Molybdenum precursors and related methods

Abstract

The present invention provides a molybdenum precursor having high purity and a method of purifying the molybdenum precursor. A method comprises: obtaining a first container comprising a solid reagent; vaporizing at least a portion of the solid reagent to produce a vapor including MoCl5 vapor and molybdenum impurity vapor; enabling at least one part of the MoCl5 vapor and at least one part of the molybdenum impurity vapor to flow to a second container; condensing at least a portion of the MoCl5 vapor in the second vessel to separate the MoCl5 from the molybdenum impurities; and removing at least a portion of the molybdenum impurity vapor from the second vessel to obtain a MoCl5 precursor.

Description

Technical Field

[0001] The present disclosure relates to molybdenum precursors and related methods, including, for example and without limitation, methods for purifying molybdenum precursors and methods for verifying low impurity levels. Background Art

[0002] The presence of impurities in precursors used in semiconductor fabrication can introduce defects and undesirable process variability. Specifically, for solid precursors, a single impurity crystal can add impurity vapor to the vapor stream at levels far higher than dissolved impurities at the same impurity level. Because vapor content is highly sensitive to impurity levels, current analytical techniques used to measure impurity levels cannot detect sufficiently low impurity levels. Summary of the Invention

[0003] Some embodiments relate to a method. In some embodiments, the method includes one or more of the following steps: obtaining a first container comprising 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 container; vaporizing at least a second portion of the solid reagent to produce a second vapor comprising a second MoCl5 vapor and a second molybdenum impurity vapor; flowing at least a portion of the second MoCl5 vapor and at least a portion of the second molybdenum impurity vapor to a second container; condensing at least a portion of the second MoCl5 vapor in the second container to separate the MoCl5 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 MoCl5 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 including a MoCl5 precursor and headspace vapor; removing the headspace vapor from the precursor container; heating the precursor container to a target temperature; measuring a total pressure within the container to obtain a measured total pressure; comparing the measured total pressure to a reference value to verify or fail to verify a low impurity content of the MoCl5 precursor, wherein the low impurity content is verified when the measured total pressure is within 1% to 10% of the true vapor pressure of the MoCl5; and wherein the low impurity content is not verified when the measured total pressure is not within 1% to 10% of the true vapor pressure of the MoCl5.

[0005] Some embodiments relate to a method. In some embodiments, the method comprises one or more of the following steps: obtaining a precursor container comprising a MoCl5 precursor and headspace vapor; removing the headspace vapor from the precursor container; heating the precursor container to a target temperature; measuring a rate of change of total pressure within the container to obtain a measured rate of change of total pressure; 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 when the rate of change of total pressure is greater than the reference value, the low impurity content of the precursor is not verified; and when the rate of change of total pressure is equal to or less than the reference value, the low impurity content of the precursor may be verified.

[0006] Some embodiments relate to a precursor container. In some embodiments, the precursor container includes a MoCl5 precursor. In some embodiments, when the precursor container is maintained at a temperature of 340K to 465K, the measured vapor pressure of the MoCl5 precursor is less than 1.3×the calculated vapor pressure of MoCl5. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Some embodiments of the present invention are described herein by way of example only and with reference to the accompanying drawings. With specific reference now to the drawings in detail, it should be emphasized that the embodiments shown are given by way of example and for purposes of illustrative discussion of embodiments of the present invention. In this regard, the description taken in conjunction with the drawings makes apparent to those skilled in the art the manner in which embodiments of the present invention may be practiced.

[0008] Figures 1A-1B is a flow chart of a method for purifying a molybdenum precursor according to some embodiments.

[0009] Figures 2A-2B is a flow chart of a method for verifying low molybdenum impurity content of a molybdenum precursor according to some embodiments.

[0010] Figure 3 is a graphical view of a vapor pressure curve according to some embodiments.

[0011] Figure 4 is a graphical view of vapor pressure versus pumping time, according to some embodiments. DETAILED DESCRIPTION

[0012] In addition to the benefits and improvements already disclosed, other objects and advantages of the present invention will become apparent from the following description and accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure that can be embodied in various forms. Furthermore, each example given for various embodiments of the present invention is intended to be illustrative and not limiting.

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

[0014] Throughout the specification and claims, unless the context clearly dictates otherwise, the following terms have the meanings explicitly associated herein. 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. All embodiments of the present invention are intended to be combined without departing from the scope or spirit of the invention.

[0015] As used herein, unless the context clearly dictates otherwise, the term "based on" is not exclusive and allows for being based on other unstated factors. In addition, throughout the specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in..." includes "in..." and "on..."

[0016] Some embodiments relate to methods for purifying a molybdenum precursor. Various embodiments of methods for purifying a molybdenum precursor are provided herein. It should be understood that any combination of steps, in any order, may be performed in a method for purifying a molybdenum precursor without departing from the scope of the present invention. Therefore, the various methods and steps depicted in the various figures should not be considered limiting, as any combination of steps in any of the figures disclosed herein may be performed in any combination without departing from the scope of the present invention.

