Removal of impurities from precursors

Abstract

A method and related system for removing impurities from a precursor are provided. The method comprises at least one thermal cycle, which includes heating a vessel containing the precursor and at least one impurity to a certain temperature for a period of time sufficient to vaporize at least a portion of the at least one impurity, measuring the vapor pressure in the vessel to obtain a measured vapor pressure and comparing the measured vapor pressure to the vapor pressure at a setpoint, and removing at least a portion of the vapor containing at least one impurity from the vessel when the measured vapor pressure is above or within the setpoint vapor pressure. Other methods and systems are provided herein.

Description

TECHNICAL FIELD

[0001] Cross-Reference to Related Applications

[0001] This application claims priority and benefit of U.S. Provisional Patent Application No. 63 / 539,025, filed on September 18, 2023, entitled "REMOVING IMPURITIES FROM PRECURSORS", the entire contents of which are incorporated herein by reference.

[0002] Field

[0002] The present disclosure relates to removal of impurities from precursors, as well as related systems and related methods.

BACKGROUND ART

[0003] Background

[0003] The presence of impurities in precursors used in semiconductor manufacturing causes defects and undesirable process variations.

SUMMARY OF THE INVENTION

[0004]

[0004] Some embodiments relate to methods. In some embodiments, the method comprises at least one thermal cycle that heats a vessel containing a precursor and at least one impurity to a temperature for a period sufficient to vaporize at least a portion of the at least one impurity, measuring the vapor pressure in the vessel to obtain a measured vapor pressure, comparing the measured vapor pressure to a set point, and removing at least a portion of the vapor comprising the at least one impurity from the vessel when the measured vapor pressure is above or within the set point vapor pressure. In some embodiments, when the vapor comprising the at least one impurity is removed from the vessel, at least 90% of the at least one impurity is removed from the vessel.

[0005]

[0005] Some embodiments relate to a method. In some embodiments, the method comprises one or more of the following steps: heating a container containing a precursor and at least one impurity to a temperature sufficient to vaporize at least a portion of the at least one impurity; measuring the vapor pressure in the container over time to obtain a plurality of measured vapor pressures and comparing the plurality of measured vapor pressures with a setpoint vapor pressure; and removing the vapor containing the at least one impurity from the container when at least one of the plurality of measured vapor pressures is greater than the setpoint vapor pressure. In some embodiments, when the vapor containing the at least one impurity is removed from the container, at least 90% of the at least one impurity is removed from the container.

[0006]

[0006] Several embodiments relate to a method. In some embodiments, the method includes obtaining a container assembly. In some embodiments, the container assembly includes a container defining an internal region. In some embodiments, the container assembly includes at least one tray located within the internal region of the container. In some embodiments, the container assembly includes a precursor located on at least one tray. In some embodiments, the container assembly includes at least one impurity located within the internal region of the container. In some embodiments, the method includes vaporizing at least a portion of the at least one impurity and heating at least the container to a first temperature sufficient to obtain a first vapor containing the at least one impurity. In some embodiments, the method includes removing the first vapor from the container such that, when the precursor is vaporized at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature.

[0007]

[0007] Several embodiments relate to a method. In some embodiments, the method includes obtaining a container assembly. In some embodiments, the container assembly includes a container defining an internal region. In some embodiments, the container assembly includes at least one tray located within the internal region of the container. In some embodiments, the container assembly includes an aluminum precursor located on at least one tray. In some embodiments, the container assembly includes at least one impurity located within the internal region of the container. In some embodiments, the at least one impurity includes water. In some embodiments, the water is located on at least one of the at least one tray, the aluminum precursor, or any combination thereof. In some embodiments, the method includes heating the container to a first temperature sufficient to vaporize at least a portion of the at least one impurity to obtain a first vapor containing at least one impurity. In some embodiments, the method includes removing the first vapor from the container such that, when the aluminum precursor is vaporized at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature.

[0008]

[0008] Several embodiments relate to a method. In some embodiments, the method includes obtaining a container assembly. In some embodiments, the container assembly includes a container defining an internal region. In some embodiments, the container assembly includes at least one tray located within the internal region of the container. In some embodiments, the container assembly includes a molybdenum precursor located on at least one tray. In some embodiments, the container assembly includes at least one impurity located within the internal region of the container. In some embodiments, the at least one impurity includes water. In some embodiments, the water is located on at least one of the at least one tray, the molybdenum precursor, or any combination thereof. In some embodiments, the method includes heating the container to a first temperature sufficient to vaporize at least a portion of the at least one impurity to obtain a first vapor containing at least one impurity. In some embodiments, the method includes removing the first vapor from the container such that, when the molybdenum precursor is vaporized at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature.

[0009]

[0009] Some embodiments relate to container assemblies. In some embodiments, the container assembly includes a container body that defines an internal region. In some embodiments, the container assembly includes a tray located in the internal region of the container body. In some embodiments, the container assembly includes a precursor located on the tray. In some embodiments, the precursor includes at least one of an aluminum precursor, a molybdenum precursor, or any combination thereof. In some embodiments, when the precursor is vaporized at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature.

[0010]

[0010] 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]

[0011] [Figure 1]

[0011] This is a flowchart of a method for removing at least one impurity according to several embodiments. [Figure 2]

[0012] This is a schematic diagram of a system for removing at least one impurity according to several embodiments. [Figure 3]

[0013] This is a flowchart of a method for removing at least one impurity according to several embodiments. [Figure 4]

[0014] This is a schematic diagram of a container assembly according to several embodiments. [Figure 5]

[0015] These are Fourier transform infrared spectra showing the presence of impurities in the container according to several embodiments. [Modes for carrying out the invention]

[0012]

[0016] 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.

[0013]

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

[0014]

[0018] 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.

[0015]

[0019] 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.).

[0016]

[0020] For example, precursors useful in the manufacture of microelectronics, such as semiconductors, contain impurities. The presence of these impurities in precursor vapor is undesirable because, in particular, impurities accumulate on the substrate and therefore need to be removed. Removing these impurities remains an ongoing challenge due to various factors, including the difficulty of minimizing or eliminating exposure to moisture and other conditions that lead to impurity generation, as well as the volatilization of impurities and contaminants. Conventional methods for removing these impurities and contaminants have various drawbacks, such as prolonged startup processes and problems controlling impurity levels.

[0017]

[0021] The methods and systems disclosed herein overcome the shortcomings of conventional processes and systems. For example, in some embodiments, the methods disclosed herein can be used to shorten the duration of start-up processes and / or pre-treatment steps performed before the precursor is used in a downstream process. In some embodiments, the methods and systems disclosed herein provide high-purity precursors suitable for the manufacture of microelectronics, such as semiconductors. In some embodiments, the methods and systems disclosed herein overcome the challenges associated with exposure to moisture, which may react to form impurities and / or contaminants. In some embodiments, the methods and systems disclosed herein remove volatile impurities. In some embodiments, the methods and systems disclosed herein provide a mechanism to complete undesirable reactions so that impurities are generated and removed, while minimizing the opportunity for impurities to be regenerated (e.g., through changes in conditions that promote reversible reactions and / or equilibrium).

[0018]

[0022] Some embodiments relate to methods for removing at least one impurity. This specification provides various embodiments of methods for removing at least one impurity. In methods for removing at least one impurity, it should be understood that any combination of steps can be performed in any order without departing from the scope of this disclosure. Therefore, it is not limiting that different methods and the steps of those methods are shown in different figures, and any combination of steps in any of the figures disclosed herein can be performed without departing from the scope of this disclosure. Unless otherwise specified herein, the terms impurity and contaminant can be used interchangeably without departing from the scope of this disclosure.

[0019]

[0023] Figure 1 is a flowchart of a method 100 for removing at least one impurity, in accordance with some embodiments. As shown in Figure 1, the method 100 for removing at least one impurity includes one or more of the following steps: heating 102 a vessel containing a precursor and at least one impurity to a temperature sufficient to vaporize at least a portion of the at least one impurity, measuring the vapor pressure within the vessel to obtain a measured vapor pressure, and comparing the measured vapor pressure to a set point vapor pressure 104, and removing 106 at least a portion of the vapor comprising the at least one impurity from the vessel.

[0020]

[0024] In step 102, in some embodiments, the method 100 includes heating the vessel containing the precursor and the at least one impurity to a temperature sufficient to vaporize at least a portion of the at least one impurity.

