Tungsten precursors and related methods

Abstract

High purity tungsten precursors and methods of purifying tungsten precursors are provided. The method of purifying a precursor may comprise at least one of the following steps: obtaining a source vessel containing WCl4, WOCl4, and one of WCl5 or WCl6; separating the WCl5 or the WCl6 from at least a first portion of the WOCl4; separating the WCl5 or the WCl6 from at least a second portion of the WOCl4; recovering the precursor in the collection container; or any combination thereof.

Description

Technical Field

[0001] The present disclosure relates to the field of tungsten precursors and related methods, which include, for example and without limitation, purification methods and methods for verifying impurity levels. Background Art

[0002] The presence of impurities in precursors for semiconductor manufacturing can lead to defects and improper process variability. Specifically, for solid precursors, individual crystals of impurities can be incorporated into the vapor stream at much higher levels than dissolved impurities at the same impurity level. Due to the high sensitivity of the vapor content to impurity levels, current analytical techniques for measuring impurity levels cannot detect impurity levels low enough. Summary of the Invention

[0003] Some embodiments relate to a method for purifying a tungsten precursor. The method for purifying a tungsten precursor may include 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 container containing one of WCl 4 , WOCl 4 , and WCl 5 or WCl 6 . In some embodiments, the method includes separating a first portion of WCl 5 or WCl 6 from WOCl 4 , where the separation includes: applying a first condition to the source container to produce a first WOCl 4 vapor; and removing at least a portion of the first WOCl 4 vapor from the source container. In some embodiments, the method includes separating a second portion of WCl 5 or WCl 6 from WOCl 4 , where the separation includes: applying a second condition to the source container to produce a WCl 4 vapor containing (e.g., any remaining) WOCl 5 or a WCl 4 vapor containing (e.g., any remaining) WOCl 6 ; flowing the WCl 5 vapor or the WCl 6 vapor stream to a collection container; applying a third condition to the collection container to produce a WCl 5 condensate or a WCl 6 condensate and a second WOCl 4 vapor; and removing the second WOCl 4 from the collection container.At least a portion of the vapor. In some embodiments, the method includes recovering a precursor in a collection container. In some embodiments, the method includes verifying a low WOCl 4 content.

[0004] Some embodiments relate to a method for verifying a low impurity content. In some embodiments, the method includes obtaining a collection container containing a WCl 5 precursor or a WCl 6 precursor. In some embodiments, the method includes applying conditions to a collection container containing a WCl 5 precursor or a WCl 6 precursor. In some embodiments, the method includes measuring at least one of the total pressure within the collection container, the rate of change of the total pressure within the collection container, or any combination thereof. In some embodiments, the method includes comparing the total pressure or the rate of change of the total pressure with a reference value to verify or not verify a low WOCl 4 content. In some embodiments, the method includes removing WOCl 4 from the collection container when a low WOCl 4 content is not verified.

[0005] Some embodiments relate to a precursor container. In some embodiments, the precursor container contains a precursor. In some embodiments, the precursor contains WCl 5 . In some embodiments, when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), WCl 5 has a vapor pressure less than 1.3 times the calculated vapor pressure of WCl 5 determined according to the following formula:

[0006]

[0007] Some embodiments relate to a precursor container. In some embodiments, the precursor container contains a precursor. In some embodiments, the precursor contains WCl 6 . In some embodiments, when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), WCl 6 has a vapor pressure less than 1.3 times the calculated vapor pressure of WCl 6 determined according to the following formula:

[0008] BRIEF DESCRIPTION OF THE DRAWINGS

[0009] By way of example only, some embodiments of the present disclosure are described herein with reference to the accompanying drawings. Referring now specifically to the drawings, it should be emphasized that the embodiments are shown by way of example and for purposes of illustrative discussion of embodiments of the present disclosure. In this regard, the description in conjunction with the drawings will make it clear to those skilled in the art how the embodiments of the present disclosure may be practiced.

[0010] Figure 1 FIG. is a flowchart of a method for purifying a tungsten precursor according to some embodiments.

[0011] Figure 2 FIG. is a flowchart of a method for separating a tungsten precursor from impurities according to some embodiments.

[0012] Figure 3 FIG. is a flowchart of a method for separating a tungsten precursor from impurities according to some embodiments.

[0013] Figure 4 FIG. is a flowchart of a method for verifying a low impurity content of a tungsten precursor according to some embodiments.

[0014] Figure 5 FIG. is a flowchart of a method for measuring a low impurity content of a tungsten precursor according to some embodiments.

[0015] Figure 6 FIG. is a flowchart of a method for measuring a low impurity content of a tungsten precursor according to some embodiments.

[0016] Figure 7 FIG. is a graphical view of a vapor pressure curve according to some embodiments.

[0017] Figure 8 FIG. is a graphical view of vapor pressure versus pumping time according to some embodiments. DETAILED DESCRIPTION

[0018] Among the benefits and improvements already disclosed, other objects and advantages of the present disclosure will become apparent from the following description in conjunction with the accompanying drawings. Specific embodiments of the present disclosure are disclosed herein; however, it should be understood that the disclosed embodiments merely illustrate the present disclosure which may be implemented in various forms. In addition, each of the examples given with respect to the various embodiments of the present disclosure is intended to be illustrative and not restrictive.

[0019] Any prior patents and publications referred to herein are incorporated by reference in their entirety.

[0020] Throughout this specification and the claims, unless the context otherwise requires, 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, but may. Additionally, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, but may. All embodiments of the present disclosure are intended to be combinable without departing from the scope or spirit of the present disclosure.

[0021] As used herein, unless the context otherwise requires, the term "based on" is not exclusive and allows for additional factors not described. Additionally, throughout this specification, the meanings of "a," "an," and "the" include plural referents. The meaning of "in" includes "in" and "on."

[0022] Some embodiments relate to a method for purifying a tungsten precursor. Various embodiments of a method for purifying a tungsten precursor are provided herein. It should be understood that any combination of steps in the method for purifying a tungsten precursor may be performed in any order without departing from the scope of the present disclosure. Accordingly, the depiction of various methods and the steps of those methods in different figures should not be 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 disclosure.

[0023] Figure 1 is a flowchart of a method 100 for purifying a tungsten precursor according to some embodiments. In some embodiments, method 100 relates to a method for purifying WCl 5 . According to Figure 1 shown, in some embodiments, the method 100 for purifying a tungsten precursor may include at least one of the following steps: a step 102 of obtaining a source container containing one of WCl 4 , WOCl 4 , and WCl 5 or WCl 6 ; a step 104 of separating a first portion of the WCl 5 or the WCl 6 from the WOCl 4 ; a step 106 of separating a second portion of the WCl 5 or the WCl 6 from the WOCl 4 ; a step 108 of recovering the precursor in a collection container; a step 110 of verifying a low WOCl 4 content of the recovered precursor; or any combination thereof.

