MOLYBDENUM PENTACHLORIDE CONDITIONING AND CRYSTALLINE PHASE MANIPULATION

Abstract

A method of conditioning MoCl.sub.5 comprises heating a container of MoCl.sub.5 to a temperature ranging from approximately 140 C. to 190 C. for a period ranging from approximately 2 hours to approximately 100 hours to produce a MoCl.sub.5-containing composition comprising approximately 10% weight to approximately 60% weight of Phase 1 MoCl.sub.5 and 90% weight to approximately 40% weight of Phase 2 MoCl.sub.5 as determined by X-ray diffraction. This MoCl.sub.5-containing composition is expected to be more thermally stable and provides stable vapor supply.

Claims

1. A method of conditioning MoCl.sub.5, the method comprising heating a container of MoCl.sub.5 to a temperature ranging from approximately 140 C. to 190 C. for a period ranging from approximately 2 hours to approximately 100 hours to produce a MoCl.sub.5-containing composition comprising approximately 10% weight to approximately 60% weight of Phase 1 MoCl.sub.5 and 90% weight to approximately 40% weight of Phase 2 MoCl.sub.5 as determined by X-ray diffraction.

2. The method of claim 1, wherein the container is selected to be non-reactive to MoCl.sub.5.

3. The method of claim 1, wherein the container is glass or glass-lined.

4. The method of claim 1, wherein the container is stainless steel.

5. The method of claim 1, wherein the container is glass, Teflon, or coated stainless steel.

6. The method of claim 1, wherein the period ranges from approximately 24 hours to approximately 72 hours.

7. The method of claim 1, wherein the period ranges from approximately 36 hours to approximately 48 hours.

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

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

10. The method of claim 1, wherein the MoCl.sub.5-containing composition comprises approximately 10% weight to approximately 60% weight of Phase 1 MoCl.sub.5 and 90% weight to approximately 40% weight of Phase 2 MoCl.sub.5.

11. The method of claim 1, wherein the MoCl.sub.5-containing composition comprises approximately 20% weight to approximately 50% weight of Phase 1 MoCl.sub.5 and 80% weight to approximately 50% weight of Phase 2 MoCl.sub.5.

12. The method of claim 1, wherein the MoCl.sub.5-containing composition comprises approximately 30% weight to approximately 55% weight of Phase 1 MoCl.sub.5 and 70% weight to approximately 45% weight of Phase 2 MoCl.sub.5.

13. The method of claim 1, wherein the MoCl.sub.5-containing composition comprises approximately 40% weight to approximately 50% weight of Phase 1 MoCl.sub.5 and 60% weight to approximately 50% weight of Phase 2 MoCl.sub.5.

14. A MoCl.sub.5-containing composition conditioned by the method of claim 1, having approximately 10% weight to approximately 60% weight of Phase 1 MoCl.sub.5 and 90% weight to approximately 40% weight of Phase 2 MoCl.sub.5.

15. The MoCl.sub.5-containing composition of claim 14, having approximately 20% weight to approximately 50% weight of Phase 1 MoCl.sub.5 and 80% weight to approximately 50% weight of Phase 2 MoCl.sub.5.

16. The MoCl.sub.5-containing composition of claim 14, having approximately 30% weight to approximately 55% weight of Phase 1 MoCl.sub.5 and 70% weight to approximately 45% weight of Phase 2 MoCl.sub.5.

17. The MoCl.sub.5-containing composition of claim 14, having approximately 40% weight to approximately 50% weight of Phase 1 MoCl.sub.5 and 60% weight to approximately 50% weight of Phase 2 MoCl.sub.5.

18. The MoCl.sub.5-containing composition of claim 14, being thermally stable and providing stable vapor supply.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0046] For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein:

[0047] FIG. 1 is a simulated PXRD spectrum of MoCl.sub.5 Phase 1 generated using Mercury software;

[0048] FIG. 2 is a diagram of materials sublimation rate vs. crystalline phase compositions MoCl.sub.5; and

[0049] FIG. 3 is a schematic diagram of the exemplary equipment in which this example was performed.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0050] Although it is disclosed that MoCl.sub.5 in vapor phase demonstrated a trigonal bipyramid structure (Ewens et al., Trans. Faraday Soc. 1938, 34, 1358.) discloses that MoCl.sub.5 in the vapor phase demonstrated a trigonal bipyramid structure, Applicants have discovered that the sublimation rate from solid MoCl.sub.5 subject to normal industrial vaporization conditions is unstable, leading to possible performance drift in processes that utilize MoCl.sub.5 vapors. In other words, as a canister of MoCl.sub.5 is depleted during a vapor deposition process, the deposition rate of the Mo-containing film is not stabilized.

