Ultra-Pure Molybdenum Dichloride Dioxide, Packaged Forms Thereof And Methods Of Preparing The Same
20240239684 ยท 2024-07-18
Inventors
- Steven A. Krouse (Tamaqua, PA, US)
- Sergei V. Ivanov (Schnecksville, PA, US)
- BRENT A. SPERLING (Center Valley, PA, US)
Cpc classification
C23C16/06
CHEMISTRY; METALLURGY
C23C16/45553
CHEMISTRY; METALLURGY
C23C16/22
CHEMISTRY; METALLURGY
International classification
Abstract
The disclosed and claimed subject matter relates to ultra-pure molybdenum dichloride dioxide (i.e., MoO2Cl2) that is substantially free of moisture (H2O), hydrogen chloride (HCl) and/or residual protons. packaged forms of the same and a method of preparing the same.
Claims
1. Ultra-pure MoO.sub.2Cl.sub.2 having less than about 30 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
2. (canceled)
3. (canceled)
4. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having less than 15 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
5-7. (canceled)
8. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having less than 3 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
9. (canceled)
10. (canceled)
11. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of H.sub.2O of less than about 250 ppm in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
12. (canceled)
13. (canceled)
14. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of H.sub.2O of less than about 125 ppm in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
15. (canceled)
16. (canceled)
17. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of H.sub.2O of less than about 50 ppm in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
18. (canceled)
19. (canceled)
20. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of H.sub.2O of less than about 15 ppm in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
21-27. (canceled)
28. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of H.sub.2O as determined by .sup.1H NMR of less than about 0.005 wt % in the physiosorbed or chemisorbed state.
29-33. (canceled)
34. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of HCl of less than about 1000 ppm in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
35-45. (canceled)
46. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of MoO.sub.2Cl.sub.2 x H.sub.20 as determined by .sup.1H NMR of less than about 0.30 wt % in the physiosorbed or chemisorbed state.
47-50. (canceled)
51. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of MoO.sub.2Cl.sub.2 x H.sub.20 as determined by .sup.1H NMR of less than about 0.10 wt % in the physiosorbed or chemisorbed state.
52-60. (canceled)
61. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a residual total content of MoO.sub.3 of less than about 0.20 wt % in the physiosorbed or chemisorbed state.
62-65. (canceled)
66. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1, wherein the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.0 g/cm.sup.3.
67-70. (canceled)
71. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1, wherein the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.5 g/cm.sup.3.
72-75. (canceled)
76. The ultra-pure MoO.sub.2Cl.sub.2 of claim 1, wherein the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 3.0 g/cm.sup.3.
77. A method of preparing the ultra-pure MoO.sub.2Cl.sub.2 of claim 1 comprising the steps of: a. charging low purity MoO.sub.2Cl.sub.2 into a pressure vessel; b. heating the vessel to a temperature sufficient to melt the low purity MoO.sub.2Cl.sub.2; c. optionally filtering the melted MoO.sub.2Cl.sub.2; d. venting the vessel to remove impurities; and e. cooling the vessel; and f. optionally re-venting the vessel.
78. (canceled)
79. The method of claim 77, wherein the step b. heating comprises heating the vessel to a temperature from about 180? C. to about 200? C.
80. A container comprising the ultra-pure MoO.sub.2Cl.sub.2 of claim 1 having a packing density of about 0.7 kg/L to about 1.5 kg/L of container external volume.
81-96. (canceled)
97. A vapor comprising the ultra-pure MoO.sub.2Cl.sub.2 of claim 1 wherein the vapor has less than 300 ppm volume of gaseous HCl.
98-103. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:
[0023]
[0024]
[0025]
[0026]
DEFINITIONS
[0027] Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for this application.
[0028] For purposes of the disclosed and claimed subject matter, the numbering scheme for the Periodic Table Groups is according to the IUPAC Periodic Table of Elements.
[0029] The term and/or as used in a phrase such as A and/or B herein is intended to include A and B. A or B, A and B.
[0030] The terms substituent. radical. group and moiety may be used interchangeably.
[0031] As used herein, the terms metal-containing complex (or more simply, complex) and precursor are used interchangeably and refer to metal-containing molecule or compound which can be used to prepare a metal-containing film by a vapor deposition process such as, for example, ALD or CVD. The metal-containing complex may be deposited on, adsorbed to, decomposed on, delivered to, and/or passed over a substrate or surface thereof, as to form a metal-containing film.