[0024] In step 102, in some embodiments, a source container containing at least one of the following is obtained: WCl 4 , WOCl 4 , WCl 5 or WCl 6 or any combination thereof. WCl 5 or WCl 6 may be present in the source container in at least one of the forms of solid, gas / vapor, or any combination thereof. For example, in some embodiments, WCl 5 or WCl 6 are present in solid form and in vapor form. In some embodiments, the solid phase of WCl 5 or WCl 6 is amorphous or crystalline. In some embodiments, WCl 5 or WCl 6 are present in the source container in the form of separated crystals. WCl 4 may be present in the source container in at least one of the forms of solid, gas / vapor, or any combination thereof. For example, in some embodiments, WCl 4 may be present in solid and vapor forms, wherein the WCl 4 vapor is substantially less than the WCl 5 vapor or the WCl 6 vapor. In some embodiments, WCl 4 are present in the source container in the form of separated crystals. In some embodiments, WCl 4 is present within the solid phase of WCl 5 or WCl 6 . For example, in some embodiments, WCl 4 is dissolved in the lattice of WCl 5 or WCl 6 . WOCl 4 may be present in the source container in at least one of the forms of solid, gas / vapor, or any combination thereof. For example, in some embodiments, WOCl 4 is present in solid form and in vapor form. The solid phase of WOCl 4 may be amorphous or crystalline. In some embodiments, WOCl 4 are present in the source container in the form of separated crystals. In some embodiments, WOCl 4 is present within the solid phase of WCl 5 . For example, in some embodiments, WOCl 4 is dissolved in the lattice of WCl 5 or WCl 6 . In some embodiments, WOCl 4 is present within WCl4 in the solid phase. WCl 4 The solid phase of may be amorphous or crystalline. For example, in some embodiments, WOCl 4 is dissolved in WCl 4 in the lattice.

[0025] The source container may be configured to control 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 wound around the source container. In some embodiments, a block heater having a shape covering at least a major portion of the outer surface of the source container is employed to heat the source container. In some embodiments, a resistive heater is employed to heat the source container. In some embodiments, a lamp heater is employed to heat the source container. In some embodiments, a heat transfer fluid at a high temperature may be brought into contact with the outer surface of the source container to effect heating and / or cooling of the source container. In some embodiments, heating is effected by irradiating the source container with infrared or other radiant energy. In some embodiments, the collection container is cooled 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 and other configurations and arrangements of heaters and / or coolers may be employed herein without departing from the scope of the present disclosure.

[0026] The source container may be configured to control pressure. The pressure of the source container can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the source container. The gas inlet line may be configured to supply pressurized gas from a pressurized gas source to the source container. Control of the pressurized gas entering the source container can be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or any combination thereof. In some embodiments, the pressurized gas comprises an inert gas. In some embodiments, the inert gas comprises at least one of helium, argon, nitrogen, or any combination thereof. In some embodiments, a vacuum line is fluidly coupled to the source container. The vacuum line may be configured to apply a vacuum to the source 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 source container may be employed herein without departing from the scope of the present disclosure.

[0027] In step 104, in some embodiments, WCl 5 is separated from a first portion of WOCl 4 . As disclosed herein (e.g., in Figure 2 ), in some embodiments, WCl may be separated by applying a first condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the source container.5 or WCl 6 is separated from a first portion of WOCl 4 to produce a first WOCl 4 vapor. In some embodiments, the first WOCl 4 can be separated from WCl 5 or WCl 6 by removing at least a portion of the first portion of WOCl 4 from the source vessel. In some embodiments, the first condition is that the total pressure in the source vessel is lower than the true vapor pressure of WOCl 4 for a given first temperature. In some embodiments, the first condition is that the total pressure in the source vessel is higher than the true vapor pressure of WCl 5 for a given first temperature. In some embodiments, when the first condition is applied, the first WOCl 4 vapor contains a greater volume of WOCl 5 than WCl 4 .

[0028] In step 106, in some embodiments, WCl 5 or WCl 6 is separated from a second portion of WOCl 4 and WCl 4 . This step may also involve or effect the separation of WCl 5 or WCl 6 from WOCl 4 . As disclosed herein (e.g., in Figure 3 ), in some embodiments, WCl 5 or WCl 6 can be separated from a second portion of WOCl 4 (and in some embodiments from WCl 4 ) by applying a second condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the source vessel, thereby producing a WCl 4 vapor containing WOCl 5 or a WCl 4 vapor containing WOCl 6 ; flowing the WCl 5 vapor or the WCl 6 vapor stream to a collection vessel; applying a third condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the collection vessel, thereby producing a WCl 5 condensate or a WCl 6 condensate and a second WOCl 4 vapor; and removing at least a portion of the second WOCl 4 vapor from the collection vessel.

[0029] In some embodiments, the second condition is that the total pressure of the source container is lower than the true vapor pressure of WCl 5 or WCl 6 for a given second temperature. In some embodiments, the second condition is that the total pressure of the source container is higher than the true vapor pressure of WCl 4 for a given second temperature. In some embodiments, when the second condition is applied, the WCl 5 vapor or the WCl 6 vapor contains a greater volume of WCl 4 than the WCl 5 or WCl 6 . In some embodiments, when the second condition is applied, the WCl 5 vapor or the WCl 6 vapor contains a greater volume of WOCl 4 than the WCl 4 . In some embodiments, the third condition is that the volume of the condensed WCl 5 or WCl 6 is greater than the volume of the condensed WOCl 4 . In some embodiments, when the third condition is applied, the WCl 5 condensate contains a greater mole fraction of WCl 4 than the WOCl 5 . In some embodiments, when the third condition is applied, the WCl 6 condensate contains a greater mole fraction of WCl 4 than the WOCl 6 .

[0030] The collection container may be configured to control the 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 strip heater is wound around the collection container. In some embodiments, a cylinder heater having a shape that covers at least a major portion of the outer surface of the collection container is employed to heat the collection container. In some embodiments, a resistive heater is employed to heat the collection container. In some embodiments, a lamp heater is employed to heat the collection container. In some embodiments, a heat transfer fluid at a high temperature may contact the outer surface of the collection container to effect heating and / or cooling of the collection container. In some embodiments, heating is effected by irradiating the collection container with infrared or other radiant energy. In some embodiments, the collection container is cooled 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 and other configurations and arrangements of heaters and / or coolers may be employed herein without departing from the scope of the present disclosure.

[0031] The collection container can be configured to control pressure. The pressure of the collection container can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the collection container. The gas inlet line can be configured to supply pressurized gas from a pressurized gas source to the collection container. Control of the pressurized gas entering the collection container can be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or any combination thereof. In some embodiments, the pressurized gas comprises an inert gas. In some embodiments, the inert gas comprises at least one of helium, argon, nitrogen, or any combination thereof. In some embodiments, a vacuum line is fluidly coupled to the collection container. The vacuum line can be configured to apply a vacuum to the collection 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 source container can be employed herein without departing from the scope of the present disclosure.

