Tungsten precursors and related methods

Abstract

High purity tungsten precursors and methods for purifying the tungsten precursors are provided. The method for purifying the precursors can include at least one of the following steps: obtaining a source container containing WCl4, WOCl4, and either WCl5 or WCl6, separating the WCl5 or WCl6 from at least a first portion of the WOCl4, separating the WCl5 or WCl6 from at least a second portion of the WOCl4, collecting the precursors in a collection container, or any combination thereof.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] This disclosure relates to the field of tungsten 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 results in defects and undesirable process variations. Specifically, in the case of solid precursors, discrete crystals of the impurity can be incorporated into 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] Some embodiments relate to a method for purifying a tungsten precursor. The method for purifying a tungsten precursor includes one or more of the following steps, which may be performed in any order and in any combination. In some embodiments, the method includes obtaining a source vessel containing WCl, WOCl, and either WCl or WCl. In some embodiments, the method includes separating the WCl or WCl from a first portion of the WOCl, the separating including applying first conditions to the source vessel to produce a first WOCl vapor and removing at least a portion of the first WOCl from the source vessel. In some embodiments, the method includes separating the WCl or WCl from a second portion of the WOCl, the separating including applying second conditions to the source vessel to generate WCl vapor containing (e.g., residual) WOCl or WCl vapor containing (e.g., residual) WOCl; flowing the WCl or WCl vapor to a collection vessel; applying third conditions to the collection vessel to generate WCl condensate or WCl condensate and second WOCl vapor; and removing at least a portion of the second WOCl vapor from the collection vessel. In some embodiments, the method includes recovering the precursor in the collection vessel. In some embodiments, the method includes verifying a low WOCl content in the precursor recovered in the collection vessel.

[0004] Some embodiments relate to a method for verifying a low content of impurities. In some embodiments, the method includes obtaining a collection vessel containing a WCl5 precursor or a WCl6 precursor. In some embodiments, the method includes applying conditions to the collection vessel containing the WCl5 precursor or the WCl6 precursor. In some embodiments, the method includes measuring at least one of a total pressure in the collection vessel, a rate of change of the total pressure in the collection vessel, or any combination thereof. In some embodiments, the method includes comparing the total pressure or the rate of change of the total pressure to a reference value to verify or not verify a low content of WOCl4. In some embodiments, if a low content of WOCl4 is not verified, removing WOCl4 from the collection vessel.

[0005] Some embodiments relate to a precursor container. In some embodiments, the precursor container includes a precursor. In some embodiments, the precursor includes WCl. In some embodiments, the WCl has a vapor pressure that is less than 1.3 times the vapor pressure of WCl when the precursor container is maintained at a temperature between 70° C. (343.15 K) and 240° C. (513.15 K), calculated according to the following formula: TIFF2025532349000002.tif12170

[0006] Some embodiments relate to a precursor container. In some embodiments, the precursor container includes a precursor. In some embodiments, the precursor includes WCl. In some embodiments, the WCl has a vapor pressure that is less than 1.3 times the vapor pressure of WCl when the precursor container is maintained at a temperature between 70° C. (343.15 K) and 240° C. (513.15 K), calculated according to the following formula: TIFF2025532349000003.tif12170

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

[0009] 1 is a flowchart of a method for separating a tungsten precursor from impurities, according to some embodiments. [Figure 3]

[0010] 1 is a flowchart of a method for separating a tungsten precursor from impurities, according to some embodiments. [Figure 4]

[0011] 1 is a flowchart of a method for verifying low impurity content in a tungsten precursor, according to some embodiments. [Figure 5]

[0012] 1 is a flowchart of a method for measuring low levels of impurities in a tungsten precursor, according to some embodiments. [Figure 6]

[0013] 1 is a flowchart of a method for measuring low levels of impurities in a tungsten precursor, according to some embodiments. [Figure 7]

[0014] FIG. 1 is a graphical representation of a vapor pressure curve according to some embodiments. [Figure 8]

[0015] 1 is a graph illustrating the relationship between vapor pressure and pumping time, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0009]

[0016] 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]

[0017] All prior patents and publications referenced herein are incorporated by reference in their entirety.

[0011]

[0018] 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]

[0019] 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]

[0020] Some embodiments relate to methods for purifying tungsten precursors. Various embodiments of methods for purifying tungsten precursors are provided herein. It will be understood that any combination of steps can be performed in any order in a method for purifying a tungsten precursor 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]

[0021] 1 is a flowchart of a method 100 for purifying a tungsten precursor, according to some embodiments. In some embodiments, the method 100 relates to a method for purifying WCl. As shown in FIG. 1, in some embodiments, the method 100 for purifying a tungsten precursor may include at least one of the following steps: obtaining 102 a source container containing WCl, WOCl, and either WCl or WCl; separating 104 the WCl or WCl from a first portion of the WOCl; separating 106 the WCl or WCl from a second portion of the WOCl; collecting 108 the precursor in a collection container; verifying 110 the recovered precursor for a low content of WOCl; or any combination thereof.

[0015]

[0022] In step 102, in some embodiments, a source container is obtained that contains at least one of WCl4, WOCl4, WCl5, or WCl6, or any combination thereof. WCl5 or WCl6 can exist in the source container in at least one of a solid, a gas / vapor, or any combination thereof. For example, in some embodiments, WCl5 or WCl6 exists as a solid and as a vapor. In some embodiments, WCl5 or WCl6 is amorphous or crystalline. In some embodiments, WCl5 or WCl6 exists in the source container as isolated crystals. WCl4 can exist in the source container in at least one of a solid, a gas / vapor, or any combination thereof. For example, in some embodiments, WCl4 can exist as a solid and as a vapor, with WCl4 vapor present in significantly less amount than WCl5 or WCl6 vapor. In some embodiments, WCl4 exists in the source container as isolated crystals. In some embodiments, WCl4 exists in the solid phase of WCl5 or WCl6. For example, in some embodiments, WOCl4 is dissolved in the crystal lattice of WCl5 or WCl6. WOCl4 can be present in the source vessel in at least one of the following forms: a solid, a gas / vapor, or any combination thereof. For example, in some embodiments, WOCl4 can exist as a solid and as a vapor. The solid phase of WOCl4 can be amorphous or crystalline. In some embodiments, WOCl4 is present in the source vessel as isolated crystals. In some embodiments, WOCl4 is present in the solid phase of WCl5. For example, in some embodiments, WOCl4 is dissolved in the crystal lattice of WCl5 or WCl6. In some embodiments, WOCl4 is present in the solid phase of WCl4. The solid phase of WCl4 can be amorphous or crystalline. For example, in some embodiments, WOCl4 is dissolved in the crystal lattice of WCl4.

