Molybdenum compound, its production method, and thin film deposition composition containing the same

Abstract

The present invention relates to a molybdenum compound, a method for producing the same, a composition for vapor deposition of a molybdenum-containing thin film containing the same, and a method for producing a molybdenum-containing thin film using the same. By employing the molybdenum compound of the present invention, which has excellent thermal stability, high volatility, and improved vapor pressure, a molybdenum-containing thin film of uniform thickness can be produced at an improved deposition rate.

Description

[Technical Field]

[0001] The present invention relates to a molybdenum compound, a method for producing the same, a composition for thin film deposition containing the same, a method for producing a thin film using the same, and a thin film containing the same. [Background technology]

[0002] Various metalorganic precursors are used to form metal thin films. A variety of techniques are used for thin film deposition, including reactive sputtering, ion-assisted deposition, sol-gel deposition, metalorganic chemical vapor deposition (MOCVD), a type of chemical vapor deposition (CVD), and atomic layer deposition (ALD), also known as atomic layer epitaxy (ALE). Chemical vapor deposition (CVD) and atomic layer deposition (ALD) offer advantages such as good composition control, high film uniformity, and good doping control. They also enable excellent conformal deposition, enabling uniform film thicknesses to be achieved even over highly nonplanar microelectronic device geometries.

[0003] Chemical vapor deposition (CVD) is a chemical process in which organometallic precursors are used to form thin films on a substrate. In a typical chemical vapor deposition (CVD) process, precursors are reacted or decomposed on the surface of the substrate while passing over the substrate in a low-pressure or atmospheric-pressure chamber. Volatile by-products are removed by a gas stream.

[0004] Atomic layer deposition (ALD) is a method that allows precise thickness control, achieves uniform film thickness, and provides excellent conformal deposition. It is a method of sequentially growing films while reacting on the substrate surface. However, the biggest drawback of ALD is its slow film growth rate per unit time. Plasma-enhanced atomic layer deposition (PEALD) is a method that can increase the process rate of ALD. Another advantage of PEALD is that it can increase reactivity at lower temperatures than ALD. Therefore, PEALD is particularly necessary for high-aspect-ratio films such as capacitors and gate spacers.

[0005] Atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) are typically performed in four steps: pulse A, in which a metalorganic first precursor forms a monolayer on the substrate; purge A, in which excess first precursor is removed; pulse B, in which a nonmetallic second precursor induces a reaction between the first precursor and the substrate; and purge B, in which unreacted material is removed. These four steps are repeated until a thin film of the desired thickness is obtained.

[0006] Thin films are used in a variety of important applications, such as semiconductor device fabrication and nanotechnology. Such applications include, for example, conductive films, high-refractive-index optical coatings, corrosion-resistant coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, gate dielectric insulating films in field-effect transistors (FETs), dielectric capacitor layers, capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits. Thin films are also used in microelectronic applications, such as high-k dielectric oxides for dynamic random access memory (DRAM) applications, infrared detectors, and ferroelectric perovskites used in non-volatile ferroelectric random access memories (NV-FeFAMs). The continued miniaturization of microelectronic components increases the need for the use of dielectric thin films.

[0007] Many current molybdenum precursors for use in CVD and ALD do not meet the performance requirements required to enable new processes for the fabrication of next-generation devices such as semiconductors. There is a need for the development of molybdenum precursors with improved thermal stability, higher volatility, increased vapor pressure, uniform deposition, and stable deposition rates. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a molybdenum compound and a method for producing the same.

[0009] Another object of the present invention is to provide a composition for depositing a molybdenum-containing thin film, which contains the molybdenum compound.

[0010] It is yet another object of the present invention to provide a method for preparing a molybdenum-containing thin film using the molybdenum-containing thin film deposition composition.

[0011] The present invention also provides a molybdenum-containing thin film containing 35% or more of molybdenum and 40% or more of nitrogen. [Means for solving the problem]

[0012] The present invention provides a molybdenum compound represented by the following Chemical Formula 1:

[0013] [ka] [In the above Chemical Formula 1, L is C1-C10 alkylene or haloC1-C10 alkylene; R1~R 10 are, independently of each other, hydrogen or C1-C10 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12 may be linked to form a ring.

