Hafnium precursor and related methods

Abstract

The precursor container contains a hafnium halide precursor. The hafnium halide precursor contains at least one impurity in a concentration of less than 1 ppm. The at least one impurity is at least one of the following: titanium contaminants, chromium contaminants, aluminum contaminants, iron contaminants, or any combination thereof. Related systems and methods are also provided, including, but are not limited to, a steam precursor supply system and a precursor purification method.

Description

Technical Field

[0005]

[0001]

[0001] This disclosure relates to high purity hafnium precursors, and related systems and methods.

[0002] Cross - Reference to Related Applications

[0002] This application claims the benefit of priority under 35 USC 119 to U.S. Provisional Patent Application No. 63 / 471,472, filed Jun. 6, 2023, the disclosure of which is hereby incorporated by reference in its entirety.

Background Art

[0003]

[0003] When impurities are present in the precursors used in semiconductor manufacturing, defects and undesirable process variations occur. Providing precursors with a sufficiently low level of impurities remains an ongoing challenge.

Summary of the Invention

[0004]

[0004] Some embodiments relate to a system including a precursor container and a deposition apparatus. In some embodiments, the deposition apparatus is provided in fluid communication with an outlet of the precursor container. In some embodiments, the precursor container contains a solid hafnium halide precursor. In some embodiments, the solid hafnium halide precursor includes at least one of hafnium(IV) chloride (HfCl₄), hafnium(IV) bromide (HfBr₄), hafnium(IV) iodide (HfI₄), hafnium(IV) fluoride (HfF₄), hafnium(III) chloride (HfCl₃), hafnium(III) bromide (HfBr₃), hafnium(III) iodide (HfI₃), hafnium(III) fluoride (HfF₃), or any combination thereof. In some embodiments, the solid hafnium halide precursor contains less than 1 ppm of at least one impurity. In some embodiments, the at least one impurity includes at least one of titanium contaminants, chromium contaminants, aluminum contaminants, iron contaminants, or any combination thereof.

[0005]

[0005] Some embodiments relate to a precursor container. In some embodiments, the precursor container contains a solid hafnium halide precursor. In some embodiments, the solid hafnium halide precursor includes at least one of hafnium(IV) chloride (HfCl4), hafnium(IV) bromide (HfBr4), hafnium(IV) iodide (HfI4), hafnium(IV) fluoride (HfF4), hafnium(III) chloride (HfCl3), hafnium(III) bromide (HfBr3), hafnium(III) iodide (HfI3), hafnium(III) fluoride (HfF3), or any combination thereof. In some embodiments, the solid hafnium halide precursor contains at least one impurity in a concentration of less than 1 ppm. In some embodiments, the at least one impurity includes at least one of titanium contaminants, chromium contaminants, aluminum contaminants, iron contaminants, or any combination thereof.

[0006]

[0006] Some embodiments relate to purification methods. In some embodiments, the method comprises one or more of the following steps: obtaining a first container containing a solid reagent containing a hafnium halide and at least one impurity; vaporizing at least a portion of the solid reagent to produce a first vapor containing a hafnium halide vapor and at least one impurity vapor; flowing at least a portion of the hafnium halide vapor and at least a portion of the at least one impurity vapor into a second container; condensing at least a portion of the hafnium halide vapor in the second container to separate at least a portion of the hafnium halide vapor from at least one impurity vapor; and removing at least a portion of the at least one impurity vapor from the second container to obtain a hafnium halide precursor.

[0007]

[0007] In this disclosure, several embodiments of the disclosure will be described only as examples, with reference to the accompanying drawings. A detailed reference to the drawings will emphasize that the embodiments shown are illustrative and intended to illustrate the embodiments of the disclosure. In this regard, a description in conjunction with the drawings will make it clear to those skilled in the art how embodiments of the disclosure can be carried out. [Brief explanation of the drawing]

[0008] [Figure 1]

[0008] This is a flowchart of a purification method according to several embodiments. [Figure 2]

[0009] This is an embodiment of a purification system. [Figure 3]

[0010] This graph shows the purity levels at different temperatures. [Modes for carrying out the invention]

[0009]

[0011] Other purposes and advantages of the disclosed advantages and improvements will become apparent from the following description in conjunction with the accompanying drawings. While detailed embodiments of the disclosed invention are disclosed herein, it should be understood that the disclosed embodiments are merely illustrative of the various forms in which the disclosed invention may be implemented. Furthermore, the examples given with respect to the various embodiments of the disclosed invention are for illustrative purposes only and not limiting purposes.

[0010]

[0012] The prior patents and publications referenced herein are incorporated by reference in their entirety.

[0011]

[0013] Throughout this specification and the claims, unless the context clearly indicates otherwise, the following terms have the meanings expressly associated herein. The phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” as used herein do not necessarily refer to the same embodiment, but may do so. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to different embodiments, but may do so. All embodiments of this disclosure are intended to be combinable without departing from the scope or spirit of this disclosure.

[0012]

[0014] As used herein, the term "based on" is not exclusive and may also refer to additional factors not listed unless the context clearly indicates otherwise. Furthermore, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" (inside) and "on" (on, against, etc.).