[0017] Figures 1A-1B FIG. 1 is a flow chart of a method 100 for purifying a molybdenum precursor according to some embodiments. Figures 1A-1B As shown in FIG, a method 100 for purifying a molybdenum precursor may include one or more of the following steps: step 102—obtaining a first container including a solid reagent; step 104—vaporizing at least a first portion of the solid reagent to generate a first vapor including a first molybdenum impurity vapor; step 106—removing at least a portion of the first molybdenum impurity vapor from the first container; step 108—vaporizing at least a second portion of the solid reagent to generate a second vapor including a second MoCl5 vapor and a second molybdenum impurity vapor; step 110—flowing at least a portion of the second MoCl5 vapor and at least a portion of the second molybdenum impurity vapor to a second container; step 112—condensing at least a portion of the second MoCl5 vapor in the second container to separate MoCl5 from the second molybdenum impurity vapor; and step 114—removing at least a portion of the second molybdenum impurity vapor from the second container to obtain a MoCl5 precursor.

[0018] At step 102, in some embodiments, a first container may be obtained. In some embodiments, the first container comprises a solid reagent. In some embodiments, the first container comprises at least one of a molybdenum precursor, a molybdenum impurity, a non-molybdenum impurity, or any combination thereof. In some embodiments, the molybdenum precursor comprises molybdenum pentachloride (MoCl5). In some embodiments, the molybdenum impurity comprises at least one of molybdenum oxychloride, molybdenum chloride (excluding MoCl5), molybdenum oxide, or any combination thereof. In some embodiments, the molybdenum impurity comprises at least one of molybdenum tetrachloride (MoCl4), molybdenum tetrachloride oxychloride (MoOCl4), molybdenum dichloride dioxygen (MoO2Cl2), molybdenum dichloride dioxygen (MoO2Cl2(H2O)), molybdenum trioxide (MoO3), or any combination thereof. In some embodiments, the molybdenum impurity comprises a non-volatile molybdenum impurity. In some embodiments, the non-volatile molybdenum impurity comprises at least one of molybdenum tetrachloride (MoCl4), molybdenum trioxide (MoO3), or any combination thereof. In some embodiments, the molybdenum impurity comprises a volatile molybdenum impurity. In some embodiments, the volatile molybdenum impurities include at least one of molybdenum tetrachloride (MoOCl4), molybdenum dichloride (MoO2Cl2), molybdenum dichloride (MoO2Cl2(H2O)), or any combination thereof. In some embodiments, the non-molybdenum impurities include compounds or molecules that do not include molybdenum. In some embodiments, the non-molybdenum impurities include at least one of HCl, hydrocarbons, metal-containing molecules, water, or any combination thereof.

[0019] The platinum precursor, the platinum impurities and / or the non-platinum impurities may independently be present in the first container in the form of 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 platinum precursor is amorphous or crystalline. In some embodiments, the solid phase of the platinum impurities is amorphous or crystalline. In some embodiments, the solid phase of the non-platinum impurities is amorphous or crystalline. In some embodiments, the solid phase is in the form of separated crystals. For example, in some embodiments, the platinum precursor is in the form of separated crystals. In some embodiments, the platinum impurities are in the form of separated crystals. In some embodiments, the non-platinum impurities are in the form of separated crystals. In some embodiments, the solid phase is dissolved in the crystal lattice of another substance. For example, in some embodiments, the platinum impurities are present in the solid phase of the platinum precursor (MoCl5). In some embodiments, the platinum impurities are dissolved in the crystal lattice of MoCl5. In some embodiments, the non-platinum impurities are present in the solid phase of the platinum precursor (MoCl5). In some embodiments, the non-platinum impurities are dissolved in the crystal lattice of MoCl5.

[0020] The solid reagent may 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 the molybdenum impurity, or any range or sub-range 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 the 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% by weight of a molybdenum impurity, 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% of a molybdenum precursor, based on the total weight of the solid reagent.

[0021] The first container may be configured to control temperature. The temperature of the first container may be controlled in any suitable manner. In some embodiments, a heat jacket is used around the first container for heating and / or cooling. In some embodiments, a band heater is wrapped around the first container. In some embodiments, the first container is heated using a block heater shaped to cover at least a substantial portion of the exterior surface of 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 heat transfer fluid at an elevated temperature may be brought into contact with the exterior surface of the first container to achieve heating and / or cooling thereof. In some embodiments, heating is achieved by applying infrared or other radiant energy to the first container. In some embodiments, cooling of the second container is achieved by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It should be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, may be employed herein without departing from the scope of the present invention.

[0022] The first container can 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 from a pressurized gas source to the first container. The pressurized gas entering the first container can be controlled 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 speed is controlled by a butterfly valve. It should be understood that other mechanisms for controlling the pressure of the first container may be employed herein without departing from the scope of the present invention.

[0023] At 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 vaporized in a first container. The vaporization 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., MoCl5 vapor). In some embodiments, the vaporization includes applying a first condition (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.

