Molybdenum precursor compound, method for preparing the same, and method for depositing molybdenum-containing thin film using the same

Abstract

This invention relates to a molybdenum precursor compound, a method for preparing the molybdenum precursor compound, a precursor composition for depositing a thin film containing the molybdenum precursor compound, a molybdenum-containing thin film using the molybdenum precursor compound, and a method for depositing the molybdenum precursor compound. The molybdenum precursor compound exhibits excellent thermal stability. Because the deposition rate can be easily adjusted during the deposition of the molybdenum-containing thin film, the film can be controlled to the desired thickness and composition. Furthermore, even on substrates with patterned (grooved) surfaces, porous substrates, plastic substrates, or substrates with complex shapes, films with excellent coverage and uniform thickness can be formed, thereby achieving high-quality molybdenum-containing thin films through atomic layer deposition (ALD).

Description

[Technical Field]

[0001] Field of Invention

[0002] The present invention relates to a molybdenum precursor compound, a method for preparing the molybdenum precursor compound, a precursor composition for forming a molybdenum thin film containing the molybdenum precursor compound, a molybdenum-containing thin film using the molybdenum precursor compound, and a method for depositing the molybdenum precursor compound. [Previous Technology]

[0003] Background of the Invention

[0004] Molybdenum-containing metal films, molybdenum-containing oxide films, nitride films, sulfide films, and carbide films can be used as diffusion barriers for metal wiring, gate metals, electrodes, etc. in semiconductor manufacturing processes. They are widely used in industrial applications as hard coating materials, sensors, channel layers, and catalysts.

[0005] In particular, because molybdenum nitride films have a high work function, they can be used as an important metal material to suppress leakage current in DRAM capacitors using high-k dielectric materials. They can replace currently used tungsten (W) metal, or, due to their low resistance, can be used as a diffusion barrier for tungsten (W) metal in 3D NAND flash memory. Furthermore, they can be used as a seed layer for growing molybdenum, and as a diffusion barrier layer in metal fabrication processes in non-memory fields such as logic devices.

[0006] At the same time, semiconductor devices with complex shapes, such as high aspect ratios and three-dimensional structures, are developing to varying degrees in both memory and non-memory fields. Suitable molybdenum-containing metal films, molybdenum-containing oxide films, and molybdenum-containing nitride films are required.

[0007] It is known that molybdenum precursor compounds such as MoCl5 and MoO2Cl2 are currently used in such molybdenum-containing thin films. Because these precursors are solid precursors, it is not convenient to control the supply of precursors, so they may not be suitable for mass production compared with liquid precursors.

[0008] In addition, Mo(tBuN)2(NMe2)2 and Mo(NMeEt)4 are called liquid molybdenum precursor compounds. Although these precursor compounds exist in liquid form, their poor thermal stability limits their ability to form molybdenum-containing thin films with excellent film quality.

[0009] Therefore, there is a need to develop a molybdenum precursor compound capable of forming molybdenum-containing metal films, molybdenum-containing oxide films, or molybdenum-containing nitride films, which has excellent thermal stability and is therefore suitable for various application fields (such as memory and non-memory fields) at process temperatures (even at high temperatures), and has excellent uniformity and quality. Furthermore, there is a need to develop a novel molybdenum precursor compound that can be used in atomic layer deposition (ALD) to deposit conformal films on structures with high order ratios. [Prior Art Documents] [Patent Documents] (Patent Document 1) Korean Patent Publication No. 2019-0024823. [Summary of the Invention]

[0010] Detailed Description of the Technical Issues of the Invention

[0011] The present invention aims to solve the problems of the prior art.

[0012] One object of the present invention is to provide a novel molybdenum precursor compound that is liquid at room temperature, which is advantageous for the process, can be deposited in a wide range of temperatures from low to high, has excellent thermal stability, and can be formed by atomic layer deposition (ALD) into molybdenum-containing metal films, molybdenum-containing oxide films or molybdenum-containing nitride films with uniform thickness and excellent quality.

[0013] Another object of the present invention is to provide a safe and efficient method for preparing the molybdenum precursor compound.

[0014] Another object of the present invention is to provide a precursor composition for depositing a thin film containing the molybdenum precursor compound.

[0015] Another object of the present invention is to provide a molybdenum-containing thin film using the molybdenum precursor compound, which has uniform thickness and excellent quality even on various substrates.

[0016] Another object of the present invention is to provide a method for depositing a molybdenum-containing thin film, wherein the molybdenum-containing thin film is deposited using a molybdenum precursor compound.

[0017] However, the problems to be solved by the present invention are not limited to those described above, and those skilled in the art will clearly understand other unmentioned problems through the following description. Solutions to the Problems

[0018] This invention provides a molybdenum precursor compound represented by Formula 1: [Formula 1]

[0019] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

[0020] Furthermore, the present invention provides a method for preparing a molybdenum precursor compound represented by Formula 1, comprising reacting a compound represented by Formula A with a compound represented by Formula B and a compound represented by Formula C in a solvent: [Formula A]

[0021] In formula A, XA and XB are each independently a halogen element, [Formula B][Formula C]

[0022] In formulas B and C, M1 and M2 are each independently an alkali metal or an alkaline earth metal, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

[0023] Furthermore, the present invention provides a composition for forming a molybdenum thin film containing the molybdenum precursor compound.

[0024] Furthermore, the present invention provides a composition for forming a molybdenum thin film, which is deposited using a molybdenum precursor compound represented by Formula 9: [Formula 9]

[0025] In Formula 9, R3 is selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl and substituted or unsubstituted C4-C8 cycloalkyl.

[0026] Furthermore, the present invention provides a molybdenum-containing thin film formed using the molybdenum precursor compound.

[0027] Furthermore, the present invention provides a method for depositing a molybdenum-containing thin film, comprising depositing a molybdenum-containing thin film on a substrate using a molybdenum precursor compound. Beneficial effects of the present invention

[0028] The molybdenum precursor compound according to the embodiments of the present invention has excellent volatility, exists in a liquid state at room temperature, which is beneficial to the process, has low resistivity, excellent thermal stability and can be deposited in a wide temperature range from low to high; therefore, molybdenum-containing thin films can be easily formed by atomic layer deposition (ALD) and chemical vapor deposition (CVD).

[0029] In particular, when using this molybdenum precursor compound to form a molybdenum-containing thin film, the deposition rate can be easily adjusted to low or high, so the film can be controlled to the desired thickness and composition. Even on substrates with uneven surfaces or patterns (grooves), porous substrates, plastic substrates, or substrates with complex three-dimensional structures, films with excellent coverage and uniform thickness can be formed; therefore, high-quality molybdenum-containing thin films can be obtained.

[0030] Accordingly, molybdenum precursor compounds possessing the above-mentioned characteristics can exhibit excellent properties depending on their application in various fields such as memory devices, logic devices, large-area display devices, and moisture-proof membranes for organic light-emitting diodes (OLEDs). In particular, due to their high aspect ratio and fine thickness controllability, they can be effectively used in semiconductor manufacturing processes.

Implementation Method

[0032] Best mode for carrying out the present invention

[0033] This application will be described in more detail below.

[0034] The advantages and features of the present invention, as well as methods of implementing them, will become apparent from the embodiments described below. However, the present invention is not limited to the embodiments described below, but may be implemented in various different forms. These embodiments are provided so that the disclosure of the present invention is thorough and complete, and that the scope of the present invention is fully conveyed to those skilled in the art. The present invention is defined only by the scope of the claims.

[0035] Furthermore, in this specification, when referring to an element being formed "on" another element, it not only means that an element is formed directly "on" another element, but also means that other elements are inserted between them.

[0036] In this specification, unless otherwise stated, when a component is referred to as "containing" an element, it should be understood that the component may also contain other elements, rather than excluding other elements.

[0037] Unless otherwise stated, all figures and expressions used herein in relation to the amount of components, reaction conditions, etc., shall be understood to be modified by the term “about”.

[0038] In this specification, unless otherwise stated, the terms “membrane” or “thin film” mean both “membrane” and “thin film”.

