Conditioning and control of the crystalline phase of molybdenum pentachloride

Abstract

A method for conditioning MoCl5, comprising heating a container of MoCl5 to a temperature in the range of approximately 140°C to 190°C for a time in the range of approximately 2 hours to approximately 100 hours to produce a MoCl5-containing composition containing approximately 10% to approximately 60% by weight of Phase 1 MoCl5 and 90% to approximately 40% by weight of Phase 2 MoCl5, as determined by X-ray diffraction. This MoCl5-containing composition is expected to be more thermally stable and provide a stable vapor supply.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Patent Application No. 18 / 134,494, filed Apr. 13, 2023, which is hereby incorporated by reference in its entirety for all purposes.

[0002] It is disclosed that the present invention relates to conditioning molybdenum pentachloride to form a specific crystal phase morphology, which enables a stable vapor pressure over a long period during a deposition process.

Background Art

[0003] In the semiconductor industry, molybdenum oxy - chlorides such as molybdenum oxytetrachloride (MoOCl4) and molybdenum dioxydichloride (MoO2Cl2) have been used for the deposition of Mo - containing films with high throughput onto various substrates. Examples include U.S. Patent Application Publication No. 2020 / 0131628A1 of Entegris, which claims a process for depositing a Mo - containing film on a substrate containing TiN, TaN, AlN, Al2O3, ZrO2, HfO2, SiO2, SiN, La2O3, RuO2, IrO2, Nb2O5, Y2O3, etc. using MoO2Cl2 vapor, and U.S. Patent Application Publication No. 2018 / 0286668A1 of Entegris, which discloses a method for depositing a Mo - containing material by CVD using MoOCl4 vapor. In the latter, the deposition using MoOCl4 can proceed at a faster rate than when using MoCl5 vapor and can achieve a low resistivity with a relatively low (but not completely oxygen - free) oxygen content.

[0004] MoCl5 has attracted interest as a CVD or ALD material used to deposit W / Mo-containing films such as W / Mo metal, W / MoSi2, W / MoX2 (where X is S, Se, or Te), W-doped amorphous carbon, and WO3 (see, for example, U.S. Patent Nos. 9,595,470, 9,230,815, 7,641,886, and U.S. Patent Application Publication 2003 / 0190424). A unique advantage of MoCl5 is its oxygen-free nature compared to its oxyhalide analogs. Using MoCl5 vapor results in extremely low oxygen content in the film, which in turn results in low resistivity.

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

[0006] U.S. Patent No. 10,510,590B2 discloses a Mo-containing layer deposition process for generating a low-resistivity film on a W-containing layer by using MoCl5 as one of the precursors, and a Mo-containing layer in which B, Si, or Ge are embedded.

[0007] Ewens et al. ("The structures of molybdenum pentachloride and tungsten hexachloride", Trans. Faraday Soc. 1938, 34, 1358) disclosed that gaseous MoCl5 exhibited a trigonal bipyramidal structure.

[0008] It remains necessary to supply a stable and reproducible MoCl5 vapor stream to the deposition process chamber over extended periods. [Overview of the project] [Means for solving the problem]

[0009] A method for conditioning MoCl5 is disclosed, which includes the step of heating a container of MoCl5 to a temperature in the range of about 140°C to 190°C (lower than the temperature of WCl5) for a time in the range of about 2 hours to about 100 hours to produce a MoCl5-containing composition containing 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: • The container is selected so as to be non-reactive to MoCl5; • The container is made of glass or has a glass lining; • The container is made of stainless steel; • The container is made of glass, Teflon, or coated stainless steel; • The time range is approximately 24 to 72 hours; • The duration is in the range of approximately 36 to 48 hours; • The temperature is in the range of approximately 150°C to 180°C; • The temperature is in the range of approximately 160°C to 170°C; The MoCl5-containing composition contains approximately 10% to 60% by weight of Phase 1 MoCl5 and approximately 90% to 40% by weight of Phase 2 MoCl5; The MoCl5-containing composition contains approximately 20% to 50% by weight of Phase 1 MoCl5 and approximately 80% to 50% by weight of Phase 2 MoCl5; The MoCl5-containing composition contains approximately 30% to 55% by weight of Phase 1 MoCl5 and approximately 70% to 45% by weight of Phase 2 MoCl5; The MoCl5-containing composition contains approximately 40% to 50% by weight of Phase 1 MoCl5 and approximately 60% to 50% by weight of Phase 2 MoCl5; • The MoCl5-containing composition is thermally stable; and • The MoCl5-containing composition provides a stable vapor supply.