[0032] As used herein, the term metal-containing film includes not only an elemental metal film as more fully defined below, but also a film which includes a metal along with one or more elements, for example a metal oxide film, metal nitride film, metal silicide film, a metal carbide film and the like. As used herein, the terms elemental metal film and pure metal film are used interchangeably and refer to a film which consists of, or consists essentially of, pure metal. For example, the elemental metal film may include 100% pure metal or the elemental metal film may include at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, or at least about 99.99% pure metal along with one or more impurities. Unless context dictates otherwise, the term metal film shall be interpreted to mean an elemental metal film.
[0033] As used herein, the term vapor deposition process is used to refer to any type of vapor deposition technique, including but not limited to, CVD and ALD. In various embodiments, CVD may take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or photo-assisted CVD. CVD may also take the form of a pulsed technique, i.e., pulsed CVD. ALD is used to form a metal-containing film by vaporizing and/or passing at least one metal complex disclosed herein over a substrate surface. For conventional ALD processes see, for example, George S. M., et al. J. Phys. Chem., 1996, 100, 13121-13131. In other embodiments, ALD may take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term vapor deposition process further includes various vapor deposition techniques described in Chemical Vapour Deposition: Precursors, Processes, and Applications; Jones, A. C.; Hitchman, M. L., Eds., The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp. 1-36.
[0034] The term about or approximately. when used in connection with a measurable numerical variable, refers to the indicated value of the variable and to all values of the variable that are within the experimental error of the indicated value (e.g., within the 95% confidence limit for the mean) or within percentage of the indicated value (e.g., ?10%, ?5%), whichever is greater.
[0035] The disclosed and claimed precursors are preferably substantially free of proton source impurities. As used herein, the term substantially free as it relates to proton source impurities means amounts of any such impurity that would individually or collectively give rise to about 30 ppm or less of protons attributable from any such impurity individually as determined by .sup.1H NMR as described in more detail below.
[0036] The disclosed and claimed precursors are also preferably substantially free of metal ions or metals such as, Li.sup.+ (Li), Na.sup.+ (Na), K.sup.+ (K), Mg.sup.2+ (Mg), Ca.sup.2+ (Ca), Al.sup.3+ (Al), Fe.sup.2+ (Fe), Fe.sup.3+ (Fe), Ni.sup.2+ (Fc), Cr.sup.3+ (Cr), titanium (Ti), vanadium (V), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu) or zinc (Zn). These metal ions or metals are potentially present from the starting materials/reactor employed to synthesize the precursors. As used herein, the term substantially free as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, Ti, V, Mn, Co, Ni, Cu or Zn means less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS.
[0037] Halo or halide refers to a halogen, F, Cl, Br or I which is linked by one bond to an organic moicty. In some embodiments, the halogen is F. In other embodiments, the halogen is Cl.
[0038] Halogenated alkyl refers to a C.sub.1 to C.sub.20 alkyl which is fully or partially halogenated.
[0039] Perfluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which the hydrogens have all been replaced by fluorine (e.g., trifluoromethyl, perfluorocthyl, perfluoropropyl, perfluorobutyl, perfluoroisopropyl, perfluorocyclohexyl and the like).
[0040] The MoO.sub.2Cl.sub.2 is substantially free of organic impurities which are from either starting materials employed during synthesis or by-products generated during synthesis. Examples include, but not limited to, alkanes, alkenes, alkynes, dienes, ethers, esters, acetates, amines, ketones, amides, aromatic compounds. As used herein, the term free of organic impurities, means 1000 ppm or less as measured by GC, preferably 500 ppm or less (by weight) as measured by GC, most preferably 100 ppm or less (by weight) as measured by GC or other analytical method for assay. Importantly the precursors preferably have purity of 98 wt % or higher, more preferably 99 wt % or higher as measured by GC when used as precursor to deposit the ruthenium-containing films.
[0041] The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that any of the incorporated literature and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.
DETAILED DESCRIPTION
[0042] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. The objects, features, advantages and ideas of the disclosed subject matter will be apparent to those skilled in the art from the description provided in the specification, and the disclosed subject matter will be readily practicable by those skilled in the art on the basis of the description appearing herein. The description of any preferred embodiments and/or the examples which show preferred modes for practicing the disclosed subject matter are included for the purpose of explanation and are not intended to limit the scope of the claims.
