High purity molybdenum-containing precursors and related systems and methods

Abstract

High purity molybdenum-containing precursors and related systems and methods are provided. A precursor delivery system includes a vaporizer vessel configured to contain a vaporizable precursor that, when vaporized, generates a precursor vapor. The precursor delivery system includes at least one protective surface treatment. The at least one protective surface treatment covers a sufficient amount of at least one gas exposed surface of the precursor delivery system to reduce an amount of at least one contaminant in a precursor vapor generated by a precursor delivery system without the at least one protective surface treatment as compared to the precursor vapor generated by the precursor delivery system without the at least one protective surface treatment.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to molybdenum-containing precursors having high purity, and related systems and methods thereof.

[0002] CROSS REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit under 35 USC 119 of U.S. Provisional Patent Application No. 63 / 523,612 filed June 27, 2023, the disclosure of which is hereby incorporated by reference in its entirety. BACKGROUND

[0004] The presence of contaminants in a precursor vapor is undesirable in precursor delivery applications, such as those related to semiconductor fabrication and manufacturing. Reducing the presence of contaminants in a precursor vapor remains a continuing challenge. SUMMARY

[0005] Some embodiments relate to a precursor delivery system. In some embodiments, the precursor delivery system includes a vaporizer vessel. In some embodiments, the vaporizer vessel is configured to contain a vaporizable precursor that, when vaporized, produces a precursor vapor. In some embodiments, the precursor delivery system includes at least one protective surface treatment. In some embodiments, the at least one protective surface treatment covers a sufficient amount of at least one gas-exposed surface of the precursor delivery system to reduce an amount of at least one contaminant in the precursor vapor compared to a precursor vapor produced by a precursor delivery system without the at least one protective surface treatment.

[0006] Some embodiments relate to a method of delivering a precursor vapor. In some embodiments, the method of delivering the precursor vapor includes obtaining a precursor delivery system. In some embodiments, the precursor delivery system includes a vaporizer vessel containing a vaporizable precursor. In some embodiments, the vaporizer vessel includes at least one protective surface treatment covering at least a portion of at least one gas-exposed surface of the vaporizer vessel. In some embodiments, the method of delivering the precursor vapor includes vaporizing at least a portion of the vaporizable precursor to produce a precursor vapor. In some embodiments, the method of delivering the precursor vapor includes flowing the precursor vapor from the vaporizer vessel to a semiconductor processing tool. In some embodiments, the at least one protective surface treatment covers a sufficient amount of at least one gas-exposed surface of the precursor delivery system to reduce an amount of at least one contaminant in the precursor vapor compared to a precursor vapor produced by a precursor delivery system without the at least one protective surface treatment. BRIEF DESCRIPTION OF DRAWINGS

[0007] Some embodiments of this disclosure are described herein by way of example only, with reference to the accompanying drawings. Detailed reference will now be made to the drawings, and it should be emphasized that the illustrated embodiments are exemplary and intended to illustrate embodiments of this disclosure. In this regard, the description taken in conjunction with the drawings will enable those skilled in the art to understand how embodiments of this disclosure can be practiced.

[0008] Figure 1 This is a schematic diagram of a precursor delivery system according to some embodiments.

[0009] Figure 2 This is a cross-sectional view of a vaporizer container according to some embodiments.

[0010] Figure 3 This is a schematic diagram of a precursor delivery method according to some embodiments.

[0011] Figure 4 This is a graphical view illustrating the degree of iron contamination in a molybdenum-containing precursor in an uncoated system by coating according to some embodiments. Detailed Implementation

[0012] Among the disclosed benefits and improvements, other objects and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Detailed embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure as it may be embodied in various forms. Furthermore, each of the examples given with respect to the various embodiments of this disclosure is intended to be illustrative rather than restrictive.

[0013] Any existing patents and publications referenced in this document are incorporated herein by full citation.

[0014] Throughout the specification and claims, unless the context clearly specifies otherwise, the following terms shall have the meanings explicitly and consequentially used herein. As used herein, the phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” do not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, as used herein, the phrases “in another embodiment” and “in some other embodiments” do not necessarily refer to different embodiments, but may refer to different embodiments. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0015] As used herein, unless the context clearly specifies otherwise, the term "based on" is non-exclusive and allows for consideration based on additional factors not described. Furthermore, throughout the specification, "a," "an," and "described" have the meaning of plural references. "In" has the meaning of both "in" and "on."

[0016] The transport of steam precursors under high temperature and pressure can be attributed to increased contamination levels due to corrosion and leaching, among other things, including, but not limited to, levels of metallic and / or particulate contaminants. As disclosed herein, in some embodiments, protective surface treatments are applied to one or more gas-exposed surfaces of the precursor transport system to reduce corrosion, leaching, and particulate contamination, thereby improving the purity of the precursor steam. It has been unexpectedly found that the presence of protective surface treatments on the gas-exposed surfaces of the precursor transport system can significantly improve the purity levels of various steam precursors (including, for example, but not limited to, molybdenum-containing precursor steam) (i.e., significantly reduce contamination levels). The precursor transport systems disclosed herein offer numerous other advantages, including, for example, but not limited to, improved performance under high temperature and / or high pressure and other process conditions. These should not be considered limiting, as these and other advantages of the embodiments disclosed herein will be apparent from the disclosure herein.

