Molybdenum precursors and related methods

Abstract

High purity molybdenum precursors and methods for purifying molybdenum precursors are provided, including obtaining a first container containing a solid reagent, evaporating at least a portion of the solid reagent to produce a vapor containing MoCl vapor and a molybdenum impurity vapor, flowing at least a portion of the MoCl vapor and at least a portion of the molybdenum impurity vapor into a second container, condensing at least a portion of the MoCl vapor in the second container to separate the MoCl from the molybdenum impurity, and removing at least a portion of the molybdenum impurity vapor from the second container to obtain a MoCl precursor.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] This disclosure relates to molybdenum precursors and related methods, including, but not limited to, purification methods, methods for verifying impurity levels, and the like. [Background technology]

[0002]

[0002] The presence of impurities in precursors used in semiconductor manufacturing can result in defects and undesirable process variations. Specifically, in the case of solid precursors, individual crystals of an impurity can add impurity vapor to the vapor stream at levels much higher than dissolved impurities at the same impurity level. Because vapor content is very sensitive to impurity levels, current analytical techniques for measuring impurity levels are unable to detect sufficiently low impurity levels. Summary of the Invention

[0003]

[0003] Some embodiments relate to a method. In some embodiments, the method includes one or more of the following steps: obtaining a first container containing a solid reagent, the solid reagent including MoCl and at least one of a molybdenum impurity, a non-molybdenum impurity, or any combination thereof; evaporating at least a first portion of the solid reagent to produce a first vapor including a first molybdenum impurity vapor; removing at least a portion of the first molybdenum impurity vapor from the first container; evaporating at least a second portion of the solid reagent to produce a second vapor including a second MoCl vapor and a second molybdenum impurity vapor; flowing at least a portion of the second MoCl vapor and at least a portion of the second molybdenum impurity vapor into a second container; condensing at least a portion of the second MoCl vapor in the second container to separate MoCl from the second molybdenum impurity vapor; and removing at least a portion of the second molybdenum impurity vapor from the second container to obtain a MoCl precursor.

[0004] Some embodiments relate to a method, in some embodiments, the method includes one or more of the following steps: obtaining a precursor container containing MoCl5 precursor and headspace vapor; removing headspace vapor from the precursor container; heating the precursor container to a target temperature; measuring the total pressure in the container to obtain a measured total pressure; and comparing the measured total pressure to a reference value to verify or not verify a low impurity content of the MoCl5 precursor, where if the measured total pressure is within 1%-10% of the true vapor pressure of MoCl5, the low impurity content is verified, and if the measured total pressure is not within 1%-10% of the true vapor pressure of MoCl5, the low impurity content is not verified.

[0005] Some embodiments relate to a method, in some embodiments, the method includes one or more of the following steps: obtaining a precursor container containing MoCl5 precursor and headspace vapor; removing headspace vapor from the precursor container; heating the precursor container to a target temperature; measuring a rate of change of total pressure in the container to obtain a measured total pressure rate of change; and comparing the measured rate of change of total pressure to a reference value to verify or not verify a low impurity content of the MoCl5 precursor, wherein if the rate of change of total pressure is greater than the reference value, the low impurity content of the precursor is not verified, and if the rate of change of total pressure is less than or equal to the reference value, the low impurity content of the precursor is verified.

[0006] Some embodiments relate to a precursor container. In some embodiments, the precursor container contains a MoCl precursor. In some embodiments, when the precursor container is maintained at a temperature between 340 K and 465 K, the measured vapor pressure of the MoCl precursor is less than 1.3 times the calculated vapor pressure of MoCl.

[0007]

[0007] Certain embodiments of the present disclosure are herein described, by way of example only, with reference to the accompanying drawings. Referring now in detail to the drawings, it is emphasized that the illustrated embodiments are exemplary and are intended for illustrative discussion of embodiments of the present disclosure. In this regard, when read in conjunction with the drawings, it will become apparent to those skilled in the art how embodiments of the present disclosure may be practiced. [Brief explanation of the drawings]

[0008] [Figure 1A] 8 is a flowchart of a method for purifying a molybdenum precursor, according to some embodiments. [Figure 1B] 1 is a flowchart of a method for purifying a molybdenum precursor, according to some embodiments. [Figure 2A]

[0009] 1 is a flowchart of a method for verifying low molybdenum impurity content of a molybdenum precursor, according to some embodiments. [Figure 2B] 1 is a flowchart of a method for verifying low molybdenum impurity content of a molybdenum precursor, according to some embodiments. [Figure 3]

[0010] FIG. 2 is a graphical representation of a vapor pressure curve, according to some embodiments. [Figure 4]

[0011] 1 is a graph illustrating the relationship between vapor pressure and pumping time, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0009]

[0012] Among the benefits and improvements disclosed, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. While detailed embodiments of the present disclosure are disclosed herein, it should be understood that the disclosed embodiments are merely exemplary of the present disclosure, which may be embodied in various forms. Moreover, the examples given of various embodiments of the present disclosure are illustrative rather than limiting.

[0010]

[0013] All prior patents and publications referenced herein are incorporated by reference in their entirety.

[0011]

[0014] Throughout this specification and claims, the following terms have the meanings expressly associated therewith unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, although they may. Additionally, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, although they may. It is intended that all embodiments of the present disclosure may be combined without departing from the scope or spirit of the disclosure.

[0012]

[0015] As used herein, the term "based on" is not exclusive and allows for the use of additional unrecited factors unless the context clearly indicates otherwise. Additionally, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0013]

[0016] Some embodiments relate to methods for purifying molybdenum precursors. Various embodiments of methods for purifying molybdenum precursors are provided herein. It will be understood that any combination of steps can be performed in any order in the methods for purifying molybdenum precursors without departing from the scope of the present disclosure. Thus, the depiction of various methods and their steps in different figures is not limiting, and any combination of steps in any of the figures disclosed herein can be performed in any combination without departing from the scope of the present disclosure.

