Methods for validating purity of wcl5 or wcl6

Abstract

This invention provides a high-purity tungsten precursor and a method for purifying the tungsten precursor. The method for purifying the precursor may include at least one of the following steps: obtaining a source container containing one of WCl4, WOCl4, and 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; recovering the precursor in a collection container; or any combination thereof.

Description

Technical Field

[0001] The present invention relates to the field of tungsten precursors and related methods, including, for example and without limitation, purification methods and methods for verifying impurity levels. Prior Art

[0002] The presence of impurities in precursors used in semiconductor manufacturing can lead to defects and undesirable process variability. Specifically, for solid precursors, isolated crystals of impurities can be incorporated into the vapor stream at much higher concentrations than dissolved impurities at the same impurity level. Due to the high sensitivity of vapor content to impurity levels, current analytical techniques for measuring impurity levels cannot 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 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 WCl4, WOCl4, and one of WCl5 or WCl6. In some embodiments, the method includes separating the WCl5 or WCl6 from a first portion of WOCl4, wherein the separating includes: applying a first condition to the source container to generate a first WOCl4 vapor; and removing at least a portion of the first WOCl4 vapor from the source container. In some embodiments, the method includes separating WCl 5 or WCl 6 from a second portion of WOCl 4, wherein the separation includes: applying a second condition to the source container, thereby producing WCl 5 vapor containing (e.g., any remaining) WOCl 4 or WCl 6 vapor containing (e.g., any remaining) WOCl 4; flowing the WCl 5 vapor or WCl 6 vapor to a collection container; applying a third condition to the collection container, thereby producing WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor; and removing at least a portion of the second WOCl 4 vapor from the collection container. In some embodiments, the method includes recovering the precursor in the collection container. In some embodiments, the method includes verifying the low WOCl 4 content of the recovered precursor in the collection container.

[0004] Some embodiments relate to a method for verifying low impurity levels. 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 the collection container containing the WCl 5 precursor or the WCl 6 precursor. In some embodiments, the method includes measuring at least one of a total pressure within the collection container, a 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 low WOC14 content. In some embodiments, the method includes removing WOC14 from the collection container when low WOC14 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 between 70° C. (343.15 K) and 240° C. (513.15 K), the WCl 5 has a vapor pressure that is less than 1.3 times the calculated vapor pressure of WCl 5 as determined by the following formula:

[0006] Some embodiments relate to a precursor container. In some embodiments, the precursor container contains a precursor. In some embodiments, the precursor contains WCl₆. In some embodiments, when the precursor container is maintained at a temperature between 70° C. (343.15 K) and 240° C. (513.15 K), the WCl₆ has a vapor pressure that is less than 1.3 times the calculated vapor pressure of WCl₆ as determined by the following formula: Simple diagram description

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

[0008] [picture] [1] is a flow chart of a method for purifying a tungsten precursor according to some embodiments.

[0009] [picture] [2] is a flow chart of a method for separating a tungsten precursor from impurities according to some embodiments.

[0010] [picture] [3] is a flow chart of a method for separating a tungsten precursor from impurities according to some embodiments.

[0011] [picture] [4] is a flow chart of a method for verifying low impurity content of a tungsten precursor according to some embodiments.

[0012] [picture] [5] is a flow chart of a method for measuring low impurity levels of a tungsten precursor according to some embodiments.

[0013] [picture] [6] is a flow chart of a method for measuring low impurity levels of a tungsten precursor according to some embodiments.

[0014] [picture] [7] is a graphical representation of a vapor pressure curve according to some embodiments.

[0015] [picture] [8] is a graphical representation of vapor pressure versus pumping time according to some embodiments. Implementation Method

[0016] Among the benefits and improvements disclosed, other objects and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the various forms in which the present invention may be embodied. Furthermore, each of the examples given with respect to the various embodiments of the present invention is intended to be illustrative and not restrictive.

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

[0018] Throughout this specification and claims, unless the context clearly dictates otherwise, the following terms have the meanings explicitly associated herein. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, although they may. Furthermore, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, although they may. All embodiments of the present invention are intended to be combinable without departing from the scope or spirit of the invention.

[0019] As used herein, unless the context clearly dictates otherwise, the term "based on" is non-exclusive and allows for being based on additional factors not described. Additionally, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0020] 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 a method for purifying a tungsten precursor can be performed in any order without departing from the scope of the present invention. Therefore, the depiction of various methods and their steps in different figures should not be limiting, as 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 invention.

[0021] [picture] [1] is a flow chart of a method 100 for purifying a tungsten precursor according to some embodiments. In some embodiments, the method 100 is related to a method for purifying WCl 5. [picture] As shown in [1], in some embodiments, the method 100 for purifying a tungsten precursor may include at least one of the following steps: step 102 of obtaining a source container containing WCl4, WOCl4, and one of WCl5 or WCl6; step 104 of separating the WCl5 or the WCl6 from a first portion of the WOCl4; step 106 of separating the WCl5 or the WCl6 from a second portion of the WOCl4; step 108 of recovering the precursor in a collection container; step 110 of verifying the low WOCl4 content of the recovered precursor; or any combination thereof.