[0010] Also disclosed are MoCl5-containing compositions containing about 10% to about 60% by weight of Phase 1 MoCl5 and 90% to about 40% by weight of Phase 2 MoCl5, conditioned by the method of the present disclosure. The disclosed MoCl5-containing compositions include one or more of the following features: It contains approximately 20% to 50% by weight of Phase 1 MoCl5 and approximately 80% to 50% by weight of Phase 2 MoCl5; It contains approximately 30% to 55% by weight of Phase 1 MoCl5 and approximately 70% to 45% by weight of Phase 2 MoCl5; It contains approximately 40% to 50% by weight of Phase 1 MoCl5 and approximately 60% to 50% by weight of Phase 2 MoCl5; • Thermally stable; and • Provides a stable steam supply.

[0011] Notation and Nomenclature Throughout the following description and claims, certain abbreviations, symbols, and terms are used, including the following:

[0012] In this specification, the indefinite article "a" or "an" means one or more.

[0013] In this specification, "about, around, approximately" in the text or claims means ±10% of the specified value.

[0014] The term "ambient temperature" refers to the ambient temperature between approximately 18°C ​​and 25°C.

[0015] In this specification, the abbreviation "RT" means room temperature or a temperature in the range of approximately 18°C ​​to approximately 25°C.

[0016] In this specification, the abbreviation "XRD" means X-ray diffraction, and "PXRD" means powder X-ray diffraction.

[0017] The term "substrate" refers to one or more materials on which a process is performed. The substrate may refer to a wafer having one or more materials on which a process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductor, solar power generation, flat panel, or LCD-TFT devices. The substrate may have one or more layers of different materials already deposited thereon in a previous manufacturing step. For example, the wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Further, the substrate may be flat or patterned. The substrate may be a photoresist film patterned with an organic material. The substrate may include a layer of an oxide (e.g., ZrO2-based material, HfO2-based material, TiO2-based material, rare earth oxide-based material, ternary oxide-based material, etc.) used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications, or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those skilled in the art will understand that the terms "film" or "layer" as used herein refer to the thickness of a material laid or spread on a surface, and that surface may be a trench or a line. Throughout this specification and the claims, the wafer and the related layers thereon are referred to as the substrate.

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

[0019] In addition, as used herein, the term "phase" refers to a crystalline solid having a regularly repeating three-dimensional arrangement of atoms. The measured powder pattern has the positions and intensities of diffraction peaks, which serve as the "fingerprint" of a particular solid crystalline phase.

[0020] In this specification, standard abbreviations for the elements of the periodic table are used. It should be understood that the elements may be referred to by these abbreviations (for example, Mo refers to molybdenum, W refers to tungsten, Si refers to silicon, C refers to carbon, etc.).

[0021] The unique CAS Registry Number (i.e., "CAS") assigned by the Chemical Abstract Service is provided to identify the specific molecule disclosed.

[0022] In this specification, ranges 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 other embodiments include from that one specific value and / or to that other specific value, as well as any combination within said range. Any range recited herein includes its endpoints, whether or not the term "comprising" is used (i.e., "x = 1 to 4" or "x is in the range of 1 to 4" includes x = 1, x = 4, and x = "any number in between").