[0043] It will also be apparent to those skilled in the art that various modifications may be made in how the disclosed subject matter is practiced based on described aspects in the specification without departing from the spirit and scope of the disclosed subject matter disclosed herein.
[0044] As noted above, the disclosed and claimed subject matter relates to ultra-pure MoO.sub.2Cl.sub.2 that is free and/or substantially free of water and other impurities (at the ppm or lower levels) for use in the electronics/semiconductor industry.
[0045] In another aspect, the disclosed and claimed subject matter relates to a method of preparing ultra-pure MoO.sub.2Cl.sub.2 that is free and/or substantially free of water and other impurities (at the ppm or lower levels) for use in the electronics/semiconductor industry.
[0046] In another aspect, the disclosed and claimed subject matter relates to packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 with high bulk density and high packing density. Such forms are provided by way of filling containers containing ultra-pure MoO.sub.2Cl.sub.2 that is free and/or substantially free of water and other impurities (at the ppm or lower levels) for use in the electronics/semiconductor industry.
[0047] The ultra-pure MoO.sub.2Cl.sub.2 can be transferred into another vessel for bulk delivery to a tool for deposition of molybdenum containing films. Additionally, the ultra-pure MoO.sub.2Cl.sub.2 shows substantially lower corrosion rate in steel (e.g., SS316) and alloys when used as a vapor.
[0048] Further embodiments and aspect of ultra-pure MoO.sub.2Cl.sub.2, methods of its preparation and containers for the same are described below.
I. Ultra-Pure MoO.SUB.2.Cl.SUB.2
A. Impurities
[0049] The disclosed and claimed subject matter includes ultra-pure MoO.sub.2Cl.sub.2 free of or substantially free of residual H.sub.2O, HCl, other impurities and other proton sources which are undesirable for use of this precursor in deposition of molybdenum-containing films. In this regard, the disclosed and claimed subject matter further provides an analytical method to detect small amount of residual MoO.sub.2Cl.sub.2 hydrate other proton source impurities in MoO.sub.2Cl.sub.2. While crystal structures of MoO.sub.2Cl.sub.2 and its hydrate are known, see, e.g., L. O. Atovmyan, Z. G. Aliev and B. M. Tarakanov, J. of Structural Chemistry, 9, 985-986 (1969) and Von F. A. Schroeder and A. N. Christensen, Z. Anorg. Allg. Chem., 392, 107-123 (1972), the detection limit of X-ray powder diffraction analytical methods is insufficient to detect low concentrations of MoO.sub.2Cl.sub.2 hydrate and other proton source impurities in MoO.sub.2Cl.sub.2. Thus, a more sensitive analytical method for measuring residual moisture, other impurities (e.g., MoO.sub.2Cl.sub.2 hydrate) and other proton source impurity (e.g., HCl) in MoO.sub.2Cl.sub.2 is needed.
[0050] Regardless of detection method, there has been no reported synthesis or availability of ultra-pure MoO.sub.2Cl.sub.2 as described herein because until now such a material was unknown and unobtainable in the art. As those skilled in the art will recognize, the primary proton impurity sources in MoO.sub.2Cl.sub.2 are derived from the reaction of MoO.sub.2Cl.sub.2 with water as follows:
##STR00001##
where the components of those reaction have the following molecular weights (MW) and maximum relative amounts produced by decomposition of MoO.sub.2Cl.sub.2 hydrate:
TABLE-US-00001 Relative Mass Compound MW (g) MoO.sub.2Cl2 x H.sub.2O 216.86 1000.0 MoO.sub.2Cl.sub.2 198.84 916.9 MoO.sub.3 143.94 663.7 HCl 36.46 336.3 H.sub.2O 18.02 83.1
[0051] Based on the above values, it is possible to level of calculate, based on .sup.1H NMR analysis, maximum total proton source impurities at the ppm level. Unless specified otherwise ppm means parts per million weight (i.e., ppmw).
