Molybdenum compound, its manufacturing 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] A variety of organometallic precursors are used to form metal thin films. A variety of techniques are used for the deposition of thin films, 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) have the advantages of good composition control, high film uniformity, good doping control, and excellent conformal deposition, allowing uniform film thickness to be achieved even on highly non-planar microelectronic device geometries.

[0003] Chemical vapor deposition (CVD) is a chemical process in which organometallic precursors are used to form thin films on substrates. In a typical chemical vapor deposition (CVD) process, precursors are reacted or decomposed on the surface of a substrate as they are passed over the substrate in a low 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, realizes uniform film thickness, and enables excellent conformal deposition. It is a method of growing a film sequentially while reacting on the surface of a substrate. However, the biggest drawback of ALD is that the process speed of growing a film per unit time is slow. Plasma-enhanced atomic layer deposition (PEALD) is one method that can increase the process speed of ALD. Plasma-enhanced atomic layer deposition (PEALD) has the advantage of being able to increase reactivity at a lower temperature than ALD. Therefore, plasma-enhanced atomic layer deposition (PEALD) is even more necessary, especially for capacitors and gate spacers, which are films with high aspect ratios.

[0005] Atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) are typically performed in four steps: pulse A, in which a first precursor, which is an organometallic, forms a monolayer on the substrate, purge A, in which an excess of the first precursor is removed, pulse B, in which a second precursor, which is a non-metallic 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, anti-corrosion 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). As microelectronic components continue to shrink in size, the need for the use of dielectric thin films increases.

[0007] Many current molybdenum precursors for use in CVD and ALD do not meet the performance requirements required to enable new processes for the manufacture 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 comprises 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 composition for depositing a molybdenum-containing thin film.

[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; 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 14 are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12 may be linked to form a ring.

[0014] In the formula 1 according to one embodiment of the present invention, L is C1-C6 alkylene, and R 1 ~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 formula 2:

[0016] [ka] [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 ~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 the steps of reacting a hydrogen source or an alkyl lithium, 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; 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 14 are each independently 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, comprising 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] A method for producing the molybdenum-containing thin film according to one embodiment of the present invention includes the steps of: a) increasing 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 produce a molybdenum-containing thin film.

[0026] In one embodiment, 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 of saturated or unsaturated hydrocarbons, hydrogen (H 2 ), argon (Ar), and helium (He).

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

[0028] The present invention provides a molybdenum-containing thin film that contains at least 35% molybdenum and at least 40% nitrogen. Effect 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 provide high film uniformity and good doping controllability by plasma-enhanced atomic layer deposition (PEALD) etc. by using a composition for depositing a molybdenum-containing thin film containing a molybdenum compound according to the present invention. Furthermore, the method can provide uniform step coverage for a three-dimensional semiconductor device.

[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 description of the drawings]

[0033] [Figure 1] 3 is a photograph showing the results of scanning electron microscope measurement of the molybdenum-containing thin film according to Example 1 of the present invention. [Diagram 2] 4 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 PREFERRED EMBODIMENTS

[0034] The present invention provides 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 thin film using the same.

[0035] As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates 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 linear or branched and may have 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and in yet another embodiment, alkyl may have 1 to 4 carbon atoms.

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

[0039] By "halo" in the present invention is meant fluorine, chlorine, bromine, or iodine.

[0040] According to the present invention, "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are replaced by halogen atoms. For example, haloalkyl is -CF 3 , -CHF 2 , -CH 2 F, -CBr 3 , -CHBr 2 , -CH 2 Br, -CCl 3 , -CHCl 2 , -CH 2 CI, -CCI 3 , -CHI 2 , -CH 2 I, -CH 2 -CF 3 , -CH 2 -CHF 2 , -CH 2 -CH 2 F, -CH 2 -CBr 3 , -CH 2 -CHBr 2 , -CH 2 -CH 2 Br, -CH 2 -CCl 3 , -CH 2 -CHCl 2 , -CH 2 -CH 2 CI, -CH 2 -CI 3 , -CH 2 -CHI 2 , -CH 2 -CH 2 I, and the like, where alkyl and halogen are as defined above.

