Compound for forming molybdenum-containing thin film, molybdenum-containing thin film, and manufacturing method thereof

Abstract

To provide: a precursor for forming a molybdenum-containing thin film that has advantages in a process due to improved thermal stability, high volatility and high vapor pressure, and can increase a deposition rate; a molybdenum-containing thin film manufactured using the same; and a manufacturing method thereof.SOLUTION: An embodiment of the present disclosure is a compound represented by Chemical Formula 1, where: R1 and R2 are each independently selected from hydrogen, a linear alkyl group having 1 to 6 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms; R3 is selected from a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 30 carbon atoms; and X is a halogen element.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a compound for forming a molybdenum-containing thin film, a molybdenum-containing thin film, and a method for producing the same, and more particularly to a compound for forming a molybdenum-containing thin film having improved thermal stability and volatility, a molybdenum-containing thin film, and a method for producing the same. [Background technology]

[0002] Molybdenum-containing thin films, such as molybdenum metal thin films, molybdenum oxide thin films, molybdenum nitride thin films, molybdenum sulfide thin films, and molybdenum carbide thin films, can be used in semiconductor processes as diffusion barrier films for metal wiring, gate lines, electrodes, etc., and are also used in various industrial applications as hard coating materials, sensors, channel layers, catalysts, etc.

[0003] Molybdenum has advantages such as a high melting point, a low thermal expansion coefficient, high thermal conductivity, a high work function resulting from low resistivity, and excellent thermal and chemical stability. Therefore, it can be used as an important metallic material to suppress leakage current in capacitors that require a high dielectric constant in highly integrated DRAMs. Furthermore, molybdenum has low resistivity and can replace tungsten (W) metal currently used in 3D NAND flash memory or be used as a diffusion barrier for tungsten (W) metal. It can also be used as a seed layer for growing molybdenum and as a diffusion barrier in metallurgical processes in non-memory fields such as logic devices.

[0004] Meanwhile, in both memory and non-memory fields, product development is becoming more diverse, including high aspect ratios and complex three-dimensional structures, creating a demand for molybdenum-containing thin films suitable for such products.

[0005] However, conventional molybdenum precursors containing biscyclopentadienyl and imide groups have poor vaporization properties, making them difficult to use in deposition processes. Furthermore, conventional molybdenum precursors containing alkylcyclopentadienyl, nitrile, and carbonyl groups contain carbonyl groups, making them highly toxic and difficult to use in high-temperature processes. Furthermore, their low vapor pressure makes them difficult to handle, making it difficult to form high-quality thin films. Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide a precursor for forming a molybdenum-containing thin film that has no process or performance problems when applied to next-generation semiconductor products, etc., has improved thermal stability, high volatility and vapor pressure, and is advantageous in process and can increase the deposition rate, a molybdenum-containing thin film formed using the precursor, and a method for manufacturing the same.

[0007] The objects of the present invention are not limited to those mentioned above, and other objects not mentioned above will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0008] A molybdenum-containing thin film-forming compound according to one embodiment of the present invention is a compound represented by Chemical Formula 1, in which R1 and R2 are each independently selected from hydrogen, a linear alkyl group having 1 to 6 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms; R3 is selected from a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 30 carbon atoms; and X is a halogen element.

[0009] [Table 1]

[0010] The molybdenum-containing thin film according to one embodiment of the present invention is manufactured by depositing a compound represented by Chemical Formula 1. A method for producing a molybdenum-containing thin film according to one embodiment of the present invention includes depositing a compound represented by Chemical Formula 1 on a substrate.

[0011] Further details of the embodiments are included in the detailed description and drawings. [Effects of the Invention]

[0012] The precursor for forming a molybdenum-containing thin film according to an embodiment of the present invention includes an alkylcyclopentadienyl group and a halogen element, and has excellent structural and thermal stability as well as high volatility, making it possible to easily form a high-quality thin film.