[0017] Figure 1 This is a schematic diagram of a precursor delivery system 100 according to some embodiments. For example... Figure 1 As shown, in some embodiments, the precursor delivery system 100 includes a vaporizer container 110. In some embodiments, the vaporizer container 110 is fluidly coupled to a semiconductor processing tool 120. In some embodiments, the vaporizer container 110 is fluidly coupled to the semiconductor processing tool 120 via a gas supply line 130. In some embodiments, a valve assembly 140 fluidly couples the vaporizer container 110 to the gas supply line 130. In some embodiments, at least one filter 150 is located in the gas supply line 130. That is, in some embodiments, at least one filter 150 is located in the flow path of the precursor vapor such that at least a portion of the precursor vapor flows through at least one filter 150. In some embodiments, at least one filter 150 includes at least one particle filter for removing particles from the precursor vapor. In some embodiments, at least the vaporizer container 110 is located in a housing 105, such as, but not limited to, a gas supply box or other enclosure. Other components of the precursor delivery system 100 may be included in the housing 105 without departing from the scope of this disclosure.

[0018] Vaporizer container 110 may be configured to contain a vaporizable precursor that generates precursor vapor upon vaporization. Precursor delivery system 100 may include at least one protective surface treatment covering at least a portion of the gas-exposed surfaces of precursor delivery system 100. As used herein, the term "protective surface treatment" includes, for example, but not limited to, at least one of a coating, a modified surface area, a passivated surface area, or any combination thereof. As used herein, the term "(a number of) gas-exposed surfaces" refers to any surface of precursor delivery system 100 that is exposed to or may be exposed to at least one of a gas, vapor, or any combination thereof. For example, in some embodiments, a gas-exposed surface is any surface that is in fluid communication with at least one of a gas, vapor, or any combination thereof at any point in time during use or non-use of precursor delivery system 100.

[0019] In some embodiments, at least one protective surface treatment includes a modified surface region. For example, in some embodiments, at least a portion of the gas-exposed surface includes a modified surface region. In some embodiments, at least one protective surface treatment is a surface modification in which the gas-exposed surface is modified (e.g., passivated) by exposure to reactive vapors. In other words, surface modification is not, for example, a coating applied to the gas-exposed surface; surface modification is a gas-exposed surface that has been chemically modified by exposure to reactive vapors. In some embodiments, the chemically modified surface region is referred to herein as a modified surface region and / or a passivated surface region.

[0020] In some embodiments, at least one protective surface treatment covers a sufficient amount of at least one gas-exposed surface of the precursor delivery system to reduce the amount of at least one contaminant in the precursor vapor compared to precursor vapor generated by a precursor delivery system without at least one protective surface treatment but otherwise identical or similar to a precursor delivery system including at least one protective surface treatment. In some embodiments, at least one protective surface treatment covers at least one non-gas-exposed surface of the precursor delivery system. That is, in some embodiments, at least one protective surface treatment covers a surface of the precursor delivery system that is not exposed to any gas. In some embodiments, the non-gas-exposed surfaces of the precursor delivery system are covered by a source reagent that, upon vaporization, exposes the underlying surface. In some embodiments, these surfaces are included within the gas-exposed surfaces of the precursor delivery system. At least one protective surface treatment may cover all or at least a portion of the gas-exposed surfaces of the precursor delivery system 100. Each of the at least one protective surface treatment may be the same or different and may vary, for example, depending on the construction material of each component of the precursor delivery system 100, the vaporizable precursor and / or the precursor vapor generated or being generated and / or the operating conditions (e.g., the temperature, pressure, etc. under which the vaporizable precursor is vaporized), etc. In some embodiments, at least one protective surface treatment covers at least a portion of at least one gas-exposed surface of the precursor delivery system 100. That is, in some embodiments, at least one protective surface treatment covers at least a portion or only a portion of at least one gas-exposed surface of the precursor delivery system 100. In some embodiments, at least one protective surface treatment covers the entire precursor delivery system 100 or all gas-exposed surfaces of the precursor delivery system 100. That is, in some embodiments, at least one protective surface treatment covers all surfaces and / or all gas-exposed surfaces of the precursor delivery system 100.

[0021] In some embodiments, at least one protective surface treatment covers at least a portion of the gas-exposed surface of the vaporizer container (disclosed in further detail below). In some embodiments, at least one protective surface treatment covers all gas-exposed surfaces of the vaporizer container (disclosed in further detail below). In some embodiments, at least a portion of at least one gas-exposed surface of a gas supply line is covered by at least one protective surface treatment. In some embodiments, at least one protective surface treatment covers all gas-exposed surfaces of a gas supply line. In some embodiments, at least a portion of at least one gas-exposed surface of at least one filter is covered by at least one protective surface treatment. In some embodiments, at least one protective surface treatment covers all gas-exposed surfaces of at least one filter. In some embodiments, at least a portion of at least one gas-exposed surface of a valve assembly is covered by at least one protective surface treatment. In some embodiments, at least one protective surface treatment covers all gas-exposed surfaces of a valve assembly. In some embodiments, at least one protective surface treatment covers at least a portion of the gas-exposed surfaces of other components of the precursor delivery system 100 (including, for example, but not limited to, at least one of orifices, pipes, gaskets, fittings, sensors (e.g., pressure sensors, temperature sensors, flow rate sensors, etc.), fasteners, or any combination thereof).