[0032] In step 108, in some embodiments, the precursor is recovered in the collection container. In some embodiments, the precursor comprises WCl 5 or WCl 6 . In some embodiments, the precursor comprises WCl 5 or WCl 6 and a low WOCl 4 content. In some embodiments, when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), the collection container containing WCl 5 or WCl 6 has a vapor pressure less than 1.1 times the calculated vapor pressure of WCl 5 determined according to the following formula:

[0033]

[0034] In some embodiments, WCl 5 or WCl 6 maintains the vapor pressure for up to 72 hours. In some embodiments, WCl 5 or WCl 6 maintains the vapor pressure for a duration of 5 minutes to 72 hours.

[0035] In step 110, in some embodiments, the low WOCl 4 content of the recovered precursor is verified. As disclosed herein (e.g., Figure 4 and Figure 5 ), in some embodiments, the low WOCl 4 content of the recovered precursor can be verified by measuring the WOCl 4 content of the precursor, thereby verifying or not verifying the low WOCl 4Content, and when the low WOCl of the precursor 4 Content is not verified, repeat at least one of step 104, step 106, or any combination thereof to remove WOCl 4 . In some embodiments, the WOCl of the precursor is measured by 4 Content: applying a fourth condition to a collection container containing the precursor; measuring the total pressure inside the collection container; and comparing the total pressure with a reference value. In some embodiments, when 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 5 or WCl 6 under the conditions), the low WOCl of the precursor 4 Content is verified. In some embodiments, when the total pressure is not within the percentage of the reference value (e.g., within 0.01% to 20% of the true vapor pressure of WCl 5 or WCl 6 under the conditions), the low WOCl of the precursor 4 Content is not verified. In some embodiments, the fourth condition is selected to stabilize the collection container at a reference temperature; stop the inlet gas flow to the collection container; short the vacuum pump to remove inert gas from the gas phase in the collection container; separate the collection container from the vacuum pump; and then monitor or measure the pressure in the collection container over time. In some embodiments, the WOCl of the precursor is measured by 4 Content: applying a fourth condition to a collection container containing the precursor; measuring the rate of change of the total pressure inside the collection container; and comparing the rate of change of the total pressure with a reference value. In some embodiments, when the rate of change of the total pressure is greater than the reference value, the low WOCl of the precursor 4 Content 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 WOCl of the precursor 4 Content is verified. In some embodiments, when the rate of change of the total pressure is 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less, the low WOCl of the precursor 4 Content is verified. In some embodiments, WCl 6 is an impurity in WCl 5 (e.g., present in the WCl 5 condensate). In some embodiments, WCl 5 is an impurity in WCl 6 (e.g., present in the WCl 6 condensate). In some embodiments, the total pressure is equal to the sum of the vapor pressure of WCl 5 and the vapor pressure of WCl 6 (e.g., total pressure = 0.6T (for WCl5 ) + 0.3T (for WCl 6 ) ≥ 0.9T).

[0036] Figure 2 Flowchart of method 200 for separating tungsten precursor from impurities according to some embodiments. According to Figure 2 shown, in some embodiments, method 200 for separating tungsten precursor from impurities may include at least one of the following steps: applying a first condition to a source container to generate a first WOCl 4 vapor in step 202; removing at least a portion of the first WOCl 4 vapor from the source container in step 204; or any combination thereof. In some embodiments, method 200 involves separating WCl 5 from a first portion of WOCl 4 described above.

[0037] In step 202, in some embodiments, a first condition is applied to the source container, thereby generating a first WOCl 4 vapor. In some embodiments, the first condition includes a first temperature of the source container. In some embodiments, the first temperature of the source container is a temperature in the range of 60°C to 170°C or any range or sub-range between 60°C and 170°C. In some embodiments, the first temperature of the source container is a temperature in the following ranges: 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.

[0038] In some embodiments, the first condition includes a first pressure of the source container. In some embodiments, the first pressure of the source container is a pressure within the range of 0.01 Torr to 100 Torr or any range or sub-range therebetween. In some embodiments, the first pressure of the source container is a pressure within the following ranges: 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 1 Torr, 0.01 Torr to 0.1 Torr, 0.1 Torr to 100 Torr, 1 Torr to 100 Torr, 5 Torr to 100 Torr, 10 Torr to 100 Torr, 15 Torr to 100 Torr, 20 Torr to 100 Torr, 25 Torr to 100 Torr, 30 Torr to 100 Torr, 35 Torr to 100 Torr, 40 Torr to 100 Torr, 45 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, or 95 Torr to 100 Torr.

[0039] In some embodiments, the first condition is that the total pressure of the source container is lower than WOCl 4 for the condition of the true vapor pressure at a given first temperature. In some embodiments, the first condition is that the total pressure of the source container is higher than WCl 5 for the condition of the true vapor pressure at a given first temperature. In some embodiments, the first condition is such that WOCl 4 evaporates while minimizing the amount of evaporated WCl 5 or WCl 6 . In some embodiments, the first condition is such that WCl 5 or WCl 6 does not evaporate. In some embodiments, the first condition is such that the separated crystals of WOCl 4 evaporate. In some embodiments, the first condition is such that WOCl 5 present in the lattice of WCl 6 or WCl 4 does not evaporate or does not evaporate significantly. Once evaporated, the first WOCl 4 vapor can be removed from the source container, thereby separating WOCl 4 from WCl 5 or WCl 6 .

[0040] First WOCl 4 The vapor may contain more than WCl 5 or WCl 6 Larger volume of WOCl 4 In some embodiments, according to the first WOCl 4 Total volume of vapor, first WOCl 4 The vapor contains less than 10 vol%, less than 9 vol%, less than 8 vol%, less than 7 vol%, less than 6 vol%, less than 5 vol%, less than 4 vol%, less than 3 vol%, less than 2 vol%, less than 1 vol%, less than 0.1 vol%, less than 0.01 vol% WCl 5 In some embodiments, according to the first WOCl 4 Total volume of vapor, first WOCl 4 The vapor comprises 0.01 vol% to 10 vol%, 0.01 vol% to 9 vol%, 0.01 vol% to 8 vol%, 0.01 vol% to 7 vol%, 0.01 vol% to 6 vol%, 0.01 vol% to 5 vol%, 0.01 vol% to 4 vol%, 0.01 vol% to 3 vol%, 0.01 vol% to 2 vol%, 0.01 vol% to 1 vol%, 0.01 vol% to 0.1 vol%, 0.1 vol% to 10 vol%, 1 vol% to 10 vol%, 2 vol% to 10 vol%, 3 vol% to 10 vol%, 4 vol% to 10 vol%, 5 vol% to 10 vol%, 6 vol% to 10 vol%, 7 vol% to 10 vol%, 8 vol% to 10 vol%, or 9 vol% to 10 vol% WCl 5 or WCl 6 .