[0041] The number of carbon atoms described in the alkyl group and the like in the present invention does not include the number of carbon atoms of the substituents. For example, C1-C10 alkyl means an alkyl group having 1 to 10 carbon atoms, not including the number of carbon atoms of 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 be described in detail below. In this regard, unless otherwise defined, the technical and scientific terms used have the meanings that are commonly understood by those having ordinary knowledge in the technical field to which the present invention belongs, and descriptions of known functions and configurations that may obscure the gist of the present invention in the following description 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; 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 14 are each independently 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, a highly reliable molybdenum-containing thin film can be obtained.

[0047] In one embodiment of the present invention, the molybdenum compound is represented by the formula 1, where L is C1-C6 alkylene, and R1 ~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 formula 2:

[0049] [ka] [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 ~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] More specifically, the molybdenum compound represented by the formula 2 is 1 ~R 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 each independently hydrogen or C1-C4 alkyl, or 11 and R12 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 formula 3:

[0052] [ka] [In the above Chemical Formula 3, R 1 ~R 4 and R 7 ~R 10 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 each independently 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 formula 3-1.

[0054] [ka] [In the above Chemical Formula 3-1, R 1 ~R 6 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 each independently hydrogen or C1-C4 alkyl, or 11 and R 12may 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 alkyl lithium, 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; 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 14 are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or 11 and R 12may be linked to form a ring, X is a halogen.

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

[0062] [ka] [In the above Chemical Formula 6, L is C1-C10 alkylene or haloC1-C10 alkylene; R 1 ~R 4 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 each independently 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 by the reaction, and may be specifically a metal hydride capable of providing a hydrogen source, specifically CaH 2 , LiAlH 4 , LiBH 4 , NaBH 4 , NaH, LiH, and KH. More specifically, the metal hydride may be LiAlH 4 or NaBH 4 It may be, but is not limited to this.

[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 has simple steps and can be easily used for 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 selected from the group consisting of hexane, pentane, dichloromethane (DCM), dichloroethane (DCE), toluene (Toluene), acetonitrile (MeCN), nitromethan, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA).

[0067] The reaction temperature may be a temperature used in ordinary organic synthesis, but may vary depending on the amount of reactants and starting materials. The reaction may be preferably performed at -80°C to 20°C, more specifically, at -70°C to 10°C, and more specifically, at -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 then extraction, distillation of the solvent under reduced pressure, and separation and purification of the target product by conventional methods such as column chromatography may be performed.

[0069] The cyclopentadiene-based compound is stably coordinated to the central metal through a resonance structure, and the thermal stability of the molybdenum compound can be significantly improved. As a result, the molybdenum compound according to an embodiment of the present invention can be used to form a thin film made 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, comprising 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 preparing the molybdenum-containing thin film may be a method commonly 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 comprises the steps of: a) increasing 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, the deposition conditions may be adjusted depending on the desired structure or thermal properties of the thin film. The deposition conditions according to one embodiment may include the input flow rate of the molybdenum compound, the input flow rate 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 rate of 1 to 1000 sccm, a transport gas rate of 1 to 5000 sccm, a reaction gas rate of 10 to 5000 sccm, a pressure of 0.1 to 10 torr, and an RF power rate 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] The substrate according to an embodiment 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 display glass substrate; 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), polyester, etc.

[0080] In one embodiment, the reactive gas includes, but is not limited to, oxygen (O 2 ), ozone (O 3 ), distilled water (H 2 O), hydrogen peroxide (H 2 O2 ), 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 of saturated or unsaturated hydrocarbons, hydrogen (H 2 The gas may be any one or a mixture of two or more selected from the group consisting of nitrogen (N), argon (Ar), and helium (He).

