Molybdenum pentachloride modulation and crystalline phase manipulation

Abstract

A method of conditioning MoCI5, the method comprising heating a container of MoCI5 to a temperature in a range of from about 140 DEG C to 190 DEG C for a period of time in a range of from about 2 hours to about 100 hours to produce a MoCI5-containing composition comprising from about 10% to about 60% by weight of phase 1 MoCI5 and from 90% to about 40% by weight of phase 2 MoCI5 as determined by X-ray diffraction. Such MoCI5-containing compositions are expected to be more thermally stable and provide a stable vapor supply.

Description

Cross-references to related applications

[0001] This application claims the benefit of U.S. Application No. 18 / 134,494, filed April 13, 2023, which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0002] This invention relates to the conditioning of molybdenum pentachloride to form a specific crystalline phase morphology. This specific crystalline phase morphology allows for a stable vapor pressure over a prolonged period during the vapor deposition process. Background Technology

[0003] The semiconductor industry has been using molybdenum oxychloride (including molybdenum tetrachloride (MoOCl4) and molybdenum dichloride (MoO2Cl2)) for high-productivity Mo-containing film deposition on a variety of substrates. Several examples include Entegris' US 2020 / 0131628 A1, which describes a method for depositing Mo-containing films on substrates including TiN, TaN, AlN, Al2O3, ZrO2, HfO2, SiO2, SiN, La2O3, RuO2, IrO2, Nb2O5, Y2O3, etc., using MoO2Cl2 vapor; and Entegris' US 2018 / 0286668 A1, which discloses a method for depositing Mo-containing materials using MoOCl4 vapor via CVD, where deposition using MoOCl4 can be performed at a higher rate than using MoCl5 vapor, achieving low resistivity and relatively low (but not zero) oxygen content.

[0004] MoCl5 has attracted interest as a CVD or ALD material for depositing W / Mo films such as W / Mo metal; W / MoSi2; W / MoX2, where X is S, Se, or Te; W-doped amorphous carbon, WO3, etc., see, for example, US 9,595,470, US 9,230,815, and US 7,641,886 and US 2003 / 0190424. A unique advantage of MoCl5 compared to its halide oxide analogs is its oxygen-free nature. The use of MoCl5 vapor provides the benefit of extremely low oxygen content in the film, and thus achieves low resistivity.

[0005] In Thin Solid Films, 1988, 166, 149, L. Hiltunen et al. disclosed the deposition of Mo using MoCl5 as a precursor. xMethods involving N. A similar application was disclosed in Juppo et al., J. Electrochem. Soc., 2000, 147, 3377. The same group also disclosed the deposition of Mo metal films using MoCl5 in J. Vac. Sci. Technol., 1998, A16, 2845.

[0006] US 10,510,590 B2 discloses a method for depositing a Mo-containing layer on a W-containing layer and a Mo-containing layer embedded with B, Si, or Ge by using MoCl5 as one of the precursors, which produces a low resistivity film.

[0007] Ewens et al. (“The structures of molybdenum pentachloride and tungstenhexachloride”, Trans. Faraday Soc. 1938, 34, 1358) disclosed that gaseous MoCl5 exhibits a trigonal bipyramidal structure.

[0008] A stable and regenerable MoCl5 vapor flux still needs to be supplied to the vapor deposition process chamber over an extended period of time. Summary of the Invention

[0009] A method for conditioning MoCl5 is disclosed, comprising heating a container of MoCl5 to a temperature ranging from about 140°C to 190°C (lower than WCl5) for a period of time ranging from about 2 hours to about 100 hours to produce a MoCl5-containing composition comprising about 10% to about 60% by weight of phase 1 (different from WCl5) MoCl5 and 90% to about 40% by weight of phase 2 MoCl5, as determined by X-ray diffraction. The disclosed method includes one or more of the following features: • Select a container that is non-reactive to MoCl5; • The container is made of glass or lined with glass; • The container is made of stainless steel; • The container is made of glass, Teflon, or coated stainless steel; • This period of time ranges from approximately 24 hours to approximately 72 hours; • This time period ranges from approximately 36 hours to approximately 48 hours; • The temperature ranges from approximately 150°C to 180°C; • The temperature ranges from approximately 160°C to 170°C; • The MoCl5-containing composition comprises approximately 10% to approximately 60% by weight of phase 1 MoCl5 and 90% to approximately 40% by weight of phase 2 MoCl5; • The MoCl5-containing composition comprises approximately 20% to approximately 50% by weight of phase 1 MoCl5 and 80% to approximately 50% by weight of phase 2 MoCl5; • The MoCl5-containing composition comprises approximately 30% to approximately 55% by weight of phase 1 MoCl5 and 70% to approximately 45% by weight of phase 2 MoCl5; • The MoCl5-containing composition comprises approximately 40% to approximately 50% by weight of phase 1 MoCl5 and 60% to approximately 50% by weight of phase 2 MoCl5; • The MoCl5-containing composition is thermally stable; and • This MoCl5-containing composition provides a stable vapor supply.

