Apparatus and method for producing molybdenum oxyhalide

Abstract

An apparatus for producing molybdenum oxyhalide according to one aspect of the present invention comprises a reaction zone to which a halogen-containing gas is supplied, wherein a raw material containing molybdenum oxide is transferred so as to pass through the reaction zone, and molybdenum oxyhalide is produced.

Description

Molybdenum oxyhalide manufacturing apparatus and method

[0001] The present disclosure relates to a device and method for producing molybdenum oxyhalide, and to a device and method capable of mass-producing molybdenum oxyhalide.

[0002] Tungsten, with its excellent thermal stability and low specific electrical resistance, is used as a wiring material in memory semiconductors. However, tungsten, used as a wiring material for 8th-generation and higher transistors, suffers from a significant increase in contact resistance when transistor circuit line widths fall below 5 nm. Consequently, molybdenum (Mo) is emerging as a next-generation material to replace tungsten.

[0003] Molybdenum (Mo) has a low bulk resistivity × mean free path value, which enables a reduction in vertical pitch in VSD (Vertical Stack Down) and enables a transition to a device structure without a barrier or adhesive layer.

[0004] In order to form molybdenum wiring through a deposition process such as atomic layer deposition or vapor phase chemical deposition, the development of a molybdenum precursor that satisfies deposition characteristics such as deposition uniformity, step coverage, and gapfill characteristics must be prioritized.

[0005] Currently, molybdenum oxyhalide is attracting attention as a molybdenum precursor that satisfies the deposition characteristics required for semiconductor wiring.

[0006] Molybdenum oxyhalides such as MoO2Cl2 and MoOCl4 can be synthesized by heating molybdenum oxide by contacting it with a halogen gas (e.g., Cl2), and high-purity molybdenum precursors are manufactured by purifying the synthesized molybdenum oxyhalides.

[0007] For molybdenum wiring to be commercially utilized in high-density memory semiconductors such as 3D NAND, mass production technology for high-purity molybdenum oxyhalide must be established, but so far, batch production of molybdenum oxyhalide is limited.

[0008] One aspect of the present disclosure is to provide a manufacturing device and method capable of mass-producing high-purity molybdenum oxyhalide.

[0009] The objectives of the present invention are not limited to the above-described content. Those skilled in the art will have no difficulty understanding the additional objectives of the present invention from the overall description of the present invention.

[0010] A molybdenum oxyhalide manufacturing device according to one aspect includes a reaction zone into which a halogen-containing gas is supplied, a raw material including molybdenum oxide is transported through the reaction zone, and molybdenum oxyhalide is produced.

[0011] In a manufacturing device according to one specific example, the raw material can be continuously transported.

[0012] In a manufacturing device according to one specific example, the average transport speed of the raw material passing through the reaction zone may be 0.01 m / hr to 10.0 m / hr.

[0013] In a manufacturing device according to one specific example, at least one energy selected from the group consisting of thermal energy, light energy, and vibration energy can be applied to the reaction zone.

[0014] A manufacturing device according to one specific example may include a case providing an internal space including the reaction zone and an energy application unit that applies energy to the reaction zone.

[0015] A manufacturing device according to one specific example may include a transport means for transporting the raw material so as to pass through the reaction zone.

[0016] In a manufacturing device according to one specific example, the transport means may include a transport shaft having a transport blade and being rotatable, or may include a belt that moves in a designed direction.

[0017] In a manufacturing device according to one specific example, the material of the case may be a non-metallic inorganic material of crystalline, amorphous, or a composite phase in which crystalline and amorphous materials are mixed.

[0018] In a manufacturing device according to one specific example, a baffle for preventing gas backflow may be provided in the internal space in front of the inflow point where the halogen-containing gas is introduced based on the direction of transport of the raw material.

[0019] A manufacturing device according to one specific example may further include a first gas supply unit including a first gas bomb storing a halogen gas and a first moisture absorber, and a second gas supply unit including a second gas bomb storing an inert gas and a second moisture absorber.

[0020] A manufacturing device according to one specific example may further include a gas purifier that removes moisture from a halogen-containing gas including a halogen gas supplied from the first gas supply unit and an inert gas supplied from the second gas supply unit.

[0021] A manufacturing device according to one specific example may further include a residue storage unit that receives and stores a residual solid phase discharged from the reaction unit, and a residue heating unit that heats the residue storage unit.

[0022] A manufacturing device according to one specific example may further include a capturing unit that receives the gaseous molybdenum oxyhalide and captures it in a solid state.

[0023] A manufacturing device according to one specific example may further include a heating unit that heats a wall surface that comes into contact with the gaseous molybdenum oxyhalide discharged from the reaction zone and defines a space used for transporting or storing the gaseous molybdenum oxyhalide.

[0024] A molybdenum oxyhalide manufacturing device according to one aspect comprises: a raw material supply unit for supplying a raw material including molybdenum oxide; a reaction zone in which a halogen-containing gas is supplied and energy is applied, and the raw material supplied from the raw material supply unit is transported to pass through the reaction zone, and molybdenum oxyhalide is generated; a capturing unit for receiving gaseous molybdenum oxyhalide discharged from the reaction transfer unit and capturing it in a solid phase; a purification unit for receiving solid molybdenum oxyhalide captured in the capturing unit and sublimating it into a gas; and a solidification unit for receiving the sublimated molybdenum oxyhalide and solidifying it.

[0025] A manufacturing device according to one specific example may further include a raw material heating unit for heating the raw material in the raw material supply unit.

[0026] A manufacturing device according to one specific example may further include a line heating unit for heating at least one line selected from the group consisting of a first line, which is a transfer line between an outlet through which gaseous molybdenum oxyhalide is discharged from the reaction transfer unit and an inlet through which the gaseous phase is introduced from the capture unit, a second line, which is a transfer line between an outlet through which sublimated molybdenum oxyhalide is discharged from the purification unit and an inlet through which the sublimated molybdenum oxyhalide is introduced from the solidification unit, and a third line, which is a transfer line between a solid phase outlet through which a residual solid phase of the reaction transfer unit is discharged and a solid phase inlet of a residue storage unit for receiving and storing the residual solid phase.

[0027] A manufacturing device according to one specific example may further include a tablet transfer unit that transfers the solid phase captured in the capturing unit to the refining unit, and a transfer heating unit that heats the tablet transfer unit.

[0028] In a manufacturing device according to one specific example, the solidification unit may include a solidification body having an internal space and an inlet formed at an upper portion through which sublimated molybdenum oxyhalide flows, a cooling plate accommodated in the solidification body and cooling the sublimated molybdenum oxyhalide, and a solidification heating unit that heats at least the upper portion of the solidification body having the inlet formed therein.

[0029] A manufacturing device according to one specific example may further include at least a housing providing an internal space in which the raw material supply unit, the reaction transfer unit, the capture unit, the purification unit, and the solidification unit are located, and a moisture removal unit for removing moisture from the atmosphere within the housing.

[0030] A method for producing molybdenum oxyhalide according to one aspect is as follows: a raw material including molybdenum oxide passes through a reaction zone, a halogen-containing gas is supplied to the reaction zone, and molybdenum oxyhalide is produced.

[0031] In a manufacturing method according to one specific example, the raw material can flow and pass through the reaction zone.

[0032] In a manufacturing method according to one specific example, the average transport speed of the raw material transported through the reaction zone may be 0.01 m / hr to 10.0 m / hr.

[0033] In a manufacturing method according to one specific example, at least one energy selected from the group consisting of thermal energy, light energy, and vibration energy can be applied to the reaction zone.

[0034] In a manufacturing method according to one specific example, the raw material may be in a state in which moisture has been removed in advance before being supplied to the reaction zone.

[0035] In a manufacturing method according to one specific example, the halogen-containing gas is a mixed gas of a halogen gas and an inert gas, and the mixed gas may be in a state in which moisture has been removed in advance before being supplied to the reaction zone.

[0036] In a manufacturing method according to one specific example, the temperature of the reaction zone may be 190 to 350°C.

[0037] In a manufacturing method according to one specific example, the time required for the raw material to pass through the reaction zone may be 10 to 600 minutes.

[0038] In a manufacturing method according to one specific example, the halogen-containing gas may be supplied to the reaction zone so that the number of moles of halogen atoms required to produce 1 mole of the molybdenum oxyhalide according to the stoichiometric ratio of the molybdenum oxyhalide is set as a reference mole number, and 1 to 10 times the reference mole number of halogen elements is supplied.

[0039] In a manufacturing method according to one specific example, a step of cooling the generated gaseous molybdenum oxyhalide and capturing it in a solid phase may be further performed.

[0040] In a manufacturing method according to one specific example, the supply of the raw material to the reaction zone and the capture into the solid phase can be performed simultaneously.

[0041] In a manufacturing method according to one specific example, a wall defining a space used for transporting the gaseous molybdenum oxyhalide discharged from the reaction zone may be heated.

[0042] A method for producing molybdenum oxyhalide according to one embodiment comprises the steps of S1) transporting a raw material including molybdenum oxide through a reaction zone where a halogen-containing gas is supplied and energy is applied, thereby generating molybdenum oxyhalide; S2) receiving and cooling the gaseous molybdenum oxyhalide generated in step S1) to capture the molybdenum oxyhalide in a solid phase; S3) sublimating the captured solid molybdenum oxyhalide into a gas; and S4) solidifying the sublimated molybdenum oxyhalide.

[0043] In a manufacturing method according to one specific example, in step S1), the raw material may be continuously supplied to the reaction zone, and in step S2), the gaseous molybdenum oxyhalide may be continuously captured.

[0044] In a manufacturing method according to one specific example, at least one wall surface selected from the group consisting of a wall surface that defines a space used for transporting the gaseous molybdenum oxyhalide discharged from the reaction zone and a wall surface that defines a space used for transporting the molybdenum oxyhalide sublimated in step S3) may be heated.

[0045] In a manufacturing method according to one specific example, the molybdenum oxyhalide captured in the solid phase may be heated when transferred to a purification unit where the sublimation of the S3) step is performed.

[0046] In a manufacturing method according to one specific example, the space where steps S1) to S4) are performed may be located under an atmosphere from which moisture has been removed.

[0047] In a manufacturing method according to one specific example, the halogen-containing gas may be a chlorine-containing gas, and the molybdenum oxyhalide may be molybdenum dioxydichloride.

[0048] In a manufacturing method according to one specific example, the molybdenum oxide may include molybdenum dioxide.

[0049] In a manufacturing method according to one specific example, the molybdenum oxyhalide may be a precursor for metal molybdenum deposition.

[0050] In a manufacturing method according to one specific example, the molybdenum oxyhalide may be a material for forming an electrode of one or more electrodes selected from an electrode group consisting of an anode and a cathode of a diode and a source, a drain, and a gate of a transistor; or a material for forming a line of one or more lines selected from a word line and a bit line of a memory device.

[0051] The present invention includes a molybdenum oxyhalide manufactured by the above-described manufacturing method.

[0052] A molybdenum oxyhalide manufacturing device and method according to one specific example can continuously produce molybdenum oxyhalide, thereby enabling mass production of molybdenum oxyhalide.

[0053] According to one specific example, the molybdenum oxyhalide manufacturing device and method can be free from contamination since the synthesis and purification are performed without exposure to the outside air.

[0054] A molybdenum oxyhalide manufacturing device and method according to one specific example can produce high-purity molybdenum oxyhalide having a purity of 5 nines (99.999%) or more.

[0055] A molybdenum oxyhalide manufacturing device and method according to one specific example can produce molybdenum oxyhalide with a high yield of 90% or more.

[0056] The various advantageous and beneficial effects of the present invention are not limited to the above-described contents, and will be more easily understood in the course of explaining specific embodiments of the present invention.

