Systems and methods for controlling precursor delivery

Abstract

Systems and methods for controlling precursor delivery. The systems and methods may include a precursor delivery vessel in fluid communication with a gas flow line. The precursor delivery vessel may include at least one tray containing vaporizable precursors. An amount of thermal energy may be provided to the at least one tray in an amount sufficient to vaporize the vaporizable precursors. The vaporized precursors may be distributed from the precursor delivery vessel to the gas flow line. The amount of thermal energy provided to the at least one tray may be adjusted to be sufficient to maintain a pressure of the vaporized precursors in the gas flow line within a pressure range.

Description

[Technical field]

[0001] The present disclosure relates to systems and methods for controlling the delivery of precursors, such as, but not limited to, vapor precursors.

[0002] Priority This document claims priority to U.S. Provisional Patent Application No. 63 / 322,195, filed March 21, 2022, which priority document is incorporated herein by reference. [Background technology]

[0003] Conventional vapor delivery systems are unable to meet the performance specifications of semiconductor processing tools and the like. Summary of the Invention

[0004] Some embodiments relate to a method for controlling precursor delivery. In some embodiments, the method includes at least one of the following steps: obtaining a precursor delivery vessel housing vaporizable precursors on at least one tray; providing a sufficient amount of thermal energy to the at least one tray to vaporize the vaporizable precursors; distributing the vaporized precursor from the precursor delivery vessel to a gas flow line; and adjusting the amount of thermal energy provided to the at least one tray to be sufficient to maintain a pressure of the vaporized precursor in the gas flow line within a pressure range. In some embodiments, the at least one tray is provided with a thermal energy of 15 Wm -1 K -1 The thermal conductivity of the material is preferably greater than 1.

[0005] In some embodiments, the vaporizable precursor comprises at least one of a metal oxyhalide, a metal halide, or any combination thereof.

[0006] In some embodiments, the vaporizable precursor comprises at least one of MoO2Cl2, MoOCl4, WO2Cl2, WOCl4, or any combination thereof.

[0007] In some embodiments, at least one tray comprises at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof.

[0008] In some embodiments, at least one tray is rated to 25 Wm -1 K -1 ~470Wm -1 K -1 The material includes a material having a thermal conductivity of

[0009] In some embodiments, the pressure range includes pressures ranging from 100 Torr to 750 Torr.

[0010] In some embodiments, the pressure range includes a pressure tolerance ranging from ±1 Torr to ±5 Torr.

[0011] In some embodiments, the vaporized precursor is generated at a temperature ranging from 100°C to 250°C.

[0012] In some embodiments, the flow rate of the vaporized precursor in the gas flow lines is in the range of 50 sccm to 600 sccm.

[0013] In some embodiments, the vaporized precursor exhibits a non-linear response to changes in temperature when the vaporized precursor has a pressure within the pressure range.

[0014] Some embodiments relate to a system for controlling precursor delivery. In some embodiments, the system includes a precursor delivery vessel that contains vaporizable precursors on at least one tray. In some embodiments, the at least one tray is heated to 15 Wm -1 K -1In some embodiments, the system includes a heater configured to provide an amount of thermal energy to the at least one tray to generate a vaporized precursor from a vaporizable precursor. The system includes a gas flow line configured to deliver the vaporized precursor from a precursor delivery vessel to a semiconductor processing tool. In some embodiments, the system includes a controller configured to adjust an amount of thermal energy provided to the at least one tray sufficient to maintain a pressure of the vaporized precursor in the gas flow line within a pressure range.

[0015] In some embodiments, the vaporizable precursor comprises at least one of a metal oxyhalide, a metal halide, or any combination thereof.

[0016] In some embodiments, the vaporizable precursor comprises at least one of MoO2Cl2, MoOCl4, WO2Cl2, WOCl4, or any combination thereof.

[0017] In some embodiments, at least one tray comprises at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof.

[0018] In some embodiments, at least one tray is rated to 25 Wm -1 K -1 ~470Wm -1 K -1 The material includes a material having a thermal conductivity of

[0019] In some embodiments, the pressure range includes pressures ranging from 100 Torr to 750 Torr.

[0020] In some embodiments, the pressure range includes a pressure tolerance ranging from ±1 Torr to ±5 Torr.

[0021] In some embodiments, the vaporized precursor is generated at a temperature ranging from 100°C to 250°C.

[0022] In some embodiments, the flow rate of the vaporized precursor in the gas flow lines is in the range of 50 sccm to 600 sccm.

[0023] In some embodiments, the vaporized precursor exhibits a non-linear response to changes in temperature when the vaporized precursor has a pressure within the pressure range. [Brief description of the drawings]

[0024] Some embodiments of the present disclosure are herein described, by way of example only, with reference to the accompanying drawings. With particular reference now to the drawings in detail, it is emphasized that the illustrated embodiments are by way of example and for illustrative purposes of embodiments of the present disclosure. In this regard, the description made with the drawings will make apparent to those skilled in the art how embodiments of the present disclosure may be practiced. [Figure 1] 1 is a flowchart of a method for controlling precursor delivery, according to some embodiments. [Diagram 2] FIG. 1 is a schematic diagram of a system for controlling precursor delivery, according to some embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Among these disclosed advantages and improvements, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Although detailed embodiments of the present disclosure are disclosed herein, it should be understood that the embodiments of the present disclosure are merely exemplary of the present disclosure, which may be embodied in various forms. Moreover, each of the examples given with respect to the various embodiments of the present disclosure are intended to be illustrative and not limiting.

[0026] All prior patents and publications referenced herein are incorporated by reference in their entirety.

[0027] Throughout the specification and claims, the following terms shall take the meanings expressly associated therewith, unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in one embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, but may. Additionally, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, but may refer to the same embodiment. It is intended that all embodiments of the present disclosure can be combined without departing from the scope or spirit of the present disclosure.

[0028] As used herein, the term "based on" is not exclusive and allows for based on additional unrecited factors unless the context clearly dictates otherwise. Additionally, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0029] FIG. 1 shows a flow chart of a method for controlling precursor delivery, according to some embodiments.