[0014] In Chemical Formula 1 according to one embodiment of the present invention, L is C1-C6 alkylene, and R1 to R 10 are, independently of each other, hydrogen or C1-C6 alkyl, and Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are each independently hydrogen or C1-C6 alkyl, or 11 and R 12 may be linked to form an alicyclic ring.

[0015] The molybdenum compound according to a preferred embodiment may be represented by the following chemical formula 2:

[0016] [ka] [In the above Chemical Formula 2, R1~R 10 are, independently of each other, hydrogen or C1-C6 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are each independently hydrogen or C1-C6 alkyl, or 11 and R 12 may be linked to form an alicyclic ring, m is an integer from 1 to 3.

[0017] In one embodiment, the molybdenum compound may be selected from the following compounds:

[0018] [ka]

[0019] The present invention provides a method for producing a molybdenum compound according to one embodiment of the present invention, which may include reacting a hydrogen source or an alkyllithium, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5 to produce a molybdenum compound represented by the following Chemical Formula 1-1:

[0020] [ka]

[0021] [ka]

[0022] [ka] [In the above chemical formulas 1-1, 4, and 5, L is C1-C10 alkylene or haloC1-C10 alkylene; R1 to R6 are each independently hydrogen or C1-C10 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12 may be linked to form a ring, X is a halogen.

[0023] The present invention provides a composition for depositing a molybdenum-containing thin film, which comprises a molybdenum compound according to one embodiment of the present invention.

[0024] The present invention also provides a method for producing a thin film using the molybdenum-containing thin film deposition composition.

[0025] The method for producing the molybdenum-containing thin film according to one embodiment of the present invention includes the steps of: a) raising the temperature of a substrate mounted in a chamber; b) injecting a reaction gas and the composition for depositing a molybdenum-containing thin film into the chamber to form a molybdenum-containing thin film.

[0026] In one embodiment, the reactive gas may be oxygen (O), ozone (O), distilled water (H), hydrogen peroxide (H), O, nitric oxide (NO), nitrous oxide (NO), nitrogen dioxide (NO), ammonia (NH), nitrogen (N), hydrazine (N), amine, diamine, carbon monoxide (CO), carbon dioxide (CO), C to C 12 The gas may be any one or more selected from saturated or unsaturated hydrocarbons, hydrogen (H2), argon (Ar), and helium (He).

[0027] The method for producing the molybdenum-containing thin film according to one embodiment of the present invention includes the steps of: c) After step b), a step of injecting a reaction gas into the chamber may be further included, and steps b) and c) may be one cycle, which may be repeated.

[0028] The present invention provides a molybdenum-containing thin film containing at least 35% molybdenum and at least 40% nitrogen. [Effects of the Invention]

[0029] The molybdenum compound according to the present invention has improved thermal stability, high volatility, and improved vapor pressure, and therefore exhibits a stable deposition rate and can form a thin film with high reliability.

[0030] The method for producing a molybdenum compound according to the present invention can easily produce a high-purity molybdenum compound in high yield on an industrial scale by simple steps.

[0031] The method for producing a molybdenum-containing thin film according to the present invention can achieve high film uniformity and good doping control by plasma-enhanced atomic layer deposition (PEALD) etc. by using a molybdenum-containing thin film deposition composition containing a molybdenum compound according to the present invention. Furthermore, the method can provide uniform step coverage for three-dimensional semiconductor devices.

[0032] The molybdenum-containing thin film according to the present invention contains 35% or more of molybdenum and 40% or more of nitrogen, and exhibits an excellent composition ratio. [Brief explanation of the drawings]

[0033] [Figure 1] 1 is a photograph showing the results of scanning electron microscope measurement of a molybdenum-containing thin film according to Example 1 of the present invention. [Figure 2] 1 is a photograph showing the results of scanning electron microscope measurement of a molybdenum-containing thin film according to Example 2 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0034] The present invention provides a molybdenum compound, a method for producing the same, a molybdenum-containing thin film deposition composition containing the same, and a method for producing a thin film using the same.