TABLE-US-00002 MoO.sub.2Cl.sub.2 x H.sub.2O H.sub.2O H.sub.2O HCl H MoO.sub.2Cl.sub.2 (wt %) (wt %) (ppm) (ppm) (ppm) Purity 0.015 0.001 12.5 50.7 1.4 Ultra- 0.030 0.003 25.0 101.4 2.8 Pure 0.060 0.005 50.0 202.9 5.6 0.090 0.008 75.0 304.3 8.3 0.121 0.010 100.0 405.7 11.1 0.151 0.013 125.1 507.2 13.9 0.301 0.025 250.1 1014.3 27.8 0.452 0.038 375.2 1521.5 41.7 Not 0.603 0.050 500.2 2028.6 55.6 Reported 0.753 0.063 625.3 2535.8 69.5 0.904 0.075 750.3 3042.9 83.4 1.055 0.088 875.4 3550.1 97.3 Currently 1.205 0.100 1000.4 4057.2 111.2 Reported 1.356 0.113 1125.5 4564.4 125.1 Purity 1.507 0.125 1250.5 5071.6 138.9 Standard
[0052] The disclosed and claimed subject matter provides ultra-pure MoO.sub.2Cl.sub.2 down to sub-2 ppm levels of proton impurities. This represents up to nearly a 100-fold increase in purity compared to known pure MoO.sub.2Cl.sub.2 and/or provided by processes for preparing MoO.sub.2Cl.sub.2.
1. Total Proton
[0053] As noted above, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter is free or substantially free of protons from physiosorbed or chemisorbed moisture and detectable by the .sup.1H NMR technique described below. Such protons include those from MoO.sub.2Cl.sub.2 hydrate, HCl, molybdic acid, etc.
[0054] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 50 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 40 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 30 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 25 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 20 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 15 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 10 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 9 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 8 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 7 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 6 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 5 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 4 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 3 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 2.5 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 2 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 1.5 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has less than about 1 ppm of protons in the physiosorbed or chemisorbed state as measured by .sup.1H NMR.
[0055] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of detectable protons as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of protons as measured by .sup.1H NMR
2. Moisture (H.SUB.2.O)
[0056] As noted above, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter is free or substantially free of residual H.sub.2O as measured by .sup.1H NMR (as described herein).
[0057] In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 250 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 200 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 150 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 100 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 75 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 50 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 25 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 20 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 15 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 12.5 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 10 ppm in the physiosorbed or chemisorbed state.
[0058] In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.030 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as determined by .sup.1H NMR is less than about 0.025 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.020 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.015 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.014 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.013 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.012 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.011 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.010 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.009 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.008 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.007 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.006 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.005 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.004 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.003 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.002 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of H.sub.2O as measured by .sup.1H NMR is less than about 0.001 wt % in the physiosorbed or chemisorbed state.
[0059] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of detectable H.sub.2O as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of H.sub.2O as measured by .sup.1H NMR.
3. Hydrochloric Acid (HCl)
A. HCl in the Physiosorbed or Chemisorbed State
[0060] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter is free or substantially free of residual HCl as measured by .sup.1H NMR (as described herein) in the physiosorbed or chemisorbed state.
[0061] In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 1000 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 900 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 800 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 700 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 600 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 550 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 500 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 450 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 400 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 350 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 300 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 250 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 200 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 150 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 125 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 90 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 80 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 70 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 60 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 50 ppm in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of HCl as measured by .sup.1H NMR is less than about 40 ppm in the physiosorbed or chemisorbed state.
[0062] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of detectable HCl as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of HCl as measured by .sup.1H NMR.
B. HCl in the Vapor State
[0063] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter is free or substantially free of residual HCl as measured by infrared spectroscopy (IR) or tunable diode laser absorption spectroscopy (TDLAS). In one embodiment, for example, the ultra-pure MoO.sub.2Cl.sub.2 vapor is free of HCl as measured by Fourier transform infrared spectroscopy (FT-IR).
[0064] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 vapor produced from ultra-pure solid MoO.sub.2Cl.sub.2 prepared by the disclosed and claimed subject matter is free of detectable HCl as measured by FT-IR peaks between 2600 and 3100 cm.sup.?1 attributed to gaseous HCl. In one embodiment HCl peak at 2799 cm.sup.?1 is used to quantify the amount of HCl in MoO.sub.2Cl.sub.2 vapor.