[0022] In step 102, in some embodiments, a source container containing at least one of the following: WCl 4, WOCl 4, WCl 5, or WCl 6, or any combination thereof, is obtained. WCl 5 or WCl 6 may be present in the source container in at least one of a solid, a gas / vapor, or any combination thereof. For example, in some embodiments, WCl 5 or WCl 6 exists in both a solid and a 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 exists in the source container as separated crystals. WCl 4 may be present in the source container in at least one of a solid, a gas / vapor, or any combination thereof. For example, in some embodiments, WCl 4 may be present in both a solid and a vapor form, wherein the WCl 4 vapor is substantially less than the WCl 5 vapor or WCl 6 vapor. In some embodiments, WCl 4 exists in the source container as separated crystals. In some embodiments, WCl 4 exists within the solid phase of WCl 5 or WCl 6. For example, in some embodiments, WCl4 is dissolved in the crystal lattice of WCl5 or WCl6. WOCl4 may be present in the source container in at least one of a solid, a gas / vapor, or any combination thereof. For example, in some embodiments, WOCl4 is present in both solid and vapor form. The solid phase of WOCl4 may be amorphous or crystalline. In some embodiments, WOCl4 is present in the source container in the form of separated 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 may be amorphous or crystalline. For example, in some embodiments, WOCl4 is dissolved in the crystal lattice of WCl4.

[0023] The source container can be configured to control temperature. The temperature of the source container can be controlled in any suitable manner. In some embodiments, a heat jacket is employed around the source container for heating and / or cooling. In some embodiments, a ribbon heater is wrapped around the source container. In some embodiments, a block heater shaped to cover at least a substantial 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 high-temperature heat transfer fluid may be placed in contact with the outer surface of the source container to achieve heating and / or cooling of the source container. In some embodiments, heating is achieved by directing infrared or other radiant energy onto the source container. In some embodiments, the collection container is cooled by a fluid, a fan, a direct thermal device, or any combination thereof. It should be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, may be employed herein without departing from the scope of the present invention.

[0024] The source container can 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 can 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 can 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 invention.

[0025] In step 104, in some embodiments, WCl 5 is separated from a first portion of WOCl 4. [picture] [2]), in some embodiments, WCl 5 or WCl 6 can be separated from a first portion of WOCl 4 by applying a first condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to a source container, thereby generating a first WOCl 4 vapor. In some embodiments, WCl 5 or WCl 6 can be separated from a first portion of WOCl 4 by removing at least a portion of the first WOCl 4 from the source container. In some embodiments, the first condition is a condition in which the total pressure of the source container is lower than the true vapor pressure of WOCl 4 for a given first temperature. In some embodiments, the first condition is a condition in which the total pressure of the source container 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 larger volume of WOCl 4 than WCl 5.

[0026] In step 106, in some embodiments, WCl 5 or WCl 6 is separated from WOCl 4 and a second portion of WCl 4. This step may also involve or allow WCl 5 or WCl 6 to be separated from WOCl 4. [picture] [3]), in some embodiments, WCl5 or WCl6 can be separated from a second portion of WOCl4- and in some embodiments, from a second portion of WCl4- by applying a second condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the source container, thereby producing WCl5 vapor containing WOCl4 or WCl6 vapor containing WOCl4; flowing the WCl5 vapor or WCl6 vapor to a collection container; applying a third condition (e.g., at least one of temperature, pressure, inert gas flow, vacuum, or any combination thereof) to the collection container, thereby producing WCl5 condensate or WCl6 condensate and a second WOCl4 vapor; and removing at least a portion of the second WOCl4 vapor from the collection container.

[0027] In some embodiments, the second condition is a condition where the total pressure of the source container is lower than the true vapor pressure of WCl 5 or WCl 6 at a given second temperature. In some embodiments, the second condition is a condition where the total pressure of the source container is higher than the true vapor pressure of WCl 4 at a given second temperature. In some embodiments, when the second condition is applied, WCl 5 vapor or WCl 6 vapor contains a larger volume of WCl 5 or WCl 6 than WCl 4. In some embodiments, when the second condition is applied, WCl 5 vapor or WCl 6 vapor contains a larger volume of WCl 4 than WCl 4. In some embodiments, the third condition is a condition where the volume of condensed WCl 5 or WCl 6 is greater than that of condensed WCl 4. In some embodiments, when the third condition is applied, the WCl 5 condensate contains a larger molar fraction of WCl 5 than that of condensed WCl 4. In some embodiments, when the third condition is applied, the WCl 6 condensate contains a larger molar fraction of WCl 6 than that of condensed WCl 4.

[0028] 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 heat jacket is used around the collection container for heating and / or cooling. In some embodiments, a ribbon heater is wrapped around the collection container. In some embodiments, the collection container is heated using a cylinder heater shaped to cover at least a substantial portion of the outer surface of the collection container. In some embodiments, the collection container is heated using a resistive heater. In some embodiments, the collection container is heated using a lamp heater. In some embodiments, a heat transfer fluid at an elevated temperature may be in contact with the outer surface of the collection container to achieve heating and / or cooling of the collection container. In some embodiments, heating is achieved by directing infrared or other radiant energy onto the collection container. In some embodiments, cooling of the collection container is achieved using a fluid, a fan, a direct thermoelectric device, or any combination thereof. It should be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, may be employed herein without departing from the scope of the present invention.