[0024] In some embodiments, the first condition is a condition in which the total pressure of the first container is lower than the true vapor pressure of the molybdenum impurities at a given first temperature. In some embodiments, the first condition is a condition in which the total pressure of the first container is higher than the true vapor pressure of the molybdenum precursor at a given first temperature. In some embodiments, the molybdenum impurities include volatile molybdenum impurities. In some embodiments, the first condition is a condition in which the molybdenum impurities are vaporized while minimizing the amount of vaporized molybdenum precursor. In some embodiments, the first condition is a condition in which the molybdenum precursor is not vaporized. In some embodiments, the first condition is a condition in which separated crystals of molybdenum impurities are vaporized. In some embodiments, the first condition is a condition in which the molybdenum impurities present in the crystal lattice of the molybdenum precursor are not vaporized or are not significantly vaporized.

[0025] The first condition may include heating the first container at a first temperature or heating it to a first temperature. In some embodiments, the first temperature is a temperature in the range of 60°C to 170°C or any range or sub-range therebetween. In some embodiments, the first temperature is a temperature 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 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.

[0026] The first condition may include pressurizing (or depressurizing) the first container at a first pressure or pressurizing (or depressurizing) it to a first pressure. In some embodiments, the first pressure is a pressure in the range of 0.01 Torr to 100 Torr or any range or sub-range therebetween. In some embodiments, the first pressure is 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 50 torr, 0.01 torr to 45 torr, 0.01 torr to 40 torr, 0.01 torr to 35 torr, 0.01 torr to 30 torr, 0.01 torr to 25 torr, 0.01 torr to 20 torr, 0.01 torr to 15 torr, 0.01 torr to 10 torr, 0.01 torr to 5 torr, 0.01 torr to 5 torr, 0.01 torr to 65 torr, 0.01 torr to 60 torr, 0.01 torr to 65 torr, 0.01 torr to 60 torr, 0.01 torr to 65 torr, 0.01 torr to 60 torr, or 95 Torr to 100 Torr.

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

[0028] At step 106, in some embodiments, at least a portion of the first molybdenum impurity vapor is removed from the first container. That is, in some embodiments, once vaporized, the first molybdenum impurity vapor can be removed from the first container to separate at least the first portion of the molybdenum impurities from the molybdenum precursor. The first molybdenum impurity vapor can be removed via an outlet of the first container. The outlet can 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 container.

[0029] At 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 vaporized in the first container. The vaporization of the molybdenum precursor and / or the solid reagent may produce a second vapor including a second molybdenum precursor vapor and a second molybdenum impurity vapor. In some embodiments, the vaporization includes applying a second condition (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.

[0030] In some embodiments, the second condition is a condition in which the total pressure of the first container is lower than the true vapor pressure of the molybdenum precursor at a given second temperature. In some embodiments, the second condition is a condition in which the total pressure of the first container is higher than the true vapor pressure of the non-volatile molybdenum impurities at a given second temperature. In some embodiments, the second condition is a condition in which the molybdenum precursor in the form of separated crystals present in the first container is vaporized. In some embodiments, the second condition is a condition in which the molybdenum precursor is vaporized while minimizing the amount of non-volatile molybdenum impurities that are vaporized. In some embodiments, the second condition is a condition in which non-volatile molybdenum impurities are not vaporized. In some embodiments, the second condition is a condition in which molybdenum impurities present in the crystal lattice of the molybdenum precursor are vaporized. In some embodiments, the second condition is a condition in which molybdenum impurities in the form of separated crystals present in the first container are vaporized. In some embodiments, when the second condition is applied, the second molybdenum precursor vapor includes a volume of molybdenum precursor greater than the volume of volatile molybdenum impurities and / or non-volatile molybdenum impurities. In some embodiments, when the second condition is applied, the second molybdenum precursor vapor includes a volume of volatile molybdenum impurities greater than the volume of non-volatile molybdenum impurities.

[0031] The second condition may include heating the first container at a second temperature or heating it to a second temperature. In some embodiments, the second temperature is a temperature in the range of 60°C to 170°C or any range or sub-range therebetween. In some embodiments, the second 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, 10 ... In some embodiments, the second temperature is greater than the first temperature. In some embodiments, the second temperature is less than the first temperature.

[0032] The second condition may include pressurizing (or depressurizing) the first container at a second pressure or pressurizing (or depressurizing) it to a second pressure. In some embodiments, the second pressure is a pressure in the range of 0.01 Torr to 100 Torr or any range or sub-range therebetween. In some embodiments, the second pressure is 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 50 torr, 0.01 torr to 45 torr, 0.01 torr to 40 torr, 0.01 torr to 35 torr, 0.01 torr to 30 torr, 0.01 torr to 25 torr, 0.01 torr to 20 torr, 0.01 torr to 15 torr, 0.01 torr to 10 torr, 0.01 torr to 5 torr, 0.01 torr to 5 torr, 0.01 torr to 65 torr, 0.01 torr to 60 torr, 0.01 torr to 65 torr, 0.01 torr to 60 torr, 0.01 torr to 65 torr, 0.01 torr to 60 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.