[0013] The effects of the present invention are not limited to the above-mentioned examples, and various other effects are included within the scope of the present invention. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a 1H-NMR spectrum of the compound according to Example 1. [Figure 2] 1 is a 1H-NMR spectrum of the compound according to Example 2. [Figure 3] 1 is a 1H-NMR spectrum of the compound according to Comparative Example 1. [Figure 4] 1 is a TGA graph of a molybdenum precursor compound according to Example 1. [Figure 5] 1 is a DSC graph of a molybdenum precursor compound according to Example 1. [Figure 6] 3 is a TGA graph of a molybdenum precursor compound according to Example 2. [Figure 7] 3 is a DSC graph of the molybdenum precursor compound according to Example 2. [Figure 8] This shows the results of XPS analysis of a molybdenum oxide thin film formed at a substrate temperature of 260°C. [Figure 9]This shows the results of XPS analysis of a molybdenum oxide thin film formed at a substrate temperature of 280°C. [Figure 10] This shows the results of XPS analysis of a molybdenum oxide thin film formed at a substrate temperature of 300°C. [Figure 11] 1 shows NMR spectra of the compound according to Example 1 measured before heat treatment and after heat treatment at 150° C. and 180° C., respectively. [Figure 12] 1 shows NMR spectra measured for the compound according to Comparative Example 1 before heat treatment and after heat treatment at 150° C. and 180° C., respectively. DETAILED DESCRIPTION OF THE INVENTION

[0015] The advantages and features of the present invention, and methods for achieving them, will become more apparent from the following detailed description of the embodiments in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and may be embodied in various different forms. These embodiments are provided solely to ensure that the disclosure of the present invention is complete and to fully convey the scope of the invention to those skilled in the art. The present invention is defined only by the scope of the claims.

[0016] In describing the present invention, if it is determined that a specific description of related publicly known technology may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. When words such as "comprise," "have," and "be made" are used in the present invention, other parts may be added as long as "only" is not used. When elements are expressed in the singular, the plural is also included unless otherwise explicitly stated.

[0017] When interpreting elements, they are interpreted as including a margin of error even if there is no other explicit description. A compound for forming a molybdenum-containing thin film according to one embodiment of the present invention can be represented by the following Chemical Formula 1. The compound represented by Chemical Formula 1 can be used as a precursor material for forming a molybdenum-containing thin film.

[0018] [Table 2]

[0019] In Chemical Formula 1, R1 and R2 can be independently selected from hydrogen, a linear alkyl group having 1 to 6 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms. In Chemical Formula 1, R3 can be selected from a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 30 carbon atoms.

[0020] In this case, the vapor pressure characteristics are excellent, so that the compound can be easily supplied and deposited during the thin film formation process, and a polymer thin film can be formed with a high deposition rate. For example, in Chemical Formula 1, R1 may be hydrogen, R2 may be a linear alkyl group having 1 to 6 carbon atoms, and R3 may be a branched alkyl group having 3 to 6 carbon atoms. In this case, the vapor pressure characteristics are excellent, making the deposition process easy, and the impurity content in the thin film is significantly reduced.

[0021] As another example, in Chemical Formula 1, R1 and R2 may be linear alkyl groups having 1 to 6 carbon atoms, and R3 may be a branched alkyl group having 3 to 6 carbon atoms. In this case, R1 and R2 may be different from each other. In this case, the vapor pressure characteristics are excellent, the deposition process is easy, and the content of impurities in the thin film is significantly reduced, allowing the formation of a high-quality molybdenum-containing thin film.

[0022] In Chemical Formula 1, X may be a halogen element. Specifically, for example, in Chemical Formula 1, X may be a halogen element such as chlorine, bromine, or iodine. Preferably, for example, X may be chlorine. The bond between Mo and a halogen element has a higher bond energy than the bond between Mo and a carbon element. Therefore, when the compound of Chemical Formula 1 containing a Mo-halogen element bond is used as a precursor for forming a molybdenum-containing thin film, a high-quality molybdenum-containing thin film with excellent thermal stability and almost no impurities can be formed.

