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

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 same, and a semiconductor device comprising the thin film, wherein the precursor comprises a organometallic compound with a novel chemical structure represented by chemical formula 1, which exhibits high volatility, high thermal stability, and a liquid state at room temperature, so that an excellent metal-silicon-containing thin film can be formed by a thin film forming process, such as chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

Description

A precursor for forming a metal-silicon-containing thin film, a method for depositing a thin film using the same, and a semiconductor device including the thin film.

[0001] The present invention relates to a precursor for forming a metal-silicon-containing thin film, a thin film deposition method using the same, and a semiconductor device including the thin film, and more particularly, to a novel thin film formation precursor for forming a thin film containing a Group 4 metal and silicon, a thin film deposition method using the same, and a semiconductor device including the thin film.

[0002] As thin films used in semiconductor devices become increasingly miniaturized and highly integrated, high-k precursors containing Group 4 transition metal compounds are used in the thin film formation process to suppress leakage current and secure high dielectric constants. At this time, in order to suppress leakage current, metal-silicate (e.g., HfSiO) thin films formed with precursors containing Group 4 transition metal compounds are preferred over Group 4 transition metal oxide thin films. x , ZrSiO x ) is known to have beneficial effects.

[0003] Thin films can be manufactured by directly contacting Group 4 transition metals with silicon. However, direct contact between Group 4 transition metal oxides and silicon can result in reduced thermal stability and increased leakage current. Conversely, silicon-doped metal-silicate thin films exhibit high dielectric constants while suppressing leakage current and exhibiting minimal mobility degradation.

[0004] To form a metal-silicate thin film, a precursor for forming a metal oxide thin film and a precursor for forming a silicon oxide thin film can be used separately. However, applying this method has the problem that the volatility and decomposition temperatures of the two precursors differ, making it difficult to set the process temperature, making it difficult to form a thin film with a uniform composition ratio, and making it difficult to ensure step coverage.

[0005] As a method to improve these problems, a technology is being developed to form a thin film using a precursor compound in which silicon is included as a ligand within the molecule of the precursor compound.

[0006] For example, in Korean Patent Publication No. 10-1216068, it was reported that when a Group 4 transition metal compound with high volatility, liquid state at room temperature, and excellent thermal stability, in which an amine group and a silylamine group are bonded to a central metal atom, is used as a precursor, excellent thin film properties, thickness, and step coverage can be secured by metalorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD).

[0007] In addition, Korean Patent Publication No. 10-0779468 discloses a technique for forming a metal silicate gate dielectric film using a Group 4 transition metal compound containing a siloxane such as Zr-bis(trimethylsiloxide)bis(thd), tetrakis(trimethylsiloxide)zirconium, tetrakis(trimethylsiloxide)hafnium, and Hf-bis(trimethylsiloxide)bis(thd).

[0008] The present invention has been made in consideration of the above-described prior arts, and its purpose is to provide a precursor for forming a thin film, which includes a compound having a novel chemical structure, in which a cyclopentadienyl ligand containing a silyl group is bonded to a central metal atom, and which is highly volatile, liquid at room temperature, and has high thermal stability.

[0009] In addition, the purpose is to provide a precursor for forming a thin film that can form an excellent metal-silicon-containing thin film by a thin film forming process such as metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

[0010] In addition, the purpose is to provide a method for forming a metal-silicon-containing thin film using the precursor for forming the thin film.

[0011] In addition, the purpose is to provide a semiconductor device including the above thin film.

[0012] The precursor for forming a thin film of the present invention for achieving the above purpose is for forming a metal-silicon containing thin film, and is characterized by including an organometallic compound represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1, M is one of the group 4 transition metals, and R 1 Inland R 4 are each independently a hydrogen atom or a C1~C5 straight-chain, branched or cyclic alkyl or alkenyl group, and R 5 is a straight or branched alkyl group of C1~C3, and R 6 Inland R 8 are each independently a hydrogen atom or a C1~C5 straight-chain, branched or cyclic alkyl or alkenyl group, and R 9 Inland R 11 are each independently a C1~C5 straight-chain, branched or cyclic alkyl group or alkenyl group, or a C1~C5 aminoalkyl group or alkoxyalkyl group.

[0016] At this time, at least one of R1 to R4 in the above chemical formula 1 may be a hydrogen atom.