[0014]

[0017] 1A-1B are flowcharts of a method 100 for purifying a molybdenum precursor, according to some embodiments. As shown in FIGS. 1A-1B, the method 100 for purifying a molybdenum precursor may include one or more of the following steps: obtaining a first container 102 containing a solid reagent; evaporating at least a first portion of the solid reagent 104 to produce a first vapor containing a first molybdenum impurity vapor; removing at least a portion of the first molybdenum impurity vapor 106 from the first container; and removing at least a second portion of the solid reagent 108 to produce a second vapor containing a second MoCl vapor and a second molybdenum impurity vapor. flowing at least a portion of the second MoCl vapor and at least a portion of the second molybdenum impurity vapor into a second container in a step 110; condensing at least a portion of the second MoCl vapor in the second container in a step 112; condensing at least a portion of the second MoCl vapor in the second container to separate MoCl from the second molybdenum impurity vapor in a step 112; and removing at least a portion of the second molybdenum impurity vapor from the second container in a step 114 to obtain the MoCl precursor.

[0015]

[0018] In step 102, in some embodiments, a first container is obtained. In some embodiments, the first container includes a solid reagent. In some embodiments, the first container includes at least one of a molybdenum precursor, a molybdenum impurity, a non-molybdenum impurity, or any combination thereof. In some embodiments, the molybdenum precursor includes molybdenum pentachloride (MoCl5). In some embodiments, the molybdenum impurity includes at least one of a molybdenum oxychloride, a molybdenum chloride (other than MoCl5), a molybdenum oxide, or any combination thereof. In some embodiments, the molybdenum impurity includes at least one of molybdenum tetrachloride (MoCl4), molybdenum oxytetrachloride (MoOCl4), molybdenum dioxydichloride (MoOCl2), molybdenum dioxydichloride (MoOCl2(H2O)), molybdenum trioxide (MoO3), or any combination thereof. In some embodiments, the molybdenum impurity includes a non-volatile molybdenum impurity. In some embodiments, the non-volatile molybdenum impurities include at least one of molybdenum tetrachloride (MoCl), molybdenum trioxide (MoO), or any combination thereof. In some embodiments, the molybdenum impurities include volatile molybdenum impurities. In some embodiments, the volatile molybdenum impurities include at least one of molybdenum oxytetrachloride (MoOCl), molybdenum dioxydichloride (MoOCl), molybdenum dioxydichloride (MoOCl(H0)), or any combination thereof. In some embodiments, the non-molybdenum impurities include molybdenum-free compounds or molecules. In some embodiments, the non-molybdenum impurities include at least one of HCl, hydrocarbons, metal-containing molecules, water, or any combination thereof.

[0016]

[0019] The molybdenum precursor, molybdenum impurities, and / or non-molybdenum impurities can independently exist in the first container in a solid phase, a gas phase, a vapor phase, or any combination thereof. In some embodiments, the solid phase is amorphous or crystalline. For example, in some embodiments, the solid phase of the molybdenum precursor is amorphous or crystalline. In some embodiments, the solid phase of the molybdenum impurities is amorphous or crystalline. In some embodiments, the solid phase of the non-molybdenum impurities is amorphous or crystalline. In some embodiments, the solid phase is free crystalline. For example, in some embodiments, the molybdenum precursor exists as free crystalline. In some embodiments, the molybdenum impurities exist as free crystalline. In some embodiments, the non-molybdenum impurities exist as free crystalline. In some embodiments, the solid phase is dissolved in the crystal lattice of another material. For example, in some embodiments, the molybdenum impurities exist within the solid phase of the molybdenum precursor (MoCl5). In some embodiments, the molybdenum impurities are dissolved in the crystal lattice of MoCl5. In some embodiments, the non-molybdenum impurities are present in the solid phase of the molybdenum precursor (MoCl5). In some embodiments, the non-molybdenum impurities are dissolved in the crystal lattice of MoCl5.

[0017]

[0020] The solid reagent can include at least one of a molybdenum precursor, a molybdenum impurity, or any combination thereof. In some embodiments, the solid reagent includes 0.1% to 15% by weight of molybdenum impurity, or any range or subrange between 0.1% and 15%, based on the total weight of the solid reagent. In some embodiments, the solid reagent includes 0.1% to 14%, 0.1% to 13%, 0.1% to 12%, 0.1% to 11%, 0.1% to 10%, 0.1% to 9%, 0.1% to 8%, 0.1% to 7%, 0.1% to 6%, 0.1% to 5%, 0.1% to 4%, 0.1% to 3%, 0.1% to 2%, 0.1% to 1%, or 0.1% to 0.5% by weight of molybdenum impurity, based on the total weight of the solid reagent. In some embodiments, the solid reagent comprises 0.5% to 15%, 1% to 15%, 2% to 15%, 3% to 15%, 4% to 15%, 5% to 15%, 6% to 15%, 7% to 15%, 8% to 15%, 9% to 15%, 10% to 15%, 11% to 15%, 12% to 15%, 13% to 15%, or 14% to 15% molybdenum impurities by weight, based on the total weight of the solid reagent. In some embodiments, the remainder of the solid reagent comprises a molybdenum precursor. For example, in some embodiments, the solid reagent comprises 40% to 99% molybdenum precursor, based on the total weight of the solid reagent.

[0018]

[0021] The first container may be configured to control its temperature. The temperature of the first container can be controlled in any suitable manner. In some embodiments, a thermal jacket for heating and / or cooling is employed around the first container. In some embodiments, a ribbon heater is wrapped around the first container. In some embodiments, a block heater having a shape that covers at least a major portion of the outer surface of the first container is used to heat the first container. In some embodiments, a resistance heater is used to heat the first container. In some embodiments, a lamp heater is used to heat the first container. In some embodiments, a block heater having a shape that covers at least a major portion of the outer surface of the first container is used to heat the first container. In some embodiments, heating is achieved by infrared or other radiant energy impinging on the first container. In some embodiments, the second container is cooled by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It will be understood that other heating and / or cooling devices and assemblies, and other configurations and arrangements of heaters and / or coolers, can be employed in the present invention without departing from the scope of the present disclosure.

[0019]

[0022] The first container may be configured to control pressure. The pressure of the first container can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the first container. The gas inlet line can be configured to supply pressurized gas to the first container from a pressurized gas source. Control of the pressurized gas to the first container can be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or any combination thereof. In some embodiments, the pressurized gas comprises an inert gas. In some embodiments, the inert gas comprises at least one of helium, argon, nitrogen, or any combination thereof. In some embodiments, a vacuum line is fluidly coupled to the first container. The vacuum line can be configured to apply a vacuum to the first container. In some embodiments, the pumping rate is controlled by a butterfly valve. It will be understood that other mechanisms for controlling the pressure of the first container can be employed in the present invention without departing from the scope of this disclosure.