[0023] Specifically, for example, the compound for forming a molybdenum-containing thin film may be a compound represented by the following Chemical Formula 2 or 3. In this case, the compound has excellent thermal stability and volatility. Therefore, by using the compound as a precursor material for forming a molybdenum-containing thin film, a high-quality molybdenum-containing thin film can be easily formed.

[0024] [Table 3]

[0025] The molybdenum-containing thin film can be formed by depositing the above-mentioned compound for forming a molybdenum-containing thin film. Hereinafter, a method for producing a molybdenum-containing thin film on a substrate using the above-mentioned compound will be specifically described.

[0026] For example, a molybdenum-containing thin film can be formed by depositing a compound on a substrate using any one of plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, plasma-enhanced atomic layer deposition, and thermal atomic layer deposition.

[0027] Specifically, for example, a method for producing a molybdenum-containing thin film includes a first step of cleaning and surface-treating a substrate, a second step of mounting the substrate in a chamber and heating the substrate, a third step of supplying a compound for forming a molybdenum-containing thin film represented by Chemical Formula 1 onto the substrate to form a monolayer, a fourth step of supplying a reactive gas into the chamber to form a molybdenum thin film, and a fifth step of purging to remove unreacted materials.

[0028] The compound for forming a molybdenum-containing thin film represented by Chemical Formula 1 is the same as that explained above, and therefore a duplicate explanation will be omitted. The first step is to clean the substrate and perform a surface treatment.

[0029] Before depositing a thin film, the substrate is washed to remove oil, moisture, and foreign matter that may be present on the substrate. The substrate can be washed using either a dry or wet method, or both methods can be used. For example, the washing can be performed using a process such as degreasing using an organic solvent, acid treatment, alkali treatment, ultrasonic cleaning, or heat treatment, but is not limited thereto.

[0030] For example, the native oxide film on the substrate surface can be removed using an etchant such as hydrofluoric acid or sulfuric acid, or by other gas-phase cleaning methods such as dry ice cleaning, UV ozone cleaning, etc. Also, to prevent the formation of an oxide film and facilitate the formation of a thin film, a surface treatment can be performed to form a protective layer on the surface of the cleaned substrate.

[0031] Before the cleaned and surface-treated substrate is loaded into the chamber, an inert gas may be purged into the chamber to remove impurities. However, this is not a limitation. By removing impurities in this manner, the generation of by-products due to side reactions can be suppressed, allowing for the formation of high-quality thin films. After the impurities are removed, the chamber may be maintained in a vacuum state for the reaction, but this is not a limitation.

[0032] The second step is a step of mounting the substrate in the chamber and heating the substrate. In the second step, the heating temperature of the substrate may be 50°C to 700°C. Preferably, the heating temperature of the substrate may be 250°C to 400°C or 250°C to 350°C. In this case, the reaction proceeds quickly and smoothly, and a high-quality thin film can be formed.

[0033] The third step is to supply the molybdenum-containing thin film forming compound represented by Chemical Formula 1 onto the substrate to form a single layer. For example, the compound for forming the molybdenum-containing thin film may be supplied into the chamber by bubbling, but is not limited thereto. If necessary, the compound may be supplied together with a carrier gas. The carrier gas may be a gas that is non-reactive with the compound, lighter than the compound, and capable of easily transporting the vaporized compound to the reaction chamber. Furthermore, controlling the flow rate of the compound supplied to the chamber allows for easy control of the reaction, including the thin film growth rate. For example, the carrier gas may include, but is not limited to, one or more selected from argon (Ar), helium (He), and neon (Ne).

[0034] A carrier gas may also be supplied into the chamber together with the compound by bubbling, but is not limited to this. When the compound for forming a molybdenum-containing thin film is supplied onto the heated substrate in this manner, a monolayer containing molybdenum is formed.