[0017] Additionally, in the above chemical formula 1, R5 may be a methyl group (Me).

[0018] In addition, in the above 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.

[0019] In addition, the organometallic compound represented by the above chemical formula 1 may be an organometallic compound represented by the following chemical formula 2.

[0020] [Chemical Formula 2]

[0021]

[0022] In the above chemical formula 2, M and R1 to R 11 is as defined in claim 1, and R 12 Inland R 17 are each independently a C1~C5 straight-chain, branched, or cyclic alkyl group or alkenyl group.

[0023] In addition, in the above chemical formula 2, the R 12 Inland R 17 One or more of the R may be a methyl group, and the R 12 Inland R 17 may all be the same.

[0024] In addition, the precursor for forming the thin film may additionally include a solvent, and the solvent may be C1-C 16 Any one or more of saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines may be used, and the solvent may be included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming the thin film.

[0025] The thin film forming method of the present invention may include a process of forming a thin film on a substrate using the precursor for forming the thin film.

[0026] At this time, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing a precursor for forming the thin film on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.

[0027] Additionally, 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).

[0028] In addition, the process of forming the precursor thin film may include a process of vaporizing the precursor for forming the thin film and transporting it into the chamber, and may also include a process of transporting the precursor for forming the thin film into the chamber using a direct liquid injection (DLI) method.

[0029] Additionally, the deposition may be performed by any 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.

[0030] Additionally, the process of forming a thin film on the substrate may include a step of supplying a precursor for forming the thin film to the substrate and applying plasma to form the thin film.

[0031] In addition, the semiconductor device of the present invention is characterized by including a thin film manufactured by the above thin film forming method.

[0032] The precursor for forming a thin film according to the present invention includes a compound having a novel chemical structure in which a cyclopentadienyl ligand containing a silyl group is bonded to a central metal atom, thereby exhibiting properties such as high volatility, liquidity at room temperature, and high thermal stability.

[0033] In addition, by performing a thin film formation process such as MOCVD or ALD using the precursor for forming the thin film, an excellent metal-silicon-containing thin film can be formed, and in particular, a thin film of a metal unit, oxide, nitride, etc. containing a Group 4 transition metal-silicon can be formed.

[0034] In addition, high-quality semiconductor devices including the above thin film can be manufactured.

[0035] Figure 1 is an organometallic compound according to Example 1. 1 This is the result of H-NMR analysis.

[0036] Figure 2 shows the results of TGA (a) and DSC (b) analysis of an organometallic compound according to Example 1.

[0037] Figure 3 is an organometallic compound according to Example 2. 1 This is the result of H-NMR analysis.

[0038] Figure 4 shows the results of TGA (a) and DSC (b) analysis of an organometallic compound according to Example 2.

[0039] The present invention will be described in more detail below. Terms and words used in this specification and claims should not be construed as limited to their conventional or dictionary meanings. Rather, they should be interpreted in a way that is consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of a term to best explain his or her invention.

[0040] A precursor for forming a thin film according to the present invention is for forming a metal-silicon-containing thin film, and includes an organometallic compound containing a silyl group represented by the following chemical formula 1 and a group 4 transition metal as a central metal atom.

[0041] [Chemical Formula 1]

[0042]

[0043] In the above chemical formula 1, M is one of the group 4 transition metals, and R 1 Inland R 4 are each independently a hydrogen atom or a C1~C5 straight-chain, branched or cyclic alkyl or alkenyl group, and R 5 is a straight or branched alkyl group of C1~C3, and R 6 Inland R 8 are each independently a hydrogen atom or a C1~C5 straight-chain, branched or cyclic alkyl or alkenyl group, and R 9 Inland R 11 are each independently a C1~C5 straight-chain, branched or cyclic alkyl group or alkenyl group, or a C1~C5 aminoalkyl group or alkoxyalkyl group.

[0044] The above-described precursor for thin film formation can form an excellent metal-silicon-containing thin film by being applied to a thin film formation process, particularly a thin film formation process such as metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). In addition, to be usable in such a thin film formation process, the thin film formation precursor is a compound that is highly volatile, exists in a liquid state at room temperature, is thermally stable, and contains a silyl group in its chemical structure.

[0045] The compound represented by the above chemical formula 1 may include various chemical structures.