[0039] In this specification, the term "alkyl (alkyl group)" encompasses straight-chain or branched alkyl groups and all their possible isomers. For example, alkyl groups include not only methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), tert-Bu (tBu), sec-butyl (secBu), etc., but also their isomers, etc., but are not limited thereto. [Molybdenum precursor compounds]

[0040] According to one embodiment of the present invention, a molybdenum precursor compound represented by Formula 1 is provided: [Formula 1]

[0041] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

[0042] Because the molybdenum precursor compound contains the special structure of Formula 1, especially the carbon ring or heterocycle bonded to molybdenum (Mo), it has very high volatility, exists in a liquid state at room temperature, can be deposited in a wide temperature range from low to high, and has excellent thermal stability; therefore, molybdenum-containing thin films can be easily formed by atomic layer deposition (ALD) and chemical vapor deposition (CVD).

[0043] In particular, when using this molybdenum precursor compound to form a molybdenum-containing thin film, a low resistivity (μΩ·cm) value can be provided, for example, 600 μΩ·cm or lower; therefore, it can be widely used as a gate electrode, diffusion barrier layer, and capacitor electrode in DRAM or NAND flash memory and logic devices that require low resistivity. Furthermore, because the deposition rate can be easily adjusted to low or high, the film can be controlled to the desired thickness and composition, and a film with excellent coverage and uniform thickness can be formed even on substrates with uneven surfaces or patterns (grooves), porous substrates, plastic substrates, or substrates with complex three-dimensional structures; therefore, high-quality molybdenum-containing thin films can be obtained. The technical significance of this molybdenum precursor compound lies in its advantageous use in various applications in the field of electronic devices and its ability to exhibit excellent properties.

[0044] Specifically, the molybdenum precursor compound can be represented by Formula 1. In the molybdenum precursor compound represented by Formula 1, the imine group is linked to molybdenum (Mo) to form a double bond with the molybdenum (Mo) metal, thereby further improving the stability of the molybdenum precursor compound; and it contains a carbon ring or heterocycle bonded to molybdenum (Mo), thereby exhibiting excellent reactivity and readily reacting on the surface, which enables the formation of thin films with very good thermal stability, achieving, for example, a low resistivity of 600 μΩ·cm or lower, and increasing the film density.

[0045] In this specification, a carbide ring refers to a monocyclic or polycyclic group having 3 to 20 carbon atoms (C3-C20) and containing only carbon as the ring-forming atom. The C3-C20 carbide ring may contain aromatic carbide ring groups or non-aromatic carbide ring groups, specifically, non-aromatic carbide ring groups.

[0046] In addition, in this specification, a heterocycle refers to a structure having the same structure as C3-C20, but containing at least one heteroatom selected from oxygen (O) and nitrogen (N) in addition to carbon (where the number of carbon atoms is 1 to 20) as the cyclic atom. Specifically, the heterocycle may contain one or more, for example two or more, for example one to four or for example one to three heteroatoms selected from oxygen (O), nitrogen (N) and carbon (C).

[0047] Furthermore, the substituents in the substituted C3-C20 carbide ring and the substituted C1-C20 heterocycle may each independently comprise C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, and C1-C20 alkoxy groups. For example, the substituents may each independently comprise C1-C20 alkyl, C1-C15 alkyl, C1-C12 alkyl, C1-C10 alkyl, or C1-C8 alkyl groups.

[0048] For example, in Formula 1, Cy1 and Cy2 may each be independently selected from substituted or unsubstituted C3-C15 carbon rings and substituted or unsubstituted C1-C15 heterocycles. For example, Cy1 and Cy2 may each be independently selected from substituted or unsubstituted C3-C12 carbon rings and substituted or unsubstituted C1-C12 heterocycles. For example, Cy1 and Cy2 may each be independently selected from substituted or unsubstituted C3-C10 carbon rings and substituted or unsubstituted C1-C10 heterocycles. For example, Cy1 and Cy2 may each be independently selected from substituted or unsubstituted C3-C8 carbon rings and substituted or unsubstituted C1-C8 heterocycles. For example, Cy1 and Cy2 may each be independently selected from substituted or unsubstituted C5-C8 carbon rings and substituted or unsubstituted C1-C8 heterocycles.

[0049] According to one embodiment of the present invention, the molybdenum precursor compound can be represented by the following formula 2. [Formula 2]

[0050] In Formula 2, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles. Specifically, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C1-C20 heterocycles.

[0051] In particular, the cyclic amine bonded to molybdenum (Mo) as shown in Formula 2 has excellent reactivity, thereby facilitating reaction on the surface to form thin films. Stable molybdenum-containing metal films, oxide films, or nitride films can be formed, and they exhibit good adhesion to the substrate. This facilitates the formation of molybdenum-containing metal films through reaction with hydrogen (H2); the formation of oxide films through reaction with ozone (O3), exhibiting high oxidizing power; and the formation of nitride films through reaction with ammonia (NH3), exhibiting high nitriding power. Furthermore, it possesses high stability, capable of deposition even at high temperatures of 300 to 550°C, for example, 350 to 550°C, and the film density can also be increased.

[0052] According to another embodiment of the present invention, the molybdenum precursor compound may be represented by the following formula 3. [Formula 3]

[0053] In Formula 3, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C1-C10 heterocycles, and Y1 and Y2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

[0054] Specifically, in Formula 3, Cy1 and Cy2 are each independently a substituted or unsubstituted C1-C6 heterocycle. Alternatively, in Formula 3, Cy1 and Cy2 may be independently selected from substituted or unsubstituted C2-C6 heterocycles, substituted or unsubstituted C3-C6 heterocycles, and substituted or unsubstituted C4-C6 heterocycles.

[0055] Furthermore, in Formula 3, Y1 and Y2 can each be independently selected from oxygen (O), nitrogen (N), and carbon (C). For example, in Formula 3, Y1 and Y2 can each be independently oxygen (O). For example, in Formula 3, Y1 and Y2 can each be independently nitrogen (N). For example, in Formula 3, Y1 and Y2 can each be independently carbon (C).

[0056] According to one embodiment of the present invention, in Formula 3, Cy1 and Cy2 may each be independently selected from substituted or unsubstituted pyrrolidine, piperidine, sulfoline, and piperidine. For example, Cy1 and Cy2 may each be independently selected from pyrrolidine, piperidine, sulfoline, 1-methylpiperidine, and 2-methylpiperidine.

[0057] According to yet another embodiment of the present invention, the molybdenum precursor compound may be represented by any one of the following formulas 4 to 8. [Formula 4][Formula 5][Formula 6][Formula 7][Formula 8].

[0058] According to one embodiment of the present invention, the molybdenum precursor compound exhibits excellent thermal stability, can be applied at, for example, 300°C to 550°C, and exists in a liquid state at room temperature, thereby enabling the preparation of molybdenum-containing thin films by ALD and CVD. In particular, a significant advantage of this molybdenum precursor compound is that it can be readily deposited by ALD in the form of atomic layer units, producing molybdenum-containing metal films, molybdenum-containing oxide films, and molybdenum-containing nitride films with uniform and excellent film properties.

[0059] When using this molybdenum precursor compound to form a molybdenum-containing thin film via ALD, growth (GPC) at a rate of 0.5 Å / cycle or higher, 0.7 Å / cycle or higher, 0.8 Å / cycle or higher, 1.0 Å / cycle or higher, and 2.0 Å / cycle or lower, 1.8 Å / cycle or lower, 1.5 Å / cycle or lower, 1.2 Å / cycle or lower, or 0.5 to 1.5 Å / cycle per ALD gas supply cycle can be achieved in the temperature range of 300°C to 550°C, for example, 300°C to 500°C.

[0060] If the GPC meets the above-mentioned range, it is more advantageous to control the desired molybdenum doping level when forming a molybdenum-containing thin film. In particular, because the molybdenum precursor compound according to embodiments of the present invention can control the GPC to a lower level compared with conventional molybdenum precursor compounds, it is possible to provide high-quality molybdenum-containing thin films that achieve the desired step ratio and thickness in processes such as DRAM capacitors requiring high step ratios and fine thickness control, and which, in particular, have extremely thin thicknesses and excellent physical and coating properties. Therefore, the advantage of this molybdenum precursor compound is that it can be advantageously used in various applications in the field of semiconductor devices.

[0061] Furthermore, the molybdenum precursor compound can have a density of 1.0 g / mol to 1.5 g / mol at 25°C. If the molybdenum precursor compound meets the above density range, it is liquid; therefore, it may have an advantage in terms of supply source. Compared with molybdenum precursor compounds such as MoO2Cl2, it may be very advantageous in terms of process or batch production rate, which is difficult to process and has poor batch production rate due to the difficulty in supplying solid precursor sources.