[0030] As shown in FIG. 1, method 100 includes one or more of the following steps: obtaining 102 a precursor delivery vessel containing vaporizable precursor on at least one tray; providing 104 an amount of thermal energy to the at least one tray; distributing 106 vaporized precursor from the precursor delivery vessel to a gas flow line; and adjusting 108 an amount of thermal energy provided to the at least one tray.

[0031] In step 102, in some embodiments, a precursor delivery vessel containing vaporizable precursor on at least one tray is obtained.

[0032] The vaporizable precursor may include a precursor that is capable of being vaporized. In some embodiments, the precursor includes a precursor that is capable of being vaporized by application of thermal energy (e.g., heat). In some embodiments, the precursor includes a precursor that is capable of being vaporized by application of irradiation (e.g., light). In some embodiments, the precursor includes a precursor that is capable of being vaporized by application of thermal energy and irradiation. The vaporizable precursor may be present on at least one tray as a solid, as a liquid, or as a solid and a liquid. For example, in some embodiments, the vaporizable precursor includes a vaporizable solid precursor. In some embodiments, the vaporizable precursor includes a vaporizable liquid precursor. In some embodiments, the vaporizable precursor includes a vaporizable solid precursor and a vaporizable liquid precursor. It will be understood that other types of vaporizable precursors may be used herein without departing from the scope of the present disclosure.

[0033] The vaporizable precursor may comprise, consist of, or consist essentially of at least one of an elemental metal, a metal halide, a metal oxyhalide, an organometallic compound, an organometallic complex, or any combination thereof.

[0034] In some embodiments, the vaporizable precursor is dimethylhydrazine, trimethylaluminum (TMA), hafnium chloride (HfCl4), zirconium chloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, tungsten carbonyl, Ba(DPM)2, bisdipivaloylmethanatostrontium (Sr(DPM)2), TiO(DPM)2, tetradipivaloylmethanatozirconium (Zr(DPM)4), decaborane, octadecaborane, boron, magnesium, gallium, indium, antimony, copper, phosphorus, arsenic, lithium, sodium tetrafluoroborate, precursors incorporating alkyl amidinate ligands, organometallic precursors, zirconium tertiary butoxide (Zr(t-

[0023] The fluorine-containing compound may comprise, consist of, or consist essentially of at least one of: tetrakisdiethylaminozirconium (Zr(Net2)4), tetrakisdiethylaminohafnium (Hf(Net2)4), tetrakis(dimethylamino)titanium (TDMAT), tertiary butyliminotris(diethylamino)tantalum (TBTDET), pentakis(dimethylamino)tantalum (PDMAT), pentakis(ethylmethylamino)tantalum (PEMAT), tetrakisdimethylaminozirconium (Zr(NMe2)4), hafnium tertiary butoxide (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), or any combination thereof.

[0035] In some embodiments, the vaporizable precursor comprises, consists of, or consists essentially of at least one of decaborane, hafnium tetrachloride, zirconium tetrachloride, indium trichloride, metal organic β-diketonate complexes, tungsten hexafluoride, cyclopentadienylcycloheptatrienyltitanium (CpTiCht), aluminum trichloride, titanium iodide, cyclooctatetraenecyclo-pentadienyltitanium, biscyclopentadienyltitanium diazide, trimethylgallium, trimethylindium, an aluminum alkyl such as trimethylaluminum, triethylaluminum, trimethylaminealane, dimethylzinc, tetramethyltin, trimethylantimony, diethylcadmium, tungsten carbonyl, or any combination thereof.

[0036] In some embodiments, the vaporizable precursor comprises, consists of, or consists essentially of at least one of elemental boron, copper, phosphorus, decaborane, gallium halides, indium halides, antimony halides, arsenic halides, gallium halides, aluminum iodide, titanium iodide, MoO2Cl2, MoOCl4, MoCl5, WCl5, WOCl4, WCl6, cyclopentadienylcycloheptatrienyltitanium (CpTiCht), cyclooctatetraenecyclopenta-dienyltitanium, biscyclopentadienyltitanium-diazide, In(CH3)2(hfac), dibromomethylstibine, tungsten carbonyl, metal organic β-diketonate complexes, metal organic alkoxide complexes, metal organic carboxylate complexes, metal organic aryl complexes, metal organic amide complexes, or any combination thereof. In some embodiments, the vaporizable precursor comprises, consists of, or consists essentially of at least one of MoO2Cl2, MoOCl4, WO2Cl2, WOCl4, or any combination thereof.

[0037] In some embodiments, the vaporizable precursor can be, for example, but not limited to, decaborane (B 10 H 14 ), pentaborane (B5H9), octadecaborane (B18H22 In some embodiments, the vaporizable precursor comprises, consists of, or consists essentially of at least one of any type of source material that can be liquefied by heating or solubilization in a solvent that includes at least one of 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 The compound may comprise, consist of, or consist essentially of 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.

[0038] In some embodiments, the solvent is an organic solvent, an inorganic solvent, or any combination thereof. In some embodiments, the solvent comprises a form of 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 will be understood that other vaporizable precursors may be used herein without departing from the present disclosure.