[0029] 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 may be employed herein without departing from the scope of the present invention.

[0030] In step 108, in some embodiments, the precursor is recovered in a 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 as determined by the following formula: 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 5 minutes to 72 hours.

[0031] In step 110, in some embodiments, the low WOCl4 content of the recovered precursor is verified. [picture] [4] and [picture] [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 4 content of the precursor, and when the low WOCl 4 content of the precursor is not verified, at least one of step 104, step 106, or any combination thereof is repeated to remove WOCl 4. In some embodiments, the WOCl 4 content of the precursor is measured by applying a fourth condition to a collection container containing the precursor; measuring the total pressure in the collection container; and comparing the total pressure with a reference value. In some embodiments, the low WOCl 4 content of the precursor is verified 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 these conditions). 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 these conditions), low WOCl 4 content of the precursor is not verified. In some embodiments, the fourth condition is selected such that the collection vessel is stabilized at the reference temperature; the inlet gas flow to the collection vessel is stopped; a short vacuum pump is used to remove inert gas from the gas phase in the collection vessel; the collection vessel is separated from the vacuum pump; and the pressure in the collection vessel is then monitored or measured over time. In some embodiments, the WOCl 4 content of the precursor is measured by applying the fourth condition to the 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 the reference value. In some embodiments, when the rate of change of the total pressure is greater than the reference value, low WOCl 4 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, low WOCl 4 content of the precursor is verified. In some embodiments, a low WCl4 content in the precursor is demonstrated 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. In some embodiments, WCl6 is an impurity in WCl5 (e.g., present in a WCl5 condensate). In some embodiments, WCl5 is an impurity in WCl6 (e.g., present in a WCl6 condensate). In some embodiments, the total pressure is equal to the sum of the vapor pressure of WCl5 and the vapor pressure of WCl6 (e.g., total pressure = 0.6T (for WCl5) + 0.3T (for WCl6) ≥ 0.9T).

[0032] [picture] [2] is a flow chart of a method 200 for separating a tungsten precursor from impurities according to some embodiments. [picture] [2] shows that in some embodiments, the method 200 for separating a tungsten precursor from impurities may include at least one of the following steps: step 202 of applying a first condition to a source container to generate a first WOCl4 vapor; step 204 of removing at least a portion of the first WOCl4 vapor from the source container; or any combination thereof. In some embodiments, the method 200 is related to separating WCl5 from the first portion of WOCl4 as described above.

[0033] In step 202, in some embodiments, a first condition is applied to the source container, thereby generating a first WOCl4 vapor. In some embodiments, the first condition comprises 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 in any range or sub-range therebetween. In some embodiments, the first temperature of the source container is a temperature in the range of 60°C to 160°C, 60°C to 150°C, 60°C to 140°C, 60°C to 130°C, 60°C to 120°C, 60°C to 110°C, 60°C to 100°C, 60°C to 90°C, 60°C to 80°C, 60°C to 70°C, 70°C to 170°C, 80°C to 170°C, 90°C to 170°C, 100°C to 170°C, 110°C to 170°C, 120°C to 170°C, 130°C to 170°C, 140°C to 170°C, 150°C to 170°C, 160°C to 170°C, 100°C to 160°C, 120°C to 160°C, 140°C to 160°C, 120°C to 150°C, 120°C to 140°C or 110°C to 150°C.

[0034] In some embodiments, the first condition comprises a first pressure of the source container. In some embodiments, the first pressure of the source 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 first pressure of the source container is a pressure in the range of 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr to 50 Torr, 0.01 Torr to 45 Torr, 0.01 Torr to 40 Torr, 0.01 Torr to 35 Torr, 0.01 Torr to 30 Torr, 0.01 Torr to 25 Torr, 0.01 Torr to 20 Torr, 0.01 Torr to 15 Torr, 0.01 Torr to 10 Torr, 0.01 Torr to 5 torr, 0.01 torr to 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 to 100 torr or 95 to 100 torr.

[0035] In some embodiments, the first condition is a condition in which the total pressure of the source container is lower than the true vapor pressure of WOCl 4 at a given first temperature. In some embodiments, the first condition is a condition in which the total pressure of the source container is higher than the true vapor pressure of WCl 5 at a given first temperature. In some embodiments, the first condition is a condition that allows WOCl 4 to evaporate while minimizing the amount of evaporated WCl 5 or WCl 6. In some embodiments, the first condition is a condition in which WCl 5 or WCl 6 does not evaporate. In some embodiments, the first condition is a condition in which separated crystals of WOCl 4 evaporate. In some embodiments, the first condition is a condition in which WOCl 4 present in the crystal lattice of WCl 5 or WCl 6 does not evaporate or does not significantly evaporate. Once evaporated, the first WOCl 4 vapor can be removed from the source container, thereby separating WOCl 4 from WCl 5 or WCl 6.