[0010] The disclosure also discloses a MoCl5-containing composition prepared by the disclosed method, having approximately 10% to approximately 60% by weight of phase 1 MoCl5 and 90% to approximately 40% by weight of phase 2 MoCl5. The disclosed MoCl5-containing composition includes one or more of the following characteristics: • It contains approximately 20% to approximately 50% by weight of phase 1 MoCl5 and 80% to approximately 50% by weight of phase 2 MoCl5; • It contains approximately 30% to approximately 55% by weight of phase 1 MoCl5 and 70% to approximately 45% by weight of phase 2 MoCl5; • It contains approximately 40% to 50% by weight of phase 1 MoCl5 and 60% to 50% by weight of phase 2 MoCl5; • It is thermally stable; and • Provides a stable supply of steam. Annotations and naming

[0011] Specific abbreviations, symbols, and terms are used throughout the following specification and claims, and include:

[0012] As used in this article, the indefinite article “a or an” means one or more species.

[0013] As used herein, “about” or “around or approximately” in the text or claims means ±10% of the value.

[0014] The term "ambient temperature" refers to the ambient temperature, which is approximately 18°C ​​to approximately 25°C.

[0015] As used in this article, the abbreviation "RT" refers to room temperature or a temperature ranging from approximately 18°C ​​to approximately 25°C.

[0016] As used in this article, the abbreviation "XRD" refers to X-ray diffraction and "PXRD" refers to powder X-ray diffraction.

[0017] The term "substrate" refers to one or more materials on which processes are performed. A substrate can refer to a wafer having one or more materials on which processes are performed. A substrate can be any suitable wafer used in the manufacture of semiconductor, photovoltaic, flat panel, or LCD-TFT devices. A substrate can also have one or more different material layers deposited thereon from previous manufacturing steps. For example, a wafer can include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon-containing layers (e.g., SiO2, SiN, SiON, SiCOH, etc.), metal-containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or combinations thereof. Furthermore, a substrate can be planar or patterned. A substrate can be an organically patterned photoresist film. The substrate may include an oxide layer used as a dielectric material (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications. Those skilled in the art will recognize that the terms "film" or "layer" as used herein refer to a material of a certain thickness laid or spread on a surface, and that surface may be trenches or lines. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as a substrate.

[0018] As used herein, the abbreviation “NAND” refers to a “Negative AND or Not AND” gate; the abbreviation “2D” refers to a 2D gate structure on a planar substrate; and the abbreviation “3D” refers to a 3D or vertical gate structure in which gate structures are stacked in the vertical direction.

[0019] In this paper, it is important to note that the term "phase" refers to a crystalline solid with a regular and repeating three-dimensional arrangement of atoms. The measured powder pattern has diffraction peak positions, and the intensity is a "fingerprint" of a specific solid crystalline phase.

[0020] This article uses standard abbreviations for elements from the periodic table. It should be understood that elements may be referred to by these abbreviations (e.g., Mo for molybdenum, W for tungsten, Si for silicon, C for carbon, etc.).

[0021] A unique CAS registry number (i.e., "CAS") assigned by the Chemical Abstracts Service is provided to identify the specific molecule disclosed.

[0022] In this document, a range may be expressed as from about one specific value and / or to about another specific value. When such a range is expressed, it should be understood that another embodiment is from that one specific value and / or to that other specific value, together with all combinations within the range. Any and all ranges listed herein include their endpoints (i.e., x = 1 to 4, or x in the range from 1 to 4, including x = 1, x = 4, and x = any number in between), regardless of whether the term "inclusive" is used.

[0023] In this document, references to "an embodiment" or "embodiment" mean that a particular feature, structure, or characteristic described with respect to that embodiment may be included in at least one embodiment of the invention. The phrase "in an embodiment" appearing in different places in the specification does not necessarily refer to the same embodiment in all instances, and individual or alternative embodiments are not necessarily mutually exclusive with other embodiments. The foregoing also applies to the term "implementation".