[0051] Further analysis demonstrates that the change in performance is due to the change of the crystal phase compositions of MoCl.sub.5. More particularly, the crystal phase of freshly sublimed MoCl.sub.5 tends to comprise a mixture of Phase 1 and Phase 3. However, during the vapor deposition process, the canister of MoCl.sub.5 is heated to a temperature ranging from approximately 70 C. to approximately 170 C., preferably 90 C. to 140 C., and the composition would gradually change to a mixture of Phase 1 and Phase 2, where Phase 2 ranges from approximately 40% to approximately 80%.

[0052] To our knowledge, the crystal structure of Phase 1 has not been reported. Phase 1 of MoCl.sub.5 is monoclinic with space group 12 as C2/m. The unit cell parameters are a=18.01 , b=17.66 , c=5.76 , and =90.18. Phase 1 of MoCl.sub.5 is isostructural to reported compounds NbCl.sub.5 (PXRD pattern: ICDD PDF Card #04-0005-4229, see Zalkin et al., (The crystal structure of NbCl.sub.5, Acta Crystallogr. 1958, 11, 615-619)), TaCl.sub.5 (PXRD pattern: ICDD PDF Card #04-109-4194, see Wimmer et al., (Li.sub.2Ba.sub.4Al.sub.2Ta.sub.2N.sub.8O, the First Barium Nitridoalumotantalate with BCT-Zeolite Type Structure, Anorg Allg Chem., 2001, 627, 180-185)), and WCl.sub.5 (see U.S. Ser. No. 10/710,896B2). The crystal structure for Phase 1 may be generated by modifying the unit cell parameters of NbCl.sub.5, TaCl.sub.5, or WCl.sub.5 with the above unit cell parameters collected from PXRD data. The corresponding Nb, Ta, or W atom is then replaced with Mo. The resulting powder XRD data is simulated using software such as Mercury or CrystDiffract software. FIG. 1 is a simulated PXRD spectrum of MoCl.sub.5 Phase 1 generated using Mercury software.

[0053] The crystal structure of Phase 2 of MoCl.sub.5 (-MoCl.sub.5) has been 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 with space group 12 as C2/m. The unit cell parameters are a=17.31(1) , b=17.81(1) , c=6.079(5) , =95.7(1).

[0054] The crystal structure of Phase 3 of MOCl.sub.5 (-MoCl.sub.5) has been disclosed in Acta Crystallogr., Sect. B: Struct. Sci. 1997, 53, 895-903 (ICDD PDF Card #04-013-3430). Different from Phase 1 and Phase 2, Phase 3 is triclinic with space group 2 as P-1. The unit cell parameters are a=6.594(6) , b=9.048(9) , c=6.074(4) , =90.81(4), =116.12(5), =108.42(4).

TABLE-US-00001 TABLE 1 X-Ray Diffraction Simulation Data for MoCl.sub.5 Phase 1, 2, and 3 2 Theta Phase 1 2 Theta Phase 2 2 Theta Phase 3 () (rel. int. %) () (rel. int. %) () (rel. int. %) 10.033 10.37 9.925 16.7 14.632 8.7 10.468 17.0 15.587 100.00 15.827 74.3 15.687 100.0 16.207 100.0 16.511 47.3 16.936 66.18 16.751 14.5 16.776 48.1 17.041 10.9 17.908 55.9 18.283 37.74 18.73 39.4 18.263 38.8 20.113 39.18 19.925 32.0 21.14 18.29 21.226 15.9 21.024 34.0 21.513 15.2 21.141 19.6 21.975 5.69 21.256 14.1 22.20 11.09 22.144 33.8 24.13 16.9 25.185 13.25 27.304 25.13 27.478 20.5 29.711 6.77 29.486 18.1 29.405 11.7 30.096 13.61 29.988 15.2 31.059 6.05 32.375 8.21 33.274 79.86 33.692 26.93