[0022] In some embodiments, at least one protective surface treatment comprises multiple protective surface treatments, wherein each surface of the precursor delivery system is independently covered by one or more of the multiple protective surface treatments. For example, in some embodiments, at least one surface of the precursor delivery system comprises a first protective surface treatment on the surface of the precursor delivery system and at least a second protective surface treatment on the first protective surface treatment. For example, in some embodiments, the surface of the precursor delivery system comprises a surface-modified region (e.g., where MgF2 is formed in the surface; not a coating) and a coating (e.g., an ALD coating) on ​​the surface-modified region. In some embodiments, at least a first surface of the precursor delivery system comprises a first protective surface treatment and at least a second surface of the precursor delivery system comprises a second protective surface treatment, wherein the first protective surface treatment and the second protective surface treatment are different (or the same or similar). In some embodiments, at least one protective surface treatment is in direct contact with the gas-exposed surface. In some embodiments, at least one protective surface treatment is a surface modification in which the gas-exposed surface is modified (e.g., passivated) by exposure to reactive vapors. In other words, the surface modification is not a coating applied to the gas-exposed surface; the surface modification is a gas-exposed surface that has been chemically modified by exposure to reactive vapors. In some embodiments, an interlayer is located between the gas-exposed surface and at least one protective surface treatment. At least one protective surface treatment may include a protective surface treatment material that reduces degradation of the gas-exposed surface, thereby preventing the introduction of contaminants into the precursor vapors during use or non-use of the precursor delivery system, or at least reducing the amount of contaminants. Contaminants can be introduced from the gas-exposed surface by at least one of corrosion, leaching, particulate contamination, or any combination thereof, optionally due to exposure to precursor vapors(s) at high temperatures and / or high pressures. In some embodiments, the protective surface treatment material of at least one protective surface treatment is a material or substance that does not react with the precursor vapors (e.g., an inert material relative to the precursor vapors under vaporization conditions).

[0023] In some embodiments, at least one protective surface treatment includes an oxide coating. In some embodiments, at least one protective surface treatment includes at least one of nickel, Al2O3, Cr2O3, gold, nitrides (e.g., titanium nitride), glass, copper, or any combination thereof. In some embodiments, passivation using germanium tetrafluoride is effective for stainless steel and nickel, which is attributed to the formation of surface Ni-F, Cr-F, and Fe-F species, which can be considered as a NiF2, CrF3, or FeF3 layer overlaid on nickel or stainless steel.

[0024] In some embodiments, at least one protective surface treatment comprises a metal, such as nickel or a metal alloy. In other embodiments, at least one protective surface treatment comprises a polymeric material, such as polytetrafluoroethylene (PTFE) or a PTFE-based material, containing a protective coating of a material available under the trademarks Teflon® and Kalrez®. In some embodiments, at least one protective surface treatment may also be formed of or otherwise comprise a material such as aluminum, copper, or gold.

[0025] In some embodiments, at least one protective surface treatment includes an atomic layer deposition (ALD) coating. In some embodiments, the ALD coating may include yttrium oxide. In some embodiments, the ALD coating may include zirconium oxide. In some embodiments, the ALD coating may include titanium dioxide. In some embodiments, the ALD coating may include AlO₂. x N y , where x is 1 to 5 and y is 1 to 5. In some embodiments, at least one protective surface treatment includes at least one of thermal atomic layer deposition (ALD) coating, physical vapor deposition (PVD) coating, chemical vapor deposition (CVD) coating, solution deposition coating, or any combination thereof.

[0026] In some embodiments, at least one protective surface treatment comprises at least one of alumina, yttrium oxide, titanium dioxide, zirconium oxide, tantalum oxide, or any combination thereof. In some embodiments, at least one gas-exposed surface is fluorinated without applying a coating to at least one gas-exposed surface. In some embodiments, the fluorinated gas-exposed surface can be formed by fluorinating the gas-exposed surface such that the gas-exposed surface is modified to include at least one of YOF, YF3, or any combination thereof.

[0027] In some embodiments, at least one protective surface treatment comprises: an oxide of the chemical formula MO, wherein M is Ca, Mg, or Be; an oxide of the chemical formula M'O2, wherein M' is a stoichiometric metal; an oxide of the chemical formula Re2O3, wherein Re is a rare earth element; or an oxide of the chemical formula Ta. x O y The oxide, wherein x is greater than 0 and y is greater than 0. In some embodiments, at least one protective surface treatment comprises a metal oxide of the chemical formula Ln₂O₃, wherein Ln is a lanthanide element.

[0028] In some embodiments, at least one protective surface treatment includes at least one of a metal nitride, a metal fluoride, or any combination thereof. In some embodiments, at least one protective surface treatment includes at least one of: aluminum oxynitride; yttrium-alumina; silicon oxide; silicon oxynitride; transition metal oxides; transition metal oxynitrides; rare earth metal oxides; rare earth metal oxynitrides; or any combination thereof. In some embodiments, the metal fluoride includes at least one of MgF2, AlF3, NiF2, or any combination thereof.

[0029] In some embodiments, at least one protective surface treatment may include at least one of an elemental metal, a metal alloy, a metal compound (e.g., a metal oxide compound), or any combination thereof. In some embodiments, at least one protective surface treatment includes at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, or any combination thereof. In some embodiments, at least one protective surface treatment includes at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, silicon, copper, magnesium oxide, or any combination thereof.

[0030] In some embodiments, at least one protective surface treatment comprises at least one of titanium dioxide, yttrium oxide, aluminum oxide, zirconium oxide, tantalum oxide, or any combination thereof. In some embodiments, at least one protective surface treatment comprises at least one of: Al₂O₃, an oxide of the chemical formula MO, wherein M is Ca, Mg, or Be; an oxide of the chemical formula M'O₂, wherein M' is a stoichiometric metal; and an oxide of the chemical formula Re₂O₃, wherein Re is a rare earth element, such as, for example, a lanthanide element; and an oxide of the chemical formula Ta. x O y The oxides, wherein x is greater than 0 and y is greater than 0. In some embodiments, the lanthanide elements may include La, Sc, or Y, or consist of La, Sc, or Y, or consist substantially of La, Sc, or Y. In some embodiments, the protective surface treatment layer may include, consist of, or consist substantially of, or optionally consist of the group consisting of: alumina, aluminum oxynitride, yttrium oxide, yttrium-alumina, silicon oxide, silicon oxynitride, transition metal oxides, transition metal oxynitrides, rare earth metal oxides, rare earth metal oxynitrides, or any combination thereof. In some embodiments, the method further includes fluorinating the protective surface treatment layer to form a coating comprising at least one of YOF, YF3, or any combination thereof.