[0035] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0036] "Comprising" as used herein is an open-ended term having the same meaning as terms such as "comprising," "containing," "having," or "characterized by," and does not exclude additional, unrecited elements, materials, or steps.

[0037] "Alkyl" according to the present invention may be either straight-chain or branched, and may have 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. In yet another embodiment, alkyl may have 1 to 4 carbon atoms.

[0038] "Alkylene" according to the present invention means a divalent organic radical derived from an "alkyl" by removing one hydrogen, where alkyl is as defined above.

[0039] "Halo" as used herein means fluorine, chlorine, bromine, or iodine.

[0040] "Haloalkyl" according to the present invention refers to an alkyl group in which one or more hydrogen atoms are replaced with a halogen atom. For example, haloalkyl includes -CF, -CHF, -CHF, -CBr, -CHBr, -CHBr, -CCl, -CHCl, -CHCI, -CCI, -CHI, -CHI, -CH-CF, -CH-CHF, -CH-CHF, -CH-CBr, -CH-CHBr, -CH-CHBr, -CH-CCl, -CH-CHCl, -CH-CHCI, -CH-CI, -CH-CHI, -CH-CHI, and the like. Here, alkyl and halogen are as defined above.

[0041] The number of carbon atoms in alkyl and the like described in the present invention does not include the number of carbon atoms in the substituents, and as an example, C1-C10 alkyl means an alkyl having 1 to 10 carbon atoms, not including the number of carbon atoms in the alkyl substituents.

[0042] "Substituted" according to the present invention means that a hydrogen atom of the substituted moiety (eg, alkyl, aryl, or cycloalkyl) is replaced with a substituent.

[0043] The present invention will now be described in detail. In this regard, unless otherwise defined, the technical and scientific terms used have the meanings that are commonly understood by those skilled in the art to which this invention pertains, and descriptions of well-known functions and configurations that may obscure the gist of the present invention will be omitted.

[0044] The present invention provides a molybdenum compound represented by the following Chemical Formula 1:

[0045] [ka] [In the above Chemical Formula 1, L is C1-C10 alkylene or haloC1-C10 alkylene; R1~R 10are, independently of each other, hydrogen or C1-C10 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12 may be linked to form a ring.

[0046] The molybdenum compound represented by Formula 1 according to the present invention exhibits excellent thermal stability, high volatility, and improved vapor pressure, and when used, it is possible to obtain a highly reliable molybdenum-containing thin film.

[0047] A molybdenum compound according to one embodiment of the present invention is a compound represented by the formula 1, wherein L is C1-C6 alkylene, and R1 to R 10 are, independently of each other, hydrogen or C1-C6 alkyl, and Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are each independently hydrogen or C1-C6 alkyl, or 11 and R 12 may be linked to form an alicyclic ring.

[0048] The molybdenum compound according to a preferred embodiment may be represented by the following chemical formula 2:

[0049] [ka] [In the above Chemical Formula 2, R1~R 10 are, independently of each other, hydrogen or C1-C6 alkyl; Y is -NR 11 R 12 , -OR 13, or -SR 14 and R 11 ~R 14 are each independently hydrogen or C1-C6 alkyl, or 11 and R 12 may be linked to form an alicyclic ring, m is an integer from 1 to 3.

[0050] The molybdenum compound represented by the formula 2 is more specifically 10 may each independently be hydrogen or C1-C4 alkyl, and Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen or C1-C4 alkyl, or 11 and R 12 may be linked to form a ring, and m is an integer of 2 to 3.

[0051] A more preferred embodiment of the molybdenum compound may be represented by the following chemical formula 3:

[0052] [ka] [In the above Chemical Formula 3, R1 to R4 and R7 to R 10 are, independently of each other, hydrogen or C1-C4 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen or C1-C4 alkyl, or 11 and R 12 may be linked by a C2-C6 alkylene to form an alicyclic ring.

[0053] More specifically, the molybdenum compound according to one embodiment of the present invention may be represented by the following chemical formula 3-1.