[0041] At step 204, in some embodiments, the first WOC1 is removed from the source container. 4 At least a portion of the vapor. The first WOCl 4 The vapor may be removed via an outlet of the source container. The outlet may be fluidly coupled to a gas exhaust line, a vacuum line, or a suitable source for removing the first WOCl from the source container. 4 Other similar lines for steam.

[0042] Figure 3 FIG. 3 is a flow chart of a method 300 for separating a tungsten precursor from impurities according to some embodiments. Figure 3 As shown, in some embodiments, the method 300 for separating a tungsten precursor from impurities may include at least one of the following steps: applying a second condition to the source container to produce a WOCl-containing 4 WCl 5 Steam or WCl 6 Step 302 of steam: WCl5 Vapor or WCl 6 Step 304 of flowing the vapor to a collection vessel; applying a third condition to the collection vessel to produce WCl 5 Condensate or WCl 6 Condensate and a second WOCl 4 Step 306 of vapor; removing the second WOCl from the collection vessel 4 At least a portion of the vapor; or any combination thereof. In some embodiments, method 300 involves causing WCl 5 or WCl 6 To be separated from a second portion of WOCl as described above 4 Causing WCl 5 or WCl 6 To be separated from a second portion of WOCl, method 300 may further cause WCl 4 or WCl 5 or WCl 6 To be separated from WCl 4 .

[0043] In step 302, in some embodiments, a second condition is applied to the source vessel to produce a WCl 4 Containing WOCl 5 Vapor or WCl 6 Vapor. In some embodiments, the second condition includes a second temperature of the source vessel. In some embodiments, the second temperature of the source vessel is a temperature in the range of 60 °C to 170 °C or any range or sub-range between 60 °C and 170 °C. In some embodiments, the second temperature of the source vessel is a temperature in the following ranges: 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. In some embodiments, the second temperature of the source vessel is greater than the first temperature of the source vessel. In some embodiments, the second temperature of the source vessel is less than the first temperature of the source vessel.

[0044] In some embodiments, the second condition includes a second pressure of the source container. In some embodiments, the second pressure of the source container is a pressure within the range of 0.01 Torr to 100 Torr or any range or sub-range therebetween. In some embodiments, the second pressure of the source container is a pressure within the following ranges: 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 1 Torr, 0.01 Torr to 0.1 Torr, 0.1 Torr to 100 Torr, 1 Torr to 100 Torr, 5 Torr to 100 Torr, 10 Torr to 100 Torr, 15 Torr to 100 Torr, 20 Torr to 100 Torr, 25 Torr to 100 Torr, 30 Torr to 100 Torr, 35 Torr to 100 Torr, 40 Torr to 100 Torr, 45 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, or 95 Torr to 100 Torr. In some embodiments, the second pressure of the source container is less than the first pressure of the source container. In some embodiments, the second pressure of the source container is greater than the first pressure of the source container.

[0045] In some embodiments, the second condition is that the total pressure of the source container is below the true vapor pressure of WCl 5 or WCl 6 for a given second temperature. In some embodiments, the second condition is that the total pressure of the source container is above the true vapor pressure of WCl 4 for a given second temperature. In some embodiments, the second condition is such that WCl 5 or WCl 6 present as separated crystals in the source container evaporates. In some embodiments, the second condition is such that WCl 5 or WCl 6 evaporates while minimizing the amount of evaporated WCl 4 . In some embodiments, the second condition is such that WCl 4 does not evaporate. In some embodiments, the second condition is such that WOCl 5 present in the lattice of WCl 6 or WCl 4Conditions for evaporation. In some embodiments, the second condition is such that WOCl present as separated crystals in the source container 4 Conditions for evaporation. In some embodiments, WCl 5 vapor or WCl 6 vapor contains a greater volume of WCl 4 than WOCl 5 or WCl 6 . In some embodiments, WCl 5 vapor or WCl 6 vapor contains a greater volume of WOCl 4 than WCl 4 . In some embodiments, WCl 5 vapor or WCl 6 vapor contains a greater volume of WCl 4 than WCl 5 or WCl 6 .

[0046] In step 304, in some embodiments, WCl 5 vapor or WCl 6 vapor flow is directed to a collection container, thereby removing WCl 4 from the WCl 5 vapor or WCl 6 vapor contained within the source container. In some embodiments, WCl 5 vapor or WCl 6 vapor contains WOCl 4 . In some embodiments, WCl 5 vapor or WCl 6 vapor contains WOCl 4 vapor.

[0047] The collection container can be configured to control 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 strip heater is wound around the collection container. In some embodiments, a cylinder heater having a shape that covers at least a major portion of the outer surface of the collection container is used to heat the collection container. In some embodiments, a resistive 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 heat transfer fluid at a high temperature can be brought into contact with the outer surface of the collection container to effect heating and / or cooling of the collection container. In some embodiments, heating is effected by irradiating the collection container with infrared or other radiant energy. In some embodiments, the collection container is cooled 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 and other configurations and arrangements of heaters and / or coolers can be employed herein without departing from the scope of the present disclosure.

[0048] The collection container can be configured to control pressure. The pressure of the collection container can be controlled in any suitable manner. In some embodiments, a gas inlet line is fluidly coupled to the collection container. The gas inlet line can be configured to supply pressurized gas from a pressurized gas source to the collection container. Control of the pressurized gas entering the collection container can be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or any combination thereof. In some embodiments, the pressurized gas includes an inert gas. In some embodiments, the inert gas includes at least one of helium, argon, nitrogen, or any combination thereof. In some embodiments, a vacuum line is fluidly coupled to the collection container. The vacuum line can be configured to apply a vacuum to the collection 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 source container can be employed herein without departing from the scope of the present disclosure.

[0049] In step 306, in some embodiments, a third condition is applied to the collection container, thereby producing WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor. In some embodiments, WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor is produced such that WCl 5 or WCl 6 combines with WOCl 4The second part is separated. In some embodiments, the third condition includes the third temperature of the collection container. In some embodiments, the third temperature of the collection container is in the range of 10°C to 100°C or any range or sub-range therebetween. In some embodiments, the third temperature of the collection container is a temperature in the following ranges: 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 container is sufficient to cause the WCl 5 vapor or the WCl 6 vapor to condense. In some embodiments, the third temperature of the collection container is a temperature sufficient to produce a second WOCl 4 vapor.

[0050] In some embodiments, the third condition includes the third pressure of the collection container. In some embodiments, the third pressure of the collection container 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 of the collection container is a pressure in the following ranges: 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 1 Torr, 0.01 Torr to 0.1 Torr, 0.1 Torr to 100 Torr, 1 Torr to 100 Torr, 5 Torr to 100 Torr, 10 Torr to 100 Torr, 15 Torr to 100 Torr, 20 Torr to 100 Torr, 25 Torr to 100 Torr, 30 Torr to 100 Torr, 35 Torr to 100 Torr, 40 Torr to 100 Torr, 45 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, or 95 Torr to 100 Torr. In some embodiments, the third pressure of the collection container is a pressure sufficient to cause the WCl 5 vapor or the WCl 6 vapor to condense. In some embodiments, the third pressure of the collection container is a pressure sufficient to produce a second WOCl 4 vapor.