[0021]

[0025] In some embodiments, the container comprises at least one of a precursor, at least one impurity, or any combination thereof. In some embodiments, the container comprises at least one of a solid precursor, a liquid precursor, a gas / vapor precursor, or any combination thereof. In some embodiments, the container comprises at least one impurity, and the impurity may be present in at least one of a solid phase, a liquid phase, a gas / vapor phase, or any combination thereof. In some embodiments, the at least one impurity comprises at least one of a volatile impurity, a non-volatile impurity, or any combination thereof. In some embodiments, the at least one impurity comprises a non-reactive impurity, and the non-reactive impurity is an impurity that is not a reaction product with water (e.g., moisture). In some embodiments, the at least one impurity is a reaction product of water. In some embodiments, the at least one impurity is a reaction product of water and the precursor (e.g., resulting from exposure of the precursor to moisture or water vapor). In some embodiments, the at least one impurity comprises a hydrolyzate. In some embodiments, the at least one impurity comprises an oxide. In some embodiments, the at least one impurity comprises at least one of HCl, an oxide, a hydrolyzed species (e.g., aluminum chloride hydrate), molybdenum dioxide chloride, or any combination thereof. In some embodiments, the at least one impurity comprises a hydrated species. In some embodiments, the at least one impurity comprises a substance other than the precursor.

[0022]

[0026] In some embodiments, the at least one impurity is molybdenum tetrachloride (MoCl4), molybdenum oxytetrachloride (MoOCl4), molybdenum dioxydichloride (MoO2Cl2), molybdenum dioxydichloride (MoO2Cl2(H2O)), molybdenum trioxide (MoO3), dichloromethane, phosgene, 1,1-dichloroethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrachloroethylene, trichloroethylene, 1,3-dichloropropane, 1,2,3-trichloropropane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,2-trichloropropane, 1,2,2-trichloropropane, 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane , comprising 1,1,2,2-tetrachloroethane, 2,2-dichloropropanoyl chloride, 1,3-dichloro-1-propene, 3,3,3-trichloro-1-propene, 1,2,3-trichloro-1-propene, 1,3-dichloro-2-methylenepropane, 1,4-dichlorobutane, 1,3-dichloro-2-butene, 1,1,3,3-tetrachloro-2-methylpropane, 1,1,2,3,3-pentachloropropane, 1,3-dichlorocyclopentane, 1,1,2,2,3,3-hexachloropropane, 1,2,3,4,5,5-hexanechloro-1,3-cyclopentadiene, trichlorocyclopentene, tetrachlorocyclopentene, pentachloronorbornene, or at least one of any combination thereof.

[0023]

[0027] In some embodiments, the precursor includes at least one of aluminum chloride (e.g., AlCl3), molybdenum chloride (e.g., MoCl5), tungsten chloride (e.g., WCl5, WCl6), or any combination thereof. In some embodiments, the precursor includes dimethylhydrazine, trimethylaluminum (TMA), hafnium chloride (HfCl4), zirconium chloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, tungsten carbonyl, Ba(DPM)2, bis-dipivaloylmethanatostrontium (Sr(DPM)2), TiO(DPM)2, tetra-dipivaloylmethanatozirconium (Zr(DPM)4), decaborane, octadecaborane, boron, magnesium, gallium, indium, antimony, copper, phosphorus, arsenic, lithium, sodium tetrafluoroborate, precursors incorporating alkylamidinate ligands, organometallic precursors, tertiary butoxydilco The precursor comprises at least one of the following: nium (Zr(t-OBu)4), tetrakisdiethylaminozirconium (Zr(Net2)4), tetrakisdiethylaminohafnium (Hf(Net2)4), tetrakis(dimethylamino)titanium (TDMAT), tert-butyliminotris(diethylamino)tantalum (TBTDET), pentakis(dimethylamino)tantalum (PDMAT), pentakis(ethylmethylamino)tantalum (PEMAT), tetrakisdimethylaminozirconium (Zr(NMe2)4), hafnium-tert-butoxide (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), or any combination thereof. In some embodiments, the precursor does not contain molybdenum pentachloride (MoCl5). In some embodiments, the precursor does not contain a tungsten precursor.

[0024]

[0028] In some embodiments, the precursor includes at least one of decaborane, hafnium tetrachloride, zirconium tetrachloride, indium trichloride, organometallic β-diketnate complexes, tungsten hexafluoride, cyclopentadienylcycloheptatrienyl titanium (CpTiCht), aluminum trichloride, titanium iodide, cyclooctatetraenecyclopentadienyl titanium, biscyclopentadienyl titanium diazide, trimethylgallium, trimethylindium, trimethylaluminum, triethylaluminum, trimethylaminealane, dimethylzinc, tetramethyltin, trimethylantimony, diethylcadmium, tungsten carbonyl, or any combination thereof.

[0025]

[0029] In some embodiments, the precursor comprises at least one of elemental metals, metal halides, metal-organic complexes, or any combination thereof. For example, in some embodiments, the precursor comprises at least one of the elements boron, copper, phosphorus, decaborane, gallium halide, indium halide, antimony halide, arsenic halide, gallium halide, aluminum iodide, titanium iodide, cyclopentadienylcycloheptatrienyl titanium (CpTiCht), cyclooctatetraenecyclopentadienyl titanium, biscyclopentadienyl titanium diazide, In(CH3)2(hfac), dibromomethylstivin, tungsten carbonyl, organometallic β-diketnate complex, organometallic alkoxide complex, organometallic aryl complex, organometallic amide complex, or any combination thereof.

[0026]

[0030] In some embodiments, the precursor comprises at least one of any kind of raw materials that can be liquefied by heating or dissolution in a solvent, for example, decaborane (B 10 H14), Pentaborane (B5H9), Octadecaborane (B18H 22The precursor includes, but is not limited to, at least one of the following: AsCl3, AsBr3, AsF3, AsF5, AsH3, As4O6, As2Se3m, As2S2, As2S3, As2S5, As2Te3, B4H 11 B4H 10 , B3H6N3, BBr3, BCl3, BF3, BF3·O(C2H5)2, BF3·HOCH3, B2H6, F2, HF, GeBr4, GeCl4, Ge F4, GeH4, H2, HCl, H2Se, H2Te, H2S, WF6, SiH4, SiH2Cl2, SiHCl3, SiCl4, SiH3Cl, NH3, N H3, Ar, Br2, HBr, BrF5, CO2, CO, COCl2, COF2, Cl2, ClF3, CF4, C2F6, C3F8, C4F8, C5F8, C HF3, CH2F2, CH3F, CH4, SiH6, He, HCN, Kr, Ne, Ni(CO)4, HNO3, NO, N2, NO2, NF3, N2O, C8H 24 It includes at least one of O4Si4, PH3, POCl3, PCl5, PF3, PFS, SbH3, SO2, SF6, SF4, Si(OC2H5)4, C4H16Si4O4, Si(CH3)4, SiH(CH3)3, TiCl4, Xe, SiF4, WOF4, TaBr5, TaCl5, TaF5, Sb(C2H5)3, Sb(CH3)3, In(CH3)3, PBr5, PBr3, RuF5, or any combination thereof.

[0027]

[0031] In some embodiments, the solvent is an organic solvent, an inorganic solvent, or any combination thereof. In some embodiments, the solvent includes arsenic, phosphorus, antimony, germanium, indium, tin, selenium, tellurium, fluorine, carbon, boron, aluminum, bromine, carbon, chlorine, nitrogen, silicon, tungsten, tantalum, ruthenium, selenium, nickel, sulfur, or any combination thereof. It should be understood that using other precursors as described herein does not constitute a departure from the disclosure.

[0028]

[0032] The precursor may contain at least one impurity in an amount of 0.1% to 15% by weight, or any range or subrange between 0.1% and 15%, based on the total weight of the precursor. In some embodiments, the precursor contains at least one impurity in an amount of 0.1% to 14% by weight, 0.1% to 13% by weight, 0.1% to 12% by weight, 0.1% to 11% by weight, 0.1% to 10% by weight, 0.1% to 9% by weight, 0.1% to 8% by weight, 0.1% to 7% by weight, 0.1% to 6% by weight, 0.1% to 5% by weight, 0.1% to 4% by weight, 0.1% to 3% by weight, 0.1% to 2% by weight, 0.1% to 1% by weight, or 0.1% to 0.5% by weight, based on the total weight of the precursor. In some embodiments, the precursor contains at least one impurity in the following proportions based on the total weight of the precursor: 0.5% to 15% by weight, 1% to 15% by weight, 2% to 15% by weight, 3% to 15% by weight, 4% to 15% by weight, 5% to 15% by weight, 6% to 15% by weight, 7% to 15% by weight, 8% to 15% by weight, 9% to 15% by weight, 10% to 15% by weight, 11% to 15% by weight, 12% to 15% by weight, 13% to 15% by weight, or 14% to 15% by weight.