[0054] [ka] [In the above chemical formula 3-1, R1 to R6 are each independently hydrogen or C1-C4 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen or C1-C4 alkyl, or 11 and R 12 may be linked by a C2-C6 alkylene to form an alicyclic ring.

[0055] In one embodiment, the molybdenum compound may be selected from, but is not limited to, the following compounds:

[0056] [ka]

[0057] The present invention provides a method for preparing a molybdenum compound according to one embodiment of the present invention, and the molybdenum compound represented by the following Chemical Formula 1-1 may be prepared by reacting a hydrogen source or an alkyllithium, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5:

[0058] [ka]

[0059] [ka]

[0060] [ka] [In the above chemical formulas 1-1, 4, and 5, L is C1-C10 alkylene or haloC1-C10 alkylene; R1 to R6 are each independently hydrogen or C1-C10 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12 may be linked to form a ring, X is a halogen.

[0061] The compound represented by the formula 4 may be prepared by reacting an alkyl lithium with a compound represented by the following formula 6:

[0062] [ka] [In the above-mentioned Chemical Formula 6, L is C1-C10 alkylene or haloC1-C10 alkylene; R1 to R4 are each independently hydrogen or C1-C10 alkyl; Y is -NR 11 R 12 , -OR 13 , or -SR 14 and R 11 ~R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12 may be linked to form a ring.

[0063] The hydrogen source according to one embodiment of the present invention is a compound capable of introducing hydrogen into the product through a reaction, and may be a metal hydride capable of providing a hydrogen source, specifically, one or more selected from CaH, LiAlH, LiBH, NaBH, NaH, LiH, and KH. More specifically, the metal hydride may be LiAlH or NaBH, but is not limited thereto.

[0064] Specifically, the alkyllithium may be a C1-C10 alkyllithium, more specifically a C1-C6 alkyllithium, and even more specifically a C1-C4 alkyllithium, and may be one or more selected from methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and n-hexyllithium, but is not limited thereto.

[0065] The method for producing the molybdenum compound is simple and allows for easy mass production.

[0066] The solvent used in the production method according to one embodiment may be any common organic solvent, but it is preferable to use one or more solvents selected from the group consisting of hexane, pentane, dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile (MeCN), nitromethan, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA).

[0067] The reaction temperature can be a temperature used in ordinary organic synthesis, but may vary depending on the amounts of reactants and starting materials. Preferably, the reaction is carried out at -80°C to 20°C, specifically, -70°C to 10°C, and more specifically, -60°C to 5°C.

[0068] The reaction is terminated after complete consumption of the starting material is confirmed by NMR or the like, and the target product may then be separated and purified by conventional methods such as extraction, distillation of the solvent under reduced pressure, and column chromatography.

[0069] The cyclopentadiene-based compound can stably coordinate to the central metal through a resonance structure, significantly improving the thermal stability of the molybdenum compound. As a result, the molybdenum compound according to one embodiment of the present invention can be used to form thin films composed of molybdenum, molybdenum nitride (MoNx), or molybdenum oxide (MoOx) with high reliability.

[0070] The cyclopentadiene-based compound may be bonded to an aminoalkyl, an alkoxyalkyl, or an alkylsulfide, thereby improving the thermal stability of the cyclopentadiene compound during the deposition process.

[0071] The present invention provides a composition for depositing a molybdenum-containing thin film, which comprises a molybdenum compound according to one embodiment of the present invention.

[0072] The present invention also provides a method for producing a molybdenum-containing thin film using the composition for depositing a molybdenum-containing thin film.

[0073] The method for manufacturing the molybdenum-containing thin film may be a conventional method used in the art, specifically, atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD).

[0074] More preferably, the method for producing the molybdenum-containing thin film according to an embodiment may be atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), or the like.

[0075] The manufacturing method according to one embodiment of the present invention includes: a) raising the temperature of a substrate mounted in a chamber; b) injecting a reaction gas and the composition for depositing a molybdenum-containing thin film into a chamber to produce a molybdenum-containing thin film.