[0033] At 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 directed to a second vessel. The vapors may flow from the first vessel through an outlet of the first vessel. The outlet may be fluidly coupled to a gas line or other similar line that is fluidly coupled to an inlet of the second vessel.

[0034] The second container may be configured to control temperature. The temperature of the second container may be controlled in any suitable manner. In some embodiments, a heat jacket is used around the second container for heating and / or cooling. In some embodiments, a band heater is wrapped around the second container. In some embodiments, the second container is heated using a block heater shaped to cover at least a substantial portion of the exterior surface of the second container. In some embodiments, a resistance heater is used to heat the second container. In some embodiments, a lamp heater is used to heat the second container. In some embodiments, a heat transfer fluid at an elevated temperature may be brought into contact with the exterior surface of the second container to achieve heating and / or cooling. In some embodiments, heating is achieved by applying infrared or other radiant energy to the second container. In some embodiments, cooling of the second container is achieved by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It should be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, may be employed herein without departing from the scope of the present invention.

[0035] The second container can be configured to control pressure. The pressure of the second container can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the second container. The gas inlet line can be configured to supply pressurized gas from a pressurized gas source to the second container. The pressurized gas entering the second container can be controlled 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 second container. The vacuum line can be configured to apply a vacuum to the second container. In some embodiments, the pumping speed is controlled by a butterfly valve. It should be understood that other mechanisms for controlling the pressure of the first container may be employed herein without departing from the scope of the present invention.

[0036] At step 112, in some embodiments, at least a portion of the second molybdenum precursor vapor is condensed in the second container 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 comprises applying a third condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the second container to produce the molybdenum precursor condensate.

[0037] The third condition may include heating the second container at or to a third temperature. In some embodiments, the third temperature is a temperature in the range of 10°C to 100°C or any range or sub-range therebetween. In some embodiments, the third temperature is a temperature 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 a temperature sufficient to condense the second molybdenum precursor vapor without condensing at least a portion of the second molybdenum impurity vapor.

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

[0039] In some embodiments, the third condition is applied to the second container to produce a platinum precursor condensate, thereby leaving a second platinum precursor vapor with a smaller amount of the second platinum precursor vapor. In some embodiments, the third condition is sufficient to condense the second platinum precursor vapor without condensing the second platinum impurity vapor or at least minimize the volume of the second platinum impurity vapor that is condensed to separate the platinum precursor and the platinum impurities. In some embodiments, the third condition is a condition in which the second platinum precursor vapor having a volume greater than the second platinum impurity vapor condenses. In some embodiments, the platinum precursor condensate includes a platinum precursor having an amount (such as a mole fraction, volume, or mass fraction) greater than the platinum impurity (if present). In some embodiments, the third condition is a condition in which the platinum impurities having a volume greater than the platinum precursor remain gasified. In some embodiments, the third condition is a condition in which the second platinum impurity vapor includes a molybdenum impurity dissolved in the lattice of the platinum precursor (and in some embodiments, separated crystals of platinum oxychloride) and gasified in the first container together with the platinum precursor. The molar fraction of MoCl5 is greater than platinum oxychloride.

[0040] At step 114, in some embodiments, at least a portion of the second molybdenum impurity vapor is removed from the second container to obtain a purified precursor (e.g., a MoCl5 precursor). That is, in some embodiments, once the molybdenum precursor has condensed, the second molybdenum impurity vapor can be removed from the second container to separate at least a portion of the molybdenum impurities from the molybdenum precursor. The second molybdenum impurity vapor can be removed via an outlet of the second container. The outlet can be fluidly coupled to a gas exhaust line, a vacuum line, or other similar line suitable for removing the second molybdenum impurity vapor from the second container.

[0041] The purified precursor can be recovered in a second container (or any other container). In some embodiments, the precursor comprises a MoCl5 precursor. In some embodiments, the precursor comprises a MoCl5 precursor having a low molybdenum impurity content. In some embodiments, the vapor pressure of the MoCl5 precursor is less than 1.3×, less than 1.2×, or less than 1.1× the calculated MoCl5 vapor pressure when the second container (or any other container) is maintained at a temperature between 340K and 465K, as determined according to the following formula:

[0042]

[0043] In some embodiments, the MoCl5 maintains vapor pressure for a duration of up to 72 hours. In some embodiments, the MoCl5 maintains vapor pressure for a duration of 5 minutes to 72 hours.