[0023] References to "one embodiment" or "an embodiment" in this specification mean that a particular feature, structure, or characteristic described in connection with that embodiment can be included in at least one embodiment of the present invention. The appearances of the phrase "one embodiment" in various places in this specification do not necessarily all refer to the same embodiment, nor are different or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term "implementation".

[0024] As used in this application, the phrase "exemplary" is used herein to serve as an example, instance, or illustration. Any aspect or design described as "exemplary" in this specification should not be construed as necessarily more preferable or advantageous than other aspects or designs. Rather, the use of the phrase "exemplary" is intended to present concepts in a concrete form.

[0025] Furthermore, the term “or” is intended to mean an inclusive “or,” not an exclusive “or.” That is, unless otherwise specified or it is clear from the context, “X adopts A or B” is intended to mean either of the natural compatible substitutions. That is, if X adopts A, if X adopts B, or if X adopts both A and B, all of the above satisfy the condition “X adopts A or B.” Also, the articles “a” and “an” used in this application and the attached claims should generally be interpreted as meaning “one or more,” unless otherwise specified or it is clear from the context that they refer to the singular form.

[0026] In a claim, “contains” is an open transitional clause, meaning that the elements of the claim specified thereafter are non-exclusive enumerations (i.e., anything else additionally included remains within the scope of “contains”). “Contains” is defined herein as necessarily encompassing the more restrictive transitional clauses “essentially from” and “consisting of.” Thus, “contains” can be replaced with “essentially from” or “consisting of,” while still remaining within the explicitly defined scope of “contains.”

[0027] In a claim, “to provide” is defined as meaning to provide, supply, make available, or prepare something. Unless the claim contains explicit language to the contrary, this step can be performed by any actor.

[0028] To better understand the nature and purpose of the present invention, please refer to the following detailed description in conjunction with the accompanying drawings. In the drawings, similar elements are assigned the same or similar reference numerals. [Brief explanation of the drawing]

[0029] [Figure 1]Figure 1 shows the simulated PXRD spectrum of phase 1 of MoCl5, generated using Mercury software. [Figure 2] Figure 2 is a diagram showing the sublimation rate of a substance against the crystalline phase composition of MoCl5. [Figure 3] Figure 3 is a schematic diagram of an exemplary apparatus in which this embodiment is implemented. [Modes for carrying out the invention]

[0030] While it has been disclosed that MoCl5 in the gas phase exhibits a trigonal bipyramidal structure (Ewens et al., Trans. Faraday Soc. 1938, 34, 1358), the applicants have discovered that under normal industrial vaporization conditions, the sublimation rate from solid MoCl5 is unstable, which can lead to performance variations in processes utilizing MoCl5 vapor. In other words, if the MoCl5 canister is consumed during the deposition process, the deposition rate of the Mo-containing film becomes unstable.

[0031] Further analysis indicates that the change in performance is due to a change in the crystalline phase composition of MoCl5. More specifically, the crystalline phase of freshly sublimated MoCl5 tends to contain a mixture of phase 1 and phase 3. However, during the deposition process, the MoCl5 canister is heated to a temperature of approximately 70°C to 170°C, preferably 90°C to 140°C, and the composition gradually changes to a mixture of phase 1 and phase 2, with phase 2 accounting for approximately 40% to 80%.