[0076] In one embodiment, deposition conditions may be adjusted depending on the desired structure or thermal properties of the thin film. Deposition conditions according to one embodiment include the input flow rate of the molybdenum compound, the input flow rates of the reaction gas and the transport gas, pressure, RF power, etc.

[0077] Non-limiting examples of the deposition conditions include a molybdenum compound supply flow rate of 1 to 1000 sccm, a carrier gas flow rate of 1 to 5000 sccm, a reaction gas flow rate of 10 to 5000 sccm, a pressure of 0.1 to 10 torr, and an RF power of 10 to 1000 W, but are not limited thereto.

[0078] In one embodiment, in step a), the substrate mounted in the chamber is heated to 200°C to 700°C, specifically, 500°C to 600°C, but is not limited thereto.

[0079] In one embodiment, the substrate may be, but is not limited to, a substrate including one or more semiconductor materials of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; an SOI (Silicon On Insulator) substrate; a quartz substrate; or a glass substrate for a display; or a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethyl methacrylate (PMMA, Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), or polyester.

[0080] In one embodiment, the reactive gas may be, but is not limited to, oxygen (O), ozone (O), distilled water (H O), hydrogen peroxide (H O), nitric oxide (NO), nitrous oxide (N O), nitrogen dioxide (NO), ammonia (NH), nitrogen (N), hydrazine (N H), amines, diamines, carbon monoxide (CO), carbon dioxide (CO), C to C 12 The gas may be any one or a mixture of two or more selected from saturated or unsaturated hydrocarbons, hydrogen (H2), argon (Ar), and helium (He).

[0081] Specifically, the reactive gas may be any one or more selected from oxygen (O), hydrogen peroxide (H), O, nitrous oxide (N), ammonia (NH), nitrogen (N), and hydrogen (H), and more particularly, may be ammonia (NH), but is not limited thereto.

[0082] In one embodiment, the transport gas in the depositing step is an inert gas, and may be any one or more selected from argon (Ar), helium (He), and nitrogen (N), specifically, but not limited to, nitrogen (N).

[0083] In one embodiment, the manufacturing method comprises: c) After step b), a step of injecting a reaction gas into the chamber may be further included, and steps b) and c) may be one cycle, which may be repeated.

[0084] In one embodiment, after injecting the transfer gas and the molybdenum compound into the chamber, a purging step may be performed to remove the molybdenum compound or a composition thereof that is not adsorbed on the substrate using the transfer gas.

[0085] In one embodiment, after injecting the reaction gas into the chamber, a purge step may be performed to remove reaction by-products and residual reaction gas using the transfer gas.

[0086] In one embodiment, the steps of injecting the molybdenum compound, purging, injecting the reaction gas, and purging constitute one cycle, which may be repeated.

[0087] A thin film fabricated by the molybdenum-containing thin film fabrication method according to one embodiment can exhibit a uniform and stable deposition rate and provide uniform step coverage for structures having a large aspect ratio.

[0088] The molybdenum-containing thin film according to the present invention may contain 35% or more of molybdenum and 40% or more of nitrogen, preferably 35% to 65% of molybdenum and 40% to 70% of nitrogen, and more preferably 35% to 50% of molybdenum and 40% to 55% of nitrogen, and the molybdenum-containing thin film according to one embodiment exhibits an excellent composition ratio.

[0089] The method for producing a molybdenum compound according to the present invention and the method for producing a thin film using the same will be described in more detail below with reference to specific examples.

[0090] However, the following examples are merely a reference for explaining the present invention in detail, and the present invention is not limited thereto, but can be realized in various forms. Furthermore, the terms used in the description of the present invention are merely for effectively describing specific examples, and are not intended to limit the present invention.

[0091] Also, unless otherwise noted, all examples were carried out under an inert atmosphere, e.g., purified nitrogen (N) or argon (Ar), using techniques commonly known in the art for handling air-sensitive materials.

[0092] Example 1: Preparation of ((CH)N(CH)Cp)MoH In a 2 L three-neck flask equipped with a magnetic stirrer and a condenser, n-butyllithium (316 ml, 2.3 M solution in n-hexane, 0.73 mol) was added, followed by addition of 500 ml of n-hexane, followed by stirring.