[0035] The fourth step is to supply a reactive gas to the chamber to form a molybdenum thin film. The reactant gas reacts with the compound on the previously formed monolayer to form a molybdenum-containing thin film, and may include, but is not limited to, at least one of O2, O3, HO, NO, NO2, NO, HO, H2, NH3, alkylamines, hydrazine derivatives, SiH4, Si2H6, BH3, B2H6, borane ammonia complex, GeH4, and PH3.

[0036] For example, a molybdenum oxide thin film can be formed by supplying O3 as a reaction gas, but is not limited thereto. For example, the pressure inside the reactor is 1×10 -1 Torr ~ 100 × 10 -1 Torr. Within this range, the reaction can proceed smoothly while ensuring process safety.

[0037] The fifth step is a purging step to remove unreacted materials. Once a thin film of a desired thickness is formed, the inside of the chamber is purged to remove unreacted materials. For example, the chamber can be purged with an inert gas such as argon (Ar), helium (He), or neon (Ne) to remove unreacted materials, but is not limited thereto.

[0038] If necessary, the method may further include a step of selectively post-treating the thin film, for example, the post-treatment may be performed by any one of an inductively coupled plasma (ICP) treatment process, a rapid thermal annealing (RTA) process, or a combination thereof, but is not limited thereto.

[0039] A method for manufacturing a molybdenum-containing thin film according to an embodiment of the present invention uses a compound represented by Chemical Formula 1, which has high thermal stability and excellent vapor pressure characteristics, as a precursor. As a result, it is easy to control the supply of reactants and the reaction during the deposition process, and a high-quality molybdenum-containing thin film with almost no impurities can be formed.

[0040] Therefore, it can be used not only for wiring and electrodes of semiconductor elements, but also for electrodes and diffusion prevention films of memory elements, thereby improving the performance of the elements. The molybdenum-containing thin film-forming compound according to the present invention and the molybdenum-containing thin film prepared therefrom will be described in more detail below with reference to the following examples, which are provided for the purpose of aiding in the understanding of the present invention and are not intended to limit the scope of the present invention.

[0041] [Example 1] A flask was charged with 11.5 g of sodium molybdate and 300 ml of dimethoxyethane (DME). After stirring the mixture at -78°C, 9.6 g of t-butylamine, 22.5 g of triethylamine, and 55.1 g of chlorotrimethylsilane were slowly added and reacted. After the reaction was complete, the solution was refluxed for an additional 16 hours. The mixture was filtered, and the solvent and volatiles were evaporated under vacuum to produce a yellow solid intermediate, (tBuN)MoClDME.

[0042] 20 ml of a 2.5 M n-BuLi hexane solution was slowly added dropwise to 4.1 g of methylcyclopentadiene (MeCp) in 200 ml of tetrahydrofuran at -78 °C to allow the reaction. After the reaction was complete, the mixture was slowly warmed to room temperature and stirred at room temperature for 4 hours to produce Li-MeCp. 300 ml of diethyl ether was added to the flask containing the reaction intermediate (tBuN)MoClDME at -78 °C. The entire amount of the Li-MeCp solution was slowly added dropwise to the flask containing the reaction intermediate (tBuN)MoClDME to allow the reaction. After the reaction was complete, the mixture was warmed to room temperature and stirred at room temperature overnight.

[0043] The mixture was filtered and reduced pressure to remove the solvent and by-products, and then distilled at a temperature of 130°C and a pressure of 0.4 Torr to obtain 8.3 g (yield: 47%) of the compound (tBuN)2(MeCp)MoCl in solid form.

[0044] [Table 4]

[0045] The obtained compound (tBuN)2(MeCp)MoCl is 1 The results were confirmed by H-NMR. The results are shown in Figure 1. Figure 1 shows the compound of Example 1. 1 1H-NMR spectrum.