[0031] In some embodiments, at least one protective surface treatment is a reaction product of a surface with a reactive gas phase. In some embodiments, the reactive gas phase may include a fluorine component. In some embodiments, the reactive gas phase may include a molecular fluorine source vapor that may be derived from a liquid or solid. In some embodiments, the fluorine component may include molecular fluorine, consist of molecular fluorine, or consist substantially of molecular fluorine. In some embodiments, the fluorine component is non-ionic, substantially non-ionic, untreated (e.g., by adding energy other than heat) to form a plasma, or any combination thereof. In some embodiments, the fluorine component may include, consist of, or consist substantially of at least one of fluorinated organic compounds, perfluorinated organic compounds, or any combination thereof. In some embodiments, for example, the fluorine component may include, consist of, or consist substantially of at least one of fluorinated alkanes, perfluorinated alkanes, fluorinated olefins, perfluorinated olefins, or any combination thereof, wherein any one or more of the above fluorine components may be linear or branched. In some embodiments, the fluorine component may include, consist of, or substantially consist of, or optionally consist of, at least one of the following groups: CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, or any combination thereof. In some embodiments, the reactive gas phase is different from plasma, the process for generating plasma, or any combination thereof.

[0032] In some embodiments, the reactive gas phase may include a gaseous fluorinated polymer derived from a non-gaseous fluorinated polymer (e.g., a solid or liquid-phase fluorinated polymer). In some embodiments, the fluorinated polymer may be a homopolymer or copolymer. In some embodiments, the fluorinated polymer may include a copolymer of at least one fluoroolefin monomer and optionally at least one non-fluorinated comonomer. In some embodiments, the fluorinated polymer may be fluorinated (i.e., partially fluorinated), perfluorinated, or may contain non-fluorinated halogen atoms, such as, for example, but not limited to, chlorine. In some embodiments, the molecular fluorine source may be liquid or solid at room temperature, but vaporized at the process temperatures disclosed herein. Non-limiting examples of fluoropolymers include, but are not limited to, at least one of the following: polymeric perfluoroalkyl ethylene having a C1 to C10 perfluoroalkyl group; polytetrafluoroethylene (PTFE); tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA); tetrafluoroethylene / hexafluoropropylene copolymer (FEP); tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA); polyhexafluoropropylene; ethylene / tetrafluoroethylene copolymer (ETFE); polytrifluoroethylene; polyvinylidene fluoride (PVDF); polyvinyl fluoride (PVF); polychlorotrifluoroethylene (PCTFE); ethylene / chlorotrifluoroethylene copolymer (ECTFE); or any combination thereof.

[0033] In some embodiments, at least one protective surface treatment (e.g., a surface-modified region, a passivated region, or any combination thereof) comprises at least one of a metal nitride, a metal fluoride, or any combination thereof. In some embodiments, at least one protective surface treatment (e.g., a surface-modified region, a passivated region, or any combination thereof) comprises at least one of: aluminum oxynitride; yttrium-alumina; silicon oxide; silicon oxynitride; transition metal oxides; transition metal oxynitrides; rare earth metal oxides; rare earth metal oxynitrides; or any combination thereof. In some embodiments, the metal fluoride comprises at least one of MgF2, AlF3, NiF2, or any combination thereof.

[0034] In some embodiments, at least one protective surface treatment is a conformal layer. In some embodiments, at least one protective surface treatment is a layer having a substantially uniform thickness or a uniform thickness. In some embodiments, at least one protective surface treatment may be a resist layer or may form on the surface of a resist substrate. In some embodiments, at least one protective surface treatment may passivate the surface of a substrate. In some embodiments, at least one protective surface treatment may be a protective layer.

[0035] In some embodiments, at least one protective surface treatment may have a thickness of 1 nm to 50 μm or any range or subrange thereof. For example, in some embodiments, the protective surface treatment layer may have a thickness of less than 5 μm, less than 1 μm, or less than 250 nm. In some embodiments, the protective surface treatment layer may have the following thicknesses: 100 nm to 250 nm, 1 nm to 4 μm, 1 nm to 3 μm, 1 nm to 2 μm, 1 nm to 1 μm, 1 nm to 900 nm, 1 nm to 850 nm, 1 nm to 800 nm, 1 nm to 750 nm, 1 nm to 700 nm, 1 nm to 650 nm, 1 nm to 600 nm, 1 nm to 550 nm, 1 nm to 450 nm, 1 nm to 400 nm, 1 nm to 350 nm, 1 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 100 nm, 1 nm to 50 nm, 50 nm to 5 μm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm. μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, 4 μm to 5 μm, 1 nm to 750 nm, 1 nm to 500 nm, 2 nm to 500 nm, 1 nm to 250 nm, 20 nm to 125 nm, 20 nm to 250 nm, 20 nm to 500 nm, 50 nm to 500 nm, 50 nm to 400 nm, 50 nm to 300 nm, 50 nm to 200 nm, 15 nm to 200 nm, 20 nm to 50 nm, 10 nm to 40 nm, 30 nm to 50 nm, 1 nm to 5 μm, 1 μm to 5 μm, 1 μm to 4 μm, 1 μm to 3 μm, 1 μm to 2 μm, 5 nm to 5 μm, 1 nm to 1 μm and / or any range or subrange thereof.

[0036] In some embodiments, at least one protective surface treatment includes a protective surface treatment formed by a vapor deposition process. Examples of vapor deposition processes include, but are not limited to, at least one of the following: chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD) processes, flowable chemical vapor deposition (FCVD) processes, atomic layer deposition (ALD) processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, or any combination thereof.