[0024] As used herein, the term “exemplary” is used to mean serving as an instance, example, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as superior to or advantageous to other aspects or designs. Rather, the use of the term “exemplary” is intended to present the concept in a concrete manner.

[0025] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise stated or clear from the context, "X adopts A or B" is intended to mean any natural inclusive arrangement. That is, if X adopts A; X adopts B; or X adopts both A and B, then "X adopts A or B" is satisfied in any of the foregoing cases. Additionally, the article "a / an" as used in this application and the appended claims should generally be interpreted as meaning "one or more" unless otherwise stated or clearly indicated from the context to the singular form.

[0026] The term “comprising” in the claims is an open-ended transitional term meaning that the subsequently defined claim elements are a non-exclusive list (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” is defined herein as necessary to encompass the more restrictive transitional terms “substantially consists of” and “consisting of”; therefore, “comprising” can be replaced by “substantially consists of” or “consisting of” and remain within the clearly defined scope of “comprising”.

[0027] In the claims, "provide" is defined as meaning to supply, provide, make available, or prepare something. The steps can, conversely, be performed by any actor even if not explicitly stated in the claims. Attached Figure Description

[0028] To further understand the nature and purpose of the present invention, reference should be made to the following detailed description in conjunction with the accompanying drawings, in which the same elements are given the same or similar reference numerals, and wherein: Figure 1 The simulated PXRD spectrum of MoCl5 phase 1 was generated using Mercury software; Figure 2 This is a graph showing the sublimation rate of the material versus the crystalline phase composition MoCl5; and Figure 3 This is a schematic diagram of an exemplary device in which this instance is performed. Detailed Implementation

[0029] Although the trigonal bipyramidal structure of gaseous MoCl5 has been disclosed (Ewens et al., Proceedings of the Faraday Society, 1938, 34, 1358), the applicants have found that the sublimation rate of solid MoCl5 is unstable under typical industrial vaporization conditions, leading to potential performance deviations in processes utilizing MoCl5 vapor. In other words, the deposition rate of Mo-containing films becomes unstable as the MoCl5 reservoir is depleted during the vapor deposition process.

[0030] Further analysis revealed that the performance variation was due to a change in the crystalline phase composition of MoCl5. More specifically, freshly sublimated MoCl5 tends to consist of a mixture of phases 1 and 3. However, during the vapor deposition process, the MoCl5 container is heated to temperatures ranging from approximately 70°C to approximately 170°C, preferably from 90°C to 140°C, and the composition gradually changes to a mixture of phases 1 and 2, with phase 2 comprising approximately 40% to approximately 80%.

[0031] To the applicant's knowledge, no crystal structure of phase 1 has been reported. Phase 1 of MoCl5 is a monoclinic crystal with space group 12 as C2 / m. The cell parameters are a = 18.01 Å, b = 17.66 Å, c = 5.76 Å, and β = 90.18°. Phase 1 of MoCl5 is similar to the reported compounds NbCl5 (PXRD pattern: ICDD PDF card number 04-0005-4229, see Zalkin et al., (“The crystal structure of NbCl5”, Acta Crystallogr. 1958, 11, 615-619)) and TaCl5 (PXRD pattern: ICDD PDF card number 04-109-4194, see Wimmer et al., (“Li2Ba4Al2Ta2N8O, the First Barium Nitridoalumotantalate with BCT-Zeolite Type Structure”, Anorg Allg Chem., 2001, 627, 180-185)). [Journal of Inorganic and General Chemistry, 2001, 627, 180-185]) and WCl5 (see US 10710896 B2) are isomorphic. The crystal structure of phase 1 can be generated by modifying the cell parameters of NbCl5, TaCl5, or WCl5 with the cell parameters above collected from PXRD data. The corresponding Nb, Ta, or W atoms are then replaced with Mo. The obtained powder XRD data are simulated using software such as Mercury or CrystDiffract. Figure 1 The simulated PXRD spectrum of MoCl5 phase 1 was generated using Mercury software.

[0032] The crystal structure of phase 2 (α-MoCl5) of MoCl5 has been disclosed in Acta Crystallographica, 1959, 12, 273 (ICDD PDF card number 04-007-5325) and Acta Crystallographica, 1967, 34, 770. Similar to phase 1, phase 2 is a monoclinic crystal with space group 12 as C2 / m. The cell parameters are a = 17.31(1) Å, b = 17.81(1) Å, c = 6.079(5) Å, β = 95.7(1)°.