[0046] 1H NMR (C6D6, 25℃): 1.23 (s, 18H), 2.15 (s, 3H), 5.64 (t, 2H), 5.91 (t, 2H) [Example 2] A yellow solid reaction intermediate (tBuN)2MoCl2DME was prepared in the same manner as in Example 1.

[0047] 20 ml of n-BuLi hexane solution (2.5 M) was slowly added dropwise to 5.3 g of ethylmethylcyclopentadiene (EtMeCp) in 200 ml of tetrahydrofuran at -78° C. After the reaction was completed, the mixture was slowly warmed to room temperature and further stirred at room temperature for 4 hours to produce Li-EtMeCp.

[0048] 300 ml of diethyl ether was added to a flask containing the reaction intermediate (tBuN)2MoCl2DME at -78°C. The entire amount of the Li-EtMeCp solution prepared was slowly added dropwise to the flask containing the reaction intermediate (tBuN)2MoCl2DME to react. After the reaction was completed, the mixture was warmed to room temperature and stirred overnight at room temperature. The mixture was filtered and reduced pressure was applied to remove the solvent and by-products. The mixture was then distilled at 150°C and 0.4 Torr pressure to obtain 5.7 g (yield: 30%) of the compound (tBuN)2(EtMeCp)MoCl in liquid form.

[0049] [Table 5]

[0050] The compound (tBuN)2(EtMeCp)MoCl obtained as above is 1 The results are shown in Figure 2. 1 1H-NMR spectrum.

[0051] 1H NMR (C6D6, 25℃): 1.04 (t, 3H), 1.18 (d, 18H), 1.95 (s, 3H), 2.27 (m, 1H), 2.49 (m, 1H), 5.59 (t, 1H), 5.66 (t, 1H), 5.70 (t, 1H) [Comparative Example 1] A flask was charged with 11.5 g of sodium molybdate and 300 mL of dimethoxyethane. After stirring the mixture at -78°C, 9.6 g of t-butylamine, 22.5 g of triethylamine, and 55.1 g of chlorotrimethylsilane were slowly added. After the reaction was complete, the solution was refluxed for an additional 16 hours. The mixture was filtered, and the solvent and volatiles were evaporated under vacuum to produce the (tBuN)MoClDME reaction intermediate as a yellow solid.

[0052] 20 ml of a 2.5 M n-BuLi hexane solution was slowly added dropwise to 3.2 g of cyclopentadiene in 200 ml of tetrahydrofuran at -78 °C. After the reaction was complete, the mixture was slowly warmed to room temperature and stirred at room temperature for 4 hours to produce Li-Cp. 300 ml of diethyl ether was added dropwise to the flask containing the reaction intermediate (tBuN)MoClDME at -78 °C. The Li-Cp solution was then slowly added dropwise to the flask containing the reaction intermediate (tBuN)MoClDME to react. After the reaction was complete, the mixture was warmed to room temperature and stirred overnight at room temperature. The mixture was filtered and decompressed to remove the solvent and by-products, and then distilled to obtain 5.1 g of the solid compound (tBuN)(Cp)MoCl.

[0053] 300 ml of diethyl ether was added to a flask containing the reaction intermediate (tBuN)2(Cp)MoCl at -78°C. 8.4 ml of a 1.6 M Li-Me diethyl ether solution was slowly added dropwise at -78°C, and the mixture was then warmed to room temperature and stirred overnight. The mixture was filtered and reduced pressure was applied to remove the solvent and by-products, followed by distillation to obtain 1.7 g (35% yield) of the liquid compound (tBuN)2(Cp)MoCH3.

[0054] The obtained compound (tBuN)2(Cp)MoCH3 is 1 The results are shown in FIG. 3. 1 1H-NMR spectrum.