[0057] Figure 1 is a schematic diagram illustrating a manufacturing device according to one specific example of the present invention.

[0058] Figure 2 is a schematic diagram illustrating a manufacturing device according to another specific example of the present invention.

[0059] FIG. 3 is a schematic diagram illustrating in detail the front area of ​​the raw material supply unit and the reaction zone in a manufacturing device according to another specific example of the present invention.

[0060] FIG. 4 is another schematic diagram illustrating in detail the front area of ​​the raw material supply unit and the reaction zone in a manufacturing device according to another specific example of the present invention.

[0061] Figure 5 is a schematic diagram of a manufacturing device according to another specific example of the present invention.

[0062] Figure 6 is a schematic diagram of a manufacturing device according to another specific example of the present invention.

[0063] Figure 7 is a schematic diagram of a manufacturing device according to another specific example of the present invention.

[0064] Figure 8 is a schematic diagram of a manufacturing device according to another specific example of the present invention.

[0065] Figure 9 is a detailed schematic diagram showing a capturing unit, a purification transport unit, and a purification unit in a manufacturing device according to another specific example of the present invention.

[0066] Figure 10 is a schematic diagram of a manufacturing device according to another specific example of the present invention.

[0067] Hereinafter, preferred embodiments of the present invention will be described with reference to the attached drawings. However, the embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0068] In addition, the embodiments of the present invention are provided to more completely explain the present invention to a person having average knowledge in the relevant technical field.

[0069] The shape and size of elements in the drawing may be exaggerated for clearer explanation.

[0070] In describing the embodiments of the present invention, if a detailed description of a known technology related to the present invention is judged to unnecessarily obscure the gist of the present invention, such detailed description will be omitted. In addition, the terms described below are terms defined in consideration of their functions in the present invention, and these may vary depending on the intention or custom of the user or operator. Therefore, the definitions should be made based on the contents throughout this specification. The terminology used in the detailed description is only for the purpose of describing the embodiments of the present invention and should in no way be limiting. Unless clearly defined otherwise, expressions in the singular form include plural meanings.

[0071] In this description, expressions such as “including” or “having” are intended to indicate certain features, numbers, steps, operations, elements, portions or combinations thereof, and should not be construed to exclude the presence or possibility of one or more other features, numbers, steps, operations, elements, portions or combinations thereof other than those described.

[0072] Unless otherwise specified in the specification of the present invention, the % unit means weight %.

[0073] In this specification and the appended claims, the terms first, second, etc. are not used in a limiting sense but are used to distinguish one component from another.

[0074] Additionally, throughout the specification, when we say that a part is 'connected' to another part, this includes not only cases where it is 'directly connected', but also cases where it is 'indirectly connected' with other elements in between.

[0075] Below, the present invention will be described in detail through each embodiment or example of the present invention. It should be noted that each embodiment or example described in this specification is not limited to a single embodiment or example, but may be combined with other embodiments or examples. Therefore, the citation of a claim in the patent claims is only an example of an embodiment, and the technical concept of the present invention should not be interpreted solely as a combination with the cited claim, and combinations with various claims also fall within the scope of the technical concept of the present invention.

[0076] The terms used herein are for the purpose of describing the invention and are not intended to limit the invention. Furthermore, the singular forms used herein also include the plural forms, unless the relevant definition clearly indicates a contrary meaning.

[0077] Unless otherwise defined, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which this invention pertains. Terms defined in the dictionary are to be interpreted to have meanings consistent with the relevant technical literature and the present disclosure.

[0078] In this specification and the appended claims, molybdenum oxide may refer, materially, to a compound between molybdenum and oxygen. In one specific example, molybdenum oxide may refer to molybdenum dioxide (MoO2), molybdenum trioxide (MoO3), Mo x O y (x is a real number from 4 to 18, y is a real number from 11 to 47 according to the stoichiometric ratio) or a mixture thereof. Mo x O y A practical example is Mo4O 11 , Mo 18 O 52 , Mo5O 14 , Mo 14 O47 Or mixtures thereof, etc., but are not limited thereto. At this time, the presented chemical formulas such as MoO2, MoO3, etc. should not be interpreted as mathematically strictly meaning the bonding ratio between molybdenum and oxygen. As is known, depending on the thermal history of molybdenum oxide, molybdenum oxide may be in an oxygen-deficient state, and molybdenum oxide may be in an oxygen-deficient state of MoO2, MoO3, Mo x O y (wherein x is a real number from 4 to 18, and y is a real number from 11 to 47) or mixtures thereof. Crystallographically, molybdenum oxide can be amorphous, crystalline (including polycrystalline or single crystal), or a composite phase of amorphous and crystalline. Molybdenum oxide can have a purity of 3nine to 5nine, but is not limited thereto.

[0079] In the present specification and the appended claims, a halogen-containing gas may mean a gaseous substance having a halogen-containing functional group or a halogen-containing moiety, or a gas containing a gaseous halogen (at least one selected from the group consisting of Hal2(g), Hal=Cl, Br, I, and F). As a specific example, the halogen-containing gas may include only a halogen gas, or a mixture of a halogen gas and an inert gas. In this case, the halogen gas may include chlorine gas, bromine gas, iodine gas, fluorine gas, or a mixture thereof. The purity of the gaseous halogen may be, but is not limited to, 4nine to 5nine. When supplying a mixed gas, the mixed gas may contain 10 to 90 volume% of an inert gas (10 to 90 volume% of a halogen-containing gas), specifically 20 to 80 volume% of an inert gas (20 to 80 volume% of a halogen-containing gas), but is not necessarily limited thereto.

[0080] In the present specification and the appended claims, the molybdenum oxyhalide may be at least one selected from the group consisting of molybdenum oxydihalide (MoOHal2, Hal=halogen), molybdenum oxytrihalide (MoO Hal3, Hal=halogen), molybdenum oxytetrahalide (MoOHal4, Hal=halogen), and molybdenum dioxydihalide (MoO2Hal2, Hal=halogen). As a practical example, the molybdenum oxyhalide may be molybdenum oxychloride that satisfies the deposition characteristics required for semiconductor wiring and can be used as a precursor for molybdenum metal deposition. The molybdenum oxychloride may be at least one selected from the group consisting of molybdenum oxydichloride, molybdenum oxytrichloride, molybdenum oxytetrachloride, and molybdenum dioxydichloride.

[0081] In this specification and the appended claims, unless otherwise specified, 'continuous' may refer to the synthesis (production) of molybdenum oxyhalide. Specifically, molybdenum oxyhalide may be synthesized by a reaction between molybdenum oxide and a halogen of a halogen-containing gas. 'Continuous' may mean that fresh molybdenum oxide is supplied to the synthesis space before the molybdenum oxide present in the space where molybdenum oxyhalide is synthesized is completely consumed, and fresh halogen-containing gas is supplied to the synthesis space before the halogen of the halogen-containing gas present in the synthesis space is completely consumed. In this case, 'complete consumption' may mean a state where substantially no more products are produced due to the reactants used in the synthesis, even though the synthesis conditions (temperature, pressure, etc.) of the synthesis space do not change.

[0082] In an experimental sense, 'continuous' based on the passage of time may mean that the average transport speed (Va) of the raw material passing through the reaction zone is 0.01 m / hr or more. In this case, the 'average' transport speed may be calculated according to the formula Va = L / (T2 - T1) using the length of the reaction zone through which the raw material passes and the time difference between the point in time when the raw material is introduced into the reaction zone (T1) and the point in time when the raw material exits (is discharged) from the reaction zone. Therefore, as long as the average transport speed is satisfied, not only the case where the raw material is continuously supplied and thus continuously discharged after passing through the reaction zone, but also the case where the transport of the raw material within the reaction zone and intermittent stops (stops in transport) are repeated and the raw material passes through the reaction zone should be interpreted as continuous. In this case, the transport of the raw material that satisfies the above-mentioned 'average' transport speed obviously means that the raw material is supplied to the reaction zone so that the transport of the raw material at the above-mentioned 'average' transport speed is continuously performed. In practice, the average transport speed of the raw material can be calculated by introducing an inert material (e.g., glass or quartz) that does not react with the halogen-containing gas in the reaction zone and is distinguishable from the raw material into the reaction zone together with the raw material and measuring the time required for the introduced inert material to be discharged.

[0083] From an experimental perspective, "continuous" at a single point in time may mean that the supply of raw materials to the reaction zone and the solid-state capture for the recovery of molybdenum oxyhalide produced in the reaction zone are performed simultaneously. Since molybdenum oxyhalide is continuously synthesized (generated) in the reaction zone, the supply of raw materials to the reaction zone and the solid-state capture of molybdenum oxyhalide can be realized simultaneously.

[0084] In this specification and the appended claims, the phrase "raw materials passing through the reaction zone" refers to raw materials that are introduced into the reaction zone, and does not mean that the raw materials pass through the reaction zone and are discharged from the reaction zone in the same state in which they were introduced. The phrase "raw materials passing through the reaction zone" may refer to a series of processes in which raw materials are introduced into the reaction zone, the introduced raw materials are transported in the reaction zone, a reaction occurs to produce molybdenum oxyhalide, and a residual solid phase is discharged from inside the reaction zone to outside the reaction zone. In this case, the residual solid phase may include a solid by-product produced by the reaction, a residual raw material, or a mixture thereof.

[0085] A molybdenum oxyhalide manufacturing device (I) according to one aspect includes a reaction zone into which a halogen-containing gas is supplied, a raw material including molybdenum oxide is transported through the reaction zone, and molybdenum oxyhalide is produced.

[0086] According to one aspect, a manufacturing device (I) can supply fresh raw material to the reaction zone before the molybdenum oxide is completely consumed in the reaction zone as the raw material containing molybdenum oxide is transported through the reaction zone. This enables continuous supply of raw material to the reaction zone. By continuously supplying raw material, the raw material is continuously transported in the reaction zone, and molybdenum oxyhalide can be continuously produced.

[0087] In terms of continuous molybdenum oxyhalide production, the manufacturing device (I) is described in detail as follows: the manufacturing device includes a reaction zone into which a halogen-containing gas is supplied, and a raw material containing molybdenum oxide is continuously supplied to the reaction zone and continuously transported through the reaction zone, thereby producing molybdenum oxyhalide. At this time, a halogen-containing gas may also be continuously supplied to the reaction zone.

[0088] In one specific embodiment, energy may be applied to the reaction zone. The energy application is intended to provide the activation energy required for molybdenum oxyhalide synthesis, and any energy that enables the production of the desired molybdenum oxyhalide from the reactant(s) of the halogen-containing gas and the raw material comprising molybdenum oxide may be used.

[0089] In a specific example, in the reaction zone, at least one energy selected from the group consisting of thermal energy, light energy, and vibrational energy can be applied to the halogen-containing gas and the raw material substantially located in the reaction zone.

[0090] Thermal energy may include Joule heat. The heat source may be located inside the reaction zone, outside the reaction zone, or both inside and outside the reaction zone. When located outside the reaction zone, the heat source may be in direct contact with the case (outer surface of the case) that defines the space including the reaction zone, or indirectly in contact with it through a refractory, etc. When the heat source is located inside the reaction zone, the heat source may be located in contact with the case (inner surface of the case) that defines the space including the reaction zone, or may be located so as to be in direct contact with the raw material including the metal oxide, or may be located so as to be indirectly heat-transferred to the raw material by a gaseous heat transfer medium. Direct contact between the raw material and the heat source may include cases where the transport means provided for transporting the raw material itself is a heat source, the heat source is provided inside the transport means, or the heat source heats the transport means so that the transport means acts as a heat transfer medium.