[0036] The first WOCl4 vapor may contain a larger volume of WOCl4 than WCl5 or WCl6. In some embodiments, the first WOCl4 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%, or less than 0.01 vol% of WCl5, based on the total volume of the first WOCl4 vapor. In some embodiments, the first WOCl4 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% WCl5 or WCl6, based on the total volume of the first WOCl4 vapor.

[0037] In step 204, in some embodiments, at least a portion of the first WOCl4 vapor is removed from the source container. The first WOCl4 vapor can be removed through an outlet of the source container. The outlet can be fluidly coupled to a gas exhaust line, a vacuum line, or other similar line suitable for removing the first WOCl4 vapor from the source container.

[0038] [picture] [3] is a flow chart of a method 300 for separating a tungsten precursor from impurities according to some embodiments. [picture] [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: step 302 of applying a second condition to a source container to generate WCl 5 vapor or WCl 6 vapor containing WOCl 4; step 304 of flowing the WCl 5 vapor or WCl 6 vapor to a collection container; step 306 of applying a third condition to the collection container to generate WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor; step 308 of removing at least a portion of the second WOCl 4 vapor from the collection container; or any combination thereof. In some embodiments, the method 300 is related to separating WCl 5 or WCl 6 from a second portion of WOCl 4 as described above. The method 300 of separating WCl 5 or WCl 6 from a second portion of WOCl 4 may also separate WCl 5 or WCl 6 from WCl 4.

[0039] In step 302, in some embodiments, a second condition is applied to the source container, thereby generating WCl 5 vapor or WCl 6 vapor comprising WOCl 4. In some embodiments, the second condition comprises a second temperature of the source container. In some embodiments, the second temperature of the source container is a temperature in the range of 60°C to 170°C or in any range or sub-range therebetween. In some embodiments, the second temperature of the source container is a temperature in the range of 60°C to 160°C, 60°C to 150°C, 60°C to 140°C, 60°C to 130°C, 60°C to 120°C, 60°C to 110°C, 60°C to 100°C, 60°C to 90°C, 60°C to 80°C, 60°C to 70°C, 70°C to 170°C, 80°C to 170°C, 90°C to In some embodiments, the second temperature of the source container is greater than the first temperature of the source container. In some embodiments, the second temperature of the source container is less than the first temperature of the source container.

[0040] In some embodiments, the second condition comprises a second pressure of the source container. In some embodiments, the second pressure of the source 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 second pressure of the source container is a pressure in the range of 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr to 50 Torr, 0.01 Torr to 45 Torr, 0.01 Torr to 40 Torr, 0.01 Torr to 35 Torr, 0.01 Torr to 30 Torr, 0.01 Torr to 25 Torr, 0.01 Torr to 20 Torr, 0.01 Torr to 15 Torr, 0.01 Torr to 10 Torr, 0.01 Torr 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.

[0041] In some embodiments, the second condition is a condition in which the total pressure of the source container is lower than the true vapor pressure of WCl 5 or WCl 6 at a given second temperature. In some embodiments, the second condition is a condition in which the total pressure of the source container is higher than the true vapor pressure of WCl 4 at a given second temperature. In some embodiments, the second condition is a condition that allows WCl 5 or WCl 6 present in the source container as separated crystals to evaporate. In some embodiments, the second condition is a condition that allows WCl 5 or WCl 6 to evaporate while minimizing the amount of evaporated WCl 4. In some embodiments, the second condition is a condition that does not allow WCl 4 to evaporate. In some embodiments, the second condition is a condition that allows WCl 4 present in the crystal lattice of WCl 5 or WCl 6 to evaporate. In some embodiments, the second condition is a condition that allows WCl 4 present in the source container as separated crystals to evaporate. In some embodiments, the WCl 5 vapor or WCl 6 vapor contains a larger volume of WCl 5 or WCl 6 than the volume of WCl 4. In some embodiments, the WCl 5 vapor or WCl 6 vapor contains a larger volume of WCl 4 than the volume of WCl 4. In some embodiments, WCl 5 vapor or WCl 6 vapor contains WCl 5 or WCl 6 that has a larger volume than WCl 4.

[0042] In step 304, in some embodiments, WCl 5 vapor or WCl 6 vapor is flowed to a collection vessel, thereby removing WCl 5 vapor or WCl 6 vapor from WCl 4 contained in the source vessel. In some embodiments, the WCl 5 vapor or WCl 6 vapor comprises WOCl 4. In some embodiments, the WCl 5 vapor or WCl 6 vapor comprises WOCl 4 vapor.

[0043] 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 heat jacket is used around the collection container for heating and / or cooling. In some embodiments, a ribbon heater is wrapped around the collection container. In some embodiments, the collection container is heated using a cylinder heater shaped to cover at least a substantial portion of the outer surface of the collection container. In some embodiments, the collection container is heated using a resistive heater. In some embodiments, the collection container is heated using a lamp heater. In some embodiments, a heat transfer fluid at an elevated temperature may be in contact with the outer surface of the collection container to achieve heating and / or cooling of the collection container. In some embodiments, heating is achieved by directing infrared or other radiant energy onto the collection container. In some embodiments, cooling of the collection container is achieved using a fluid, a fan, a direct thermoelectric device, or any combination thereof. It should be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, may be employed herein without departing from the scope of the present invention.