[0020]

[0023] In step 104, in some embodiments, at least a first portion of the solid reagent and / or at least a first portion of the molybdenum impurity is evaporated in the first container. The evaporation of the solid reagent and / or the molybdenum impurity can produce a first vapor including a first molybdenum impurity vapor. In some embodiments, the first vapor includes a first molybdenum precursor vapor (e.g., MoCl vapor). In some embodiments, the evaporation includes applying first conditions (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the first container to produce the first molybdenum impurity vapor.

[0021]

[0024] In some embodiments, the first conditions are conditions in which the total pressure of the first vessel is below the true vapor pressure of the molybdenum impurity at a given first temperature. In some embodiments, the first conditions are conditions in which the total pressure of the first vessel is above the true vapor pressure of the molybdenum precursor at a given first temperature. In some embodiments, the molybdenum impurity comprises a volatile molybdenum impurity. In some embodiments, the first conditions are conditions in which the molybdenum impurity evaporates while minimizing the amount of molybdenum precursor that evaporates. In some embodiments, the first conditions are conditions in which the molybdenum precursor does not evaporate. In some embodiments, the first conditions are conditions in which free crystals of the molybdenum impurity evaporate. In some embodiments, the first conditions are conditions in which the molybdenum impurity present in the crystal lattice of the molybdenum precursor does not evaporate, or does not evaporate appreciably.

[0022]

[0025] The first condition may include heating the first container to a first temperature. In some embodiments, the first temperature is in the range of 60°C to 170°C, or any range or subrange between 60°C and 170°C. In some embodiments, the first temperature is in the range of 60°C to 160°C, 60°C to 150°C, 60°C to 140°C, 60°C to 130°C, 60°C to 120°C, 60°C to 110°C, 60°C to 100°C, 60°C to 90°C, 60°C to 80°C, 60°C to 70°C, 70°C to 170°C, 80°C to 170°C, 90°C to 170°C, 100°C, or 120°C. The temperature is in the range of 100°C to 160°C, 120°C to 160°C, 140°C to 160°C, 120°C to 150°C, 120°C to 140°C, or 110°C to 150°C.

[0023]

[0026] The first condition can include pressurizing (or depressurizing) the first container to a first pressure. In some embodiments, the first pressure is in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the first pressure is in the range of 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr to rr~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr~2 5Torr, 0.01Torr~20Torr, 0.01Torr~15Torr, 0.01Torr~10Torr, 0.01Torr~5Torr, 0.01Torr~1Torr, 0 .01Torr~0.1Torr, 0.1Torr~100Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Torr~10 0Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, 45Torr The pressure is in the range of 50 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, or 95 Torr to 100 Torr.

[0024]

[0027] The first vapor can include a molybdenum impurity (e.g., first molybdenum impurity vapor) at a volume greater than the molybdenum precursor (e.g., first molybdenum precursor vapor). In some embodiments, the first vapor includes less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.1%, or less than 0.01% of the molybdenum precursor, based on the total volume of the first vapor. In some embodiments, the first molybdenum impurity vapor comprises 0.01% to 10%, 0.01% to 9%, 0.01% to 8%, 0.01% to 7%, 0.01% to 6%, 0.01% to 5%, 0.01% to 4%, 0.01% to 3%, 0.01% to 2%, 0.01% to 1%, 0.01% to 0.1%, 0.1% to 10%, 1% to 10%, 2% to 10%, 3% to 10%, 4% to 10%, 5% to 10%, 6% to 10%, 7% to 10%, 8% to 10%, or 9% to 10% molybdenum precursor by volume, based on the total volume of the first vapor.

[0025]

[0028] In step 106, in some embodiments, at least a portion of the first molybdenum impurity vapor is removed from the first vessel. That is, in some embodiments, once the first molybdenum impurity vapor is vaporized, it may be removed from the first vessel, and at least a first portion of the molybdenum impurity may be separated from the molybdenum precursor. The first molybdenum impurity vapor may be removed through an outlet of the first vessel. The outlet may be fluidly coupled to a gas exhaust line, a vacuum line, or other similar line suitable for removing the first molybdenum impurity vapor from the first vessel.

[0026]

[0029] In step 108, in some embodiments, at least a second portion of the solid reagent and / or at least a second portion of the molybdenum precursor is evaporated in the first container. The evaporation of the molybdenum precursor and / or solid reagent may produce a second vapor including a second molybdenum precursor vapor and a second molybdenum impurity vapor. In some embodiments, the evaporation includes applying second conditions (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the first container to produce the second molybdenum precursor vapor and / or the second molybdenum impurity vapor.

[0027]

[0030] In some embodiments, the second conditions are conditions under which the total pressure of the second container is below the true vapor pressure of the molybdenum precursor at a given first temperature. In some embodiments, the second conditions are conditions under which the total pressure of the first container is above the true vapor pressure of the non-volatile molybdenum impurities at a given second temperature. In some embodiments, the second conditions are conditions under which the molybdenum precursor present as free crystals in the first container is evaporated. In some embodiments, the second conditions are conditions under which the molybdenum precursor is evaporated while minimizing the amount of non-volatile molybdenum impurities that evaporate. In some embodiments, the second conditions are conditions under which the non-volatile molybdenum impurities are not evaporated. In some embodiments, the second conditions are conditions under which the molybdenum impurities present in the crystal lattice of the molybdenum precursor are evaporated. In some embodiments, the second conditions are conditions under which the molybdenum impurities present in the first container as isolated crystals are evaporated. In some embodiments, when the second conditions are applied, the second molybdenum precursor vapor comprises a greater volume of molybdenum precursor than volatile molybdenum impurities and / or non-volatile molybdenum impurities, hi some embodiments, when the second conditions are applied, the second molybdenum precursor vapor comprises a greater volume of volatile molybdenum impurities than non-volatile molybdenum impurities.