[0016]

[0023] The source container can be configured to control its temperature. The temperature of the source container can be controlled in any suitable manner. In some embodiments, a thermal jacket for heating and / or cooling is employed around the source container. In some embodiments, a ribbon heater is wrapped around the source container. In some embodiments, a block heater shaped to cover at least a major portion of the exterior surface of the source container is used to heat the source container. In some embodiments, a resistance heater is used to heat the source container. In some embodiments, a lamp heater is used to heat the source container. In some embodiments, a hot heat transfer fluid can be contacted with the exterior surface of the source container to heat and / or cool the source container. In some embodiments, heating is achieved by infrared or other radiant energy impinging on the source container. In some embodiments, the collection 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 this disclosure.

[0017]

[0024] The source vessel may be configured to control pressure. The pressure of the source vessel can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the source vessel. The gas inlet line can be configured to supply pressurized gas from a pressurized gas source to the source vessel. Control of the pressurized gas to the source vessel 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 source vessel. The vacuum line can be configured to apply a vacuum to the source vessel. 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 source vessel can be employed in the present invention without departing from the scope of the present invention.

[0018]

[0025] In step 104, in some embodiments, WCl is separated from the first portion of WOCl. As disclosed herein (e.g., FIG. 2), in some embodiments, WCl or WCl can be separated from the first portion of WOCl by applying first conditions (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the source vessel to produce a first WOCl vapor. In some embodiments, WCl or WCl can be separated from the first portion of WOCl by removing at least a portion of the first WOCl from the source vessel. In some embodiments, the first condition is a condition in which the total pressure of the source vessel is below the true vapor pressure of WOCl at a given first temperature. In some embodiments, the first condition is a condition in which the total pressure of the source vessel is above the true vapor pressure of WOCl at a given first temperature. In some embodiments, when the first condition is applied, the first WOCl vapor comprises a larger volume of WOCl than WCl.

[0019]

[0026] In step 106, in some embodiments, WC15 or WC16 is separated from WOC14 and the second portion of WC14. This step can separate WC15 or WC16 from WOC14, or the separation can result in separation of WC15 or WC16. As disclosed herein (e.g., FIG. 3), in some embodiments, WC15 or WC16 can be separated from WOC14 and, in some embodiments, the second portion of WC14 by: applying second conditions (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the source vessel to produce WOCl vapor containing WOCl or WCl vapor containing WOCl; flowing the WCl or WCl vapor to a collection vessel; applying third conditions (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the collection vessel to produce WCl condensate or WCl condensate and second WOCl vapor; and removing at least a portion of the second WOCl vapor from the collection vessel.

[0020]

[0027] In some embodiments, the second condition is a condition where the total pressure of the source vessel is below the true vapor pressure of WCl5 or WCl6 at a given second temperature. In some embodiments, the second condition is a condition where the total pressure of the source vessel is above the true vapor pressure of WCl4 at a given second temperature. In some embodiments, when the second condition is applied, the WCl5 or WCl6 vapor contains a larger volume of WCl5 or WCl6 than WCl4. In some embodiments, when the second condition is applied, the WCl5 or WCl6 vapor contains a larger volume of WOCl4 than WCl4. In some embodiments, the third condition is a condition where a larger volume of WCl5 or WCl6 condenses than WOCl4. In some embodiments, when the third condition is applied, the WCl5 condensate contains a larger mole fraction of WCl5 than WOCl4. In some embodiments, when the third condition is applied, the WCl6 condensate contains a larger mole fraction of WCl6 than WOCl4.

[0021]

[0028] The collection container can be configured to control its temperature. The temperature of the collection container can be controlled in any suitable manner. In some embodiments, a thermal jacket for heating and / or cooling is employed around the collection container. In some embodiments, a ribbon heater is wrapped around the collection container. In some embodiments, a block heater shaped to cover at least a major portion of the exterior surface of the collection container is used to heat the collection container. In some embodiments, a resistance heater is used to heat the collection container. In some embodiments, a lamp heater is used to heat the collection container. In some embodiments, a hot heat transfer fluid can be contacted with the exterior surface of the collection container to heat and / or cool the collection container. In some embodiments, heating is achieved by infrared or other radiant energy impinging on the collection container. In some embodiments, the collection 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 this disclosure.

[0022]

[0029] The collection vessel can be configured to control pressure. The pressure of the collection vessel can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the collection vessel. The gas inlet line can be configured to supply pressurized gas to the collection vessel from a pressurized gas source. Control of the pressurized gas to the collection vessel 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 collection vessel. The vacuum line can be configured to apply a vacuum to the collection vessel. 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 source vessel can be employed in the present invention without departing from the scope of the present invention.

[0023]

[0030] In step 108, in some embodiments, the precursor is collected in a collection vessel. In some embodiments, the precursor includes WCl or WCl. In some embodiments, the precursor includes WCl or WCl and a low content of WOCl. In some embodiments, the collection vessel containing WCl or WCl has a vapor pressure that is less than 1.1 times the calculated vapor pressure of WCl, determined according to the following equation, when the precursor vessel is maintained at a temperature between 70° C. (343.15 K) and 240° C. (513.15 K): TIFF2025532349000004.tif12170 In some embodiments, WCl5 or WCl6 maintains vapor pressure for up to 72 hours. In some embodiments, WCl5 or WCl6 maintains vapor pressure for between 5 minutes and 72 hours.

