowly added dropwise at -40°C and stirred at room temperature for 14 hours. After the reaction was completed, the resulting reaction solution was depressurized to remove the solvent and volatile side products. The remaining liquid was purified at 75.7°C (6.7 mTorr) to obtain 15.4 g of Compound 2 (83% yield) as a transparent liquid.

Figure 1 shows the nuclear magnetic resonance (NMR) analysis data for the produced compound, confirming its chemical structure as shown in Compound 2 below. Furthermore, Figure 2 shows the results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis.

¹ H-NMR (400MHz, C ₆ D ₆ , 25℃): δ 5.979-5.787 (m, 4H, C ₅ H ₄ -CH ₂ ), δ 3.034 (s, 18H, Hf-(N(C H ₃ ) ₂ ) ₃ ), δ 1.995 (s, 2H, C ₅ H ₄ -C H ₂ ), δ 0.009(s,9H,-CH ₂ -Si-( CH ₃ ) ₃ )

[Example 2] Preparation of (Cp-CH ₂ SiMe ₃ )Zr(DMA) ₃ Compound

Under a nitrogen atmosphere, 5.0 g of tetrakis(dimethylamino)zirconium [Zr(NMe ₂ ) ₄ ] (0.0187 mol) and 50 ml of n-hexane were placed in a 100 ml Schlenk flask. Next, 3.0 g of Compound 1 (0.0196 mol), produced in Synthesis Example 1, was slowly added dropwise at -40°C and stirred at room temperature for 14 hours. After the reaction was complete, the resulting reaction solution was depressurized to remove the solvent and volatile side products. The remaining liquid after removal was purified at 82.1°C (7.1 mTorr) to obtain 4.0 g of light yellow liquid compound 3 (yield: 57.1%).

Figure 3 shows the nuclear magnetic resonance (NMR) analysis data for the produced compound, confirming its chemical structure as shown in Compound 3 below. Furthermore, Figure 4 shows the analysis results using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).

¹ H-NMR (400MHz, C ₆ D ₆ , 25℃): δ 6.007-5.806 (m, 4H, C ₅ H ₄ -CH ₂ ), δ 2.998 (s, 18H, Zr-(N(C H ₃ ) ₂ ) ₃ ), δ 1.974 (s, 2H, C ₅ H ₄ -C H ₂ ), δ 0.005(s,9H,-CH ₂ -Si-( CH ₃ ) ₃ )

The analysis results of the synthesized compounds by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) are shown in Table 1.

Thermogravimetric analysis (TGA) and differential scanning calorimetry (SDC) analysis results confirmed that the synthesized compound possesses volatility and thermal stability suitable for use as a precursor for deposition of Group 4 transition metal-silicon thin films.

In addition, the viscosity analysis results of the synthesized compounds are shown in Table 2.

When a precursor is injected into an atomic layer deposition (ALD) or chemical vapor deposition (CVD) apparatus in liquid form using a liquid delivery system (LDS) and then vaporized using a flash evaporator, high-viscosity precursors can easily clog the evaporator and make quantitative transfer difficult. Considering these issues, it is believed that compound 2, due to its lower viscosity, can be more easily used as an atomic layer deposition (ALD) or chemical vapor deposition (CVD) precursor.

While the present invention has been described above with reference to preferred embodiments, the present invention is not limited to the aforementioned embodiments. Persons skilled in the art may make various modifications and alterations without departing from the spirit of the present invention. Such modifications and alterations should be construed as falling within the scope of the present invention and the appended patent applications.

without.

Claims (20)

A thin film forming precursor for forming a metal-silicon containing thin film, comprising an organometallic compound represented by the following chemical formula 1: In Chemical Formula 1, M is a Group 4 transition metal, _R1 to _R4 are each independently a hydrogen atom or a _C1 - _C5 linear, branched, or cyclic alkyl or alkenyl group, _R5 is a _C1 - _C3 linear or branched alkyl group, ^R6 to _R8 are each independently a hydrogen atom or a C1-C5 linear, branched, or cyclic alkyl or alkenyl group, and _R9 to _R11 are each independently _{a C1} -C5 linear, branched, or cyclic alkyl or alkenyl group, or _{a C1} - _C5 aminoalkyl or alkoxyalkyl _group . The thin film forming precursor as described in claim 1, wherein in the chemical formula 1, at least one of R ₁ to R ₄ is a hydrogen atom. The thin film forming precursor as claimed in claim 1, wherein in the chemical formula 1, the R ₅ is a methyl group (Me). The thin film forming precursor as described in claim 1, wherein in the chemical formula 1, at least one of R ₆ to R ₈ is a methyl group. The thin film forming precursor as claimed in claim 1, wherein in the chemical formula 1, R ₆ to R ₈ are all the same. The thin film forming precursor according to claim 1, wherein the organometallic compound represented by Chemical Formula 1 is an organometallic compound represented by the following Chemical Formula 2. [Chemical Formula 2] In Formula 2, M and _R1 to _R11 are the same as defined in Claim 1, and _R12 to _R17 are each independently a _C1 - _C5 linear, branched, or cyclic alkyl or alkenyl group. The thin film forming precursor as described in claim 6, wherein in the chemical formula 2, at least one of R ₁₂ to R ₁₇ is a methyl group. The thin film forming precursor as described in claim 6, wherein in the chemical formula 2, R ₁₂ to R ₁₇ are all the same. The thin film forming precursor as described in claim 1, wherein the thin film forming precursor further comprises a solvent. The thin film forming precursor as claimed in claim 9, wherein the solvent is one or more of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, ethylene glycol dimethyl ether, esters, tetrahydrofuran, and tertiary amines. The thin film forming precursor as described in claim 9, wherein the solvent comprises 1 to 99 wt % relative to the total weight of the thin film forming precursor. A thin film forming method comprising: forming a thin film on a substrate using the thin film forming precursor as described in claim 1 or claim 9. The thin film forming method as described in claim 12, wherein the process of forming a thin film on a substrate includes: a process of forming a precursor film by depositing the thin film forming precursor on the surface of the substrate; and a process of causing the precursor film to react with a reactive gas. The thin film forming method as described in claim 13, wherein the reactive gas is one or more of 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 ). The thin film forming method as described in claim 13, wherein the process of forming a precursor thin film includes: a process of vaporizing the precursor for thin film formation and transferring it into the interior of a chamber. The thin film forming method as described in claim 13, wherein the process of forming a precursor thin film includes: a process of transferring the thin film forming precursor into the interior of the chamber by direct liquid injection (DLI). The thin film forming method as described in claim 13, wherein the deposition is performed by any one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and an atomic layer deposition (ALD) process. The thin film forming method as described in claim 17, wherein the deposition is performed by a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma chemical vapor deposition (HDPCVD) process, or a plasma-enhanced atomic layer deposition (PEALD) process. The thin film forming method as described in claim 13, wherein the process of forming a thin film on a substrate includes: supplying the thin film forming precursor to the substrate and forming the thin film by applying plasma. A semiconductor device comprising a thin film manufactured by the thin film forming method as described in claim 12.