Preparation method of MoO2Cl2

Abstract

The present invention relates to a method for manufacturing MoO2Cl2. According to one embodiment of the manufacturing method, particulate MoO2Cl2 in the form of a solid powder is provided, thereby facilitating the recovery, quality control, and transportation of the product. Furthermore, high-purity MoO2Cl2 can be provided in a high yield without a separate purification process.

Description

Technology Field

[0001] The present disclosure relates to a method for manufacturing MoO2Cl2. Background Technology

[0002] Molybdenum oxide is used as an important raw material in various industrial fields, including catalysts, alloys, electronic materials, and chemical intermediates, and among them, the demand for molybdenum deoxydichloride (MoO2Cl2) as a semiconductor precursor is increasing.

[0003] With the recent advancement of artificial intelligence (AI) technology and the resulting demand for high-capacity 3D NAND flash memory and ultra-high stacking technology, it is essential to improve the performance of metal wiring, which directly affects memory performance and reliability, and molybdenum is attracting attention as a next-generation metal wiring material. Previously, tungsten (W) was mainly used as a metal wiring material, but tungsten wiring is unsuitable for ultra-high stacking because its resistance rises sharply as the number of memory layers increases and a barrier layer is necessarily required. In addition, in nano-scale, narrow, and deep circuits, tungsten is not completely filled, leading to problems such as the occurrence of pinholes.

[0004] On the other hand, molybdenum has various advantages, such as having an electrical resistance more than 50% lower than tungsten, providing excellent fine packing characteristics, and eliminating the need for a separate barrier layer due to a low risk of wafer damage during the deposition process. For these reasons, molybdenum is attracting attention as a next-generation metal wiring material, and the development of molybdenum deposition processes and molybdenum precursors is actively underway.

[0005] Molybdenum deoxydichloride (MoO2Cl2) is widely used as a major molybdenum precursor, and a common method for producing MoO2Cl2 involves reacting a molybdenum raw material with chlorine gas to generate gaseous MoO2Cl2, which is then condensed to precipitate in solid form.

[0006] However, in these conventional methods, non-uniform gas dispersion and poor contact between solid and gaseous raw materials result in low reaction efficiency, reduced product purity and yield, and quality variability. Furthermore, the process of separating and recovering precipitated solid products requires additional equipment and labor, which lowers production efficiency. Since these issues are exacerbated when the reaction scale is increased, making the method unsuitable for scale-up, a new manufacturing process is required. The problem to be solved

[0007] One aspect of the present invention provides a manufacturing method capable of recovering high-quality MoO2Cl2 in a powdered particulate form through a simplified process.

[0008] Another aspect of the present invention provides a metal wiring for a semiconductor process manufactured using MoO2Cl2 obtained by the above manufacturing method. means of solving the problem

[0009] One aspect of the present invention provides a method for producing MoO2Cl2, comprising the steps of: dispersing chlorine gas into a reactor through a porous distribution plate and reacting it with molybdenum oxide particles to produce gaseous MoO2Cl2; transferring the gaseous MoO2Cl2 to a condensation unit to precipitate solid MoO2Cl2; and melting the solid MoO2Cl2 to obtain liquid MoO2Cl2 and high-pressure spraying the liquid MoO2Cl2 to obtain particulate MoO2Cl2.

[0010] The porous distribution plate may include pores ranging from 0.01 μm to 1,000 μm.

[0011] The above reaction may be carried out while stirring the molybdenum oxide particles.

[0012] The melting may be performed in a closed system and may be performed at 170 to 300 ℃.

[0013] The above high-pressure injection may be injected through the injection section into the recovery section under a pressure of 2 to 50 atmospheres.

[0014] The pressure of the above recovery unit may be atmospheric pressure to 3 atmospheres, and the temperature may be 20 to 40 ℃.

[0015] The average particle size of the above particulate MoO2Cl2 may be 50 μm to 1,000 μm.

[0016] The above-mentioned gaseous MoO2Cl2 may be transferred to a condensation unit through a transfer unit including a filter.

[0017] The above filter may include pores of 0.001 μm to 0.1 μm.

[0018] The above reaction may be carried out at 100 ℃ to 700 ℃.

[0019] The above precipitation may be performed at -20 ℃ to 150 ℃.

[0020] Another aspect of the present invention provides a semiconductor process metal wiring manufactured by depositing particulate MoO2Cl2 manufactured by the above manufacturing method.