[0062] Furthermore, the molybdenum precursor compound can have a vapor pressure of 0.1 to 1.5 Torr at a temperature of about 100°C. If the above vapor pressure range is met, it is advantageous that the source can be supplied via a bypass or bubbling method, which may be advantageous in terms of process.

[0063] In addition, the molybdenum precursor compound may have a boiling point (bp) of, for example, 80°C to 120°C, 90°C to 115°C, or 100°C to 110°C.

[0064] According to one embodiment of the present invention, the molybdenum precursor compound has a TG50 (°C) of, for example, 180°C to 300°C, 180°C to 250°C, 185°C to 300°C, 188°C to 280°C, 188°C to 250°C, or 200°C to 250°C, wherein TG50 is the temperature at which the weight of the molybdenum precursor compound decreases by 50% while being heated from room temperature to 500°C at a heating rate of 10°C / min in thermogravimetric analysis (TGA). TG50 (°C) may be, for example, 180°C to 250°C.

[0065] According to one embodiment of the present invention, the residual weight (W500) of the molybdenum precursor compound measured by thermogravimetric analysis (TGA) at 500°C is, for example, less than 20% by weight, for example, 15% by weight or less, for example, less than 15% by weight, for example, 13% by weight or less, for example, 12% by weight or less, for example, 10% by weight or less, for example, 8% by weight or less, for example, 7% by weight or less, for example, 5% by weight or less, for example, 4.5% by weight or less, for example, 3% by weight or less, for example, 2% by weight or less, for example, 1.5% by weight or less, for example, 1% by weight or less, or for example, 0.5% by weight or less.

[0066] Specifically, the residual weight (W500) of the molybdenum precursor compound, as measured by thermogravimetric analysis (TGA) at 500°C, is 1.5% by weight or less.

[0067] According to one embodiment of the present invention, the molybdenum precursor compound may have a weight residual rate (WR500) of 80% or higher, according to the following Equation 1. [Equation 1] Weight residual rate (WR500, %) = × 100

[0068] In Equation 1, W25 is the initial weight of the molybdenum precursor compound at 25°C, and W500 is the weight of the molybdenum precursor compound at 500°C when the temperature is increased from 25°C to 500°C at a heating rate of 10°C / min.

[0069] Specifically, the molybdenum precursor compound may have a weight residue (WR500) of, for example, 85% by weight or higher, 87% by weight or higher, 88% by weight or higher, 89% by weight or higher, 90% by weight or higher, 92% by weight or higher, 93% by weight or higher, 95% by weight or higher, 97% by weight or higher, or 98% by weight or higher. If the molybdenum precursor compound has a weight residue (WR500) within the above range, it has excellent volatility, and therefore is more advantageous for forming molybdenum-containing metal films, oxide films, and nitride films at temperatures, for example, 300°C or higher, specifically 300 to 550°C, for example, 350°C to 550°C. In particular, its great advantage is that uniform and excellent film properties in the form of atomic layer units can be achieved by ALD. [Method for preparing molybdenum precursor compound]

[0070] According to one embodiment of the present invention, a method for preparing a molybdenum precursor compound represented by Formula 1 is provided.

[0071] The molybdenum precursor compound represented by Formula 1 can be prepared by various methods. According to an embodiment of the present invention, a method for preparing a molybdenum precursor compound comprises reacting a compound represented by Formula A with a compound represented by Formula B and a compound represented by Formula C in a solvent: [Formula A] In Formula A, XA and XB are each independently a halogen element, [Formula B] [Formula C]

[0072] In formulas B and C, M1 and M2 are each independently an alkali metal or an alkaline earth metal, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

[0073] In formula A, XA and XB can each be F, Cl, Br or I independently; and in formulas B and C, M1 and M2 can each be Li, Na, K or Mg independently.

[0074] Specifically, the molybdenum precursor compound represented by Formula 1 can be prepared by a reaction as shown in the following reaction flow 1. [Reaction Flow 1] First step: Second step:

[0075] In reaction process 1, XA, XB, M1, M2, Cy1, Cy2, X1 and X2 are defined as above.

[0076] As shown in reaction flow 1, the molybdenum precursor compound of Formula 1 can be readily prepared by substitution reaction of the halide of Formula A with the ring of Formula B and C, for example, cyclic amine, in a solvent such as a polar solvent, a nonpolar solvent or a mixture thereof (i.e., halide-cyclic amine substitution reaction), followed by purification.

[0077] The molar ratio of the compound represented by formula A to the compounds represented by formulas B and C may be 1 to 2.5, for example 1 to 2.

[0078] The halide-cyclic amine substitution reaction can be carried out in a solvent at 25°C to 50°C for 12 to 24 hours.

[0079] As a solvent, oxygen-containing dimethoxyethane is used in the first step of reaction process 1 for the synthesis of the ligand. In the second step of reaction process 1, one or more of the following can be used: alkanes having 5 to 8 carbon atoms, toluene, ethers, tetrahydrofuran, and mono- to tetra-ethylene glycol dimethyl ether. For example, hexane, pentane, toluene, or combinations thereof can be used. Specifically, hexane is preferred because it has a boiling point of 78°C and is stable.

[0080] According to one embodiment of the present invention, for example, a method for preparing a molybdenum precursor compound represented by Formula 5 from the molybdenum precursor compound will be described below.

[0081] In the compound represented by Formula 5, Cy1 and Cy2 are each piperidine groups. As shown in reaction procedure 1, bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand ((tBuN)2MoCl2(C4H10O2)) and lithium piperidine (Li-N(CH2)5) are added dropwise to a solvent in which toluene (a weakly polar solvent) and hexane (a nonpolar solvent) are mixed, and then the reaction solution is stirred at room temperature for 12 hours.

[0082] After the reaction is complete, the solvent is removed under reduced pressure, and the product is distilled under reduced pressure to obtain the molybdenum precursor compound of Formula 5. To suppress decomposition reactions caused by moisture or oxygen during the reaction, the reaction can be carried out under a nitrogen (N2) or argon (Ar) stream. [Precursor composition for thin film deposition]

[0083] According to one embodiment of the present invention, a composition for forming a molybdenum thin film is provided, comprising a molybdenum precursor compound represented by Formula 1.

[0084] Furthermore, the present invention provides a composition for forming a molybdenum thin film deposited using a molybdenum precursor compound represented by Formula 9: [Formula 9]

[0085] In Formula 9, R3 is selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl and substituted or unsubstituted C4-C8 cycloalkyl.

[0086] Furthermore, the molybdenum precursor compound may be, for example, a molybdenum precursor compound represented by the following formula 10: [Formula 10]

[0087] The composition may further include an oxygen source comprising at least one selected from the group consisting of: water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxides (NO, N2O), nitrogen oxide plasma (N2O plasma), oxynitrides (N2O2), hydrogen peroxide (H2O2), and ozone (O3); and a nitrogen source comprising at least one selected from the group consisting of: nitrogen (N2), ammonia (NH3), ammonia plasma (NH3 plasma), hydrazine (N2H4), and nitrogen plasma (N2 plasma). Furthermore, the composition may further include hydrogen (H2).

[0088] Specifically, the composition may include, for example, at least one of the group consisting of: hydrogen (H2), nitrogen (N2) and ammonia (NH3).

[0089] The composition may include, for example, at least one of the following: water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxides (NO, N2O), nitrogen oxide plasma (N2O plasma), oxygen nitrate (N2O2), hydrogen peroxide (H2O2) and ozone (O3).

[0090] The composition may include, for example, at least one of the group consisting of: ammonia (NH3), ammonia plasma (HN3 plasma), hydrazine (N2H4) and nitrogen plasma (N2 plasma).

[0091] More specifically, the composition may contain at least one selected from the group consisting of: hydrogen (H2), ozone (O3), and ammonia (NH3). [Molybdenum-containing thin film]

[0092] According to one embodiment of the present invention, a molybdenum-containing thin film formed using a molybdenum precursor compound represented by Formula 1 can be provided.

[0093] According to one embodiment of the present invention, a molybdenum-containing thin film formed using a molybdenum precursor compound represented by Formula 9 or a composition for forming a molybdenum thin film can be provided.

[0094] The molybdenum-containing film can have a thickness of several nanometers (nm) to several micrometers (μm) and can be applied for various different applications.