[0032] To the best of our knowledge, the crystal structure of phase 1 has not been reported. Phase 1 of MoCl5 is monoclinic, and its space group is 12(C2 / m). The unit cell parameters are a=18.01Å, b=17.66Å, c=5.76Å, and β=90.18°. Phase 1 of MoCl5 is isomorphic to previously reported compounds such as NbCl5 (PXRD pattern: ICDD PDF card #04-0005-4229, see Zalkin et al., "The crystal structure of NbCl5", Acta Crystallogr. 1958, 11, 615-619)), TaCl5 (PXRD pattern: ICDD PDF card #04-109-4194, see Wimmer et al., "Li2Ba4Al2Ta2N8O, the First Barium Nitridoalumotantalate with BCT-Zeolite Type Structure", Anorg Allg Chem., 2001, 627, 180-185)), and WCl5 (see U.S. Patent No. 10710896B2). The crystal structure of Phase 1 can be generated by modifying the unit cell parameters of NbCl5, TaCl5, or WCl5 using the above unit cell parameters collected from PXRD data. Subsequently, the corresponding Nb, Ta, or W atoms are replaced with Mo. The resulting powder XRD data are simulated using software such as Mercury or CrystDiffract. Figure 1 shows the simulated PXRD spectrum of phase 1 of MoCl5 produced using Mercury software.

[0033] The crystal structure of phase 2 (α-MoCl5) of MoCl5 is disclosed in Acta Crystallogr., 1959, 12, 273 (ICDD PDF card #04-007-5325) and Acta Crystallogr., 1967, 34, 770. Similar to phase 1, phase 2 is monoclinic and has a space group of 12 (C2 / m). The unit cell parameters are a = 17.31(1) Å, b = 17.81(1) Å, c = 6.079(5) Å, and β = 95.7(1)°.

[0034] The crystal structure of phase 3 (β-MoCl5) of MoCl5 is disclosed in Acta Crystallogr., Sect.B: Struct.Sci. 1997, 53, 895-903 (ICDD PDF card #04-013-3430). Unlike phases 1 and 2, phase 3 is triclinic and has a space group of 2(P-1). The unit cell parameters are a=6.594(6)Å, b=9.048(9)Å, c=6.074(4)Å, θ=90.81(4)°, β=116.12(5)°, and γ=108.42(4)°.

[0035] [Table 1]

[0036] MoCl5 contains at least two disclosed crystalline phases (γ-MoCl5 and δ Although γ-MoCl5 (-MoCl5) is present, it was not present in detectable concentrations in the materials handled by the inventors. γ-MoCl5 (ICDD PDF card #04-007-2432, Acta Crystallogr., Sect.B: Struct.Sci. 1997, 53, 895-903) is orthorhombic and has a space group of 62 (Pnma). The unit cell parameters are a=11.700(9)Å, b=17.874(10)Å, and c=6.085(3)Å. δ -MoCl5 (ICDD PDF card #04-013-3431, Acta Crystallogr., Sect.B: Struct.Sci.1997, 53, 895-903) is a monoclinic crystal with a space group of 14 (P21 / a). The unit cell parameters are a=12.162 Å, b=11.750 Å, c=9.468 Å, and β=108.88°.

[0037] All crystalline phases are MoCl5 dimers (i.e., Mo2Cl 10) is included. Each Mo atom has a pseudo-octahedral structure bonded to four non-bonding Cl atoms and two bonding Cl atoms. As a result, the phase transition from phase 1 to phase 2 is a non-diffusion transition. In other words, no major reconstruction of the crystal structure is observed. In a non-diffusion transition, atoms change their positions slightly in a relatively harmonious manner without disrupting the original bonds (see, for example, D.A. Porter et al., Phase transformations in metals and alloys, Chapman & Hall, 1992, p. 172).

[0038] As shown in the following examples, MoCl5 containing phase 1 and phase 2, phase 1 and phase 3, or phases 1, 2, and 3 in different proportions was prepared using different methods. PXRD measurements were performed using a Bruker D8-Advance diffractometer (CuKα, λ=1.5418Å). A highly airtight, low-background dome-shaped sample holder was used. To handle air-sensitive materials without exposure to air / moisture, samples were prepared and sealed in a nitrogen-filled glove box. The material was ground into a fine powder using an agate mortar and pestle in the nitrogen-filled glove box. The powder had an average particle size in the range of approximately 20 μm to 200 μm. The X-ray power was 1600–2000 W, and the detector was a Lynxeye XE-T energy-dispersive composite silicon strip detector. Powder patterns were collected using θ-θ scan mode (2θ range = 8°–70°, step size 0.01°).