[0013]

[0015] Some embodiments relate to high-purity and ultra-high-purity hafnium halide precursors, as well as related systems and methods. The hafnium halide precursors disclosed herein have low impurity levels. The hafnium halide precursors disclosed herein have impurity levels that have not been achievable with conventional purification methods. At least one advantage of the hafnium halide precursors disclosed herein is that when the hafnium halide precursor is supplied to a downstream tool (e.g., a tool used in semiconductor manufacturing or other similar processes), the hafnium halide precursor, once vaporized, is supplied to the tool at a controllable constant flow rate without significant surges or fluctuations in flow rate. These are not limiting, and these and other advantages will become apparent upon consideration of the disclosures described herein.

[0014]

[0016] Figure 1 is a flowchart of purification method 100 according to several embodiments. As shown in Figure 1, purification method 100 may include one or more of the following steps: obtaining a first container containing a solid reagent containing a hafnium halide and at least one impurity 102; vaporizing at least a portion of the solid reagent to produce a first vapor containing a hafnium halide vapor and at least one impurity vapor 104; flowing at least a portion of the hafnium halide vapor and at least a portion of the at least one impurity vapor into a second container 106; condensing at least a portion of the hafnium halide vapor in the second container to separate at least a portion of the hafnium halide vapor from at least one impurity vapor 108; and removing at least a portion of the at least one impurity vapor from the second container to obtain a hafnium halide precursor 110.

[0015]

[0017] In some embodiments, the purification method 100 includes obtaining a first container containing a solid reagent 102.

[0016]

[0018] The solid reagent may contain a hafnium halide. The hafnium halide may include at least one of hafnium(IV) halides, hafnium(III) halides, or any combination thereof. For example, in some embodiments, the hafnium halide may include at least one of hafnium(IV) chloride (HfCl4), hafnium(IV) bromide (HfBr4), hafnium(IV) iodide (HfI4), hafnium(IV) fluoride (HfF4), hafnium(III) chloride (HfCl3), hafnium(III) bromide (HfBr3), hafnium(III) iodide (HfI3), hafnium(III) fluoride (HfF3), or any combination thereof. Under the conditions of the first container, the solid reagent may exist as a solid. However, it will be understood that the conditions of the first container may change so that the reagent exists in another phase, such as gas, vapor, liquid, solid, or at least one of any combination thereof.

[0017]

[0019] The solid reagent may contain at least one impurity. This at least one impurity may include at least one of the following: titanium contaminants, chromium contaminants, aluminum contaminants, iron contaminants, or any combination thereof. As used herein, the term "titanium contaminant" refers to a substance other than a hafnium halide, which includes titanium. As used herein, the term "chromium contaminant" refers to a substance other than a hafnium halide, which includes chromium. As used herein, the term "aluminum contaminant" refers to a substance other than a hafnium halide, which includes aluminum. As used herein, the term "iron contaminant" refers to a substance other than a hafnium halide, which includes iron. In some embodiments, at least one impurity includes at least one of the following: titanium halides, titanium oxides, titanium nitrides, titanium ligand complexes, chromium halides, chromium oxides, chromium nitrides, chromium ligand complexes, aluminum halides, aluminum oxides, aluminum nitrides, aluminum ligand complexes, iron halides, iron oxides, iron nitrides, iron ligand complexes, or any combination thereof.

[0018]

[0020] The solid reagent may contain at least one impurity in a concentration of at least 1 ppm. For example, in some embodiments, the solid reagent contains at least one impurity in a concentration of 1 ppm to 1000 ppm, or any range or subrange of 1 ppm to 1000 ppm. In some embodiments, the solid reagent is available in concentrations of 1 ppm to 900 ppm, 1 ppm to 800 ppm, 1 ppm to 700 ppm, 1 ppm to 600 ppm, 1 ppm to 500 ppm, 1 ppm to 400 ppm, 1 ppm to 300 ppm, 1 ppm to 200 ppm, 1 ppm to 100 ppm, 1 ppm to 90 ppm, 1 ppm to 80 ppm, 1 ppm to 70 ppm, 1 ppm to 60 ppm, 1 ppm to 50 ppm, 1 ppm to 40 ppm, 1 ppm to 30 ppm, 1 ppm to 20 ppm, 1 ppm to 10 ppm, 100 ppm to 1000 ppm, and 200 ppm. Contains at least one impurity in the following concentrations: 1000ppm, 300ppm-1000ppm, 400ppm-1000ppm, 500ppm-1000ppm, 600ppm-1000ppm, 700ppm-1000ppm, 800ppm-1000ppm, 900ppm-1000ppm, 10ppm-100ppm, 20ppm-100ppm, 30ppm-100ppm, 40ppm-100ppm, 50ppm-100ppm, 60ppm-100ppm, 70ppm-100ppm, 80ppm-100ppm, or 90ppm-100ppm.

[0019]

[0021] The first container may be configured to contain a solid reagent. In some embodiments, the first container has at least one inlet, at least one outlet, or any combination thereof. In some embodiments, the first container has an outlet configured to be in fluid communication with a second container, which will be described later.

[0020]

[0022] The first vessel may be configured to control its temperature. The temperature of the first vessel can be controlled in any suitable manner. In some embodiments, a heat jacket for heating and / or cooling is used around the first vessel. In some embodiments, a ribbon heater is wrapped around the first vessel. In some embodiments, a block heater having a shape that covers at least a large portion of the outer surface of the first vessel is used to heat the first vessel. In some embodiments, a resistance heater is used to heat the first vessel. In some embodiments, a lamp heater is used to heat the first vessel. In some embodiments, heating and / or cooling can be achieved by bringing a hot heat transfer fluid into contact with the outer surface of the first vessel. In some embodiments, heating is performed by infrared or other radiant energy irradiated onto the first vessel. In some embodiments, the first vessel is cooled by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It will be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, can be adopted in the present invention without departing from the scope of this disclosure.