[0021] The above semiconductor process metal wiring may be any one selected from metal wiring of NAND flash memory, bit lines and word lines of 10 nm class or smaller DRAM, and ultra-fine circuit wiring of system semiconductors. Effects of the invention

[0022] A method for producing MoO2Cl2 according to one embodiment of the present invention can maximize reactivity and provide a high-quality particulate product, and can minimize variations in product quality.

[0023] Specifically, a manufacturing method according to one embodiment can improve reaction efficiency by maximizing the contact area with the solid raw material, molybdenum oxide, by finely and uniformly dispersing chlorine gas through the pores of a porous distribution plate. In addition, since the gas flow is not concentrated locally, the occurrence of localized over-reaction or unreacted regions can be prevented, and reaction conditions are maintained homogeneously throughout the reaction, thereby minimizing variations in product quality.

[0024] In addition, a manufacturing method according to one embodiment can provide particulate MoO2Cl2 in the form of solid powder through melting and high-pressure spraying technology, and can facilitate the recovery and transportation of the product.

[0025] In addition, the manufacturing method according to one embodiment can ensure reproducibility and minimize variations in product quality even when scaled up to an industrial scale. Brief explanation of the drawing

[0026] FIG. 1 is a schematic diagram of a manufacturing apparatus used in one embodiment. Figure 2 is a schematic diagram of a reactor used in one embodiment. Specific details for implementing the invention

[0027] Unless otherwise defined in this specification, all technical and scientific terms have the same meaning as generally understood by those skilled in the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0028] The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context.

[0029] Throughout this specification, the terms “comprising,” “having,” “containing,” or “having” any component mean that, unless specifically stated otherwise, other components are not excluded but may be included, and do not exclude elements, materials, or processes not additionally listed.

[0030] The numerical ranges used herein include lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the defined range, all of which are limited, and all possible combinations of upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0031] Unless otherwise specifically defined in this specification, “about” may be considered to be a value within 30%, 25%, 20%, 15%, 10%, or 5% of the specified value.

[0032] The present disclosure will be described in detail below. However, this is merely illustrative and the present disclosure is not limited to the specific embodiments described illustratively.

[0033] One aspect of the present invention provides a method for producing high-quality particulate MoO2Cl2 in a high yield.

[0034] Specifically, a method for producing MoO2Cl2 according to one embodiment may comprise the steps of: dispersing chlorine gas into a reactor through a porous distribution plate and reacting it with molybdenum oxide particles to produce gaseous MoO2Cl2; transferring the gaseous MoO2Cl2 to a condensation section to precipitate solid MoO2Cl2; and melting the solid MoO2Cl2 to obtain liquid MoO2Cl2, and high-pressure spraying the liquid MoO2Cl2 to obtain particulate MoO2Cl2.

[0035] A manufacturing method according to one embodiment can improve reaction efficiency by maximizing the contact area with the solid raw material, molybdenum oxide, through the pores of a porous distribution plate and dispersing chlorine gas into the reactor. Additionally, reaction conditions are maintained uniformly throughout the reaction, allowing for the provision of high-purity MoO2Cl2 with consistent quality. Furthermore, by utilizing a technique to obtain liquid MoO2Cl2 and inject it under high pressure, it is possible to provide MoO2Cl2 in the form of a solid powder with high bulk density, offering advantages in recovery, transport, and storage. Moreover, when applying the particles to a molybdenum thin film deposition process, they facilitate easy transport into the deposition equipment, prevent contamination of the equipment, and provide a highly uniform thin film surface free from the influence of fine particles, thereby offering various advantages in application.

[0036] The above reactor may be an impeller-stirred type reactor (10), and the reaction may be performed while stirring the molybdenum oxide particles, and regardless of the scale of the reaction, the contact between the raw materials may be smoother, the reaction efficiency may be further improved, and it may be more advantageous for mass production application.

[0037] The reactor may have a void space between the porous distribution plate (110) and the chlorine gas introduction pipe (120) as shown in FIG. 2, and an appropriate pressure may be applied in the void space, thereby allowing the chlorine gas to be more evenly dispersed into the reactor through the porous distribution plate and facilitating contact between the raw materials.