[0029]

[0033] The container can be configured to control its temperature. The temperature of the container can be controlled by any suitable method. In some embodiments, a thermal jacket for heating and / or cooling is used around the container. In some embodiments, a ribbon heater is wrapped around the container. In some embodiments, a block heater having a shape that covers at least a large portion of the outer surface of the container is used to heat the container. In some embodiments, a resistance heater is used to heat the container. In some embodiments, a lamp heater is used to heat the container. 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 container. In some embodiments, heating is performed by infrared or other radiant energy irradiated onto the container. In some embodiments, the container is cooled by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It will be understood that other heating and / or cooling devices and assemblies, 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.

[0030]

[0034] The container may be heated to a temperature and / or for a period of time sufficient to vaporize at least one impurity. In some embodiments, the container is heated to a temperature and / or for a period of time sufficient to complete the reaction between the precursor and water or other substances. In some embodiments, completing the reaction reduces the likelihood of it proceeding in the reverse direction. In some embodiments, completing the reaction generates all undesirable by-products, and the purity of the precursor can be improved by removing the generated by-products from the container. In some embodiments, the reaction does not proceed to completion.

[0031]

[0035] The container can be heated to a temperature of 50°C to 300°C, or any range or subrange between 50°C and 300°C. In some embodiments, the container is heated to a temperature of 50°C to 290°C, 50°C to 280°C, 50°C to 270°C, 50°C to 260°C, 50°C to 250°C, 50°C to 240°C, 50°C to 230°C, 50°C to 220°C, 50°C to 210°C, 50°C to 200°C, 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, or 50°C to 60°C. In some embodiments, the container can withstand temperatures of 60°C to 300°C, 70°C to 300°C, 80°C to 300°C, 90°C to 300°C, 100°C to 300°C, 100°C to 250°C, 100°C to 200°C, 110°C to 300°C, 120°C to 300°C, 130°C to 300°C, 140°C to 300°C, 150°C to 300°C, and 160°C to 300°C. It is heated to a temperature of 170°C-300°C, 180°C-300°C, 190°C-300°C, 200°C-300°C, 210°C-300°C, 220°C-300°C, 230°C-300°C, 240°C-300°C, 250°C-300°C, 260°C-300°C, 270°C-300°C, 280°C-300°C, or 290°C-300°C.

[0032]

[0036] The container can be maintained at the heating temperature for any range or subrange of 30 seconds to 7 days, or 30 seconds to 7 days. In some embodiments, the container can be heated for periods of 1 minute to 7 days, 1 hour to 7 days, 4 hours to 7 days, 12 hours to 7 days, 24 hours to 7 days, 1 day to 7 days, 2 days to 7 days, 3 days to 7 days, 4 days to 7 days, 5 days to 7 days, 6 days to 7 days, 30 seconds to 6 days, 30 seconds to 5 days, 30 seconds to 4 days, 30 seconds to 3 days, 30 seconds to 2 days, 30 seconds to 1 day, 30 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 4 hours, 4 hours to 48 hours, 4 hours to 24 hours, 8 hours to 48 hours, 8 hours to 24 hours, 12 hours to 24 hours, 12 hours to 48 hours, 24 hours to 48 hours, or 36 hours to 48 hours.

[0033]

[0037] The vessel can be configured to control pressure. The pressure in the vessel can be controlled by any suitable method. In some embodiments, a gas inlet line is fluidly coupled to the vessel. The gas inlet line can be configured to supply pressurized gas to the vessel from a pressurized gas source. Control of pressurized gas to the 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 vessel. The vacuum line can be configured to apply a vacuum to the 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 vessel can be employed in the present invention without departing from the scope of this disclosure. In some embodiments, the method includes depressurizing the vessel. In some embodiments, the method includes pressurizing the vessel. In some embodiments, depressurizing and / or pressurizing is performed between heating.

[0034]

[0038] The container can be pressurized (or depressurized) to a pressure of 0.001 Torr to 100 Torr, or any range or subrange within that range. In some embodiments, the pressure can be 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 .01Torr~35Torr, 0.01Torr~30Torr, 0.01Torr~25Torr, 0.01Torr~20Torr, 0.01Torr~15Torr, 0.01Torr~10Torr, 0.01Torr~ 5Torr, 0.01Torr~4Torr, 0.01Torr~3Torr, 0.01Torr~2Torr, 0.01Torr~1Torr, 0.01Torr~0.1Torr, 0.001Torr~10Torr, 0.001 Torr~5Torr, 0.001Torr~4Torr, 0.001Torr~3Torr, 0.001Torr~2Torr, 0.001Torr~1Torr, 0.001Torr~0.1Torr, 0.1Torr~100 Torr, 1Torr~100Torr, 5Torr~100Torr, 10Torr~100Torr, 15Torr~100Torr, 20Torr~100Torr, 25Torr~100Torr, 30Torr~100Torr rr is a pressure in the range of 35 Torr~100 Torr, 40 Torr~100 Torr, 45 Torr~100 Torr, 50 Torr~100 Torr, 55 Torr~100 Torr, 60 Torr~100 Torr, 65 Torr~100 Torr, 70 Torr~100 Torr, 75 Torr~100 Torr, 80 Torr~100 Torr, 85 Torr~100 Torr, 90 Torr~100 Torr, or 95 Torr~100 Torr.

[0035]

[0039] In step 104, in some embodiments, method 100 includes measuring the vapor pressure inside a container to obtain a measured vapor pressure and comparing the measured vapor pressure with the setpoint vapor pressure.

[0036]

[0040] In some embodiments, the vapor pressure in the container is measured once or multiple times. In some embodiments, the vapor pressure in the container is measured over time. In some embodiments, the vapor pressure in the container is monitored over time. In some embodiments, the vapor pressure in the container is measured in real time. In some embodiments, the vapor pressure in the container is measured using a pressure sensor. In some embodiments, the vapor pressure in the container is measured using a pressure probe. In some embodiments, once the vapor pressure in the container is measured, it is transmitted to a controller. In some embodiments, once the vapor pressure in the container is measured, it is transmitted to a processor. In some embodiments, the processor and / or controller receive signals from the sensor and / or probe and convert the signals into the measured vapor pressure. In some embodiments, the measured vapor pressure is stored in memory. In some embodiments, each measured vapor pressure is compared to a setpoint vapor pressure.

[0037]

[0041] In some embodiments, the setpoint vapor pressure is a vapor pressure value. In some embodiments, the setpoint vapor pressure is a vapor pressure range. In some embodiments, the setpoint vapor pressure is at least higher than the vapor pressure of the precursor. In some embodiments, the setpoint vapor pressure is greater than or equal to the vapor pressure of the precursor. In some embodiments, the setpoint vapor pressure is a vapor pressure range, with the lower limit of the range being equal to the vapor pressure of the precursor. In some embodiments, the setpoint vapor pressure is a vapor pressure range, with the lower limit of the range being higher than the vapor pressure of the precursor. In some embodiments, the vapor pressure of the precursor refers to the vapor pressure of the precursor in its pure form under the conditions or measurements described in the literature. The vapor pressure of the precursor may be useful as the setpoint vapor pressure because a vapor pressure exceeding the setpoint vapor pressure may indicate the presence of vapor and / or gas species other than the vaporized precursor.

[0038]

[0042] In step 106, in some embodiments, method 100 includes step 106 of removing at least a portion of the vapor containing at least one impurity from the container.

[0039]

[0043] In some embodiments, at least a portion of the vapor containing at least one impurity is removed from the vessel so that at least a portion of the impurity is separated from the precursor. In some embodiments, at least a portion of the vapor containing at least one impurity is removed through an outlet of the vessel. In some embodiments, at least a portion of the vapor containing at least one impurity is removed through an outlet fluidly connected to a gas discharge line. In some embodiments, at least a portion of the vapor containing at least one impurity is removed through an outlet fluidly connected to a vacuum line (e.g., removed under vacuum). In some embodiments, at least a portion of the vapor containing at least one impurity is removed by opening a valve. In some embodiments, removing at least a portion of the vapor containing impurities from the vessel includes removing the vapor phase in the headspace of the vessel. In some embodiments, removing at least a portion of the vapor containing impurities from the vessel includes pumping at least a portion of the vapor out of the vessel. In some embodiments, removal and heating are performed simultaneously.