[0065] In one embodiment, the absorbance of 2799 cm.sup.?1 HCl peak in MoO.sub.2Cl.sub.2 vapor is less than 100?10.sup.?4 Absorbance Units/meter at 0.5 cm.sup.?1 resolution. In one embodiment, the absorbance of 2799 cm.sup.?1 HCl peak in MoO.sub.2Cl.sub.2 vapor is less than 50?10.sup.?4 Absorbance Units/meter at 0.5 cm.sup.?1 resolution. In one embodiment, the absorbance of 2799 cm.sup.?1 HCl peak in MoO.sub.2Cl.sub.2 vapor is less than 10?10.sup.?4 Absorbance Units/meter at 0.5 cm.sup.?1 resolution. In one embodiment, the absorbance of 2799 cm.sup.?1 HCl peak in MoO.sub.2Cl.sub.2 vapor is less than 5?10.sup.?4 Absorbance Units/meter at 0.5 cm.sup.?1 resolution. In one embodiment, the absorbance of 2799 cm.sup.?1 HCl peak in MoO.sub.2Cl.sub.2 vapor is less than 1?10.sup.?4 Absorbance Units/meter at 0.5 cm.sup.?1 resolution.
[0066] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of detectable HCl as measured by IR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of HCl as measured by IR.
[0067] In one embodiment, the disclosed and claimed subject matter includes a vapor (i.e., gas) that includes, consist essentially of or consists of MoO.sub.2Cl.sub.2 where the vapor is free or substantially free of gaseous HCl. In one embodiment, the concentration of gaseous HCl in the MoO.sub.2Cl.sub.2 vapor is less than 300 ppm volume as measured by IR. In one embodiment, the concentration of gaseous HCl in the MoO.sub.2Cl.sub.2 vapor is less than 150 ppm volume as measured by IR. In one embodiment, the concentration of gaseous HCl in the MoO.sub.2Cl.sub.2 vapor is less than 100 ppm volume as measured by IR. In one embodiment, the concentration of gaseous HCl in the MoO.sub.2Cl.sub.2 vapor is less than 60 ppm volume as measured by IR. In one embodiment, the concentration of gaseous HCl in the MoO.sub.2Cl.sub.2 vapor is less than 30 ppm volume as measured by IR. In one embodiment, the concentration of gaseous HCl in the MoO.sub.2Cl.sub.2 vapor is less than 15 ppm volume as measured by IR. In one embodiment, the concentration of gaseous HCl in MoO.sub.2Cl.sub.2 vapor is less than 3 ppm volume as measured by IR.
4. MoO.sub.2Cl.sub.2 Hydrate
[0068] As noted above, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter is free or substantially free of residual MoO.sub.2Cl.sub.2 hydrate as measured by .sup.1H NMR (as described herein). Commonly used chemical formulas to describe the hydrate as MoO.sub.2Cl.sub.2 x H.sub.2O and MoO(OH).sub.2Cl.sub.2, H.sub.2MoO.sub.3Cl.sub.3.
[0069] In one embodiment, the residual total content of MoO.sub.2Cl.sub.2x H.sub.2O as measured by .sup.1H NMR is less than about 0.30 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.25 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.20 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.15 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.14 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.13 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.12 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.11 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.10 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.09 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.08 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.07 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.06 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.05 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.04 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.03 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.02 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.015 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR is less than about 0.01 wt % in the physiosorbed or chemisorbed state.
[0070] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of detectable MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 is free of MoO.sub.2Cl.sub.2 x H.sub.2O as measured by .sup.1H NMR.
4. MoO.SUB.3
[0071] As noted above, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter is free or substantially free of residual MoO.sub.3. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.20 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.15 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.14 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.13 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.12 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.11 wt % in the physiosorbed or chemisorbed state. In one embodiment, the residual total content of MoO.sub.3 is less than about 0.10 wt % in the physiosorbed or chemisorbed state.
B. Bulk Density
[0072] As noted above, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter exhibits unexpectedly high bulk densities approaching 3.0 g/cm.sup.3 and above. Bulk density of MoO.sub.2Cl.sub.2 is defined as the mass of MoO.sub.2Cl.sub.2 sample per volume occupied by the sample, expressed in g/cm.sup.3. MoO.sub.2Cl.sub.2 is typically manufactured in a powder or crystal form with low bulk density, less than 1 g/cm.sup.3, and high surface area. For example, the bulk densities of the disclosed and claimed ultra-pure MoO.sub.2Cl.sub.2 more than doubles the previously reported bulk density values for MoO.sub.2Cl.sub.2 described in WO Publication No. 2020/021786 (0.8-1.2 g/cm.sup.3).