[0039] At least one tray may include or be constructed of a material having a thermal conductivity above a threshold thermal conductivity. For example, in some embodiments, at least one tray may have a thermal conductivity above 15 Wm -1 K -1 In some embodiments, at least one tray comprises, consists of, or consists essentially of a material having a thermal conductivity of at least 16 Wm -1 K -1 , at least 17Wm -1 K -1 , at least 18Wm -1 K -1 , at least 19Wm -1 K -1 , at least 20Wm -1 K -1 , at least 25Wm -1 K -1 , at least 50Wm -1 K -1 , at least 75Wm -1 K -1 , at least 100Wm -1 K -1 , at least 150Wm -1 K -1 , at least 200Wm -1 K -1 , at least 250Wm -1 K -1 , at least 300Wm -1 K -1 , at least 350Wm -1 K -1 , at least 400Wm -1 K-1 , at least 450Wm -1 K -1 , at least 500Wm -1 K -1 , at least 550Wm -1 K -1 , or at least 600Wm -1 K -1 In some embodiments, at least one tray comprises, consists of, or consists essentially of a material having a thermal conductivity of 16 Wm -1 K -1 ~1000Wm -1 K -1 For example, in some embodiments, at least one tray comprises, consists of, or consists essentially of a material having a thermal conductivity of 25 Wm -1 K -1 ~750Wm -1 K -1 , 25Wm -1 K -1 ~470Wm -1 K -1 , 25Wm -1 K -1 ~500Wm -1 K -1 , 100Wm -1 K -1 ~500Wm -1 K -1 , or 150Wm -1 K -1 ~500Wm -1 K -1 In some embodiments, the thermal conductivity of the material is the same as or at least similar to the thermal conductivity of the at least one tray (e.g., within 0.1% to 5% of the thermal conductivity of the at least one tray).

[0040] In some embodiments, at least one tray may further include or be composed of a material having a thermal conductivity below a threshold thermal conductivity. For example, in some of these embodiments, the overall thermal conductivity of at least one tray is greater than a threshold thermal conductivity (e.g., 15 Wm -1 K-1 At least one tray may further comprise or be composed of a material having a thermal conductivity below the threshold thermal conductivity, provided that the thermal conductivity is greater than or equal to any of the thermal conductivity thresholds and ranges disclosed herein. For example, in some embodiments, at least one tray may further comprise or be composed of a material having a thermal conductivity below the threshold thermal conductivity of 15 Wm -1 K -1 Materials with thermal conductivity greater than 15 Wm -1 K -1 and a material having a thermal conductivity of less than or equal to 15 Wm -1 K -1 (or any of the thermal conductivity thresholds and ranges disclosed herein). In some embodiments, the proportions or relative amounts of each material are greater than 15 Wm -1 K -1 The thermal conductivity thresholds and ranges may be varied to provide at least one tray with an overall thermal conductivity greater than (or any of the thermal conductivity thresholds and ranges disclosed herein).

[0041] Non-limiting examples of materials for the at least one tray include, for example and without limitation, at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof, in some embodiments, the at least one tray does not include at least one of the above.

[0042] In some embodiments, for example, at least one tray comprises, consists of, or consists essentially of at least one of silver, copper, aluminum, lead, nickel, gold, iron, zinc, rhodium, lithium, beryllium, sodium, magnesium, potassium, calcium, rubidium, strontium, cesium, barium, radium, scandium, titanium, vanadium, chromium, cobalt, gallium, germanium, arsenic, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, palladium, cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, thallium, neodymium, promethium, holmium, erbium, thulium, thorium, protactinium, uranium, ytterbium, lutetium, oxides thereof, mixed oxides thereof, or any combination thereof (e.g., as mixtures thereof, alloys thereof, etc.). In some embodiments, at least one tray does not include at least one of the above.

[0043] In some embodiments, at least one tray comprises, consists of, or consists essentially of at least one of silicon, boron, carbon, nitrogen, fluorine, oxygen, germanium, arsenic, antimony, chlorine, bromine, iodine, or any combination thereof, hi some embodiments, at least one tray does not comprise at least one of the above.

[0044] In some embodiments, at least one tray comprises, consists of, or consists essentially of at least one of a carbon material. In some embodiments, the carbon material comprises at least one of graphene, graphite, carbon nanoparticles (e.g., carbon nanotubes), or any combination thereof. In some embodiments, the graphene comprises at least one of graphene having 1-3 layers (e.g., very few layer graphene (vFLG)), graphene having 2-5 layers (e.g., few layer graphene (FLG)), graphene having 2-10 layers (e.g., multilayer graphene (MLG)), graphene nanoplatelets (e.g., stacks of graphene sheets (GNPs)), graphene oxide, reduced graphene oxide, graphene powder, graphene solution, graphene paste, graphene nanoplatelets (e.g., graphene sheets having a thickness of 1-3 nm and at least one lateral dimension of 100 nm to 100 μm), functionalized graphene, or any combination thereof. In some embodiments, at least one tray comprises at least one of graphite, crystalline graphite, amorphous graphite, agglomerated graphite (e.g., nodular graphite or vein graphite), graphite fiber, brass, silicon carbide coated graphite, or any combination thereof, hi some embodiments, at least one tray does not comprise at least one of the above.

[0045] In some embodiments, at least one tray is made of the following materials: silver, silver alloys, copper, copper alloys, aluminum, aluminum alloys, lead, nickel, nickel clad, stainless steel, graphite, crystalline graphite, amorphous graphite, agglomerated graphite (e.g., chunky graphite or vein graphite), pyrolytic carbon coated graphite, graphite fibers, very few layer graphene (vFLG), few layer graphene (FLG), multilayer graphene (MLG), graphene nanoplatelets (GNP), graphene oxide, reduced graphene oxide, graphene powder, graphene solution, graphene paste, graphene nanoplatelets, functionalized graphene, brass, silicon carbide coated graphite, glass ceramic, aluminum nitride, silicon carbide, alumina, silicon nitride, zirconia, beryllium oxide, boron nitride, zinc oxide, alumina, cupric oxide, carbon nanotubes, brass, diamond, gold, iron, zinc, zinc oxide, aluminum Mina, cupric oxide, carbon nanotubes, rhodium, lithium, beryllium, sodium, magnesium, potassium, calcium, rubidium, strontium, cesium, barium, radium, scandium, titanium, vanadium, chromium, cobalt, gallium, germanium, arsenic, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, palladium, cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, The at least one tray may comprise, consist of, or consist essentially of at least one of osmium, iridium, platinum, thallium, boron, carbon, silicon, nitrogen, fluorine, oxygen, germanium, arsenic, antimony, chlorine, bromine, iodine, neodymium, promethium, holmium, erbium, thulium, thorium, protactinium, uranium, ytterbium, lutetium, a polymer, or any combination thereof (e.g., as a mixture or alloy of two or more of any of the foregoing materials). In some embodiments, at least one tray does not comprise at least one of the above.