[0091] The light of the light energy may include heat, and the heat may include infrared or near-infrared light. The application of the light energy may include irradiation of light. The light source may be located within the reaction zone, outside the reaction zone, or both inside and outside the reaction zone. As a non-limiting example, the energy may be applied by irradiating the raw material with light from an infrared or near-infrared light source located within the reaction zone at a certain distance from the raw material.

[0092] The vibration energy may include microwaves, ultrasound, or both. The application of vibration energy may include irradiation with microwaves and / or ultrasound. As a non-limiting example, the energy may be applied by irradiating the raw material with microwaves and / or ultrasound from a microwave and / or ultrasound source positioned at a predetermined distance from the raw material.

[0093] When applying energy, different types of energy can be applied to the raw material simultaneously or at different times (based on the raw material being transported). For example, thermal energy can be applied to the reaction zone simultaneously with light energy. In another example, thermal energy can be applied to the reaction zone, and a region where light energy is applied and a region where light energy is not applied can be formed in the reaction zone, so that the raw material can pass through both the region where thermal energy is applied and the region where both thermal energy and light energy are applied simultaneously, and pass through the reaction zone.

[0094] As described above, the manufacturing device (I) may include a case that divides a space (internal space) including a reaction zone and an energy application unit that applies energy to the reaction zone.

[0095] The case defines an internal space for generating molybdenum oxyhalide, and a halogen-containing gas is supplied to at least a portion of the internal space provided by the case, so that a reaction zone can be formed.

[0096] The energy application unit can apply at least one energy selected from the group consisting of thermal energy, light energy, and vibrational energy described above to the reaction zone.

[0097] In addition, the manufacturing device (I) may include a conveying means for conveying the raw material through the reaction zone. The conveying means may be located within the reaction zone. The conveying means being located within the reaction zone may mean that at least a moving part for conveying the raw material by positioning the raw material in the conveying means is located within the reaction zone. A connecting part for connecting to a power source for driving the conveying means or a fixing part for fixing the conveying means may be located within the reaction zone or outside the reaction zone.

[0098] The conveying means may be any means commonly used to convey powder in a designed direction. For example, the conveying means may include a conveying shaft having conveying blades and being rotatable. Alternatively, the conveying means may include a belt moving in a designed direction. In this case, the designed direction may be a straight line, but is not necessarily limited thereto. A representative example of a conveying means including a conveying shaft having conveying blades and being rotatable is a screw conveyor, and a representative example of a conveying means including a belt moving in a designed direction is a belt conveyor.

[0099] Hereinafter, a manufacturing device (I) according to one specific example will be described with reference to the drawings.

[0100] In the drawing, a conveying means including a conveying shaft having a conveying blade and being rotatable is illustrated, but the present invention is not limited to the specific type of conveying means. However, when the conveying means includes a conveying shaft having a conveying blade and being rotatable, the raw material is physically rotated, dropped, mixed, and moved by the conveying blade, so that even when a large amount of raw material is being conveyed, it can smoothly and homogeneously come into contact with the halogen-containing gas, which is more practical.

[0101] In addition, although the energy application unit in the drawing is illustrated assuming a case where heat is applied, the present invention is not limited by the type of energy applied. However, among the energies described above, providing activation energy by thermal energy is more practical, because even if a large amount of raw materials are supplied, energy can be applied uniformly to the raw materials, and even if the path of the reaction zone through which the raw materials pass is long, a constant amount of energy can be applied to the raw materials being transported easily. Hereinafter, the energy application unit that applies thermal energy is collectively referred to as a case heating unit.

[0102] FIG. 1 is a schematic diagram illustrating a manufacturing device (I) according to one specific example, which includes a case (110) providing an internal space including a reaction zone (UZ), a case heating unit (130) for heating at least a portion of the case (110), and a transport means (120).

[0103] The raw material (RM) can react with a halogen-containing gas supplied from the reaction zone (UZ), and gaseous molybdenum oxyhalide can be generated through this reaction. As the raw material (RM) continuously passes through the reaction zone (UZ), molybdenum oxyhalide can be continuously generated in the reaction zone (UZ).

[0104] In one specific example, the case (110) may be cylindrical or polygonal so that the raw material (RM) can be transported in a straight line and pass through the reaction zone (UZ), but the present invention is not limited to the spherical shape of the case (110) and the internal space provided by the case (110).

[0105] An internal space for synthesizing (generating) molybdenum oxyhalide may be defined by the case (110). Halogen gas may be supplied to at least a portion of the internal space defined by the case (110), and a reaction zone (UZ) in which the halogen gas exists may be formed. The area of ​​the case (110) heated by the case heating unit (130) may include the reaction zone (UZ). Alternatively, the reaction zone (UZ) may include the area of ​​the case (110) heated by the case heating unit (130).

[0106] As a practical example, the reaction zone (UZ) may be a region where a halogen-containing gas is supplied from an internal space and at the same time, a region heated by a case heating unit (130). Specifically, the reaction zone (UZ) may include a uniform zone. For example, the reaction zone (UZ) may be identical to the uniform zone. The uniform zone is a section where the temperature is maintained substantially constant regardless of the position of a sphere within the region. The temperature of the reaction zone (UZ) (the temperature of the uniform zone) may be a reaction temperature (synthesis temperature, Trx, ℃) at which molybdenum oxide and a halogen-containing gas react to synthesize molybdenum oxyhalide.

[0107] The uniform zone can be formed by a case heating unit (130) that heats at least a portion of the case (110), and the length of the uniform zone can be adjusted by the length of the case (110) heated by the case heating unit (130). The case heating unit (130) can be positioned at the top, bottom, and / or side of the desired case (110) area, or can be positioned to surround the desired case (110) area.

[0108] In the case (110), a supply port (111) for supplying the raw material (RM) may be formed in the forward direction (as shown by an arrow in FIG. 1) of the raw material (RM), specifically, in the forward direction, that is, the area between the front end of the case (110) and the starting point of the reaction zone (UZ). At this time, the raw material (RM) supplied through the supply port (111) may pass through the reaction zone (UZ) by the transport means (120) and be transported toward the rear end of the case (110). The raw material continuously supplied from the supply port (111) may continuously pass through the reaction zone (UZ) by the transport means (120).

[0109] Although FIG. 1 illustrates an example in which a single supply port (111) is positioned at the front, two or more supply ports may be formed spaced apart along the raw material (RM) transport path, and raw materials may be supplied to each supply port. If necessary, at least some of the two or more supply ports may be positioned in an area where a reaction zone (UZ) is formed.

[0110] The transport means (120) can transport the raw material (RM) so that it passes through a reaction zone (UZ) into which a halogen-containing gas (gas) is supplied. The transport means (120) can transport the raw material (RM) from one end of the case (110) to the other end of the case (110) within the case (110).

[0111] As in one specific example of FIG. 1, the transport means (120) may include a transport shaft (122) that is rotatably provided and has a transport blade (121). For clearer recognition in the schematic diagram of FIG. 1, the transport blade (121) is indicated by a line. The transport shaft (122) having the transport blade (121) may be located inside the case (110).

[0112] A transfer shaft (122) having a transfer blade (121) is fixed by a magnetic coupling and can be rotated by a rotating magnetic field. Specifically, as in an example illustrated in FIG. 1, the transfer means (120) may include a rotating magnet (142) that is formed at a 90° angle with a driving magnet (141) at a constant interval, and the rotating magnet (142) can be rotated by an attractive and repulsive force generated between the rotating magnet (142) and the driving magnet (141). The transfer shaft (122) may be connected (fixed) to the rotating magnet (142) so that it can rotate integrally when the rotating magnet (142) rotates.

[0113] By the rotation of the transfer shaft (122) which is provided rotatably and has a transfer blade (121), the raw material (RM) supplied through the supply port (111) can be transferred to pass through the reaction zone (UZ).

[0114] If necessary, the conveying blade (121) may have a porous structure. A more smooth flow of the halogen-containing gas and the gaseous molybdenum oxyhalide in the reaction zone (UZ) can be ensured by the conveying blade having a porous structure. The porous structure may be formed by providing the conveying blade with through-holes penetrating in the thickness direction thereof, or the blade itself may have a porous network structure such as a mesh. The porosity of the conveying blade may be defined as the ratio of the area occupied by the pores to the area of ​​the blade surface. The porosity of each blade of the conveying blade may be the same, increase, or decrease depending on the conveying direction of the raw material (RM). It goes without saying that the conveying blade (121) may have a non-porous structure.

[0115] The halogen-containing gas (gas) may be introduced into an area where the reaction zone (UZ) begins, specifically, an area having a temperature of Trx-50°C to Trx within the case when the temperature of the reaction zone (UZ) is Trx (°C). A gas inlet (112) through which the halogen-containing gas (gas) is introduced may be located in the area where the reaction zone (UZ) begins. In order to suppress temperature fluctuations within the reaction zone (UZ) due to the introduction of the halogen-containing gas and to allow smoother contact between the raw material and the halogen-containing gas at the point where the halogen-containing gas is introduced, the halogen-containing gas may be introduced by a diffuser.

[0116] For example, the diffuser may include a gas inlet (112), a passage (113) through which gas introduced into the gas inlet (112) flows, and a scattering nozzle (114) that is connected to the passage (113) and disperses a halogen-containing gas into the internal space. The diffuser may be provided integrally with the case (110) or may be provided as a separate unit from the case (110). In this case, when the diffuser is provided integrally with the case, at least the scattering nozzle (114) may have a structure extending from a wall of an adjacent case (110), thereby allowing the internal space partitioned by the case (110) to remain sealed. When the diffuser is provided as a separate unit from the case, the wall of the case (110) in contact with the diffuser may be a porous wall provided with holes through which the halogen-containing gas to be dispersed may flow. At this time, the pores of the porous wall are directly connected to the flow path (113) of the diffuser, so that the wall area of ​​the case (110) where the pores are formed can also function as a diffuser nozzle.

[0117] The diffuser may be positioned above the area where the reaction zone (UZ) starts, as in the example of Fig. 1, or may be positioned at one or more selected locations from the upper, lower and side of the area where the reaction zone (UZ) starts, or may be formed to surround the area where the reaction zone (UZ) starts, but is not limited thereto.

[0118] In addition, in the example of Fig. 1, an example is shown in which one diffuser is positioned at the starting point of the reaction zone (UZ), but two or more diffusers may be formed spaced apart along the transport path of the raw material (RM), and a halogen-containing gas may be supplied to each diffuser. The two or more diffusers may each be positioned in an area where the reaction zone (UZ) is formed.

[0119] In the internal space, a partition wall (150) may be provided in front of the inflow point where the halogen-containing gas is introduced in the direction of raw material transport to prevent gas backflow. Specifically, the partition wall (150) may be located between the supply port (111) through which the raw material (RM) is supplied and the halogen-containing gas inlet port (112). In order to prevent gas backflow and ensure smooth raw material transport by the transport blade, the partition wall (150) provided in the case (110) may be provided to seal at least the upper portion of the transport shaft (122) based on the transport shaft (122), but to leave a portion of the lower portion of the transport shaft (122) open.

[0120] The halogen-containing gas may be a mixture of a halogen gas and an inert gas (e.g., nitrogen, argon, neon, helium, etc.) as a carrier. The purity of the halogen gas and the purity of the inert gas may be 4 or 5, but are not limited thereto.

[0121] The case (110) may include a first discharge port (101, see FIG. 2) located at the end of the reaction zone (UZ). A gaseous phase including the synthesized molybdenum oxyhalide may be discharged through the first discharge port (101). The first discharge port (101) may be formed at a location where the gaseous phase can be smoothly discharged, and for example, may be located on the upper side of the rear region, which is the region between the end of the reaction zone (UZ) and the rear end of the case, based on the raw material transport direction.