[0046] In one embodiment, at least one of R1 to R4 in the above chemical formula 1 may be a hydrogen atom. In addition, in the above chemical formula 1, R5 may be a methyl group (Me). In addition, in the above 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.

[0047] Compounds with such exemplary chemical structures are suitable for application in thin film formation processes because they exist in a liquid state at room temperature.

[0048] In addition, the organometallic compound represented by the above chemical formula 1 may be an organometallic compound represented by the following chemical formula 2.

[0049] [Chemical Formula 2]

[0050]

[0051] In the above chemical formula 2, M and R1 to R 11 is as defined in claim 1, and R 12 Inland R 17 are each independently a C1~C5 straight-chain, branched, or cyclic alkyl group or alkenyl group.

[0052] The compound represented by the chemical formula 2 is R 12 Inland R 17 One or more of the R may be a methyl group, and the R 12 Inland R 17 All of them may exemplify the same chemical structure.

[0053] In addition, the precursor for forming the thin film may additionally include a solvent. The solvent may be C1-C 16 The solvent may be one or more of a saturated or unsaturated hydrocarbon, a ketone, an ether, a glyme, an ester, tetrahydrofuran, or a tertiary amine, and the solvent may be included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming the thin film.

[0054] The precursor, which may or may not contain a solvent, can be vaporized, and the deposition process can be performed by supplying it into the chamber. Alternatively, a soluble solvent can be appropriately selected and added depending on the properties of the organometallic compound. In other words, depending on the type of organometallic compound, if it exists in a liquid state at room temperature, the deposition process can be performed without a separate solvent.

[0055] The thin film forming method of the present invention is characterized by including a process of forming a thin film on a substrate using the precursor for forming the thin film.

[0056] At this time, the precursor for forming the thin film may additionally include a solvent as described above, and the solvent may be included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming the thin film.

[0057] A method for forming a metal-silicon-containing thin film using a precursor for forming a thin film including an organometallic compound represented by the above chemical formula 1 can be performed according to a method for manufacturing a thin film by a conventional deposition process, except that the precursor for forming a thin film includes an organometallic compound represented by the chemical formula 1 or 2. Specifically, the deposition can be performed by any 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.

[0058] That is, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing a precursor for forming the thin film on the surface of the substrate by the process described above, and a process of reacting the precursor thin film with a reactive gas.

[0059] 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 carried out in the presence of an oxidizing gas such as water vapor, oxygen, or ozone, a metal-silicon oxide thin film may be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, various thin films such as a metal-silicon thin film or a metal nitride-silicon thin film may be formed.

[0060] Additionally, the process for forming the precursor thin film may include a process of vaporizing the precursor for thin film formation and transporting it inside the chamber. At this time, the volatility and structural and thermal stability of the precursor for thin film formation may be major factors determining the efficiency of deposition on the substrate inside the chamber.

[0061] In addition, after supplying a 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 a step of supplying a precursor for forming a thin film to the substrate and applying plasma to form a thin film.

[0062] In addition, as the substrate for forming the thin film, any substrate used in semiconductor manufacturing that needs to be coated with a metal thin film due to technical operation can be used without any special restrictions. Specifically, a silicon substrate (Si), a silicon oxide substrate (SiO2), a silicon nitride substrate (SiN), a silicon oxynitride substrate (SiON), a titanium nitride substrate (TiN), a tantalum nitride substrate (TaN), a tungsten substrate (W), or a noble metal substrate, such as a platinum substrate (Pt), a palladium substrate (Pd), a rhodium substrate (Rh), or a gold substrate (Au), can be used.

[0063] In the process of transporting the precursor for forming the above thin film into the chamber, a method of transporting the precursor through a volatilized gas, a direct liquid injection (DLI) method, or a liquid transport method of transporting the organometallic compound by dissolving it in an organic solvent may be used. The method of transporting the precursor through a volatilized gas may be performed by placing a container containing the precursor in a constant temperature bath, bubbling with an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen to evaporate the precursor, and then transporting it onto a substrate for forming a metal thin film, or by using a liquid delivery system (LDS) to change a liquid precursor into a gaseous state through a vaporizer, and then transporting it onto a substrate for forming a thin film.

[0064] In the case of a liquid transport method in which a precursor is transported by dissolving it in an organic solvent, it can be used in the form of a composition comprising an organometallic compound represented by Chemical Formula 1 or Chemical Formula 2 and a solvent as described above. If the organometallic compound has a high viscosity and is difficult to sufficiently vaporize in a liquid transport type vaporizer, the deposition process can be effectively performed by using it in the form of a composition including a solvent.

