Preparation method of MoO2Cl2

Abstract

The present invention relates to a method for manufacturing MoO2Cl2. According to one embodiment of the manufacturing method, high-quality MoO2Cl2 can be manufactured with a high yield, and variations in product quality and loss of raw materials can be minimized.

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 a major molybdenum precursor. However, conventional methods for manufacturing MoO2Cl2 involve reacting solid molybdenum raw materials with chlorine gas. This method suffers from problems such as reduced reactivity due to uneven gas dispersion, localized over-reaction, and excessive consumption of chlorine gas. Furthermore, poor contact between the solid and gaseous raw materials results in low reaction efficiency, reduced product purity and yield, and quality variability. These issues are exacerbated when the reaction scale is increased, making the process unsuitable for scale-up and thus requiring a new manufacturing process. The problem to be solved

[0006] One aspect of the present invention provides a manufacturing method capable of providing high-quality MoO2Cl2 in high yield through a simplified process.

[0007] 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

[0008] One aspect of the present invention provides a method for producing MoO2Cl2, comprising: a reaction step of producing gaseous MoO2Cl2 by reacting molybdenum oxide particles with chlorine gas in a reactor; and a collection step of collecting solid MoO2Cl2 by transferring the gaseous MoO2Cl2 to a condensation unit, wherein the chlorine gas is dispersed and introduced into the reactor through a porous distribution plate.

[0009] The porous distribution plate may include pores ranging from 0.01 μm to 1,000 μm.

[0010] According to one embodiment, the method for producing the above MoO2Cl2 may involve carrying out the reaction while stirring the molybdenum oxide particles.

[0011] The above reactor may be an impeller-stirred type reactor.

[0012] The above-mentioned gaseous MoO2Cl2 may be transferred to a condensation unit through a transfer unit including a filter.

[0013] The above filter may include pores of 0.001 μm to 0.1 μm.

[0014] The above capture step may further include a step of recirculating unreacted chlorine gas to the reactor.

[0015] The above molybdenum oxide may be molybdenum dioxide.

[0016] The average particle size of the molybdenum oxide particles may be 1,000 μm to 5,000 μm.

[0017] The temperature of the reactor above may be 100 ℃ to 700 ℃.

[0018] The temperature of the above condensation section may be -20 ℃ to 150 ℃.

[0019] The temperature of the above transfer unit may be 100 ℃ to 700 ℃.

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

[0021] According to one embodiment, the semiconductor process metal wiring may be 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. Effects of the invention

[0022] According to a method for producing MoO2Cl2 according to one embodiment of the present invention, reactivity can be maximized and a high-quality product can be provided, and the variation in product quality can be minimized.

[0023] Specifically, the 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. Furthermore, the manufacturing method according to one embodiment can produce high-purity MoO2Cl2 without a separate purification process, thereby improving productivity. It can be usefully applied as a precursor in purity-sensitive semiconductor processes and, in particular, can be effectively utilized as a metal wiring material for next-generation memory devices that require high purity.

[0024] In addition, the manufacturing method according to one embodiment can ensure the reproducibility of reaction conditions even when scaled up to an industrial scale, and can simultaneously achieve improved productivity and environmental friendliness by maximizing reaction efficiency to reduce unreacted materials and recycling unreacted gases to minimize raw material consumption. Brief explanation of the drawing

[0025] Figure 1 is a schematic diagram of a reactor of a manufacturing apparatus used in one embodiment. FIG. 2 is a schematic diagram showing an enlarged view of the bottom of the reactor used in one embodiment. Figure 3 is ICP-MS data of MoO2Cl2 prepared in one embodiment. Specific details for implementing the invention

[0026] Unless otherwise defined in this invention, all technical and scientific terms have the same meaning as generally understood by those skilled in the art to which this invention pertains. The terms used in the description of this invention are merely for the purpose of effectively describing specific embodiments and are not intended to limit the invention.