[0051] In some embodiments, a third condition is applied to the collection vessel to produce WCl 5 condensate or WCl 6 condensate and WOCl 4 vapor. In some embodiments, the third condition is sufficient to cause WCl 5 or WCl 6 to condense without causing WOCl 4 to condense or at least minimize the volume of the condensed WOCl 4 so as to separate WCl 5 or WCl 6 from WOCl 4 In some embodiments, the third condition is that the volume of the condensed WCl 5 or WCl 6 is greater than that of WOCl 4 In some embodiments, the WCl 5 condensate or WCl 6 condensate contains a greater amount (e.g., mole fraction, volume, or mass fraction) of WCl 4 condensate than WOCl 5 condensate (if present), if any. In some embodiments, the third condition is that the volume of the evaporated WOCl 6 is greater than that of WCl 4 or WCl 5 or WCl 6 In some embodiments, the third condition is that the WOCl 4 vapor contains WOCl 5 or WCl 6 dissolved in the lattice of WCl 4 (and in some embodiments, the separated crystals of WOCl 4 ), and the WOCl 5 or WCl 6 evaporated together with WCl 4 in the source vessel.

[0052] In step 308, in some embodiments, at least a portion of the second WOCl 4 vapor is removed from the collection vessel. The second WOCl 4 vapor can be removed via an outlet of the collection vessel. The outlet can be fluidly coupled to a gas discharge line, a vacuum line, or other similar lines suitable for removing the second WOCl 4 vapor from the collection vessel.

[0053] Figure 4 is a flowchart of a method 400 for verifying a low impurity content of a tungsten precursor according to some embodiments. According to Figure 4As shown, in some embodiments, a method 400 for verifying a low impurity content of a tungsten precursor may include at least one of the following steps: measuring the WOCl of the precursor 4 content to verify or not verify the low WOCl of the precursor 4 content in step 402; comparing with a reference value to verify or not verify the low WOCl 4 in step 404; step 406: when the low WOCl 4 content of the precursor is not verified, (e.g., by repeating at least one of the following: step 104 (e.g., including but not limited to Figure 2 any one or more of the steps), step 106 (e.g., including but not limited to Figure 3 any one or more of the steps) or any combination thereof) to further remove WOCl 4 ; or any combination thereof. In some embodiments, when the low WOCl 4 content is verified, the precursor is ready for use 408. In some embodiments, method 400 relates to a method for verifying the low WOCl 4 content of a tungsten precursor.

[0054] Figure 5 is a flowchart of a method 500 for measuring the low impurity content of a tungsten precursor according to some embodiments. As Figure 5 shown, in some embodiments, a method 500 for measuring the low impurity content of a tungsten precursor may include at least one of the following steps: applying a fourth condition to a collection container containing a WCl 5 precursor or a WCl 6 precursor in step 502; measuring at least one characteristic in the collection container in step 504; comparing the at least one characteristic with a reference value in step 506. Although not shown, in some embodiments, method 500 for measuring the low impurity content of a tungsten precursor further includes a step of removing any vapors and / or gases from the collection container before performing step 502. Although not shown, in some embodiments, the fourth condition is selected to stabilize the collection container at a reference temperature; stop the inlet gas flow to the collection container; short the vacuum pump to remove inert gas from the gas phase in the collection container; separate the collection container from the vacuum pump; and then monitor or measure the pressure in the collection container over time. In some embodiments, method 500 relates to a method for measuring the low WOCl 4 content of the tungsten precursor as described above.

[0055] In step 502, in some embodiments, to a collection container containing a WCl 5 precursor or a WCl 6A fourth condition is imposed on the collection container for the precursor. In some embodiments, the fourth condition includes a fourth temperature of the collection container. In some embodiments, the fourth temperature of the collection container is a temperature in the range of 60 °C to 170 °C or any range or sub-range between 60 °C and 170 °C. In some embodiments, the fourth temperature of the collection container is a temperature in the following ranges: 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.

[0056] In some embodiments, the fourth condition includes a fourth pressure of the collection container. In some embodiments, the fourth pressure of the collection container is a pressure in the range of 0.01 Torr to 100 Torr or any range or sub-range therebetween. In some embodiments, the fourth pressure of the collection container is a pressure in the following ranges: 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 1 Torr, 0.01 Torr to 0.1 Torr, 0.1 Torr to 100 Torr, 1 Torr to 100 Torr, 5 Torr to 100 Torr, 10 Torr to 100 Torr, 15 Torr to 100 Torr, 20 Torr to 100 Torr, 25 Torr to 100 Torr, 30 Torr to 100 Torr, 35 Torr to 100 Torr, 40 Torr to 100 Torr, 45 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, or 95 Torr to 100 Torr.

[0057] In some embodiments, the fourth condition is that the total pressure in the collection container is WCl 5 or WCl 6conditions within 10% of the true vapor pressure of. In some embodiments, the fourth condition is that the total pressure of the collection vessel is less than WOCl 4 conditions of the true vapor pressure of.

[0058] In step 504, in some embodiments, at least one characteristic within the collection vessel is measured. In some embodiments, the at least one characteristic measured is 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 pressure per unit time. For example, in some embodiments, the rate of change of the total pressure is the rate of increase of pressure in torr per minute. In some embodiments, the rate of change of the total pressure is the rate of increase of pressure in millitorr per minute. In some embodiments, the rate of change of the total pressure within the collection vessel is measured over a duration between 30 seconds and 24 hours. It should be understood that the rate of change of the total pressure can be in any suitable pressure unit and time unit. It should be further understood that the duration over which the rate of change of the total pressure within the collection vessel is measured can vary depending on the composition of the precursor (e.g., impurity level) and the selected temperature of the fourth condition.

[0059] In step 506, in some embodiments, the total pressure within the collection vessel is compared with a reference value. In some embodiments, when the total pressure is within 0.01% to 20% (including the endpoints) of the reference value or any range or sub-range therebetween, the low WOCl 4 content of the precursor is verified. In some embodiments, when the total pressure is not within 0.01% to 20% of the reference value, the low WOCl 4 content of the precursor is not verified. In some embodiments, the reference value is the true vapor pressure of WCl 5 under the conditions (e.g., the selected temperature). In some embodiments, if the total pressure measured under the conditions is within 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%, 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% of the true vapor pressure of WCl 5 then the low WOCl 4 content is verified.