[0028]

[0031] The second condition can include heating the first container at or to a second temperature. In some embodiments, the second temperature is in the range of 60°C to 170°C, or any range or subrange between 60°C and 170°C. In some embodiments, the second temperature is in the range of 60°C to 160°C, 60°C to 150°C, 60°C to 140°C, 60°C to 130°C, 60°C to 120°C, 60°C to 110°C, 60°C to 100°C, 60°C to 90°C, 60°C to 80°C, 60°C to 70°C, 70°C to 170°C, 80°C to 170°C, 90°C to 170°C, 100°C, or any range or subrange between 60°C to 170°C. The second temperature is in the range of 100°C to 170°C, 110°C to 170°C, 120°C to 170°C, 130°C to 170°C, 140°C to 170°C, 150°C to 170°C, 160°C to 170°C, 100°C to 160°C, 120°C to 160°C, 140°C to 160°C, 120°C to 150°C, 120°C to 140°C, or 110°C to 150°C. In some embodiments, the second temperature is higher than the first temperature. In some embodiments, the second temperature is lower than the first temperature.

[0029]

[0032] The second condition can include pressurizing (or depressurizing) the first container at or to a second pressure. In some embodiments, the second pressure is in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the second pressure is in the range of 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr to rr~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr~2 5Torr, 0.01Torr~20Torr, 0.01Torr~15Torr, 0.01Torr~10Torr, 0.01Torr~5Torr, 0.01Torr~1Torr, 0 .01Torr~0.1Torr, 0.1Torr~100Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Torr~10 0Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, 45Torr In some embodiments, the second pressure is in the range of 50 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, or 95 Torr to 100 Torr. In some embodiments, the second pressure is less than the first pressure. In some embodiments, the second pressure is greater than the first pressure.

[0030]

[0033] In step 110, in some embodiments, at least a portion of the second molybdenum precursor vapor and at least a portion of the second molybdenum impurity vapor are flowed into a second vessel. The vapors are flowed from the first vessel through an outlet of the first vessel. The outlet can be fluidly connected to a gas line or other similar line that is fluidly connected to an inlet of the second vessel.

[0031]

[0034] The second container may be configured to control its temperature. The temperature of the second container may be controlled in any suitable manner. In some embodiments, a heating and / or cooling thermal jacket is employed around the second container. In some embodiments, a ribbon heater is wrapped around the second container. In some embodiments, a block heater shaped to cover at least a major portion of the exterior surface of the second container is employed to heat the second container. In some embodiments, a resistance heater is employed to heat the second container. In some embodiments, a lamp heater is employed to heat the second container. In some embodiments, a hot heat transfer fluid may be brought into contact with the exterior surface of the second container to provide heating and / or cooling. In some embodiments, heating is achieved by infrared or other radiant energy applied to the second container. In some embodiments, the second container is cooled by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It will be understood that other heating and / or cooling devices and assemblies, as well as other heater and / or cooler configurations and arrangements, may be employed in the present invention without departing from the scope of the present disclosure.

[0032]

[0035] The second container may be configured to control pressure. The pressure of the second container may be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly connected to the second container. The gas inlet line may be configured to supply pressurized gas from a pressurized gas source to the second container. Control of the pressurized gas to the second container may be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or a combination thereof. In some embodiments, the pressurized gas comprises an inert gas. In some embodiments, the inert gas comprises at least one of helium, argon, nitrogen, or any combination thereof. In some embodiments, a vacuum line is fluidly connected to the second container. The vacuum line may be configured to apply a vacuum to the second container. In some embodiments, the pumping rate is controlled by a butterfly valve. It will be appreciated that other mechanisms for controlling the pressure of the first container may be employed herein without departing from the scope of this disclosure.

[0033]

[0036] In step 112, in some embodiments, at least a portion of the second molybdenum precursor vapor is condensed in the second vessel to separate the molybdenum precursor from the second molybdenum impurity vapor. In some embodiments, the condensation produces a molybdenum precursor condensate. In some embodiments, the condensation includes applying a third condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or a combination thereof) to the second vessel to produce the molybdenum precursor condensate.

[0034]

[0037] The third condition includes heating the second vessel to or at a third temperature. In some embodiments, the third temperature is in the range of 10°C to 100°C, or any range or subrange therebetween. In some embodiments, the third temperature is in the range of 20°C to 100°C, 30°C to 100°C, 40°C to 100°C, 50°C to 100°C, 60°C to 100°C, 70°C to 100°C, 80°C to 100°C, 90°C to 100°C, 10°C to 90°C, 10°C to 80°C, 10°C to 70°C, 10°C to 60°C, 10°C to 50°C, 10°C to 40°C, 10°C to 30°C, or 10°C to 20°C. In some embodiments, the third temperature is sufficient to condense the second molybdenum precursor vapor without condensing at least a portion of the second molybdenum impurity vapor.

[0035]

[0038] The third condition may include pressurizing (or depressurizing) the second container to a third pressure. In some embodiments, the third pressure is in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the third pressure is in the range of 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr ~25Torr, 0.01Torr~20Torr, 0.01Torr~15Torr, 0.01Torr~10Torr, 0.01Torr~5Torr, 0.01Torr~1Tor r, 0.01Torr~0.1Torr, 0.1Torr~100Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Torr ~100Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, In some embodiments, the third pressure is sufficient to condense the second molybdenum precursor vapor without condensing at least a portion of the second molybdenum impurity vapor.

[0036]

[0039] In some embodiments, third conditions are applied to the second vessel to produce a molybdenum precursor condensate, leaving a smaller amount of second molybdenum precursor vapor in the second molybdenum precursor vapor. In some embodiments, the third conditions are sufficient to condense the second molybdenum precursor vapor but without condensing the second molybdenum impurity vapor, or at least minimize the volume of the second molybdenum impurity vapor that is condensed to separate the molybdenum precursor from the molybdenum impurity. In some embodiments, the third conditions are conditions that result in a larger volume of the second molybdenum precursor vapor condensing than the second molybdenum impurity vapor. In some embodiments, the molybdenum precursor condensate contains a greater amount (e.g., mole fraction, volume, or mass fraction) of molybdenum precursor than the molybdenum impurity (if any). In some embodiments, the third conditions are conditions that result in a larger volume of the molybdenum impurity remaining vaporized than the molybdenum precursor. In some embodiments, the third condition is one in which the second molybdenum impurity vapor comprises molybdenum impurity dissolved in the crystal lattice of the molybdenum precursor (and, in some embodiments, isolated crystals of molybdenum oxychloride) and vaporized with the molybdenum precursor in the first vessel, and comprises a molybdenum impurity of MoCl5 at a mole fraction greater than that of molybdenum oxychloride.