[0037] When a vaporizable precursor is vaporized using the precursor delivery system 100, precursor vapor with high purity is generated. In some embodiments, the vaporizable precursor is a molybdenum-containing source reagent that produces a molybdenum-containing precursor upon vaporization. In some embodiments, the molybdenum-containing source reagent and / or the molybdenum-containing precursor includes at least one of molybdenum pentachloride (MoCl5), molybdenum oxychloride, molybdenum chloride (other than MoCl5), molybdenum oxide, or any combination thereof. In some embodiments, the molybdenum-containing source reagent and / or the molybdenum-containing precursor includes at least one of molybdenum tetrachloride (MoCl4), molybdenum tetrachloride (MoOCl4), molybdenum dichlorodioxide (MoO2Cl2), molybdenum dichlorodioxide (MoO2Cl2(H2O)), molybdenum trioxide (MoO3), or any combination thereof. In some embodiments, the molybdenum-containing source reagent and / or the molybdenum-containing precursor includes at least one of molybdenum tetrachloride (MoCl4), molybdenum trioxide (MoO3), or any combination thereof. In some embodiments, the molybdenum-containing source reagent and / or molybdenum-containing precursor includes at least one of molybdenum tetrachloride (MoOCl4), molybdenum dichloride (MoO2Cl2), molybdenum dichloride (MoO2Cl2(H2O)), or any combination thereof. In some embodiments, the molybdenum-containing precursor is a precursor vapor, a precursor gas, or any combination thereof. In some embodiments, the precursor vapor includes MoO2Cl2 vapor. In some embodiments, the precursor vapor includes MoCl5 vapor.

[0038] In some embodiments, the precursor vapor includes at least one contaminant at less than 10 ppm, at least one contaminant at less than 9 ppm, at least one contaminant at less than 8 ppm, at least one contaminant at less than 7 ppm, at least one contaminant at less than 6 ppm, at least one contaminant at less than 1 ppm, at least one contaminant at less than 5 ppm, at least one contaminant at less than 4 ppm, at least one contaminant at less than 3 ppm, at least one contaminant at less than 2 ppm, at least one contaminant at less than 1 ppm, at least one contaminant at less than 0.5 ppm, at least one contaminant at less than 0.1 ppm, at least one contaminant at less than 0.01 ppm, at least one contaminant at less than 0.009 ppm, at least one contaminant at less than 0.008 ppm, at least one contaminant at less than 0.007 ppm, at least one contaminant at less than 0.006 ppm, at least one contaminant at less than 0.005 ppm, at least one contaminant at less than 0.004 ppm, at least one contaminant at less than 0.003 ppm, at least one contaminant at less than 0.002 ppm, or at least one contaminant at less than 0.001 ppm.

[0039] In some embodiments, "at least one contaminant less than a specified amount" can refer to all contaminants. For example, in some embodiments, "at least one contaminant less than 10 ppm" can mean that the total amount of all contaminants is less than 10 ppm. In some embodiments, "at least one contaminant less than a specified amount" can refer to individual contaminants. For example, in some embodiments, "at least one contaminant less than 10 ppm" can mean that a first contaminant is present in an amount of less than 10 ppm, a second contaminant is present in an amount of less than 10 ppm, and so on, wherein the total amount of the first and second contaminants may, but is not required to, exceed 10 ppm.

[0040] In some embodiments, the precursor vapor includes at least one contaminant between 0.0001 ppm and 10 ppm, or any range or subrange between 0.0001 ppm and 10 ppm. For example, in some embodiments, the precursor vapor includes at least one thermal contaminant between the following: 0.0001 ppm to 10 ppm, 0.0001 ppm to 9 ppm, 0.0001 ppm to 8 ppm, 0.0001 ppm to 7 ppm, 0.0001 ppm to 6 ppm, 0.0001 ppm to 5 ppm, 0.0001 ppm to 4 ppm, 0.0001 ppm to 3 ppm, 0.0001 ppm to 2 ppm, 0.0001 ppm to 1 ppm, 0.0001 ppm to 0.9 ppm, 0.0001 ppm to 0.8 ppm, 0.0001 ppm to 0.7 ppm, 0.0001 ppm to 0.6 ppm, 0.0001 ppm to 0.5 ppm, 0.0001 ppm to 0.4 ppm, and 0.0001 ppm to 0.3 ppm. ppm, 0.0001 ppm to 0.2 ppm, 0.0001 ppm to 0.1 ppm, 0.0001 ppm to 0.01 ppm, 0.0001 ppm to 0.009 ppm, 0.0001 ppm to 0.008 ppm, 0.0001 ppm to 0.007 ppm, 0.0001 ppm to 0.006 ppm, 0.0001 ppm to 0.005 ppm, 0.0001 ppm to 0.004 ppm, 0.0001 ppm to 0.003 ppm, 0.0001 ppm to 0.002 ppm, 0.0001 ppm to 0.001 ppm, 0.0001 ppm to 10 ppm, 0.01 ppm to 10 ppm, 0.1 ppm to 10 ppm, 1 ppm to 10 ppm, 2 ppm to 10 ppm, 3 ppm to 10 ppm, 4 ppm to 10 ppm, 5 ppm to 10 ppm, 6 ppm to 10 ppm, 7 ppm to 10 ppm, 8 ppm to 10 ppm or 9 ppm to 10 ppm.

[0041] In some embodiments, the range of at least one contaminant may refer to all contaminants. For example, in some embodiments, at least one contaminant at 0.0001 ppm to 10 ppm may represent the total amount of all contaminants present in the range of 0.0001 ppm to 10 ppm. In some embodiments, the range of at least one contaminant may refer to individual contaminants. For example, in some embodiments, at least one contaminant at 0.0001 ppm to 10 ppm may represent the presence of a first contaminant at 0.0001 ppm to 10 ppm, a second contaminant at 0.0001 ppm to 10 ppm, etc., wherein the total amount of the first and second contaminants may, but is not required to, exceed 10 ppm.