[0122] Conditions for injecting halogen-containing gas, temperature of the reaction zone, length of the reaction zone, transport speed of raw materials passing through the reaction zone, etc. can be determined by considering the specific substance of the desired molybdenum oxyhalide.

[0123] Hereinafter, specific conditions for continuous synthesis of molybdenum oxyhalide, particularly specific conditions advantageous for continuous synthesis of molybdenum dioxydichloride, are provided.

[0124] When continuously synthesizing molybdenum dioxydichloride useful as a precursor for molybdenum metal deposition, it is preferable to perform the reaction under high concentration halogen at a temperature lower than the reaction temperature typically used in batch synthesis, and synthesize molybdenum dioxydichloride.

[0125] The raw material may be molybdenum oxide in particle form, or molybdenum dioxide in substantially particle form. In this case, the particle may have a size of tens of micrometers to tens of millimeters, substantially 100 ㎛ to 5 mm, specifically 100 ㎛ to 2 mm, in terms of having a wider contact area with the halogen-containing gas and smooth mobility, but is not limited thereto. The molybdenum dioxide particles may be polycrystalline particles, as well as granules in which a plurality of particles are aggregated, or a molded body formed by molding molybdenum dioxide in powder form into a desired size and shape. The molybdenum dioxide may have a purity of 3 to 5, but is not limited thereto.

[0126] The temperature (Trx) of the reaction zone (UZ) may be 190 to 350°C, preferably 200 to 300°C, more preferably 200 to 250°C, and even more preferably 200 to 220°C.

[0127] The halogen-containing gas may be supplied to the reaction zone so that the number of moles of halogen atoms required to produce 1 mole of molybdenum oxyhalide according to the stoichiometric ratio of molybdenum oxyhalide is taken as the reference mole number, and 1 to 10 times, specifically 2 to 5 times, and more specifically 2 to 3 times the reference mole number of halogen elements are supplied. In other words, when producing 1 mole of molybdenum oxyhalide according to the stoichiometric ratio of molybdenum oxyhalide, n MO Molybdenum oxide of moles is required, n hal When moles (reference moles) of halogen atoms are required, n hal Not even 10n hal A halogen-containing gas can be supplied to the reaction zone so that halogen elements (halogen atoms) are supplied. Accordingly, kn of halogen atoms are supplied to the reaction zone per unit time. MO When raw materials containing molybdenum oxide are supplied, kn per unit time hal 10kn or less hal A halogen-containing gas may be supplied to the reaction zone so that the halogen element is supplied. At this time, k is a positive real number and may be determined according to the production capacity of molybdenum oxyhalide of the designed device. As a practical example, if molybdenum oxide is molybdenum dioxide and molybdenum dioxydichloride is to be produced, n MO is 1 mole, and n hal is 2 moles, and thus, a halogen-containing gas can be supplied to the reaction zone so that 2 to 20 moles of halogen elements (halogen atoms) are supplied when 1 mole of molybdenum dioxide is supplied.

[0128] When the raw material passes through the reaction zone without stopping by the conveying means, the conveying speed of the raw material may be 0.01 m / hr to 10.00 m / hr, preferably 0.01 m / hr to 5.00 m / hr, more preferably 0.10 m / hr to 1.00 m / hr, and even more preferably 0.30 m / hr to 0.90 m / hr. In addition, or independently of this, the average conveying speed of the raw material may be 0.01 m / hr to 10.00 m / hr.

[0129] The reaction zone (UZ) may have a length such that it takes 10 to 600 minutes, preferably 60 to 300 minutes, and more preferably 60 to 180 minutes for the raw material to pass through the reaction zone (UZ) based on the raw material transport speed described above.

[0130] As the raw material is continuously supplied to the reaction zone, the halogen-containing gas can also be continuously supplied to the reaction zone, and preferably, the supply amount (n) of the above-described halogen element hal Not even 10n hal ) can be supplied to satisfy the requirements. The gaseous molybdenum oxyhalide synthesized in the reaction zone can be continuously discharged to the rear end of the reaction zone by being carried by a halogen-containing gas, specifically, an inert gas in the halogen-containing gas.

[0131] Fig. 2 is a schematic diagram illustrating a manufacturing device (I) according to another specific example of the present invention. As in the example illustrated in Fig. 2, the manufacturing device may include a first gas supply unit and a second gas supply unit. The first gas supply unit may include a first gas cylinder (210) storing halogen gas and a first moisture absorber (230), and the second gas supply unit may include a second gas cylinder (220) storing inert gas and a second moisture absorber (240).

[0132] In the first gas supply unit for supplying halogen gas to the reaction zone (UZ), the halogen gas discharged from the first gas bomb (210) passes through the first moisture adsorber (230) and can be supplied to the reaction zone with moisture removed.

[0133] In addition, a second gas supply unit for supplying an inert gas, which is a carrier gas, to the reaction zone may be provided. Inert gas discharged from a second gas bomb (220) storing the inert gas may pass through a second moisture absorber (240), so that the inert gas with moisture removed may be supplied to the reaction zone.

[0134] The first moisture adsorber (230) and the second moisture adsorber (240) are each equipped with a moisture adsorbent and can remove moisture in the gas through adsorption. The moisture adsorbent may be provided in the form of a column or module, and may be provided in a replaceable form.

[0135] FIG. 2 illustrates an example in which a single moisture adsorber is provided for each gas supply section, but is not limited thereto. Two or more moisture adsorbers may be provided for each gas supply section. The first gas supply section may include two or more first moisture adsorbers connected to the first gas bomb (210), and / or the second gas supply section may include two or more second moisture adsorbers connected to the second gas bomb (220). At this time, two or more moisture adsorbers connected to the same gas bomb may be used alternately and selectively. Through this, when the adsorbent of a moisture adsorber to which gas was being supplied needs to be replaced or regenerated, gas is supplied to another moisture adsorber that was not in use, and moisture in the gas is removed, so that gas from which moisture has been removed can be continuously supplied to the reaction zone without interruption in the gas supply.

[0136] The halogen-containing gas continuously supplied to the reaction zone has a significant effect on the degree of moisture contamination of the continuously synthesized molybdenum oxyhalide. As shown in the schematic diagram of Fig. 2, the halogen gas and the inert gas from which moisture has been removed by the moisture adsorber (230, 240) can be mixed to form a halogen-containing gas stream, and the halogen-containing gas stream can undergo secondary moisture removal by the gas purifier (250) located upstream of the gas inlet (112). The gas purifier (250) can remove moisture not removed by the moisture adsorber (230, 240) and / or contaminated moisture passing through the gas path, thereby supplying a halogen-containing gas substantially free of moisture to the reaction zone. The gas purifier (250) may be a purifier capable of removing moisture in the gas to a level of 1 ppm or less by using a solvent trap or the like. Unlike the illustration in Figure 2, halogen-only gas, from which moisture has been removed by a moisture adsorber and a gas purifier, can be supplied to the reaction zone as a halogen-containing gas. By the moisture adsorber and the gas purifier, the moisture content of the halogen-containing gas can be controlled to 1 mass ppm or less.

[0137] It goes without saying that the manufacturing device may include a conventional valve (231, 232, 241, 242) for controlling the flow (path) of gas, a conventional mass flow controller (MFC) (233, 243) for controlling the flow rate of gas, a pump for transporting gas, etc.

[0138] Fig. 3 is a detailed schematic diagram of a manufacturing device (I) according to one specific example, and is a schematic diagram specifically illustrating the front area of ​​the raw material supply unit and the reaction zone. As illustrated in Fig. 3, the manufacturing device (I) may further include a raw material supply unit (400) and a raw material heating unit (410) for heating the raw material supply unit (400). The raw material stored in the raw material supply unit (400) may be heated by the raw material heating unit (410) so that moisture adsorbed on the raw material may be desorbed and removed. The temperature at which the raw material is heated by the raw material heating unit (410) may be in the range of 100 to 250°C, specifically, in the range of 100 to 200°C, but is not limited thereto, and any temperature at which moisture is smoothly removed may be used.

[0139] The supply port (111) of the case (110) is connected to the raw material supply unit (400), so that raw materials stored in the raw material supply unit (400) can be introduced into the internal space of the case (110) through the supply port (111), and the introduced raw materials can be transferred by the transfer blade (121) and introduced into the reaction zone (UZ).

[0140] As illustrated in an example in FIG. 3, an inert gas (inter gas), preferably an inert gas from which moisture has been removed, may be supplied to the raw material supply unit (400). For more effective removal of moisture within the raw material, it is preferable that the inert gas be introduced into the lower portion of the raw material supply unit (400).

[0141] To this end, a sealing wall (160) that divides the internal space of the case may be positioned in front of the supply port (111) based on the raw material transport direction. A second gas inlet (116) through which an inert gas is introduced may be provided in the shear region, which is the space between the front end of the case (110) and the sealing wall (160), and the wall of the case adjacent to the raw material supply unit (400) in the shear region may be a porous wall provided with holes (115) that can connect the shear region and the internal space of the raw material supply unit (400).

[0142] At this time, the inert gas supplied to the second gas inlet (116) may be an inert gas supplied by the second gas supply unit with moisture removed. Specifically, the inert gas stream that has passed through the second moisture adsorber (240) may be branched into a first inert gas stream and a second inert gas stream, and the first inert gas generated by the branching may be mixed with the halogen gas from which moisture has been removed, and the second inert gas may be supplied to the raw material supply unit (400) through the second gas inlet (116).

[0143] As in the example of Fig. 3, by supplying an inert gas with moisture removed through the lower portion of the raw material supply unit (400), more rapid moisture removal of the raw material can be achieved, and the raw material located in the lower portion of the raw material supply unit (400), which is the raw material immediately before being supplied to the supply port (111), can be effectively prevented from being re-contaminated with moisture. At this time, it goes without saying that the raw material supply unit (400) may further be provided with a vent port (not shown) through which a gas phase including moisture desorbed from the raw material is discharged. As described above, the raw material with moisture removed may be supplied to the reaction zone, and at this time, the moisture content of the raw material may be controlled at a level of several tens to several hundred mass ppm, specifically, at a level of 10 to 500 mass ppm.

[0144] Fig. 4 is a detailed schematic diagram of a manufacturing device (I) according to one specific example, and is another schematic diagram showing in detail the front area of ​​the raw material supply unit and the reaction zone. As in the example illustrated in Fig. 4, the raw material supply unit (400) may further include a stirrer (420). By further providing the stirrer (420) in the raw material supply unit (400), the raw material can be supplied more smoothly to the supply port (111), and at the same time, the raw material can come into contact with the inert gas flowing in from the bottom of the raw material supply unit (400) more smoothly and uniformly, so that more rapid and homogeneous moisture removal can be achieved.

[0145] The agitator (420) may include a rotating shaft and blades coupled to the rotating shaft. Examples of the spherical shape and structure of the blades include, but are not limited to, straight blades, open turbine blades, propeller blades, disk turbine blades, anchor blades, ribbon blades, spiral blades, or combinations thereof. In one example of FIG. 4, a straight blade is radially coupled to the rotating shaft, and the radially coupled blade(s) form a blade array, with three blade arrays positioned spaced apart from each other in the axial direction of the rotating shaft. However, the spherical structure and shape of the blades may be any shape that causes flow in the raw material and does not impede the flow of the inert gas, and the present invention is not limited by the structure and shape of the spherical agitator.

[0146] Fig. 5 is a schematic diagram of a manufacturing device (I) according to another specific example, wherein the manufacturing device further includes a capturing unit (300). The gas discharged through the first discharge port (101) described above can be introduced into the capturing unit (300) through the first inlet port (301). The capturing unit (300) can cool the gas introduced through the first inlet port (301) to capture gaseous molybdenum oxyhalide as a solid.