[0044] 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 may be employed herein without departing from the scope of the present invention.

[0045] In step 306, in some embodiments, a third condition is applied to the collection vessel, thereby generating WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor. In some embodiments, generating the WCl 5 condensate or WCl 6 condensate and the second WOCl 4 vapor separates the WCl 5 or WCl 6 from the second portion of the WOCl 4. In some embodiments, the third condition comprises 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 sub-range therebetween. In some embodiments, the third temperature of the collection container is a temperature in the range of 20°C to 100°C, 30°C to 100°C, 40°C to 100°C, 50°C to 100°C, 60°C to 100°C, 70°C to 100°C, 80°C to 100°C, 90°C to 100°C, 10°C to 90°C, 10°C to 80°C, 10°C to 70°C, 10°C to 60°C, 10°C to 50°C, 10°C to 40°C, 10°C to 30°C, or 10°C to 20°C. In some embodiments, the third temperature of the collection container is a temperature sufficient to condense WCl 5 vapor or WCl 6 vapor. In some embodiments, the third temperature of the collection container is a temperature sufficient to generate a second WOCl 4 vapor.

[0046] In some embodiments, the third condition comprises a 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 range of 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr to 50 Torr, 0.01 Torr to 45 Torr, 0.01 Torr to 40 Torr, 0.01 Torr to 35 Torr, 0.01 Torr to 30 Torr, 0.01 Torr to 25 Torr, 0.01 Torr to 20 Torr, 0.01 Torr to 15 Torr, 0.01 Torr to 10 Torr, 0.01 Torr In some embodiments, the third pressure of the collection vessel is a pressure sufficient to condense WCl 5 vapor or WCl 6 vapor. In some embodiments, the third pressure of the collection vessel is a pressure sufficient to generate a second WOCl 4 vapor.

[0047] In some embodiments, a third condition is applied to the collection container, thereby generating WCl 5 condensate or WCl 6 condensate and WOCl 4 vapor. In some embodiments, the third condition is sufficient to condense WCl 5 or WCl 6 without condensing WOCl 4, or at least to minimize the volume of condensed WOCl 4, thereby separating WCl 5 or WCl 6 from WOCl 4. In some embodiments, the third condition is a condition in which the volume of condensed WCl 5 or WCl 6 is greater than that of WOCl 4. In some embodiments, the WCl 5 condensate or WCl 6 condensate comprises a greater amount (e.g., molar fraction, volume fraction, or mass fraction) of WCl 5 condensate or WCl 6 condensate than the WOCl 4 condensate (if present). In some embodiments, the third condition is a condition in which the volume of WOCl 4 remaining evaporated is greater than that of WCl 5 or WCl 6. In some embodiments, the third condition is a condition in which the WOCl4 vapor comprises WOCl4 dissolved in the crystal lattice of WCl5 or WCl6 (and in some embodiments, isolated crystals of WOCl4), and WOCl4 evaporated together with WCl5 or WCl6 in the source container.

[0048] In step 308, in some embodiments, at least a portion of the second WOCl4 vapor is removed from the collection container. The second WOCl4 vapor can be removed via an outlet of the collection container. The outlet can be fluidly coupled to a gas exhaust line, a vacuum line, or other similar line suitable for removing the second WOCl4 vapor from the collection container.

[0049] [picture] [4] is a flow chart of a method 400 for verifying low impurity content of a tungsten precursor according to some embodiments. [picture] [4], in some embodiments, the method 400 for verifying the low impurity content of the tungsten precursor may include at least one of the following steps: step 402 of measuring the WOCl4 content of the precursor to verify or not verify the low WOCl4 content of the precursor; step 404 of comparing with a reference value to verify or not verify the low WOCl4; step 406: when the low WOCl4 content of the precursor is not verified, (for example, by repeating at least one of the following: step 104 (for example, including but not limited to) [picture] [2]), step 106 (including but not limited to any one or more of the steps [picture] [3]) or any combination thereof) further removes WOCl4; or any combination thereof. In some embodiments, when the low WOCl4 content is verified, the precursor is ready for use 408. In some embodiments, method 400 relates to a method for verifying the low WOCl4 content of a tungsten precursor.

[0050] [picture] [5] is a flow chart of a method 500 for measuring low impurity levels of a tungsten precursor according to some embodiments. [picture] [5] As shown, in some embodiments, the method 500 for measuring the low impurity content of a tungsten precursor may include at least one of the following steps: step 502 of applying a fourth condition to a collection container containing a WCl 5 precursor or a WCl 6 precursor; step 504 of measuring at least one characteristic within the collection container; and step 506 of comparing the at least one characteristic with a reference value. Although not shown, in some embodiments, the method 500 for measuring the low impurity content of a tungsten precursor further includes the step of removing any vapor and / or gas 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; remove the inert gas from the gas phase in the collection container by a short vacuum pump; 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 method 500 relates to a method for measuring the low WOCl 4 content of a tungsten precursor as described above.

[0051] In step 502, in some embodiments, a fourth condition is applied to the collection container containing the WCl 5 precursor or the WCl 6 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 in 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 10 ...00°C, 60°C to 100°C, 60°C to 100°C, 60°C to 100°C, 60°C to 100°C, 60°C to 100°C, 60°C to 100°C, 60°C to 100°C, 60°C to 100°C, 60° 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.