[0055] There are at least two more disclosed crystalline phases of MOCl.sub.5 (-MoCl.sub.5 and -MoCl.sub.5), but not present in detectable concentration in the materials we handled. -MOCl.sub.5 (ICDD PDF Card #04-007-2432, Acta Crystallogr., Sect. B: Struct. Sci. 1997, 53, 895-903) is orthorhombic with space group 62 as Pnma. The unit cell parameters are a=11.700(9) , b=17.874(10) , c=6.085(3) . -MoCl.sub.5 (ICDD PDF Card #04-013-3431, Acta Crystallogr., Sect. B: Struct. Sci. 1997, 53, 895-903) is monoclinic with space group 14 as P21/a. The unit cell parameters are a=12.162 , b=11.750 , c=9.468 , =108.88.

[0056] All crystalline phases contain MoCl.sub.5 dimer (i.e., Mo.sub.2Cl.sub.10). Each Mo atom is in a pseudo-octahedral geometry connected to four non-shared Cl atoms and two shared Cl atoms. As a result, the phase conversion from Phase 1 to Phase 2 is a diffusionless transformation. In other words, no major reorganization of the crystal structure is observed. In diffusionless transformations, the atoms change their positions slightly in a relatively coordinated manner without interruption of the original bonding (see, e.g., D. A. Porter et al., Phase transformations in metals and alloys, Chapman & Hall, 1992, p. 172).

[0057] As shown in the examples that follow, different methods were used to prepare MoCl.sub.5 containing different percentages of Phase 1 and Phase 2, Phase 1 and Phase 3, or Phase 1, 2, and 3 materials. PXRD measurements were performed on a Bruker D8-Advance diffractometer (Cu K radiation, A=1.5418 ). Leak tight low background dome sample holders are used. Samples are prepared and sealed in a nitrogen filled glovebox so that the air-sensitive materials were handled without air/moisture exposure.

[0058] Inside a nitrogen filled glovebox, materials is grounded into fine powders with an agate mortar and pestle. The powder had an average particle size ranging from approximately 20 um to approximately 200 um. X-ray output is 1600-2000 W, and the detector is Lynxeye XE-T energy dispersive compound silicon stripe detector. The powder patterns were collected using a - scan mode (range 2=8-70, step size of 0.01).

[0059] The Rietveld method and reference crystal structures of FIG. 1 and Table 1 were used to determine the percentage of each crystal phase in a variety of MoCl.sub.5 samples. More particularly, the background was determined and removed from each data set. The remaining diffraction peaks were matched to the reference patterns of FIG. 1 and Table 1 to determine the phase composition percentage.

[0060] To be specific, for MoCl.sub.5 samples Which are normally mixtures of two phases (phase 1 and Phase 2, or Phase 1 and Phase 3), diffraction peaks in the data were matched to reference patterns for Phases 1, 2, and 3 listed in Table. The XRD data were then used to refine the relative phase fractions of the two crystalline phases in each sample. The final fits of the calculated diffraction intensities from the refined sample model to the raw XRD data was performed. The fits are usually good and refined phase fractions can be obtained. Bruker Topas v6.0 and MDI-Jade2010 were used.

[0061] Applicants have discovered that the Phase 1, Phase 2, and Phase 3 crystalline phases of MoCl.sub.5 have different vapor pressures. FIG. 2 is a diagram of materials sublimation rate vs. crystalline phase compositions of MoCl.sub.5. As shown in FIG. 2, samples containing higher concentrations of Phase 1 have a higher sublimation rate in comparison to samples containing lower concentrations of Phase 1. Therefore, Phase 1 has a higher vapor pressure than Phase 2 and Phase 3. As shown, supplying MoCl.sub.5 that contains a mixture of Phase 1 and Phase 3, or Phase 1 and Phase 2 crystalline material will cause a vapor pressure variation over time because Phase 1 depletes faster than Phase 2 and Phase 3 (i.e., Phase 1 has a higher vapor pressure), even in the absence of any phase conversion. At 100 C. 100 sccm N.sub.2 carrier gas isotherm measurement conditions, sublimation rate of Phase 1 0.02692 wt %/min, sublimation rate of Phase 2 is 0.02187 wt %/min, and sublimation rate of Phase 3 is 0.01947 wt %/min. Phase 1 is 23% more volatile than Phase 2, and Phase 1 is 38% more volatile than Phase 3.