[0073] In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.0 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.1 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.2 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.3 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.4 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.5 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.6 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.7 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.8 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 2.9 g/cm.sup.3. In one embodiment, the ultra-pure MoO.sub.2Cl.sub.2 has a bulk density of greater than about 3.0 g/cm.sup.3.
II. Method of Preparing Ultra-Pure MoO.SUB.2.Cl.SUB.2
[0074] As noted above, the disclosed and claimed subject matter also relates to a method of preparing ultra-pure MoO.sub.2Cl.sub.2 in which Low purity molybdenum dichloride dioxide (e.g., that includes molybdenum dichloride dioxide hydrate, H.sub.2MoO.sub.3Cl.sub.2) is heated above its melting point in a sealed vessel. In one aspect of this embodiment, the container headspace is vented at least once to remove hydrogen chloride and other by-products present in crude molybdenum dichloride dioxide.
[0075] Without being bound by theory it is believed that heating low purity MoO.sub.2Cl.sub.2 above its melting point results in decomposition of MoO.sub.2Cl.sub.2 hydrate and other impurities (e.g., hydrogen chloride and water molecules). This does not appear to happen in processes in which MoO.sub.2Cl.sub.2 is not treated above its melting point. During the melting process molybdenum trioxide by-product may settle to the bottom of the vessel allowing better separation from hydrogen chloride by-product. Notably, this approach stands in stark contrast to known procedures for purifying these types of precursors. For example, WO2019/115361 describes a method for purification of various precursors below their melting points. However, it has been unexpectedly observed that performing the melting step is much more efficient and critical for removing residual traces of H.sub.2O and HCl trapped in the solid in order to arrive at ultra-pure MoO.sub.2Cl.sub.2 having previously unattainable purity levels. Indeed, a further advantage of disclosed and claimed process is the ability to filter molten MoO.sub.2Cl.sub.2 to remove insoluble impurities, for example MoO.sub.3 and MoO.sub.2.
[0076] Given the above, in one embodiment, the disclosed and claimed process for preparing ultra-pure MoO.sub.2Cl.sub.2 includes the steps of: [0077] a. charging low purity MoO.sub.2Cl.sub.2 into a pressure vessel; [0078] b. heating the vessel to a temperature (ca. from about 180? C. to about 200? C.) sufficient to melt the low purity MoO.sub.2Cl.sub.2; [0079] c. optionally filtering the molten MoO.sub.2Cl.sub.2 to remove insoluble impurities (e.g., MoO.sub.3 and MoO.sub.2); [0080] d. venting the vessel to remove impurities (e.g., HCl gas); and [0081] e. cooling the vessel; and [0082] f. optionally re-venting the vessel.
In one aspect of this embodiment, steps a-f are repeated until the vessel is filled. In one aspect of this embodiment, one or more of steps a-f is repeated until the vessel is filled. In one aspect of this embodiment, the vessel is constructed of non-corrosive material, such as for example stainless steel, nickel, Monel, Hastelloy, nickel coated stainless steel, etc. In another aspect of this embodiment, the vessel is equipped with at least one valve and is connected to a metal system comprising pressure gage and a second vessel.
[0083] In one embodiment, low purity MoO.sub.2Cl.sub.2 powder is charged into a pressure vessel. The vessel with MoO.sub.2Cl.sub.2 is heated from about 180? C. to about 200? C. to completely melt the low purity MoO.sub.2Cl.sub.2. The vessel is cooled to ambient temperature and the vessel headspace is evacuated or purged with inert gas to remove residual hydrogen chloride gas and other potential impurities present in the vapor phase. In one aspect of this embodiment, the vessel is constructed of non-corrosive material, such as for example stainless steel, nickel, Monel, Hastelloy, nickel coated stainless steel, etc. In another aspect of this embodiment, the vessel is equipped with at least one valve and is connected to a metal system comprising pressure gage and a second vessel.