[0027] The singular form used in the present invention may be intended to include the plural form unless specifically indicated in the context.

[0028] Throughout the invention, the terms “comprising,” “having,” “containing,” or “having” any component mean that, unless specifically stated otherwise, other components are not excluded but may be additionally included, and do not exclude elements, materials, or processes not additionally listed.

[0029] The numerical range used in the present invention includes lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the defined range, all of the specified values, and all possible combinations of upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in the present invention, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0030] Unless otherwise specifically defined in the present invention, "about" may be considered to be a value within 30%, 25%, 20%, 15%, 10%, or 5% of the specified value.

[0031] 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.

[0032] In conventional technology for the production of MoO2Cl2, problems such as reduced reaction efficiency, localized reactions, decreased product purity and yield, and quality variability were inevitable due to the uneven dispersion of chlorine gas and poor contact between solid and gaseous raw materials. Although various attempts were made to overcome these limitations, such as the introduction of rotary kiln reactors, the improvement in reaction efficiency remained limited. Furthermore, challenges remained for commercial application, including excessive energy consumption and the requirement for additional purification processes.

[0033] One aspect of the present invention provides a method for manufacturing MoO2Cl2 that can produce high-quality MoO2Cl2 in a high yield through a simplified manufacturing process, and can minimize product quality variation and raw material loss.

[0034] Specifically, a manufacturing method according to one embodiment comprises: a reaction step of producing gaseous MoO2Cl2 by reacting molybdenum oxide particles with chlorine gas in a reactor; and a collection step of collecting solid MoO2Cl2 by transferring the gaseous MoO2Cl2 to a condensation unit, wherein the chlorine gas is dispersed and introduced into the reactor through a porous distribution plate.

[0035] A manufacturing method according to one embodiment solves the problems of the aforementioned prior art. By dispersing chlorine gas into the reactor through the pores of a porous distribution plate, the contact area with the solid raw material, molybdenum oxide, is maximized, thereby improving reaction efficiency. Furthermore, reaction conditions are maintained uniformly throughout the reaction, enabling the provision of high-purity MoO2Cl2 with consistent quality.

[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 (11) and the chlorine gas introduction pipe (12) 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 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 the reaction efficiency and product purity can be further improved.

[0040] 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.

[0041] The above capture step may further include a step of recirculating unreacted chlorine gas to the reactor, which can further improve productivity.

[0042] The average particle size of the molybdenum oxide particles above may be 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.

[0043] The above molybdenum oxide may be molybdenum dioxide (MoO2), and the reaction can be carried out under lower temperature conditions.

[0044] The temperature of the reactor 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, upper limits and lower limits of the numerical range.

[0045] 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, for example, it may be 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, and may include all possible combinations of intermediate values ​​of each of the above values, and upper and lower limits of the numerical range.

[0046] The temperature of the condensation section is not significantly limited as long as it is a temperature at which gaseous MoO2Cl2 can be precipitated, but for example, it may be -20 ℃ to 150 ℃, or -20 ℃ to 130 ℃, or 0 ℃ to 100 ℃, or 50 ℃ to 150 ℃, or 50 ℃ to 100 ℃, 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.

[0047] 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.

[0048] 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.

[0049] In addition, a method for manufacturing MoO2Cl2 according to one embodiment may further include: a melting step in which the solid MoO2Cl2 is melted to obtain liquid MoO2Cl2 after a collection step in which the gaseous MoO2Cl2 is transferred to a condensation unit to collect solid MoO2Cl2; and a granulation step in which the liquid MoO2Cl2 is sprayed at high pressure to obtain particulate MoO2Cl2.

[0050] For example, a method for producing MoO2Cl2 according to one embodiment may comprise: a reaction step of producing gaseous MoO2Cl2 by reacting molybdenum oxide particles with chlorine gas in a reactor; a collection step of collecting solid MoO2Cl2 by transferring the gaseous MoO2Cl2 to a condenser; a melting step of obtaining liquid MoO2Cl2 by melting the obtained solid MoO2Cl2 after changing the condenser to a closed system; and a granulation step of obtaining particulate MoO2Cl2 by high-pressure spraying the liquid MoO2Cl2.