[0060] In step 506, in some embodiments, the rate of change of the total pressure within the collection vessel 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 WOCl 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 WOCl content of the precursor is verified. For example, in some embodiments, when the rate of change of the total pressure is 20% or less, 15% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less per unit minute, the low WOCl content of the precursor is 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 for the lower temperature of the fourth condition, the limit value of the pressure rise rate will be lower. 4 When the rate of change of the total pressure is greater than the reference value, the low WOCl 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 WOCl content of the precursor is verified. 4 For example, in some embodiments, when the rate of change of the total pressure is 20% or less, 15% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less per unit minute, the low WOCl content of the precursor is verified. 4 For example, in some embodiments, when the rate of change of the total pressure is 20% or less, 15% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less per unit minute, the low WOCl content of the precursor is 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 for the lower temperature of the fourth condition, the limit value of the pressure rise rate will be lower.

[0061] Figure 6 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content 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 inlet gas flow to the collection vessel is stopped; an inert gas is removed from the gas phase in the collection vessel by a short vacuum pump; the collection vessel is separated from the vacuum pump; and the pressure in the collection vessel is then monitored or measured over time. Figure 6 As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof. 5 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof. 6 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof. 5 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof. 6 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof. 4 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof. 4 Is a flowchart of method 600 for verifying low impurity content according to some embodiments. As shown, in some embodiments, method 600 for verifying low impurity content may include 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 within the collection vessel (e.g., at least one of the rate of change of the total pressure within the collection vessel, the total pressure within 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 when the low WOCl content is not verified in step 610; or any combination thereof.

[0062] Some embodiments relate to tungsten precursors having impurity levels low enough such that when supplied to a tool used in semiconductor manufacturing or other similar processes, the tungsten precursor is supplied to the tool at a controlled, constant flow rate upon evaporation, with no significant peaks or variations in the flow rate. In some embodiments, a precursor container is provided. The precursor container may contain a tungsten precursor, such as but not limited to WCl 5 precursor or WCl 6 precursor. The impurities may include, for example and without limitation, at least one of WOCl 4 , WCl 4 , or any combination thereof.

[0063] In some embodiments, when the WCl 5 precursor is contained in the precursor container, the precursor has a vapor pressure less than 1.3 times the calculated vapor pressure of WCl 5 as determined by the following formula when the precursor container is maintained at a temperature of 70 °C to 240 °C (or any range or sub-range therebetween):

[0064]

[0065] In some embodiments, when the WCl 5 precursor is contained in the precursor container, the precursor has a vapor pressure less than 1.1 times the calculated vapor pressure of WCl 5 as determined by the following formula when the precursor container is maintained at a temperature of 70 °C to 240 °C (or any range or sub-range therebetween):

[0066]

[0067] In some embodiments, when the WCl 6 precursor is contained in the precursor container, the precursor has a vapor pressure less than 1.3 times the calculated vapor pressure of WCl 6 as determined by the following formula when the precursor container is maintained at a temperature of 70 °C to 240 °C (or any range or sub-range therebetween):

[0068]

[0069] In some embodiments, when the WCl 6 precursor is contained in the precursor container, the precursor has a vapor pressure less than 1.1 times the calculated vapor pressure of WCl 6 as determined by the following formula when the precursor container is maintained at a temperature of 70 °C to 240 °C (or any range or sub-range therebetween):

[0070]

[0071] WCl 5 or WCl 6 can maintain the vapor pressure for an indefinite period of time. In some embodiments, WCl 5 or WCl 6 maintains the vapor pressure for a duration of up to 72 hours. In some embodiments, WCl 5 or WCl 6 maintains the vapor pressure for a duration of from 5 minutes to 72 hours or any range or sub-range therebetween.

[0072] Aspect

[0073] Various aspects are described below. It should be understood that any one or more of the features recited in the following aspects can be combined with any one or more of the other aspects.

[0074] Aspect 1. A method, comprising:

[0075] a) obtaining a source container containing one of WCl 4 , WOCl 4 , and WCl 5 or WCl 6 ;

[0076] b) separating the WCl 5 or the WCl 6 from a first portion of the WOCl 4 , wherein the separation comprises:

[0077] applying a first condition to the source container to produce a first WOCl 4 vapor;

[0078] removing at least a portion of the first WOCl 4 vapor from the source container;

[0079] c) separating the WCl 5 or the WCl 6 from a second portion of the WOCl 4 , wherein the separation comprises:

[0080] applying a second condition to the source container to produce a WCl 4 vapor containing WOCl 5 or a WCl 4 vapor containing WOCl 6 ;

[0081] flowing the WCl 5 vapor or the WCl 6 vapor stream to a collection container;

[0082] Apply a third condition to the collection container to produce WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor;

[0083] Remove at least a portion of the second WOCl 4 vapor from the collection container; and

[0084] d) Recover the precursor in the collection container.

[0085] Aspect 2. The method according to aspect 1, wherein the first condition is that the total pressure of the source container is lower than the true vapor pressure of WOCl 4 for a given first temperature.

[0086] Aspect 3. The method according to any one of aspects 1 to 2, wherein the first condition is that the total pressure of the source container is higher than the true vapor pressure of WCl 5 or WCl 6 for a given first temperature.

[0087] Aspect 4. The method according to any one of aspects 1 to 3, wherein when the first condition is applied, the first WOCl 4 vapor contains a larger volume of WOCl than WCl 5 or WCl 6 . 4

[0088] Aspect 5. The method according to any one of aspects 1 to 4, wherein the second condition is that the total pressure of the source container is lower than the true vapor pressure of the WCl 5 or the WCl 6 for a given second temperature.

[0089] Aspect 6. The method according to aspect 4, wherein the second condition is that the total pressure of the source container is higher than the true vapor pressure of the WCl 4 for a given second temperature.

[0090] Aspect 7. The method according to any one of aspects 1 to 6, wherein when the second condition is applied, the WCl 5 vapor contains a larger volume of the WCl than the WCl 4 . 5

[0091] Aspect 8. The method according to any one of aspects 1 to 7, wherein when the second condition is applied, the WCl 6 vapor contains a larger volume of the WCl than the WCl 4 volume.​​6 .

[0092] Aspect 9. The method according to any one of Aspects 1 to 8, wherein when the second condition is applied, the WCl 5 vapor contains more of the WOCl 4 than the volume of the WCl 4 .

[0093] Aspect 10. The method according to any one of Aspects 1 to 9, wherein when the second condition is applied, the WCl 6 vapor contains more of the WOCl 4 than the volume of the WCl 4 .

[0094] Aspect 11. The method according to any one of Aspects 1 to 10, wherein the third condition is the condition that the volume of the condensed WCl 5 is greater than that of the WOCl 4 .

[0095] Aspect 12. The method according to any one of Aspects 1 to 11, wherein the third condition is the condition that the volume of the condensed WCl 6 is greater than that of the WOCl 4 .

[0096] Aspect 13. The method according to any one of Aspects 1 to 12, wherein when the third condition is applied, the condensate of the WCl 5 contains a higher mole fraction of WCl 4 than WOCl 5 .