[0055] 1 H NMR (C6D6, 25℃): 1.05 (s, 3H), 1.24 (s, 18H), 5.82 (s, 5H) [Experimental Example 1] Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed on the compounds prepared in Examples 1 and 2, respectively. Thermogravimetric analysis was performed by heating a specimen to 400°C at a rate of 10°C / min while injecting argon gas at a pressure of 1.5 bar / min. Differential scanning calorimetry was performed by heating a specimen to 400°C at a rate of 10°C / min. The results are shown in FIGS. 4 to 7. FIG. 4 is a TGA graph of the molybdenum precursor compound according to Example 1, and FIG. 5 is a DSC graph of the molybdenum precursor compound according to Example 1. FIG. 6 is a TGA graph of the molybdenum precursor compound according to Example 2, and FIG. 7 is a DSC graph of the molybdenum precursor compound according to Example 2.

[0056] First, referring to FIG. 4 and FIG. 6, both the compound of formula 2 and the compound of formula 3 have a half-life (T 50 ) are about 203°C and about 204°C, respectively, which indicates that the vapor pressure characteristics are excellent. Therefore, it can be predicted that the precursor supply and deposition process will be easy during the deposition process.

[0057] 5 and 7, it can be seen that the compound of Chemical Formula 2 begins to thermally decompose at a temperature of about 230° C. or higher, and the compound of Chemical Formula 3 begins to thermally decompose at a temperature of about 250° C. or higher, indicating that the thermal stability of Chemical Formula 3 is relatively high.

[0058] [Experimental Example 2] Produced according to Example 1 ( t Molybdenum oxide (MoO) thin films were formed using the precursor compound (BuN)2(MeCp)MoCl, and analyzed by X-ray photoelectron spectroscopy (XPS). Specifically, the MoO thin films were formed using atomic layer deposition (ALD), which sequentially supplies a molybdenum precursor and a reactant gas. Silicon (Si) wafers were used as substrates. During the deposition process, the substrates were heated to 200°C, 220°C, 240°C, 260°C, 280°C, and 300°C. The precursor compound, housed in a stainless steel container, was heated to 110°C, and the temperature of the line through which the substrate passed was heated to 150°C. Argon (Ar) gas was used as the carrier gas at a flow rate of 100 sccm, and the precursor compound was supplied to the reactor using a bubbler-type container. The internal pressure of the reactor was maintained at 1 torr. The precursor compound gas was supplied to the reactor for 3 seconds, followed by purging with argon gas at 1000 sccm for 15 seconds, followed by ozone (O) gas, a reactive gas, at 600 sccm for 3 seconds, followed by purging with argon gas at 1000 sccm for 15 seconds. This cycle was repeated 100 times to form a molybdenum oxide (MoO) thin film.

[0059] The deposition results of the molybdenum oxide thin films formed by the above process under the conditions of substrate temperatures of 200° C., 220° C., 240° C., 260° C., 280° C. and 300° C. are shown in Table 1 below.

[0060] Table 1

[0061] [Table 6]

[0062] Referring to Table 1, it can be seen that as the heating temperature of the substrate increases during deposition, the thickness of the thin film increases and the growth rate of the thin film also increases. [Experimental Example 3] Molybdenum-containing thin films were formed by repeating the ALD deposition process in the same manner as in Experimental Example 2, except that only the molybdenum precursor compound gas was supplied and purged. The substrate was heated to 260°C, 280°C, and 300°C. The thin films formed were analyzed by X-ray fluorescence spectrometry (XRF). The results are shown in Table 2 below.

[0063] Table 2

[0064] [Table 7]

[0065] Referring to Table 2, it can be seen that the process of supplying only the molybdenum precursor and purging was repeated, and the difference in molybdenum strength at temperatures of 260°C, 280°C, and 300°C was not significant, indicating that thermal decomposition did not occur within the temperature range of 260°C to 300°C.