[0065] These solvents must have the property of dissolving solid substances or be solvents capable of dissolving and dispersing liquid substances. In addition, it is desirable to select a solvent that enhances the viscosity reduction effect and volatility improvement effect of the composition for forming a thin film by considering the boiling point, density, and vapor pressure conditions of the solvent, thereby enabling the formation of a thin film with improved uniformity and step coverage characteristics of the deposited thin film.

[0066] In addition, when supplying the precursor for forming the thin film into the chamber, in order to further improve the electrical characteristics, i.e., the electrostatic capacitance, of the metal thin film to be finally formed, a metal precursor including at least one metal (M") selected from silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta) and lanthanide atoms may be optionally further supplied as a second metal precursor. The second metal precursor may be an alkylamide compound or an alkoxy compound including the metal.

[0067] The supply of the second metal precursor may be performed in the same manner as the supply method of the precursor for forming the thin film, and the second metal precursor may be supplied onto the substrate for forming the thin film together with the precursor for forming the thin film, or may be supplied sequentially after the supply of the precursor for forming the thin film is completed.

[0068] It is preferable that the precursor for forming a thin film as described above and optionally the second metal precursor be maintained at a temperature of 100 to 200°C, more preferably 130 to 180°C, before being supplied into the reaction chamber to contact the substrate for forming the thin film.

[0069] In addition, after the step of supplying the precursor for forming a thin film, and prior to supplying the reactive gas, a process of purging the inside of the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be performed to assist the movement of the precursor for forming the thin film and optionally the second metal precursor onto the substrate, to ensure that the inside of the reactor has an appropriate pressure for deposition, and to discharge impurities, etc., existing in the chamber to the outside. At this time, the purging of the inert gas is preferably performed so that the pressure inside the reactor becomes 1 to 5 Torr.

[0070] After the supply of the above precursors is completed, 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.

[0071] In addition, the heat treatment, plasma treatment, or light irradiation treatment process is intended to provide thermal energy for the deposition of a metal precursor and can be performed according to conventional methods. Preferably, the treatment process is performed so that the temperature of the substrate within the reactor is 100 to 1,000°C, preferably 300 to 500°C, in order to produce a metal thin film having the desired physical state and composition at a sufficient growth rate.

[0072] In addition, during the above treatment process, a process of purging the inside of the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be performed to help the reactive gas move onto the substrate as described above, to ensure that the inside of the reactor has an appropriate pressure for deposition, and to discharge impurities or byproducts existing inside the reactor to the outside.

[0073] As described above, the process of introducing a precursor, introducing a reactive gas, and introducing an inert gas is considered one cycle. By repeating this process for one or more cycles, a metal-containing thin film can be formed.

[0074] Specifically, when an oxidizing gas is used as a reactive gas, the thin film manufactured may include a metal oxide of the following chemical formula 3 as a second metal precursor:

[0075] [Chemical Formula 3]

[0076] (M 1-a M" a )O b

[0077] In the above 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 atoms.

[0078] This method for forming a metal-silicon-containing thin film uses a precursor with excellent thermal stability, so that the deposition process can be performed at a higher temperature than in the past, and a high-purity metal-silicon, metal oxide-silicon, or metal nitride-silicon thin film can be formed without particle contamination or carbon impurity contamination due to thermal decomposition of the precursor. Accordingly, the thin film formed by the thin film forming method of the present invention can be usefully applied to a high-k dielectric film in a semiconductor device, for example, a gate dielectric film of a MOS, a gate dielectric film of a capacitor or a non-volatile memory device, etc.

[0079] In another embodiment, a metal-silicon-containing thin film formed by the method for forming the thin film 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).

[0080] In addition, since the semiconductor device has the same configuration as a conventional semiconductor device except that it includes a thin film according to the present invention as a dielectric film requiring high dielectric constant characteristics within the device, a detailed description of the configuration of the semiconductor device is omitted in this specification.

[0081] The effects of the present invention are explained through the following examples.