[0024]

[0031] In step 110, in some embodiments, the recovered precursor is verified for a low WOCl content. As disclosed herein (e.g., FIGS. 4 and 5), in some embodiments, the recovered precursor can be verified for a low WOCl content by measuring the precursor's WOCl content to verify or not verify the precursor's low WOCl content. If the precursor's low WOCl content is not verified, the precursor can be verified for a low WOCl content by repeating at least one of steps 104, 106, or any combination thereof to remove the WOCl content. In some embodiments, the precursor's WOCl content is measured by applying a fourth condition to a collection vessel containing the precursor, measuring the total pressure in the collection vessel, and comparing the total pressure to a reference value. In some embodiments, the precursor's low WOCl content is verified if the total pressure is within a percentage of the reference value (e.g., within 0.01% to 20% of the true vapor pressure of WCl or WCl at the condition). In some embodiments, if the total pressure is not within a percentage of a reference value (e.g., within 0.01% to 20% of the true vapor pressure of WCl5 or WCl6 at the condition), the low WOCl4 content of the precursor is not verified. In some embodiments, the fourth condition is selected to stabilize the collection vessel at a reference temperature, the inlet gas flow to the collection vessel is stopped, a short-throw vacuum pump removes inert gas from the vapor phase in the collection vessel, the collection vessel is isolated from the vacuum pump, and the pressure in the collection vessel is then monitored or measured over time. In some embodiments, the WOCl4 content of the precursor is measured by applying the fourth condition to a collection vessel containing the precursor, measuring the rate of change of the total pressure in the collection vessel, and comparing the rate of change of the total pressure to a reference value. In some embodiments, if the rate of change of the total pressure is greater than the reference value, the low WOCl4 content of the precursor is not verified. In some embodiments, if the rate of change of the total pressure is equal to or less than the reference value, the low WOCl4 content of the precursor is verified. In some embodiments, a low precursor content of WOCl4 is verified when the rate of change of total pressure is 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less.In some embodiments, WCl is an impurity in WCl (e.g., present in a WCl condensate). In some embodiments, WCl is an impurity in WCl (e.g., present in a WCl condensate). In some embodiments, the total pressure is equal to the sum of the WCl vapor pressure and the WCl vapor pressure (e.g., total pressure = 0.6T (for WCl) + 0.3T (for WCl) > 0.9T).

[0025]

[0032] 2 is a flowchart of a method 200 for separating a tungsten precursor from impurities, according to some embodiments. As shown in FIG. 2, in some embodiments, the method 200 for separating a tungsten precursor from impurities can include at least one of the following steps: applying first conditions to a source vessel to produce a first WOCl vapor in step 202, removing at least a portion of the first WOCl vapor from the source vessel in step 204, or any combination thereof. In some embodiments, the method 200 relates to separating WCl from a first portion of the WOCl, as described above.

[0026]

[0033] In step 202, in some embodiments, first conditions are applied to the source vessel to generate a first WOCl vapor. In some embodiments, the first conditions include a first temperature of the source vessel. In some embodiments, the first temperature of the source vessel is in the range of 60°C to 170°C, or any range or subrange of temperatures between 60°C and 170°C. In some embodiments, the first temperature of the source vessel 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 to 180°C, 180°C to 210°C, 210°C to 220°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 41 The temperature is in the range of 0°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.

[0027]

[0034] In some embodiments, the first condition includes a first pressure in the source vessel. In some embodiments, the first pressure in the source vessel is a pressure in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the first pressure in the source vessel 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, 0.0 1Torr~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~1Torr , 0.01Torr~0.1Torr, 0.1Torr~100Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Torr~1 00Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, 45T orr 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.

[0028]

[0035] In some embodiments, the first condition is a condition where the total pressure of the source vessel is below the true vapor pressure of WOCl4 at a given first temperature. In some embodiments, the first condition is a condition where the total pressure of the source vessel is above the true vapor pressure of WCl5 at a given first temperature. In some embodiments, the first condition is a condition where WOCl4 evaporates while minimizing the amount of WCl5 or WCl6 that evaporates. In some embodiments, the first condition is a condition where WCl5 or WCl6 does not evaporate. In some embodiments, the first condition is a condition where isolated crystals of WOCl4 are vaporized. In some embodiments, the first condition is a condition where WOCl4 present in the WCl5 or WCl6 crystal lattice does not evaporate, or does not evaporate appreciably. Upon evaporation, the first WOCl4 vapor can be removed from the source vessel, separating the WOCl4 from the WCl5 or WCl6.

[0029]

[0036] The first WOCl vapor can include more WOCl than WCl or WCl. In some embodiments, the first WOCl 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% by volume of WCl, based on the total volume of the first WOCl vapor. In some embodiments, the first WOCl 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% WCl or WCl by volume, based on the total volume of the first WOCl vapor.

[0030]

[0037] In step 204, in some embodiments, at least a portion of the first WOCl vapor is removed from the source vessel. The first WOCl vapor can be removed through an outlet in the source vessel. The outlet can be fluidly connected to a gas exhaust line, a vacuum line, or other similar line suitable for removing the first WOCl vapor from the source vessel.

[0031]

[0038] 3 is a flowchart of a method 300 for separating a tungsten precursor from impurities, according to some embodiments. As shown in FIG. 3 , in some embodiments, the method 300 for separating a tungsten precursor from impurities can include at least one of the following steps: applying second conditions to a source vessel 302 to produce WCl or WCl vapor containing WOCl; flowing the WCl or WCl vapor to a collection vessel 304; applying third conditions to a collection vessel 306 to produce a WCl or WCl condensate and a second WOCl vapor; removing at least a portion of the second WOCl vapor from the collection vessel 308; or any combination thereof. In some embodiments, the method 300 relates to separating WCl or WCl from the second portion of WOCl, as described above. The method 300 for separating WCl or WCl from the second portion of WOCl can also separate WCl or WCl from WOCl.