[0052] In some embodiments, the fourth condition comprises 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 to 100 torr or 95 to 100 torr.

[0053] In some embodiments, the fourth condition is a condition in which the total pressure of the collection container is within 10% of the true vapor pressure of WCl 5 or WCl 6. In some embodiments, the fourth condition is a condition in which the total pressure of the collection container is lower than the true vapor pressure of WOCl 4.

[0054] In step 504, in some embodiments, at least one characteristic within the collection container is measured. In some embodiments, the at least one characteristic measured is 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 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 / minute. In some embodiments, the rate of change of the total pressure is the rate of increase of pressure in millitorr / minute. In some embodiments, the rate of change of the total pressure within the collection container 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 expressed in any suitable pressure and time units. It should further be understood that the duration for measuring the rate of change of the total pressure within the collection container can vary depending on the composition of the precursor (e.g., impurity content) and the temperature selected for the fourth condition.

[0055] In step 506, in some embodiments, the total pressure within the collection container is compared to a reference value. In some embodiments, when the total pressure is between 0.01% and 20% (inclusive) of the reference value, or any range or sub-range therebetween, the low WOCl4 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 WOCl4 content of the precursor is not verified. In some embodiments, the reference value is the actual vapor pressure of WCl5 under the conditions (e.g., a selected temperature). In some embodiments, low WOCl4 content is verified if the total pressure measured under the conditions is within 1%-15%, 1%-14%, 1%-13%, 1%-12%, 1%-11%, 1%-10%, 1%-9%, 1%-8%, 1%-7%, 1%-6%, 1%-5%, 1%-4%, 1%-3%, 1%-2%, 2%-15%, 3%-15%, 4%-15%, 5%-15%, 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% of the true vapor pressure of WCl5.

[0056] In step 506, in some embodiments, the rate of change of the total pressure within the collection container is compared to a reference value. In some embodiments, when the rate of change of the total pressure is greater than the reference value, low WOCl4 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, low WOCl4 content of the precursor is verified. For example, in some embodiments, low WOCl4 content of the precursor is verified 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. 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 lower temperatures in the fourth condition, the limit of the pressure rise rate will be lower.

[0057] [picture] [6] is a flow chart of a method 600 for verifying low impurity content according to some embodiments. [picture] [6] shows that in some embodiments, the method 600 for verifying low impurity content may include at least one of the following steps: step 602 of obtaining a collection container containing a WCl 5 precursor or a WCl 6 precursor; step 604 of applying conditions to the collection container containing the WCl 5 precursor or the WCl 6 precursor; step 606 of measuring at least one characteristic within the collection container (e.g., at least one of the rate of change of the total pressure within the collection container, the total pressure within the collection container, or any combination thereof); step 608 of comparing the at least one characteristic with a reference value; step 610 of removing WOCl 4 from the collection container when low WOCl 4 content is not verified; or any combination thereof. Although not shown, in some embodiments, the conditions are selected so that the collection container is stabilized at a reference temperature; the inlet gas flow to the collection container is stopped; a short vacuum pump removes inert gas from the gas phase in the collection container; the collection container is separated from the vacuum pump; and the pressure in the collection container is then monitored or measured over time.

[0058] Some embodiments relate to a tungsten precursor having a sufficiently low impurity content 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 controllable, constant flow rate during evaporation without 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, a WCl 5 precursor or a WCl 6 precursor, having a sufficiently low impurity content. The impurities may include, for example, and without limitation, at least one of WOCl 4 , WCl 4 , or any combination thereof.

[0059] In some embodiments, when a WCl5 precursor is contained in a precursor container, when the precursor container is maintained at a temperature of 70° C. to 240° C. (or any range or sub-range therebetween), the precursor has a vapor pressure of less than 1.3 times the calculated vapor pressure of WCl5 as determined according to the following formula: . In some embodiments, when a WCl5 precursor is contained in a precursor container, when the precursor container is maintained at a temperature of 70° C. to 240° C. (or any range or sub-range therebetween), the precursor has a vapor pressure of less than 1.1 times the calculated vapor pressure of WCl5 as determined according to the following formula:

[0060] In some embodiments, when a WCl 6 precursor is contained in a precursor container, when the precursor container is maintained at a temperature of 70° C. to 240° C. (or any range or sub-range therebetween), the precursor has a vapor pressure of less than 1.3 times the calculated vapor pressure of WCl 6 as determined according to the following formula: In some embodiments, when a WCl 6 precursor is contained in a precursor container, when the precursor container is maintained at a temperature of 70° C. to 240° C. (or any range or sub-range therebetween), the precursor has a vapor pressure of less than 1.1 times the calculated vapor pressure of WCl 6 as determined according to the following formula: WCl 5 or WCl 6 can maintain this vapor pressure for an indefinite period of time. In some embodiments, WCl 5 or WCl 6 maintains this vapor pressure for a duration of up to 72 hours. In some embodiments, WCl 5 or WCl 6 maintains this vapor pressure for a duration of 5 minutes to 72 hours, or any range or sub-range therebetween.