[0039] The percentage proportions of each crystalline phase in various MoCl5 samples were determined using the Rietveld method and the reference crystal structures in Figure 1 and Table 1. More specifically, background noise was determined and removed from each dataset. The remaining diffraction peaks were then compared with the reference patterns in Figure 1 and Table 1 to determine the proportions of the phase composition.

[0040] Specifically, for MoCl5 samples, which are typically mixtures of two phases (phase 1 and phase 2, or phase 1 and phase 3), the diffraction peaks in the data were compared to the reference patterns of phase 1, phase 2, and phase 3 listed in the table. Then, the relative phase fractions of the two crystalline phases in each sample were refined using XRD data. A final fitting was performed between the diffraction intensities calculated from the refined sample model and the raw XRD data. The fitting was generally good, and refined phase fractions could be obtained. Bruker Topas v6.0 and MDI-Jade2010 were used.

[0041] The applicants discovered that phases 1, 2, and 3, which are crystalline phases of MoCl5, have different vapor pressures. Figure 2 is a diagram of the sublimation rate of a substance against the crystalline phase composition of MoCl5. As shown in Figure 2, a sample containing a high concentration of phase 1 sublimes faster than a sample containing a low concentration of phase 1. Therefore, phase 1 has a higher vapor pressure than phases 2 and 3. As shown, when MoCl5 containing a crystalline substance that is a mixture of phases 1 and 3, or phases 1 and 2, is supplied, phase 1 is consumed faster than phases 2 and 3 (i.e., phase 1 has a higher vapor pressure), so even without phase conversion, a fluctuation in vapor pressure occurs over time. Under isothermal measurement conditions of 100°C and 100 sccm of 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. Phase 1 is approximately 23% more volatile than Phase 2, and Phase 1 is approximately 38% more volatile than Phase 3.

[0042] In addition, as shown in Example 4, during the deposition process, phase 3 is converted to phase 1 and then partially converted to phase 2. This conversion further exacerbates the vapor pressure fluctuations.

[0043] The resulting difference in vapor pressure, as well as the changes in overall volatility due to the conversion of substances from phase 3 to phase 1 and then from phase 1 to phase 2, may destabilize the tool's performance and may increase the need to adjust instrument parameters to shorten the lifespan of the MoCl5 substance and maintain a sufficient and stable supply of MoCl5 vapor to the deposition tool.

[0044] Ideally, it is preferable to provide a product composed of a single phase. However, due to the nature of phase transformation under high-temperature operating conditions, even if starting with a single-phase substance, the phase composition will inevitably change when the substance is sublimated under heating. More specifically, the transformation from phase 3 to phase 1 occurs at a lower temperature and faster rate than the transformation from phase 1 to phase 2, which occurs at a relatively high temperature and slow rate. While the transformation from phase 3 to phase 1 can occur completely, the transformation from phase 1 to phase 2 is only partial and reaches equilibrium without becoming a pure single-phase substance.

[0045] Therefore, in order to achieve a stable vapor pressure over time, the ratio of phase 1 to phase 2 must be maintained at a constant equilibrium state. As shown in Example 3, the mixture of phase 1 and phase 3 of MoCl5 is partially converted to a mixture of phase 1 and phase 2 of MoCl5 during the deposition process. The applicants found that the material containing a large amount of phase 2 is not converted back to phase 1. As a result, the MoCl5 of phase 2 can be supplied at any temperature.

[0046] By heating MoCl5 to a temperature slightly below its melting point, a mixture of phase 3 and phase 1 can be converted into a substance containing a large amount of phase 2 (i.e., a melting point of 194°C). Phase conversion occurs more rapidly at higher temperatures.