[0032]

[0039] In step 302, in some embodiments, second conditions are applied to the source vessel to produce WCl vapor or WCl vapor containing WOCl. In some embodiments, the second conditions include a second temperature of the source vessel. In some embodiments, the second temperature of the source vessel is in the range of 60°C to 170°C, or any range or subrange of temperatures between 60°C and 170°C. In some embodiments, the second temperature of the source vessel 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 to 180°C, 180°C to 210°C, 210°C to 250°C, 250°C to 300°C, 250°C to 310°C, 250°C to 320°C, 250°C to 330°C, 250°C to 340°C, 250°C to 350°C, 250°C to 360°C, 250°C to 370°C, 250°C to 380°C, 250°C to 400°C, 250°C to 410°C, 250°C to 420°C, 250°C to 430°C, 250° The temperature ranges from 0°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 of the source container is higher than the first temperature of the source container. In some embodiments, the second temperature of the source container is lower than the first temperature of the source container.

[0033]

[0040] In some embodiments, the second condition includes a second pressure in the source vessel. In some embodiments, the second pressure in the source vessel is a pressure in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the second pressure in the source vessel 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, 0.0 1Torr~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~1Torr , 0.01Torr~0.1Torr, 0.1Torr~100Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Torr~1 00Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, 45T In some embodiments, the second pressure in the source vessel is less than the first pressure in the source vessel. In some embodiments, the second pressure in the source vessel is greater than the first pressure in the source vessel.

[0034]

[0041] In some embodiments, the second conditions are conditions where the total pressure of the source container is below the true vapor pressure of WCl or WCl at a given second temperature. In some embodiments, the second conditions are conditions where the total pressure of the source container is above the true vapor pressure of WCl at a given second temperature. In some embodiments, the second conditions are conditions where WCl or WCl present as isolated crystals in the source container evaporate. In some embodiments, the second conditions are conditions where WCl or WCl evaporates while minimizing the amount of WCl evaporated. In some embodiments, the second conditions are conditions where WCl does not evaporate. In some embodiments, the second conditions are conditions where WOCl present in the crystal lattice of WCl or WCl evaporates. In some embodiments, the second conditions are conditions where WOCl present as isolated crystals in the source container evaporate. In some embodiments, the WCl or WCl vapor comprises a larger volume of WCl or WCl than WOCl. In some embodiments, the WCl5 or WCl6 vapor comprises a larger volume of WOCl4 than WCl4. In some embodiments, the WCl5 or WCl6 vapor comprises a larger volume of WCl5 or WCl6 than WCl4.

[0035]

[0042] In step 304, in some embodiments, WCl or WCl vapor is flowed to a collection vessel to remove WCl or WCl vapor from WCl contained in the source vessel. In some embodiments, the WCl or WCl vapor comprises WOCl. In some embodiments, the WCl or WCl vapor comprises WOCl.

[0036]

[0043] The collection container can be configured to control its temperature. The temperature of the collection container can be controlled in any suitable manner. In some embodiments, a thermal jacket for heating and / or cooling is employed around the collection container. In some embodiments, a ribbon heater is wrapped around the collection container. In some embodiments, a block heater shaped to cover at least a major portion of the exterior surface of the collection container is used to heat the collection container. In some embodiments, a resistance heater is used to heat the collection container. In some embodiments, a lamp heater is used to heat the collection container. In some embodiments, a hot heat transfer fluid can be contacted with the exterior surface of the collection container to heat and / or cool the collection container. In some embodiments, heating is achieved by infrared or other radiant energy impinging on the collection container. In some embodiments, the collection 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 this disclosure.

[0037]

[0044] The collection vessel can be configured to control pressure. The pressure of the collection vessel can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the collection vessel. The gas inlet line can be configured to supply pressurized gas to the collection vessel from a pressurized gas source. Control of the pressurized gas to the collection vessel 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 collection vessel. The vacuum line can be configured to apply a vacuum to the collection vessel. 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 source vessel can be employed in the present invention without departing from the scope of the present invention.

[0038]

[0045] In step 306, in some embodiments, third conditions are applied to the collection vessel such that a WCl5 condensate or a WCl6 condensate and a second WOCl4 vapor are produced. In some embodiments, the WCl5 or WCl6 condensate and the second WOCl4 vapor are produced, thereby separating the WCl5 or WCl6 from the second portion of the WOCl4. In some embodiments, the third conditions include a third temperature of the collection vessel. In some embodiments, the third temperature of the collection vessel is a temperature in the range of 10° C. to 100° C., or any range or subrange therebetween. In some embodiments, the third temperature of the collection vessel 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 of the collection vessel is sufficient to condense WCl5 vapor or WCl6 vapor. In some embodiments, the third temperature of the collection vessel is sufficient to result in a second WOCl4 vapor.

[0039]

[0046] In some embodiments, the third condition includes a third pressure in the collection vessel. In some embodiments, the third pressure in the collection vessel is a pressure in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the third pressure in the collection vessel 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. 01Torr~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr r~25Torr, 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~1 00Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, 45T In some embodiments, the third pressure in the collection vessel is sufficient to condense the WCl5 vapor or WCl6 vapor. In some embodiments, the third pressure in the collection vessel is sufficient to result in a second WOCl4 vapor.