[0093] While maintaining the internal temperature of the mixture at 0°C, (2-dimethylaminoethyl)cyclopentadiene was slowly added and stirred at room temperature for 2 hours. The solvent was then removed under reduced pressure to obtain 95 g of Li(2-dimethylaminoethyl)cyclopentadiene (yield: 92%).

[0094] A mixture of Li(2-dimethylaminoethyl)cyclopentadiene (95 g, 0.66 mol) and LiAlH4 (10.8 g, 0.29 mol) was added to a 2 L two-necked flask equipped with a magnetic stirrer and a condenser, and then 1000 mL of THF was added. The mixture was stirred while maintaining the internal temperature at -50°C.

[0095] MoCl5 (78 g, 0.29 mol) was placed in a 2 L three-neck flask equipped with a magnetic stirrer and a condenser, followed by 100 ml of toluene and 1000 ml of THF, and the mixture was stirred while maintaining the internal temperature at -50°C.

[0096] A mixture of Li(2-dimethylaminoethyl)cyclopentadiene and LiAlH4 was slowly added to the mixture, and heat and gas evolution were observed, along with a color change to dark reddish-brown. The solvent was then removed under reduced pressure, and the residue was extracted with n-pentane (1500 ml). The resulting dark red solution was filtered, and the solvent was removed under reduced pressure, yielding approximately 43 g (38% yield based on MoCl5) of a dark reddish-brown liquid, ((CH3)2N(CH2)2Cp)2MoH2. 1H NMR(400 MHz, C6D6) δ 4.2-4.8 (m, 8H), 2.4 (s, 8H), 2.0 (s, 12H), -8.3 (s, 2H)

[0097] Example 2: Preparation of ((CH)O(CH)Cp)MoH In a 2 L three-neck flask equipped with a magnetic stirrer and a condenser, n-butyllithium (122 ml, 2.3 M solution in n-hexane, 0.28 mol) was added, followed by addition of 300 ml of n-hexane, followed by stirring.

[0098] While maintaining the internal temperature of the mixture at 0°C, (2-methoxyethyl)cyclopentadiene was slowly added and stirred at room temperature for 2 hours. The solvent was then removed under reduced pressure to obtain 33 g of Li(2-methoxyethyl)cyclopentadiene (yield: 91.6%).

[0099] A mixture of Li(2-methoxyethyl)cyclopentadiene (95 g, 0.66 mol) and LiAlH4 (10.8 g, 0.29 mol) was added to a 1 L two-necked flask equipped with a magnetic stirrer and a condenser, followed by addition of 500 mL of THF. The mixture was stirred while maintaining the internal temperature at -50°C.

[0100] MoCl5 (30 g, 0.11 mol) was placed in a 2 L three-neck flask equipped with a magnetic stirrer and a condenser, followed by 50 ml of toluene and 500 ml of THF, and the mixture was stirred while maintaining the internal temperature at -50°C.

[0101] A mixture of Li(2-methoxyethyl)cyclopentadiene and LiAlH4 was slowly added to the mixture, and heat generation and gas evolution were observed, along with a color change to dark reddish-brown. The solvent was then removed under reduced pressure, and the residue was extracted with n-pentane (1000 ml). The resulting dark red solution was filtered, and the solvent was removed under reduced pressure, yielding approximately 22 g (53% yield based on MoCl5) of a dark reddish-brown liquid, ((CH3)O(CH2)2Cp)2MoH2. 1 H NMR(400 MHz, C6D6) δ 4.2-4.8 (m, 8H), 3.3-3.4 (t, 4H), 3.1 (s, 6H), 2.4-2.5 (t, 4H), 3.1 (s, 6H), 1.0 (m,2H), -8.4 (s, 2H).

[0102] [Example 3] Production of molybdenum-containing thin film using ((CH3)2N(CH2)2Cp)2MoH2 Using the molybdenum compound according to Example 1, a molybdenum-containing thin film was prepared by plasma-enhanced atomic layer deposition (PEALD) using ammonia (NH3) as a reactive gas.