[0047] Phase conversions that typically occur during the deposition process (i.e., at temperatures in the range of approximately 70°C to 120°C) are much slower than phase conversions that occur at 140°C to 180°C. During the deposition process, MoCl5 vapor is produced using a solid precursor evaporator heated to temperatures in the range of approximately 70°C to 180°C. The solid precursor vaporizer is typically a stainless steel container with at least one inlet and outlet connected to shut-off valves. If the solid precursor vaporizer is heated to temperatures above 150°C for extended periods to convert the substance from phase 1 to phase 2, the vaporizer may corrode, and the MoCl5 may become contaminated with stainless steel elements such as Cr, Fe, and Ni.

[0048] Performing the phase conversion in a separate container allows for a faster phase conversion than that occurring during the deposition process. The container is selected to withstand both the material and its properties during heating. The container is also selected to minimize the risk of impurity contamination of MoCl5. Suitable containers include glass containers, quartz containers, and glass-coated containers. After MoCl5 is converted into a substance rich in phase 2, this can be filled into a solid precursor vaporizer for use in the deposition process, enabling a stable vapor supply.

[0049] At temperatures ranging from approximately 140°C to below the melting point of MoCl5 (194°C). This approach allows for higher temperatures and, consequently, faster processing, while minimizing the risk of contamination, as long as the surface exposed to MoCl5 is not metallic. Thus, Example 4 also demonstrates that MoCl5 is stable in this temperature range, as evidenced by the low amount of non-volatile residue observed in the TGA after treatment.

[0050] Stainless steel can be treated to improve its corrosion resistance. Examples of treatments include electropolishing (EP), coating with metal oxides or SiO2, lamination, and plating. However, below 140°C, it takes more than three days for the proportion of phase 2 material to exceed 50% from a material with a high proportion of phase 1.

[0051] When primarily supplying Phase 1, MoCl5 needs to be kept at a temperature (<100°C) such that partial conversion from Phase 1 to Phase 2 is sufficiently suppressed (typically less than 10%) over the lifespan of the package in the instrument (2 weeks to 24 months). [Examples]

[0052] The following non-limiting embodiments are provided to further illustrate embodiments of the present invention. However, these embodiments are not intended to be exhaustive, nor are they intended to limit the scope of the invention described herein.

[0053] Example 1: Vacuum sublimation Equipment: Glass sublimation apparatus set and cooling device. Crude MoCl5 was placed at the bottom of a glass sublimation apparatus set. The sublimation apparatus was then placed inside the heating mantle and properly assembled. The sublimation apparatus set was evacuated to a range of 1 mTorr to 10 Torr. The cooling system was maintained at a temperature range of 0 to 30°C using a coolant. The temperature of the heating mantle was maintained at a range of 140 to 180°C. After heating, the power to the heating mantle was turned off and it was allowed to cool. Then, the pressure of the sublimation apparatus set was restored with an inert gas, and it was carefully disassembled, after which the solid material was recovered from the sublimation apparatus. XRD analysis was performed on the solid material samples (batches 1 to 5 below) to quantify the crystalline phase. The XRD analysis results are shown in Table 2.

[0054] [Table 2]

[0055] Example 2: Carrier gas-assisted sublimation Equipment: Coated stainless steel sublimation apparatus set Crude MoCl5 was placed at the bottom of the coated stainless steel sublimation apparatus. The top cover was placed over the sublimation apparatus, and then the sublimation apparatus and cover were secured together with clamps. A heating mantle (cover) was positioned to cover the top cover. One of the KF40 joints of the stainless steel tubing was connected to the cover of the sublimation apparatus using a KF40 Kalez gasket and secured with a clamp. Another KF40 joint of the stainless steel tubing was connected to the inlet of the lid of the recovery pot. A vacuum line was connected to the outlet of the lid of the recovery pot. An N2 carrier gas line was connected to the purge port of the sublimation apparatus.