[0095] For example, the thickness of the molybdenum-containing thin film can be about 1 nm or more, about 5 nm or more, about 10 nm or more, about 15 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, or about 50 nm or more. Furthermore, the thickness of the molybdenum-containing thin film can be about 500 nm or less, about 450 nm or less, about 400 nm or less, about 350 nm or less, about 300 nm or less, about 250 nm or less, about 200 nm or less, about 150 nm or less, or about 100 nm or less. Specifically, the thickness of the molybdenum-containing thin film can be individually selected from about 1 nm to about 500 nm.

[0096] The molybdenum-containing film can be formed on a substrate.

[0097] The substrate may be a molybdenum semiconductor wafer, a compound semiconductor wafer, or a plastic sheet (PI, PET, and PES), but is not limited thereto. Substrates with holes or trenches may be used, and porous substrates with a large surface area may be used.

[0098] When the molybdenum precursor compound according to an embodiment of the present invention has a specific structure of Formula 1 or Formula 9, it has low density and high thermal stability, which allows for the efficient formation of molybdenum-containing thin films using CVD and ALD in a wide range of temperatures. In particular, even in the temperature range of 300°C to 550°C, molybdenum-containing thin films, such as molybdenum-containing metal films, molybdenum-containing oxide films, and molybdenum-containing nitride films, can be uniformly formed on substrates with patterns (grooves) or fine irregularities on their surfaces, porous substrates, or plastic substrates with a thickness of several micrometers to tens of nanometers. This produces the excellent effect that the molybdenum-containing thin film can be uniformly formed on the entire surface of the substrate, covering the deepest surface of the fine irregularities or patterns (grooves) and the upper surface of the fine irregularities or patterns (grooves).

[0099] According to one embodiment of the present invention, the molybdenum-containing thin film may be formed on a substrate containing bumps or patterns (grooves) having an aspect ratio of 1 to 50 and a width of 10 nm to 1 μm or less.

[0100] Specifically, the aspect ratio may be about 1 or greater, about 2 or greater, about 3 or greater, about 5 or greater, about 7 or greater, about 10 or greater, or about 15 or greater. In addition, the aspect ratio may be about 50 or less, about 45 or less, about 40 or less, about 35 or less, about 30 or less, about 25 or less, or about 20 or less.

[0101] Furthermore, the width can be approximately 10 nm or greater, approximately 15 nm or greater, approximately 20 nm or greater, approximately 25 nm or greater, approximately 30 nm or greater, approximately 35 nm or greater, or approximately 40 nm or greater. Additionally, the width can be approximately 1 μm or less, approximately 900 nm or less, approximately 800 nm or less, approximately 700 nm or less, approximately 600 nm or less, approximately 500 nm or less, or approximately 450 nm or less.

[0102] The molybdenum-containing thin film may be selected from at least one of the group consisting of: molybdenum-containing metal films, molybdenum-containing oxide films and molybdenum-containing nitride films.

[0103] Furthermore, according to one embodiment of the present invention, the molybdenum-containing thin film may have a low resistivity (μΩ·cm) of 600 μΩ·cm or lower.

[0104] Specifically, the resistivity of the molybdenum-containing thin film can be, for example, 400 to 600 μΩ·cm, for example, 450 to 600 μΩ·cm, for example, 500 to 600 μΩ·cm, for example, 450 to 590 μΩ·cm, for example, 500 to 588 μΩ·cm, for example, 500 to 580 μΩ·cm, for example, 500 to 570 μΩ·cm, for example, 500 to 560 μΩ·cm, for example, 500 to 550 μΩ·cm, for example, 500 to 530 μΩ·cm, or for example, 500 to 520 μΩ·cm. Furthermore, the resistivity of the molybdenum-containing thin film can be, for example, 550 to 590 μΩ·cm, for example, 560 to 590 μΩ·cm, or for example, 560 to 588 μΩ·cm.

[0105] Specifically, the resistivity of the molybdenum-containing thin film is 400 to 600 μΩ·cm in the case of molybdenum nitride film, and 20 to 50 μΩ·cm in the case of molybdenum metal film.

[0106] Therefore, this molybdenum-containing thin film can be used as a gate electrode, diffusion barrier layer, and capacitor electrode in DRAM or NAND flash memory and logic devices requiring low resistivity, and can be applied according to different application purposes. [Method for depositing molybdenum-containing thin films]

[0107] According to one embodiment of the present invention, a method for depositing a molybdenum-containing thin film is provided, which includes depositing a molybdenum-containing thin film on a substrate (plate) using a molybdenum precursor compound represented by Formula 1.

[0108] According to another embodiment of the present invention, a method for depositing a molybdenum-containing thin film is provided, comprising depositing a molybdenum-containing thin film on a substrate (plate) using a molybdenum precursor compound represented by Formula 9 or a composition for forming a molybdenum thin film.

[0109] Specifically, it may include supplying a molybdenum precursor compound represented by Formula 1 or the composition for forming a thin film in a gaseous state to form a molybdenum-containing metal film, a molybdenum-containing oxide film or a molybdenum-containing nitride film on a substrate, but is not limited thereto.

[0110] The substrate is as described above.

[0111] The deposition method of the thin film can be any method and / or equipment known in the art; if necessary, one or more additional reactive gases, etc., can be used.

[0112] According to one embodiment of the present invention, in the method for depositing a molybdenum-containing thin film, a substrate is contained in a reaction chamber, and then a transport gas or a dilution gas is used to transfer the molybdenum precursor compound onto the substrate to deposit the molybdenum-containing thin film.

[0113] Specifically, the deposition can be carried out by chemical vapor deposition (CVD), specifically metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), at a temperature of 300°C to 550°C, for example, 350°C to 550°C.

[0114] In particular, even within a temperature range of 300°C to 550°C, molybdenum-containing metal films, molybdenum-containing oxide films, and molybdenum-containing nitride films can be uniformly formed on patterned (grooved) substrates, porous substrates, or plastic substrates. A uniform film can be formed on the substrate, covering the deepest surface and the upper surface of the fine patterned (grooved) pattern having an aspect ratio of about 1 to 50 or greater and a width of 1 μm to 10 nm or less.

[0115] Here, a deposition temperature of 300°C to 550°C, for example 350°C to 550°C, makes it applicable to memory devices, logic devices, and display devices. Because of the wide process temperature range, deposition is preferably performed at the above deposition temperature for application in various fields.

[0116] In addition, it is preferable to use at least one mixed gas selected from the group consisting of argon (Ar), nitrogen (N2), helium (He) and hydrogen (H2) as the transport gas or dilution gas.

[0117] Furthermore, the method of delivering the molybdenum precursor compound onto the substrate may be at least one method selected from the group consisting of: bubbling method, wherein the molybdenum precursor compound is forcibly vaporized using a transport gas or dilution gas; liquid delivery system (LDS) method, wherein the precursor is supplied in liquid phase at room temperature to be vaporized by a vaporizer; vapor flow control (VFC) method, wherein the precursor is directly supplied using its vapor pressure; and bypass method.

[0118] For example, if the vapor pressure is high, a vapor flow control (VFC) method can be used. If the vapor pressure is low, at least one supply method selected from the group consisting of: a bypass method by heating the container to vaporize; and a bubbling method using argon (Ar) or nitrogen (N2).

[0119] More specifically, the conveying method includes a bubbling method or a heating vaporization bypass method, wherein the bubbling method can be carried out using a conveying gas in a temperature range of 100°C to 150°C and a pressure of 0.1 to 10 Torr, and the heating vaporization bypass method can be carried out using a vapor pressure of 0.1 to 1.5 Torr in a temperature range of room temperature to 100°C.

[0120] In addition, in order to vaporize the molybdenum precursor compound, it can be transported using, for example, argon (Ar) or nitrogen (N2), thermal energy or plasma can be used during deposition, or a bias voltage can be applied to the substrate.

[0121] Meanwhile, in order to deposit a molybdenum-containing metal film during thin film deposition, at least one of the group consisting of hydrogen (H2), neutral nitrogen (N2) and ammonia (NH3) can be used as the reaction gas.

[0122] In addition, in order to deposit a molybdenum oxide film (Mo2O3, MoO3) during film deposition, at least one of the following can be used as the reactant gas: water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxide (NO, N2O), nitrogen oxide plasma (N2O plasma), oxygen nitrate (N2O2), hydrogen peroxide (H2O2) and ozone (O3).