[0061] [Style]

[0062] Various aspects are described below. It should be understood that any one or more features described in the following aspects can be combined with any one or more other aspects. Aspect 1. A method comprising: a) obtaining a source container containing WCl 4, WOCl 4 and one of WCl 5 or WCl 6; b) separating the WCl 5 or the WCl 6 from the first portion of the WOCl 4, wherein the separation comprises: applying a first condition to the source container to generate a first WOCl4 vapor; removing at least a portion of the first WOCl4 vapor from the source container; c) separating the WCl 5 or the WCl 6 from the second portion of the WOCl 4, wherein the separation comprises: Applying a second condition to the source container to generate WCl 5 vapor containing WOCl 4 or WCl 6 vapor containing WOCl 4; The WCl 5 vapor or the WCl 6 vapor flows to a collection container; Applying a third condition to the collection vessel to produce WCl 5 condensate or WCl 6 condensate and a second WOCl 4 vapor; removing at least a portion of the second WOCl4 vapor from the collection vessel; and d) Recovering the precursor in a collection container. Aspect 2. The method of Aspect 1, wherein the first condition is a condition in which the total pressure of the source container is lower than the true vapor pressure of WOCl 4 at a given first temperature. Aspect 3. The method of any one of Aspects 1 to 2, wherein the first condition is a condition in which the total pressure of the source container is higher than the true vapor pressure of WCl 5 or WCl 6 at a given first temperature. Aspect 4. The method of any one of Aspects 1 to 3, wherein when the first condition is applied, the first WOCl 4 vapor comprises a greater volume of WOCl 4 than WCl 5 or WCl 6. Aspect 5. The method of any one of Aspects 1 to 4, wherein the second condition is a condition in which the total pressure of the source container is lower than the actual vapor pressure of the WCl 5 or the WCl 6 at a given second temperature. Aspect 6. The method of Aspect 4, wherein the second condition is a condition in which the total pressure of the source container is higher than the actual vapor pressure of the WCl 4 at a given second temperature. Aspect 7. The method of any one of Aspects 1 to 6, wherein when the second condition is applied, the WCl 5 vapor comprises a larger volume of WCl 5 than of WCl 4 . Aspect 8. The method of any one of Aspects 1 to 7, wherein when the second condition is applied, the WCl 6 vapor comprises a larger volume of the WCl 6 than the WCl 4 . Aspect 9. The method of any one of Aspects 1 to 8, wherein when the second condition is applied, the WCl 5 vapor comprises a larger volume of the WOCl 4 than the WCl 4 . Aspect 10. The method of any one of Aspects 1 to 9, wherein when the second condition is applied, the WCl 6 vapor comprises a larger volume of the WOCl 4 than the WCl 4 . Aspect 11. The method of any one of Aspects 1 to 10, wherein the third condition is a condition in which the volume of the condensed WCl 5 is larger than that of the WOCl 4 . Aspect 12. The method of any one of Aspects 1 to 11, wherein the third condition is a condition in which the volume of the condensed WCl 6 is larger than that of the WOCl 4. Aspect 13. The method of any one of Aspects 1 to 12, wherein when the third condition is applied, the WCl 5 condensate comprises a greater molar fraction of WCl 5 than WOCl 4 . Aspect 14. The method of any one of Aspects 1 to 13, wherein when the third condition is applied, the WCl 6 condensate comprises a greater molar fraction of WCl 6 than WOCl 4 . Aspect 15. The method of any one of Aspects 1 to 14, further comprising: e) Verify the low WOCl4 content of the precursor present in the collection vessel. Aspect 16. The method of Aspect 15, wherein the verifying step e) comprises: e1) measuring the WOCl 4 content of the precursor, thereby verifying or not verifying the low WOCl 4 content of the precursor; e2) when the low WOCl 4 content of the precursor is not verified, repeating at least one of step b), step c), or any combination thereof, to remove the WOCl 4 . Aspect 17. The method of Aspect 16, wherein the measuring step e1) comprises: applying a fourth condition to the collection container containing the precursor; measuring at least one characteristic within the collection container; and The measured characteristic is compared with a reference value. Aspect 18. The method of Aspect 17, wherein the at least one characteristic is the total pressure within the collection container. wherein the low WOCl 4 content is verified when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 5; Wherein, the low WOCl 4 content is not verified when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 5. Aspect 19. The method of Aspect 17, wherein the at least one characteristic is the total pressure within the collection container. wherein the low WOCl 4 content is verified when the total pressure is within 1% to 10% of the true vapor pressure of the WCl 6; Wherein, the low WOCl 4 content is not verified when the total pressure is not within 1% to 10% of the true vapor pressure of the WCl 6. Aspect 20. The method of Aspect 17, wherein the at least one characteristic is a rate of change of the total pressure within the collection vessel, 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; wherein when the 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; The reference value is a 5% change in total pressure per minute. Aspect 21. The method of aspect 17, wherein the fourth condition is a condition in which the total pressure of the collection container is lower than the true vapor pressure of the WOCl 4 . Aspect 22. A method for verifying low impurity content, the method comprising: Obtaining a collection container containing a WCl 5 precursor or a WCl 6 precursor; Applying 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 to a reference value; When the low WOCl 4 content is not verified, the WOCl 4 is removed from the collection container. Aspect 23. The method of Aspect 22, wherein the at least one characteristic is the total pressure within the collection container, wherein the low WOCl 4 content is verified when the total pressure is within 10% of the true vapor pressure of the WCl 5; 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. Aspect 24. The method of Aspect 22, wherein the at least one characteristic is a total pressure within the collection vessel. wherein the low WOCl 4 content is verified when the total pressure is within 1% of the true vapor pressure of the WCl 6; Wherein, the low WOCl 4 content is not verified when the total pressure is not within 1% of the true vapor pressure of the WCl 6. Aspect 25. The method of Aspect 22, wherein the at least one characteristic is a rate of change of the total pressure within the collection vessel, 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; wherein when the 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; The reference value is a 5% change in total pressure per minute. Aspect 26. A precursor container comprising: Contains WCl 5 precursor, 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 that is less than 1.1 times the true vapor pressure of WCl 5. Aspect 27. The precursor container of Aspect 26, wherein the true vapor pressure of WCl 5 is calculated according to the following formula: . Aspect 28. The precursor container of Aspect 26, wherein the WCl5 maintains the vapor pressure within the precursor container for a period of up to 72 hours. Aspect 29. A precursor container comprising: Contains precursors of WCl 6, 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 that is less than 1.1 times the true vapor pressure of WCl 6. Aspect 30. The precursor container of Aspect 29, wherein the true vapor pressure of WCl 6 is calculated according to the following formula: . Aspect 31. The precursor container of Aspect 29, wherein the WCl6 maintains the vapor pressure within the precursor container for a period of up to 72 hours. Example 1