[0103] A silicon substrate on which silicon oxide had been grown was loaded into the deposition chamber, and the temperature of the substrate was adjusted to 400°C. A stainless steel bubbler vessel was filled with ((CH3)2N(CH2)2Cp)2MoH2 prepared in Example 1 as an organometallic precursor, and the temperature was adjusted to 100°C.

[0104] During the plasma-enhanced atomic layer deposition (PEALD) process, the process pressure was adjusted to 10 Torr or less by adjusting the throttle valve. The organometallic precursor was injected into the deposition chamber for 5 seconds using nitrogen gas (100 sccm) as a carrier gas. Nitrogen gas (500 sccm) was used to purge the deposition chamber for 3 seconds to remove the organometallic precursor and reaction by-products remaining in the deposition chamber.

[0105] Ammonia (NH3) (2,000 sccm / RF power 400 W) was injected as a reactive gas for 3 seconds to deposit a molybdenum-containing nitride thin film, followed by purging with nitrogen gas (500 sccm) for 3 seconds to remove residual reactive gas and reaction by-products.

[0106] The above process constitutes one cycle, and by repeating 1000 cycles, a molybdenum-containing nitride thin film with a thickness of 320 Å was produced, as shown in Figure 1. AES analysis of the molybdenum-containing thin film revealed that the molybdenum (Mo) content and nitrogen (N) content were measured to be 41.8% and 45.4%, respectively, confirming that a molybdenum nitride film had indeed been formed.

[0107] [Example 4] Preparation of molybdenum-containing thin film using ((CH3)O(CH2)2Cp)2MoH2 Using the molybdenum compound according to Example 2, a molybdenum-containing thin film was prepared by plasma-enhanced atomic layer deposition (PEALD) using ammonia (NH3) as a reactant gas.

[0108] A silicon substrate on which silicon oxide had been grown was loaded into the deposition chamber, and the temperature of the substrate was adjusted to 400°C. A stainless steel bubbler vessel was filled with ((CH3)O(CH2)2Cp)2MoH2 prepared in Example 2 as an organometallic precursor, and the temperature was adjusted to 100°C.

[0109] During the plasma-enhanced atomic layer deposition (PEALD) process, the process pressure was adjusted to 10 Torr or less by adjusting the throttle valve. The organometallic precursor was injected into the deposition chamber for 5 seconds using nitrogen gas (100 sccm) as a carrier gas. Nitrogen gas (500 sccm) was used to purge the deposition chamber for 3 seconds to remove the organometallic precursor and reaction by-products remaining in the deposition chamber.

[0110] Ammonia (NH3) (2,000 sccm / RF power 400 W) was injected as a reactive gas for 3 seconds to deposit a molybdenum-containing nitride thin film, followed by purging with nitrogen gas (500 sccm) for 3 seconds to remove residual reactive gas and reaction by-products.

[0111] The above process constitutes one cycle, and by repeating 1,000 cycles, a molybdenum-containing nitride thin film with a thickness of 270 Å was produced, as shown in Figure 2. AES analysis of the molybdenum-containing thin film revealed that the molybdenum (Mo) content and nitrogen (N) content were measured to be 41.3% and 46.5%, respectively, confirming that a molybdenum nitride film had indeed been formed.

[0112] Therefore, the molybdenum compound according to one embodiment of the present invention has improved thermal stability, high volatility, and improved vapor pressure, and when used to produce a thin film, it exhibits a uniform and stable deposition rate, can form a highly reliable thin film, can provide a uniform film thickness for a three-dimensional device, and can produce a thin film that exhibits an excellent composition ratio of molybdenum and nitrogen.

[0113] As described above, the present invention has been described using specific and limited examples and comparative examples. However, these are merely provided for a more general understanding of the present invention, and the present invention is not limited to the above examples. Those skilled in the art will appreciate that various modifications and variations can be made based on these descriptions.