[0123] Furthermore, in order to deposit a molybdenum nitride film (MoN, MN) during thin film deposition, at least one of the following can be used as the reactant gas: ammonia (NH3), ammonia plasma (HN3 plasma), hydrazine (N2H4), and nitrogen plasma (N2 plasma). Mode for carrying out the invention

[0124] The present invention will be described in detail below with reference to examples. The following examples are for illustrative purposes only, and the scope of the invention is not limited thereto. Example <Preparation Example> Preparation of bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand: (tBuN)2MoCl2(C4H10O2):

[0125] Approximately 70 g (approximately 0.34 mol) of sodium molybdate (Na2MoO4) and approximately 2,000 ml of dimethoxyethane (C4H10O2) were placed in a flame-dried 3-liter Schlenk flask and kept at room temperature. While stirring the mixture in the flask, approximately 137.59 g (approximately 1.36 mol) of triethylamine ((C2H5)3N) and approximately 295.4 g (approximately 2.72 mol) of trimethylchlorosilane ((CH3)3SiCl) were slowly added dropwise. Under these conditions, fumes were produced and a white solid was formed. Approximately 49.7 g (approximately 0.68 mol) of tributylamine (tBuNH2) was slowly added dropwise to the flask, and the reaction solution was stirred under reflux for approximately 12 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile byproducts were removed under reduced pressure to obtain 125 g of dark green solid. ¹H-NMR (400 MHz, CDCl₃, 25℃): δ 3.85, (m, 4H, CH₃OCH₂CH₂OCH₃), δ 3.78 (s, 6H, CH₃OCH₂CH₂OCH₃), δ 1.53 (s, 18H, (CH₃)₃CN)Mo) <Example 1> Preparation of bis-tert-butylimino-dipyrrolidyl-molybdenum:(tBuN)₂Mo[N(CH₂)₄]₂ [Equation 4]

[0126] Approximately 13.9 g (approximately 0.2 mol) of pyrrolidine (C4H9N) and approximately 500 ml of toluene (C7H8) were placed in a flame-dried 1-liter Schlenk flask, and the temperature was maintained between -10 and 0 °C. Using a sleeve, approximately 52.1 g (approximately 0.2 mol) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours to obtain Li-N(CH2)4.

[0127] Approximately 39 g (0.1 mol) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand (tBuN)2MoCl2 (C4H10O2) obtained in Preparation Example 1 and approximately 500 ml of toluene (C7H8) were placed in another flame-dried 2-liter Schlenk flask and kept at -30°C to -20°C. Pre-synthesized Li-N(CH2)4 was slowly added dropwise, and the temperature was slowly raised to 50°C, followed by stirring for 12 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to obtain approximately 25 g (yield: approximately 66%) of a brown liquid represented by Formula 4. Density: 1.32 g / mol (at 25 °C) Boiling point (bp): 101 °C (0.3 Torr) (at 309.4 °C, 760 mmHg) 1H-NMR (400 MHz, C6D6, 25 °C): δ 4.035, 4.023, 4.011 (t, 8H, MoN(CH2CH2CH2CH2)), δ 1.569, 1.554 (m, 8H, MoN(CH2CH2CH2CH2)), δ 1.444 (s, 18H, (CH3)3CNMo) <Example 2> Preparation of bis-tert-butylimino-dipiperidinyl-molybdenum:(tBuN)2Mo[N(CH2)5]2 [Equation 5]

[0128] Approximately 16.6 g (approximately 0.2 moles) of piperidine (C5H11N) and approximately 500 ml of toluene (C7H8) were placed in a flame-dried 1-liter Schlenk flask, and the temperature was maintained between -10 and 0 °C. Using a sleeve, approximately 52.1 g (approximately 0.2 moles) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours to obtain Li-N(CH2)5.

[0129] Approximately 39 g (0.1 mol) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand (tBuN)2MoCl2 (C4H10O2) obtained in Preparation Example 1 and approximately 500 ml of toluene (C7H8) were placed in another flame-dried 2-liter Schlenk flask and maintained at approximately -30°C to -20°C. Pre-synthesized Li-N(CH2)5 was slowly added dropwise, and the temperature was slowly raised to approximately 50°C, followed by stirring for approximately 12 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to obtain approximately 27 g (yield: approximately 66.4%) of a yellow liquid represented by Formula 5. Density: 1.33 g / mol (at 25 °C) Boiling point (bp): 103 °C (0.26 Torr) (at 314.9 °C, 760 mmHg) ¹H-NMR (400 MHz, C₆D₆, 25 °C): δ 3.896, 3.883, 3.870 (t, 8H, MoN(CH₂CH₂CH₂CH₂)) δ 1.616, 1.604 (m, 8H, MoN(CH₂CH₂CH₂CH₂)), δ 1.491, 1.475 (m, 4H, MoN(CH₂CH₂CH₂CH₂)) δ 1.413 (s, 18H, (CH₃)₃CNMo) <Example 3> Preparation of bis-tert-butylimino-dihydroxylino-molybdenum:(tBuN)2Mo[N(CH2)2O(CH2)2)]2 [Equation 6]

[0130] Approximately 18.73 g (approximately 0.2 mol) of iodine (C4H9NO) and approximately 500 ml of toluene (C7H8) were placed in a flame-dried 1-liter Schlenk flask, and the temperature was maintained at approximately -10 to 0 °C. Using a sleeve, approximately 52.1 g (approximately 0.2 mol) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours to obtain N(CH2)2O(CH2)2.

[0131] Approximately 39 g (approximately 0.1 moles) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand (tBuN)2MoCl2 (C4H10O2) obtained in Preparation Example 1 and approximately 500 ml of toluene (C7H8) were placed in another flame-dried 2-liter Schlenk flask and maintained at approximately -30°C to -20°C. The previously synthesized Li-N(CH2)2O(CH2)2 was slowly added dropwise, and the temperature was slowly raised to 50°C, followed by stirring for approximately 12 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to obtain approximately 22 g (yield: approximately 53.6%) of a brown liquid represented by Formula 6. Density: 1.31 g / mol (at 25 °C) Boiling point (bp): 108 °C (0.3 Torr) (at 319.2 °C, 760 mmHg) ¹H-NMR (400 MHz, C₆D₆, 25 °C): δ 3.761, 3.749, 3.737 (t, 8H, MoN(CH₂CH₂OCH₂CH₂CH₂)) δ 3.667, 3.655, 3.643 (t, 8H, MoN(CH₂CH₂OCH₂CH₂CH₂)), δ 1.299 (s, 18H, (CH₃)₃CNMo) <Example 4> Preparation of bis-tert-butylimino-bis-4-methylpiperyl-molybdenum:(tBuN)2Mo[N(CH2)2N(CH3)(CH2)2]2 [Equation 7]

[0132] Approximately 72.12 g (0.72 mol) of 1-methylpiperazine (C5H12N2) and approximately 1,000 ml of toluene (C7H8) were placed in a flame-dried 2-liter Schlenk flask, and the temperature was maintained at approximately -10 to 0 °C. Using a sleeve, approximately 192.2 g (approximately 0.72 mol) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours to obtain Li-[N(CH2)2N(CH3)(CH2)2].

[0133] Approximately 125 g (approximately 0.31 moles) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand (tBuN)2MoCl2 (C4H10O2) obtained in Preparation Example 1 and approximately 1000 ml of toluene (C7H8) were slowly added dropwise to another flame-dried 3-liter Schlenk flask, which was maintained at approximately -30°C to -20°C. Pre-synthesized Li-[N(CH2)2N(CH3)(CH2)2] was then slowly added dropwise, and the temperature was slowly raised to 50°C, followed by stirring for approximately 12 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure, yielding approximately 70 g (yield: approximately 51.7%) of an orange liquid represented by Formula 7. Density: 1.34 g / mol (at 25 °C) Boiling point (bp): 121 °C (0.38 Torr) (at 332.5 °C, 760 mmHg) ¹H-NMR (400 MHz, C6D6, 25 °C): δ 3.986, 3.974, 3.963 (t, 8H, MoN(CH2CH2N(CH3)CH2CH2)) δ 2.397, 2.385, 2.373 (t, 8H, MoN(CH2CH2N(CH3)CH2CH2)), δ 2.143 (s, 3H, MoN(CH2CH2N(CH3)CH2CH2)) δ 1.382 (s, 18H, (CH3)3CNMo) <Example 5> Preparation of bis-tert-butylimino-bis-2-methylpiperidinyl-molybdenum:(tBuN)2Mo[NCH(CH3)(CH2)4]2 [Equation 8]

[0134] Approximately 39.25 g (0.35 mol) of 2-methylpiperidine (C6H13N) and approximately 500 ml of toluene (C7H8) were placed in a flame-dried 1-liter Schlenk flask, and the temperature was maintained at approximately -10 to 0 °C. Using a sleeve, approximately 106.3 g (approximately 0.35 mol) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours to obtain Li-[NCH(CH3)(CH2)4].