[0038] The porous distribution plate may include pores ranging from 0.01 μm to 1,000 μm, and specifically, it may be a sintered mesh filter in which pores of 0.1 μm to 1,000 μm, 1 μm to 1,000 μm, or 10 μm to 1,000 μm in size are evenly formed. The porous distribution plate may have a gradient in which the size of the pores formed on the distribution plate gradually increases as it moves away from the chlorine gas introduction pipe. The gradient may be continuous or may have a step shape depending on the distance. When having the gradient, the pressure of the chlorine gas introduced into the reactor is evenly distributed and introduced into the reactor, thereby maintaining the reactivity inside the reactor uniformly and enabling the production of a product of higher purity.

[0039] The average particle size of the molybdenum oxide particles is not particularly limited, but for example, it may be 100 μm or more, 300 μm or more, 1,000 μm to 5,000 μm, or 1,000 μm to 3,000 μm, or 1,000 μm to 2,000 μm, and the reaction efficiency can be further improved.

[0040] The above molybdenum oxide may be molybdenum dioxide (MoO-2), and the reaction can be carried out under lower temperature conditions.

[0041] The reaction temperature between the molybdenum oxide particles and chlorine gas may be 100°C to 700°C, or 100°C to 500°C, or 100°C to 300°C, or 150°C to 300°C, and may include all possible combinations of intermediate values ​​of each of the above values, and upper and lower limits of the above numerical ranges.

[0042] The above-described gaseous MoO2Cl2 may be transferred to a condensation unit through a transfer unit including a filter, and impurities or particulate raw materials or by-products are removed by the filter unit to obtain a product with superior purity, and furthermore, the reaction efficiency and the purity of the product can be improved.

[0043] The above filter is not particularly limited as long as it is a filter having pores of 0.001 μm to 0.1 μm or 0.01 μm to 0.1 μm evenly formed, but for example, it may be a sintered mesh filter.

[0044] The temperature of the above-mentioned transfer section is not limited as long as it is a temperature at which the gaseous product does not condense, but may include, for example, 100°C to 700°C, or 100°C to 500°C, or 100°C to 300°C, or 150°C to 500°C, or 150°C to 300°C, or intermediate values ​​of each of the above values, and all possible combinations of upper and lower limits of the numerical range.

[0045] The above precipitation temperature is not significantly limited as long as it is a temperature at which gaseous MoO2Cl2 can be precipitated, but, for example, it may include -20°C to 150°C, or -20°C to 130°C, or 0°C to 100°C, or 50°C to 150°C, or 50°C to 100°C, or intermediate values ​​of each of the above values, and all possible combinations of upper and lower limits of the above numerical range.

[0046] The melting described above may be performed in a closed system or under a nitrogen atmosphere. If the melting step is performed in an open system, it is converted to a closed system for liquefaction because vaporization occurs and the material is lost.

[0047] The melting temperature is not significantly limited as long as it is the temperature at which the precipitated solid MoO2Cl2 melts, but for example, it may be 180°C or higher, or 200°C or higher, or 300°C or lower, or 250°C or lower, or 220°C or lower, and specifically, it may be 180°C to 300°C, or 180°C to 250°C, and may include all possible combinations of intermediate values ​​of each of the above values, and upper and lower limits of the above numerical range.

[0048] The liquid MoO2Cl2 may be atomized by spraying it outwardly through pressurization using an inert gas heated to the same temperature into the interior of the spraying section combined with the container (condensation section) where the melting is performed.

[0049] The pressure in the high-pressure injection step is not specifically limited, but, for example, may be 2 atmospheres or more, 3 atmospheres or more, 5 atmospheres or more, 10 atmospheres or more, 20 atmospheres or more, 100 atmospheres or less, or 50 atmospheres or less. Specifically, it may be injected through the injection section to the recovery section under a pressure of 2 to 50 atmospheres, or 2 to 20 atmospheres, or 2 to 10 atmospheres, or 2 to 5 atmospheres, and may include all possible combinations of intermediate values ​​of each of the above values, and upper and lower limits of the numerical range.

[0050] The above injection method is not significantly limited as long as it allows for obtaining particulate MoO2Cl2 by spraying liquid MoO2Cl2, but, for example, it may be a spray injection, and specifically, the injection part may include a spray nozzle, an orifice, or a combination thereof.