[0040]

[0044] In some embodiments, if the measured vapor pressure is above or within the setpoint vapor pressure, at least a portion of the vapor containing at least one impurity is removed from the container. In some embodiments, if the measured vapor pressure is above 1x the setpoint vapor pressure, at least a portion of the vapor containing at least one impurity is removed from the container. In some embodiments, if the measured vapor pressure is above 1.1x, 1.2x, 1.3x, 1.4x, or 1.5x the setpoint vapor pressure, at least a portion of the vapor containing at least one impurity is removed from the container. In some embodiments, if the measured vapor pressure is higher than the setpoint vapor pressure, the container may be further maintained at the heating temperature for 30 seconds to 7 days, or any range or subrange of 30 seconds to 7 days, before removing at least a portion of the vapor containing at least one impurity. In some embodiments, the container may be heated for an additional period of 1 minute to 7 days, 1 hour to 7 days, 4 hours to 7 days, 12 hours to 7 days, 24 hours to 7 days, 1 day to 7 days, 2 days to 7 days, 3 days to 7 days, 4 days to 7 days, 5 days to 7 days, 6 days to 7 days, 30 seconds to 6 days, 30 seconds to 5 days, 30 seconds to 4 days, 30 seconds to 3 days, 30 seconds to 2 days, 30 seconds to 1 day, 30 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 4 hours, 4 hours to 48 hours, 4 hours to 24 hours, 8 hours to 48 hours, 8 hours to 24 hours, 12 hours to 24 hours, 12 hours to 48 hours, 24 hours to 48 hours, or 36 hours to 48 hours.

[0041]

[0045] In some embodiments, the container is cooled so that the temperature after cooling is lower than the temperature at which the container was heated, before removing at least a portion of the vapor containing at least one impurity. In some embodiments, the container is cooled to a temperature sufficient to condense at least a portion of the vapor containing the precursor, before removing at least a portion of the vapor containing at least one impurity. In some embodiments, the container is cooled to ambient temperature before removing at least a portion of the vapor containing at least one impurity. In some embodiments, after cooling the container, the container is held at the cooling temperature for 30 seconds to 7 days, or any range or subrange between 30 seconds and 7 days, before removing at least a portion of the vapor containing at least one impurity. In some embodiments, the container may be heated for an additional period of 1 minute to 7 days, 1 hour to 7 days, 4 hours to 7 days, 12 hours to 7 days, 24 hours to 7 days, 1 day to 7 days, 2 days to 7 days, 3 days to 7 days, 4 days to 7 days, 5 days to 7 days, 6 days to 7 days, 30 seconds to 6 days, 30 seconds to 5 days, 30 seconds to 4 days, 30 seconds to 3 days, 30 seconds to 2 days, 30 seconds to 1 day, 30 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 4 hours, 4 hours to 48 hours, 4 hours to 24 hours, 8 hours to 48 hours, 8 hours to 24 hours, 12 hours to 24 hours, 12 hours to 48 hours, 24 hours to 48 hours, or 36 hours to 48 hours.

[0042]

[0046] In some embodiments, at least a portion of the vapor containing at least one impurity is removed while the container is heated. In some embodiments, at least a portion of the vapor containing at least one impurity is removed in real time in response to a signal from a controller. For example, in some embodiments, whenever the continuously monitored and / or measured vapor pressure exceeds the setpoint vapor pressure, the controller and / or processor transmits a signal to remove at least a portion of the vapor containing at least one impurity from the container.

[0043]

[0047] Removal is sufficient to remove all or at least part of at least one impurity from the container. In some embodiments, removal removes at least one impurity in sufficient quantity, so the start-up and / or pre-treatment period is shorter than the start-up and / or pre-treatment period for containers to which the method disclosed herein is not applied. In some embodiments, removal is sufficient to omit the start-up and / or pre-treatment step. In some embodiments, removal allows the precursor to be vaporized after performing the method disclosed herein and the vapor pressure to be measured, resulting in a measured vapor pressure of 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% of the vapor pressure of the precursor (e.g., if impurity-free). In some embodiments, after performing the method disclosed herein and then vaporizing the precursor, the precursor has a purity of at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99%, at least 99.9%, at least 99.99%, at least 99.999%, or at least 99.9999%, up to 100%.

[0044]

[0048] The method may include at least one thermal cycle. In some embodiments, the thermal cycle includes heating the container to a first temperature sufficient to vaporize at least a portion of at least one impurity, cooling the container to a second temperature, and removing at least a portion of the vapor containing at least one impurity. In some embodiments, the method includes 1 to 100 thermal cycles or more. For example, in some embodiments, the method includes thermal cycles 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, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, or 90 to 100. In some embodiments, at least one thermal cycle includes measuring vapor pressure and comparing the measured vapor pressure to a setpoint vapor pressure. In some embodiments, at least one thermal cycle includes transmitting one or more signals disclosed herein.

[0045]

[0049] In some embodiments, when the method is performed in real time, the container can be heated to a temperature sufficient to vaporize at least a portion of at least one impurity, and the vapor containing at least one impurity can be removed (e.g., without cooling). In some embodiments, the vapor containing at least one impurity is removed in response to a signal. A signal is transmitted when the measured vapor pressure, which is continuously monitored and / or measured in real time, reaches a vapor pressure equal to or greater than a setpoint. In some embodiments, the method is performed until the target vapor pressure is maintained or stabilized, thereby indicating that at least a portion of at least one impurity has been removed. In some embodiments, the target vapor pressure is the setpoint vapor pressure. Once maintained, the container is cooled and filled with an inert gas as needed.

[0046]

[0050] In some embodiments, the method may further include filling the container with an inert gas after removing at least a portion of the vapor containing at least one impurity. In some embodiments, the inert gas includes at least one of hydrogen, argon, helium, nitrogen, or any combination thereof. In some embodiments, the method may further include filling the container with one or more of the precursors disclosed herein before heating the container. In some embodiments, the method may further include vaporizing the precursors after removing at least a portion of the vapor containing at least one impurity and passing the precursors through a semiconductor processing tool. In some embodiments, after removing at least a portion of the vapor containing at least one impurity, the container has a lower content of at least one impurity than a control container that has not undergone at least one thermal cycle.

[0047]

[0051] Figure 2 is a schematic diagram of a system 200 for removing at least one impurity according to several embodiments. In some embodiments, the system 200 includes a vessel 202 containing a precursor and at least one impurity. In some embodiments, the system 200 includes at least one of a pressure sensor (not shown), a controller 204, a processor 206, a gas discharge line 208, a valve (not shown), or any combination thereof. In some embodiments, the pressure sensor is configured to measure the vapor pressure in the vessel 202. In some embodiments, the pressure sensor is configured to transmit a signal to at least one of the controller 204 and / or the processor 206. In some embodiments, the pressure sensor is configured to store the measured vapor pressure. In some embodiments, the processor 206 is configured to compare the measured vapor pressure with a setpoint vapor pressure. In some embodiments, the processor 206 is configured to transmit a signal to the controller 204 when the measured vapor pressure becomes equal to or greater than the setpoint vapor pressure. In some embodiments, the controller 204 is configured to activate a valve or to remove vapor containing at least one impurity from the vessel 202. In some embodiments, vapor containing at least one impurity is removed from the container 202 through the outlet of the container 202 and the gas discharge line 208. In some embodiments, the controller 204 and the processor 206 are the same.

[0048]

[0052] Figure 3 is a flowchart of Method 300 for removing at least one impurity according to several embodiments. As shown in Figure 3, in some embodiments, Method 300 for removing at least one impurity includes one or more of the following steps: obtaining a container 302, applying at least a vacuum to the container 304, heating the container to at least a first temperature 306, cooling the container to at least a second temperature 308, and removing at least a first vapor from the container 310. It will be understood that one or more of the above steps may be performed or not performed without departing from the scope of this disclosure. Furthermore, it will be understood that one or more of the above steps may be performed in any order. In some embodiments, Method 300 for removing at least one impurity is performed as a pretreatment step or as part of a startup process, for example. For example, in some embodiments, Method 300 for removing at least one impurity is performed before vaporizing a precursor for supply to a semiconductor tool. For example, in some embodiments, although not shown, method 300 further includes vaporizing at least a portion of the precursor, heating a container to a temperature sufficient to obtain a vaporized precursor, and passing the vaporized precursor through a semiconductor tool (e.g., a vapor deposition apparatus).