[0033] The crystal structure of phase 3 (β-MoCl5) of MoCl5 has been disclosed in Acta Crystallographica, Section B: Structural Science, 1997, 53, 895-903 (ICDD PDF card number 04-013-3430). Unlike phases 1 and 2, phase 3 is a triclinic crystal with space group 2 as P-1. The cell parameters are a = 6.594(6) Å, b = 9.048(9) Å, c = 6.074(4) Å, α = 90.81(4)°, β = 116.12(5)°, γ = 108.42(4)°. Table 1. X-ray diffraction simulation data of MoCl5 phases 1, 2 and 3

[0034] At least two other disclosed crystalline phases of MoCl5 exist (γ-MoCl5 and...). γ-MoCl5), but it is not present in detectable concentrations in the materials we treated. γ-MoCl5 (ICDD PDF card number 04-007-2432, Acta Crystallographica, Chapter B: Structural Science, 1997, 53, 895-903) is an orthorhombic crystal with space group 62 as Pnma. The cell parameters are a = 11.700(9) Å, b = 17.874(10) Å, c = 6.085(3) Å. -MoCl5 (ICDD PDF card number 04-013-3431, Acta Crystallographica, Chapter B: Structural Science, 1997, 53, 895-903) is a monoclinic crystal with space group 14 as P21 / a. The cell parameters are a = 12.162 Å, b = 11.750 Å, c = 9.468 Å, β = 108.88°.

[0035] All crystalline phases contain MoCl5 dimers (i.e., Mo2Cl). 10Each Mo atom is in a pseudo-octahedral geometry connected to four non-shared Cl atoms and two shared Cl atoms. Therefore, the phase transition from phase 1 to phase 2 is a diffusionless transition. In other words, no major reorganization of the crystal structure is observed. In a diffusionless transition, atoms slightly change their positions in a relatively coordinated manner without interrupting the original bonds (see, for example, DA Porter et al., Phase transformations in metals and alloys, Chapman & Hall, 1992, p. 172).

[0036] As illustrated in the following examples, MoCl5 materials containing varying percentages of phases 1 and 2, phases 1 and 3, or phases 1, 2, and 3 were prepared using different methods. PXRD measurements were performed on a Bruker D8 advanced diffractometer (Cu Kα radiation, λ = 1.5418 Å). A leak-sealed low-background dome sample holder was used. Samples were prepared and sealed in a nitrogen-filled glove box to handle air-sensitive materials without air / moisture exposure. Inside the nitrogen-filled glove box, the material was ground into a fine powder using an agate mortar and pestle. The average particle size of the powder ranged from approximately 20 μm to approximately 200 μm. X-ray output was 1600–2000 W, and the detector was a Lynxeye XE-T energy-dispersive composite silicon strip detector. Powder patterns were collected using an θ-θ scanning mode (range 2θ = 8°–70°, step size 0.01°).

[0037] Using Rietveld's method and Figure 1 The percentage of each crystalline phase in the various MoCl5 samples was determined using the reference crystal structures in Table 1. More specifically, background was measured and removed from each dataset. The remaining diffraction peaks were compared with... Figure 1 The phase composition percentage was determined by matching the reference pattern in Table 1.

[0038] Specifically, for MoCl5 samples that are typically a mixture of two phases (phase 1 and phase 2, or phase 1 and phase 3), the diffraction peaks in the data are matched to reference patterns for phases 1, 2, and 3 listed in the table. The relative phase fractions of the two crystalline phases in each sample are then refined using XRD data. A final fit is performed between the calculated diffraction intensities from the refined sample model and the original XRD data. The fit is generally good, and the refined phase fractions are obtained. Bruker Topas v6.0 and MDI-Jade 2010 are used.