[0037]

[0040] In step 114, in some embodiments, at least a portion of the second molybdenum impurity vapor is removed from the second vessel to obtain a purified precursor, such as a MoCl precursor. That is, in some embodiments, once the molybdenum precursor is condensed, the second molybdenum impurity vapor can be removed from the second vessel to separate at least a portion of the molybdenum impurity from the molybdenum precursor. The second molybdenum impurity vapor can be removed through an outlet of the second vessel. The outlet can be fluidly coupled to a gas exhaust line, vacuum line, or other similar line suitable for removing the second molybdenum impurity vapor from the second vessel.

[0038]

[0041] The purified precursor may be collected in a second vessel (or any other vessel). In some embodiments, the precursor comprises a MoCl precursor. In some embodiments, the precursor comprises a MoCl precursor having a low molybdenum impurity content. In some embodiments, the MoCl precursor has a vapor pressure, when the second vessel (or any other vessel) is maintained at a temperature between 340 K and 465 K, that is less than 1.3 times, less than 1.2 times, or less than 1.1 times the calculated vapor pressure of MoCl, as determined according to the following formula: TIFF2025541116000002.tif10170 In some embodiments, MoCl5 maintains vapor pressure for up to 72 hours. In some embodiments, MoCl5 maintains vapor pressure for between 5 minutes and 72 hours.

[0039]

[0042] In some embodiments, the MoCl precursor has a low molybdenum impurity content, ie, the MoCl precursor contains 0.01 wt. % to 2 wt. % molybdenum impurities, or any range or subrange therebetween, based on the total weight of the MoCl precursor. In some embodiments, the MoCl precursor comprises between 0.01% and 1.9%, between 0.01% and 1.8%, between 0.01% and 1.7%, between 0.01% and 1.6%, between 0.01% and 1.5%, between 0.01% and 1.4%, between 0.01% and 1.3%, between 0.01% and 1.2%, between 0.01% and 1.1%, between 0.01% and 1%, between 0.01% and 0.9%, between 0.01% and 0.8%, between 0.01% and 0.7%, between 0.01% and 0.6%, between 0.01% and 0.5%, between 0.01% and 0.4%, between 0.01% and 0.3%, between 0.01% and 0.2%, between 0.01% and 0.1%, or between 0.01% and 0.05% by weight of molybdenum impurities. In some embodiments, the MoCl5 precursor comprises between 0.05 wt% and 1 wt%, between 0.1 wt% and 1 wt%, between 0.2 wt% and 1 wt%, between 0.3 wt% and 1 wt%, between 0.4 wt% and 1 wt%, between 0.5 wt% and 1 wt%, between 0.6 wt% and 1 wt%, between 0.7 wt% and 1 wt%, between 0.8 wt% and 1 wt%, or between 0.9 wt% and 1 wt% of molybdenum impurities based on the total weight of the MoCl5 precursor.

[0040]

[0043] 2A-2B are flowcharts of a method 200 for verifying low molybdenum impurity content in a molybdenum precursor, according to some embodiments. As shown in FIGS. 2A-2B, in some embodiments, the method 200 for verifying low molybdenum impurity content in a molybdenum precursor can include one or more of the following steps: providing a precursor container containing MoCl precursor and headspace vapors in step 202; removing headspace vapors from the precursor container in step 204; heating the precursor container to a target temperature in step 206; measuring at least one property within the container to obtain a measured property in step 208; and comparing the measured property to a reference value in step 210 to verify or not verify low impurity content in the MoCl precursor.

[0041]

[0044] In step 202, a precursor container containing MoCl precursor and headspace vapors is obtained. The headspace vapors may include any vapors present in the headspace of the precursor container. In some embodiments, the headspace vapors include at least one of a molybdenum precursor, a molybdenum impurity, an inert material, a non-molybdenum vapor, or a combination thereof.

[0042]

[0045] In step 204, headspace vapors are removed from the precursor container. Headspace vapors can be removed from the precursor container through an outlet in the precursor container. The outlet can be fluidly connected to a gas exhaust line, a vacuum line, or other similar line suitable for removing headspace vapors from the precursor container.

[0043]

[0046] In step 206, the precursor container is heated to or at a target temperature. In some embodiments, the target temperature is a temperature in the range of 60°C to 170°C, or any range or subrange between 60°C and 170°C. In some embodiments, the target temperature is 60°C to 160°C, 60°C to 150°C, 60°C to 140°C, 60°C to 130°C, 60°C to 120°C, 60°C to 110°C, 60°C to 100°C, 60°C to 90°C, 60°C to 80°C, 60°C to 70°C, 70°C to 170°C, 80°C to 170°C, 90°C to 170°C, 100°C to 180°C, 190°C to 210°C, 220°C to 240°C, 230°C to 250°C, 240°C to 260°C, 250°C to 280°C, 260°C to 300°C, 270°C to 310°C, 280°C to 320°C, 290°C to 330°C, 340°C to 350°C, 350°C to 360°C, 360°C to 370°C, 370°C to 380°C, 380°C to 400°C, 390°C to 410°C, 420°C to 430°C, 430°C to 450°C, 440°C to 450°C, 450° The temperature is in the range of 100°C to 160°C, 120°C to 160°C, 140°C to 160°C, 120°C to 150°C, 120°C to 140°C, or 110°C to 150°C.