[0021]

[0023] The first vessel may be configured to control pressure. The pressure in the first vessel can be controlled by any suitable method. In some embodiments, a gas inlet line is fluidly coupled to the first vessel. The gas inlet line may be configured to supply pressurized gas from a pressurized gas source to the first vessel. Control of the pressurized gas to the first vessel can be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or any combination thereof. In some embodiments, the pressurized gas 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 provided that is in fluid communication with the first vessel. The vacuum line may be configured to apply a vacuum to the first vessel. In some embodiments, the pumping speed is controlled by a butterfly valve. It will be understood that other mechanisms for controlling the pressure in the first vessel can be employed in the present invention without departing from the scope of this disclosure.

[0022]

[0024] In some embodiments, the purification method 100 includes vaporizing at least a portion of a solid reagent 104 to produce a first vapor containing a hafnium halide vapor and at least one impurity vapor.

[0023]

[0025] Vaporizing 104 may include applying at least one condition sufficient to vaporize at least a portion of the solid reagent. The at least one condition can be applied to at least one of the first container, the solid reagent, or any combination thereof. In some embodiments, vaporizing 104 includes heating the first container and / or the solid reagent to a temperature sufficient to vaporize at least a portion of the solid reagent. In some embodiments, vaporizing 104 includes cooling the first container and / or the solid reagent to a temperature sufficient to vaporize at least a portion of the solid reagent. In some embodiments, vaporizing 104 includes pressurizing the first container at a pressure sufficient to vaporize at least a portion of the solid reagent or to a sufficient pressure. In some embodiments, vaporizing 104 includes depressurizing the first container at a pressure sufficient to vaporize at least a portion of the solid reagent or to a sufficient pressure. In some embodiments, vaporizing 104 includes supplying or flowing an inert gas into the first container.

[0024]

[0026] Vaporization 104 may include heating the first container and / or the solid reagent. For example, in some embodiments, vaporization 104 of at least a portion of the solid reagent includes heating the first container and / or the solid reagent to 50°C to 200°C, or any range or partial range of 50°C to 200°C. In some embodiments, vaporizing at least a portion of the solid reagent 104 involves placing the first container and / or the solid reagent at 50°C to 190°C, 50°C to 180°C, 50°C to 170°C, 50°C to 160°C, 50°C to 150°C, 50°C to 140°C, 50°C to 130°C, 50°C to 120°C, 50°C to 110°C, 50°C to 100°C, 50°C to 90°C, 50°C to 80°C, 50°C to 70°C, 50°C to 60°C, 60°C to 200°C, 70°C to 200°C, 80°C to 200°C, and 90°C. This includes heating to a temperature of ~200°C, 100°C~200°C, 110°C~200°C, 120°C~200°C, 130°C~200°C, 140°C~200°C, 150°C~200°C, 160°C~200°C, 170°C~200°C, 180°C~200°C, 190°C~200°C, 90°C~140°C, 100°C~140°C, 110°C~140°C, 120°C~140°C, 130°C~140°C, 90°C~130°C, 90°C~120°C, 90°C~110°C, or 90°C~100°C.

[0025]

[0027] Vaporization 104 may include pressurizing or depressurizing the first container. For example, in some embodiments, vaporization 104 of at least a portion of the solid reagent includes pressurizing or depressurizing the first container to 0.01 Torr to 100 Torr, or any range or partial range of 0.01 Torr to 100 Torr. In some embodiments, the pressure is 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr ~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr~25T orr, 0.01Torr~20Torr, 0.01Torr~15Torr, 0.01Torr~10Torr, 0.01Torr~5Torr, 0.01Torr~1Torr, 0.0 These are pressures in the range of 1 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.

[0026]

[0028] Vaporizing 104 may be sufficient to vaporize at least a portion of the solid reagent. In some embodiments, vaporizing 104 may be sufficient to vaporize from 1% to 99% (or any range or sub-range between 1% and 99%) of the weight of the solid reagent, based on the initial total weight of the solid reagent. As used herein, the term "total initial weight of the solid reagent" refers to the total weight of the solid reagent before vaporization. For example, in some embodiments, vaporizing 104 may be sufficient to vaporize from 1% to 95%, 1% to 90%, 1% to 80%, 1% to 70%, 1% to 60%, 1% to 50%, 1% to 40%, 1% to 30%, 1% to 20%, 1% to 10%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99%, or 95% to 99% of the weight of the solid reagent, based on the total initial weight of the solid reagent. In some embodiments, vaporizing may be sufficient to vaporize the entire solid reagent.

[0027]

[0029] The first vapor may include hafnium halide vapor. The hafnium halide vapor can include at least one of hafnium(IV) halide vapor, hafnium(III) halide vapor, or any combination thereof. For example, in some embodiments, the hafnium halide vapor includes at least one of hafnium(IV) chloride (HfCl4) vapor, hafnium(IV) bromide (HfBr4) vapor, hafnium(IV) iodide (HfI4) vapor, hafnium(IV) fluoride (HfF4) vapor, hafnium(III) chloride (HfCl3) vapor, hafnium(III) bromide (HfBr3) vapor, hafnium(III) iodide (HfI3) vapor, hafnium(III) fluoride (HfF3) vapor, or any combination thereof.