[0046] In some embodiments, at least one tray, or a material of at least one tray, is inert or non-reactive with at least one of the vaporizable precursor, the vaporized precursor, the carrier gas, or any other material with which the at least one tray is in contact or is brought into contact.

[0047] In step 104, in some embodiments, an amount of thermal energy is provided to at least one tray.

[0048] Thermal energy may be provided to at least one tray in an amount sufficient to vaporize the vaporizable precursor. For different vaporizable precursors, the amount of thermal energy sufficient to vaporize the vaporizable precursor may vary depending on, for example, but not limited to, the vaporizable precursor, the phase in which the vaporizable precursor is present on the at least one tray, the conditions and parameters under which the vaporization is taking place (e.g., temperature, pressure, etc.), or any combination thereof. In some embodiments, for example, the amount of thermal energy sufficient to vaporize a vaporizable liquid precursor may depend on the heat of vaporization of the vaporizable liquid precursor. In some embodiments, the amount of thermal energy sufficient to vaporize a vaporizable solid precursor may depend on the heat of sublimation of the vaporizable solid precursor. In some embodiments, the amount of thermal energy required to vaporize a vaporizable precursor in solid or liquid form may depend on the particular vaporizable precursor being vaporized.

[0049] The thermal energy provided to the at least one tray may be provided in the form of heat. In some embodiments, for example, providing thermal energy to the at least one tray includes heating the at least one tray to a temperature sufficient to vaporize the vaporizable precursor. In some embodiments, providing thermal energy to the at least one tray includes heating the at least one tray to a temperature sufficient to vaporize the vaporizable precursor. In some embodiments, providing thermal energy to the at least one tray includes heating the at least one tray to a temperature sufficient to vaporize the vaporizable precursor. In some embodiments, providing thermal energy to the at least one tray includes heating the at least one tray to a temperature sufficient to vaporize the vaporizable precursor. In some embodiments, providing thermal energy to the at least one tray includes heating the at least one tray to a temperature sufficient to vaporize the vaporizable precursor.

[0050] The temperature sufficient to vaporize the vaporizable precursor can be a temperature in the range of 100° C. to 250° C. In some embodiments, for example, the temperature sufficient to vaporize the vaporizable precursor is a temperature in the range of 110° C. to 180° C., 120° C. to 170° C., 120° C. to 150° C., 120° C. to 140° C., 125° C. to 135° C., 130° C. to 190° C., 140° C. to 180° C., 150° C. to 170° C., 155° C. to 165° C., or any other subrange between 100° C. to 250° C. In some embodiments, the vaporized precursor is generated at a temperature in the range of 100° C. to 250° C.

[0051] In step 106, in some embodiments, the vaporized precursor is dispensed from a precursor delivery vessel into a gas flow line.

[0052] The vaporized precursor may be dispensed from the precursor delivery vessel to a gas flow line. In some embodiments, dispensing the vaporized precursor from the precursor delivery vessel may include exhausting the vaporized precursor to a gas flow line. In some embodiments, dispensing the vaporized precursor from the precursor delivery vessel may include releasing the vaporized precursor to a gas flow line. In some embodiments, dispensing the vaporized precursor from the precursor delivery vessel may include flowing the vaporized precursor to a gas flow line. In some embodiments, dispensing the vaporized precursor from the precursor delivery vessel may include feeding the vaporized precursor to a gas flow line. In some embodiments, dispensing the vaporized precursor from the precursor delivery vessel may include delivering the vaporized precursor to a gas flow line. In some embodiments, dispensing the vaporized precursor from the precursor delivery vessel may include pumping the vaporized precursor into a gas flow line.

[0053] In some embodiments, the vaporized precursor is delivered from the precursor delivery vessel with a carrier gas. The carrier gas may include a non-reactive or inert gas. In some embodiments, the carrier gas includes at least one of helium, neon, argon, krypton, xenon, nitrogen, or any combination thereof.

[0054] The gas flow lines may be in fluid communication with the tools. The tools may be located downstream of the precursor delivery vessel. The tools may include any vapor precursor utilizing process. In some embodiments, for example, the tools may include semiconductor manufacturing processes. In some embodiments, the tools include at least one of the following processes: ion implantation, epitaxial growth, plasma etching, reactive ion etching, metallization, physical vapor deposition, chemical vapor deposition, plasma deposition, photolithography, cleaning, doping, or any combination thereof, among others. In some embodiments, the tools are part of manufacturing processes such as semiconductor devices and products, microelectronic devices and products, photovoltaic devices and products, or flat panel display devices and products. Other tools may be used herein without departing from the present disclosure.

[0055] In step 108, in some embodiments, the amount of thermal energy delivered to at least one tray is adjusted.

[0056] The thermal energy provided to the at least one tray can be adjusted to an amount sufficient to maintain the pressure of the vaporized precursor in the gas flow line within the pressure range. In some embodiments, the amount of thermal energy provided to the at least one tray is increased (e.g., by heating to increase the temperature of the at least one tray, the vaporizable precursor, or any combination thereof). In some embodiments, the amount of thermal energy provided to the at least one tray is decreased (e.g., by not heating (or by actively cooling) to decrease the temperature of the at least one tray, the vaporizable precursor, or any combination thereof). In some embodiments, the gas flow line includes a carrier gas in addition to the vaporized precursor. In some of these embodiments, the adjustment of the thermal energy is sufficient to maintain the pressure of the vaporized precursor and carrier gas in the gas flow line within the pressure range.