[0049]

[0053] In step 302, in some embodiments, the method 300 for removing at least one impurity includes obtaining a container.

[0050]

[0054] It will be understood that one or more of the containers disclosed herein can be used without departing from the scope of this disclosure. In some embodiments, the container is part of a container assembly. The container may define an internal area and may have an inlet and an outlet. The container may house one or more components located inside the container. For example, in some embodiments, the container includes at least one tray located within the internal area of ​​the container. The number of trays located inside the container may range from 1 to 100 trays, or any number between 1 and 100 trays. In some embodiments, at least one tray is placed on a structural support and loaded into the container. In some embodiments, at least one tray is pressed against the inner wall (or other inner surface) of the container. In some embodiments, at least one tray is bonded, fixed, or otherwise mechanically fixed to the container.

[0051]

[0055] The container may contain or be configured to contain a precursor. It will be understood that one or more of the precursors disclosed herein may be used without departing from the scope of this disclosure. For example, in some embodiments, the precursor includes, but is not limited to, an aluminum precursor, such as AlCl3. In some embodiments, the precursor includes, but is not limited to, a molybdenum precursor, such as MoO2Cl2. In some embodiments, the precursor is located on at least one tray. In some embodiments, the precursor is mounted on at least one tray. In some embodiments, the precursor is located on the inner surface of the container, the inner surface of the container being a surface other than the surface of at least one tray. In some embodiments, the precursor (e.g., located on each of at least one tray) may be present in the container in an amount sufficient to vaporize.

[0052]

[0056] At least one tray may be composed of at least one of the following: carbon material, metallic material, ceramic material, polymer material, or any combination thereof. For example, in some embodiments, at least one tray includes at least one metal, metallic alloy, graphite (e.g., high-density graphite), pyrolytic carbon, or any combination thereof. In some embodiments, at least one tray includes stainless steel. In some embodiments, at least one tray includes graphite. In some embodiments, at least one tray includes graphite and a pyrolytic carbon coating positioned on the graphite.

[0053]

[0057] At least one impurity may be located within the internal region of the container. In some embodiments, at least one impurity is present in at least one tray. In some embodiments, at least one impurity is present in the precursor. In some embodiments, at least one impurity is present on the inner surface of the container. It will be understood that the presence of one or more of the impurities disclosed herein in the container does not constitute a departure from the scope of this disclosure. For example, in some embodiments, at least one impurity includes a hydrated compound, such as, among other things, a hydrated aluminum compound, a hydrated molybdenum compound, or any combination thereof. In some embodiments, at least one impurity includes water. In some embodiments, water may exist in the form of water (i.e., water moisture). In some embodiments, water may exist in the form of liquid water. In some embodiments, water may exist in the form of water vapor. In some embodiments, at least one impurity exists in such a form that when at least one impurity vaporizes (e.g., when the container is heated), at least one impurity (or at least a portion thereof) reacts with the precursor to form an undesirable compound, such as a contaminant.

[0054]

[0058] Where a container is part of a container assembly, the container assembly may include additional components, but this will not deviate from the scope of this disclosure. Non-limiting examples of additional components include, for example, at least one of a mass flow meter, a volumetric flow meter, a pressure sensor, a temperature sensor, a valve, a valve assembly, a controller, a processor, other components disclosed herein, or any combination thereof.

[0055]

[0059] In step 304, in some embodiments, the method 300 for removing at least one impurity includes applying at least a vacuum to the container.

[0056]

[0060] The container can be configured to control the pressure. In some embodiments, the application includes depressurizing the container. In some embodiments, the application includes pumping the container to reduce the pressure inside the container. In some embodiments, this process includes pumping the container to reduce the pressure inside the container to less than 0.8 times the setpoint vapor pressure. In some embodiments, the application includes pumping the container to reduce the pressure inside the container to less than 0.7 times, 0.6 times, 0.5 times, 0.4 times, 0.3 times, 0.2 times, or 0.1 times the setpoint vapor pressure. In some embodiments, the application includes pumping the container for a certain period of time to reduce the pressure inside the container. In some embodiments, the set time is 5 seconds to 120 seconds, or any range or subrange between 5 seconds and 120 seconds. In some embodiments, the set time is 5 to 110 seconds, 5 to 100 seconds, 5 to 90 seconds, 5 to 80 seconds, 5 to 70 seconds, 5 to 60 seconds, 5 to 50 seconds, 5 to 40 seconds, 5 to 30 seconds, 5 to 20 seconds, 5 to 10 seconds, 10 to 120 seconds, 20 to 120 seconds, 30 to 120 seconds, 40 to 120 seconds, 50 to 120 seconds, 60 to 120 seconds, 70 to 120 seconds, 80 to 120 seconds, 90 to 120 seconds, 100 to 120 seconds, or 110 to 120 seconds.

[0057]

[0061] In some embodiments, the application includes depressurizing the vessel. In some embodiments, the application includes pumping the vessel to reduce the pressure inside the vessel. In some embodiments, the application includes reducing the pressure inside the vessel. In some embodiments, the application includes connecting a vacuum pump to the vessel. In some embodiments, the application includes operating the vacuum pump connected to the vessel. In some embodiments, the application includes reducing the pressure inside the vessel to a reference pressure. In some embodiments, the application includes connecting a vacuum line to the vessel. The vacuum line may be configured to apply a vacuum to the vessel. In some embodiments, the pumping speed may be controlled by a butterfly valve. It will be understood that other mechanisms for controlling the pressure inside a vessel may be employed in the present invention without departing from the scope of this disclosure.

[0058]

[0062] The reference pressure can include pressures between 1mTorr and 1000mTorr, or any range or subrange between 1mTorr and 1000mTorr. For example, in some embodiments, the reference pressure can be 1mTorr to 900mTorr, 1mTorr to 800mTorr, 1mTorr to 700mTorr, 1mTorr to 600mTorr, 1mTorr to 500mTorr, 1mTorr to 400mTorr, 1mTorr to 300mTorr, 1mTorr to 200mTorr, 1mTorr to 100mTorr, 1mTorr to 90mTorr, 1mTorr to 80mTorr, 1mTorr to 70mTorr, 1mTorr to 60mTorr, 1mTorr to 50mTorr, 1mTorr These pressures are approximately 40mTorr, 1mTorr~30mTorr, 1mTorr~20mTorr, 1mTorr~10mTorr, 1mTorr~50mTorr, 100mTorr~1000mTorr, 200mTorr~1000mTorr, 300mTorr~1000mTorr, 400mTorr~1000mTorr, 500mTorr~1000mTorr, 600mTorr~1000mTorr, 700mTorr~1000mTorr, 800mTorr~1000mTorr, or 900mTorr~1000mTorr.

[0059]

[0063] The container may be kept under vacuum, reference pressure, or reduced pressure for a period of 30 seconds to 7 days, or any range or subrange of 30 seconds and 7 days. In some embodiments, the container may be kept under vacuum for a period of 1 minute to 7 days, 1 hour to 7 days, 12 hours to 7 days, 24 hours to 7 days, 1 day to 7 days, 2 days to 7 days, 3 days to 7 days, 4 days to 7 days, 5 days to 7 days, 6 days to 7 days, 30 seconds to 6 days, 30 seconds to 5 days, 30 seconds to 4 days, 30 seconds to 3 days, 30 seconds to 2 days, 30 seconds to 1 day, 30 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 4 hours, 1 hour to 12 hours, 1 hour to 8 hours, 1 hour to 6 hours, 8 hours to 48 hours, 8 hours to 24 hours, 12 hours to 24 hours, 12 hours to 48 hours, 24 hours to 48 hours, or 36 hours to 48 hours.

[0060]

[0064] In step 306, in some embodiments, the method 300 for removing at least one impurity includes heating the container to at least a first temperature.

[0061]

[0065] The container can be configured to control its temperature. The temperature of the container can be controlled by any suitable method. In some embodiments, a thermal jacket for heating and / or cooling is used around the container. In some embodiments, a ribbon heater is wrapped around the container. In some embodiments, a block heater having a shape that covers at least a large portion of the outer surface of the container is used to heat the container. In some embodiments, a resistance heater is used to heat the container. In some embodiments, a lamp heater is used to heat the container. 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 container. In some embodiments, heating is performed by infrared or other radiant energy irradiated onto the container. In some embodiments, the container is cooled by a fluid, a fan, a direct thermoelectric device, or any combination thereof. It will be understood that other heating and / or cooling devices and assemblies, 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.