[0081] Specifically, the reaction gas is oxygen (O 2 ), hydrogen peroxide (H 2 O 2 ), nitrous oxide (N 2 O), ammonia (NH 3 ), nitrogen (N 2 ), and hydrogen (H 2 ), more specifically, ammonia (NH 3 ), but is not limited to this.

[0082] In one embodiment, the transport gas in the depositing step is an inert gas, such as argon (Ar), helium (He), and nitrogen (N 2 ), specifically, nitrogen (N 2 ), but is not limited to these.

[0083] In one embodiment, the method comprises: The method may further include a step of injecting a reaction gas into the chamber after the step c) and the step c) constitute one cycle, and the cycle 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 purging step may be performed to remove reaction by-products and residual reaction gas using the transport gas.

[0086] In one embodiment, a cycle of the molybdenum compound injection step, purging, reaction gas injection step, and purging may be repeated.

[0087] A thin film produced by the molybdenum-containing thin film production method according to an embodiment can exhibit uniform and stable deposition rates and provide uniform step coverage for structures having large aspect ratios.

[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 describing the present invention in detail, and the present invention is not limited thereto, and can be realized in various forms. Furthermore, the terms used in the description of the present invention are merely for the purpose of effectively describing specific examples, and are not intended to limit the present invention.

[0091] Also, unless otherwise noted, all examples are performed in an inert atmosphere, such as purified nitrogen (N 2 ) or argon (Ar) using techniques commonly known in the art for handling air-sensitive materials.

[0092] [Example 1] ((CH 3 ) 2 N(CH 2 ) 2 Cp) 2 MoH 2 Manufacturing Into 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. Then, the solvent was removed under reduced pressure to obtain 95 g (yield: 92%) of Li(2-dimethylaminoethyl)cyclopentadiene.

[0094] In a 2 L two-neck flask equipped with a magnetic stirrer and a condenser, add Li(2-dimethylaminoethyl)cyclopentadiene (95 g, 0.66 mol) and LiAlH 4 (10.8 g, 0.29 mol) were mixed and added, then 1000 ml of THF was added, and the mixture was stirred while maintaining the internal temperature at -50°C.

[0095] In a 2 L three-neck flask containing a magnetic stirrer and a condenser, add MoCl 5 (78 g, 0.29 mol) was added, followed by adding 100 ml of toluene and 1000 ml of THF, and then stirring while maintaining the internal temperature at -50°C.

[0096] The mixture was added with Li(2-dimethylaminoethyl)cyclopentadiene and LiAlH 4When the mixture was slowly poured in, heat generation and gas generation were confirmed, and a color change to dark reddish brown was observed. 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 through a filtration apparatus, and the solvent was removed under reduced pressure to reveal a dark reddish brown liquid, ((CH 3 ) 2 N(CH 2 ) 2 Cp) 2 MoH 2 Approximately 43g (MoCl 5 The product was obtained in a standard yield of 38%). 1 H 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] ((CH 3 )O(CH 2 ) 2 Cp) 2 MoH 2 Manufacturing Into 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. Then, the solvent was removed under reduced pressure to obtain 33 g of Li(2-methoxyethyl)cyclopentadiene (yield: 91.6%).

[0099] In a 1 L two-neck flask equipped with a magnetic stirrer and a condenser, add Li(2-methoxyethyl)cyclopentadiene (95 g, 0.66 mol) and LiAlH 4 (10.8 g, 0.29 mol) were mixed and added, and then 500 ml of THF was added, and the mixture was stirred while maintaining the internal temperature at -50°C.

[0100] In a 2 L three-neck flask containing a magnetic stirrer and a condenser, add MoCl 5 (30 g, 0.11 mol) was added, followed by adding 50 ml of toluene and 500 ml of THF, and then stirring while maintaining the internal temperature at -50°C.