[0042] In some embodiments, the amount of at least one contaminant is the amount present in the precursor vapor after exposure at a temperature of at least 100°C for 180 days. In some embodiments, the amount of at least one contaminant is the amount present in the precursor vapor after exposure at a temperature of 100°C to 1000°C for 1 day to 180 days (or any range or subrange between 1 day and 180 days). In some embodiments, the amount of at least one contaminant is the amount present in the precursor vapor after exposure at the following temperatures for 180 days: 120°C to 200°C, 120°C to 190°C, 120°C to 180°C, 120°C to 170°C, 120°C to 160°C, 120°C to 150°C, 120°C to 140°C, 120°C to 130°C, 130°C to 200°C, 140°C to 200°C, 150°C to 200°C, 160°C to 200°C, 170°C to 200°C, 180°C to 200°C, or 190°C to 200°C.

[0043] In some embodiments, at least one contaminant includes at least one iron (Fe) contaminant, at least one nickel (Ni) contaminant, or any combination thereof. In some embodiments, at least one contaminant includes any contaminant, impurity (whether gaseous, vaporous, or solid (e.g., particles)) or other substance that reduces the purity of the precursor vapor. In some embodiments, at least one iron contaminant includes at least one of ferric chloride, ferric oxide, ferric chloride oxychloride, ferric hydroxychloride, or any combination thereof. In some embodiments, at least one nickel contaminant includes at least one of nickel chloride, nickel oxide, nickel chloride oxychloride, nickel hydroxychloride, or any combination thereof.

[0044] Figure 2This is a cross-sectional view of a vaporizer container 200 according to some embodiments. The vaporizer container 200 may include a container 202 having an inlet 204 and an outlet 206. The container 202 may define an internal volume 208 of the vaporizer container 200. In some embodiments, the container 202 is completely closed. In some embodiments, the container 202 includes a cover 214 coupled or removably coupled to a container body, wherein the cover 214 defines the internal volume 208 of the vaporizer container 200 when engaging with the container body. In some embodiments, at least one of the inlet 204, the outlet 206, or any combination thereof is located in the cover 214. The container 202 may contain or be configured to contain a vaporizable precursor that, upon vaporization, produces precursor vapor that can be discharged through the outlet, such as, for example, but not limited to, molybdenum-containing vapor. In some embodiments, the vaporizer container 200 includes at least one tray 210 located within the internal volume 208 of the container 202. In some embodiments, at least one tray 210 is configured to contain a vaporizable precursor. At least one of the pallets 210 may include a base 216 and a sidewall 218 extending upward from the outer edge of the base 216. At least one pallet 210 may be configured to contact the inner surface of the container 202.

[0045] In some embodiments, the protective surface treatment covers the entire vaporizer container 200. For example, in some embodiments, the protective surface treatment covers all gas-exposed surfaces of the vaporizer container 200. In some embodiments, the protective surface treatment covers only a portion of the gas-exposed surfaces of the vaporizer container 200. In some embodiments, the protective surface treatment covers at least a portion of the inlet 204 of the vaporizer container 200. In some embodiments, the protective surface treatment covers at least a portion of the gas-exposed surface of the outlet 206 of the vaporizer container. In some embodiments, the protective surface treatment covers at least a portion of the surface defining the internal volume 208 of the vaporizer container 200. In some embodiments, the protective surface treatment covers at least a portion of the gas-exposed surface of the cover 214. In some embodiments, the protective surface treatment covers at least a portion of the gas-exposed surface of at least one tray 210. In some embodiments, the protective surface treatment covers at least a portion of the gas-exposed surface of at least one tray base 216. In some embodiments, the protective surface treatment covers at least a portion of the top surface of at least one tray base 216. In some embodiments, the protective surface treatment covers at least a portion of the bottom surface of at least one tray base 216. In some embodiments, the protective surface treatment covers at least a portion of the gas-exposed surface of at least one sidewall of the tray 210. In some embodiments, any one or more protective surface treatments on any one or more components of the vaporizer container 200 are the same and / or different.

[0046] Figure 3This is a schematic diagram of a precursor delivery method according to some embodiments. For example... Figure 3 As shown, in some embodiments, the precursor delivery method includes obtaining a precursor delivery system 302. In some embodiments, the precursor delivery method includes vaporizing at least a portion of a vaporizable precursor 304 to generate precursor vapor. In some embodiments, the precursor delivery method includes flowing the precursor vapor from a vaporizer container 306 to a semiconductor processing tool.

[0047] In step 302, in some embodiments, the precursor delivery method includes obtaining a precursor delivery system. Any of the precursor delivery systems disclosed herein may be used without departing from the scope of this disclosure. For example, in some embodiments, the precursor delivery system includes a vaporizer container housing a vaporizable precursor and at least one protective surface treatment covering at least a portion of at least one gas-exposed surface of the vaporizer container. In some embodiments, the at least one protective surface treatment covers a sufficient amount of at least one gas-exposed surface of the precursor delivery system to reduce the amount of at least one contaminant in the precursor vapor compared to precursor vapor generated by a precursor delivery system without at least one protective surface treatment.

[0048] In step 304, in some embodiments, the precursor delivery method includes vaporizing at least a portion of the vaporizable precursor to generate precursor vapor. In some embodiments, vaporization includes heating the vaporizer container. In some embodiments, vaporization includes heating the vaporizable precursor. In some embodiments, vaporization includes pressurizing the vaporizer container. In some embodiments, vaporization includes depressurizing the vaporizer container. In some embodiments, vaporization includes flowing a carrier gas into and / or through the vaporizer container. In some embodiments, vaporization includes flowing an inert gas into and / or through the vaporizer container.