[0057] A change in the amount of thermal energy provided to the at least one tray results in a corresponding change in the pressure of the vaporized precursor in the gas flow lines. The pressure of the vaporized precursor in the gas flow lines may exhibit at least one of a linear response to changes in thermal energy, a non-linear response to changes in thermal energy, or any combination thereof. In some embodiments, for example, the pressure of the vaporized precursor in the gas flow lines may exhibit a linear or substantially linear response to changes in temperature. In some embodiments, the pressure of the vaporized precursor in the gas flow lines may exhibit a non-linear or substantially non-linear response to changes in temperature. In some embodiments, the pressure of the vaporized precursor in the gas flow lines may exhibit a linear or substantially linear response within a first temperature range and a non-linear or substantially non-linear response within a second temperature range.

[0058] As used herein, the term "response ratio" of a vaporizable precursor may refer to a ratio of X:Y, where X is the change in thermal energy (e.g., change in temperature (°C)) supplied to at least one tray, and Y is the change in pressure (Torr) of the vaporized precursor in the gas flow line. For example, a response ratio of 1:5 may refer to a vaporizable precursor that exhibits a 5 Torr increase or decrease in pressure in the gas flow line in response to a 1°C increase or decrease in temperature. The response ratio of a vaporizable precursor may be within the range of 1:0.1 to 1:500, or any subrange between 1:01 to 1:500. In some embodiments, for example, the response ratio of vaporizable precursors can be in the range of 1:0.1 to 1:100, 1:1 to 1:100, 1:1 to 1:75, 1:1 to 1:50, 1:1 to 1:25, 1:1 to 1:20, 1:1 to 1:15, 1:1 to 1:10, or 1:1 to 1:5.

[0059] The pressure of the vaporized precursor in the gas flow lines can be understood to have a linear or substantially linear response to changes in temperature, with the vaporized precursor exhibiting a constant response ratio over a given temperature range. The pressure of the vaporized precursor in the gas flow lines can be understood to have a non-linear or substantially non-linear response to changes in temperature, with the vaporized precursor exhibiting two or more response ratios over a given temperature range.

[0060] The pressure range may include a pressure and a pressure tolerance. As used herein, the term "pressure tolerance" refers to an allowable pressure variation relative to a set pressure. For example, for a pressure of 500 Torr and a pressure tolerance of ±5 Torr, the pressure range may be defined as 500 Torr ±5 Torr. That is, the pressure range may include pressures in the range of 495 Torr to 505 Torr.

[0061] The pressure range can include pressures ranging from 100 Torr to 750 Torr. For example, in some embodiments, the pressure ranges are 100 Torr to 750 Torr, 100 Torr to 700 Torr, 100 Torr to 650 Torr, 100 Torr to 600 Torr, 100 Torr to 550 Torr, 100 Torr to 500 Torr, 100 Torr to 450 Torr, 100 Torr to 400 Torr, 100 Torr to 350 Torr, 100 Torr to 300 Torr, 100 Torr to 250 Torr, 100 Torr to 200 Torr, 100 Torr to 15 ...250 Torr, 100 Torr to 300 Torr, 100 Torr to 350 Torr, 100 Torr to 450 Torr, 100 Torr to 500 Torr, 100 Torr to 500 Torr, The pressure may include pressures in the ranges of 50 Torr to 750 Torr, 200 Torr to 750 Torr, 250 Torr to 750 Torr, 300 Torr to 750 Torr, 350 Torr to 750 Torr, 400 Torr to 750 Torr, 450 Torr to 750 Torr, 500 Torr to 750 Torr, 550 Torr to 750 Torr, 600 Torr to 750 Torr, 650 Torr to 750 Torr, 700 Torr to 750 Torr, or any other subrange therebetween between 100 Torr and 750 Torr.

[0062] The pressure range may include a pressure tolerance in the range of ±0.1 Torr to ±50 Torr. In some embodiments, the pressure range includes a pressure tolerance in the range of ±0.1 Torr to ±40 Torr, ±0.1 Torr to ±30 Torr, ±0.1 Torr to ±20 Torr, ±0.1 Torr to ±10 Torr, ±0.1 Torr to ±5 Torr, ±1 Torr to ±5 Torr, ±1 Torr to ±10 Torr, or ±1 Torr to ±20 Torr. In some embodiments, the pressure range includes a pressure tolerance of ±0.1 Torr, ±1 Torr, ±2 Torr, ±4 Torr, ±5 Torr, ±8 Torr, ±10 Torr, ±12 Torr, ±14 Torr, ±15 Torr, ±18 Torr, ±20 Torr, ±22 Torr, ±24 Torr, ±25 Torr, ±28 Torr, ±30 Torr, ±32 Torr, ±34 Torr, ±35 Torr, ±38 Torr, ±40 Torr, ±42 Torr, ±44 Torr, ±45 Torr, ±48 Torr, ±50 Torr, or any other pressure tolerance between ±1 Torr and ±50 Torr.

[0063] The amount of thermal energy delivered to the at least one tray can be adjusted sufficient to maintain a flow rate of the vaporized precursor in the gas flow lines within a flow rate range.

[0064] A flow rate range may include a flow rate and a flow rate tolerance. As used herein, the term "flow rate tolerance" refers to an acceptable flow rate variation relative to a set flow rate. For example, for a flow rate of 500 sccm and a flow rate tolerance of ±5 sccm, the flow rate range may be defined as 500 sccm ±5 sccm. That is, the flow rate range may include flow rates in the range of 495 sccm to 505 sccm.

[0065] The flow rate of the vaporized precursor can be in the range of 50 sccm to 750 sccm. For example, in some embodiments, the flow rate of the vaporized precursor can be in the range of 50 sccm to 750 sccm, 50 sccm to 700 sccm, 50 sccm to 650 sccm, 50 sccm to 600 sccm, 50 sccm to 550 sccm, 50 sccm to 500 sccm, 50 sccm to 450 sccm, 50 sccm to 400 sccm, 50 sccm to 350 sccm, 50 sccm to 300 sccm, 50 sccm to 250 sccm, 50 sccm to 200 sccm, 50 sccm to 150 sccm, 50 sccm to 100 sccm, 100 sccm to 750 sccm, 150 sccm, The flow rate may be in the range of 50 sccm to 750 sccm, 200 sccm to 750 sccm, 250 sccm to 750 sccm, 300 sccm to 750 sccm, 350 sccm to 750 sccm, 400 sccm to 750 sccm, 450 sccm to 750 sccm, 500 sccm to 750 sccm, 550 sccm to 750 sccm, 500 sccm to 700 sccm, 550 sccm to 700 sccm, 600 sccm to 700 sccm, 500 sccm to 650 sccm, 500 sccm to 600 sccm, or any other subrange between 50 sccm and 750 sccm.