[0114] Therefore, the spirit of the present invention should not be limited to the above-described embodiments, and it can be said that not only the scope of the attached claims, but also anything equivalent to the scope of the claims or any equivalent modifications thereof, all fall within the scope of the spirit of the present invention.

Claims

1. A molybdenum compound represented by the following chemical formula 1. 【Chemistry 1】 [In the above Chemical Formula 1, L is C1-C10 alkylene or haloC1-C10 alkylene; R １ ~R １０ are each independently hydrogen or C1-C10 alkyl, Y is -NR １１ R １２ , -OR １３ , or -SR １４ and R １１ R 13 to R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl.

2. In the above Chemical Formula 1, L is C1-C6 alkylene; R １ ~R １０ are each independently hydrogen or C1-C6 alkyl, Y is -NR １１ R １２ , -OR １３ , or -SR １４ and R １１ 2. The molybdenum compound according to claim 1, wherein R 13 to R 12 are hydrogen or may be linked together to form an alicyclic ring, and R 13 to R 14 are each independently hydrogen or C1-C10 alkyl.

3. 2. The molybdenum compound according to claim 1, which is represented by the following chemical formula 2: 【Chemistry 2】 [In the above chemical formula 2, R １ ~R １０ are each independently hydrogen or C1-C6 alkyl, Y is -NR １１ R １２ , -OR １３ , or -SR １４ and R １１ R13 to R12 may be hydrogen or may be linked together to form an alicyclic ring, R13 and R14 are each independently hydrogen or C1-C6 alkyl, and m is an integer of 1 to 3.

4. A molybdenum compound selected from compounds represented by the following chemical formula: 【Transformation 3】

5. A method for producing a molybdenum compound, comprising the step of reacting a hydrogen source or an alkyllithium, a compound of the following chemical formula 4, and a compound of the following chemical formula 5 to produce a molybdenum compound represented by the following chemical formula 1-1: 【Chemistry 4】 【Transformation 5】 【Transformation 6】 [In the above chemical formulas 1-1, 4, and 5, L is C1-C10 alkylene or haloC1-C10 alkylene; R １ ~R ６ are each independently hydrogen or C1-C10 alkyl, Y is -NR １１ R １２ , -OR １３ , or -SR １４ and R １１ R 13 to R 14 are, independently of each other, hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl; X is a halogen.

6. A compound for vapor deposition of a molybdenum-containing thin film, which is the molybdenum compound according to any one of claims 1 to 4.

7. A method for producing a molybdenum-containing thin film, comprising producing a thin film using a molybdenum compound represented by the following chemical formula 1: 【Transformation 7】 [In the above Chemical Formula 1, L is C1-C10 alkylene or haloC1-C10 alkylene; R 1 to R 10 are each independently hydrogen or C1-C10 alkyl; Y is —NR 11 R 12 , —OR 13 , or —SR 14 ; R 11 to R 14 are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or R 11 and R 12 may be linked together to form a ring.]

8. a) raising the temperature of a substrate mounted in a chamber; b) injecting a reaction gas and the molybdenum compound into the chamber to produce a molybdenum-containing thin film, the method for producing a molybdenum-containing thin film according to claim 7 .

9. The reactive gas is oxygen (O ２ ), ozone (O ３ ), distilled water (H ２ O), hydrogen peroxide (H ２ O ２ ), nitric oxide (NO), nitrous oxide (N ２ O), nitrogen dioxide (NO ２ ), ammonia (NH ３ ), nitrogen (N ２ ), hydrazine (N ２ H ４ ), amines, diamines, carbon monoxide (CO), carbon dioxide (CO ２ ), C １ ~C １２ saturated or unsaturated hydrocarbons, hydrogen (H ２ 9. The method for producing a molybdenum-containing thin film according to claim 8, wherein the gas is any one or more selected from the group consisting of argon (Ar) and helium (He).

10. The method for producing a molybdenum-containing thin film according to claim 8, further comprising the step of: c) injecting a reaction gas into the chamber after step b).

11. The method for producing a molybdenum-containing thin film according to claim 10 , wherein the steps b) and c) constitute one cycle, and the cycle is repeated.

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