[0147] The capturing unit (300) may include a capturing body (310) having an internal space and receiving a gas introduced through a first inlet (301) and a first cooling unit (320) for cooling the introduced gas. The gaseous molybdenum oxyhalide continuously synthesized in the reaction zone (UZ) is continuously discharged through the first discharge port (101) of the case (110), and accordingly, the gaseous molybdenum oxyhalide is continuously introduced into the capturing unit (300) through the first inlet port (301) and cooled by the first cooling unit (320), so that the molybdenum oxyhalide can be continuously solidified.

[0148] To ensure smooth inflow, the residual gas remaining after molybdenum oxyhalide capture by solidification may be discharged. Accordingly, if necessary, the capture body (310) may further include a first vent port (302) for discharging the remaining residual gas.

[0149] In the capturing body (310), the first inlet (301) and the first vent (302) may be formed at positions where smooth gas inflow and smooth residual gas discharge occur. For example, the first inlet (301) may be located at the upper side of the capturing body (310), and the first vent (302) may be located at the top of the capturing body (310), but the present invention is not limited thereto.

[0150] In the capturing unit (300), the first cooling unit (320) may be provided at a location where it can smoothly cool the gas phase introduced into the capturing body (310). For example, the first cooling unit (320) may be provided at the lower end and / or lower side of the capturing body (310) by cooling the gas phase introduced through the first inlet (301) and collecting the solid molybdenum oxyhalide by gravity at the lower end of the capturing body (310).

[0151] Depending on the specific material of the target molybdenum oxyhalide, the temperature at which the gas phase is cooled by the first cooling unit (320) can be determined. In the case of capturing molybdenum dioxydichloride useful as a precursor for molybdenum metal deposition, the first cooling unit (320) can cool the gas phase introduced into the capturing body (310) to a temperature of 20 to 120°C, preferably 60 to 110°C, and more preferably 90 to 110°C, in order to solidify (transform into a solid phase) the continuously introduced molybdenum dioxydichloride. When the gas phase is cooled to a temperature of 90 to 110°C to solidify the molybdenum dioxydichloride, it is advantageous because the density of the captured molybdenum dioxydichloride can be increased to 1 g / L or more.

[0152] In detail, the first cooling unit (320) can form a temperature zone of 20 to 120°C, preferably 60 to 110°C, and more preferably 90 to 110°C in a region including the lower end of the capturing body (310) and a side surface adjacent to the lower end. For example, when the height from the lower end to the upper end of the capturing body (310) is H, the region having the temperature set by the first cooling unit (320) may be a region of 0H (lower end) to 0.9H, specifically, 0H (lower end) to 0.7H, but is not necessarily limited thereto. At this time, the first inlet (301) of the capturing body (310) may be located on a side surface or an upper surface of the region corresponding to 0.9H to 0.99H.

[0153] In one specific example, the manufacturing device may further include a heating unit that heats a wall surface that comes into contact with the gaseous molybdenum oxyhalide discharged from the reaction zone and defines a space used for transporting or storing the gaseous molybdenum oxyhalide.

[0154] A heating unit that heats a wall that divides a space used for transport or storage can stably maintain a gaseous molybdenum oxyhalide in a gaseous state during transport or storage, and at the same time, can prevent molybdenum oxyhalide from solidifying (forming heterogeneous nuclei and growing) on ​​the wall that divides the transport or storage space.

[0155] As shown in the schematic diagram of another specific example of a manufacturing device (I) illustrated in FIG. 6, the manufacturing device (I) may further include a line heating unit (510) for heating a transport line through which gaseous molybdenum oxyhalide is transported. Specifically, the line heating unit (510) may heat a first line (L1), which is a transport line between a first outlet (101) through which gaseous molybdenum oxyhalide generated in a reaction zone (UZ) is discharged and a first inlet (301) through which gaseous molybdenum oxyhalide is introduced from a capture unit (300).

[0156] Since the manufacturing device (I) includes a line heating unit (510), the gaseous molybdenum oxyhalide being transported can be prevented from solidifying on the wall of the transport line, thereby preventing the transport line from being clogged. In addition, the gaseous molybdenum oxyhalide being transported can be stably maintained in the gaseous state, thereby improving the production yield. Furthermore, the gaseous molybdenum oxyhalide being transported can be prevented from being contaminated with moisture. To this end, the line heating unit (510) can heat the first line (L1) to a temperature of 170 to 230°C, preferably 180 to 220°C, and more preferably 200 to 220°C.

[0157] FIG. 7 is a schematic diagram of a manufacturing device (I) according to another specific example, wherein the manufacturing device (I) may further include a residue storage unit (610) that supplies and stores a residual solid phase discharged through a reaction zone (UZ), and is a drawing illustrating an example that further includes a residue heating unit (620) that heats the residue storage unit (610).

[0158] The residue storage unit (610) is connected through a third line (L3), which is a transfer line between an outlet through which the residue solid is discharged outside the case (110) and an inlet through which the residue solid is introduced from the residue storage unit (610), or at least the lower part of the rear end of the case (110) based on the direction of transfer of the raw material is opened, so that the residue solid can be supplied to the residue storage unit (610) through the open lower part.

[0159] From a gas perspective, the residue storage unit (610) may be in communication with molybdenum oxyhalide synthesis parts, such as the reaction zone (UZ) or the internal space of the capture body (310). Accordingly, by heating the residue storage unit (610) through the residue heating unit (620), it is possible to prevent the molybdenum oxyhalide from being contaminated by moisture during the synthesis process, and at the same time, to prevent unwanted solidification of the molybdenum oxyhalide.

[0160] When a third line (L3) is provided, the line heating unit (510) can also heat the third line (L3). By heating the third line (L3) by the line heating unit (510), solidification of molybdenum oxyhalide on the inner wall of the third line can be prevented as well.

[0161] The residue heating unit (620) and the line heating unit (510) can independently heat the residue storage unit (610) and the third line (L3) to a temperature of 170 to 250°C, preferably a temperature of 180 to 230°C, and more preferably a temperature of 200 to 220°C, respectively. At this time, the residue heating unit (620) and / or the line heating unit (510) can heat the residue storage unit (610) and / or the third line to a temperature higher than the temperature (Trx) of the reaction zone. Specifically, the residue heating unit (620) can heat the residue storage unit (610) to a temperature of higher than Trx to Trx + 50°C, and together with or independently of this, the line heating unit (510) can heat the third line to a temperature of higher than Trx to Trx + 50°C. In this case, it is possible to effectively prevent the gaseous molybdenum oxyhalide discharged from the reaction zone from flowing into the residue storage unit (610).

[0162] A molybdenum oxyhalide manufacturing device (II) according to one embodiment comprises: a raw material supply unit for supplying a raw material including molybdenum oxide; a reaction zone in which a halogen-containing gas is supplied and energy is applied, a reaction transfer unit in which the raw material supplied from the raw material supply unit is transferred to pass through the reaction zone and molybdenum oxyhalide is generated; a capturing unit for receiving gaseous molybdenum oxyhalide discharged from the reaction transfer unit and capturing it in a solid phase; a purification unit for receiving solid molybdenum oxyhalide captured in the capturing unit and sublimating it into a gas; and a solidification unit for receiving sublimated molybdenum oxyhalide and solidifying it.

[0163] In other words, the molybdenum oxyhalide manufacturing device (II) according to one embodiment may further include, together with the manufacturing device (I) according to the embodiment described above, a purification unit that receives the solid molybdenum oxyhalide captured in the capturing unit and sublimates it into a gas; and a solidification unit that receives the sublimated molybdenum oxyhalide and solidifies it. Accordingly, the manufacturing device (II) according to one embodiment includes all the contents of the manufacturing device (I) described above with reference to FIGS. 1 to 7, and the manufacturing device including the reaction zone, case, and transport means to which the halogen-containing gas is supplied may correspond to the reaction transport unit.

[0164] Fig. 8 is a schematic diagram illustrating a manufacturing device (II) according to one specific example. As shown in the schematic diagram in Fig. 8, the molybdenum oxyhalide manufacturing device (II) may include a raw material supply unit (400), a reaction transfer unit (100) including a reaction zone (UZ), a collection unit (300), a purification unit (700), and a solidification unit (800).

[0165] The raw material supply unit (400) supplies raw materials to the reaction transfer unit (100), and the reaction transfer unit (100) continuously transfers the supplied raw materials through the reaction zone to continuously synthesize molybdenum oxyhalide. The capture unit (300) converts the synthesized gaseous molybdenum oxyhalide (g) into a solid phase and captures it, the purification unit (700) sublimates the captured molybdenum oxyhalide (s) into a gas to purify the molybdenum oxyhalide, and the solidification unit (800) converts the sublimated molybdenum oxyhalide (g) back into a solid phase to produce the final product, molybdenum oxyhalide (s).

[0166] The solid phase captured in the capturing unit (300) can be transferred to the purification unit (700) via the purification transport unit (910). In addition, capture is continuously performed by solidification of molybdenum oxyhalide in the capturing unit (300), but the purification transport unit (910) does not necessarily continuously transfer the captured solid to the purification unit (700). The purification transport unit (910) can transfer the captured solid to the purification unit (700) continuously or at regular time intervals (discontinuously).

[0167] The purification unit (700) can sublimate solid molybdenum oxyhalide(s). The purity of the molybdenum oxyhalide can be improved by the purification action through sublimation.

[0168] The purification unit (700) may include a purification body (710) having an internal space and containing a solid molybdenum oxyhalide (s) that is moved and introduced through a purification transport unit (910), and a purification heating unit (720) that heats the molybdenum oxyhalide (s) contained in the purification body (710). The purification heating unit (720) may be located at the bottom and / or the side of the purification body (710), and may surround the top, bottom, and side of the purification body (710). If necessary, the purification unit (700) may further include a vacuum exhaust unit (not shown) that can reduce the pressure inside the purification body (710). This is because the sublimation temperature of the molybdenum oxyhalide varies depending on the pressure.

[0169] The internal pressure of the purifier body (710) can be adjusted to a set pressure by a vacuum exhaust unit (not shown), and the molybdenum oxyhalide (s) contained in the purifier body (710) can be heated to a set sublimation temperature by the purifier heating unit (720). The molybdenum oxyhalide (g) sublimated in the purifier unit (700) can be discharged through the second discharge port (701) provided in the purifier body (710).

[0170] Depending on the specific material of the target molybdenum oxyhalide, the pressurization conditions (pressure and temperature) can be determined. When sublimating molybdenum dioxydichloride useful as a precursor for molybdenum metal deposition, the sublimation of the molybdenum dioxydichloride (s) contained in the purification body (710) can be atmospheric pressure sublimation, and the molybdenum dioxydichloride (s) can be sublimated by heating it to a temperature of 170 to 230°C, preferably 180 to 220°C, and more preferably 200 to 220°C by the purification heating unit (720).

[0171] The sublimated molybdenum oxyhalide (g) discharged from the purification unit (700) through the second discharge port (701) can be introduced into the solidification unit (800). The solidification unit (800) can cool the sublimated molybdenum oxyhalide (g) to produce the final product, molybdenum oxyhalide (s). That is, the sublimated molybdenum oxyhalide (g) can be re-cooled in the solidification unit (800) and solidified and recovered within the solidification unit (800).

[0172] The solidification unit (800) may include a solidification body (810) having an internal space in which sublimated molybdenum oxyhalide (g) gas is accommodated, and a second cooling unit (820) that cools the molybdenum oxyhalide (g) accommodated in the solidification body (810). At this time, a cooling plate (830) cooled by the second cooling unit (820) is provided inside the solidification body (810), so that solidification of the molybdenum oxyhalide can be performed centered on the cooling plate (830).