[0062]

[0066] The container may be heated to a temperature and / or for a period of time sufficient to vaporize at least a portion of at least one impurity and obtain a first vapor (e.g., impurity vapor) containing at least one impurity. In some embodiments, at least a portion of the precursor is vaporized, and the resulting first vapor contains the precursor (e.g., precursor vapor). In some embodiments, the container is heated to a temperature and / or for a period of time sufficient to vaporize at least one impurity, while simultaneously minimizing the amount of precursor vaporized. In some embodiments, the amount of precursor vaporized is controlled by controlling the temperature and / or pressure in the container to vaporize at least one impurity without vaporizing the precursor, or to minimize the amount of precursor vaporized. In some embodiments, the container is heated to a temperature and / or for a period of time sufficient to complete the reaction between the precursor and water or other substances. In some embodiments, completing the reaction reduces the likelihood of it proceeding in the reverse direction. In some embodiments, completing the reaction generates all undesirable by-products, and the purity of the precursor can be improved by removing the generated by-products from the container. In some embodiments, the reaction does not proceed to completion.

[0063]

[0067] The container can be heated to a first temperature of 50°C to 300°C, or to any range or subrange between 50°C and 300°C. In some embodiments, the container is heated to a first temperature of 50°C to 290°C, 50°C to 280°C, 50°C to 270°C, 50°C to 260°C, 50°C to 250°C, 50°C to 240°C, 50°C to 230°C, 50°C to 220°C, 50°C to 210°C, 50°C to 200°C, 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, or 50°C to 60°C. In some embodiments, the container is suitable for temperatures of 60°C to 300°C, 70°C to 300°C, 80°C to 300°C, 90°C to 300°C, 100°C to 300°C, 100°C to 250°C, 100°C to 200°C, 110°C to 300°C, 120°C to 300°C, 130°C to 300°C, 140°C to 300°C, 150°C to 300°C, 160°C to 300°C, It is heated to a first temperature of 170°C-300°C, 180°C-300°C, 190°C-300°C, 200°C-300°C, 210°C-300°C, 220°C-300°C, 230°C-300°C, 240°C-300°C, 250°C-300°C, 260°C-300°C, 270°C-300°C, 280°C-300°C, or 290°C-300°C.

[0064]

[0068] The container can be heated for a period of time from 30 seconds to 7 days, or any range or subrange of 30 seconds and 7 days. In some embodiments, the container can be heated for a period of time from 1 minute to 7 days, 1 hour to 7 days, 12 hours to 7 days, 24 hours to 7 days, 1 day to 7 days, 2 days to 7 days, 3 days to 7 days, 4 days to 7 days, 5 days to 7 days, 6 days to 7 days, 30 seconds to 6 days, 30 seconds to 5 days, 30 seconds to 4 days, 30 seconds to 3 days, 30 seconds to 2 days, 30 seconds to 1 day, 30 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 4 hours, 1 hour to 12 hours, 1 hour to 8 hours, 1 hour to 6 hours, 8 hours to 48 hours, 8 hours to 24 hours, 12 hours to 24 hours, 12 hours to 48 hours, 24 hours to 48 hours, or 36 hours to a maximum of 48 hours.

[0065]

[0069] In step 308, in some embodiments, the method 300 for removing at least one impurity includes cooling the container to at least a second temperature.

[0066]

[0070] The container may be cooled to a second temperature for a period of time sufficient to separate at least one impurity from the precursor. In some embodiments, if the first vapor contains the precursor, the cooling is sufficient to condense at least a portion of the precursor vapor and separate the precursor from at least one impurity. In some embodiments, if the first vapor contains the precursor, the cooling is sufficient to separate at least a portion of the precursor from at least one impurity. In some embodiments, the second temperature is sufficient to condense the precursor vapor without condensing the impurity vapor, or at least with a minimal amount of impurity vapor condensed.

[0067]

[0071] The second temperature may be lower than the first temperature. For example, in some embodiments, the container may be cooled to a second temperature between 0°C and 150°C, or to any range or subrange between 0°C and 150°C. In some embodiments, the container is cooled to a temperature of 10°C to 150°C, 20°C to 150°C, 30°C to 150°C, 40°C to 150°C, 50°C to 150°C, 60°C to 150°C, 70°C to 150°C, 80°C to 150°C, 90°C to 150°C, 100°C to 150°C, 110°C to 150°C, 120°C to 150°C, 130°C to 150°C, 140°C to 150°C, 0°C to 140°C, 0°C to 130°C, 0°C to 120°C, 0°C to 110°C, 0°C to 100°C, 0°C to 90°C, 0°C to 80°C, 0°C to 70°C, 0°C to 60°C, 0°C to 50°C, 0°C to 40°C, 0°C to 30°C, 0°C to 20°C, or 0°C to 10°C.

[0068]

[0072] In step 310, in some embodiments, the method 300 for removing at least one impurity includes removing at least one first vapor from the container.

[0069]

[0073] In some embodiments, at least a portion of the first vapor containing at least one impurity is separated from the precursor by removing at least a portion of the first vapor containing at least one impurity from the vessel. In some embodiments, at least a portion of the first vapor containing at least one impurity is removed through an outlet of the vessel. In some embodiments, at least a portion of the first vapor containing at least one impurity is removed through an outlet fluidly connected to a gas discharge line. In some embodiments, at least a portion of the first vapor containing at least one impurity is removed through an outlet fluidly connected to a vacuum line (e.g., removed under vacuum). In some embodiments, at least a portion of the first vapor containing at least one impurity is removed by opening a valve. In some embodiments, removing at least a portion of the first vapor containing impurities from the vessel includes removing the vapor phase in the headspace of the vessel.

[0070]

[0074] In some embodiments, if the measured vapor pressure is above or below the setpoint vapor pressure, at least a portion of the first vapor containing at least one impurity is removed from the container. In some embodiments, before removing at least a portion of the first vapor containing at least one impurity, the container is cooled to a temperature lower than the temperature at which it was heated. In some embodiments, before removing at least a portion of the first vapor containing at least one impurity, the container is cooled to a temperature sufficient to condense at least a portion of the first vapor containing the precursor. In some embodiments, at least a portion of the first vapor containing at least one impurity is removed while the container is being heated. In some embodiments, at least a portion of the first vapor containing at least one impurity is removed in real time in response to a signal from the controller. For example, in some embodiments, whenever the continuously monitored and / or measured measured vapor pressure exceeds the setpoint vapor pressure, the controller and / or processor transmit a signal to remove at least a portion of the vapor containing at least one vapor from the container.

[0071]

[0075] The first vapor may be removed from the container such that, when the precursor is vaporized (or subsequently vaporized) at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 20% of the theoretical vapor pressure of the precursor at the purification temperature. For example, in some embodiments, the first vapor is removed from the container such that, when the precursor is vaporized at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or 0.1% of the theoretical vapor pressure of the precursor at the purification temperature. In some embodiments, after performing the method disclosed herein and then vaporizing the precursor, the precursor has a purity of at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99%, at least 99.9%, at least 99.99%, at least 99.999%, or at least 99.9999%, up to 100%.

[0072]

[0076] In some embodiments, the method 300 for removing at least one impurity does not include the step of removing the precursor from at least one tray and refilling the precursor into at least one tray. In some embodiments, the method 300 for removing at least one impurity does not include the step of exposing an internal region of a container assembly to the ambient environment (e.g., ambient temperature, ambient pressure, or any combination thereof) or the ambient environment, which may introduce contaminants and / or impurities into the container. In some embodiments, the method 300 for removing at least one impurity does not include the step of flowing a second vapor containing the precursor from the container to a semiconductor manufacturing apparatus (e.g., when the method is not performed in a semiconductor manufacturing facility).

[0073]

[0077] In some embodiments, method 300 includes obtaining a container assembly. In some embodiments, the container assembly includes a container defining an internal region. In some embodiments, the container assembly includes at least one tray located within the internal region of the container. In some embodiments, the container assembly includes an aluminum precursor located on at least one tray. In some embodiments, the container assembly includes at least one impurity located within the internal region of the container, the at least one impurity being water. In some embodiments, the water is located on at least one of the at least one tray, the aluminum precursor, or any combination thereof. In some embodiments, method 300 includes heating the container to a first temperature sufficient to vaporize at least a portion of the at least one impurity to obtain a first vapor containing the at least one impurity. In some embodiments, when vaporizing the aluminum precursor at the purification temperature to obtain a vaporized precursor, method 300 includes removing the first vapor from the container such that the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature.