[0056] After the system leak test, the temperature controller was switched on with the following settings: ·Bottom of sublimation device: 190±20℃ ·Lid: 2000±20℃ ·Transfer pipe: 220±20℃ • Lid of collection pot: 225±20℃

[0057] N2 purge flow meter 10-500 atm cm 3 The temperature was set to a range of / min (sccm). After heating, the heating mantle switch was turned off, the sublimation apparatus was cooled to below 60°C, and then the carrier gas N2 was stopped. The recovery pot was carefully disassembled, and then the solid material was recovered. XRD analysis was performed on the solid material sample to quantify the crystalline phase. The results of the XRD analysis are shown in Table 3.

[0058] [Table 3]

[0059] Example 3: In-Situ Phase Transformation Immediately sublimated MoCl5 (electronics grade quality) produced by the method described in Example 1 was placed in a sublimation apparatus or solid precursor vaporizer and maintained at a temperature range of approximately 70°C to 120°C. Over time, all of phase 3 disappeared, and a mixture of phase 1 and phase 2 was formed. After more than 50% of the MoCl5 material in the canister was consumed during the deposition process over 2 to 24 months, the concentration of phase 2 increased to more than 30%. Under standard sublimation and usage conditions, it is estimated that it takes longer than 2 months to form a material in which phase 2 MoCl5 is the majority. The results are shown in 4.

[0060] [Table 4]

[0061] Example 4: Conditioning on a small scale (<20g) In a glove box, 10-20 grams of freshly sublimated MoCl5 solid, prepared by the method described in Example 1, were placed in a 316 L stainless steel tube. The tube was sealed in a nitrogen-filled glove box. The stainless steel tube containing the MoCl5 was then heated in a heat bath or oven at a temperature in the range of 70°C to 190°C for a set period of time. After that, the stainless steel tube was removed from the heat bath or oven, allowed to cool for 1 hour, and then returned to the glove box. A shiny mass was observed inside the stainless steel tube. This could be crushed into shiny crystals. The resulting shiny mass was collected and XRD analysis was performed to quantify the crystalline phase. The results are shown in Tables 5A-5D.

[0062] [Table 5]

[0063] [Table 6]

[0064] [Table 7]

[0065] [Table 8]

[0066] Example 5: Conditioning on a large scale (approximately 500g) Figure 3 is a schematic diagram of an exemplary apparatus for carrying out this embodiment. As shown, a bottle 104 was placed in an oven 102. A valve 108 was connected to the lid 106 of the bottle 104. The bottle 104 may be a coated stainless steel bottle. The valve 108 can be used for vacuuming, positive pressurization, and leak checking of the seal. Reference numeral 110 indicates a heating element in the oven 102. Those skilled in the art will further recognize the source of the apparatus. Some customization of components may be necessary based on the desired temperature range, pressure range, local regulations, etc.

[0067] In a glove box (not shown), 5500 g (±50 g) of freshly sublimated MoCl prepared by the method described in Example 1 or Example 2 was placed in bottle 104. Bottle 104 here can be a coated 8 L stainless steel bottle. Bottle 104 was then checked for leaks by the vacuum spike method and the He outboard method. Bottle 104 was then heated in oven 102 at 170°C for 24 to 48 hours. After the time requirement was met, heating in oven 102 was stopped. Bottle 104 was slowly cooled in oven 102 to below 60°C. Bottle 104 was then removed from oven 102 and returned to the glove box. The lid 106 of bottle 104 was disassembled, and the large, shiny black mass formed in bottle 104 at the bottom of bottle 104 was transferred to a glass mortar. The large, shiny black mass was coarsely ground in a glass mortar and pestle to obtain crystalline powder. The crystalline powder product was recovered, and XRD analysis was performed to quantify the crystalline phase. Table 6 shows that this process repeatedly yields a product containing approximately 50–60 wt% of phase 2.