[0135] Approximately 69.8 g (approximately 0.175 moles) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand (tBuN)2MoCl2 (C4H10O2) obtained in Preparation Example 1 and approximately 500 ml of toluene (C7H8) were slowly added dropwise to another flame-dried 2-liter Schlenk flask, which was maintained at approximately -30°C to -20°C. Pre-synthesized Li-[NCH(CH3)(CH2)4] was then slowly added dropwise, and the temperature was slowly raised to room temperature, followed by stirring for approximately 12 hours. After the reaction was complete, the salts formed during the reaction were removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to obtain approximately 50 g (yield: approximately 65.75%) of a brown liquid represented by Formula 8. Density: 1.35 g / mol (at 25℃) Boiling point (bp): 110℃ (0.3 Torr) (at 322℃, 760 mmHg) 1H-NMR (400 MHz, C6D6, 25℃): δ 4.251 (m, 2H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 3.776 (m, 2H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 3.631 (m, 1H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 3.509 (m, 1H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 1.700 (m, 4H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 1.575 (m, 4H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 1.489, 1.472 (d, 3H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 1.459, 1.441 (d, 3H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 1.338 (m, 4H, MoN(NCH(CH3)(CH2CH2CH2CH2)) δ 1.433, 1.423, 1.412 (t, 18H, (CH3)3CNMo) <Example 6> Preparation of bis-tert-butylimino-cyclopentadienyl-methyl-molybdenum:(tBuN)2MoCp(CH3) [Equation 10]

[0136] Approximately 12.8 g (approximately 0.193 moles) of cyclopentadiene (C5H5) and approximately 500 ml of n-hexane (C6H14) were placed in a flame-dried 1-liter Schlenk flask, and the temperature was maintained at approximately -10 to 0 °C. Using a sleeve, approximately 51.5 g (approximately 0.193 moles) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 4 hours to obtain Li-C5H5.

[0137] Approximately 77 g (0.193 mol) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand ((tBuN)2MoCl2(C4H10O2)) and approximately 500 ml of diethyl ether (C2H6O) were placed into another flame-dried 2-liter Schlenk flask and kept at approximately -10°C to 0°C. Pre-synthesized Li-C5H5 was slowly added dropwise, and the temperature was slowly raised to room temperature, followed by stirring for 12 hours. After the reaction was complete, the salt formed in the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to obtain 62 g (0.183 mol) of the solid intermediate bis-tert-butylimino-cyclopentadiene-chloro-molybdenum (tBuN)2MoCpCl.

[0138] The intermediate obtained above and about 500 ml of diethyl ether (C2H6O) were transferred into another 1-liter Schlenk flask and kept at about -10°C to 0°C. Using a sleeve, about 91.5 g (0.201 mol) of methyllithium (MeLi, 1.6 M ether solution) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. After the reaction was complete, the salt formed in the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to give about 30 g (yield: 48.83%) of an orange liquid represented by Formula 10. Density: 1.12 g / mol (at 25°C) Boiling point (bp): 70°C (0.4 Torr) (at 259.7°C, 760 mmHg) ¹H-NMR (400 MHz, C₆D₆, 25°C): δ 5.816 (s, 5H, MoC₅H₅) δ 1.232 (s, 18H, (CH₃)₃CNMo) δ 1.056 (s, 3H, MoCH₃) <Comparative Example 1> Tetra(ethylmethylamino)molybdenum(VI)Mo(NCH₃C₂H₅)₄

[0139] Approximately 305.8 g (approximately 1.097 mol) of n-BuLi and approximately 1 liter of n-hexane were placed in a flame-dried 3-liter Schlenk flask, and the temperature was lowered to approximately 0°C. Approximately 66 g (1.116 mol) of HN(CH3)(C2H5) was slowly added dropwise to the flask, and the temperature of the reaction solution was slowly raised to room temperature while stirring for approximately 4 hours. Then, approximately 250 ml of THF was added to the flask, and the flask was cooled to 0°C. Approximately 50 g (approximately 0.183 mol) of MoCl5 dissolved in n-hexane was slowly added dropwise to the flask, and the reaction solution was stirred at room temperature for approximately 18 hours. The reaction was then further stirred under reflux for 2 hours to complete the reaction. After the reaction was complete, the solution was filtered through a diatomaceous earth mat and glass frit, and the solvent in the filtrate was removed under reduced pressure. The solution was then distilled under reduced pressure to give approximately 16 g (yield: approximately 27%) of the deep purple liquid compound represented in Comparative Example 1. <Comparative Example 2> bis(tert-butylimino)bis(dimethylamino)molybdenum(tBuN)2Mo(N(CH3)2]2

[0140] Approximately 1,000 ml of n-hexane was placed into a flame-dried 2-liter Schlenk flask. Using a sleeve, approximately 58 g (approximately 0.22 mol) of n-butyllithium (n-BuLi, 23%) was slowly added dropwise, and the temperature was maintained at approximately -10 to 0 °C. Approximately 29.75 g (approximately 0.66 mol) of dimethylamine (C2H6N) was slowly bubbled into the flask, and the temperature was raised to room temperature. The mixture was stirred for 3 hours to obtain Li-N(CH3)2.

[0141] Approximately 39 g (0.1 mol) of the bis-tert-butylimino-dichloro-molybdenum-dimethoxyethane ligand (tBuN)2MoCl2 (C4H10O2) obtained in Preparation Example 1 and approximately 500 ml of toluene (C7H8) were placed in another flame-dried 2-liter Schlenk flask and maintained at -30°C to -20°C. Pre-synthesized Li-N(CH3)2 was slowly added dropwise, and the temperature was slowly raised to 50°C, followed by stirring for 12 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile byproducts were removed by distillation under reduced pressure to obtain approximately 25 g (yield: approximately 69.6%) of the orange liquid represented in Comparative Example 2. Test Example <Test Example 1> Structural Analysis of Molybdenum Precursor Compounds

[0142] The structures of the molybdenum precursor compounds prepared in Examples 1 to 6 were analyzed by 1H-NMR analysis. The results are shown in Figure 1. <Test Example 2> Thermal Properties Analysis of Molybdenum Precursor Compounds

[0143] Thermogravimetric analysis (TGA) was performed to analyze the thermal properties of the molybdenum precursor compounds prepared in Examples 2, 5 and 6 and Comparative Examples 1 and 2. The results are shown in Figure 2.

[0144] In thermogravimetric analysis (TGA), the weight change of the molybdenum precursor compound is measured while the temperature is raised from room temperature to approximately 500°C at a heating rate of approximately 10°C / min in a nitrogen (N2) environment. Specifically, the vaporization initiation temperature (°C) of the molybdenum precursor compound and the temperature TG50 (°C) at which the weight of the molybdenum precursor compound decreases by 50% are measured.

[0145] Furthermore, the weight residue (WR500, %) of the molybdenum precursor compounds prepared in Examples 2, 5, and 6 and Comparative Examples 1 and 2 of the present invention was evaluated using the following Equation 1: [Equation 1] Weight residue (WR500, %) = ×100

[0146] In Equation 1, W25 is the initial weight (weight %) of the molybdenum precursor compound at 25°C, and W500 is the weight (weight %) of the molybdenum precursor compound at 500°C when the temperature is increased from 25°C to 500°C at a heating rate of 10°C / min.

[0147] Thermogravimetric analysis (TGA) measurement results are shown in Figure 2 and Table 1 below: [Table 1] Vaporization initiation temperature (°C) TG 50 (°C) W 500 (weight%) WR 500 (%) Example 2 206.23 227.56 0.22 99.78 Example 5 213.32 234.20 1.28 98.72 Example 6 162.0 188.52 0.13 99.87 Comparative Example 1 145.0 193.42 34.24 65.76 Comparative Example 2 145.61 181.31 15.46 84.54

[0148] As can be seen from Figure 2, the molybdenum precursor compounds in Comparative Examples 1 and 2 exhibited two-stage curves due to poor thermal stability, resulting in significant residues, or decomposition during the analytical process. In contrast, the molybdenum precursor compounds prepared in Examples 2, 5, and 6 of this invention showed residue volatilization without decomposition. These TGA properties demonstrate sufficient volatility for application in processes using ALD.