[0044]

[0047] In some embodiments, the precursor container is pressurized (or depressurized) to a target pressure, hi some embodiments, the target pressure is a pressure in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the target pressure is between 0.01 Torr and 95 Torr, between 0.01 Torr and 90 Torr, between 0.01 Torr and 85 Torr, between 0.01 Torr and 80 Torr, between 0.01 Torr and 75 Torr, between 0.01 Torr and 70 Torr, between 0.01 Torr and 65 Torr, between 0.01 Torr and 60 Torr, between 0.01 Torr and 55 Torr, between 0.01 Torr and 50 Torr, between 0.01 Torr and 45 Torr, between 0.01 Torr and 40 Torr, between 0.01 Torr and 35 Torr, between 0.01 Torr and 30 Torr, between 0.01 Torr and 25 Torr, between 0.01 Torr and 20 Torr, between 0.01 Torr and 15 Torr, between 0.01 Torr and 10 Torr, between 0.01 Torr and 5 Torr, between 0.01 Torr and 1 Torr r, 0.01Torr~0.1Torr, 0.1Torr~100Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Tor r~100Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr , 45Torr to 100Torr, 50Torr to 100Torr, 55Torr to 100Torr, 60Torr to 100Torr, 65Torr to 100Torr, 70Torr to 100Torr, 75Torr to 100Torr, 80Torr to 100Torr, 85Torr to 100Torr, 90Torr to 100Torr, or 95Torr to 100Torr.

[0045]

[0048] In step 208, at least one property is measured in the precursor container to obtain a measured property. In some embodiments, the at least one property is at least one of the total pressure in the precursor container, the rate of change of the total pressure in the precursor container, or a combination thereof. In some embodiments, the rate of change of the total pressure is the rate of increase of the pressure per unit time. For example, in some embodiments, the rate of change of the total pressure is the rate of increase of the pressure in Torr per minute. In some embodiments, the rate of change of the total pressure is the rate of increase of the pressure in millitorr per minute. In some embodiments, the rate of change of the total pressure in the precursor container is measured over a period of time between 30 seconds and 24 hours. It will be understood that the rate of change of the total pressure can be expressed in any suitable pressure units and time units. It will further be understood that the period over which the rate of change of the total pressure in the precursor container is measured can vary depending on the composition of the precursor (e.g., impurity levels) and the selected target temperature and / or target pressure.

[0046]

[0049] In some embodiments, the target temperature and / or target pressure are selected so that the total pressure in the precursor container is within 10% of the true vapor pressure of MoCl. In some embodiments, the target temperature and / or target pressure are selected so that the total pressure in the precursor container is equal to or less than the true vapor pressure of the molybdenum impurity. In some embodiments, the target temperature and target pressure are selected to stabilize the precursor container at a reference temperature; the inlet gas flow to the precursor container is stopped; a short vacuum pump is applied to remove the inert gas from the vapor phase in the precursor container; the precursor container is isolated from the vacuum pump; and the pressure in the precursor container is then monitored or measured over time.

[0047]

[0050] In step 210, the measured properties are compared to reference values ​​to verify or not verify the low impurity content of the MoCl precursor. In some embodiments, if the low impurity content of the MoCl precursor is verified, the MoCl precursor is ready for use 212. In some embodiments, if the low impurity content of the MoCl precursor is not verified, the method further includes step 214 of further removing molybdenum impurities from the MoCl precursor.

[0048]

[0051] In some embodiments, the measured total pressure is compared to a reference value to verify or not verify the low impurity content of the MoCl5 precursor. In some embodiments, the low molybdenum impurity content of the MoCl5 precursor is verified if the total pressure is within 0.01%-20% of the reference value, or any range or subrange therebetween. In some embodiments, the low molybdenum impurity content of the MoCl5 precursor is not verified if the total pressure is not within 0.01%-20% of the reference value. In some embodiments, the reference value is the true vapor pressure of MoCl5 at the conditions (e.g., the selected temperature, the selected pressure, or any combination thereof).

[0049] In some embodiments, the measured total pressure is between 1% and 15%, 1% and 14%, 1% and 13%, 1% and 12%, 1% and 11%, 1% and 10%, 1% and 9%, 1% and 8%, 1% and 7%, 1% and 6%, 1% and 5%, 1% and 4%, 1% and 3%, 1% and 2%, 2% and 15%, 3% and 15%, 4% and 15%, 5% and 15%, 6% and 15%, 7% and A low molybdenum impurity content is verified if the measured total pressure is within 15%, 8%-15%, 9%-15%, 10%-15%, 11%-15%, 12%-15%, 13%-15%, 14%-15%, 2%-10%, 3%-10%, 4%-10%, 5%-10%, 6%-10%, 7%-10%, 8%-10%, or 9%-10% of the true vapor pressure of MoCl5. In some embodiments, a low impurity content is verified if the measured total pressure is within 1%-10% of the true vapor pressure of MoCl5. In some embodiments, a low impurity content is not verified if the measured total pressure is not within 1%-10% of the true vapor pressure of MoCl5. In some embodiments, once a low molybdenum impurity content is verified, the MoCl5 precursor is ready for use.

[0050]

[0053] In some embodiments, the rate of change of the total pressure in the precursor container is compared to a reference value. In some embodiments, if the rate of change of the total pressure is greater than the reference value, the precursor is not verified for low molybdenum impurity content. In some embodiments, if the rate of change of the total pressure is equal to or less than the reference value, the precursor is verified for low molybdenum impurity content. For example, in some embodiments, the MoCl5 precursor is verified for low molybdenum impurity content if the rate of change of the total pressure is 20% or less, 15% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less per unit time. In some embodiments, the reference value is 50 mT / min or less. For example, in some embodiments, the reference value is 45 mT / min or less, 40 mT / min or less, 35 mT / min or less, 30 mT / min or less, 25 mT / min or less, 20 mT / min or less, 15 mT / min or less, 10 mT / min or less, or 5 mT / min or less. It can be seen that when the temperature is low, the limit value of the pressure rise rate is also low.

[0051]

[0054] Some embodiments relate to a molybdenum precursor having a sufficiently low impurity level that, when delivered to a tool used in semiconductor manufacturing or other similar processes, the molybdenum precursor, upon vaporization, is delivered to the tool at a controllable, constant flow rate without significant spikes or fluctuations in flow rate. In some embodiments, a precursor container is provided. The precursor container may contain a molybdenum precursor, such as, but not limited to, a MoCl precursor having a sufficiently low level of molybdenum impurities. In some embodiments, the MoCl precursor, when contained in the precursor container, has a vapor pressure of less than 1.3, less than 1.2, or less than 1.1 times the calculated vapor pressure of MoCl when the precursor container is maintained at a temperature between 70°C and 240°C (or any range or subrange therebetween), as determined according to the following formula: TIFF2025541116000003.tif10170 MoCl5 can maintain its vapor pressure indefinitely. In some embodiments, MoCl5 maintains its vapor pressure for up to 72 hours. In some embodiments, MoCl5 maintains its vapor pressure for 5 minutes to 72 hours, or any range or subrange therebetween.