[0066] [Experimental Example 4] As in Experimental Example 2, molybdenum oxide thin films were formed by heating the substrate to 260°C, 280°C, and 300°C. The compositions of the thin films thus formed were analyzed by X-ray photoelectron spectroscopy (XPS). The results are shown in FIGS. 8 to 10. FIG. 8 shows the XPS analysis results of the molybdenum oxide thin film formed at a substrate temperature of 260°C, FIG. 9 shows the XPS analysis results of the molybdenum oxide thin film formed at a substrate temperature of 280°C, and FIG. 10 shows the XPS analysis results of the molybdenum oxide thin film formed at a substrate temperature of 300°C.

[0067] 8 to 10, it can be seen that chlorine impurities are not detected regardless of the temperature conditions, and carbon impurities are not detected in the thin film except in the very first cycle. This shows that when using the precursor compounds according to the embodiments of the present invention, it is possible to form a molybdenum oxide-containing thin film with extremely low contents of impurities such as chlorine and carbon, even at low temperatures. This means that the thin film can be used in a variety of applications, such as as an electrode or a diffusion barrier film, in devices such as DRAM and flash memory.

[0068] [Experimental Example 5] To compare the thermal stability of the compounds according to Example 1 and Comparative Example 1, 0.7 mL of the compound according to Example 1 was placed in each of two high-pressure reactors, and 0.7 mL of the compound according to Comparative Example 1 was placed in each of two high-pressure reactors. Two samples each according to Example 1 and Comparative Example 1 were heated in a furnace at 150°C and 180°C for one hour, and then cooled to room temperature. NMR analysis was performed on each sample cooled to room temperature. The resulting NMR spectra are shown in Figures 11 and 12. Figure 11 shows the NMR spectra of the compound according to Example 1 before heat treatment and after heat treatment at 150°C and 180°C, respectively. Figure 12 shows the NMR spectra of the compound according to Comparative Example 1 before heat treatment and after heat treatment at 150°C and 180°C, respectively.

[0069] Referring to FIG. 11, it can be seen that the NMR data of the molybdenum precursor of Example 1 remains unchanged even after heat treatment at 150° C. and 180° C. 12, it can be seen that, in the case of the molybdenum precursor of Comparative Example 1, after heat treatment at 150°C and 180°C, peaks that were not present in the NMR spectrum before heat treatment were present. These peaks that appeared after heat treatment can be considered to be peaks due to impurities generated by thermal decomposition of the compound. Therefore, it can be seen that the molybdenum precursor of Comparative Example 1 has poorer thermal stability than the compound of Example 1, resulting in the generation of impurities due to thermal decomposition.

[0070] This shows that the compound of Example 1 exhibits high thermal stability due to the presence of a Mo-Cl bond having a relatively high bond energy compared to the Mo-C bond contained in the compound of Comparative Example 1.

[0071] The compound for forming a molybdenum-containing thin film, the molybdenum-containing thin film, and a method for manufacturing the same according to various embodiments of the present invention can be described as follows. The compound for forming a molybdenum-containing thin film according to one embodiment of the present invention is a compound represented by the following Chemical Formula 1.

[0072] [Table 8]

[0073] In Chemical Formula 1, R1 and R2 are each independently selected from hydrogen, a linear alkyl group having 1 to 6 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms; R3 is selected from a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 30 carbon atoms; and X is a halogen element.

[0074] According to another feature of the invention, R1 may be hydrogen, R2 may be a linear alkyl group having 1 to 6 carbon atoms, and R3 may be a branched alkyl group having 3 to 6 carbon atoms. According to another feature of the present invention, R1 and R2 are linear alkyl groups having 1 to 6 carbon atoms, R3 is a branched alkyl group having 3 to 6 carbon atoms, and R1 and R2 may be different from each other.

[0075] According to another aspect of the present invention, the compound may be represented by the following formula 2 or 3:

[0076] [Table 9]

[0077] The molybdenum-containing thin film according to one embodiment of the present invention is manufactured by depositing the compound for forming the molybdenum-containing thin film. A method for manufacturing a molybdenum-containing thin film according to an embodiment of the present invention includes depositing the compound for forming a molybdenum-containing thin film on a substrate.