[0149] In addition, as can be seen from Table 1, most of the molybdenum precursor compounds in Examples 2, 5 and 6 of the present invention vaporize at around 200°C, and TG50 (°C), which is the temperature at which the weight of the molybdenum precursor compound decreases by 50%, is about 188°C to 235°C.

[0150] Furthermore, the residual weight (W500) of the molybdenum precursor compound at about 500°C is about 0% to 1.3% by weight. In contrast, the residual weight (W500) of the molybdenum precursor compounds of Comparative Examples 1 and 2 at about 500°C is about 15% to 35% by weight, which is significantly higher than the residual weight (W500) of the molybdenum precursor compounds of the examples.

[0151] Meanwhile, the molybdenum precursor compounds of Examples 2, 5 and 6 have a weight residue of about 98.72% or higher (WR500).

[0152] In contrast, the weight residue (WR500) of the molybdenum precursor compounds in Comparative Examples 1 and 2 was about 65% to 85%, which was significantly higher than the weight residue (WR500) of the molybdenum precursor compounds in Examples 2, 5 and 6.

[0153] Therefore, the molybdenum precursor compounds of the present invention exhibit excellent volatility; thus, they are confirmed to be excellent precursors capable of forming molybdenum-containing metal films, oxide films, and nitride films, particularly in the temperature range of 300°C to 550°C, for example, 350°C to 550°C. <Test Example 3> Deposition characteristics of molybdenum precursor compounds with ammonia (NH3)

[0154] The molybdenum precursor compounds prepared in Examples 2 and 6 were used in the ALD process. NH3 was used as the reactant gas to deposit molybdenum-containing nitride films.

[0155] First, a silicon oxide substrate (plate) (1,000 Å) was used as the substrate for preparing a molybdenum nitride thin film. The silicon oxide substrate was a silicon oxide substrate whose surface had been cleaned with acetone and distilled water (DI-water) to remove organic matter, the purpose of which was to remove organic matter from the surface of the silicon oxide substrate.

[0156] To deposit a molybdenum-containing nitride film, the ALD cycle was repeated 200 times and the substrate temperature was set to approximately 550°C. The molybdenum precursor compounds were placed in stainless steel containers and heated to approximately 100°C for use. In this case, the precursor compounds were supplied in gaseous form to the reaction chamber of the reactor using argon gas flowing at a flow rate of approximately 200 sccm and a process pressure of approximately 1 Torr.

[0157] In order to confirm the optimal resistivity characteristics of each molybdenum nitride film, the ALD gas supply cycle was repeated 100 times to form the molybdenum nitride film, wherein the molybdenum precursor compound prepared in Example 2 was supplied for about 20 seconds (precursor compound supply step); argon (Ar) was supplied for about 5 seconds to remove the molybdenum precursor compound (gas) remaining in the reactor (precursor compound purification step); NH3 was supplied as a reaction gas for about 20 seconds (NH3 supply step); and argon (Ar) was supplied for about 5 seconds to remove the NH3 remaining in the reactor (NH3 purification step).

[0158] Meanwhile, in the case of the molybdenum precursor compound prepared in Example 6, the ALD gas supply cycle is repeated 100 times to form a molybdenum nitride film, wherein the molybdenum precursor compound is supplied for about 3 seconds (precursor compound supply step); argon (Ar) is supplied for about 10 seconds to remove the molybdenum precursor compound (gas) remaining in the reactor (precursor compound purification step); NH3 is supplied as a reaction gas for about 20 seconds (NH3 supply step); and argon (Ar) is supplied for about 10 seconds to remove the NH3 remaining in the reactor (NH3 purification step).

[0159] The sheet resistivity (μΩ / sq) of the molybdenum-containing nitride film deposited on a silicon oxide thin film substrate was measured using a 4PPS (4-point probe system), and the thickness of the molybdenum-containing nitride film was measured using a transmission electron microscope (TEM). The measured thicknesses of the molybdenum-containing nitride film were 90.6 Å and 320.5 Å, respectively. TEM images of the molybdenum-containing nitride film formed using the molybdenum precursor compounds prepared according to Examples 2 and 6 are shown in Figures 4 and 5, respectively.

[0160] As can be seen from Figures 4 and 5, the surface of the molybdenum-containing nitride film formed using the molybdenum precursor compounds prepared in Examples 2 and 6 is uniform. It is formed uniformly in the form of atomic layer units, rather than growing with a rough and uneven surface. Since the growth rate is difficult to control in CVD, it is also difficult to control the thickness.

[0161] At the same time, the resistivity (μΩ·cm) of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared according to Examples 2 and 6 was measured.

[0162] Specifically, the resistivity of the molybdenum-containing nitride film was measured at room temperature using an AIT CMT-SR1000N instrument.

[0163] The resistivity measurement results of the molybdenum nitride thin film are shown in Figure 3.

[0164] As can be seen from Figure 3, the resistivity values ​​of the molybdenum-containing nitride films formed using the molybdenum precursor compounds prepared according to Examples 2 and 6 are 587.5 μΩ·cm and 503.2 μΩ·cm, respectively. They are suitable for use as nitride films for electrodes requiring low resistivity.

[0165] For example, the molybdenum precursor compound of the present invention is an excellent precursor for use as a gate electrode, diffusion barrier, and capacitor electrode in DRAM or NAND flash memory and logic devices requiring low resistivity. <Test Example 4> Deposition characteristics of molybdenum precursor compound with ammonia (NH3) plasma

[0166] The molybdenum precursor compound prepared in Example 6 was used in the ALD process. NH3 plasma was used as the reaction gas to deposit a molybdenum-containing nitride film.

[0167] First, a silicon oxide substrate (plate) (1,000 Å) was used as the substrate for preparing a molybdenum nitride thin film. The silicon oxide substrate was a silicon oxide substrate whose surface had been cleaned with acetone and distilled water (DI-water) to remove organic matter, the purpose of which was to remove organic matter from the surface of the silicon oxide substrate.

[0168] To deposit a molybdenum-containing nitride film, the ALD cycle was repeated 100 times, and the substrate temperature was set to 350°C, 400°C, and 450°C. The molybdenum precursor compound was placed in a stainless steel container and heated to approximately 100°C for use. In this case, argon gas was flowed at a flow rate of approximately 200 sccm and a process pressure of approximately 1 Torr to supply the precursor compound in a gaseous state to the reaction chamber of the reactor.

[0169] To confirm the optimal resistivity characteristics of each molybdenum-containing nitride film, the following steps were performed: The molybdenum precursor compound was supplied for approximately 3 seconds (precursor compound supply step); argon (Ar) was supplied for approximately 10 seconds to remove residual molybdenum precursor compound (gas) in the reactor (precursor compound purification step); it was exposed to NH3 plasma for approximately 20 seconds (NH3 plasma exposure step); and argon (Ar) was supplied for approximately 10 seconds to remove residual NH3 plasma in the reactor (NH3 plasma purification step). The NH3 plasma was used at 500 sccm and 500 W.

[0170] The sheet resistivity (μΩ / sq) of the molybdenum-containing nitride film deposited on the silicon oxide thin film substrate was measured using a 4PPS (4-point probe system), and its thickness was measured using TEM. The thicknesses of the molybdenum-containing nitride film measured at 350 °C, 400 °C, and 450 °C were 57.6 Å, 79.5 Å, and 91.8 Å, respectively. TEM images of the molybdenum-containing nitride film formed using the molybdenum precursor compound prepared according to Example 6 are shown in Figures 6, 7, and 8, respectively.

[0171] As can be seen from Figures 6, 7 and 8, the surface of the molybdenum-containing nitride film formed using the molybdenum precursor compound prepared in Example 6 is uniform.

[0172] At the same time, the composition of the molybdenum-containing nitride films at temperatures of 350°C, 400°C and 450°C was identified by Auger electron spectroscopy (AES) analysis.

[0173] As can be seen from Figures 9, 10 and 11, the molybdenum-containing nitride film prepared in Example 6 has a low carbon content of 10% or less. In addition, the molybdenum-containing nitride film prepared in Example 6 has a molybdenum to nitrogen ratio of approximately 1:0.8.

[0174] At the same time, the resistivity (μΩ·cm) of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared according to Example 6 was measured.