[0044] In some embodiments, the MoCl5 precursor has a low molybdenum impurity content. In some embodiments, the MoCl5 precursor comprises 0.01 wt% to 2 wt% or any range or sub-range between 0.01% and 2% molybdenum impurities, based on the total weight of the MoCl5 precursor. In some embodiments, the MoCl5 precursor comprises 0.01 wt% to 1.9 wt%, 0.01 wt% to 1.8 wt%, 0.01 wt% to 1.7 wt%, 0.01 wt% to 1.6 wt%, 0.01 wt% to 1.5 wt%, 0.01 wt% to 1.4 wt%, 0.01 wt% to 1.3 wt%, 0.01 wt% to 1.2 wt%, 0.01 wt% to 1.1 wt%, ... 0.01 wt% to 1 wt%, 0.01 wt% to 0.9 wt%, 0.01 wt% to 0.8 wt%, 0.01 wt% to 0.7 wt%, 0.01 wt% to 0.6 wt%, 0.01 wt% to 0.5 wt%, 0.01 wt% to 0.4 wt%, 0.01 wt% to 0.3 wt%, 0.01 wt% to 0.2 wt%, 0.01 wt% to 0.1 wt% or 0.01 wt% to 0.05 wt% molybdenum impurities. In some embodiments, the MoCl5 precursor includes 0.05 wt% to 1 wt%, 0.1 wt% to 1 wt%, 0.2 wt% to 1 wt%, 0.3 wt% to 1 wt%, 0.4 wt% to 1 wt%, 0.5 wt% to 1 wt%, 0.6 wt% to 1 wt%, 0.7 wt% to 1 wt%, 0.8 wt% to 1 wt%, or 0.9 wt% to 1 wt% of molybdenum impurities based on the total weight of the MoCl5 precursor.

[0045] Figures 2A-2B is a flow chart of a method 200 for verifying a low molybdenum impurity content of a molybdenum precursor according to some embodiments. Figures 2A-2B As shown in FIG, in some embodiments, a method 200 for verifying a low molybdenum impurity content of a molybdenum precursor may include one or more of the following steps: step 202—obtaining a precursor container including a MoCl5 precursor and a headspace vapor; step 204—removing the headspace vapor from the precursor container; step 206—heating the precursor container to a target temperature; step 208—measuring at least one property within the container to obtain a measured property; and step 210—comparing the measured property to a reference value to verify or not verify the low impurity content of the MoCl5 precursor.

[0046] At step 202, a precursor vessel comprising a MoCl5 precursor and a headspace vapor is obtained. The headspace vapor may include any vapor present in the headspace of the precursor vessel. In some embodiments, the headspace vapor comprises at least one of a molybdenum precursor, a molybdenum impurity, an inert, a non-molybdenum vapor, or any combination thereof.

[0047] At step 204, headspace vapor is removed from the precursor container. The headspace vapor can be removed from the precursor container through an outlet of the precursor container. The outlet can be fluidly coupled to a gas exhaust line, a vacuum line, or other similar line suitable for removing headspace vapor from the precursor container.

[0048] At step 206, the precursor container is heated at or to 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 sub-range therebetween. In some embodiments, the target temperature is a temperature 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 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.

[0049] In some embodiments, the precursor container is pressurized (or depressurized) to a target pressure. In 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 a pressure 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 50 torr, 0.01 torr to 45 torr, 0.01 torr to 40 torr, 0.01 torr to 35 torr, 0.01 torr to 30 torr, 0.01 torr to 25 torr, 0.01 torr to 20 torr, 0.01 torr to 15 torr, 0.01 torr to 10 torr, 0.01 torr to 5 torr, 0.01 torr to 0. or 95 Torr to 100 Torr.

[0050] At step 208, at least one property is measured within the precursor container to obtain a measured property. In some embodiments, the at least one property is at least one of the total pressure within the precursor container, the rate of change of the total pressure within the precursor container, or any combination thereof. In some embodiments, the rate of change of the total pressure is the rate of increase of pressure per unit time. For example, in some embodiments, the rate of change of the total pressure is the rate of increase of pressure expressed in Torr / minute. In some embodiments, the rate of change of the total pressure is the rate of increase of pressure expressed in millitorr / minute. In some embodiments, the rate of change of the total pressure within the precursor container is measured for a period of 30 seconds to 24 hours. It should be understood that the rate of change of the total pressure can be expressed in any suitable pressure units and time units. It should further be understood that the duration of measuring the rate of change of the total pressure within the precursor container can vary depending on the composition of the precursor (e.g., impurity levels) and the selected target temperature and / or target pressure.

[0051] In some embodiments, the target temperature and / or target pressure are selected so that the total pressure of the precursor vessel is within 10% of the true vapor pressure of MoCl5. In some embodiments, the target temperature and / or target pressure are selected so that the total pressure of the precursor vessel is below the true vapor pressure of the molybdenum impurity. In some embodiments, the target temperature and target pressure are selected to stabilize the precursor vessel at a reference temperature; stop the inlet gas flow to the precursor vessel; apply a short vacuum pump to remove the inert gas from the vapor phase in the precursor vessel; disconnect the precursor vessel from the vacuum pump; and then monitor or measure the pressure in the precursor vessel over time.

[0052] At step 210, the measured properties are compared with reference values to verify or not verify the low impurity content of the MoCl5 precursor. In some embodiments, when the low impurity content of the MoCl5 precursor is verified, the MoCl5 precursor is ready for use 212. In some embodiments, when the low impurity content of the MoCl5 precursor is not verified, the method further includes step 214 - further removing molybdenum impurities from the MoCl5 precursor.