[0040]

[0047] In some embodiments, third conditions are applied to the collection vessel to produce a WCl5 or WCl6 condensate and a second WOCl4 vapor. In some embodiments, the third conditions are sufficient to condense WCl5 or WCl6 without condensing WOCl4, or at least to separate WCl5 or WCl6 from WOCl4 while minimizing the volume of condensed WOCl4. In some embodiments, the third conditions are conditions that result in a greater volume of WCl5 or WCl6 condensing than WOCl4. In some embodiments, the WCl5 or WCl6 condensate contains more WCl5 or WCl6 condensate (e.g., by mole fraction, volume, or mass fraction) than WOCl4 condensate (if present). In some embodiments, the third conditions are conditions that result in a greater volume of WOCl4 remaining vaporized than WCl5 or WCl6. In some embodiments, the third condition is one in which the WOCl vapor contains WOCl dissolved in the crystal lattice of WCl or WCl (and, in some embodiments, isolated WOCl crystals) and evaporated with WCl or WCl in the source vessel.

[0041]

[0048] In step 308, in some embodiments, at least a portion of the second WOCl vapor is removed from the collection vessel. The second WOCl vapor can be removed through an outlet in the collection vessel. The outlet can be fluidly connected to a gas exhaust line, a vacuum line, or other similar line suitable for removing the second WOCl vapor from the source vessel.

[0042]

[0049] FIG. 4 is a flowchart of a method 400 for verifying a low impurity content of a tungsten precursor, according to some embodiments. As shown in FIG. 4 , in some embodiments, the method 400 for verifying a low impurity content of a tungsten precursor can include at least one of the following steps: measuring the WOCl content of the precursor in step 402 to verify or not verify the precursor's low WOCl content; verifying or comparing the WOCl content to a reference value in step 404 to verify the precursor's low WOCl content; and, if the precursor's low WOCl content is not verified, further removing WOCl in step 406 (e.g., by repeating at least one of step 104 (e.g., including, but not limited to, one or more of the steps of FIG. 2 ), step 106 (e.g., including, but not limited to, one or more of the steps of FIG. 3 ), or any combination thereof), or any combination thereof. In some embodiments, if the precursor is verified to have a low WOCl content, the precursor is ready for use in 408. In some embodiments, the method 400 relates to a method for verifying low content WOCl4 of tungsten precursor.

[0043]

[0050] FIG. 5 is a flowchart of a method 500 for measuring low impurity content in a tungsten precursor, according to some embodiments. As shown in FIG. 5 , in some embodiments, the method 500 for measuring low impurity content in a tungsten precursor can include at least one of the following steps: applying a fourth condition to a collection vessel containing a WCl5 precursor or a WCl6 precursor in step 502; measuring at least one property in the collection vessel in step 504; and comparing the at least one property to a reference value in step 506. While not shown, in some embodiments, the method 500 for measuring low impurity content in a tungsten precursor further includes removing vapor and / or gas from the collection vessel before performing step 502. Although not shown, in some embodiments, the fourth condition is selected to stabilize the collection vessel at a reference temperature, stopping the inlet gas flow to the collection vessel, using a short-distance vacuum pump to remove inert gas from the vapor phase in the collection vessel, isolating the collection vessel from the vacuum pump, and then monitoring or measuring the pressure in the collection vessel over time. In some embodiments, the method 500 relates to a method for measuring low content WOCl4 in tungsten precursors as described above.

[0044]

[0051] In step 502, in some embodiments, fourth conditions are applied to a collection vessel containing a WCl5 precursor or a WCl6 precursor. In some embodiments, the fourth conditions include a fourth temperature of the collection vessel. In some embodiments, the fourth temperature of the collection vessel 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 fourth temperature of the collection vessel 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, or 100°C. The temperature ranges are 00°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.

[0045]

[0052] In some embodiments, the fourth condition includes a fourth pressure in the collection vessel. In some embodiments, the fourth pressure in the collection vessel is a pressure in the range of 0.01 Torr to 100 Torr, or any range or subrange therebetween. In some embodiments, the fourth pressure in the collection vessel 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. 01Torr~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr r~25Torr, 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~1 00Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr, 35Torr~100Torr, 40Torr~100Torr, 45T orr 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.

[0046]

[0053] In some embodiments, the fourth condition is a condition in which the total pressure in the collection vessel is within 10% of the true vapor pressure of WCl5 or WCl6, hi some embodiments, the fourth condition is a condition in which the total pressure in the collection vessel is below the true vapor pressure of WOCl4.

[0047]

[0054] In step 504, in some embodiments, at least one property is measured within the collection vessel. In some embodiments, the at least one property is measured as at least one of the total pressure within the collection vessel, the rate of change of the total pressure within the collection vessel, or any 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 within the collection vessel is measured over a period of 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 also be understood that the period for measuring the rate of change of the total pressure within the collection vessel can vary depending on the composition of the precursor (e.g., impurity level) and the temperature selected for the fourth condition.

[0048]

[0055] In step 506, in some embodiments, the total pressure in the collection vessel is compared to a reference value. In some embodiments, if the total pressure is within 0.01% to 20% (inclusive) of the reference value, or any range or subrange therebetween, a low precursor content of WOCl4 is verified. In some embodiments, if the total pressure is not within 0.01% to 20% of the reference value, a low precursor content of WOCl4 is not verified. In some embodiments, the reference value is the true vapor pressure of WCl at the conditions (e.g., the selected temperature). 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 10% of the true vapor pressure of WCl5 at the conditions. A low content of WOCl4 is verified if it is in the range of 5%, 6%-15%, 7%-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%.

[0049]

[0056] In step 506, in some embodiments, the rate of change of the total pressure in the collection vessel is compared to a reference value. In some embodiments, if the rate of change of the total pressure is greater than the reference value, a low WOCl4 precursor content is not verified. In some embodiments, if the rate of change of the total pressure is equal to or less than the reference value, a low WOCl4 precursor content is verified. For example, in some embodiments, a low WOCl4 precursor content is verified 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 minute. In some embodiments, the reference value is 50 mT or less per minute. 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. When the temperature of the fourth condition is low, the limit value of the pressure rise rate is low.