[0039] The applicants have discovered that the crystalline phases 1, 2 and 3 of MoCl5 have different vapor pressures. Figure 2 This is a graph showing the relationship between the sublimation rate of the material and the crystalline phase composition of MoCl5. (Example:) Figure 2 As shown, the sample containing a higher concentration of phase 1 exhibits a higher sublimation rate compared to the sample containing a lower concentration of phase 1. Therefore, phase 1 has a higher vapor pressure than phases 2 and 3. As illustrated, supplying MoCl5 containing a mixture of crystalline materials of phases 1 and 3, or phases 1 and 2, will cause a change in vapor pressure over time because phase 1 is consumed faster than phases 2 and 3 even in the absence of any phase transformation (i.e., phase 1 has a higher vapor pressure). Under isothermal conditions of 100°C and 100 sccm N2 carrier gas, the sublimation rate of phase 1 is approximately 0.02692 wt% / min, the sublimation rate of phase 2 is approximately 0.02187 wt% / min, and the sublimation rate of phase 3 is 0.01947 wt% / min. The volatility of phase 1 is approximately 23% higher than that of phase 2, and approximately 38% higher than that of phase 3.

[0040] Furthermore, as shown in Example 4, during the vapor deposition process, phase 3 transforms into phase 1, and then partially transforms into phase 2. This transformation further exacerbates the vapor pressure shift.

[0041] The difference in vapor pressure and the accompanying changes in overall volatility caused by the transformation from phase 3 to phase 1 and then from phase 1 to phase 2 lead to potential instability in tool performance and may shorten the use of MoCl5 material. In addition, equipment parameters must be adjusted to ensure a sufficient and stable supply of MoCl5 vapor to the vapor deposition tool.

[0042] Ideally, products composed of a single phase are preferred. However, due to the nature of phase transformation that persists under elevated operating conditions, even starting from a single-phase material, the phase composition will inevitably change when the material is sublimated upon heating. More specifically, phase 3 to phase 1 transformation occurs at lower temperatures and faster rates compared to phase 1 to phase 2 transformations that occur at relatively higher temperatures and slower rates. Phase 3 to phase 1 transformations can be complete; however, phase 1 to phase 2 transformations are partial and will reach equilibrium rather than a purely single-phase material.

[0043] Therefore, a constant and balanced phase 1:phase 2 ratio must be maintained to supply a stable vapor pressure over time. As shown in Example 3, during the vapor deposition process, a mixture of phase 1 and phase 3 of MoCl5 partially transforms into a mixture of phase 1 and phase 2 of MoCl5. The applicant found that the phase 2-rich material does not transform back into phase 1. Therefore, phase 2 MoCl5 can be supplied at any temperature.

[0044] MoCl5 can be heated to just below its melting point to transform it from a mixture of phase 3 and phase 1 into a phase 2-rich material (i.e., mp = 194°C). At higher temperatures, the phase transformation occurs more rapidly.

[0045] Phase transformations that typically occur during vapor deposition (i.e., at temperatures ranging from approximately 70°C to approximately 120°C) are much slower than those occurring at 140°C to 180°C. During vapor deposition, MoCl5 vapor is typically generated using a solid precursor vaporizer heated to temperatures ranging from approximately 70°C to approximately 180°C. The solid precursor vaporizer is typically a stainless steel vessel with at least one inlet and one outlet connected to an isolation valve. Heating the solid precursor vaporizer to temperatures above 150°C for an extended period to transform the material from phase 1 to phase 2 can lead to corrosion of the vaporizer and contamination of the MoCl5 with stainless steel elements such as Cr, Fe, Ni, etc.

[0046] Phase transformation in a separate container allows for a faster transformation than that occurring during the vapor deposition process. The container is chosen for its resistance to both material properties and its characteristics under heating. It is also selected to limit the risk of introducing any impurities into the MoCl5. Suitable containers include glass containers, quartz containers, glass-coated containers, etc. After the MoCl5 is transformed into a phase 2-rich material, it can be filled into a solid precursor vaporizer for the vapor deposition process to ensure a stable vapor supply.

[0047] Temperatures range from approximately 140°C to 194°C below the melting point of MoCl5. This method allows for higher temperatures and thus faster processing with a limited risk of contamination, provided the surface exposed to MoCl5 is not metallic. Therefore, Example 4 also demonstrates that MoCl5 is stable within this temperature range, as illustrated by the low amount of non-volatile residues observed by TGA after processing.

[0048] Stainless steel can be treated to improve its corrosion resistance. Exemplary treatments include electropolishing (EP), coating with metal oxides, SiO2, laminates, plating, etc. However, at temperatures of 140°C or lower, it takes far more than three days to go from a material rich in phase 1 to a material rich in phase 2 with >50% phase 2.