[0049] In some embodiments, vaporization is performed at temperatures ranging from 100°C to 1000°C or any range or subrange between 100°C and 1000°C. For example, in some embodiments, vaporization is performed at temperatures of: 100°C to 900°C, 100°C to 800°C, 100°C to 700°C, 100°C to 600°C, 100°C to 500°C, 100°C to 400°C, 100°C to 300°C, 100°C to 200°C, 200°C to 1000°C, 300°C to 1000°C, 400°C to 1000°C, 500°C to 1000°C, 600°C to 1000°C, 700°C to 1000°C, 800°C to 1000°C, or 900°C to 1000°C. In some embodiments, vaporization is performed at the following temperatures: 120°C to 200°C, 120°C to 190°C, 120°C to 180°C, 120°C to 170°C, 120°C to 160°C, 120°C to 150°C, 120°C to 140°C, 120°C to 130°C, 130°C to 200°C, 140°C to 200°C, 150°C to 200°C, 160°C to 200°C, 170°C to 200°C, 180°C to 200°C, or 190°C to 200°C.

[0050] In some embodiments, vaporization is performed at pressures ranging from 0.01 Torr to 760 Torr, or any range or subrange between 0.01 Torr and 760 Torr. In some embodiments, for example, vaporization is performed at pressures within the following ranges: 0.01 Torr to 750 Torr, 0.01 Torr to 700 Torr, 0.01 Torr to 650 Torr, 0.01 Torr to 600 Torr, 0.01 Torr to 550 Torr, 0.01 Torr to 500 Torr, 0.01 Torr to 450 Torr, 0.01 Torr to 400 Torr, 0.01 Torr to 350 Torr, 0.01 Torr to 300 Torr, 0.01 Torr to 250 Torr, 0.01 Torr to 200 Torr, 0.01 Torr to 150 Torr, 0.01 Torr to 100 Torr, and 0.01 Torr to 50 Torr. 0.01 to 25 to 10 to 5 to 1 to 1, 0.01 to 0.1 to 5, 50 to 760 to 100 to 760 to 150 to 760 to 200 to 760 to 250 to 760 to 300 to 760 to 350 to 760 to 400 to 760 to 450 to 760 to 500 to 760 to 550 to 760 to 600 to 760 to 650 to 760 to 760 or 700 to 760 to 760 to 600 to 76 ...

[0051] In step 304, in some embodiments, the precursor delivery method includes flowing precursor vapor from a vaporizer container 306 to a semiconductor processing tool. In some embodiments, the flow includes pumping and / or pumping the precursor vapor from the vaporizer container to the semiconductor processing tool. In some embodiments, the flow includes applying a vacuum to flow the precursor vapor from the vaporizer container to the semiconductor processing tool. In some embodiments, the flow includes discharging the precursor vapor from the vaporizer container, for example, through an outlet. In some embodiments, the flow includes flowing the precursor vapor through a gas supply line fluidly coupled to the semiconductor processing tool and the vaporizer container. In some embodiments, the flow includes flowing the precursor vapor through at least one filter located in the gas supply line. In some embodiments, the flow includes flowing the precursor vapor through a valve assembly fluidly coupling the vaporizer container and the gas supply line.

[0052] In some embodiments, the semiconductor processing tool includes an ion implantation device.

[0053] Example 1

[0054] The iron contamination levels in MoO2Cl2 and MoCl5 precursor vapors generated by an uncoated precursor delivery system with stainless steel gas-exposed surfaces and by a coated precursor delivery system were measured and compared at high temperatures of 140°C and 150°C. The coated precursor delivery system includes an Al2O3 coating on the gas-exposed surfaces. Figure 4 As shown in the graphic view illustrating the degree of iron contamination in molybdenum-containing precursors in an uncoated system, the coated precursor delivery system reduces metal contamination at high temperatures for both MoO2Cl2 and MoCl5 precursor vapors. In contrast, the uncoated precursor delivery system shows a significant increase in iron contamination at 140°C.

[0055] Aspects

[0056] The following describes various aspects. It should be understood that any one or more of the features listed in (several) of the following aspects may be combined with any one or more other aspects.

[0057] Aspect 1. A precursor delivery system comprising:

[0058] A vaporizer container configured to contain a vaporizable precursor, which generates precursor vapor upon vaporization; and

[0059] At least one protective surface treatment;

[0060] The at least one protective surface treatment covers a sufficient amount of at least one gas-exposed surface of the precursor delivery system to reduce the amount of at least one contaminant in the precursor vapor compared to precursor vapor generated by a precursor delivery system without the at least one protective surface treatment.

[0061] Aspect 2. The precursor delivery system according to aspect 1, wherein the vaporizable precursor comprises a molybdenum-containing reagent.

[0062] Aspect 3. The precursor delivery system according to any one of aspects 1 to 2, wherein the precursor vapor comprises MoO2Cl2 vapor.

[0063] Aspect 4. The precursor delivery system according to any one of aspects 1 to 3, wherein the precursor vapor comprises MoCl5 vapor.

[0064] Aspect 5. The precursor delivery system according to any one of aspects 1 to 4, wherein the precursor vapor includes at least one contaminant at a concentration of less than 10 ppm after exposure at a temperature of at least 140°C for 180 days.

[0065] Aspect 6. The precursor delivery system according to any one of aspects 1 to 5, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the precursor delivery system.

[0066] Aspect 7. The precursor delivery system according to any one of aspects 1 to 6, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the vaporizer container.

[0067] Aspect 8. The precursor delivery system according to any one of aspects 1 to 7, further comprising:

[0068] A gas supply line that couples the vaporizer container fluid to the semiconductor processing tool.

[0069] At least a portion of at least one gas-exposed surface of the gas supply pipeline is covered by the at least one protective surface treatment.

[0070] Aspect 9. The precursor delivery system according to aspect 8, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the gas supply line.

[0071] Aspect 10. The precursor delivery system according to aspect 8, further comprising:

[0072] At least one filter is located in the gas supply line.