[0053] In some embodiments, the measured total pressure is compared to a reference value to verify or fail to verify the low impurity content of the MoCl5 precursor. In some embodiments, the low molybdenum impurity content of the MoCl5 precursor is verified when the total pressure is within 0.01% to 20% of the reference value, or any range or sub-range therebetween. In some embodiments, the low molybdenum impurity content of the MoCl5 precursor is failed to be verified when the total pressure is not within 0.01% to 20% of the reference value. In some embodiments, the reference value is the actual vapor pressure of MoCl5 under different conditions (e.g., a selected temperature, a selected pressure, or any combination thereof).

[0054] In some embodiments, if the total pressure is measured at 1% to 15%, 1% to 14%, 1% to 13%, 1% to 12%, 1% to 11%, 1% to 10%, 1% to 9%, 1% to 8%, 1% to 7%, 1% to 6%, 1% to 5%, 1% to 4%, 1% to 3%, 1% to 2%, 2% to 15%, 3% to 15%, 4% to 15% of the actual vapor pressure of MoCl5 under different conditions, %, 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%, 14% to 15%, 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%, then the low molybdenum impurity content can be verified. In some embodiments, the low impurity content can be verified when the measured total pressure is within 1% to 10% of the true vapor pressure of MoCl5. In some embodiments, the low impurity content is not verified when the measured total pressure is not within 1% to 10% of the true vapor pressure of MoCl5. In some embodiments, when the low molybdenum impurity content is verified, the MoCl5 precursor is ready for use.

[0055] In some embodiments, the rate of change of the total pressure within the precursor container is compared to a reference value. In some embodiments, when the rate of change of the total pressure is greater than the reference value, the low molybdenum impurity content of the precursor is not verified. In some embodiments, when the rate of change of the total pressure is equal to or less than the reference value, the low molybdenum impurity content of the precursor may be verified. For example, in some embodiments, when the rate of change of the total pressure per unit time 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, the low molybdenum impurity content of the MoCl5 precursor may be verified. 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 will be appreciated that at lower temperatures, the limit on the rate of pressure rise will be lower.

[0056] Some embodiments relate to a molybdenum precursor having a sufficiently low impurity level so that when supplied to a tool used in semiconductor fabrication or other similar processes, the molybdenum precursor is supplied to the tool at a controllable constant flow rate when vaporized without significant flow rate spikes or variations. In some embodiments, a precursor container is provided. The precursor container may include a molybdenum precursor, such as (and not limited to) a MoCl5 precursor having a sufficiently low level of molybdenum impurities. In some embodiments, when contained in the precursor container, the vapor pressure of the MoCl5 precursor (when the precursor container is maintained at a temperature of 70°C to 240°C (or any range or sub-range therebetween)) is less than 1.3×, less than 1.2×, or less than 1.1× the calculated MoCl5 vapor pressure, as determined according to the following formula:

[0057]

[0058] MoCl5 can maintain the vapor pressure for an indefinite duration. In some embodiments, MoCl5 maintains the vapor pressure for a duration of up to 72 hours. In some embodiments, MoCl5 maintains the vapor pressure for a duration of 5 minutes to 72 hours, or any range or sub-range therebetween.

[0059] aspect

[0060] It should be understood that any one or more features recited in the following aspects may be combined with any one or more other aspects.

[0061] Aspect 1. A method comprising:

[0062] obtaining a first container comprising a solid reagent comprising MoCl5 and at least one of a molybdenum impurity, a non-molybdenum impurity, or any combination thereof;

[0063] vaporizing at least a first portion of the solid reagent to produce a first vapor including a first molybdenum impurity vapor;

[0064] removing at least a portion of the first molybdenum impurity vapor from the first container;

[0065] vaporizing at least a second portion of the solid reagent to produce a second vapor comprising a second MoCl5 vapor and a second molybdenum impurity vapor;

[0066] allowing at least a portion of the second MoCl5 vapor and at least a portion of the second molybdenum impurity vapor to flow to a second container;

[0067] condensing at least a portion of the second MoCl 5 vapor in the second container to separate the MoCl 5 from the second molybdenum impurity vapor; and

[0068] At least a portion of the second molybdenum impurity vapor is removed from the second container to obtain a MoCl5 precursor.

[0069] Aspect 2. The method of claim 1, wherein the molybdenum impurity comprises at least one of MoOCl4, MoO2Cl2, MoO2Cl2(H2O), MoO3, or any combination thereof.

[0070] Aspect 3. The method according to claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoOCl4 based on the total weight of the solid reagent.

[0071] Aspect 4. The method of claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoO2Cl2 based on the total weight of the solid reagent.

[0072] Aspect 5. The method of claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoO2Cl2(H2O) based on the total weight of the solid reagent.

[0073] Aspect 6. The method according to claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoO 3 based on the total weight of the solid reagent.