[0049] With the primary supply of phase 1, and given that MoCl5 must be maintained at T (< 100°C), the partial conversion of phase 1 to phase 2 is sufficiently limited (typically < 10%) during the duration of use on the equipment (2 weeks to 24 months) at that temperature. Example

[0050] The following non-limiting examples are provided to further illustrate embodiments of the invention. However, these examples are not intended to cover all situations and are not intended to limit the scope of the invention described herein. Example 1: Vacuum sublimation

[0051] Equipment: Glass sublimation unit and cooler.

[0052] Crude MoCl5 was added to the bottom of the glass sublimator assembly. The sublimator was then placed in the heating mantle and properly assembled. The sublimator assembly was vacuumed to the range of 1 mTorr to 10 Torr. The cooler was maintained using a coolant with a temperature range of 0 to 30°C. The heating mantle temperature was maintained in the range of 140 to 180°C. After heating, the heating mantle was closed and allowed to cool. The sublimator assembly was then backfilled with inert gas, carefully disassembled, and the solid material from the sublimator was collected. Solid material samples (lots 1 to 5 below) were subjected to XRD analysis to quantify the crystalline phase. The XRD analysis results are shown in Table 2. Table 2 Example 2: Sublimation with Carrier Gas Assist

[0053] Equipment: Coated stainless steel sublimation unit.

[0054] Load crude MoCl5 into the bottom of the coated stainless steel sublimator. Place the top cap on the sublimator and secure the sublimator and cap together with clamps. Place the heating mantle (cap) to cover the top cap. Connect one KF 40 connector of the stainless steel tubing to the sublimator cap using a KF 40 Kalrez gasket and secure it with clamps. Connect the other KF 40 connector of the stainless steel tubing to the receiving tank cap inlet. Connect the vacuum line to the receiving tank cap outlet. Connect the N2 carrier gas line to the sublimator purge port.

[0055] After the system leak test, turn on the temperature controller and set it as follows: • Bottom of sublimator: 190 + / - 20°C • Lid: 2000 + / - 20°C • Transfer tubing: 220 + / - 20°C • Receiving can lid: 225 + / - 20°C

[0056] Set the N2 purge flow meter to 10-500 atm / cm. 3The range is / min (sccm). After heating, the heating mantle is closed, and the sublimator is cooled to below 60°C, and then the carrier gas N2 is turned off. The receiving vessel is carefully disassembled, and the solid material is then collected. The solid material sample is subjected to XRD analysis to quantify the crystalline phase. The XRD analysis results are shown in Table 3. Table 3 Example 3: In-situ phase transition

[0057] Freshly vacuum-sublimated (electronic-grade quality) MoCl5 prepared by the method described in Example 1 was added to a sublimator or solid precursor vaporizer and maintained at a temperature ranging from approximately 70°C to 120°C. Over time, all of Phase 3 disappeared, forming a mixture of Phase 1 and Phase 2. During the 2–24 month vapor deposition process, after more than 50% of the MoCl5 material in the tank was consumed, the concentration of Phase 2 increased to 30% or more. It is considered that under standard sublimation and standard operating conditions, it may take more than 2 months to produce material that is predominantly Phase 2 MoCl5. The results are listed in Table 4. Table 4 Example 4: Small-scale adjustment (< 20 g)

[0058] In a glove box, 10-20 grams of freshly sublimated MoCl5 solid, prepared by the method described in Example 1, was added to a 316L stainless steel tube. The tube was sealed in a nitrogen-filled glove box. The stainless steel tube containing MoCl5 was then heated by immersion in a hot bath or in an oven at a temperature ranging from 70°C to 190°C for a period of time. The stainless steel tube was then removed from the hot bath or oven and allowed to cool for 1 hour before being returned to the glove box. A lustrous cake-like substance was observed in the stainless steel tube, which could be broken down into bright crystals. The lustrous cake-like product was collected and subjected to XRD analysis to quantify the crystalline phase. The results are listed in Tables 5A to 5D. Table 5A Table 5B Table 5C Table 5D Example 5: Large-scale regulation (approximately 500 g)

[0059] Figure 3This is a schematic diagram of an exemplary apparatus in which this example is performed. As shown, a can 104 is placed in an oven 102. A valve 108 is fluidly connected to the lid 106 of the can 104. The can 104 may be a coated stainless steel can. The valve 108 can be used to introduce vacuum, positive pressure, and leak check seals. The number 110 indicates the heating element in the oven 102. Those skilled in the art will further recognize the sources used for this apparatus. A certain level of customization of these components may be required based on desired temperature ranges, pressure ranges, local regulations, etc.

