Manufacturing apparatus of particulate MoO2Cl2

Abstract

The present invention relates to a particulate MoO2Cl2 manufacturing apparatus. According to one embodiment of the manufacturing apparatus, particulate MoO2Cl2 in the form of 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 particulate MoO2Cl2 manufacturing apparatus. 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, these conventional methods require additional equipment and labor to separate and recover the precipitated solid product, which leads to reduced production efficiency. Meanwhile, US 20240239684 A1 proposes a method to increase the purity and bulk density of the product by melting and filtering MoO2Cl2; however, even in this case, MoO2Cl2 is formed in a crystalline form, making separation and recovery difficult, and it has the disadvantage of insufficient performance as a deposition precursor due to insufficient vaporization characteristics. Furthermore, because gas dispersion is non-uniform and contact between solid and gaseous raw materials is not smooth, the purity and yield of the product are reduced, and quality variability occurs. These problems are exacerbated when the reaction scale is increased, making it unsuitable for scale-up, thus requiring a new manufacturing process. The problem to be solved

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

[0008] One aspect of the present invention provides a particulate MoO2Cl2 manufacturing apparatus comprising: a spraying unit that sprays liquid MoO2Cl2 at high pressure; and a recovery unit that cools the sprayed liquid MoO2Cl2 to granulate it and obtain particulate MoO2Cl2.

[0009] The average particle size of the above particulate MoO2Cl2 may be 50 μm to 1,000 μm.

[0010] According to one embodiment, the particulate MoO2Cl2 manufacturing apparatus may further comprise: a reactor in which a reaction between molybdenum oxide particles and chlorine gas is performed and gaseous MoO2Cl2 is produced; a transfer section connected to the upper part of the reactor and in which gaseous MoO2Cl2 discharged from the reactor is transferred; and a condensation section connected to the rear end of the transfer section and in which the transferred gaseous MoO2Cl2 is precipitated as a solid.

[0011] The above condensation unit can be changed to a closed system, and the solid MoO2Cl2 precipitated in the closed system condensation unit may be melted to produce liquid MoO2Cl2.

[0012] The above reactor may include a porous distribution plate.

[0013] The porous distribution plate may include pores ranging from 0.01 μm to 1,000 μm.

[0014] The above reactor includes a gas inlet pipe at the bottom and may include an empty space between the gas inlet pipe and the porous distribution plate.

[0015] The above reactor may be an impeller-stirred type reactor.

[0016] The above transfer unit may include a filter.

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

[0018] A MoO2Cl2 manufacturing apparatus according to one embodiment of the present invention can provide particulate MoO2Cl2 in the form of solid powder through melting and high-pressure spraying technology, can uniformly control particle size, facilitate the recovery and transportation of the product, and improve productivity.

[0019] In addition, the MoO2Cl2 manufacturing apparatus according to one embodiment can improve reaction efficiency by maximizing the contact area with the solid raw material, molybdenum oxide. Furthermore, since the gas flow is not concentrated locally, it can prevent the occurrence of localized over-reaction or unreacted regions, and the reaction conditions can be maintained homogeneously throughout the reaction.

[0020] 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

[0021] 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

[0022] 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.

[0023] The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] One aspect of the present invention provides an apparatus for producing high-quality particulate MoO2Cl2 with a high yield.

[0029] Specifically, a particulate MoO2Cl2 manufacturing apparatus according to one embodiment may include: a spraying unit that sprays liquid MoO2Cl2 at high pressure; and a recovery unit that cools the sprayed liquid MoO2Cl2 to granulate it and obtain particulate MoO2Cl2.

[0030] A manufacturing apparatus according to one embodiment is equipped with a spraying unit that sprays liquid MoO2Cl2 at high pressure, thereby enabling the provision of MoO2Cl2 in the form of a solid powder with high bulk density, which can provide advantages in recovery, transport, and storage. Furthermore, when applied to a molybdenum thin film deposition process, the particulate MoO2Cl2 facilitates easy transport into the deposition equipment, prevents contamination of the deposition equipment, and provides a highly uniform thin film surface without the influence of fine particles, thus offering various advantages in application.

[0031] 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.

[0032] The above-mentioned spraying unit may include a spray nozzle, an orifice, or a combination thereof.

[0033] In one embodiment, the pressure of the high-pressure injection is not specifically limited, but may be, for example, 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.

[0034] In one embodiment, the temperature of the recovery unit is not particularly limited as long as it is below the temperature at which the liquid MoO2Cl2 is cooled and granulated 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, and considering economics and work convenience, it may be 20 to 50°C, 20 to 40°C, or 20 to 30°C, specifically room temperature, thereby obtaining particulate MoO2Cl2 in the form of solid powder. 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.