[0097] Aspect 14. The method according to any one of Aspects 1 to 13, wherein when the third condition is applied, the condensate of the WCl 6 contains a higher mole fraction of WCl 4 than WOCl 6 .

[0098] Aspect 15. The method according to any one of Aspects 1 to 14, further comprising:

[0099] e) verifying a low WOCl 4 content of the precursor present in the collection container.

[0100] Aspect 16. The method according to Aspect 15, wherein the verification step e) comprises:

[0101] e1) measuring the WOCl 4 content of the precursor, thereby verifying or not verifying the low WOCl 4 content of the precursor;

[0102] e2) When the low WOCl of the precursor 4 content is not verified, repeat at least one of step b), step c), or any combination thereof to remove the WOCl 4 .

[0103] Aspect 17. The method according to aspect 16, wherein the measuring step e1) comprises:

[0104] Applying a fourth condition to the collection container containing the precursor;

[0105] Measuring at least one property within the collection container; and

[0106] Comparing the measured property with a reference value.

[0107] Aspect 18. The method according to aspect 17, wherein the at least one property is the total pressure within the collection container,

[0108] wherein when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 5 , the low WOCl 4 content is verified;

[0109] wherein when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 5 , the low WOCl 4 content is not verified.

[0110] Aspect 19. The method according to aspect 17, wherein the at least one property is the total pressure within the collection container,

[0111] wherein when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 6 , the low WOCl 4 content is verified;

[0112] wherein when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 6 , the low WOCl 4 content is not verified.

[0113] Aspect 20. The method according to aspect 17, wherein the at least one property is the rate of change of the total pressure within the collection container,

[0114] wherein when the rate of change of the total pressure is greater than the reference value, the low WOCl 4 content of the precursor is not verified;

[0115] Wherein when the rate of change of the total pressure is equal to or less than the reference value, the low WOCl of the precursor is 4 verified;

[0116] Wherein the reference value is a 5% change in the total pressure per minute.

[0117] Aspect 21. The method according to aspect 17, wherein the fourth condition is that the total pressure of the collection container is lower than the 4 true vapor pressure of the WOCl.

[0118] Aspect 22. A method for verifying a low impurity content, the method comprising:

[0119] Obtaining a collection container containing a WCl 5 precursor or a WCl 6 precursor;

[0120] Applying conditions to the collection container containing the WCl 5 precursor or the WCl 6 precursor;

[0121] Measuring at least one property within the collection container;

[0122] Comparing the at least one property with a reference value;

[0123] When the low WOCl 4 content is not verified, removing the WOCl 4 from the collection container.

[0124] Aspect 23. The method according to aspect 22, wherein the at least one property is the total pressure within the collection container,

[0125] wherein when the total pressure is within 10% of the true vapor pressure of the WCl 5 the low WOCl 4 content is verified;

[0126] wherein when the total pressure is not within 10% of the true vapor pressure of the WCl 5 the low WOCl 4 content is not verified.

[0127] Aspect 24. The method according to aspect 22, wherein the at least one property is the total pressure within the collection container,

[0128] wherein when the total pressure is within 1% of the true vapor pressure of the WCl 6 the low WOCl 4 content is verified;

[0129] wherein when the total pressure is not within 1% of the true vapor pressure of the WCl 6 the low WOCl content of the precursor is not verified; 4

[0130] Aspect 25. The method according to aspect 22, wherein the at least one characteristic is the rate of change of the total pressure within the collection container,

[0131] wherein when the rate of change of the total pressure is greater than a reference value, the low WOCl 4 content of the precursor is not verified;

[0132] wherein when a second rate of change of the total pressure is equal to or less than the reference value, the low WOCl 4 content of the precursor is verified;

[0133] wherein the reference value is a 5% change in total pressure per minute.

[0134] Aspect 26. A precursor container comprising:

[0135] a precursor comprising WCl 5

[0136] wherein when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), the WCl 5 has a vapor pressure less than 1.1 times the true vapor pressure of WCl 5

[0137] Aspect 27. The precursor container according to aspect 26, wherein the true vapor pressure of the WCl 5 is calculated according to the following formula:

[0138]

[0139] Aspect 28. The precursor container according to aspect 26, wherein the WCl 5 maintains the vapor pressure within the precursor container for a period of up to 72 hours.

[0140] Aspect 29. A precursor container comprising:

[0141] a precursor comprising WCl 6

[0142] wherein when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), the WCl 6 has a vapor pressure less than 1.1 times the true vapor pressure of WCl 6 ​​​​​

[0143] Aspect 30. The precursor container according to aspect 29, wherein WCl 6 The true vapor pressure of is calculated according to the following formula:

[0144]

[0145] Aspect 31. The precursor container according to aspect 29, wherein the WCl 6 Maintains the vapor pressure within the precursor container for a period of up to 72 hours.

[0146] Example 1

[0147] 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 certain temperature and stabilize for 30 minutes. Pump the ampoule for a predetermined pumping time. Subsequently, separate the pressure measurement manifold from the pump and measure the pressure as a function of time for 5 minutes. The process can be repeated multiple times as needed to achieve the desired purity level.

[0148] Example 2

[0149] 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. Pump the ampoule to remove the inert gas, and then heat it to the desired temperature and stabilize for 30 minutes. Pump the ampoule for 10 seconds. Allow the ampoule to thermally equilibrate again for 5 minutes while pumping the pressure measurement manifold. Subsequently, separate the pressure measurement manifold from the pump and open it to the ampoule for pressure measurement. Measure the pressure as a function of time for 5 minutes. Since the initial pressure measurement value is within 10% of the true vapor pressure of WCl 5 the material is verified. If the pressure rise rate is less than about 3% / minute, the material can also be verified.

[0150] Example 3

[0151] 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. Pump the ampoule to remove the inert gas, and then heat it to the desired temperature and stabilize for 30 minutes. Pump the ampoule for 10 seconds. Allow the ampoule to thermally equilibrate again for 5 minutes while pumping the pressure measurement manifold. Subsequently, separate the pressure measurement manifold from the pump and open it to the ampoule for pressure measurement. Measure the pressure as a function of time for 5 minutes. Since the pressure rise rate is less than 3% / minute, the material is verified.

[0152] Example 4

[0153] The equations representing the measured vapor pressures for tungsten chloride and tungsten oxychloride materials are presented below.

[0154]

[0155]

[0156]

[0157] Figure 7 Is a graphical view of the vapor pressure curve according to some embodiments. Figure 8 Is a graphical view of the vapor pressure versus pumping time according to some embodiments.

[0158] It should be understood that changes can be made in detail without departing from the scope of the present disclosure, particularly in terms of the construction materials employed, as well as the shape, size, and arrangement of the components. This specification and the described embodiments are examples, where the true scope and spirit of the present disclosure are indicated by the appended claims.