[0066] The flow rate ranges may include flow rate tolerances ranging from ±0.1 sccm to ±50 sccm, in some embodiments, the flow rate ranges include flow rate tolerances of ±0.1 sccm, ±1 sccm, ±2 sccm, ±4 sccm, ±5 sccm, ±8 sccm, ±10 sccm, ±12 sccm, ±14 sccm, ±15 sccm, ±18 sccm, ±20 sccm, ±22 sccm, ±24 sccm, ±25 sccm, ±28 sccm, ±30 sccm, ±32 sccm, ±34 sccm, ±35 sccm, ±38 sccm, ±40 sccm, ±42 sccm, ±44 sccm, ±45 sccm, ±48 sccm, ±50 sccm, or any other flow rate tolerance between ±1 sccm and ±50 sccm.

[0067] FIG. 2 is a schematic diagram of a system 200 for controlling precursor delivery, according to some embodiments.

[0068] As shown in FIG. 2, the system 200 may optionally include a precursor delivery vessel 202 disposed in an interior volume of an enclosure 204. The precursor delivery vessel 202 may house vaporizable precursors on at least one tray. A thermal energy unit 206 may be in thermal communication with the precursor delivery vessel 202 to provide a sufficient amount of thermal energy to the at least one tray to vaporize the vaporizable precursors. The vaporized precursors may be distributed from the precursor delivery vessel 202 to a tool 208, such as, but not limited to, a semiconductor processing tool, via a gas flow line 210. A sensor 212 and a flow controller 214 may be fluidly disposed in the gas flow line 210 between the precursor delivery vessel 202 and the tool 208. It will be appreciated that other configurations may be used without departing from the scope of the present disclosure.

[0069] The precursor delivery vessel 202 may contain vaporizable precursors on at least one tray disposed in the interior volume of the precursor delivery vessel 202. In some embodiments, the at least one tray comprises multiple trays. In some embodiments, the multiple trays are stacked within the interior volume of the precursor delivery vessel 202. In some embodiments, the multiple trays are attached to the interior volume of the precursor delivery vessel 202 (e.g., secured, fastened, etc. to an interior surface of the precursor delivery vessel 202). In some embodiments, the multiple trays are suspended within the interior volume of the precursor delivery vessel 202. In some embodiments, the multiple trays are expandable such that one or more trays in an expanded configuration are wedged (e.g., by applying pressure or other force) against an interior surface within the interior volume of the precursor delivery vessel 202.

[0070] It will be appreciated that the precursor delivery vessel 202 may include additional elements such as, but not limited to, at least one of a carrier gas inlet for introducing a carrier gas, an inlet, an outlet, a control valve, a pressure regulator, or any combination thereof, among others.

[0071] The thermal energy unit 206 may be configured to provide a sufficient amount of thermal energy (e.g., in the form of heat) to at least one tray of the precursor delivery vessel 202 to vaporize the vaporizable material. The thermal energy unit 206 is not particularly limited, so long as the at least one tray is brought to a desired temperature level and maintained at such temperature level in an accurate and reliable manner. In some embodiments, the thermal energy unit 206 is a thermal jacket wrapped around the precursor delivery vessel 202. In some embodiments, the thermal energy unit 206 is a ribbon heater wrapped around the precursor delivery vessel 202. In some embodiments, the thermal energy unit 206 is a block heater having a shape that covers at least a portion (or most) of the exterior surface of the precursor delivery vessel 202. In some embodiments, the thermal energy unit 206 is a heat transfer fluid in fluid communication with the precursor delivery vessel 202 (e.g., via a heat exchanger unit).

[0072] Gas flow line 210 may fluidly connect precursor delivery vessel 202 to tool 208. Gas flow line 210 may include pipes, conduits, or other structures that define a lumen through which vaporized precursor (and in some embodiments, carrier gas) can flow. Sensor 212 and flow controller 214 may be fluidly disposed in gas flow line 210 between precursor delivery vessel 202 and tool 208. Sensor 212 may comprise any device capable of sensing (e.g., measuring) a property of vaporized precursor in gas flow line 210. For example, in some embodiments, the property includes at least one of a pressure of vaporized precursor (and, e.g., in some embodiments, carrier gas), a flow rate of vaporized precursor (and, e.g., in some embodiments, carrier gas), a temperature of vaporized precursor (and, e.g., in some embodiments, carrier gas), or any combination thereof. In some embodiments, flow controller 214 comprises a mass flow controller, among other flow controllers.

[0073] The system 200 may further include a controller 216. In some embodiments, the controller may be configured to receive a signal to monitor a characteristic of the vaporized precursor in the gas flow line 210. In some embodiments, the controller may be configured to send a signal to control a characteristic of the vaporized precursor in the gas flow line 210. For example, in some embodiments, the controller 216 receives a signal from the sensor 212 continuously or intermittently over time. In some embodiments, the controller 216 sends a signal to the thermal energy unit 206 in response to the signal received from the sensor 212. In some embodiments, the controller 216 may be configured to monitor and control the pressure, flow rate, or another characteristic of the vaporized precursor in the gas flow line by receiving a signal from the sensor 212 and sending a signal to the thermal energy unit 206.