[0050]

[0057] 6 is a flowchart of a method 600 for verifying a low content of impurities, according to some embodiments. As shown in FIG. 6, in some embodiments, the method 600 for verifying a low content of impurities includes at least one of the following steps: obtaining a collection vessel containing a WCl precursor or a WCl precursor in step 602; applying conditions to the collection vessel containing a WCl precursor or a WCl precursor in step 604; measuring at least one characteristic in the collection vessel (e.g., at least one of a rate of change of total pressure in the collection vessel, a total pressure in the collection vessel, or any combination thereof) in step 606; comparing the at least one characteristic to a reference value in step 608; removing WOCl from the collection vessel if a low content of WOCl is not verified in step 610; or any combination thereof. Although not shown, in some embodiments, conditions are selected to stabilize the collection vessel at a reference temperature, the flow of inlet gas to the collection vessel is stopped, a short vacuum pump removes the inert gas from the vapor phase in the collection vessel, the collection vessel is isolated from the vacuum pump, and the pressure in the collection vessel is then monitored or measured over time.

[0051]

[0058] Some embodiments relate to a tungsten precursor having a sufficiently low impurity level that, when delivered to a tool used in semiconductor manufacturing or other similar processes, the tungsten precursor, once vaporized, 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 tungsten precursor, such as, for example, but not limited to, a WCl precursor or a WCl precursor, having a sufficiently low level of impurities, including, for example, but not limited to, at least one of WOCl, WCl, or a combination thereof.

[0052]

[0059] In some embodiments, the WCl precursor, when contained in a precursor container, has a vapor pressure that is less than 1.3 times the calculated vapor pressure of WCl 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: TIFF2025532349000005.tif12170 In some embodiments, the WCl precursor, when contained in a precursor container, has a vapor pressure that is less than 1.1 times the calculated vapor pressure of WCl 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: TIFF2025532349000006.tif12170

[0053]

[0060] In some embodiments, the WCl precursor, when contained in a precursor container, has a vapor pressure that is less than 1.3 times the calculated vapor pressure of WCl 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 formula: In some embodiments, the WCl precursor, when contained in a precursor container, has a vapor pressure that is less than 1.1 times the calculated vapor pressure of WCl 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: TIFF2025532349000008.tif9170 WCl5 or WCl6 can maintain vapor pressure indefinitely. In some embodiments, WCl5 or WCl6 maintains vapor pressure for up to 72 hours. In some embodiments, WCl5 or WCl6 maintains vapor pressure for 5 minutes to 72 hours, or any range or subrange therebetween.

[0054]