[0074]

[0078] In some embodiments, method 300 includes obtaining a container assembly. In some embodiments, the container assembly includes a container defining an internal region. In some embodiments, the container assembly includes at least one tray located within the internal region of the container. In some embodiments, the container assembly includes a molybdenum precursor located on at least one tray. In some embodiments, the container assembly includes at least one impurity located within the container. In some embodiments, the at least one impurity includes water. In some embodiments, the water is located on at least one of the at least one tray, the molybdenum precursor, or any combination thereof. In some embodiments, method 300 includes heating the container to a first temperature sufficient to vaporize at least a portion of the at least one impurity to obtain a first vapor containing at least one impurity. In some embodiments, method 300 includes removing the first vapor from the container such that, when the molybdenum precursor is vaporized at the purification temperature to obtain a vaporized precursor, the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature.

[0075]

[0079] Figure 4 is a schematic cross-sectional view of a container assembly according to several embodiments. The container 400 houses a tray assembly 402 within an internal region 404 of the container 400. The internal region 404 has an inner wall surface 406. The tray assembly 402 includes trays 408, each configured to contain a vaporizable precursor. Each tray 408 of the tray assembly 402 includes a portion 410 configured to be in contact (e.g., thermal contact, physical contact, etc.) with the inner wall surface 406 of the container 400. Surface contact of the portion 410 with the inner wall surface 406 facilitates heat transfer from the container 400 to each tray 408, and consequently, heat transfer from each tray 408 to the vaporizable precursor on each tray 408. Various fluid channels are provided within the internal region 404 of the container 400 so that the fluid can optionally flow upward, downward, or both within the container 400. The container 400 is shown to have a generally cylindrical inner chamber. However, it will be understood that the internal region 404 of the ampoule may have other shapes without departing from the scope of this disclosure.

[0076]

[0080] One or more embodiments disclosed herein may be combined without departing from the scope or spirit of this disclosure.

[0077]

[0081] manner

[0082] 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 It is a method, At least one thermal cycle, A container containing a precursor and at least one impurity is heated to a certain temperature for a period of time sufficient to vaporize at least a portion of the at least one impurity. To obtain the measured vapor pressure, the vapor pressure inside the container is measured and compared with the setpoint vapor pressure. When the measured vapor pressure is above or within the setpoint vapor pressure, the method involves removing at least a portion of the vapor containing at least one impurity from the container. A method comprising at least one thermal cycle, which includes removing at least a portion of the vapor containing at least one impurity from a container, such that when the vapor containing at least one impurity is removed, at least 90% of the at least one impurity is removed from the container. Appearance 2 The method according to embodiment 1, wherein the precursor is a solid precursor containing at least one impurity. Appearance 3 The method according to embodiment 1 or 2, wherein the container is heated to a temperature of 50°C to 300°C. Pattern 4 The method according to any one of embodiments 1 to 3, wherein the container is heated to a temperature of 100°C to 250°C. Appearance 5 The method according to any one of embodiments 1 to 4, wherein the container is heated to a temperature of 100°C to 200°C. Appearance 6 The method according to any one of embodiments 1 to 5, wherein the container is maintained at the above temperature for a period of 30 seconds to 7 days. Appearance 7 The method according to any one of embodiments 1 to 6, wherein the container is maintained at the above temperature for a period of 4 to 48 hours. Appearance 8 The method according to any one of embodiments 1 to 7, wherein the container is maintained at the above temperature for a period of 4 to 24 hours. Appearance 9 The method according to any one of embodiments 1 to 8, wherein the setpoint vapor pressure is greater than the vapor pressure of the precursor. Appearance 10 The method according to any one of embodiments 1 to 9, wherein the setpoint vapor pressure is within the vapor pressure range, and the lower limit of the vapor pressure range is a pressure greater than the vapor pressure of the precursor. Appearance 11 The method according to any one of embodiments 1 to 10, further comprising cooling the container before removing at least a portion of the vapor containing at least one impurity from the container. Appearance 12 The method according to any one of embodiments 1 to 11, comprising 1 to 100 thermal cycles. Appearance 13 The method according to any one of embodiments 1 to 12, wherein when vapor containing at least one impurity is removed from the container, at least 99% of the at least one impurity is removed from the container. Appearance 14 It is a method, A container containing a precursor and at least one impurity is heated to a temperature sufficient to vaporize at least a portion of the at least one impurity, To obtain multiple vapor pressure measurements, the vapor pressure inside the container is measured over time, and these multiple measured vapor pressures are compared with the setpoint vapor pressure. When at least one of several measured vapor pressures is greater than the setpoint vapor pressure, vapor containing at least one impurity is removed from the container. A method comprising removing vapor containing at least one impurity from a container, wherein at least 90% of the at least one impurity is removed from the container when the vapor containing at least one impurity is removed from the container. Appearance 15 The method according to embodiment 14, wherein vapor containing at least one impurity is removed from the container while the container is under heating. Appearance 16 The method according to embodiment 14 or 15, further comprising cooling the container when at least two of the multiple measured vapor pressures change by less than 5% over time. Appearance 17 The method according to embodiment 16, further comprising filling the container with an inert gas after cooling the container. Appearance 18 The method according to any one of embodiments 14 to 17, wherein the container is heated to a temperature of 50°C to 300°C. Appearance 19 The method according to any one of embodiments 14 to 18, wherein the container is maintained at the temperature for a period of 30 seconds to 7 days. Appearance 20 The method according to any one of embodiments 14 to 19, wherein when vapor containing at least one impurity is removed from the container, at least 99% of the at least one impurity is removed from the container. Appearance 21 It is a method, The objective is to obtain a container assembly, The container assembly is A container that defines the internal region. At least one tray located in the internal region of the container, A precursor located on at least one tray, and at least one impurity To obtain a container assembly including, Heating the container to a first temperature sufficient to vaporize at least a portion of at least one impurity and obtain a first vapor containing at least one impurity, When obtaining a vaporized precursor by vaporizing the precursor at the purification temperature, the first vapor is removed from the container so that the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature. A method that includes this. Appearance 22 The method according to embodiment 21, wherein the precursor comprises an aluminum precursor. Appearance 23 The method according to embodiment 22, wherein the aluminum precursor comprises AlCl3. Pattern 24 At least one impurity, Contains hydrated aluminum compounds, The method according to embodiment 22, wherein the hydrated aluminum compound is positioned on the aluminum precursor before heating. Appearance 25 The method according to embodiment 21, wherein the precursor comprises a molybdenum precursor. Appearance 26 The method according to embodiment 25, wherein the molybdenum precursor comprises MoO2Cl2. Appearance 27 At least one impurity, Contains water, The method according to embodiment 25, wherein water is placed on the molybdenum precursor before heating. Appearance 28 At least one impurity, Contains water, The method according to any one of embodiments 21 to 27, wherein water is placed in at least one tray before heating. Appearance 29 The method according to any one of embodiments 21 to 28, wherein at least one tray contains at least one of graphite, pyrolytic carbon, or any combination thereof. Appearance 30 The method according to any one of embodiments 21 to 29, wherein at least one tray comprises a metal alloy. Appearance 31 The method according to any one of embodiments 21 to 30, wherein the heating is performed at a temperature of 50°C to 300°C. Appearance 32 The method according to any one of embodiments 21 to 31, wherein heating is performed at a pressure of 1 mTorr to 1000 mTorr. Appearance 33 The method further includes cooling the container from a first temperature to a second temperature after heating and before removal, The method according to any one of embodiments 21 to 32, wherein the second temperature is lower than the first temperature. Appearance 34 The method according to any one of embodiments 21 to 33, further comprising applying a vacuum sufficient to reduce the pressure inside the container before heating. Appearance 35 The method according to any one of embodiments 21 to 34, wherein the step of removing the precursor from at least one tray and refilling the precursor onto at least one tray is not included. Appearance 36 The method according to any one of embodiments 21 to 35, which does not include the step of exposing the internal region of the container assembly to the surrounding environment. Appearance 37 The method according to any one of embodiments 21 to 36, wherein the step of flowing a second vapor containing a precursor from a container to a semiconductor tool is not included. Appearance 38 It is a method, The objective is to obtain a container assembly, The container assembly is A container that defines the internal region. At least one tray located in the internal region of the container, Aluminum precursors located on at least one tray, and At least one impurity, including water, Water is present in at least one of the trays, aluminum precursors, or any combination thereof, and contains at least one impurity including water. To obtain a container assembly that includes, Heating the container to a first temperature sufficient to vaporize at least a portion of at least one impurity and obtain a first vapor containing at least one impurity, When obtaining a vaporized precursor by vaporizing the precursor at the purification temperature, the first vapor is removed from the container so that the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature. A method that includes this. Appearance 39 It is a method, The objective is to obtain a container assembly, The container assembly is A container that defines the internal region. At least one tray located in the internal region of the container, A molybdenum precursor located on at least one tray, and At least one impurity, including water, Water is present in at least one of the trays, molybdenum precursors, or any combination thereof, and at least one impurity containing water. To obtain a container assembly that includes, Heating the container to a first temperature sufficient to vaporize at least a portion of at least one impurity and obtain a first vapor containing at least one impurity, When obtaining a vaporized precursor by vaporizing a molybdenum precursor at the purification temperature, the first vapor is removed from the container so that the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature. A method that includes this. Pattern 40 A container assembly, The container body that defines the internal region, A tray located in the internal area of ​​the container body, and Precursor located on the tray Includes, The precursor comprises at least one of an aluminum precursor, a molybdenum precursor, or any combination thereof. When a vaporized precursor is obtained by vaporizing the precursor at the purification temperature, the vapor pressure of the vaporized precursor is within 10% of the theoretical vapor pressure of the precursor at the purification temperature. Container assembly.