[0074] In some embodiments, for example, the controller 216 is configured to maintain the pressure in the gas flow line 210 within the pressure range. If the pressure of the vaporized precursor in the gas flow line 210 is measured to be outside the pressure range, the controller 216 can be configured to adjust the amount of thermal energy delivered to the at least one tray in an amount sufficient to maintain the pressure of the vaporized precursor (and in some embodiments, the carrier gas) in the gas flow line 210 within the pressure range. For example, the controller 216 can be configured to increase the amount of thermal energy delivered to the at least one tray in response to the measured pressure being less than a lower pressure limit of the pressure range. The controller 216 can be configured to decrease the amount of thermal energy delivered to the at least one tray (or stop the delivery of thermal energy) in response to the measured pressure being greater than an upper pressure limit of the pressure range.

[0075] In some embodiments, the controller 216 may be configured to monitor and control other parameters such as, for example, but not limited to, the flow rate of the vaporized precursor (and in some embodiments, the carrier gas) in the gas flow lines. For example, in some embodiments, the controller is configured to maintain the flow rate of the vaporized precursor (and in some embodiments, the carrier gas) in the gas flow lines within a flow rate range. If the flow rate of the vaporized precursor in the gas flow line 210 is measured to be outside the flow rate range, the controller 216 may be configured to adjust the amount of thermal energy delivered to the at least one tray. For example, the controller 216 may be configured to increase the amount of thermal energy delivered to the at least one tray in response to the measured flow rate being less than a lower flow rate of the flow rate range. The controller 216 may be configured to decrease the amount of thermal energy delivered to the at least one tray in response to the measured flow rate being greater than an upper flow rate of the flow rate range.

[0076] In some embodiments, the controller 216 is a special-purpose computing device that includes at least one of a processor, a memory, a program, or any combination thereof (e.g., the controller 216 is not a general-purpose computer). In some embodiments, the program includes an adaptive or intelligent program configured to regulate the supply of thermal energy without human intervention.

[0077] The tools 208 may include any vapor precursor-based process. In some embodiments, for example, the tools 208 may include a semiconductor manufacturing process. In some embodiments, the tools 208 include at least one of the following processes: ion implantation, epitaxial growth, plasma etching, reactive ion etching, metallization, physical vapor deposition, chemical vapor deposition, plasma deposition, photolithography, cleaning, doping, or any combination thereof, among others. In some embodiments, the tools are part of a manufacturing process for semiconductor devices and products, microelectronic devices and products, photovoltaic devices and products, or flat panel display devices and products, etc. Other tools may be used herein without departing from the present disclosure.

[0078] System 200 and components of system 200 may be provided in other arrangements and configurations with additional elements (or fewer elements). The additional elements may include additional flow paths and flow path circuitry, such as, but not limited to, flow path selectors, flow control valves, mass flow controllers, pressure regulators, restricted flow orifice elements, thermocouples, monitoring and control devices (such as, for example, process gas monitoring instruments for monitoring process conditions of gas precursors dispensed from the precursor delivery vessels, such as, but not limited to, pressure, temperature, flow rate, concentration, etc.), leak detection devices, automatic purge devices and associated actuators for purging the system, the precursor delivery vessel, or any components thereof upon detection of a leak from one or more of the precursor delivery vessels and the system, additional heaters for inputting thermal energy to the precursor delivery vessel and its contents, additional heaters for maintaining the temperature of the exhaust and delivery lines, or any combination thereof.

[0079] Aspects

[0080] Various aspects are described below. It should be understood that any one or more of the features described in the following aspects can be combined with any one or more of the other aspects. Aspect 1. Obtaining a precursor delivery vessel containing vaporizable precursors on at least one tray, comprising: At least one tray is 15Wm -1 K -1 3. A material having a thermal conductivity greater than Obtaining a precursor delivery vessel; providing at least one tray with a sufficient amount of thermal energy to vaporize a vaporizable precursor; Dispensing vaporized precursor from a precursor delivery vessel into a gas flow line; adjusting an amount of thermal energy provided to the at least one tray sufficient to maintain a pressure of the vaporized precursor in the gas flow line within a pressure range; The method includes: Aspect 2. The method of aspect 1, wherein the vaporizable precursor comprises at least one of a metal oxyhalide, a metal halide, or any combination thereof. Embodiment 3. The method of any of embodiments 1-2, wherein the vaporizable precursor comprises at least one of MoO2Cl2, MoOCl4, WO2Cl2, WOCl4, or any combination thereof. Example 4. The method of any of Examples 1-3, wherein at least one tray comprises at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof. Aspect 5. At least one tray is 25Wm -1 K -1 ~470Wm -1 K -1 The method of any of embodiments 1-4, comprising a material having a thermal conductivity of Embodiment 6. The method of any one of embodiments 1 to 5, wherein the pressure range comprises a pressure ranging from 100 Torr to 750 Torr. Aspect 7. The method of any one of aspects 1-6, wherein the pressure range comprises a pressure tolerance in the range of ±1 Torr to ±5 Torr. Embodiment 8. The method of any one of embodiments 1 to 7, wherein the vaporized precursor is generated at a temperature in the range of 100°C to 250°C. Embodiment 9. The method of any of embodiments 1-8, wherein the flow rate of the vaporized precursor in the gas flow lines is in the range of 50 sccm to 600 sccm. Embodiment 10. The method of any of embodiments 1-9, wherein the vaporized precursor exhibits a non-linear response to changes in temperature when the vaporized precursor has a pressure within the pressure range. Embodiment 11. A precursor delivery vessel housing vaporizable precursors on at least one tray, comprising: At least one tray is 15Wm -1 K -1 3. A material having a thermal conductivity greater than a precursor delivery vessel; a heater configured to provide an amount of thermal energy to the at least one tray to generate a vaporized precursor from the vaporizable precursor; a gas flow line configured to deliver vaporized precursor from the precursor delivery vessel to a semiconductor processing tool; a controller configured to adjust an amount of thermal energy delivered to the at least one tray sufficient to maintain a pressure of the vaporized precursor in the gas flow line within a pressure range; A system comprising: Aspect 12. The system of aspect 11, wherein the vaporizable precursor comprises at least one of a metal oxyhalide, a metal halide, or any combination thereof. Embodiment 13. The system of any of embodiments 11-12, wherein the vaporizable precursor comprises at least one of MoO2Cl2, MoOCl4, WO2Cl2, WOCl4, or any combination thereof. Example 14. A system described in any of Examples 11 to 13, wherein at least one tray comprises at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof. Aspect 15. At least one tray has a capacity of 25 Wm -1 K -1 ~470Wm -1 K -1 15. The system of any one of embodiments 11 to 14, comprising a material having a thermal conductivity of Embodiment 16. The system of any of embodiments 11 to 15, wherein the pressure range includes a pressure range of 100 Torr to 750 Torr. Aspect 17. A system described in any of aspects 11 to 16, wherein the pressure range includes a pressure tolerance in the range of ±1 Torr to ±5 Torr. Embodiment 18. The system of any one of embodiments 11 to 17, wherein the vaporized precursor is generated at a temperature in the range of 100°C to 250°C. Embodiment 19. The system of any of embodiments 11-18, wherein the flow rate of the vaporized precursor in the gas flow lines is in the range of 50 sccm to 600 sccm. Embodiment 20. The system of any of embodiments 11-19, wherein the vaporized precursor exhibits a non-linear response to changes in temperature when the vaporized precursor has a pressure within the pressure range.