[0101] The mixture was added with Li(2-methoxyethyl)cyclopentadiene and LiAlH 4 When the mixture was slowly poured in, heat generation and gas generation were confirmed, and a color change to dark reddish brown was observed. 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 through a filtration apparatus, and the solvent was removed under reduced pressure to reveal a dark reddish brown liquid, ((CH 3 )O(CH 2 ) 2 Cp) 2 MoH 2 Approximately 22g (MoCl 5 The standard yield was 53%). 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] ((CH 3 ) 2 N(CH 2 ) 2 Cp) 2 MoH 2 Fabrication of Molybdenum-Containing Thin Films Using The molybdenum compound according to Example 1 was used, and ammonia (NH 3 ) was used to fabricate molybdenum-containing thin films by plasma-enhanced atomic layer deposition (PEALD).

[0103] A silicon substrate on which silicon oxide was grown was loaded into the deposition chamber, and the temperature of the substrate was adjusted to 400° C. The (CH 3 ) 2 N(CH 2 ) 2 Cp) 2 MoH 2 was charged as the 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 as a carrier gas (100 sccm). Nitrogen gas (500 sccm) was used for 3 seconds to purge the organometallic precursor and reaction by-products remaining in the deposition chamber.

[0105] Ammonia (NH) was used as the reactant gas. 3 ) (2,000 sccm / RF power 400 W) was injected 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 reaction gases and reaction by-products.

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

[0107] [Example 4] ((CH 3 )O(CH 2 ) 2 Cp) 2 MoH 2 Fabrication of Molybdenum-Containing Thin Films Using The molybdenum compound according to Example 2 was used, and ammonia (NH 3) was used to fabricate molybdenum-containing thin films by plasma-enhanced atomic layer deposition (PEALD).

[0108] A silicon substrate on which silicon oxide was grown was loaded into the deposition chamber, and the temperature of the substrate was adjusted to 400° C. The (CH 3 )O(CH 2 ) 2 Cp) 2 MoH 2 was charged as the 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 as a carrier gas (100 sccm). Nitrogen gas (500 sccm) was used for 3 seconds to purge the organometallic precursor and reaction by-products remaining in the deposition chamber.

[0110] Ammonia (NH) was used as the reactant gas. 3 ) (2,000 sccm / RF power 400 W) was injected 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 reaction gases and reaction by-products.

[0111] The above process constitutes one cycle, and by repeating 1000 cycles, a molybdenum-containing nitride thin film having a thickness of 270 Å was produced, as shown in Figure 2. As a result of AES analysis of the molybdenum-containing thin film, the molybdenum (Mo) content and nitrogen (N) content were measured to be 41.3% and 46.5%, respectively, confirming that a molybdenum nitride film was indeed formed.

[0112] For this reason, the molybdenum compound according to one embodiment of the present invention has improved thermal stability, high volatility, and improved vapor pressure, and therefore 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 exhibiting 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. A person having ordinary knowledge in the field to which the present invention belongs can make various modifications and variations from such descriptions.

[0114] Therefore, the idea of ​​the present invention should not be limited to the above-mentioned embodiments, and it can be said that not only the scope of the attached claims, but also equivalents to the scope of the claims or equivalent modifications all fall within the scope of the idea 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 １４ are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or １１ and R １２ may be linked to form a ring.

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 ~R １４ are each independently hydrogen or C1-C6 alkyl, or １１ and R １２ may be linked to form an alicyclic ring.

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 ~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.

4. 2. The molybdenum compound of claim 1 which is selected from the following compounds: 【Chemistry 3】

5. A method for producing a molybdenum compound, comprising the step of reacting a hydrogen source or an alkyl lithium, 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. 【Chemistry 4】 【Chemistry 5】 【Chemistry 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 １４ are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl, or １１ and R １２ may be linked to form a ring, X is a halogen.

6. A composition for vapor deposition of a molybdenum-containing thin film, comprising 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 by using the molybdenum-containing thin film deposition composition according to claim 6.

8. 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 produce a molybdenum-containing thin film.

9. The reaction 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 at least one selected from the group consisting of nitrogen (N), 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 reactive 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) form one cycle, and the cycle is repeated.

12. A molybdenum-containing thin film containing 35% or more of molybdenum and 40% or more of nitrogen.

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