[0028]

[0030] The first vapor may contain at least one impurity vapor. The at least one impurity vapor may include at least one of titanium contaminant vapor, chromium contaminant vapor, aluminum contaminant vapor, iron contaminant vapor, or any combination thereof. In some embodiments, the at least one impurity vapor includes at least one of titanium halide vapor, titanium oxide vapor, titanium nitride vapor, titanium ligand complex vapor, chromium halide vapor, chromium oxide vapor, chromium nitride vapor, chromium ligand complex vapor, aluminum halide vapor, aluminum oxide vapor, aluminum nitride vapor, aluminum ligand complex vapor, iron halide vapor, iron oxide vapor, iron nitride vapor, iron ligand complex vapor, or any combination thereof.

[0029]

[0031] The first vapor may contain hafnium halide vapor in a volume of 1% to 99%, or any range or subrange between 1% to 99% of the volume of hafnium halide vapor, based on the total volume of the first vapor. In some embodiments, the first vapor may contain hafnium halide vapor in a volume of 1% to 90%, 1% to 80%, 1% to 70%, 1% to 60%, 1% to 50%, 1% to 40%, 1% to 30%, 1% to 20%, 1% to 10%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, or 90% to 99%, based on the total amount of the first vapor.

[0030]

[0032] The first vapor may contain at least one impurity vapor in an amount of 1% to 99% by volume, or at least one impurity vapor in any range or partial range of 1% to 99% by volume, based on the total volume of the first vapor. In some embodiments, the first vapor contains at least one impurity vapor in an amount of 1% to 90%, 1% to 80%, 1% to 70%, 1% to 60%, 1% to 50%, 1% to 40%, 1% to 30%, 1% to 20%, 1% to 10%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, or 90% to 99%, based on the total amount of at least one impurity vapor.

[0031]

[0033] In some embodiments, the purification method 100 includes passing at least a portion of the hafnium halide vapor and at least a portion of the vapor of at least one impurity into a second vessel 106.

[0032]

[0034] Hafnium halide vapor and at least one impurity vapor can be flowed from the first vessel to the second vessel via the outlet of the first vessel. The outlet of the first vessel may be provided to fluidly communicate with the second vessel via a gas line or other similar fluid line, piping, or conduit. In some embodiments, flow 106 includes transporting at least some of the hafnium halide vapor and at least some of the at least one impurity vapor to the second vessel. In some embodiments, flow 106 includes pumping at least some of the hafnium halide vapor and at least some of the at least one impurity vapor to the second vessel. In some embodiments, flow 106 includes releasing at least some of the hafnium halide vapor and at least some of the at least one impurity vapor to the second vessel. In some embodiments, flow 106 includes transporting at least some of the hafnium halide vapor and at least some of the at least one impurity vapor to the second vessel.

[0033]

[0035] The second vessel may be configured to control its temperature. The temperature of the second vessel can be controlled in any suitable manner. In some embodiments, a heat jacket for heating and / or cooling is used around the second vessel. In some embodiments, a ribbon heater is wrapped around the second vessel. In some embodiments, a block heater having a shape that covers at least a large portion of the outer surface of the second vessel is used to heat the second vessel. In some embodiments, a resistance heater is used to heat the second vessel. In some embodiments, a lamp heater is used to heat the second vessel. In some embodiments, heating and / or cooling can be achieved by bringing a hot heat transfer fluid into contact with the outer surface of the second vessel. In some embodiments, heating is performed by infrared or other radiant energy irradiated onto the second vessel. In some embodiments, the second vessel is cooled by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It will be understood that other heating and / or cooling devices and assemblies, as well as other configurations and arrangements of heaters and / or coolers, can be adopted in the present invention without departing from the scope of this disclosure.

[0034]

[0036] The second vessel may be configured to control pressure. The pressure in the second vessel can be controlled by any suitable method. In some embodiments, a gas inlet line is provided that is in fluid communication with the second vessel. The gas inlet line may be configured to supply pressurized gas from a pressurized gas source to the second vessel. Control of the pressurized gas to the second vessel can be achieved by at least one of a pressure regulator, a needle valve, a mass flow controller, a downstream pressure controller, or any combination thereof. In some embodiments, the pressurized gas 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 second vessel. The vacuum line may be configured to apply a vacuum to the second vessel. In some embodiments, the pumping speed is controlled by a butterfly valve. It will be understood that other mechanisms for controlling the pressure in the second vessel can be employed in the present invention without departing from the scope of this disclosure.

[0035]

[0037] In some embodiments, the purification method 100 includes condensing at least a portion of the hafnium halide vapor in a second vessel 108 in order to separate at least a portion of the hafnium halide vapor from at least one impurity vapor.

[0036]

[0038] Condensing 108 may include applying at least one condition sufficient to condense at least a portion of the hafnium halide vapor in the second vessel. The at least one condition can be applied to at least one of the second vessel, the hafnium halide vapor, at least one impurity vapor, or any combination thereof. In some embodiments, condensing includes cooling the second vessel and / or the hafnium halide vapor to a temperature sufficient to condense at least a portion of the hafnium halide vapor in the second vessel. In some embodiments, condensing 108 includes pressurizing the second vessel to a pressure sufficient to condense at least a portion of the hafnium halide vapor in the second vessel. In some embodiments, condensing 108 includes depressurizing the second vessel to a pressure sufficient to condense at least a portion of the hafnium halide vapor in the second vessel, or to a sufficient pressure.