[0173] The solidification body (810) may be provided with a second inlet (801) through which sublimated molybdenum oxyhalide (g) is introduced and a second vent (802) through which unreacted residual gas is discharged. At this time, the second inlet (801) and the second vent (802) may be spaced apart from each other and positioned at the upper end of the solidification body (810), but are not necessarily limited thereto.

[0174] The cooling temperature for solidification may be determined depending on the specific material of the desired molybdenum oxyhalide. When solidifying molybdenum dioxydichloride, which is useful as a precursor for molybdenum metal deposition, to recover the final product, molybdenum dioxydichloride(s), the cooling temperature (temperature of the cooling plate) by the second cooling unit (820) may be in the range of -30 to 20°C, but is not necessarily limited thereto.

[0175] FIG. 9 is a detailed schematic diagram illustrating a capturing unit (300), a tablet transport unit (910), a refining unit (700), and a solidifying unit (800) in a manufacturing device (II) according to one specific example. As in the example illustrated in FIG. 9, the manufacturing device (II) may further include a transport heating unit (920) that heats the tablet transport unit (910). By heating the solid molybdenum oxyhalide transported through the tablet transport unit (910) by the transport heating unit (920), contamination by moisture, etc. can be prevented and the purity of the obtained final product can be improved. The tablet transport unit (910) can be heated to a temperature of 50 to 120°C, specifically, a temperature of 80 to 120°C, and more specifically, a temperature of 100 to 120°C by the transport heating unit (920).

[0176] An example of Fig. 9 illustrates a screw-type tablet transport unit (910) in which a space through which solid molybdenum oxyhalide is moved is defined by a case. As in the example illustrated in Fig. 9, the case (911) of the tablet transport unit (910) is connected to the lower end of the collecting unit (300) at the front in the transport direction, so that the solid molybdenum oxyhalide captured in the collecting unit (300) can flow into the tablet transport unit (910). In addition, the case (911) of the tablet transport unit (910) is opened at least at the lower end of the rear end in the transport direction, so that the solid molybdenum oxyhalide can be supplied to the tablet transport unit (700) through the open lower end. At this time, as in an example illustrated in FIG. 9, the transfer shaft (912) on which the blade is formed can also be fixed by a magnetic coupling and rotated by a rotating magnetic field, and one end (the rear end) of the transfer shaft (912) that is not fixed by the magnetic coupling can be fixed to the tablet body (710). The example of the tablet transfer unit (910) illustrated in FIG. 9 has a structure that can minimize unwanted heat loss during the transfer process, but the tablet transfer unit is not limited to the screw type of FIG. 9. The tablet transfer unit can be used as a general transfer device that can transfer a solid powder phase in a desired direction within a partitioned space.

[0177] As an example shown in FIG. 9, the solidification unit (800) may further include at least a solidification heating unit (840) that heats the upper portion of the solidification body (810) where the second inlet (801) is located.

[0178] The solidification heating unit (840) heats the sublimated molybdenum oxyhalide (g) introduced through the second inlet (801) and, together with the second cooling unit (820), can form a temperature gradient in the solidification body (810). By this temperature gradient, rapid solidification (crystallization) of the molybdenum oxyhalide can be achieved without clogging of the second line (L2) and the second inlet (801).

[0179] The solidification heating unit (840) can heat the upper region including the upper portion of the solidification body (810) to a temperature of 170 to 230°C, preferably 180 to 220°C, and more preferably 200 to 220°C. As a result, a temperature gradient can be formed between the upper region having a temperature of 170 to 230°C and the cooling plate located in the lower region of the solidification body having a temperature of -30 to 20°C.

[0180] Specifically, when the height from the lower end to the upper end of the solidification body (810) is Hc, the cooling plate (830) cooled by the second cooling unit (820) may be positioned in the lower region of the solidification body (810), specifically in the lower region from the lower end (0) to 0.1Hc to 0.4Hc. In addition, the solidification heating unit (840) may be positioned to heat the upper region, specifically in the upper region from the upper end to 0.6Hc to 0.9Hc. By the temperature gradient formed in the height direction of the solidification body (810), a final product of high-purity molybdenum oxyhalide (s) with a high production yield and prevention of contamination may be produced.

[0181] In addition, as in an example illustrated in FIG. 9, a second line (L2), which is a transfer line between a second discharge port (701) through which molybdenum oxyhalide sublimated in a purification unit (700) is discharged and a second inlet port (801) through which molybdenum oxyhalide sublimated in a solidification unit (800) is introduced, can be heated by a line heating unit (510). By heating the second line (L2) by the line heating unit (510), solidification of the gaseous molybdenum oxyhalide being transferred is prevented, thereby preventing pipe clogging and, further, preventing moisture contamination. The second line (L2) can be heated independently of the first line (L1) and the third line (L3) described above by the line heating unit (510) to a temperature of 170 to 230°C, preferably a temperature of 180 to 220°C, and more preferably a temperature of 200 to 220°C.

[0182] FIG. 10 is a schematic diagram of a manufacturing device according to one specific example, in which the manufacturing device further includes a housing (1100) and a moisture removal unit (1200), and further includes a halogen adsorption unit (1300).

[0183] The housing (1100) can provide an internal space filled with air, in which at least a raw material supply unit (400), a reaction transfer unit (100), a collection unit (300), a purification unit (700), and a solidification unit (800) are located. The moisture removal unit (1200) can remove moisture from the air within the housing (1100). Specifically, the moisture removal unit (1200) can remove moisture from the air within the housing, thereby allowing the interior of the housing to be filled with dry air. The housing (1100) is configured to allow additional raw material input to the raw material supply unit (400) or to return the final product (molybdenum oxyhalide) generated in the solidification unit (800), and even when there is a risk of the synthesis space connecting the raw material supply unit (400) - reaction transfer unit (100) - collection unit (300) - purification unit (700) - solidification unit (800) being exposed to the outside air, it can prevent moisture from penetrating into the synthesis space. The moisture concentration of the atmosphere (dry air) within the housing may be 10 mass ppm or less, specifically 5 mass ppm or less, and more specifically 0.1 to 1 mass ppm.

[0184] As in the example illustrated in FIG. 10, the manufacturing device may further include a halogen adsorption unit (1300) connected to the first vent port (302) of the capturing body (310) and the second vent port (802) of the solidifying body (810). Unreacted halogen gas may exist in the gas vented from the capturing body (310) and the solidifying body (810). The halogen adsorption unit may receive the residual gas vented from the first vent port (302) and the second vent port (802), and adsorb and remove the unreacted halogen gas that may exist in the residual gas. In addition, although not illustrated in the drawing, if necessary, the manufacturing device may further include a valve and a vacuum pump provided in the vent line, and it goes without saying that when venting is necessary, the residual gas of the capturing body or the solidifying body may be vented to the vent port using the valve and the vacuum pump.

[0185] Including the case of the reaction transfer unit, at least the material (contact part material) of the parts that come into contact with the halogen-containing gas within the reaction transfer unit (e.g., transfer blades, transfer shafts, partitions for preventing gas inflow, diffusers, etc.) may be a material having chemical resistance to halogen gases. Representative examples of the contact part material include nickel-molybdenum alloys including nickel-chromium-iron-molybdenum alloys, nickel, chromium-molybdenum-tungsten alloys, or nickel-chromium-molybdenum alloys; nickel-chromium alloys including nickel-chromium-iron-titanium alloys, nickel-chromium-niobium alloys, or nickel-chromium-aluminum alloys; ceramics such as glass, quartz, or alumina; and / or fluororesins such as polytetrafluoroethylene; and the chemical resistance of the device can be ensured by providing such contact part materials in the form of a coating layer or a body. It is okay to use commercialized materials as these contact part materials, and a representative example of a commercial material is Hastelloy. ® (Hastelloy ® ) alloy, Inconel ® (Inconel ® ) alloy, Teflon ®(Teflon ® ) It is okay to use the product.

[0186] The above-described molybdenum oxyhalide manufacturing device can continuously produce molybdenum oxyhalide having a purity of 5 or higher, with moisture contamination prevented, at a production yield superior to that of batch production.

[0187] In addition, the molybdenum oxyhalide manufacturing device is based on a synthetic scheme for manufacturing molybdenum oxyhalide by reaction of molybdenum oxide and halogen gas, and can manufacture high-purity molybdenum oxyhalide with a production yield of 90% or more even at a low reaction temperature (Trx), for example, a temperature of 200 to 220°C. A production yield of 90% or more is significantly higher than that of a conventional batch-type molybdenum oxyhalide manufacturing device.

[0188] In addition, the molybdenum oxyhalide manufacturing device can manufacture high-density molybdenum oxyhalide in which the density of both the synthesized molybdenum oxyhalide (molybdenum oxyhalide captured in the capturing unit) and the purified molybdenum oxyhalide (molybdenum oxyhalide obtained in the solidification unit) is 1.0 g / L or more.

[0189] In addition, the above-described manufacturing device may further include a control unit that is connected to one or more units selected from the transport means, the case heating unit, the first cooling unit, the refining heating unit, the second cooling unit, the solidification heating unit, the line heating unit, the transport heating unit, and the residue heating unit to control at least one or more elements among the transport speed of the raw material by the transport means of the reaction transport unit, the temperature (Trx) heated by the case heating unit, the temperature cooled by the first cooling unit, the temperature heated by the refining heating unit, the temperature cooled by the second cooling unit, the temperature heated by the solidification heating unit, the temperatures of the first, second, and third lines heated by the line heating unit, the temperature heated by the transport heating unit, and the temperature heated by the residue heating unit.

[0190] The present invention includes a method for producing molybdenum oxyhalide using the above-described manufacturing apparatus. Hereinafter, when describing the method for producing molybdenum oxyhalide, the manufacturing method includes all of the details described above regarding the manufacturing apparatus.

[0191] A method for manufacturing molybdenum oxyhalide according to one aspect is as follows: a raw material including molybdenum oxide passes through a reaction zone, a halogen-containing gas is supplied to the reaction zone, and molybdenum oxyhalide is generated.

[0192] A raw material containing molybdenum oxide can be continuously supplied to the reaction zone, and molybdenum oxyhalide can be continuously produced. When the raw material is continuously supplied, a halogen-containing gas can also be continuously supplied to the reaction zone.

[0193] In one specific embodiment, at least one energy selected from the group consisting of thermal energy, light energy, and vibrational energy may be applied to the reaction zone, and the application of such energy may provide the activation energy required for molybdenum oxyhalide synthesis. Preferably, the energy applied to the reaction zone may include thermal energy.

[0194] In one embodiment, the raw material can flow through the reaction zone. The flow of the raw material is advantageous because it allows continuous contact with a fresh, halogen-rich gas. When the direction of the raw material's net transport is the x-axis, the flow of the raw material can include both an x-axis component, a z-axis component perpendicular to the x-axis direction, and a y-axis component. At any point in time when the particulate raw material is being transported, the x-axis component, the z-axis component, and the y-axis component may be random and different for each particle. However, since the x-axis component is the direction in which the net transport occurs, it may have a size (average value) corresponding to the net transport from the perspective of the entire raw material. The particulate raw material can be physically rotated, dropped, mixed, and moved by this flow. In terms of the device, the flow of the raw material can occur by the rotation of a rotating shaft equipped with a transport blade, thereby transporting the raw material.

[0195] In one specific example, the raw material may be dehydrated before being supplied to the reaction zone. Dehydration of the raw material may be accomplished by applying heat, or by applying heat and an inert gas from which moisture has been removed.