[0078] According to another aspect of the present invention, deposition may be performed by any one of plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, plasma-enhanced atomic layer deposition, and thermal atomic layer deposition.

[0079] According to another aspect of the present invention, a method for producing a thin film includes a first step of cleaning and surface treating a substrate; a second step of mounting the substrate in a chamber and heating the substrate; a third step of supplying a compound onto the substrate to form a monolayer; a fourth step of supplying a reactive gas into the chamber to form a molybdenum thin film; and a fifth step of purging to remove unreacted materials.

[0080] According to another feature of the present invention, in the second step, the heating temperature of the substrate may be 50°C to 700°C. According to another aspect of the present invention, the reactive gas may include at least one of O2, O3, H2O, NO, NO2, N2O, H2O2, H2, NH3, alkylamines, hydrazine derivatives, SiH4, Si2H6, BH3, B2H6, borane ammonia complex, GeH4, and PH3.

[0081] Although the present invention has been described in detail through examples, the present invention is not necessarily limited to these examples and can be variously modified within the scope of the technical concept of the present invention. Therefore, the disclosed examples are for illustrative purposes only and do not limit the technical concept of the present invention. Therefore, the above-described examples should be understood as illustrative in all respects and not restrictive. The scope of the present invention should be interpreted by the following claims, and all technical concepts within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

Claims

1. A compound for forming a molybdenum-containing thin film represented by the following formula 1. Table 1 In the above Chemical Formula 1, R １ and R ２ are each independently selected from hydrogen, a linear alkyl group having 1 to 6 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms; R ３ is selected from linear alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 30 carbon atoms, and X is a halogen element.

2. The R １ is hydrogen, and R ２ is a linear alkyl group having 1 to 6 carbon atoms, and R ３ 2. The compound for forming a molybdenum-containing thin film according to claim 1, wherein is a branched alkyl group having 3 to 6 carbon atoms.

3. The R １ and R ２ is a linear alkyl group having 1 to 6 carbon atoms, and R ３ is a branched alkyl group having 3 to 6 carbon atoms, and １ and R ２ The molybdenum-containing thin film-forming compound according to claim 1 , wherein:

4. 2. The compound for forming a molybdenum-containing thin film according to claim 1, wherein the compound is represented by the following Chemical Formula 2 or 3: Table 2

5. A molybdenum-containing thin film produced by vapor deposition of the compound according to any one of claims 1 to 4.

6. A method for producing a molybdenum-containing thin film, comprising the step of depositing a compound according to any one of claims 1 to 4 onto a substrate.

7. 7. The method of claim 6, wherein the deposition is performed by any one of plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, plasma-enhanced atomic layer deposition, and thermal atomic layer deposition.

8. The method for producing the thin film includes: A first step of cleaning and surface treating the substrate; a second step of mounting the substrate in a chamber and heating the substrate; a third step of dispensing the compound onto the substrate to form a monolayer; A fourth step of supplying a reactive gas to the chamber to form a molybdenum thin film; and 7. The method for producing a molybdenum-containing thin film according to claim 6, further comprising a fifth step of purging to remove unreacted materials.

9. 9. The method for producing a molybdenum-containing thin film according to claim 8, wherein the heating temperature of the substrate in the second step is 50° C. to 700° C.

10. The reaction gas is O ２ , O ３ , H ２ O, NO, NO ２ , N ２ O, H ２ O ２ , H ２ , N.H. ３ , alkylamines, hydrazine derivatives, SiH ４ , Si ２ H ６ , B.H. ３ , B ２ H ６ , borane ammonia complex, GeH ４ and PH ３ The method for producing a molybdenum-containing thin film according to claim 8 , comprising at least one of the following steps:

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