[0082] [Synthesis Example 1] Preparation of Cp-CH2Si(Me)3 Compound

[0083] In a nitrogen atmosphere, 6 g (0.151 mol) of sodium hydride (NaH, 60%) and 150 ml of THF were charged into a 1,000 ml Schlenk flask, and 10 g (0.151 mol) of cyclopentadiene was slowly added dropwise at room temperature, followed by stirring at room temperature for 5 hours. After the reaction was completed, 18.6 g (0.151 mol) of (chloromethyl)trimethylsilane was added dropwise to the obtained reaction solution at room temperature. The reaction solution was stirred under reflux at 80°C for 24 hours. After the reaction was completed, the reaction solution was filtered, and the obtained solution was reduced in pressure to remove the solvent and volatile by-products. The removed remaining liquid was purified at 38.6°C (1.3 Torr) to obtain 8.1 g (yield 35.2%) of a transparent liquid compound 1.

[0084] [Compound 1]

[0085]

[0086] 1 H-NMR (400MHz, CDCl3, 25℃): Mixture, δ 6.421-5.801(m, 3H, C5H5-CH2), δ 2.961-2.950, 2.862-2.852, (q, 2H, C5H5-CH2), δ 1.905-1.902, 1.829-1.827 (d, 2H, C5H5-CH2), δ 0.011, 0.000(s, 9H, -CH2-Si-(CH3)3)

[0087] [Example 1] Preparation of (Cp-CH2SiMe3)Hf(DMA)3 compound

[0088] In a nitrogen atmosphere, 14.2 g (0.040 mol) of tetrakis(dimethylamino)hafnium [Hf(NMe2)4] and 120 ml of n-hexane were added to a 250 ml Schlenk flask. Then, 6.4 g (0.042 mol) of compound 1 prepared in Synthesis Example 1 was slowly added dropwise at -40°C, and the mixture was stirred at room temperature for 14 hours. After the reaction was completed, the reaction solution was reduced in pressure to remove the solvent and volatile by-products. The remaining liquid was purified at 75.7°C (6.7 mTorr) to obtain 15.4 g (83% yield) of a transparent liquid compound 2.

[0089] The NMR analysis data of the manufactured compound are as shown in Figure 1, and it was determined to have the same chemical structure as Compound 2 below. In addition, the TGA and DSC analysis results are as shown in Figure 2.

[0090] [Compound 2]

[0091]

[0092] 1 H-NMR (400MHz, C6D6, 25℃): δ 5.979-5.787(m, 4H,C5H4-CH2), δ 3.034(s, 18H,Hf-(N(CH3)2)3), δ 1.995 (s, 2H, C5H4-CH2), δ 0.009(s, 9H, -CH2-Si-(CH3)3)

[0093] [Example 2] Preparation of (Cp-CH2SiMe3)Zr(DMA)3 compound

[0094] In a nitrogen atmosphere, 5.0 g (0.0187 mol) of tetrakis(dimethylamino)zirconium [Zr(NMe2)4] and 50 ml of n-hexane were added to a 100 ml Schlenk flask. Then, 3.0 g (0.0196 mol) of compound 1 prepared in Synthesis Example 1 was slowly added dropwise at -40°C, and the mixture was stirred at room temperature for 14 hours. After the reaction was completed, the reaction solution was reduced in pressure to remove the solvent and volatile by-products. The remaining liquid was purified at 82.1°C (7.1 mTorr) to obtain 4.0 g (yield 57.1%) of pale yellow liquid compound 3.

[0095] The NMR analysis data of the manufactured compound are as shown in Figure 3, and it was determined to have the same chemical structure as Compound 3 below. In addition, the TGA and DSC analysis results are as shown in Figure 4.

[0096] [Compound 3]

[0097]

[0098] 1 H-NMR (400MHz, C6D6, 25℃): δ 6.007-5.806(m, 4H,C5H4-CH2), δ 2.998(s, 18H,Zr-(N(CH3)2)3), δ 1.974 (s, 2H, C5H4-CH2), δ 0.005(s, 9H, -CH2-Si-(CH3)3)

[0099] The TGA and DSC analysis results of the synthesized compounds are shown in Table 1.

[0100] * TGA (1 / 2) (℃) ** TGA residue (%)DSC (℃)Compound 21870.4351Compound 31910.9314* TGA (1 / 2) (℃): Temperature at which the precursor loses 50% of its total weight.** TGA residue (℃): Weight ratio of the residue at 350℃.