[0035] According to one embodiment, the particulate MoO2Cl2 manufacturing apparatus may further comprise: a reactor in which a reaction between molybdenum oxide particles and chlorine gas is performed and gaseous MoO2Cl2 is produced; a transfer section connected to the upper part of the reactor and in which gaseous MoO2Cl2 discharged from the reactor is transferred; and a condensation section connected to the rear end of the transfer section and in which the transferred gaseous MoO2Cl2 is precipitated as a solid.

[0036] The above condensation unit can be changed to a closed system, and by raising the temperature of the condensation unit in the closed system, the precipitated solid MoO2Cl2 may melt to produce liquid MoO2Cl2, and when the temperature of the condensation unit in an open system is raised, MoO2Cl2 Liquid MoO2Cl2 cannot be obtained because it is lost through vaporization.

[0037] In one embodiment, 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 numerical range.

[0038] The above reactor may be an impeller-stirred type reactor, which facilitates smoother contact between raw materials regardless of the reaction scale, further improves reaction efficiency, and is more advantageous for mass production application.

[0039] The above reactor may include a porous distribution plate, and in this case, chlorine gas may be introduced into the reactor through the porous distribution plate. In this case, the reaction efficiency can be further improved by making the dispersion of gas within the reactor uniform and facilitating the contact area between raw materials.

[0040] The reactor may include a gas inlet pipe at the bottom and a void space between the gas inlet pipe and a porous distribution plate, and an appropriate pressure is 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.

[0041] 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 gas inlet 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.

[0042] The above transfer unit may include a filter, and impurities can be removed by the filter to obtain a product with superior purity, and the reaction efficiency and the purity of the product can also 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] In one embodiment, the molybdenum oxide may be molybdenum dioxide (MoO-2), and the reaction may be carried out under lower temperature conditions.

[0045] In one embodiment, the reaction temperature between the molybdenum oxide particles and the 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, upper limits and lower limits of the numerical range.

[0046] In one embodiment, the temperature of the 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.

[0047] In one embodiment, the 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 numerical range.

[0048] In addition, the MoO2Cl2 manufacturing apparatus according to one embodiment can provide high-purity MoO2Cl2 of 95% or more, 98% or more, 99% or more, or 99.999% or more with a certain quality, and can be usefully applied as a precursor in semiconductor processes sensitive to purity. The MoO2Cl2 produced from the manufacturing apparatus according to one embodiment may be used as a precursor for metal wiring deposition in semiconductor processes, and in particular, the MoO2Cl2 may be used as a deposition precursor for next-generation ultra-fine semiconductor wiring processes, such as metal wiring in NAND flash memory, bit lines and word lines in 10 nm class or smaller DRAM, and ultra-fine circuit wiring in system semiconductors.

[0049] 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.

[0050] [시시예 1]

[0051] 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.

[0052] 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%.

[0053] 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.

[0054] 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.

[0055] 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

[0056] 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.

[0057] 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

[0058] 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 particulate MoO2Cl2 manufacturing apparatus comprising: a reactor in which a reaction between molybdenum oxide particles and chlorine gas is performed to produce gaseous MoO2Cl2; a transfer section connected to the upper part of the reactor and in which gaseous MoO2Cl2 discharged from the reactor is transferred; a condensation section connected to the rear end of the transfer section, in which the transferred gaseous MoO2Cl2 is precipitated as a solid and the solid MoO2Cl2 is melted to produce liquid MoO2Cl2; a spraying section for high-pressure spraying of liquid MoO2Cl2; and a recovery section for cooling the sprayed liquid MoO2Cl2 to granulate it to obtain particulate MoO2Cl2; wherein the condensation section can be changed to a closed system, and the precipitated solid MoO2Cl2 is melted in the closed system condensation section to produce liquid MoO2Cl2. Claim 2 A particulate MoO2Cl2 manufacturing apparatus according to claim 1, wherein the average particle size of the particulate MoO2Cl2 is 50 μm to 1,000 μm. Claim 3 delete Claim 4 delete Claim 5 A particulate MoO2Cl2 manufacturing apparatus according to claim 1, wherein the reactor comprises a porous distribution plate. Claim 6 A particulate MoO2Cl2 manufacturing apparatus according to claim 5, wherein the porous distribution plate comprises pores of 0.01 μm to 1,000 μm. Claim 7 A particulate MoO2Cl2 manufacturing apparatus according to claim 5, wherein the reactor includes a gas inlet pipe at the bottom and includes an empty space between the gas inlet pipe and a porous distribution plate. Claim 8 In claim 1, the above reactor is an impeller-stirred type reactor, a particulate MoO2Cl2 manufacturing apparatus. Claim 9 A particulate MoO2Cl2 manufacturing apparatus according to claim 1, wherein the transfer unit includes a filter. Claim 10 A particulate MoO2Cl2 manufacturing apparatus according to claim 9, wherein the filter comprises pores of 0.001 μm to 0.1 μm.

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