[0051] The above melting step may be performed by containing MoO2Cl2 in a closed system and then melting it. If the melting step is performed in an open system, it is converted to a closed system to liquefy it, as it is lost due to vaporization.

[0052] The melting step may be performed under a nitrogen atmosphere, and 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 ℃ or higher, or 190 ℃ or higher, or 200 ℃ or higher, or 300 ℃ or lower, or 250 ℃ or lower, or 220 ℃ or lower, and specifically, it may be 180 ℃ to 300 ℃, or 180 ℃ to 250 ℃, or 190 ℃ to 250 ℃, or 200 ℃.

[0053] By pressurizing the inside of the injection section combined with the melting vessel (condensation section) using an inert gas heated to the same temperature, the liquid MoO2Cl2 may be sprayed into the recovery section and atomized.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] [Example 1]

[0059] 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, 210°C for the transfer section, and 80°C for the condensation section. After the temperature increase was completed, chlorine (Cl2) gas was dispersed into the reactor through a porous distribution plate (11) 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 obtained gaseous MoO2Cl2 was transferred to the condensation section after removing unreacted particles and impurities through a transfer section equipped with a sintered filter 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.

[0060] In order to liquefy the solid MoO2Cl2 product precipitated in the above condensation section, the condensation section 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 section to a recovery section at room temperature pressurized to 1 atmosphere while maintaining 3 atmospheres of pressure, so that the MoO2Cl2 was rapidly cooled and solidified to obtain particulate MoO2Cl2 with a yield of 97%.

[0061] 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 Fig. 3, 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. 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.

[0062] [Comparative Example 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 11: Porous distribution board 12: Chlorine gas inlet pipe

Claims

Claim 1 A method for producing MoO2Cl2, comprising: a reaction step of producing gaseous MoO2Cl2 by reacting molybdenum oxide particles with chlorine gas in a reactor; and a collection step of collecting solid MoO2Cl2 by transferring the gaseous MoO2Cl2 to a condensation section, wherein the chlorine gas is dispersed and introduced into the reactor through a porous distribution plate, and a void space is provided between the porous distribution plate and the chlorine gas inlet pipe. 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 the molybdenum oxide particles. Claim 4 A method for producing MoO2Cl2 according to claim 1, wherein the reactor is an impeller-stirred type reactor. Claim 5 A method for manufacturing MoO2Cl2 according to claim 1, wherein the manufactured gaseous MoO2Cl2 is transferred to a condensation unit through a transfer unit including a filter. Claim 6 A method for manufacturing MoO2Cl2 according to claim 5, wherein the filter comprises pores of 0.001 μm to 0.1 μm. Claim 7 A method for producing MoO2Cl2 according to claim 1, further comprising a step of recirculating unreacted chlorine gas from the capture step to a reactor. Claim 8 A method for manufacturing MoO2Cl2, wherein the molybdenum oxide in claim 1 is molybdenum dioxide. Claim 9 A method for manufacturing MoO2Cl2 according to claim 1, wherein the average particle size of the molybdenum oxide particles is 1,000 μm to 5,000 μm. Claim 10 A method for producing MoO2Cl2 according to claim 1, wherein the temperature of the reactor is 100 ℃ to 700 ℃. Claim 11 A method for manufacturing MoO2Cl2 according to claim 1, wherein the temperature of the condensation section is -20 ℃ to 150 ℃. Claim 12 A method for manufacturing MoO2Cl2 according to claim 5, wherein the temperature of the transfer section is 100 ℃ to 700 ℃. Claim 13 A semiconductor process metal wiring manufactured by depositing MoO2Cl2 manufactured by a manufacturing method according to any one of claims 1 to 12. Claim 14 In claim 13, 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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