[0175] Specifically, the resistivity of molybdenum nitride thin films was measured at room temperature using AIT’s CMT-SR1000N equipment.

[0176] The resistivity measurement results of the molybdenum nitride thin film are shown in Figure 12.

[0177] As can be seen from Figure 12, the resistivity values ​​of the molybdenum-containing nitride films formed using the molybdenum precursor compound prepared according to Example 6 are 893.3 μΩ·cm (350℃), 647.5 μΩ·cm (400℃), and 367.8 μΩ·cm (450℃), respectively. These are suitable for use as nitride films for electrodes requiring low resistivity.

[0178] For example, the molybdenum precursor compound of the present invention is an excellent precursor that can be used as a gate electrode, diffusion barrier and capacitor electrode in DRAM or NAND flash memory and logic devices that require low resistivity. [Simplified Explanation of the Diagram]

[0031] Figure 1 is the 1H-NMR spectrum of the molybdenum precursor compounds prepared according to Examples 1 to 6 of this application. Figure 2 is a thermogravimetric analysis (TGA) measurement result of the molybdenum precursor compounds prepared according to Examples 2, 5 and 6 of this application and Comparative Examples 1 and 2. Figure 3 is a resistivity graph showing the molybdenum-containing nitride thin films formed using the molybdenum precursor compounds prepared according to Examples 2 and 6 of this application. Figure 4 is a transmission electron microscope (TEM) image of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared according to Example 2 of this application. Figure 5 is a TEM image of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared according to Example 6 of this application. Figure 6 is a TEM image of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared according to Example 6 of this application and plasma at 350°C. Figure 7 is a TEM image of a molybdenum-containing nitride film formed at 400°C using the molybdenum precursor compound and plasma prepared according to Example 6 of this application. Figure 8 is a TEM image of a molybdenum-containing nitride film formed at 450°C using the molybdenum precursor compound and plasma prepared according to Example 6 of this application. Figure 9 shows the component analysis results of a molybdenum-containing nitride film formed at 350°C using the molybdenum precursor compound and plasma prepared according to Example 6 of this application, wherein the analysis was performed by Auger electron spectroscopy (AES). Figure 10 shows the component analysis results of a molybdenum-containing nitride film formed at 400°C using the molybdenum precursor compound and plasma prepared according to Example 6 of this application, wherein the analysis was performed by AES. Figure 11 shows the component analysis results of a molybdenum-containing nitride film formed at 450°C using the molybdenum precursor compound and plasma prepared according to Example 6 of this application, wherein the analysis was performed by AES. Figure 12 is a graph showing the growth per cycle (GPC) and resistivity of a molybdenum nitride film formed using a molybdenum precursor compound prepared according to Example 6 of this application and plasma.

Claims

1. A molybdenum precursor compound represented by Formula 1: [Formula 1] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C5 carbon rings, substituted or unsubstituted C7-C20 carbon rings, unsubstituted C6 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

2. The molybdenum precursor compound of claim 1, which is represented by the following formula 2: [Formula 2] In formula 2, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C1-C20 heterocycles.

3. The molybdenum precursor compound of claim 1 is represented by the following formula 3: [Formula 3] In formula 3, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C1-C20 heterocycles, and Y1 and Y2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

4. The molybdenum precursor compound of claim 1 is represented by any one of the following formulas 4 to 8: [Formula 4] [Formula 5] [Formula 6] [Formula 7] and [Formula 8].

5. The molybdenum precursor compound of claim 1, wherein the molybdenum precursor compound has a TG50 (°C) of 180°C to 300°C, wherein TG50 is the temperature at which the weight of the molybdenum precursor compound decreases by 50% when heated from room temperature to 500°C at a heating rate of 10°C / min in thermogravimetric analysis (TGA).

6. The molybdenum precursor compound of claim 5, wherein the molybdenum precursor compound has a weight residue (WR500) of 80% or higher according to the following Equation 1: [Equation 1] Weight residue (WR500, %) = × 100 In Equation 1, W25 is the initial weight of the molybdenum precursor compound at 25°C, and W500 is the weight of the molybdenum precursor compound at 500°C when the temperature is increased from 25°C to 500°C at a heating rate of 10°C / min.

7. A composition for forming a molybdenum thin film comprising a molybdenum precursor compound represented by Formula 1: [Formula 1] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

8. A composition for forming a molybdenum film, the molybdenum film being deposited using a molybdenum precursor compound represented by Formula 9: [Formula 9] In Formula 9, R3 is selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl and substituted or unsubstituted C4-C8 cycloalkyl.

9. The composition for forming a molybdenum thin film as claimed in claim 8 is represented by the following formula 10: [Formula 10] 10. A method for preparing a molybdenum precursor compound represented by Formula 1, comprising reacting a compound represented by Formula A with a compound represented by Formula B and a compound represented by Formula C in a solvent: [Formula A] In Formula A, XA and XB are each independently a halogen element, [Formula B] [Formula C] In Formulas B and C, M1 and M2 are each independently an alkali metal or an alkaline earth metal, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C), [Formula 1] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

11. The method for preparing molybdenum precursor compounds as claimed in claim 10, wherein, In formula A, XA and XB are each independently F, Cl, Br or I; and in formulas B and C, M1 and M2 are each independently Li, Na, K or Mg.

12. The method for preparing a molybdenum precursor compound as claimed in claim 10, wherein the solvent comprises one or more of the group consisting of: alkanes having 5 to 8 carbon atoms, toluene, ethers, tetrahydrofuran, and mono- to tetra-ethylene glycol dimethyl ether.

13. A molybdenum-containing thin film formed using a molybdenum precursor compound represented by Formula 1: [Formula 1] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

14. The molybdenum-containing thin film of claim 13, wherein the molybdenum-containing thin film has a resistivity of 600 μΩ·cm or lower.

15. The molybdenum-containing thin film of claim 13, wherein the molybdenum-containing thin film is selected from at least one of the group consisting of: molybdenum-containing metal films, molybdenum-containing oxide films and molybdenum-containing nitride films.

16. A method for depositing a molybdenum-containing thin film, comprising depositing a molybdenum-containing thin film on a substrate using a molybdenum precursor compound represented by Formula 1: [Formula 1] In Formula 1, Cy1 and Cy2 are each independently selected from substituted or unsubstituted C3-C20 carbon rings and substituted or unsubstituted C1-C20 heterocycles, and X1 and X2 are each independently selected from oxygen (O), nitrogen (N) and carbon (C).

17. The method for depositing a molybdenum-containing thin film as claimed in claim 16, wherein the deposition is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 300°C to 550°C.

18. The method for depositing a molybdenum-containing thin film as claimed in claim 16, wherein the molybdenum precursor compound is delivered to the substrate by at least one of the following methods: bubbling, liquid delivery system (LDS), vapor flow control (VFC), and bypass.

19. The method for depositing a molybdenum-containing thin film as claimed in claim 18, wherein the transport method comprises a bubbling method or a bypass method by heating and vaporization, the bubbling method being carried out using a transport gas with a temperature range of 100°C to 150°C and a vapor pressure of 0.1 to 10 Torr, and the bypass method by heating and vaporization being carried out using a vapor pressure of 0.1 to 1.5 Torr in a temperature range of room temperature to 100°C.

20. The method for depositing a molybdenum-containing thin film as claimed in claim 16, wherein, During deposition, thermal energy or plasma is used, or a bias voltage is applied to the substrate.

21. The method for depositing a molybdenum-containing thin film as claimed in claim 16, wherein the molybdenum-containing thin film comprises a molybdenum-containing metal film, and during deposition a reaction gas comprising at least one of the group consisting of hydrogen (H2), nitrogen (N2) and ammonia (NH3).

22. The method for depositing a molybdenum-containing thin film as claimed in claim 16, wherein the molybdenum-containing thin film comprises a molybdenum-containing oxide thin film, and during deposition a reactive gas comprising at least one of the group consisting of: water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxides (NO, N2O), nitrogen oxide plasma (N2O plasma), oxygen nitrate (N2O2), hydrogen peroxide (H2O2), and ozone (O3).

23. The method for depositing a molybdenum-containing thin film as claimed in claim 16, wherein the molybdenum-containing thin film comprises a molybdenum-containing nitride film, and during deposition a reactive gas comprising at least one of the group consisting of: ammonia (NH3), ammonia plasma (HN3 plasma), hydrazine (N2H4), and nitrogen plasma (N2 plasma).

Images