[0060] In a glove box (not shown), 500 g (+ / - 50 g) of freshly sublimed MoCl5 prepared by the method described in Example 1 or Example 2 is added to jar 104. Here, jar 104 may be an 8L coated stainless steel jar. The jar 104 is then checked for leaks by vacuum burst and external He testing. Afterward, jar 104 is heated at 170°C for 24–48 hours using oven 102. After the time requirement is met, the heating of oven 102 is turned off. Jar 104 is allowed to cool slowly within oven 102 to below 60°C. Jar 104 is then removed from oven 102 and transferred back to the glove box. The lid 106 of jar 104 is removed, and a large, glossy black cake-like substance formed on the bottom of jar 104 is poured into a glass mortar. The large, glossy black cake-like substance is coarsely ground with a glass mortar and pestle to obtain a crystalline powder. The crystalline powder product was collected and subjected to XRD analysis to quantify the crystalline phase. Table 6 shows that repeating this process yielded a phase 2 material with approximately 50%–60% by weight. Table 6

[0061] These MoCl5 materials are thermally stable and would be suitable for providing a stable vapor supply of MoCl5 vapor during vapor deposition or etching processes.

[0062] Although embodiments of the invention have been shown and described, those skilled in the art can modify them without departing from the spirit or teachings of the invention. The embodiments described herein are exemplary only and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, the scope of which should include all equivalent forms of the subject matter of the claims.

[0063] It should be understood that many additional changes in details, materials, steps, and arrangements of parts that have been described and elucidated to explain the essence of the invention can be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Therefore, the invention is not intended to be limited to the specific embodiments given above and / or in the drawings.

Claims

1. A method for adjusting MoCl5, the method comprising: A container of MoCl5 is heated to a temperature ranging from about 140°C to 190°C for a period of time ranging from about 2 hours to about 100 hours to produce a MoCl5-containing composition comprising about 10% to about 60% by weight of phase 1 MoCl5 and 90% to about 40% by weight of phase 2 MoCl5, as determined by X-ray diffraction.

2. The method as described in claim 1, wherein, The container was selected to be non-reactive to MoCl5.

3. The method as described in claim 1, wherein, The container is made of glass or glass-lined, stainless steel, coated stainless steel, or Teflon.

4. The method of claim 1, wherein, This period of time ranges from approximately 24 hours to approximately 72 hours.

5. The method of claim 1, wherein, This period of time ranges from approximately 36 hours to approximately 48 hours.

6. The method of claim 1, wherein, The temperature ranges from approximately 150°C to 180°C.

7. The method of claim 1, wherein, The temperature ranges from approximately 160°C to 170°C.

8. The method according to any one of claims 1 to 7, wherein, The MoCl5-containing composition comprises approximately 10% to approximately 60% by weight of phase 1 MoCl5 and 90% to approximately 40% by weight of phase 2 MoCl5.

9. The method according to any one of claims 1 to 7, wherein, The MoCl5-containing composition comprises approximately 20% to approximately 50% by weight of phase 1 MoCl5 and 80% to approximately 50% by weight of phase 2 MoCl5.

10. The method according to any one of claims 1 to 7, wherein, The MoCl5-containing composition comprises approximately 30% to approximately 55% by weight of phase 1 MoCl5 and 70% to approximately 45% by weight of phase 2 MoCl5.

11. The method according to any one of claims 1 to 7, wherein, The MoCl5-containing composition comprises approximately 40% to approximately 50% by weight of phase 1 MoCl5 and 60% to approximately 50% by weight of phase 2 MoCl5.

12. A MoCl5-containing composition adjusted by the method of claim 1, having about 10% to about 60% by weight of phase 1 MoCl5 and 90% to about 40% by weight of phase 2 MoCl5.

13. The MoCl5-containing composition of claim 12, having about 20% to about 50% by weight of phase 1 MoCl5 and 80% to about 50% by weight of phase 2 MoCl5.

14. The MoCl5-containing composition of claim 12, having about 30% to about 55% by weight of phase 1 MoCl5 and 70% to about 45% by weight of phase 2 MoCl5.

15. The MoCl5-containing composition of claim 12, having about 40% to about 50% by weight of phase 1 MoCl5 and 60% to about 50% by weight of phase 2 MoCl5.

16. The MoCl5-containing composition according to any one of claims 12 to 15, which is thermally stable and provides a stable vapor supply.

Images