[0061] Aspects

[0062] Various aspects are described below, and it should be understood that any one or more of the features described in the following aspects can be combined with any one or more of the other aspects. Aspect 1 a) obtaining a source vessel containing WCl, WOCl, and either WCl or WCl; b) separating WCl or WCl from a first portion of WOCl, said separating comprising: applying first conditions to a source vessel to generate a first WOCl vapor; and removing at least a portion of the first WOCl vapor from the source vessel; and c) separating WCl or WCl from a second portion of WOCl, applying second conditions to the source vessel to produce WCl vapor with WOCl or WCl vapor with WOCl; flowing the WCl5 vapor or WCl6 vapor into a collection vessel; applying third conditions to the collection vessel to produce a WCl condensate or a WCl condensate and a second WOCl vapor; and removing at least a portion of the second WOCl vapor from the collection vessel; and separating the d) recovering the precursor in a collection vessel; A method comprising: Aspect 2 2. The method of embodiment 1, wherein the first condition is a condition in which the total pressure of the source vessel is below the true vapor pressure of WOCl4 at the given first temperature. Aspect 3 3. The method of any one of claims 1 to 2, wherein the first condition is a condition in which the total pressure of the source vessel exceeds the true vapor pressure of WCl5 or WCl6 at a given first temperature. Aspect 4 Aspect 4. The method of any one of aspects 1 to 3, wherein when the first condition applies, the first WOCl4 vapor comprises a larger volume of WOCl4 than WCl5 or WCl6. Aspect 5 The method of any one of Aspects 1 to 4, wherein the second condition is a condition where the total pressure of the source vessel is below the true vapor pressure of WCl5 or WCl6 at the given second temperature. Aspect 6 The method of embodiment 4, wherein the fourth condition is a condition in which the total pressure of the source vessel exceeds the true vapor pressure of WCl4 at the given second temperature. Aspect 7 Aspect 7. The method of any one of aspects 1-6, wherein when the second condition applies, the WCl5 vapor comprises a larger volume of WCl5 than WCl4. Aspect 8 Aspect 8. The method of any one of aspects 1 to 7, wherein when the second condition applies, the WCl vapor comprises a larger volume of WCl than WCl. Aspect 9 Aspect 9. The method of any one of aspects 1-8, wherein when the second condition applies, the WCl5 vapor comprises a larger volume of WOCl4 than WCl4. Aspect 10 Aspect 10. The method of any one of aspects 1 to 9, wherein when the second condition applies, the WCl vapor comprises a larger volume of WOCl than WCl. Aspect 11 A method according to any one of aspects 1 to 10, wherein the third conditions are conditions under which a larger volume of WCl5 than WOCl4 is condensed. Aspect 12 12. The method of any one of aspects 1 to 11, wherein the third conditions are conditions under which a larger volume of WCl6 than WOCl4 is condensed. Aspect 13 13. The method of any one of aspects 1-12, wherein if the third condition applies, the WCl condensate comprises a greater mole fraction of WCl than WOCl . Aspect 14 14. The method of any one of aspects 1-13, wherein if the third condition applies, the WCl 6 condensate comprises a greater mole fraction of WCl 6 than WOCl 4 . Aspect 15 15. The method of any one of aspects 1-14, further comprising: e) verifying a low content of WOCl4 of precursor present in the collection vessel. Aspect 16 The step e) of verifying e1) measuring the WOCl4 content of the precursor to verify or not verify a low content of WOCl4 in the precursor; and e2) if a low content of WOCl4 in the precursor is not verified, repeating at least one of step b), step c), or any combination thereof, to remove WOCl4. 16. The method of embodiment 15, comprising: Aspect 17 The measuring step e1) applying a fourth condition to the collection vessel containing the precursor; measuring at least one characteristic within the collection vessel; and Comparing measured properties with reference values 17. The method of embodiment 16, comprising: Aspect 18 the at least one property is a total pressure in the collection vessel; Low content WOCl4 is verified when the total pressure is within 1%-10% of the true vapor pressure of WCl5. 18. The method of embodiment 17, wherein the low content of WOCl4 is not verified if the total pressure is not within 1% to 10% of the true vapor pressure of WCl5. Aspect 19 the at least one property is a total pressure in the collection vessel; Low content WOCl4 is verified when the total pressure is within 1%-10% of the true vapor pressure of WCl6. 18. The method of embodiment 17, wherein the low content of WOCl4 is not verified if the total pressure is not within 1% to 10% of the true vapor pressure of WCl6. Aspect 20 the at least one characteristic is a rate of change of total pressure in the collection vessel; If the rate of change of total pressure is larger than the reference value, the WOCl4 with low content of precursor is not verified. If the rate of change of total pressure is below the reference value, the low content of precursor WOCl4 is verified. 18. The method of embodiment 17, wherein the reference value is a 5% change in total pressure per minute. Aspect 21 18. The method of embodiment 17, wherein the fourth condition is a condition in which the total pressure of the collection vessel is below the true vapor pressure of WOCl4. Aspect 22 1. A method for verifying low levels of impurities, comprising: obtaining a collection vessel containing a WCl5 precursor or a WCl6 precursor; applying conditions to a collection vessel containing a WCl5 precursor or a WCl6 precursor; Measuring at least one characteristic within the collection vessel; comparing at least one characteristic to a reference value; If low WOCl4 content has not been verified, remove WOCl4 from the collection container and A method comprising: Aspect 23 the at least one property is a total pressure in the collection vessel; Low content WOCl4 is verified when the total pressure is within 10% of the true vapor pressure of WCl5. 23. The method of embodiment 22, wherein the low content of WOCl4 is not verified if the total pressure is not within 10% of the true vapor pressure of WCl5. Aspect 24 the at least one property is a total pressure in the collection vessel; Low content WOCl4 is verified when the total pressure is within 1% of the true vapor pressure of WCl6. 23. The method of embodiment 22, wherein the low content of WOCl4 is not verified if the total pressure is not within 1% of the true vapor pressure of WCl6. Aspect 25 the at least one characteristic is a rate of change of total pressure in the collection vessel; If the rate of change of total pressure is larger than the reference value, the low content of precursor WOCl4 is not verified. If the second rate of change of total pressure is below the reference value, the low content of precursor WOCl4 is verified; 23. The method of embodiment 22, wherein the reference value is a 5% change in total pressure per minute. Aspect 26 a precursor container containing a precursor comprising WCl5, WCl5 has a vapor pressure that is less than 1.1 times the true vapor pressure of WCl5 when the precursor container is maintained at a temperature between 70 °C (343.15 K) and 240 °C (513.15 K). Aspect 27 The true vapor pressure of WCl5 is given by the following equation: 27. A precursor container according to embodiment 26, wherein the precursor container is calculated according to: TIFF2025532349000009.tif12170Aspect 28 27. The precursor container of embodiment 26, wherein the WCl 5 maintains a vapor pressure in the precursor container for up to 72 hours. Aspect 29 a precursor container containing a precursor comprising WCl6, A precursor container, wherein WCl6 has a vapor pressure that is less than 1.1 times the true vapor pressure of WCl6 when the precursor container is maintained at a temperature between 70°C (343.15K) and 240°C (513.15K). Aspect 30 The true vapor pressure of WCl6 is given by the following equation: 30. A precursor container according to embodiment 29, wherein the precursor container is calculated according to: TIFF2025532349000010.tif7170Embodiment 31 The precursor container of embodiment 29, wherein WCl6 maintains vapor pressure in the precursor container for up to 72 hours.

[0055] Example 1

[0063] 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 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.

[0056] Example 2

[0064] 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 actual vapor pressure of WCl5. Materials can also be verified if the pressure rise rate is less than approximately 3% / min.

[0057] Example 3

[0065] 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.

[0058] Example 4

[0066] The equations that describe the measured vapor pressures of tungsten chloride and tungsten oxychloride materials are shown below: TIFF2025532349000011.tif44170

[0059]

[0067] Figure 7 is a graphical representation of a vapor pressure curve according to some embodiments. Figure 8 is a graphical representation of vapor pressure versus pumping time according to some embodiments.

[0060]

[0068] 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. a) WOCl ４ and WCl ５ Or WCl ６ obtaining a source container containing either b) WOCl ４ From the first part of WCl ５ Or WCl ６ and separating the compound from the compound, the compound comprising: First WOCl ４ applying first conditions to the source vessel to generate steam; and First WOCl ４ Removing at least a portion of the vapor from the source vessel. WOC1 containing ４ From the first part of WCl ５ Or WCl ６ and c) WOCl ４ From the second part of WCl ５ Or WCl ６ and separating the compound from the compound, the compound comprising: WOCl ４ WCl containing ５ Steam or WOC1 ４ WCl containing ６ applying second conditions to the source vessel to generate steam; WCl ５ Steam or WCl ６ allowing the vapor to flow into a collection vessel; WCl ５ Condensate or WCl ６ condensate, and the second WOC1 ４ applying a third condition to the collection vessel to generate a vapor; and The second WOC1 from the collection container ４ Removing at least a portion of the vapor. WOC1 containing ４ From the second part of WCl ５ Or WCl ６ and d) collecting the precursor in a collection vessel; A method comprising:

2. The source vessel is WCl ４ The method of claim 1 further comprising:

3. The first condition is that the total pressure in the source vessel is less than the WOC1 ４ 2. The method of claim 1, wherein the temperature is below the true vapor pressure of

4. The first condition is that the total pressure in the source vessel is equal to the WCl ５ or WCl ６ 4. The method of claim 3, wherein the vapor pressure exceeds the true vapor pressure of