[0073] At least a portion of at least one gas-exposed surface of the at least one filter is covered by the at least one protective surface treatment.

[0074] Aspect 11. The precursor delivery system according to aspect 10, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the at least one filter.

[0075] Aspect 12. The precursor delivery system according to aspect 8, further comprising:

[0076] Valve assembly, which fluidly couples the vaporizer container and the gas supply line.

[0077] At least a portion of at least one gas-exposed surface of the valve assembly is covered by the at least one protective surface treatment.

[0078] Aspect 13. The precursor delivery system according to aspect 12, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the valve assembly.

[0079] Aspect 14. The precursor delivery system according to any one of aspects 1 to 13, wherein the at least one protective surface treatment comprises at least one of a coating, a surface-modified region, or any combination thereof.

[0080] Aspect 15. A method comprising:

[0081] A precursor delivery system is obtained, the precursor delivery system comprising:

[0082] Vaporizer container, which contains a vaporizable precursor; and

[0083] At least one protective surface treatment that covers at least a portion of at least one gas-exposed surface of the vaporizer container;

[0084] Vaporize at least a portion of the vaporizable precursor to generate precursor vapor; and

[0085] The precursor vapor is allowed to flow from the vaporizer container to the semiconductor processing tool.

[0086] The at least one protective surface treatment covers a sufficient amount of the at least one gas-exposed surface of the precursor delivery system to reduce the amount of at least one contaminant in the precursor vapor compared to precursor vapor generated by a precursor delivery system without the at least one protective surface treatment.

[0087] Aspect 16. The method according to aspect 15, wherein the precursor vapor comprises MoO2Cl2 vapor.

[0088] Aspect 17. The method according to any one of aspects 15 to 16, wherein the precursor vapor comprises MoCl5 vapor.

[0089] Aspect 18. The method according to any one of aspects 15 to 17, wherein the precursor vapor comprises at least one of iron contaminants, nickel contaminants, or any combination thereof, less than 10 ppm.

[0090] Aspect 19. The method according to any one of aspects 15 to 18, wherein the vaporizable precursor is vaporized at a temperature of 145°C or higher.

[0091] Aspect 20. The method according to any one of aspects 15 to 19, wherein the vaporizable precursor is vaporized at a pressure of 0.01 Torr to 760 Torr.

[0092] It should be understood that detailed changes may be made without departing from the scope of this disclosure, particularly regarding the construction materials used and the shape, size, and arrangement of components. This specification and the described embodiments are merely examples, and the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. A precursor delivery system, comprising: A vaporizer container configured to contain a vaporizable precursor, which generates precursor vapor upon vaporization; and At least one protective surface treatment; The at least one protective surface treatment covers a sufficient amount of at least one gas-exposed surface of the precursor delivery system to reduce the amount of at least one contaminant in the precursor vapor compared to precursor vapor generated by a precursor delivery system without the at least one protective surface treatment.

2. The precursor delivery system according to claim 1, wherein the vaporizable precursor comprises a molybdenum-containing reagent.

3. The precursor delivery system according to claim 1, wherein the precursor vapor comprises MoO2Cl2 vapor.

4. The precursor delivery system according to claim 1, wherein the precursor vapor comprises MoCl5 vapor.

5. The precursor delivery system of claim 1, wherein the precursor vapor comprises at least one contaminant at a concentration of less than 10 ppm after exposure at a temperature of at least 140°C for 180 days.

6. The precursor delivery system of claim 1, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the precursor delivery system.

7. The precursor delivery system of claim 1, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the vaporizer container.

8. The precursor delivery system according to claim 1, further comprising: A gas supply line that couples the vaporizer container fluid to the semiconductor processing tool. At least a portion of at least one gas-exposed surface of the gas supply pipeline is covered by the at least one protective surface treatment.

9. The precursor delivery system of claim 8, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the gas supply line.

10. The precursor delivery system according to claim 8, further comprising: At least one filter is located in the gas supply line. At least a portion of at least one gas-exposed surface of the at least one filter is covered by the at least one protective surface treatment.

11. The precursor delivery system of claim 10, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the at least one filter.

12. The precursor delivery system according to claim 8, further comprising: Valve assembly, which fluidly couples the vaporizer container and the gas supply line. At least a portion of at least one gas-exposed surface of the valve assembly is covered by the at least one protective surface treatment.

13. The precursor delivery system of claim 12, wherein the at least one protective surface treatment covers all gas-exposed surfaces of the valve assembly.

14. The precursor delivery system of claim 1, wherein the at least one protective surface treatment comprises at least one of a coating, a surface-modified region, or any combination thereof.

15. The precursor delivery system of claim 1, wherein the at least one protective surface treatment further covers at least one non-gas-exposed surface of the precursor delivery system.

16. A method comprising: A precursor delivery system is obtained, the precursor delivery system comprising: Vaporizer container, which contains a vaporizable precursor; and At least one protective surface treatment that covers at least a portion of at least one gas-exposed surface of the vaporizer container; Vaporize at least a portion of the vaporizable precursor to generate precursor vapor; and The precursor vapor is allowed to flow from the vaporizer container to the semiconductor processing tool. The at least one protective surface treatment covers a sufficient amount of the at least one gas-exposed surface of the precursor delivery system to reduce the amount of at least one contaminant in the precursor vapor compared to precursor vapor generated by a precursor delivery system without the at least one protective surface treatment.

17. The method of claim 16, wherein the precursor vapor comprises MoO2Cl2 vapor.

18. The method of claim 16, wherein the precursor vapor comprises MoCl5 vapor.

19. The method of claim 16, wherein the precursor vapor comprises at least one of iron contaminants, nickel contaminants, or any combination thereof, at less than 10 ppm.

20. The method of claim 16, wherein the vaporizable precursor is vaporized at a temperature of 145°C or higher.

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