Claims

1. A method, comprising: a) Obtain a source container containing one of WOCl 4 and WCl 5 or WCl 6 ; b) separating the WCl 5 or the WCl 6 from a first portion of the WOCl 4 , wherein the separation comprises: Apply a first condition to the source container to produce a first WOCl 4 vapor; Removing at least a portion of the first WOCl 4 vapor from the source container; c) separating the said WCl 5 or the said WCl 6 from a second part of the said WOCl 4 , wherein the separation comprises: Apply a second condition to the source container, thereby producing WCl vapor containing WOCl 4 or WCl vapor containing WOCl 5 ; 4 or WCl vapor containing WOCl 6 ; Cause the WCl 5 vapor or the WCl 6 vapor stream to flow to the collection container; Apply a third condition to the collection container, thereby producing WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor; Remove at least a portion of the second WOCl 4 vapor from the collection vessel; and d) Recovering a precursor in a collection container.

2. The method according to claim 1, wherein the source container further contains WCl 4 .

3. The method according to claim 1, wherein the first condition is that the total pressure of the source container is lower than the true vapor pressure of WOCl 4 for a given first temperature.

4. The method according to claim 3, wherein the first condition is that the total pressure of the source container is higher than the true vapor pressure of WCl 5 or WCl 6 for a given first temperature.

5. The method according to claim 1, wherein when the first condition is applied, the first WOCl 4 vapor contains more WOCl 5 or WCl 6 by volume than WCl 4 .

6. The method according to claim 1, wherein the second condition is that the total pressure of the source container is lower than the WCl 5 or the WCl 6 condition of the true vapor pressure for a given second temperature.

7. The method according to claim 2, wherein the second condition is that the total pressure of the source container is higher than the true vapor pressure of WCl 4 for a given second temperature.

8. The method according to claim 2, wherein when the second condition is applied, the WCl 5 vapor contains more of the WCl 4 by volume than the WCl 5 .

9. The method according to claim 2, wherein when the second condition is applied, the WCl 6 vapor contains the WCl 4 in a volume greater than that of the WCl 6 .

10. The method according to claim 2, wherein when the second condition is applied, the WCl 5 vapor contains the WOCl 4 in a volume greater than that of the WCl 4 .

11. The method according to claim 2, wherein when the second condition is applied, the WCl 6 vapor contains more of the WOCl 4 than the volume of the WCl 4 .

12. The method according to claim 1, wherein the third condition is that the volume of the condensation of the WCl 5 is greater than that of the WOCl 4 .

13. The method according to claim 1, wherein the third condition is that the volume of condensation of the WCl 6 is greater than that of the WOCl 4 .

14. The method according to claim 1, wherein when the third condition is applied, the WCl 5 condensate contains a greater molar fraction of WCl than WOCl 4 5 .​ 15. The method according to claim 1, wherein when the third condition is applied, the WCl 6 condensate contains a greater molar fraction of WCl 4 than WOCl 6 .

16. The method according to claim 1, further comprising: e) Verify the low WOCl 4 content of the precursor present in the collection container.

17. The method according to claim 16, wherein the verification step e) comprises: e1) Measuring the WOCl of the precursor, thereby verifying or not verifying the low WOCl 4 content of the precursor; 4 content; e2) When the low WOCl of the precursor 4 content is not verified, repeat at least one of step b), step c), or any combination thereof to remove the WOCl 4 .

18. The method according to claim 17, wherein the measurement step e1) comprises: Applying a fourth condition to the collection container containing the precursor; Measuring at least one characteristic within the collection container; and Comparing the measured characteristic with a reference value.

19. The method according to claim 18, wherein the at least one characteristic is the total pressure within the collection container, wherein when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 5 the low WOCl 4 content is verified; wherein when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 5 the low WOCl 4 content is not verified.

20. The method according to claim 18, wherein the at least one characteristic is the total pressure within the collection container, wherein when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 6 the low WOCl 4 content is verified; Wherein when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 6 the low WOCl 4 content is not verified.

21. The method according to claim 18, wherein the at least one characteristic is the rate of change of the total pressure within the collection container, Wherein when the rate of change of the total pressure is greater than the reference value, the low WOCl of the precursor 4 content is not verified; wherein when the rate of change of the total pressure is equal to or less than the reference value, the low WOCl of the precursor is verified; 4 content is verified; wherein the reference value is a 5% change in total pressure per minute.

22. The method according to claim 18, wherein the fourth condition is that the total pressure of the collection container is lower than the true vapor pressure of WOCl 4 .

23. A method for verifying a low impurity content, the method comprising: Obtain a collection container containing a WCl 5 precursor or a WCl 6 precursor; Apply conditions to the collection container containing the WCl 5 precursor or the WCl 6 precursor. Measuring at least one characteristic within the collection container; Comparing the at least one characteristic with a reference value; When the low WOCl 4 content is not verified, remove the WOCl 4 from the collection container.

24. The method according to claim 23, wherein the at least one characteristic is the total pressure within the collection container, Wherein when the total pressure is within 10% of the true vapor pressure of the WCl 5 , the low WOCl 4 content is verified; Wherein when the total pressure is not within 10% of the true vapor pressure of the WCl 5 the low WOCl 4 content is not verified.

25. The method according to claim 23, wherein the at least one characteristic is the total pressure within the collection container, wherein when the total pressure is within 1% of the true vapor pressure of the WCl 5 , the low WOCl 4 content is verified; Wherein when the total pressure is not within 1% of the true vapor pressure of the WCl 5 the low WOCl 4 content is not verified.

26. The method according to claim 23, wherein the at least one characteristic is the total pressure within the collection container, wherein when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 6 , the low WOCl 4 content is verified; wherein when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 6 the low WOCl 4 content is not verified.

27. The method according to claim 23, wherein the at least one characteristic is the rate of change of the total pressure within the collection container, Wherein when the rate of change of the total pressure is greater than the reference value, the low WOCl of the precursor 4 content is not verified; Wherein when the second change rate of the total pressure is equal to or less than the reference value, the low WOCl of the precursor 4 content is verified; wherein the reference value is a 5% change in total pressure per minute.

28. A precursor container, comprising: Containing a precursor of WCl 5 and Wherein when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), the WCl 5 has a vapor pressure less than 1.3 times the true vapor pressure of WCl 5 .

29. The precursor container according to claim 28, wherein the true vapor pressure of WCl 5 is calculated according to the following formula:

30. The precursor container according to claim 28, wherein the WCl 5 Maintain the vapor pressure within the precursor container for a period of up to 72 hours.

31. A precursor container, comprising: Containing a precursor of WCl 6 and wherein when the precursor container is maintained at a temperature of 70 °C (343.15 K) to 240 °C (513.15 K), the WCl 6 has a vapor pressure less than 1.1 times the true vapor pressure of WCl 6 .

32. The precursor container according to claim 31, wherein the true vapor pressure of WCl 6 is calculated according to the following formula:

33. The precursor container according to claim 31, wherein the WCl 6 Maintain the vapor pressure within the precursor container for a period of up to 72 hours.

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