[0062] Additionally, as shown in Example 4, Phase 3 converts to Phase 1, and then converts partially to Phase 2 during the vapor deposition processes. This conversion further exacerbates the vapor pressure drift.

[0063] The accompanying change in the overall volatility due to the difference in vapor pressures and the conversion of Phase 3 to Phase 1, and then Phase 1 material to Phase 2 results in potentially unstable on tool performance, and may shorten the use of the MoCl.sub.5 materials and the necessity to adjust equipment parameters in order to be able to maintain a sufficient and stable supply of MoCl.sub.5 vapors to the vapor deposition tool.

[0064] Ideally, it is preferable that we offer a product composed of a single phase. However, due to the nature of ongoing phase conversion at elevated usage condition, even starting from a single-phase materials, upon subliming the materials under heat, phase composition will change inevitably. To be more specific, Phase 3 to Phase 1 conversion occurs at lower temperature and faster rate than Phase 1 to Phase 2 conversion which occurs at a relatively higher temperature and slower rate. Phase 3 to Phase 1 conversion can be complete, however, Phase 1 to Phase 2 conversion is partial and will reach an equilibrium instead of a pure single-phase materials.

[0065] To this end, a constant and equilibrated Phase 1: Phase 2 ratio must be maintained in order to offer a stable vapor pressure over time. As shown in Example 3, Phase 1 and 3 mixture of MoCl.sub.5 converts partially to Phase 1 and 2 mixture of MoCl.sub.5 during the vapor deposition process. Applicants have discovered that the Phase 2-rich material does not convert back to Phase 1. As a result, Phase 2 MoCl.sub.5 may be supplied at any temperatures.

[0066] MoCl.sub.5 may be heated to a temperature just below its melting point in order to convert it from Phase 3 and Phase 1 mixture material to Phase 2 rich material (i.e., m.p.=194 C.). The phase conversion occurs faster at the higher temperatures.

[0067] The phase conversion that typically occurs during the vapor deposition process (i.e., at temperatures ranging from approximately 70 to approximately 120 C.) occurs much slower than the phase conversion that occurs between 140 C. at 180 C. During the vapor deposition process, the vapors of MoCl.sub.5 are typically generated using a solid precursor vaporizer heated to a temperature ranging from approximately 70 C. to approximately 180 C. The solid precursor vaporizer is typically a stainless steel vessel, with at least an inlet and an outlet connected to isolation valves. Heating the solid precursor vaporizer to temperatures above 150 C. for extended period in order to convert the material from Phase 1 to Phase 2 may result in corrosion of the vaporizer, and contamination of the MoCl.sub.5 by stainless steel elements, such as Cr, Fe, Ni, etc.

[0068] Performing the phase conversion in a separate vessel enables faster phase conversion than occurs during the vapor deposition process. The vessel is chosen to withstand the both the material and its properties when heated. The vessel is also chosen to limit the risk of imparting any impurities into the MoCl.sub.5. Suitable vessels including glass vessels, quartz vessels, glass coated vessels, etc. After the MoCl.sub.5 converted to Phase 2-rich material, it may be filled into a solid precursor vaporizer for use in the vapor deposition process, to enable stable vapor supply.

[0069] At a temperature ranging from approximately 140 C. to below the MoCl.sub.5 melting point 194 C. Using this approach enables a higher temperature and hence faster treatment with a limited risk of contamination, provided that the surface exposed to the MoCl.sub.5 is not metallic. As such, Example 4 also indicates that MoCl.sub.5 is stable in this temperature region, as exemplified by the low amount of non-volatile residue observed by TGA after the treatment.

[0070] Stainless steel may be treated to enhance corrosion resistance. Exemplary treatment includes electropolishing (EP), coating with metal oxide, SiO.sub.2, laminates, platings, etc. However, the time required to reach>50% Phase 2 material from Phase 1-rich material takes more than three days at 140 C. or lower.

[0071] By supplying predominantly Phase 1, in which case the MoCl.sub.5 has to be kept at a T (<100 C.) at which the Phase 1 to Phase 2 partial conversion is sufficiently limited (typically <10%) over the duration of the usage of the package on the equipment (between 2 weeks and 24 months).