[0101] Through the above TGA and DSC analysis results, it was confirmed that the synthesized compound has properties of volatility and thermal stability suitable for use as a precursor for thin film deposition containing Group 4 transition metal-silicon.

[0102] Additionally, the results of analyzing the viscosity of the synthesized compound are shown in Table 2.

[0103] Neat viscosity (cPs) Compound 211.9

[0104] When a precursor is injected in a liquid state as LDS for ALD or CVD and vaporized using a flash evaporator, high-viscosity precursors are prone to clogging of the vaporizer and difficult to quantitatively transport. In this regard, compound 2 was judged to be more suitable for use as an ALD or CVD precursor due to its low viscosity.

[0105] While the present invention has been described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments, and various modifications and variations are possible by those skilled in the art without departing from the spirit of the invention. Such modifications and variations are deemed to fall within the scope of the present invention and the appended claims.

Claims

1. As a precursor for forming a thin film for forming a metal-silicon containing thin film, A precursor for forming a thin film, characterized in that it comprises an organometallic compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, M is one of the group 4 transition metals, R1 to R4 are each independently a hydrogen atom or a C1 to C5 straight-chain, branched or cyclic alkyl group or alkenyl group, R5 is a C1 to C3 straight-chain or branched alkyl group, R6 to R8 are each independently a hydrogen atom or a C1 to C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R9 to R 11 are each independently a C1~C5 straight-chain, branched or cyclic alkyl group or alkenyl group, or a C1~C5 aminoalkyl group or alkoxyalkyl group.

2. In claim 1, A precursor for forming a thin film, characterized in that at least one of R1 to R4 in the above chemical formula 1 is a hydrogen atom.

3. In claim 1, A precursor for forming a thin film, characterized in that in the above chemical formula 1, R5 is a methyl group (Me).

4. In claim 1, A precursor for forming a thin film, characterized in that at least one of R6 to R8 in the above chemical formula 1 is a methyl group.

5. In claim 1, A precursor for forming a thin film, characterized in that in the above chemical formula 1, R6 to R8 are all the same.

6. In claim 1, A precursor for forming a thin film, characterized in that the organometallic compound represented by the above chemical formula 1 is an organometallic compound represented by the following chemical formula 2. [Chemical Formula 2] In the above chemical formula 2, M and R1 to R 11 is as defined in claim 1, R 12 Inland R 17 are each independently a C1~C5 straight-chain, branched, or cyclic alkyl group or alkenyl group.

7. In claim 6, In the above chemical formula 2, the R 12 Inland R 17 A precursor for forming a thin film, characterized in that at least one of the groups is a methyl group.

8. In claim 6, In the above chemical formula 2, the R 12 Inland R 17 A precursor for forming a thin film, all of which are characterized by the same thing.

9. In claim 1, A precursor for forming a thin film, characterized in that the precursor for forming a thin film additionally contains a solvent.

10. In claim 9, The above solvent is C1-C 16 A precursor for forming a thin film, characterized in that it is one or more of a saturated or unsaturated hydrocarbon, ketone, ether, glyme, ester, tetrahydrofuran, and tertiary amine.

11. In claim 9, A precursor for forming a thin film, characterized in that the solvent is included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming a thin film.

12. A method for forming a thin film, characterized by including a process for forming a thin film on a substrate using a precursor for forming a thin film according to claim 1 or 9.

13. In claim 12, The process of forming a thin film on the above substrate is: A process of forming a precursor thin film by depositing the precursor for forming the thin film on the surface of a substrate; A process of reacting the above precursor thin film with a reactive gas; A thin film forming method characterized by including:

14. In claim 13, A method for forming a thin film, characterized in that the above 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).

15. In claim 13, A method for forming a thin film, characterized in that the process for forming the precursor thin film includes a process for vaporizing the precursor for forming the thin film and transporting it into the chamber.

16. In claim 13, A method for forming a thin film, characterized in that the process for forming the precursor thin film includes a process for transporting the precursor for forming the thin film into the chamber through a direct liquid injection (DLI) method.

17. In claim 13, A method for forming a thin film, characterized in that the above 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, 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.

18. In claim 13, The process of forming a thin film on the above substrate is: A thin film forming method comprising a step of supplying a precursor for forming the thin film to a substrate and applying plasma to form a thin film.

19. A semiconductor device characterized by including a thin film manufactured by the thin film forming method of claim 12.

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