[0037]

[0039] Condensing 108 may include cooling the second vessel and / or the hafnium halide vapor. In some embodiments, condensing 108 of at least a portion of the hafnium halide vapor in the second vessel includes cooling the second vessel to a temperature of -50°C to 200°C, or any range or partial range of -50°C to 200°C. In some embodiments, condensing 108 of at least a portion of the hafnium halide vapor in the second vessel includes cooling the second vessel to a temperature of -50°C to 20°C, or any range or partial range between -50°C and 20°C. For example, in some embodiments, step 108 of condensing at least a portion of the hafnium halide vapor in the second vessel is performed by heating the second vessel to -50°C~200°C, -40°C~200°C, -30°C~200°C, -20°C~200°C, -10°C~200°C, 0°C~200°C, 10°C~200°C, 20°C~200°C, 30°C~200°C, 40°C~200°C, 50°C~200°C, 60°C~200°C, 70°C~200°C, 80°C~ This includes cooling to temperatures of 200°C, 90°C to 200°C, 100°C to 200°C, 110°C to 200°C, 120°C to 200°C, 130°C to 200°C, 140°C to 200°C, 150°C to 200°C, 160°C to 200°C, 170°C to 200°C, 180°C to 200°C, 190°C to 200°C, -50°C to 10°C, -50°C to 0°C, -50°C to -10°C, -50°C to -20°C, -50°C to -30°C, or -50°C to -40°C. In some embodiments, the temperature is sufficient to condense the hafnium halide precursor vapor without condensing at least a portion of at least one impurity vapor.

[0038]

[0040] Condensing 108 may include pressurizing or depressurizing the second vessel. For example, in some embodiments, condensing 108 of at least a portion of the hafnium halide vapor includes pressurizing or depressurizing the second vessel to 0.01 Torr to 100 Torr, or any range or partial range of 0.01 Torr to 100 Torr. In some embodiments, the pressure is 0.01 Torr to 95 Torr, 0.01 Torr to 90 Torr, 0.01 Torr to 85 Torr, 0.01 Torr to 80 Torr, 0.01 Torr to 75 Torr, 0.01 Torr to 70 Torr, 0.01 Torr to 65 Torr, 0.01 Torr to 60 Torr, 0.01 Torr to 55 Torr, 0.01 Torr ~50Torr, 0.01Torr~45Torr, 0.01Torr~40Torr, 0.01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr~25T orr, 0.01Torr~20Torr, 0.01Torr~15Torr, 0.01Torr~10Torr, 0.01Torr~5Torr, 0.01Torr~1Torr, 0.0 These are pressures in the range of 1 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 pressure is sufficient to condense the hafnium halide precursor vapor without condensing at least a portion of at least one impurity vapor.

[0039]

[0041] In some embodiments, the purification method 100 includes removing at least a portion of impurity vapor from a second vessel 110 in order to obtain a hafnium halide precursor. In one embodiment, removing at least a portion of impurity vapor from the second vessel 110 includes passing the impurity vapor to a trap.

[0040]

[0042] When the hafnium halide vapor is condensed, removing at least a portion of at least one impurity vapor from the second vessel 110 may be sufficient to separate at least a portion of at least one impurity vapor from the hafnium halide precursor. In some embodiments, removal 110 includes removing at least a portion of at least one impurity vapor from the second vessel via the outlet of the second vessel. In some embodiments, removal 110 includes discharging at least a portion of at least one impurity vapor from the second vessel via the outlet of the second vessel. In some embodiments, removal 110 includes evacuating at least a portion of at least one impurity vapor from the second vessel via the outlet of the second vessel. In some embodiments, removal 110 includes releasing at least a portion of at least one impurity vapor from the second vessel via the outlet of the second vessel. In some embodiments, the outlet of the second vessel is in fluid communication with at least one gas discharge line, vacuum line, or other similar gas line suitable for removing at least a portion of at least one impurity vapor from the second vessel.

[0041]