EXAMPLES

[0072] The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the inventions described herein.

Example 1: Vacuum Sublimation

[0073] Equipment: Glass sublimator set and a chiller.

[0074] Crude MoCl.sub.5 was added to the bottom of the glass sublimator set. The sublimator was then placed into a heating mantle and properly assembled. The sublimator set was pulling vacuum to a range of 1 mTorr to 10 Torr. The chiller was maintained with a coolant at temperature ranging from 0 to 30 C. The heating mantle temperature was maintained ranging from 140 to 180 C. After heating, the heating mantle was turned off and allowed to cool. The sublimator set was then backfilled with inert gas, carefully disassembled and solid materials from the sublimator were then collected. Solid material samples (batch 1 to 5 below) were submitted for XRD analysis to quantify crystalline phases. The XRD analysis results are shown in Table 2.

TABLE-US-00002 TABLE 2 Batch Phase 1 (%) Phase 3 (%) Batch 1 35 65 Batch 2 27 73 Batch 3 59 41 Batch 4 44 56 Batch 5 31 69

Example 2: Carrier Gas Assisted Sublimation

[0075] Equipment: Coated stainless steel sublimator set.

[0076] Crude MoCl.sub.5 was loaded to the bottom of the coated stainless steel sublimator. Top lid was put on the sublimator and then the sublimator and the lid were secured together with clamp. Placed a heating mantle (lid) to cover the top lid. Connect one KF 40 joint of a stainless steel tubing to the lid of the sublimator with a KF 40 Kalrez gasket and secure it with clamp. Connect the other KF 40 joint of the stainless steel tubing to a receiving pot lid inlet. Connect a vacuum line to the receiving pot lid outlet. Connect N.sub.2 carrier gas line to a sublimator purging port.

[0077] After system leak test, turn on temperature controllers with the following set up: [0078] Sublimator bottom: 190+/20 C. [0079] Lid: 2000+/20 C. [0080] Transfer tubing: 220+/20 C. [0081] Recing pot lid: 225+/20 C.

[0082] Set N.sub.2 purging flow meter to a range of 10-500 atm cm.sup.3/min (sccm). After heating, turn off heating mantels and cool the sublimator below 60 C., and then turn off carrier gas N.sub.2. The receiving pot was carefully disassembled, and solid materials were then collected. Solid material samples were submitted for XRD analysis to quantify crystalline phases. The XRD analysis results are shown in Table 3.

TABLE-US-00003 TABLE 3 Batch Phase 1 (%) Phase 3 (%) Batch 1 66 34 Batch 2 79 21 Batch 3 84 16

Example 3: In-Situ Phase Change

[0083] Freshly vacuum sublimed (electronics grade quality) MoCl.sub.5 made by the method described in Example 1 was added to a sublimator or a solid precursor vaporizer, and maintained at a temperature ranging from approximately 70 C. and 120 C. Overtime, all Phase 3 disappeared, and a mixture of Phase 1 and Phase 2 were formed. After more than 50% of the MoCl.sub.5 material in a canister has been consumed during a vapor deposition process for a period of 2-24 months, Phase 2 concentration increased to 30% or more. It is believed that under standard sublimation and on standard usage conditions, it may take more than 2 months to produce the materials which majority is Phase 2 MoCl.sub.5. The results are listed in Table 4.

TABLE-US-00004 TABLE 4 Initial Final % (w/w) % Phase 1 % Phase 2 Batch Weight (g) Weight (g) Consumed Remaining Remaining 1 502 135 73 43 57 2 500 246 51 49 51

Example 4: Conditioning at Small Scale (<20 g)

[0084] In a glovebox, 10-20 grams of freshly sublimed MoCl.sub.5 solids made by the method described in Example 1 were added to 316L stainless steel tubings. The tubings were sealed inside a nitrogen filled glovebox. The stainless steel tubings with MoCl.sub.5 were than heated by either submerging in heat bathes or ovens at a temperature ranging from 70 C. to 190 C. for a period of time. The stainless steel tubings were then removed from the heat bathes or ovens and allowed to cool down in 1 hr, and then brought back to the glovebox. A shiny cake was observed in the stainless steel tubings, which could be broken into shining crystallines. The shiny cake product was collected and submitted for XRD analysis to quantify crystalline phases. The results are listed in Tables 5A to 50.