[0078] Example 1

[0083] An AlCl3 precursor containing impurities was filled into an ampoule and subjected to a first thermal cycle. Specifically, the ampoule was heated to 140°C and held at that temperature for 8 hours. When the vapor pressure inside the ampoule exceeded the theoretical vapor pressure of the precursor under the measurement conditions, the ampoule was cooled, and the amount of impurities in the headspace was measured by FTIR, shown in Figure 5 as code 502 (approximately 100~10 Torr). Next, the headspace of the ampoule was evacuated to remove the vapor containing impurities. The ampoule was subjected to a second thermal cycle. The amount of impurities present in the headspace was measured again by FTIR and reported in Figure 5 as code 504 (<1 Torr).

[0079] Example 2

[0084] The MoO2Cl2 precursor containing impurities was filled into ampoules and subjected to a first thermal cycle. Specifically, the ampoules were heated to 140°C and held at that temperature for 4–24 hours. If the measured pressure inside the ampoule exceeded 1–1.5 times the theoretical vapor pressure of the precursor under the measurement conditions, the ampoule's headspace was pumped for 5–120 seconds to reduce the pressure and remove impurity-containing vapor. After waiting 30–500 seconds, the pressure inside the ampoule was measured again. This procedure was repeated until the measured pressure inside the ampoule was within 1–1.2 times the theoretical vapor pressure of the precursor under the measurement conditions. The ampoules were then cooled, and the amount of impurities present in the headspace was measured using FTIR and a pressure transducer. If the desired purity was not obtained, the ampoules were subjected to further heat treatment until a precursor with a purity of 99% or higher was obtained.

[0080] Example 3

[0085] MoCl5 precursors containing impurities were filled into ampoules and subjected to a first thermal cycle. Specifically, the ampoules were heated to 140°C and held at that temperature for 4–24 hours. If the measured pressure inside the ampoule exceeded 1–1.5 times the theoretical vapor pressure of the precursor under the measurement conditions, the ampoule's headspace was pumped for 5–120 seconds to reduce the pressure and remove impurity-containing vapors. After waiting 30–500 seconds, the pressure inside the ampoule was measured again. This procedure was repeated until the measured pressure inside the ampoule was within 1–1.2 times the theoretical vapor pressure of the precursor under the measurement conditions. The ampoules were then cooled, and the amount of impurities present in the headspace was measured using FTIR and a pressure transducer. If the desired purity was not obtained, the ampoules were subjected to further heat treatment until a precursor with a purity of 99% or higher was obtained.

[0081] Example 4

[0086] A WCl5 precursor containing impurities was filled into ampoules and subjected to a first thermal cycle. Specifically, the ampoules were heated to 140°C and held at that temperature for 4–24 hours. If the measured pressure inside the ampoule exceeded 1–1.5 times the theoretical vapor pressure of the precursor under the measurement conditions, the ampoule's headspace was pumped for 5–120 seconds to reduce the pressure and remove impurity-containing vapor. After waiting 30–500 seconds, the pressure inside the ampoule was measured again. This procedure was repeated until the measured pressure inside the ampoule was within 1–1.2 times the theoretical vapor pressure of the precursor under the measurement conditions. The ampoules were then cooled, and the amount of impurities present in the headspace was measured using FTIR and a pressure transducer. If the desired purity was not obtained, the ampoules were subjected to further heat treatment until a precursor with a purity of 99% or higher was obtained.

[0082] Example 5

[0087] An AlCl3 precursor containing impurities was filled into an ampoule and subjected to a first thermal cycle. Specifically, the ampoule was heated to 140°C and held at that temperature for 4–24 hours. If the measured pressure inside the ampoule exceeded 1–1.5 times the theoretical vapor pressure of the precursor under the measurement conditions, the ampoule was maintained at the heated temperature for a further 4–24 hours. The pressure was measured again, and if the measured pressure did not decrease by at least 0.1 times the theoretical vapor pressure, the ampoule was cooled and held at the cooled temperature for 4–24 hours. Next, the headspace of the ampoule was evacuated to remove impurity-containing vapor. The amount of impurities present in the headspace was measured using FTIR and a pressure transducer. If the desired purity was not obtained, the ampoule was subjected to further heat treatment until a precursor with a purity of 99% or higher was obtained.

[0083]

[0088] 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. It is a method, At least one thermal cycle, A container containing a precursor and at least one impurity is heated to a temperature sufficient for a period of time to vaporize at least a portion of the at least one impurity. To obtain the measured vapor pressure, the vapor pressure inside the container is measured and compared with the setpoint vapor pressure. When the measured vapor pressure is above or within the setpoint vapor pressure, the method involves removing at least a portion of the vapor containing at least one impurity from the container. When vapor containing at least one impurity is removed from the container, at least 90% of the at least one impurity is removed from the container, and at least a portion of the vapor containing at least one impurity is removed from the container. A method comprising at least one thermal cycle including the following.

2. The method according to claim 1, wherein the precursor is a solid precursor containing at least one impurity.

3. The method according to claim 1, wherein the container is heated to a temperature of 50°C to 300°C.

4. The method according to claim 1, wherein the container is heated to a temperature of 100°C to 250°C.

5. The method according to claim 1, wherein the container is heated to a temperature of 100°C to 200°C.

6. The method according to claim 1, wherein the container is maintained at a certain temperature for a period of 30 seconds to 7 days.

7. The method according to claim 1, wherein the container is maintained at a certain temperature for a period of 4 to 48 hours.

8. The method according to claim 1, wherein the container is maintained at a certain temperature for a period of 4 to 24 hours.

9. The method according to claim 1, wherein the setpoint vapor pressure is greater than the vapor pressure of the precursor.

10. The method according to claim 1, wherein the setpoint vapor pressure is within the vapor pressure range, and the lower limit of the vapor pressure range is a pressure greater than the vapor pressure of the precursor.

11. The method according to claim 1, further comprising cooling a container before removing at least a portion of the vapor containing at least one impurity from the container.

12. The method according to claim 1, comprising 1 to 100 thermal cycles.

13. The method according to claim 1, wherein when vapor containing at least one impurity is removed from the container, at least 99% of the at least one impurity is removed from the container.

14. It is a method, Heating a container containing a precursor and at least one impurity to a temperature sufficient to vaporize at least a portion of the at least one impurity, To obtain multiple vapor pressure measurements, the vapor pressure inside the container is measured over time, and these multiple measured vapor pressures are compared with the setpoint vapor pressure. When at least one of the multiple measured vapor pressures is greater than the setpoint vapor pressure, vapor containing at least one impurity is removed from the container. When vapor containing at least one impurity is removed from the container, at least 90% of the at least one impurity is removed from the container. A method that includes this.

15. The method according to claim 14, wherein vapor containing at least one impurity is removed from the container while the container is under heating.

16. The method according to claim 14, further comprising cooling the container when at least two of a plurality of measured vapor pressures change by less than 5% over time.

17. The method according to claim 16, further comprising filling the container with an inert gas after cooling the container.

18. The method according to claim 14, wherein the container is heated to a temperature of 50°C to 300°C.

19. The method according to claim 14, wherein the container is maintained at the temperature for a period of 30 seconds to 7 days.

20. The method according to claim 14, wherein when vapor containing at least one impurity is removed from the container, at least 99% of the at least one impurity is removed from the container.

Images