[0081] It will be understood that changes may be made in details, particularly in matters of the materials of construction employed and the shape, size and arrangement of parts without departing from the scope of the present disclosure. The specification and described embodiments are examples, with the true scope and spirit of the present disclosure being indicated by the following claims. EXAMPLES

[0082] A precursor delivery vessel was obtained that was fluidly coupled to a gas flow line. The gas flow line included a pressure sensor for measuring the pressure of the vaporized precursor flowing through the gas flow line. The gas flow line also included a flow meter for measuring the flow rate of the vaporized precursor flowing through the gas flow line. The tray of the precursor delivery vessel was loaded with MoO2Cl2 as a vaporizable precursor. The tray was heated to a temperature sufficient to vaporize the vaporizable precursor. The pressure of the vaporized precursor was monitored for 30 minutes while adjusting the heat supplied to the tray. It was found that by adjusting the heat supplied to the tray, the flow rate and pressure of the vaporized precursor in the gas flow line could be maintained above 600 sccm and 500 Torr, respectively.

Claims

1. Obtaining a precursor delivery vessel containing vaporizable precursor on at least one tray, The at least one tray is 15 Wm －１ K －１ 3. A material having a thermal conductivity greater than Obtaining a precursor delivery vessel; providing a sufficient amount of thermal energy to the at least one tray to vaporize the vaporizable precursor; distributing the vaporized precursor from the precursor delivery vessel to a gas flow line; adjusting the amount of thermal energy delivered to the at least one tray sufficient to maintain a pressure of the vaporized precursor in the gas flow lines within a pressure range; A method comprising:

2. The method of claim 1 , wherein the vaporizable precursor comprises at least one of a metal oxyhalide, a metal halide, or any combination thereof.

3. The vaporizable precursor is MoO ２ C ２ , MoOCl ４ , W.O. ２ C ２ , WOCl ４ or any combination thereof.

4. The method of claim 1 , wherein the at least one tray comprises at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof.

5. The at least one tray has a capacity of 25 Wm －１ K －１ ~470Wm －１ K －１ The method of claim 1 , further comprising the step of:

6. The method of any one of claims 1 to 5, wherein the pressure range comprises a pressure in the range of 100 Torr to 750 Torr.

7. The method of any one of claims 1 to 6, wherein the pressure range includes a pressure tolerance in the range of ±1 Torr to ±5 Torr.

8. The method of any one of claims 1 to 7, wherein the vaporized precursor is generated at a temperature in the range of 100°C to 250°C.

9. The method of any one of claims 1 to 8, wherein the flow rate of the vaporized precursor in the gas flow lines is in the range of 50 sccm to 600 sccm.

10. 10. The method of claim 1, wherein the vaporized precursor exhibits a non-linear response to changes in temperature when the vaporized precursor has a pressure within the pressure range.

11. A precursor delivery vessel containing vaporizable precursors on at least one tray, comprising: The at least one tray is 15 Wm －１ K －１ 3. A material having a thermal conductivity greater than a precursor delivery vessel; a heater configured to provide an amount of thermal energy to the at least one tray to generate a vaporized precursor from the vaporizable precursor; a gas flow line configured to deliver the vaporized precursor from the precursor delivery vessel to a semiconductor processing tool; a controller configured to adjust the amount of thermal energy delivered to the at least one tray sufficient to maintain a pressure of vaporized precursor in the gas flow lines within a pressure range; A system comprising:

12. 12. The system of claim 11, wherein the vaporizable precursor comprises at least one of a metal oxyhalide, a metal halide, or any combination thereof.

13. The vaporizable precursor is MoO ２ C ２ , MoOCl ４ , W.O. ２ C ２ , WOCl ４ 13. The system of claim 11 or 12, comprising at least one of:

14. 14. The system of claim 11, wherein the at least one tray comprises at least one of a ceramic material, a polymeric material, a metallic material, or any combination thereof.

15. The at least one tray has a capacity of 25 Wm －１ K －１ ~470Wm －１ K －１ 15. The system of claim 11, comprising a material having a thermal conductivity of

16. The system of any one of claims 11 to 15, wherein the pressure range comprises a pressure in the range of 100 Torr to 750 Torr.

17. 17. The system of claim 11, wherein the pressure range includes a pressure tolerance in the range of ±1 Torr to ±5 Torr.

18. The system of any one of claims 11 to 17, wherein the vaporized precursor is generated at a temperature in the range of 100°C to 250°C.

19. The system of any one of claims 11 to 18, wherein a flow rate of the vaporized precursor in the gas flow lines is in the range of 50 sccm to 600 sccm.

20. 20. The system of claim 11, wherein the vaporized precursor exhibits a non-linear response to changes in temperature when the vaporized precursor has a pressure within the pressure range.

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