[0063] The material is loaded into an ampoule and sealed with a valve under inert conditions. The ampoule is mounted on a system that controls temperature, measures absolute pressure, and allows pumping. The ampoule is heated to a desired temperature and allowed to stabilize for 30 minutes. The ampoule is pumped for the desired pumping time. Subsequently, the pressure measurement manifold is disconnected from the pump, and the pressure change over time is measured for 5 minutes. This process can be repeated as many times as necessary to achieve the desired purity level. Example 2

[0064] 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, then heat to the desired temperature and stabilize for 30 minutes. Pump the ampoule for 10 seconds. Allow the ampoule to equilibrate again for 5 minutes while pumping the pressure measurement manifold. Then, disconnect the pressure measurement manifold from the pump and open it to the ampoule for pressure measurement. Measure the pressure change over time for 5 minutes. Because the initial pressure measurement is within 10% of the true vapor pressure of WCl 5, the material is certified. If the rate of pressure rise is less than approximately 3% / minute, the material is also certified. Example 3

[0065] The material was loaded into an ampoule and sealed with a valve under inert conditions. The ampoule was mounted on a system that controlled temperature, measured absolute pressure, and allowed to pump. The ampoule was pumped to remove the inert gas, then 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 equilibrate again for 5 minutes while the pressure measurement manifold was pumped. The pressure measurement manifold was then disconnected from the pump and opened to the ampoule for pressure measurement. The pressure change over time was measured for 5 minutes. The material was certified because the rate of pressure rise was less than 3% / minute. Example 4

[0066] The equation representing the measured vapor pressure for tungsten chloride and tungsten oxychloride materials is presented below. Material A B WCl 6 11.429 -4894 WCl 5 11.119 -4634 WCl 5+WCl 6 11.605 -4759 WOCl 4 12.094 -4584

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

[0068] It should be understood that changes may be made in detail, particularly in the materials of construction employed, and the shape, size, and arrangement of parts, without departing from the scope of the invention. This specification and the described embodiments are examples, with the true scope and spirit of the invention being indicated by the appended claims.

[0069] 100: Method 102: Steps 104: Steps 106: Steps 108: Steps 110: Steps 200:Method 202: Steps 204: Steps 300: Method 302: Steps 304: Steps 306: Steps 308: Steps 400:Method 402: Steps 404: Steps 406: Steps 500:Method 502: Steps 504: Steps 506: Steps 600:Method 602: Step 604: Steps 606: Steps 608: Steps 610: Steps

Claims

1. A method for verifying the purity of WCl5 or WCl6, comprising: heating a source container containing WOCl4 and one of WCl5 or WCl6; measuring the vapor pressure in the heated source container; and comparing the measured vapor pressure with the true vapor pressure of WCl5 or WCl6, wherein the purity is verified when the measured vapor pressure is within 10% of the true vapor pressure, and wherein the purity is not verified when the measured vapor pressure is not within 10% of the true vapor pressure.

2. As in request item 1, where the source container contains WCl5.

3. As in request item 1, where the source container contains WCl6.

4. A method for verifying the purity of WCl5 or WCl6, comprising: heating a source container containing WOCl4 and one of WCl5 or WCl6; and measuring the rate of vapor pressure change in the heated source container; wherein the purity is verified when the measured rate of vapor pressure change is less than 5% per minute, and the purity is not verified when the measured rate of vapor pressure change is not less than 5% per minute.

5. As in request item 4, where the source container contains WCl5.

6. As in request item 4, where the source container contains WCl6.

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