[0196] Together with or independently of this, the halogen-containing gas may be a mixed gas of a halogen gas and an inert gas, and the mixed gas may be in a state in which moisture has been removed in advance before being supplied to the reaction zone. Specifically, moisture may be removed from the halogen gas by adsorption, and after moisture has been removed from the inert gas by adsorption, the two gases may be mixed to form a mixed gas, and moisture may be removed again from the mixed gas using a solvent trap or the like, and then the mixed gas may be supplied to the reaction zone.

[0197] Specific conditions for continuous synthesis of molybdenum oxyhalides, particularly favorable specific conditions for continuous synthesis of molybdenum dioxydichloride, are as follows.

[0198] The raw material may be particulate molybdenum oxide, or substantially particulate molybdenum dioxide.

[0199] The temperature (Trx) of the reaction zone (UZ) may be 190 to 350°C, preferably 200 to 300°C, more preferably 200 to 250°C, and even more preferably 200 to 220°C.

[0200] According to the stoichiometric ratio of molybdenum oxyhalide, n is produced when 1 mole of molybdenum oxyhalide is produced. MO Molybdenum oxide of moles is required, n hal When moles (reference moles) of halogen atoms are required, n hal Not even 10n hal Mol, specifically 2n hal Not even 5n hal Mol, more specifically 2n hal Not in the 3n hal A halogen-containing gas can be supplied to the reaction zone so that a mole of halogen elements (halogen atoms) are supplied. As a practical example, if the molybdenum oxide is molybdenum dioxide and molybdenum dioxydichloride is to be produced, n MO is 1 mole, and n hal The halogen-containing gas can be supplied to the reaction zone so that 2 moles and 2 to 20 moles of halogen elements (halogen atoms) are supplied.

[0201] When the raw material is continuously supplied to the reaction zone, the feed rate of the raw material may be 0.01 m / hr to 10.00 m / hr, preferably 0.01 m / hr to 5.00 m / hr, more preferably 0.10 m / hr to 1.00 m / hr, and even more preferably 0.30 m / hr to 0.90 m / hr. In addition, or independently of this, the average feed rate of the raw material may be 0.01 m / hr to 10.00 m / hr.

[0202] The time required for the raw material to pass through the reaction zone (UZ) may be from 10 minutes to 600 minutes, preferably from 60 minutes to 300 minutes, and more preferably from 60 minutes to 180 minutes.

[0203] In one specific example, the manufacturing method may further include a step of cooling the molybdenum oxyhalide produced in the gas phase in the reaction zone and capturing it in a solid phase. That is, the manufacturing method may include a step of transporting a raw material including molybdenum oxide through a reaction zone to which a halogen-containing gas is supplied to produce molybdenum oxyhalide; and a step of cooling the molybdenum oxyhalide produced in the gas phase and capturing it in a solid phase.

[0204] At this time, the wall defining the space used for transporting the gaseous molybdenum oxyhalide discharged from the reaction zone may be heated. The wall may be heated to a temperature of 170 to 230°C, preferably 180 to 220°C, and more preferably 200 to 220°C. The wall defining the space used for transport may correspond to the first line described above.

[0205] A method for manufacturing molybdenum oxyhalide according to one embodiment may include the steps of S1) transporting a raw material including molybdenum oxide through a reaction zone where a halogen-containing gas is supplied and energy is applied, thereby generating molybdenum oxyhalide; S2) receiving and cooling the gaseous molybdenum oxyhalide generated in step S1) to capture the molybdenum oxyhalide in a solid phase; S3) sublimating the captured solid molybdenum oxyhalide into a gas; and S4) solidifying the sublimated molybdenum oxyhalide.

[0206] According to one specific example, a method for producing molybdenum oxyhalide comprises continuously synthesizing molybdenum oxyhalide by reaction between a halogen-containing gas and molybdenum oxide, and continuously solidifying the molybdenum oxyhalide to produce a solid molybdenum oxyhalide.

[0207] In the continuous production of molybdenum oxyhalide as described above, a manufacturing method according to one specific example may include a step of continuously supplying and transporting a raw material including molybdenum oxide to a reaction zone in which a constant temperature is maintained by energy application and a halogen-containing gas is supplied, so that gaseous molybdenum oxyhalide is continuously synthesized; a step of continuously supplying and cooling a gas phase containing the continuously produced gaseous molybdenum oxyhalide to capture the molybdenum oxyhalide in a solid phase; a step of sublimating the captured solid molybdenum oxyhalide; and a step of solidifying the sublimated molybdenum oxyhalide gas.

[0208] After continuous synthesis of molybdenum oxyhalide and continuous solid-phase capture, the solid molybdenum oxyhalide can be purified through sublimation of S3) and solidification of S4), thereby producing molybdenum oxyhalide (final product) with improved purity.

[0209] Commercial mass production of molybdenum oxyhalide is possible by manufacturing molybdenum oxyhalide based on the synthesis of molybdenum oxyhalide through continuous synthesis and continuous capture, and purification through sublimation and solidification (solidification).

[0210] The method for manufacturing molybdenum oxyhalide may further include, before step S1), a step of heating the raw material and supplying an inert gas from which moisture has been removed to the raw material. Through this, the raw material from which moisture has been removed can be supplied to the reaction zone.

[0211] In step S1), a halogen-containing gas from which moisture has been removed can be supplied to the reaction zone.

[0212] In the capture step S2), continuous capture can be performed on the heated molybdenum oxyhalide-containing gas. Specifically, the molybdenum oxyhalide (g) produced in the step S1) is transferred to the capture unit for capture in the step S2) in a heated state at a constant temperature (T1), so that capture can be performed on the molybdenum oxyhalide-containing gas heated to a constant temperature (T1). The heating of the transported molybdenum oxyhalide-containing gas can be performed by heating a wall surface (corresponding to the first line) that defines a space used for transporting the gaseous molybdenum oxyhalide discharged from the reaction zone.

[0213] In the sublimation of step S3), a heated solid molybdenum oxyhalide can be supplied and sublimated. Specifically, the solid molybdenum oxyhalide(s) produced by the capture of step S2) is transferred to a purification unit for sublimation of step S3) in a state heated to a constant temperature (T2), so that sublimation can be performed on the molybdenum oxyhalide solid heated to a constant temperature (T2). The heating of the molybdenum oxyhalide captured in the solid state can be performed by heating a transport means (corresponding to a purification transport unit) of the captured molybdenum oxyhalide.

[0214] S4) When solidifying in step S4), the heated molybdenum oxyhalide gas can be solidified. Specifically, the molybdenum oxyhalide (g) sublimated in step S3) is transferred to a solidification section where cooling for solidification in step S4) is performed while being heated to a constant temperature (T3), so that solidification can be performed on the molybdenum oxyhalide (g) heated to a constant temperature (T3). The heating of the sublimated molybdenum oxyhalide can be performed by heating a wall surface (corresponding to the second line) that defines a space used for transporting the sublimated molybdenum oxyhalide. When solidifying in step S4), solidification can be performed under conditions where a thermal gradient exists from the temperature T3 of the transported molybdenum oxyhalide (g) to the solidification temperature at which solidification occurs.

[0215] A step of adsorbing and removing halogen gas from the residual gas remaining during and / or after the capture and / or solidification of step S2) and / or solidification of step S4) may be further performed.

[0216] In an advantageous example, the temperature (Trx), T1, T3, and sublimation temperature of the reaction zone may be the same, and the heating temperature of the raw material may also be the same as the temperature of the reaction zone. This allows for a constant thermal state (temperature) to be maintained without thermal fluctuations from the solid raw material to the gaseous intermediate product (synthesized molybdenum oxyhalide, sublimated molybdenum oxyhalide), other than cooling for the capture step or cooling for solidification.

[0217] As an example, molybdenum dioxidedichloride, which is useful as a precursor for molybdenum metal deposition, the temperature of the uniform zone (Trx), T1, T3, sublimation temperature and heating temperature of the raw material can be the same at a temperature of 200 to 220°C.

[0218] As an example, molybdenum dioxydichloride, which is useful as a precursor for molybdenum metal deposition, can be captured at atmospheric pressure and a temperature of 20 to 120°C, preferably 60 to 110°C, more preferably 90 to 110°C. The captured molybdenum dioxydichloride(s) can be heated and maintained at a temperature T2 of 50 to 120°C, specifically 80 to 120°C, more specifically 100 to 120°C. The molybdenum dioxydichloride(s) heated and maintained at T2 can be sublimated by heating to a temperature of 170 to 230°C, specifically 190 to 210°C. Solidification of the molybdenum heated and maintained at a temperature T3 can be performed at -30 to 20°C.

[0219] The space where steps S1) to S4) are performed may be located under a dehumidified atmosphere. In this case, each space where steps S1) to S4) are performed may be connected to each other based on meteorological conditions and collectively referred to as a synthetic space. Accordingly, the synthetic space may be located under a dehumidified atmosphere, specifically, under dry air.

[0220] In the above-described manufacturing device or manufacturing method, the halogen-containing gas may be a chlorine-containing gas, and the molybdenum oxyhalide may be molybdenum dioxydichloride.

[0221] In the above-described manufacturing device or manufacturing method, molybdenum oxyhalide may be a precursor for metal molybdenum deposition. In this case, the deposition may include, but is not limited to, CVD, PECVD, or ALD.

[0222] In the above-described manufacturing device or manufacturing method, molybdenum oxyhalide may be a material for forming electrodes of one or more electrodes selected from an electrode group consisting of an anode and a cathode of a diode and a source, a drain, and a gate of a transistor, or a material for forming lines of one or more lines selected from a word line and a bit line of a memory device. At this time, the transistor may include a junction transistor or a field effect transistor. The diode may include a pn diode or a pin diode. However, the electrodes and lines described above are useful uses of molybdenum oxyhalide and are not limited thereto. For example, molybdenum oxyhalide may be a material for forming electrodes of various electronic devices and energy devices, such as electrodes of display devices and electrodes of energy generating devices such as solar cells.

[0223] The present invention includes a molybdenum oxyhalide manufactured by a manufacturing method.

[0224] Hereinafter, an example of producing molybdenum dioxydichloride as a final product, which is useful as a precursor for molybdenum metal deposition, is provided using a device according to the schematic diagram of Fig. 10. At this time, the atmosphere inside the housing was dry air (moisture content of 1 mass ppm or less). At this time, for easier understanding by those skilled in the art, the above-mentioned kn hal 10kn or less hal The halogen element supply conditions are satisfied, but the supply conditions of the halogen-containing gas are expressed by expressing the unit as the volume of chlorine gas supplied per unit mass of molybdenum dioxide.

[0225] (Example)

[0226] Molybdenum dioxide powder (100 μm to 1 mm in size) was used as a raw material, the raw material was heated to a temperature of 200°C, and nitrogen gas from which moisture was removed by a moisture adsorber was supplied to the raw material, thereby controlling the moisture content of the molybdenum dioxide to 100 mass ppm or less.

[0227] A halogen-containing gas, chlorine gas alone whose moisture content was controlled to 1 mass ppm or less by a moisture adsorber and a gas purifier, or chlorine gas from which moisture was removed by a moisture adsorber and nitrogen gas from which moisture was removed by a moisture adsorber were mixed to form a mixed gas, and then moisture in the gas was removed again by a gas purifier (maintaining the moisture content to 1 mass ppm or less) and then supplied to the uniform zone starting area. In Table 1, the inert gas concentration (%) refers to the volume fraction of nitrogen gas contained in the mixed gas.