[0052]

[0055] Aspects

[0056] Various aspects are described below. It should be understood that any one or more of the features listed in the following aspects can be combined with any one or more other aspects. Aspect 1 obtaining a first container containing a solid reagent, the solid reagent comprising MoCl5 and at least one of a molybdenum impurity, a non-molybdenum impurity, or any combination thereof; vaporizing at least a first portion of the solid reagent to produce a first vapor comprising a first molybdenum impurity vapor; removing at least a portion of the first molybdenum impurity vapor from the first vessel; vaporizing at least a second portion of the solid reagent to produce a second vapor including a second MoCl vapor and a second molybdenum impurity vapor; flowing at least a portion of the second MoCl vapor and at least a portion of the second molybdenum impurity vapor into a second vessel; condensing at least a portion of the second MoCl vapor in the second vessel to separate the MoCl from the second molybdenum impurity vapor; removing at least a portion of the second molybdenum impurity vapor from the second vessel to obtain a MoCl precursor; A method comprising: Aspect 2 10. The method of claim 1, wherein the molybdenum impurities include at least one of MoOCl, MoOCl, MoO(H), MoO, or any combination thereof. Aspect 3 3. The method of claim 2, wherein the solid reagent comprises 0.1% to 15% by weight of MoOCl4, based on the total weight of the solid reagent. Aspect 4 3. The method of claim 2, wherein the solid reagent comprises 0.1% to 15% by weight of MoO2Cl2, based on the total weight of the solid reagent. Aspect 5 3. The method of claim 2, wherein the solid reagent comprises 0.1% to 15% by weight of MoO2Cl2(H2O), based on the total weight of the solid reagent. Aspect 6 3. The method of claim 2, wherein the solid reagent comprises 0.1% to 15% by weight of MoO3, based on the total weight of the solid reagent. Aspect 7 10. The method of claim 1, wherein the solid reagent comprises 0.1% to 5% by weight of molybdenum impurity, based on the total weight of the solid reagent. Aspect 8 10. The method of claim 1, wherein the first vapor comprises a first molybdenum impurity vapor at a volume greater than MoCl. Aspect 9 10. The method of claim 1, wherein the second vapor comprises a greater volume of the second MoCl vapor than the second molybdenum impurity vapor. Aspect 10 10. The method of claim 1, wherein the MoCl5 precursor comprises 0.01 wt% to 1 wt% MoOCl4, based on the total weight of the MoCl5 precursor. Aspect 11 10. The method of claim 1, wherein the MoCl precursor comprises 0.01 wt. % to 1 wt. % MoO2Cl2, based on the total weight of the MoCl5 precursor. Aspect 12 10. The method of claim 1, wherein the MoCl precursor comprises 0.01 wt. % to 1 wt. % MoO2Cl2(H2O), based on the total weight of the MoCl5 precursor. Aspect 13 10. The method of claim 1, wherein the MoCl5 precursor comprises 0.1 wt% to 1 wt% MoO3, based on the total weight of the MoCl5 precursor. Aspect 14 obtaining a precursor container containing MoCl precursor and headspace vapor; removing headspace vapors from the precursor container; heating the precursor container to a target temperature; measuring the total pressure within the vessel to obtain a measured total pressure; MoC l5 The measured total pressure is compared to a reference value to verify or not verify that the precursor has a low impurity content. Including, Low impurity content is verified if the measured total pressure is within 1% to 10% of the true vapor pressure of MoCl5. If the measured total pressure is not within 1%-10% of the true vapor pressure of MoCl5, the low impurity content will not be verified. method. Aspect 15 15. The method of claim 14, further comprising further removing molybdenum impurities from the MoCl precursor if low impurity levels are not verified. Aspect 16 obtaining a precursor container containing MoCl precursor and headspace vapor; removing headspace vapors from the precursor container; heating the precursor container to a target temperature; measuring a rate of change of total pressure within the vessel to obtain a measured total pressure rate of change; MoC l5 The measured total pressure rate of change is compared to a reference value to verify or not verify that the precursor has a low impurity content. Including, If the rate of change of the total pressure is greater than the reference value, the low impurity content of the precursor is not verified; If the rate of change of the total pressure is below the reference value, the low impurity content of the precursor is verified. method. Aspect 17 17. The method of claim 16, wherein the reference value is a 5% change in total pressure per minute. Aspect 18 17. The method of claim 16, further comprising further removing molybdenum impurities from the MoCl precursor if low impurity levels are not verified. Aspect 19 Precursor vessel containing MoCl5 precursor Including, The MoCl5 precursor has a measured vapor pressure less than 1.3 times the calculated vapor pressure of MoCl5 when the precursor container is maintained at a temperature between 340 K and 465 K. Embodiment 20. The article of claim 1, wherein the calculated vapor pressure of MoCl5 is calculated according to the following formula: TIFF2025541116000004.tif10170 [Example]

[0053] Example 1

[0057] The material was filled into ampoules and sealed with valves under inert conditions. The ampoules were placed in a system that controlled temperature, measured absolute pressure, and enabled pumping. The ampoules were heated to a constant temperature and allowed to stabilize for 30 minutes. The ampoules were pumped for a predetermined pumping time. The pressure measurement manifold was then isolated from the pump, and pressure was measured as a function of time for 5 minutes. This process can be repeated as many times as necessary to achieve the desired purity level.

[0054] Example 2

[0058] The material was filled into an ampoule and sealed with a valve under inert conditions. The ampoule was placed in a system that controlled temperature, measured absolute pressure, and enabled pumping. After pumping and purging the inert gas, the ampoule was heated to the desired temperature and allowed to stabilize for 30 minutes. The ampoule was pumped for 10 seconds. The ampoule was allowed to thermally re-equilibrate for 5 minutes while pumping the pressure measurement manifold. The pressure measurement manifold was then separated from the pump and opened to the ampoule for pressure measurements. Pressure was measured as a function of time for 5 minutes. The material was verified because the initial pressure measurement was within 10% of the true vapor pressure of MoCl5. A pressure rise rate of less than approximately 3% / min may also verify the material.