[0074] Aspect 7. The method of claim 1 , wherein the solid reagent comprises 0.1 wt % to 5 wt % of the molybdenum impurity based on the total weight of the solid reagent.

[0075] Aspect 8. The method of claim 1, wherein the first vapor comprises the first molybdenum impurity vapor having a volume greater than that of the MoCl 5 .

[0076] Aspect 9. The method of claim 1, wherein the second vapor comprises the second MoCl 5 vapor having a larger volume than the second molybdenum impurity vapor.

[0077] Aspect 10. The method of claim 1, wherein the MoCl5 precursor comprises 0.01 wt% to 1 wt% of MoOCl4 based on the total weight of the MoCl5 precursor.

[0078] Aspect 11. The method of claim 1 , wherein the MoCl 5 precursor comprises 0.01 wt % to 1 wt % MoO 2 Cl 2 based on the total weight of the MoCl 5 precursor.

[0079] Aspect 12. The method of claim 1, wherein the MoCl5 precursor comprises 0.01 wt% to 1 wt% MoO2Cl2(H2O) based on the total weight of the MoCl5 precursor.

[0080] Aspect 13. 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.

[0081] Aspect 14. A method comprising:

[0082] obtaining a precursor vessel comprising a MoCl5 precursor and a headspace vapor;

[0083] removing the headspace vapor from the precursor container;

[0084] heating the precursor container to a target temperature;

[0085] measuring a total pressure within the container to obtain a measured total pressure;

[0086] comparing the measured total pressure with a reference value to verify or not verify the low impurity content of the MoCl5 precursor,

[0087] wherein the low impurity content can be verified when the measured total pressure is within 1% to 10% of the true vapor pressure of the MoCl5;

[0088] Wherein low impurity content is not verified when the measured total pressure is not within 1% to 10% of the true vapor pressure of the MoCl 5 .

[0089] Aspect 15. The method of claim 14, further comprising further removing the molybdenum impurity from the MoCl5 precursor when the low impurity level is not verified.

[0090] Aspect 16. A method comprising:

[0091] obtaining a precursor vessel comprising a MoCl5 precursor and a headspace vapor;

[0092] removing the headspace vapor from the precursor container;

[0093] heating the precursor container to a target temperature;

[0094] measuring a rate of change of a total pressure within the container to obtain a measured rate of change of the total pressure;

[0095] comparing the measured rate of change of the total pressure with a reference value to verify or not verify the low impurity content of the MoCl5 precursor,

[0096] wherein when the rate of change of the total pressure is greater than the reference value, the low impurity content of the precursor is not verified;

[0097] When the rate of change of the total pressure is equal to or less than the reference value, the low impurity content of the precursor may be verified.

[0098] Aspect 17. The method of claim 16, wherein the reference value is 5% total pressure change / minute.

[0099] Aspect 18. The method of claim 16, further comprising further removing the molybdenum impurity from the MoCl5 precursor when the low impurity level is not verified.

[0100] Aspect 19. An article comprising:

[0101] a precursor container comprising a MoCl5 precursor,

[0102] Wherein when the precursor container is maintained at a temperature of 340K to 465K, the measured vapor pressure of the MoCl5 precursor is less than 1.3×the calculated vapor pressure of MoCl5.

[0103] Aspect 20. The article of claim 1, wherein the calculated MoCl 5 vapor pressure is calculated according to the following formula:

[0104]

[0105] Example 1

[0106] Load the material into an ampoule and seal it with a valve under inert conditions. Mount the ampoule on a system that controls temperature, measures absolute pressure, and allows pumping. Heat the ampoule to a desired temperature and allow it to stabilize for 30 minutes. Pump the ampoule for a predetermined pumping time. Then, isolate the pressure measurement manifold from the pump and measure the pressure over time for 5 minutes. Repeat this process as many times as necessary to achieve the desired purity level.

[0107] Example 2

[0108] The material is loaded into an ampoule and sealed under inert conditions using a valve. The ampoule is mounted on a system that controls temperature, measures absolute pressure, and allows pumping. The ampoule is pumped to remove the inert gas, then heated to the desired temperature and allowed to stabilize for 30 minutes. The ampoule is pumped for 10 seconds. The ampoule is allowed to thermally reequilibrate for 5 minutes while the pressure measurement manifold is pumped. The pressure measurement manifold is then isolated from the pump and the ampoule is opened for pressure measurement. The pressure is measured over time for 5 minutes. The material can be verified because the initial measured pressure is within 10% of the true vapor pressure of MoCl5. If the rate of pressure increase is less than approximately 3% / minute, the material is also verified.

[0109] Example 3

[0110] The material is loaded into an ampoule and sealed under inert conditions using a valve. The ampoule is mounted on a system that controls temperature, measures absolute pressure, and allows pumping. The ampoule is pumped to remove the inert gas, then heated to the desired temperature and allowed to stabilize for 30 minutes. The ampoule is pumped for 10 seconds. The ampoule is allowed to thermally equilibrate for 5 minutes while the pressure measurement manifold is pumped. The pressure measurement manifold is then isolated from the pump and the ampoule is opened for pressure measurement. The pressure is measured over time for 5 minutes. The material is confirmed as the rate of pressure increase is less than 3% / minute.