[0051] The temperature of the recovery unit is not specifically limited as long as it is a temperature below the temperature at which liquid MoO2Cl2 solidifies outside after spraying, but, for example, it may be 0°C or higher, or 10°C or higher, or 20°C or higher, or 30°C or higher, or 150°C or lower, or 100°C or lower, or 50°C or lower, or an intermediate value of each of the above values. Considering economics and ease of operation, it may be 20 to 50°C, 20 to 40°C, or 20 to 30°C, specifically room temperature, through which particulate MoO2Cl2 in the form of solid powder can be obtained. In addition, the pressure of the recovery unit may be the same as the pressure of the spraying unit, or 2 atmospheres or less, or 1 atmosphere or less, specifically 1 atmosphere to 3 atmospheres, or 1 to 2 atmospheres.

[0052] The average particle size of the above-mentioned particulate MoO2Cl2 may include 10 μm to 10,000 μm, or 50 μm to 10,000 μm, or 50 μm to 5,000 μm, or 50 μm to 1,000 μm, or 100 μm to 1,000 μm, or 200 μm to 500 μm, or intermediate values ​​of each of the above values, or all possible combinations of the upper and lower limits of the above numerical ranges, thereby increasing the density of the product and preventing contamination by dust or loss during the transport process. In addition, when applying the above-mentioned product to a thin film deposition process, it may have advantages such as preventing contamination of the deposition equipment and increasing the smoothness of the surface of the thin film being manufactured.

[0053] A method for manufacturing MoO2Cl2 according to one embodiment can provide high-purity MoO2Cl2 of a certain quality, for example, 95% or more, or 98% or more, or 99% or more, or 99.999% or more, by satisfying the above composition, and can be usefully applied as a precursor in semiconductor processes sensitive to purity.

[0054] MoO2Cl2 produced by the above manufacturing method according to one embodiment may be used as a precursor for metal wiring deposition in a semiconductor process, and in particular, the MoO2Cl2 may be used as a deposition precursor for next-generation ultra-fine semiconductor wiring processes, such as metal wiring of NAND flash memory, bit lines and word lines of DRAM of 10 nm or less, and ultra-fine circuit wiring of system semiconductors.

[0055] The above-described embodiment will be explained in more detail below through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the claims.

[0056] [시시예 1]

[0057] Molybdenum dioxide (MoO2) powder was filled into a stirred-type reactor (10) to a volume of 50% relative to the reactor, and a carrier gas (Ar / N2) was introduced into the reactor. The temperatures of the manufacturing apparatus were set to 200°C for the reactor (10), 210°C for the transfer section (20), and 80°C for the condensation section (40). After the temperature increase was completed, chlorine (Cl2) gas was dispersed into the reactor through a porous distribution plate (110) containing pores of 10 μm to 1,000 μm in size, and the reaction was carried out under stirring while maintaining the pressure of the reactor at 1 atmosphere to synthesize gaseous MoO2Cl2. The above-mentioned gaseous MoO2Cl2 was transferred to a condensation section after removing unreacted particles and impurities through a transfer section equipped with a sintering filter (30) with 0.1 μm pores, and the gaseous MoO2Cl2 product was solidified and precipitated on the surface of the condensation section to collect solid MoO2Cl2.

[0058] In order to liquefy the solid MoO2Cl2 product precipitated in the above condensation unit, the condensation unit was changed to a closed system state and the interior was maintained in a nitrogen gas atmosphere. The solid MoO2Cl2 was melted in a 200°C atmosphere to obtain liquid MoO2Cl2, and then sprayed through the injection unit (50) to a recovery unit (60) at room temperature pressurized to 1 atmosphere while maintaining 3 atmospheres, so that the MoO2Cl2 was rapidly cooled and solidified to obtain powdered particulate MoO2Cl2 with a yield of 97%.

[0059] The average particle size (D50) of the manufactured particulate MoO2Cl2 was 100 μm as a result of PSA analysis, and the impurity was less than 4,460 ppb as a result of ICP-MS analysis in Table 1 below, confirming that it is possible to manufacture high-purity MoO2Cl2 with a purity of 99.9995% or higher. Additionally, it was confirmed that MoO2Cl2 of consistent quality can be manufactured by repeating the manufacturing method according to Example 1 above. In other words, it can be seen that high-quality MoO2Cl2 can be manufactured with a high yield through the manufacturing method according to one embodiment of the present invention, and that the quality variation of the product can be minimized.

[0060] In addition, the manufacturing method according to one embodiment provides particulate MoO2Cl2 in the form of a solid powder, which facilitates the recovery, quality control, and transportation of the product and can significantly improve productivity.