[0043] The resulting hafnium halide precursor may contain at least one impurity in the range of greater than 0 ppm to 1 ppm, or any range or subrange between greater than 0 ppm and 1 ppm. In some embodiments, the hafnium halide precursor may contain 0.001 ppm to 1 ppm, 0.002 ppm to 1 ppm, 0.003 ppm to 1 ppm, 0.004 ppm to 1 ppm, 0.005 ppm to 1 ppm, 0.006 ppm to 1 ppm, 0.007 ppm to 1 ppm, 0.008 ppm to 1 ppm, 0.009 ppm to 1 ppm, 0.01 ppm to 1 ppm, 0.02 ppm to 1 ppm, 0.03 ppm to 1 ppm, and 0.04 ppm. It contains at least one impurity in the following concentrations: 0.05 ppm to 1 ppm, 0.06 ppm to 1 ppm, 0.07 ppm to 1 ppm, 0.08 ppm to 1 ppm, 0.09 ppm to 1 ppm, 0.1 ppm to 1 ppm, 0.2 ppm to 1 ppm, 0.3 ppm to 1 ppm, 0.4 ppm to 1 ppm, 0.5 ppm to 1 ppm, 0.6 ppm to 1 ppm, 0.7 ppm to 1 ppm, 0.8 ppm to 1 ppm, or 0.9 ppm to 1 ppm. In some embodiments, the hafnium halide precursor is expressed in concentrations of 0.001 ppm to 0.9 ppm, 0.001 ppm to 0.8 ppm, 0.001 ppm to 0.7 ppm, 0.001 ppm to 0.6 ppm, 0.001 ppm to 0.5 ppm, 0.001 ppm to 0.4 ppm, 0.001 ppm to 0.3 ppm, 0.001 ppm to 0.2 ppm, 0.001 ppm to 0.1 ppm, 0.001 ppm to 0.09 ppm, 0.001 ppm to 0.08 ppm, 0.001 ppm to 0.07 ppm, 0.001 ppm to 0.06 ppm, and 0.0 It contains at least one impurity in the following concentrations: 0.01 ppm to 0.05 ppm, 0.001 ppm to 0.04 ppm, 0.001 ppm to 0.03 ppm, 0.001 ppm to 0.02 ppm, 0.001 ppm to 0.01 ppm, 0.001 ppm to 0.009 ppm, 0.001 ppm to 0.008 ppm, 0.001 ppm to 0.007 ppm, 0.001 ppm to 0.006 ppm, 0.001 ppm to 0.005 ppm, 0.001 ppm to 0.004 ppm, 0.001 ppm to 0.003 ppm, or 0.001 ppm to 0.002 ppm.In some embodiments, the hafnium halide precursor exists in at least one of the following states: solid, vapor, gas, liquid, or any combination thereof. In some embodiments, the hafnium halide precursor is not present in at least one of the following states: vapor, gas, liquid, or any combination thereof.

[0042]

[0044] Some embodiments relate to a system. The system may include a precursor container. In some embodiments, the precursor container contains a hafnium halide precursor. In some embodiments, the hafnium halide precursor contains at least one impurity in a concentration of less than 1 ppm. In some embodiments, the system includes a deposition apparatus. The deposition apparatus may be in fluid communication with the precursor container. For example, in some embodiments, the deposition apparatus is in fluid communication with the outlet of the precursor container.

[0043]

[0045] In some embodiments, the hafnium halide precursor has a sufficiently low impurity level so that when the hafnium halide precursor is vaporized into hafnium halide vapor, the hafnium halide vapor is supplied to the deposition apparatus at a supply rate of no more than 5%, 4%, 3%, 2%, or 1% of the initial supply rate (e.g., the supply rate of hafnium halide vapor initially supplied to the deposition apparatus). In some embodiments, when the hafnium halide precursor is supplied to a tool used in semiconductor manufacturing or other similar processes, when the hafnium halide precursor is vaporized, it is supplied to the tool at a controllable constant flow rate without significant spikes or fluctuations in flow rate.

[0044]

[0046] The hafnium halide precursor may contain at least one impurity in the range of greater than 0 ppm to 1 ppm, or any range or subrange between greater than 0 ppm and 1 ppm. In some embodiments, the hafnium halide precursor may contain 0.001 ppm to 1 ppm, 0.002 ppm to 1 ppm, 0.003 ppm to 1 ppm, 0.004 ppm to 1 ppm, 0.005 ppm to 1 ppm, 0.006 ppm to 1 ppm, 0.007 ppm to 1 ppm, 0.008 ppm to 1 ppm, 0.009 ppm to 1 ppm, 0.01 ppm to 1 ppm, 0.02 ppm to 1 ppm, 0.03 ppm to 1 ppm, and 0.04 ppm. It contains at least one impurity in the following concentrations: 0.05 ppm to 1 ppm, 0.06 ppm to 1 ppm, 0.07 ppm to 1 ppm, 0.08 ppm to 1 ppm, 0.09 ppm to 1 ppm, 0.1 ppm to 1 ppm, 0.2 ppm to 1 ppm, 0.3 ppm to 1 ppm, 0.4 ppm to 1 ppm, 0.5 ppm to 1 ppm, 0.6 ppm to 1 ppm, 0.7 ppm to 1 ppm, 0.8 ppm to 1 ppm, or 0.9 ppm to 1 ppm. In some embodiments, the hafnium halide precursor is expressed in concentrations of 0.001 ppm to 0.9 ppm, 0.001 ppm to 0.8 ppm, 0.001 ppm to 0.7 ppm, 0.001 ppm to 0.6 ppm, 0.001 ppm to 0.5 ppm, 0.001 ppm to 0.4 ppm, 0.001 ppm to 0.3 ppm, 0.001 ppm to 0.2 ppm, 0.001 ppm to 0.1 ppm, 0.001 ppm to 0.09 ppm, 0.001 ppm to 0.08 ppm, 0.001 ppm to 0.07 ppm, 0.001 ppm to 0.06 ppm, and 0.0 It contains at least one impurity in the following concentrations: 0.01 ppm to 0.05 ppm, 0.001 ppm to 0.04 ppm, 0.001 ppm to 0.03 ppm, 0.001 ppm to 0.02 ppm, 0.001 ppm to 0.01 ppm, 0.001 ppm to 0.009 ppm, 0.001 ppm to 0.008 ppm, 0.001 ppm to 0.007 ppm, 0.001 ppm to 0.006 ppm, 0.001 ppm to 0.005 ppm, 0.001 ppm to 0.004 ppm, 0.001 ppm to 0.003 ppm, or 0.001 ppm to 0.002 ppm.In some embodiments, the hafnium halide precursor exists in at least one of the following states: solid, gas, liquid, or any combination thereof. In some embodiments, the hafnium halide precursor is not present in at least one of the following states: gas, liquid, or any combination thereof.