[0111] Example 4

[0112] The equations representing the measured vapor pressures of molybdenum chloride and molybdenum oxychloride are presented below:

[0113]

[0114] Material A B <![CDATA[MoCl5]]> 10.976 -4354 <![CDATA[MoOCl4]]> 10.418 -3540 <![CDATA[MoO2Cl2]]> 9.840 -4270

[0115] Figure 3 is a graphical representation of a vapor pressure curve according to some embodiments. Figure 4 is a graphical view of vapor pressure versus pumping time according to some embodiments.

[0116] It is to be understood that changes may be made in detail, particularly as to the materials of construction employed and the shape, size, and arrangement of parts without departing from the scope of the present disclosure.The specification and illustrated embodiments are examples, with the true scope and spirit of the invention being indicated by the following claims.

Claims

1. A method comprising: obtaining a first container comprising a 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 including a first molybdenum impurity vapor; removing at least a portion of the first molybdenum impurity vapor from the first container; vaporizing at least a second portion of the solid reagent to produce a second vapor comprising a second MoCl5 vapor and a second molybdenum impurity vapor; allowing at least a portion of the second MoCl5 vapor and at least a portion of the second molybdenum impurity vapor to flow to a second container; Condensing at least a portion of the second MoCl5 vapor in the second container to separate the MoCl5 from the second molybdenum impurity vapor; and At least a portion of the second molybdenum impurity vapor is removed from the second container to obtain a MoCl5 precursor.

2. The method of claim 1, wherein the molybdenum impurity comprises at least one of MoOCl4, MoO2Cl2, MoO2Cl2(H2O), MoO3, or any combination thereof.

3. The method according to claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoOCl4 based on the total weight of the solid reagent.

4. The method of claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoO2Cl2 based on the total weight of the solid reagent.

5. The method of claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoO2Cl2(H2O) based on the total weight of the solid reagent.

6. The method of claim 2, wherein the solid reagent comprises 0.1 wt% to 15 wt% of the MoO3 based on the total weight of the solid reagent.

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

8. The method of claim 1, wherein the first vapor comprises the first molybdenum impurity vapor having a volume greater than that of the MoCl5.

9. The method of claim 1, wherein the second vapor comprises the second MoCl5 vapor having a volume greater than that of the second molybdenum impurity vapor.

10. The method of claim 1, wherein the MoCl5 precursor comprises 0.01 wt% to 1 wt% of MoOCl4 based on the total weight of the MoCl5 precursor.

11. The method of claim 1, wherein the MoCl5 precursor comprises 0.01 wt% to 1 wt% of MoO2Cl2 based on the total weight of the MoCl5 precursor.

12. The method of claim 1, wherein the MoCl5 precursor comprises 0.01 wt% to 1 wt% of MoO2Cl2(H2O) based on the total weight of the MoCl5 precursor.

13. The method of claim 1, wherein the MoCl5 precursor comprises 0.1 wt% to 1 wt% of MoO3 based on the total weight of the MoCl5 precursor.

14. A method comprising: obtaining a precursor vessel comprising a MoCl5 precursor and a headspace vapor; removing the headspace vapor from the precursor container; heating the precursor container to a target temperature; measuring a total pressure within the precursor container to obtain a measured total pressure; comparing the measured total pressure to a reference value to verify or not verify a low impurity content of the MoCl5 precursor, wherein the low impurity content of the MoCl5 precursor is verified when the measured total pressure is within 1% to 10% of a true vapor pressure of the MoCl5; Wherein the low impurity content of the MoCl 5 precursor is not verified when the measured total pressure is not within 1% to 10% of the true vapor pressure of the MoCl 5 .

15. The method of claim 14, further comprising removing molybdenum impurities from the MoCl5 precursor when the low impurity content is not verified.

16. A method comprising: obtaining a precursor vessel comprising a MoCl5 precursor and a headspace vapor; removing the headspace vapor from the precursor container; heating the precursor container to a target temperature; measuring a rate of change of a total pressure within the precursor container to obtain a measured rate of change of the total pressure; comparing the measured rate of change of the total pressure with a reference value to verify or not verify the low impurity content of the MoCl5 precursor, wherein when the rate of change of the total pressure is greater than the reference value, the low impurity content of the MoCl5 precursor is not verified; When the rate of change of the total pressure is equal to or less than the reference value, the low impurity content of the MoCl5 precursor can be verified.

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

18. The method of claim 16, further comprising removing molybdenum impurities from the MoCl5 precursor when the low impurity content is not verified.

19. An article comprising: a precursor container comprising a MoCl5 precursor, Wherein when the precursor container is maintained at a temperature of 340K to 465K, the measured vapor pressure of the MoCl5 precursor is less than 1.3×the calculated vapor pressure of MoCl5.

20. The article of claim 19, wherein the calculated MoCl5 vapor pressure is calculated according to the following formula:

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