5. When the first condition is applied, the first WOC1 ４ The steam is WCl ５ or WCl ６ Larger volumes of WOCl ４ The method of claim 1 , comprising:

6. The second condition is that the total pressure in the source vessel is less than the WCl ５ or WCl ６ 2. The method of claim 1, wherein the temperature is below the true vapor pressure of

7. The second condition is that the total pressure in the source vessel is less than the WCl ４ 3. The method of claim 2, wherein the vapor pressure exceeds the true vapor pressure of

8. If the second condition is applied, WCl ５ The steam is WCl ４ Larger volumes of WCl ５ The method of claim 2 , comprising:

9. If the second condition is applied, WCl ６ The steam is WCl ４ A volume of WCl greater than ６ The method of claim 2 , comprising:

10. If the second condition is applied, WCl ５ The steam is WCl ４ Larger volumes of WOCl ４ The method of claim 2 , comprising:

11. If the second condition is applied, WCl ６ The steam is WCl ４ Larger volumes of WOCl ４ The method of claim 2 , comprising:

12. The third condition is WOC1 ４ Larger volumes of WCl ５ The method of claim 1 , wherein the condensation conditions are:

13. The third condition is WOC1 ４ Larger volumes of WCl ６ The method of claim 1 , wherein the condensation conditions are:

14. If the third condition is applied, WCl ５ The condensate is WOC1 ４ Larger mole fractions of WCl ５ The method of claim 1 , comprising:

15. If the third condition is applied, WCl ６ The condensate is WOC1 ４ Larger mole fractions of WCl ６ The method of claim 1 , comprising:

16. e) WOC1 with a low content of precursor present in the collection vessel ４ The method of claim 1 , further comprising verifying:

17. The step e) of verifying e1) WOCl with low precursor content ４ To verify or not verify the precursor WOC1 ４ measuring the content of, and e2) WOCl with low precursor content ４ If is not verified, WOCl ４ repeating at least one of step b), step c), or any combination thereof, to remove 17. The method of claim 16, comprising:

18. The measuring step e1) applying a fourth condition to a collection vessel containing the precursor; measuring at least one characteristic within the collection vessel; and Comparing measured properties with reference values 18. The method of claim 17, comprising:

19. the at least one property is a total pressure in the collection vessel; The total pressure is WCl ５ If the true vapor pressure of the ４ is verified, The total pressure is WCl ５ If the true vapor pressure of the ４ 20. The method of claim 18, wherein is not verified.

20. the at least one property is a total pressure in the collection vessel; The total pressure is WCl ６ If the true vapor pressure of the ４ is verified, The total pressure is WCl ６ If the true vapor pressure of the ４ 20. The method of claim 18, wherein is not verified.

21. the at least one characteristic is a rate of change of total pressure in the collection vessel; If the rate of change of the total pressure is greater than the reference value, the precursor has a low content of WOC1. ４ is not verified, If the rate of change of the total pressure is less than the reference value, the precursor has a low content of WOC1. ４ is verified, 20. The method of claim 18, wherein the reference value is a 5% change in total pressure per minute.

22. The fourth condition is that the total pressure in the collection vessel is equal to or greater than WOC1. ４ 19. The method of claim 18, wherein the temperature is below the true vapor pressure of

23. 1. A method for verifying low levels of impurities, comprising: WCl ５ Precursor or WCl ６ obtaining a collection vessel containing the precursor; WCl ５ Precursor or WCl ６ applying conditions to a collection vessel containing the precursor; Measuring at least one characteristic within the collection vessel; comparing at least one characteristic to a reference value; Low content of WOCl ４ If this is not verified, remove the WOCl from the collection container. ４ and removing A method comprising:

24. the at least one property is a total pressure in the collection vessel; The total pressure is WCl ５ If the true vapor pressure of the low content of WOC1 is within 10% of the true vapor pressure of the ４ is verified, The total pressure is WCl ５ If the true vapor pressure of ４ 24. The method of claim 23, wherein is not verified.

25. the at least one property is a total pressure in the collection vessel; The total pressure is WCl ５ If the true vapor pressure of the low content of WOC1 is within 1% of the ４ is verified, The total pressure is WCl ５ If the true vapor pressure of ４ 24. The method of claim 23, wherein is not verified.

26. the at least one property is a total pressure in the collection vessel; The total pressure is WCl ６ If the true vapor pressure of the ４ is verified, The total pressure is WCl ６ If the true vapor pressure of the ４ 24. The method of claim 23, wherein is not verified.

27. the at least one characteristic is a rate of change of total pressure in the collection vessel; If the rate of change of the total pressure is greater than the reference value, the precursor has a low content of WOC1. ４ is not verified, If the second rate of change of the total pressure is less than or equal to the reference value, the WOCl ４ is verified, 20. The method of claim 18, wherein the reference value is a 5% change in total pressure per minute.

28. WCl ５ a precursor container containing a precursor comprising WCl ５ is the temperature of WCl when the precursor container is maintained at a temperature between 70°C (343.15K) and 240°C (513.15K). ５ has a vapor pressure less than 1.3 times the true vapor pressure of Precursor vessel.

29. WCl ５ The true vapor pressure of 29. The precursor container of claim 28, calculated according to:

30. WCl ５ 29. The precursor container of claim 28, wherein the vapor pressure within the precursor container is maintained for up to 72 hours.

31. WCl ６ a precursor container containing a precursor comprising WCl ６ is the temperature of WCl when the precursor container is maintained at a temperature between 70°C (343.15K) and 240°C (513.15K). ６ a precursor container having a vapor pressure of less than 1.1 times the true vapor pressure of the precursor.

32. WCl ６ The true vapor pressure of 32. The precursor container of claim 31 , calculated according to:

33. WCl ６ 32. The precursor container of claim 31 , wherein the vapor pressure within the precursor container is maintained for up to 72 hours.

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