[0045]

[0047] Figure 2 shows an embodiment of system 200 for the purification of hafnium halide precursors. System 200 includes a first pipe 250, a first vessel 260, a first scale 270, a second pipe 210, a second vessel 230, a second scale 240, and a trap 220. System 200 may include a plurality of valves, as shown in Figure 2, for example.

[0046]

[0048] System 200 can be used to reduce the amount of titanium impurities in a hafnium halide precursor. In one embodiment, the components of System 200 are stainless steel, for example, 304 or 316L stainless steel.

[0047]

[0049] The first vessel 260 contains the precursor to be purified. The first vessel 260 rests on the first scale 270. The first vessel is connected to the second vessel 230 via the first piping 250. The first vessel 260 may include an integrated heater. In some embodiments, the first vessel 260 has a heater that is thermally in communication with the first vessel 260 in order to heat the first vessel 260 to a desired temperature.

[0048]

[0050] The first scale 270 supports the first container 260 and provides a weight for the first container 260. The weight for the first container 260 can be used to monitor the amount of precursor material in the first container 260. This allows monitoring of the processing of the precursor material in the first container 260.

[0049]

[0051] The first piping 250 connects the first container 260 to the second container 230. The heated precursor can move from the first container 260 to the second container 230 through the first piping 250. In some embodiments, the heated precursor moves through the first piping 250 as vapor. The first piping 250 may be heated. For example, heating tape may be wrapped around the first piping 250.

[0050]

[0052] The second vessel 230 receives vapor from the first piping 250 and condenses the precursor vapor back into a solid. In some embodiments, the second vessel 230 is heated. The second vessel 230 may be heated to a lower temperature than the first vessel 260. In one embodiment, the second vessel 230 is maintained at room temperature. In another embodiment, the second vessel 230 is cooled. The second vessel rests on the second scale 240. In some embodiments, the outlet of the second vessel 230 is configured to fluidly communicate with the second piping 210, a vacuum line, or other similar gas line suitable for removing at least a portion of at least one impurity vapor from the second vessel 230. The second piping 210 can be connected to a trap 220 to capture impurity vapor.

[0051]

[0053] A second scale 240 is used to monitor the amount of precursor material accumulated in the second container 230 during the purification process. The second scale 240 can be used in conjunction with the first scale 270 to monitor the process and determine when to stop the purification process. In some embodiments, the majority of the precursor material in the first container 260 is transferred to the second container 230, as verified by the first scale 270 and the second scale 240.

[0052]

[0054] The trap 220 is used to control the presence of impurities flowing into the second container 230. The trap 220 is connected to the second container by the second piping 210.

[0053]

[0055] Figure 3 is a graph showing purity levels at different temperatures. As you can see, batches produced at 50°C contain a wide range of titanium levels, including some exceeding 1 ppm. In contrast, batches produced by the described method at temperatures of at least 100°C have much lower levels of titanium impurities.

[0054]

[0056] manner

[0057] Various embodiments are described below. Please understand that one or more of the features described in the following embodiments can be combined with one or more of the features of the other embodiments. Appearance 1 A system comprising a precursor container containing a solid HfCl4 precursor, wherein the solid HfCl4 precursor contains less than 1 ppm of titanium contaminants. Appearance 2 The system according to embodiment 1, wherein the solid HfCl4 precursor contains a titanium contaminant in a concentration of more than 0 ppm to 1 ppm. Appearance 3 The system according to embodiment 1 or 2, wherein the solid HfCl4 precursor contains 0.001 ppm to 1 ppm of titanium contaminants. Pattern 4 The system according to any one of embodiments 1 to 3, wherein the solid HfCl4 precursor contains 0.01 ppm to 1 ppm of titanium contaminants. Embodiment 5: The system according to any one of Embodiments 1 to 4, wherein the titanium contaminant comprises at least one of a titanium halide, titanium oxide, titanium nitride, titanium ligand complex, or any combination thereof. Appearance 6 Further including a deposition apparatus, The deposition apparatus is fluid-coupled to the outlet of the precursor container, according to any one of embodiments 1 to 6. Appearance 7 The system according to embodiment 6, wherein when the solid HfCl4 precursor is vaporized into HfCl4 vapor, the HfCl4 vapor is supplied to the deposition apparatus at a supply rate of no more than 5% of the initial supply rate. Embodiment 8: The system according to any one of Embodiments 1 to 7, wherein the solid HfCl4 precursor further comprises at least one of a chromium contaminant, an aluminum contaminant, an iron contaminant, or any combination thereof. Appearance 9 It is a method, Obtaining a first container containing a solid reagent, wherein the solid reagent contains HfCl4 and at least one impurity, To produce a first vapor containing HfCl4 vapor, at least one impurity vapor, or any combination thereof, at least a portion of a solid reagent is vaporized. To pass at least a portion of the HfCl4 vapor and at least a portion of the impurity vapor into a second container, In order to separate HfCl4 from impurity vapor, at least a portion of the HfCl4 vapor in the second container is condensed, In order to obtain the HfCl4 precursor, at least a portion of the impurity vapor is removed from the second container. A method that includes this. Appearance 10 The method according to embodiment 9, wherein the solid reagent contains at least 1 ppm of titanium contaminant. Appearance 11 The method according to embodiment 9 or 10, wherein the solid reagent contains 1 ppm to 100 ppm of titanium contaminants. Appearance 12 The method according to any one of embodiments 9 to 11, wherein the solid reagent contains 1 ppm to 1000 ppm of titanium contaminants. Appearance 13 The method according to any one of embodiments 9 to 12, wherein at least one impurity comprises at least one of titanium contaminants, chromium contaminants, aluminum contaminants, iron contaminants, or any combination thereof. Appearance 14 The method according to any one of embodiments 9 to 13, wherein at least one impurity comprises at least one of a titanium halide, titanium oxide, titanium nitride, titanium ligand complex, or any combination thereof. Appearance 15 The method according to any one of embodiments 9 to 14, wherein the vaporization described above includes heating the first container to a temperature of at least 50°C. Appearance 16 The method according to any one of embodiments 9 to 15, wherein the vaporization described above includes heating the first container to a temperature of 90°C to 140°C. Appearance 17 The method according to any one of embodiments 9 to 16, wherein the condensation described above includes cooling the second container to a temperature below 20°C. Appearance 18 The method according to any one of embodiments 9 to 17, wherein the HfCl4 precursor contains a titanium contaminant in a concentration of more than 0 ppm to 1 ppm. Appearance 19 The method according to any one of embodiments 9 to 18, wherein the HfCl4 precursor contains 0.001 ppm to 1 ppm of titanium contaminants. Appearance 20 The method according to any one of embodiments 9 to 19, wherein the HfCl4 precursor contains 0.001 ppm to 1 ppm of titanium contaminants.