[0068] [Table 9]

[0069] These MoCl5 materials are thermally stable and are considered suitable for a stable supply of MoCl5 vapor during deposition or etching processes.

[0070] While embodiments of the present invention have been shown and described, those skilled in the art can modify these without departing from the spirit or teachings of the invention. The embodiments described herein are illustrative and not limiting. Many variations and modifications of the compositions and methods are possible and fall within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein but is limited only by the appended claims, which include all equivalents of the subject matter of the claims.

[0071] It will be understood that many additional modifications in the details, materials, steps, and arrangement of components described and illustrated herein to illustrate the nature of the present invention can be made by those skilled in the art within the principles and scope of the invention as expressed in the appended claims. Accordingly, the present invention is not intended to be limited to the specific embodiments of the examples and / or appended drawings shown above.

Claims

1. MoCl ５ A method for conditioning, MoCl ５ The container is heated to a temperature in the range of approximately 140°C to 190°C for a period of approximately 2 hours to approximately 100 hours, and approximately 10% to 60% by weight of Phase 1 MoCl is determined by X-ray diffraction. ５ And, 90% to approximately 40% by weight of Phase 2 MoCl ５ MoCl containing ５ A method comprising producing a composition containing the active ingredient.

2. The container is MoCl ５ The method according to claim 1, which is selected to be non-reactive to.

3. The method according to claim 1, wherein the container is made of glass, glass-lined, stainless steel, coated stainless steel, or Teflon.

4. The method according to claim 1, wherein the aforementioned time is in the range of approximately 24 hours to approximately 72 hours.

5. The method according to claim 1, wherein the aforementioned time is in the range of approximately 36 hours to approximately 48 hours.

6. The method according to claim 1, wherein the temperature is in the range of approximately 150°C to 180°C.

7. The method according to claim 1, wherein the temperature is in the range of approximately 160°C to 170°C.

8. The aforementioned MoCl ５ The composition contains about 10 wt% to about 60 wt% of MoCl in Phase 1 ５ and about 90 wt% to about 40 wt% of MoCl in Phase 2 ５ The method according to any one of claims 1 to 7, which contains the above substances.

9. The aforementioned MoCl ５ The composition contains approximately 20% to 50% by weight of Phase 1 MoCl ５ And, 80% to approximately 50% by weight of Phase 2 MoCl ５ The method according to any one of claims 1 to 7, comprising the above.

10. The aforementioned MoCl ５ The composition contains approximately 30% to 55% by weight of Phase 1 MoCl ５ And, 70% to approximately 45% by weight of Phase 2 MoCl ５ The method according to any one of claims 1 to 7, comprising the above.

11. The aforementioned MoCl ５ The composition contains approximately 40% to 50% by weight of Phase 1 MoCl ５ And, 60% to approximately 50% by weight of Phase 2 MoCl ５ The method according to any one of claims 1 to 7, comprising the above.

12. A mixture of about 10% to about 60% by weight of Phase 1 MoCl, conditioned by the method described in claim 1. ５ And, 90% to approximately 40% by weight of Phase 2 MoCl ５ MoCl containing ５ Containing composition.

13. Approximately 20% to 50% by weight of Phase 1 MoCl ５ And, 80% to approximately 50% by weight of Phase 2 MoCl ５ The MoCl according to claim 12, which contains the above. ５ Containing composition.

14. Approximately 30% to 55% by weight of Phase 1 MoCl ５ And, 70% to approximately 45% by weight of Phase 2 MoCl ５ The MoCl according to claim 12, which contains the above. ５ Containing composition.

15. Approximately 40% to 50% by weight of Phase 1 MoCl ５ And, 60% to approximately 50% by weight of Phase 2 MoCl ５ The MoCl according to claim 12, which contains the above. ５ Containing composition.

16. MoCl according to any one of claims 12 to 15, which is thermally stable and provides a stable steam supply. ５ Containing composition.

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