[0228] Raw material transport speed (V), temperature of uniform zone (T rx ), residue storage temperature (T res ), first line temperature (T L1 ), capture temperature (cooling temperature by the first cooling unit, T Sol ), temperature of the refined transport section (temperature heated by the transport heating section, T tra ), sublimation temperature (temperature at which the refining heating element is heated, Tsub ), second line temperature (T L2 ), the temperature (T) heated by the solidification heating unit cryH ) / solidification temperature (cooling temperature by the first cooling unit, T cryL ), the volume of chlorine gas supplied per unit mass of molybdenum dioxide (HR), and the time required to pass through the uniform zone (Rx T) are summarized in Table 1.

[0229] (Table 1)

[0230]

[0231] The density (density of the captured molybdenum dioxydichloride, den1) during the synthesis of molybdenum dioxydichloride, the density of the final molybdenum dioxydichloride obtained by solidification (den2), the production yield (Y) of the final molybdenum dioxydichloride, the purity (P), the moisture contamination (M), and the production rate of the final molybdenum dioxydichloride are summarized in Table 2.

[0232] (Table 2)

[0233]

[0234] For comparison, 1 g of molybdenum dioxide powder heated to 200°C to remove moisture was placed in a batch reactor, and chlorine gas from which moisture had been removed was injected at a rate of 20 cc / min, and the reaction was carried out at 200°C for 60 minutes. Thereafter, the batch reactor was cooled to 25°C to obtain solid molybdenum dioxide, which was then transferred to a purifier, sublimated at 200°C, and solidified again at -20°C to obtain the final molybdenum dioxide dichloride manufactured in a batch manner. The molybdenum dioxide dichloride manufactured in a batch manner was severely contaminated with moisture, and its production yield was only 85%. The above embodiment is one example, and the present invention is not limited thereto.

[0235] The above embodiments are merely examples and the present invention is not limited thereto. Anything that has substantially the same configuration and achieves the same operational effects as the technical concepts described in the claims of the present invention is included within the technical scope of the present invention.

Claims

1. Contains a reaction zone into which halogen-containing gas is supplied, The raw material containing molybdenum oxide is transported through the reaction zone, A molybdenum oxyhalide manufacturing device, wherein molybdenum oxyhalide is produced.

2. In paragraph 1, A molybdenum oxyhalide manufacturing device in which the above raw materials are continuously transported.

3. In paragraph 1, A molybdenum oxyhalide manufacturing device, wherein the average transport speed of raw materials passing through the above reaction zone is 0.01 m / hr to 10.0 m / hr.

4. In paragraph 1, A molybdenum oxyhalide manufacturing device, wherein at least one energy selected from the group consisting of thermal energy, light energy, and vibrational energy is applied to the above reaction zone.

5. In paragraph 1, The above manufacturing device, A case providing an internal space including the above reaction zone and A molybdenum oxyhalide manufacturing device comprising an energy applying unit that applies energy to the above reaction zone.

6. In paragraph 5, A molybdenum oxyhalide manufacturing device, wherein the manufacturing device includes a transport means for transporting the raw material so as to pass through the reaction zone.

7. In paragraph 6, A molybdenum oxyhalide manufacturing device, wherein the above-mentioned transport means includes a transport shaft having a transport blade and being rotatably provided, or includes a belt moving in a designed direction.

8. In paragraph 5, The material of the above case is a molybdenum oxyhalide manufacturing device, which is a non-metallic inorganic material of a crystalline, amorphous, or composite phase in which crystalline and amorphous phases are mixed.

9. In paragraph 5, A molybdenum oxyhalide manufacturing device, wherein a baffle is provided in the internal space in front of the inflow point where the halogen-containing gas flows in based on the direction of transport of the raw material to prevent gas backflow.

10. In paragraph 1, The above manufacturing device A first gas supply unit including a first gas cylinder storing halogen gas and a first moisture absorber, and A molybdenum oxyhalide manufacturing apparatus further comprising a second gas supply unit including a second gas cylinder storing an inert gas and a second moisture absorber.

11. In paragraph 10, The above manufacturing device A molybdenum oxyhalide manufacturing apparatus further comprising a gas purifier for removing moisture from a halogen-containing gas including a halogen gas supplied from the first gas supply unit and an inert gas supplied from the second gas supply unit.

12. In paragraph 1, The above manufacturing device A molybdenum oxyhalide manufacturing device further comprising a residue storage unit that receives and stores a residual solid phase discharged from the above reaction unit, and a residue heating unit that heats the residue storage unit.

13. In paragraph 1, The above manufacturing device, A molybdenum oxyhalide manufacturing device further comprising a capturing unit that receives the above molybdenum oxyhalide in a gaseous state and captures it in a solid state.

14. In any one of paragraphs 1 to 13, A molybdenum oxyhalide manufacturing device, wherein the above manufacturing device further includes a heating unit that heats a wall surface defining a space used for transporting or storing the gaseous molybdenum oxyhalide, which comes into contact with the gaseous molybdenum oxyhalide discharged from the reaction zone.

15. Raw material supply unit for supplying raw materials containing molybdenum oxide; A reaction transport section including a reaction zone into which a halogen-containing gas is supplied and energy is applied, and a raw material supplied from the raw material supply section is transported through the reaction zone, and molybdenum oxyhalide is generated; A capturing unit that receives gaseous molybdenum oxyhalide discharged from the above reaction transfer unit and captures it in a solid phase; A purification unit that supplies the solid molybdenum oxyhalide captured in the above capturing unit and sublimates it into a gas; and A molybdenum oxyhalide manufacturing device including a solidification unit that supplies the above-mentioned sublimated molybdenum oxyhalide and solidifies it.

16. In paragraph 15, A molybdenum oxyhalide manufacturing device, wherein the above manufacturing device further includes a raw material heating unit for heating the raw material in the raw material supply unit.

17. In paragraph 15, The above manufacturing device A first line, which is a transfer line between an outlet through which gaseous molybdenum oxyhalide is discharged from the above reaction transfer section and an inlet through which the gaseous phase flows into the above capture section; A second line, which is a transfer line between an outlet through which the sublimated molybdenum oxyhalide is discharged in the above purification unit and an inlet through which the sublimated molybdenum oxyhalide is introduced in the above solidification unit; and A molybdenum oxyhalide manufacturing device further comprising a line heating unit for heating at least one line selected from a group consisting of a third line, which is a transfer line between a solid phase discharge port through which the residual solid phase of the reaction transfer unit is discharged and a solid phase inlet port of a residue storage unit through which the residual solid phase is supplied and stored.

18. In Article 15 A molybdenum oxyhalide manufacturing device, wherein the manufacturing device further includes a purification transport unit that transports the solid phase captured in the capturing unit to the purification unit, and a transport heating unit that heats the purification transport unit.

19. In Article 15 The above high-temperature part A solidified body having an internal space and an inlet formed at the upper end into which sublimated molybdenum oxyhalide is introduced, A cooling plate that is accommodated in the above solidified body and cools the sublimated molybdenum oxyhalide; and A molybdenum oxyhalide manufacturing device comprising a solidification heating unit for heating at least the upper part of a solidification body in which the inlet is formed.

20. In Article 15 The above manufacturing device comprises at least a housing providing an internal space in which the raw material supply section, reaction transfer section, capture section, refining section and solidification section are located; A molybdenum oxyhalide manufacturing device further comprising a moisture removal unit for removing moisture from the atmosphere within the housing.

21. The raw material containing molybdenum oxide passes through the reaction zone, A halogen-containing gas is supplied to the above reaction zone, A method for producing molybdenum oxyhalide, wherein molybdenum oxyhalide is produced.

22. In paragraph 21, A method for producing molybdenum oxyhalide, wherein the above raw material flows and passes through the above reaction zone.

23. In paragraph 21, A method for producing molybdenum oxyhalide, wherein the average transport speed of the raw material transported through the reaction zone is 0.01 m / hr to 10.0 m / hr.

24. In paragraph 21, A method for producing molybdenum oxyhalide, wherein at least one energy selected from the group consisting of thermal energy, light energy and vibrational energy is applied to the above reaction zone.

25. In paragraph 21, A method for producing molybdenum oxyhalide, wherein the above raw material has moisture removed in advance before being supplied to the reaction zone.

26. In paragraph 21, A method for producing molybdenum oxyhalide, wherein the halogen-containing gas is a mixed gas of a halogen gas and an inert gas, and moisture is removed from the mixed gas before being supplied to the reaction zone.

27. In paragraph 21, A method for producing molybdenum oxyhalide, wherein the temperature of the above reaction zone is 190 to 350°C.

28. In paragraph 21, A method for producing molybdenum oxyhalide, wherein the time required for the above raw material to pass through the above reaction zone is 10 to 600 minutes.

29. In Article 21 A method for producing molybdenum oxyhalide, wherein the halogen-containing gas is supplied to the reaction zone so that 1 to 10 times the reference mole number of halogen atoms required to produce 1 mole of the molybdenum oxyhalide according to the stoichiometric ratio of the molybdenum oxyhalide is supplied as a reference mole number.

30. In Article 21 A method for producing molybdenum oxyhalide, further comprising the step of cooling the generated gaseous molybdenum oxyhalide and capturing it in a solid phase.

31. In Article 30 A method for producing molybdenum oxyhalide, wherein supply of the raw material to the above reaction zone and capture into the above solid phase are performed simultaneously.

32. In paragraph 30, A method for producing molybdenum oxyhalide, wherein the wall surface defining the space used for transporting the gaseous molybdenum oxyhalide discharged from the above reaction zone is heated. 33.S1) A step of transporting a raw material containing molybdenum oxide through a reaction zone where a halogen-containing gas is supplied and energy is applied, thereby generating molybdenum oxyhalide; S2) A step of supplying and cooling the gaseous molybdenum oxyhalide produced in the step S1) to capture the molybdenum oxyhalide in a solid phase; S3) a step of sublimating the captured solid molybdenum oxyhalide into gas; and S4) A method for producing molybdenum oxyhalide, comprising the step of solidifying sublimated molybdenum oxyhalide.

34. In paragraph 33, A method for producing molybdenum oxyhalide, wherein the raw material is continuously supplied to the reaction zone in the step S1), and the gaseous molybdenum oxyhalide is continuously captured in the step S2).

35. In paragraph 33, A wall defining a space used for transporting the gaseous molybdenum oxyhalide discharged from the above reaction zone; and A method for producing molybdenum oxyhalide, wherein at least one wall surface selected from a group consisting of wall surfaces that define a space used for transporting molybdenum oxyhalide sublimated in the above step S3) is heated.

36. In paragraph 33, A method for producing molybdenum oxyhalide, wherein the molybdenum oxyhalide captured in the above solid phase is heated when transferred to a purification unit where the sublimation of the above S3) step is performed.

37. In paragraph 33, A method for producing molybdenum oxyhalide, wherein the space in which the above steps S1) to S4) are performed is located under an atmosphere from which moisture has been removed.

38. In any one of paragraphs 21 to 37, A method for producing molybdenum oxyhalide, wherein the halogen-containing gas is a chlorine-containing gas and the molybdenum oxyhalide is molybdenum dioxydichloride.

39. In any one of paragraphs 21 to 37, A method for producing molybdenum oxyhalide, wherein the above molybdenum oxide is molybdenum dioxide.

40. In any one of paragraphs 21 to 37, The above molybdenum oxyhalide is a method for producing molybdenum oxyhalide, which is a precursor for metal molybdenum deposition.

41. In any one of paragraphs 21 to 37, The above molybdenum oxyhalide is a material for forming electrodes of one or more electrodes selected from an electrode group consisting of an anode and a cathode of a diode and a source, a drain, and a gate of a transistor; or a method for producing molybdenum oxyhalide, which is a material for forming lines of one or more lines selected from a word line and a bit line of a memory device.

42. Molybdenum oxyhalide manufactured by a manufacturing method according to any one of claims 21 to 37.

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