[0055] Example 3

[0059] The material was filled into an ampoule and sealed with a valve under inert conditions. The ampoule was placed in a system that controlled temperature, measured absolute pressure, and enabled pumping. After pumping and purging the inert gas, the ampoule was heated to the desired temperature and allowed to stabilize for 30 minutes. The ampoule was pumped for 10 seconds. The ampoule was allowed to thermally re-equilibrate for 5 minutes while pumping the pressure measurement manifold. The pressure measurement manifold was then separated from the pump and opened to the ampoule for pressure measurement. Pressure was measured as a function of time for 5 minutes. The material was verified as the pressure increase rate was less than 3% / min.

[0056] Example 4

[0060] The equations that describe the measured vapor pressures of molybdenum chloride and molybdenum oxide are shown below: TIFF2025541116000005.tif10170TIFF2025541116000006.tif23170

[0057]

[0061] Figure 3 is a graphical illustration of a vapor pressure curve according to some embodiments. Figure 4 is a graphical illustration of vapor pressure versus pumping time according to some embodiments.

[0058]

[0062] It will be understood that changes may be made in details, particularly in matters of materials of construction employed and shape, size and arrangement of parts without departing from the scope of the present disclosure. The specification and described embodiments are examples, with the true scope and spirit of the present disclosure being indicated by the following claims.

Claims

1. obtaining a first container containing a solid reagent, the solid reagent being MoCl ５ and at least one of molybdenum impurities, non-molybdenum impurities, or any combination thereof; vaporizing at least a first portion of the solid reagent to produce a first vapor comprising a first molybdenum impurity vapor; removing at least a portion of the first molybdenum impurity vapor from the first vessel; The second MoCl ５ vaporizing at least a second portion of the solid reagent to produce a second vapor comprising the vapor and a second molybdenum impurity vapor; The second MoCl ５ flowing at least a portion of the vapor and at least a portion of the second molybdenum impurity vapor into a second vessel; MoCl ５ a second container of MoCl2 to separate the second impurity vapor from the second impurity vapor. ５ condensing at least a portion of the vapor; MoCl ５ removing at least a portion of the second molybdenum impurity vapor from the second vessel to obtain a precursor; A method comprising:

2. The molybdenum impurity is MoOCl ４ , MoO ２ Cl ２ , MoO ２ Cl ２ (H ２ O), MoO ３ or any combination thereof.

3. The solid reagent contains 0.1% to 15% by weight of MoOCl, based on the total weight of the solid reagent. ４ The method of claim 2 , comprising:

4. The solid reagent contains 0.1% to 15% by weight of MoO based on the total weight of the solid reagent. ２ Cl ２ The method of claim 2 , comprising:

5. The solid reagent contains 0.1% to 15% by weight of MoO ２ Cl ２ (H ２ O) based on the total weight of the solid reagent, according to the method of claim 2.

6. The solid reagent contains 0.1% to 15% by weight of MoO based on the total weight of the solid reagent. ３ The method of claim 2 , comprising:

7. 10. The method of claim 1, wherein the solid reagent comprises 0.1% to 5% by weight of molybdenum impurity, based on the total weight of the solid reagent.

8. The first vapor is MoCl ５ The method of claim 1 including a larger volume of the first molybdenum impurity vapor.

9. The second vapor is a second MoCl having a volume greater than the second molybdenum impurity vapor. ５ The method of claim 1 , comprising steam.

10. MoCl ５ The precursor is MoCl ５ 0.01 wt % to 1 wt % MoOCl, based on the total weight of the precursor ４ The method of claim 1 , comprising:

11. MoCl ５ The precursor is MoCl ５ 0.01 wt % to 1 wt % MoO based on the total weight of the precursor ２ Cl ２ The method of claim 1 , comprising:

12. MoCl ５ The precursor is MoCl ５ 0.01 wt % to 1 wt % MoO based on the total weight of the precursor ２ Cl ２ (H ２ 0). The method of claim 1 , comprising:

13. MoCl ５ The precursor is MoCl ５ 0.1% to 1% by weight of MoO, based on the total weight of the precursor ３ The method of claim 1 , comprising:

14. MoCl ５ obtaining a precursor container containing precursor and headspace vapor; removing headspace vapors from the precursor container; heating the precursor container to a target temperature; measuring the total pressure in the precursor container to obtain a measured total pressure; MoC ｌ５ The measured total pressure is compared to a reference value to verify or not verify that the precursor has a low impurity content. Including, The measured total pressure is MoCl ５ If the true vapor pressure of MoCl is within 1% to 10% of ５ The low impurity content of the precursor was verified, The measured total pressure is MoCl ５ If the vapor pressure of MoCl is not within 1% to 10% of the true vapor pressure of ５ Low impurity content of precursors not verified method.

15. If low impurity content is not verified, MoCl ５ 15. The method of claim 14, further comprising removing molybdenum impurities from the precursor.

16. MoCl ５ obtaining a precursor container containing precursor and headspace vapor; removing headspace vapors from the precursor container; heating the precursor container to a target temperature; measuring a rate of change of total pressure in the precursor container to obtain a measured total pressure rate of change; MoC ｌ５ The measured total pressure rate of change is compared to a reference value to verify or not verify that the precursor has a low impurity content. Including, If the rate of change of the total pressure is greater than the reference value, MoCl ５ The low impurity content of the precursor was not verified, If the rate of change of the total pressure is equal to or less than the reference value, MoCl ５ The low impurity content of the precursor is verified method.

17. 17. The method of claim 16, wherein the reference value is a 5% change in total pressure per minute.

18. If low impurity content is not verified, MoCl ５ 17. The method of claim 16, further comprising removing molybdenum impurities from the precursor.

19. MoCl ５ a precursor container containing a precursor Including, MoCl ５ The precursor was calculated to be MoCl when the precursor vessel was maintained at a temperature between 340 K and 465 K. ５ 1. The article of claim 1, wherein the article has a measured vapor pressure of less than 1.3 times the vapor pressure of the article.

20. Calculated MoCl ５ 20. The article of claim 19, wherein the vapor pressure of

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