TABLE-US-00005 TABLE 5A Phase Phase Phase Phase Phase Batch 1 3 Temp. Time 1 2 3 1 (%) (%) ( C.) (hr) (%) (%) (%) Run 1 59 41 100 24 81 0 19 Run 2 120 92 0 8 Run 3 140 100 0 0 Run 4 160 49 54 0

TABLE-US-00006 TABLE 5B Phase Phase Phase Phase Phase Batch 1 3 Temp. Time 1 2 3 1 (%) (%) ( C.) (week) (%) (%) (%) Run 1 59 41 100 1 70 0 30 Run 2 2 73 0 27 Run 3 4 89 0 11

TABLE-US-00007 TABLE 5C Phase Phase Phase Phase Phase Batch 1 3 Temp. Time 1 2 3 1 (%) (%) ( C.) (week) (%) (%) (%) Run 1 59 41 120 1 80 20 0 Run 2 2 78 22 0 Run 3 4 71 29 0

TABLE-US-00008 TABLE 5D Phase Phase Phase Phase 1 3 Temp. Time 1 2 Sample (%) (%) ( C.) (hr) (%) (%) Batch 1 Run 1 35 65 170 6 23 77 Batch 1 Run 2 35 65 170 6 17 83 Batch 2 Run 1 27 73 170 6 25 75 Batch 2 Run 2 27 73 170 6 28 72 Batch 3 Run 1 59 41 170 6 18 82 Batch 3 Run 2 59 41 170 6 26 74

Example 5: Large Scale Conditioning (500 g)

[0085] FIG. 3 is a schematic diagram of the exemplary equipment in which this example was performed. As shown, jar 104 was placed in oven 102. Valve 108 was fluidly connected to lid 106 of jar 104. Jar 104 may be a coated stainless steel jar. Valve 108 may be used for introducing vacuum, positive pressure, and leak check the sealing. Numeral 110 shows a heating element in oven 102. One of ordinary skill in the art will further recognize the sources for the equipment. Some level of customization of the components may be required based upon the desired temperature range, pressure range, local regulations, etc.

[0086] In a glovebox (not shown), 500 g (+/50 g) grams of freshly sublimed MoCl.sub.5 made by the method described in Example 1 or Example 2 was added to jar 104. Here jar 104 may be an 8 L coated stainless steel jar. Jar 104 was then leak checked by vacuum spiking and He outboard methods. Afterwards, jar 104 was heated at 170 C. for 24-48 hours using oven 102. After the time requirement was met, heating of oven 102 was turned off. Jar 104 was allowed to slowly cool to below 60 C. inside oven 102. Jar 104 was then removed from oven 102 and transferred back into the glovebox. Lid 106 of jar 104 was disassembled and a big shiny black cake on the bottom of jar 104 was formed in jar 104 that was poured into a glass mortar. Crystalline powders were obtained by roughly grinding the big shiny black cake with the glass mortar and a pestle.

[0087] A product of crystalline powders was collected and submitted for XRD analysis to quantify crystalline phases. Table 6 demonstrates that this process repeatedly yields product having approximately 50-60% weight of Phase 2 material.

TABLE-US-00009 TABLE 6 Phase Phase Phase Phase 1 3 Temp. Time 1 2 Sample (%) (%) ( C.) (hr) (%) (%) Batch 1 32 68 170 24 48 52 Batch 2 30 70 170 36 45 55 Batch 3 45 55 170 48 46 54 Batch 4 59 41 170 24 45 55 Batch 5 50 50 170 36 42 58 Batch 6 56 44 170 48 42 58

[0088] These MoCl.sub.5 materials are thermally stable and would be suitable to provide a stable vapor supply of MoCl.sub.5 vapor during a vapor deposition or etching processes.

[0089] While embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and not limiting. Many variations and modifications of the composition and method are possible and within the scope of the invention. Accordingly the scope of protection is not limited to the embodiments described herein, but is only limited by the claims which follow, the scope of which shall include all equivalents of the subject matter of the claims.

[0090] It will be understood that many additional changes in the details, materials, steps, and arrangement of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above and/or the attached drawings.