[0061] ICP-MS(ppb) Ag <50 Mg <100 Al <200 Mn <20 As <50 With <200 Oh! <500 It is <50 B <20 Pb <20 They <50 Pt <20 Be <20 Rb <20 Yes <20 Yes <20 Yes <200 Rh <20 CD <100 Ru <200 What? <100 Saturday <20 Cr <100 Father <20 Cs <20 Sn <100 Cu <50 Sr <20 Fe <500 No <200 Yes <20 No <200 Ge <20 Th <20 Hf <200 U <20 In <200 V <100 Ir <20 W <50 K <200 Zn <100 Here <200 Zr <100

[0062] [비교예 1]

[0063] The above Example 1 was carried out in the same manner, except that a reactor without a porous distribution plate was used. Although the reaction was performed for the same amount of time as in Example 1, particulate MoO2Cl2 was obtained with a yield of 71%, and the reaction efficiency was significantly reduced compared to Example 1 due to the large amount of unreacted MoO2 raw material remaining. In addition, it was confirmed that when the manufacturing method was repeated, the yield fluctuated significantly and changes in quality were caused.

[0064] As described above, the present disclosure has been explained by specific details and limited embodiments, but this is provided only to aid in a more comprehensive understanding of the present disclosure. The present disclosure is not limited to the above embodiments, and various modifications and variations are possible from this description by those skilled in the art to which the present disclosure pertains.

[0065] Accordingly, the present disclosure is not limited to the embodiments described above, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to be within the scope of the present disclosure. Explanation of the symbols

[0066] 10: Reactor 20: Transfer section 30: Filter 40: Condenser 50: Spray part 60: Recovery unit 110: Porous distribution plate 120: Gas inlet pipe

Claims

Claim 1 A method for producing MoO2Cl2, comprising: a step of dispersing chlorine gas into a reactor through a porous distribution plate and reacting it with molybdenum oxide particles to produce gaseous MoO2Cl2; a step of transferring the gaseous MoO2Cl2 to a condensation section to precipitate solid MoO2Cl2; and a step of melting the solid MoO2Cl2 in a closed system to obtain liquid MoO2Cl2, and high-pressure spraying the liquid MoO2Cl2 to obtain particulate MoO2Cl2. Claim 2 A method for manufacturing MoO2Cl2 according to claim 1, wherein the porous distribution plate comprises pores of 0.01 μm to 1,000 μm. Claim 3 A method for producing MoO2Cl2 according to claim 1, wherein the reaction is performed while stirring molybdenum oxide particles. Claim 4 delete Claim 5 A method for manufacturing MoO2Cl2 according to claim 1, wherein the melting is performed at 180 to 300 ℃. Claim 6 A method for manufacturing MoO2Cl2 according to claim 1, wherein the high-pressure injection is performed by injecting through an injection section into a recovery section under a pressure of 2 to 50 atmospheres. Claim 7 A method for producing MoO2Cl2 according to claim 6, wherein the pressure of the recovery unit is atmospheric pressure to 3 atmospheres. Claim 8 A method for manufacturing MoO2Cl2 according to claim 6, wherein the temperature of the recovery section is 20 to 40 ℃. Claim 9 A method for manufacturing MoO2Cl2 according to claim 1, wherein the average particle size of the particulate MoO2Cl2 is 50 μm to 1,000 μm. Claim 10 A method for manufacturing MoO2Cl2 according to claim 1, wherein the above-mentioned gaseous MoO2Cl2 is transferred to a condensation unit through a transfer unit including a filter. Claim 11 A method for manufacturing MoO2Cl2 according to claim 10, wherein the filter comprises pores of 0.001 μm to 0.1 μm. Claim 12 A method for producing particulate MoO2Cl2 according to claim 1, wherein the reaction is performed at 100 ℃ to 700 ℃. Claim 13 A method for producing particulate MoO2Cl2 according to claim 1, wherein the precipitation is performed at -20 ℃ to 150 ℃. Claim 14 A semiconductor process metal wiring manufactured by depositing particulate MoO2Cl2 manufactured by a manufacturing method according to any one of claims 1 to 3 and claims 5 to 13. Claim 15 In claim 14, the semiconductor process metal wiring is any one selected from the metal wiring of a NAND flash memory, the bit line and word line of a 10 nm class or smaller DRAM, and the ultra-fine circuit wiring of a system semiconductor.

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