[0055] In particular, please understand that the constituent materials, shapes, sizes, and arrangements of components used may be modified in detail without departing from the scope of this disclosure. This specification and the embodiments described herein are examples, and the true scope and spirit of the disclosure are indicated by the subsequent claims.

Claims

1. solid HfCl ４ A system comprising a precursor container containing a precursor, solid HfCl ４ The precursor system contains less than 1 ppm of titanium contaminants.

2. solid HfCl ４ The system according to claim 1, wherein the precursor contains a titanium contaminant in a concentration of more than 0 ppm to 1 ppm.

3. solid HfCl ４ The system according to claim 1, wherein the precursor contains 0.001 ppm to 1 ppm of titanium contaminants.

4. solid HfCl ４ The system according to claim 1, wherein the precursor contains 0.01 ppm to 1 ppm of titanium contaminants.

5. The system according to claim 1, wherein the titanium contaminant comprises at least one of a titanium halide, a titanium oxide, a titanium nitride, a titanium ligand complex, or any combination thereof.

6. Further including a deposition apparatus, The deposition apparatus is fluidly coupled to the outlet of the precursor container, according to claim 1.

7. solid HfCl ４ The precursor is HfCl ４ When vaporized into steam, HfCl ４ The system according to claim 6, wherein steam is supplied to the deposition apparatus at a supply rate of no more than 5% of the initial supply rate.

8. Solid HfCl ４ The system of claim 1, wherein the precursor further comprises at least one of chromium contaminants, aluminum contaminants, iron contaminants, or any combination thereof.

9. It is a method, HfCl ４ and to obtain a first container containing a solid reagent containing at least one impurity, HfCl ４ To produce a first vapor containing vapor, at least one impurity vapor, or any combination thereof, at least a portion of a solid reagent is vaporized. HfCl ４ The process involves flowing at least a portion of the steam and at least a portion of the impurity steam into a second container, HfCl ４ To separate it from impurity vapor, HfCl in the second container ４ Condensing at least a portion of the vapor, HfCl ４ In order to obtain the precursor, at least a portion of the impurity vapor is removed from the second container. A method that includes this.

10. The method according to claim 9, wherein the solid reagent contains at least 1 ppm of titanium contaminant.

11. The method according to claim 9, wherein the solid reagent contains 1 ppm to 100 ppm of titanium contaminants.

12. The method according to claim 9, wherein the solid reagent contains 1 ppm to 1000 ppm of titanium contaminants.

13. The method according to claim 9, wherein at least one impurity comprises at least one of a titanium contaminant, a chromium contaminant, an aluminum contaminant, an iron contaminant, or any combination thereof.

14. The method according to claim 9, wherein at least one impurity comprises at least one of a titanium halide, titanium oxide, titanium nitride, titanium ligand complex, or any combination thereof.

15. The method according to claim 9, wherein the vaporization includes heating the first container to a temperature of at least 50°C.

16. The method according to claim 9, wherein the vaporization includes heating the first container to a temperature of 90°C to 140°C.

17. The method according to claim 9, wherein the condensation includes cooling the second container to a temperature of less than 20°C.

18. HfCl ４ The method according to claim 9, wherein the precursor contains a titanium contaminant in a concentration of more than 0 ppm to 1 ppm.

19. HfCl ４ The method according to claim 9, wherein the precursor contains 0.001 ppm to 1 ppm of a titanium contaminant.

20. HfCl ４ The method according to claim 9, wherein the precursor contains 0.01 ppm to 1 ppm of a titanium contaminant.

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