[0084] In another embodiment, low purity MoO.sub.2Cl.sub.2 powder is charged into a pressure vessel equipped with at least one valve and is connected to a metal system comprising pressure gage and a second vessel. The vessel with the low purity MoO.sub.2Cl.sub.2 is heated from about 180? C. to about 200? C. C to completely melt MoO.sub.2Cl.sub.2 powder. At this temperature the headspace of the vessel is vented to a second vessel (including inert gas) at a pressure lower compared to the vessel with MoO.sub.2Cl.sub.2. This step may be repeated until MoO.sub.2Cl.sub.2 vessel pressure is within 20% from expected MoO.sub.2Cl.sub.2 vapor pressure at vessel temperature. In one aspect of this embodiment, the vessel is constructed of non-corrosive material, such as for example stainless steel, nickel, Monel, Hastelloy, nickel coated stainless steel, etc. It should be notes that this in this embodiment, the vessel with the low purity MoO.sub.2Cl.sub.2 could alternatively be vented or evacuated at lower temperature.
[0085] As noted above, the method can include filtering the molten MoO.sub.2Cl.sub.2 to remove solids insoluble in the melt. Filtration of the melt enables the removal of decomposition by-products and impurities, if any, formed during heating and is not possible when the precursor is treated below the melting point.
III. Packaged Forms of Ultra-Pure MoO.SUB.2.Cl.SUB.2
[0086] As noted above, the disclosed and claimed subject matter relates to packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 with high bulk density and high packing density. Such forms are provided by way of filling containers containing ultra-pure MoO.sub.2Cl.sub.2 that is free and/or substantially free of water and other impurities (at the ppm or lower levels) for use in the electronics/semiconductor industry.
[0087] The handling of low bulk density powders with high surface area can easily give rise to moisture contamination. Packaging low bulk density powder with high surface area into containers designed for semiconductor manufacturing can also result in dusting and contamination of container parts with powder. It is also desirable in the semiconductor industry to supply precursor materials in containers with minimal space/footprint requirements due to expensive fab floor space. Thus, containers with small footprint and high packing densities are preferred for chemical delivery cabinets.
[0088] In this regard, WO Patent Application Publication No. 2020/021786 describes a process for producing MoO.sub.2Cl.sub.2 that includes sublimating and reaggregating a crude molybdenum oxychloride in a reduced-pressure atmosphere. However, the MoO.sub.2Cl.sub.2 produced by this process had a relatively low bulk density (ca. less than 1.2 g/cm.sup.3). Although precursor vaporizing equipment is known (see, e.g., U.S. Patent Application Publication No. 2019/0186003 which provides a vaporizer for vaporizing and delivering vapor to deposition tools) such equipment contains multiple trays and is not suitable for filling the vaporizer with molten solid to achieve optimal (i.e., the highest possible) packing density.
[0089] As described above, the ultra-pure MoO.sub.2Cl.sub.2 of the disclosed and claimed subject matter exhibits unexpectedly high bulk densities approaching 3.0 g/cm.sup.3. As such, the ultra-pure MoO.sub.2Cl.sub.2 can be provided in packaged forms (e.g., in a canister container where the pressure does not exceed the sum of molybdenum dichloride dioxide partial pressure and partial pressure of inert gas used to backfill canister headspace). As explained above, the bulk density of MoO.sub.2Cl.sub.2 is defined as the mass of MoO.sub.2Cl.sub.2 sample per volume occupied by the sample, expressed in g/cm.sup.3. The packing density of a packaged form of the ultra-pure MoO.sub.2Cl.sub.2 is defined as the fraction of the total external volume of the packaged form containing the ultra-pure MoO.sub.2Cl.sub.2, excluding any valve manifold, expressed as kg of MoO.sub.2C.sub.2/liter (external volume). Given the unprecedented high bulk densities the ultra-pure MoO.sub.2Cl.sub.2 packaged forms of the same similarly achieve unprecedented packing densities.
[0090] In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 0.7 kg/L to about 1.5 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 0.7 kg/L to about 1.0 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.0 kg/L to about 1.5 kg/L of container external volume.
[0091] In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 0.7 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 0.8 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 0.9 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.0 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.1 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.2 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.3 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.4 kg/L of container external volume. In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 have a packing density of about 1.5 kg/L of container external volume.
[0092] In one embodiment, the packaged forms of the ultra-pure MoO.sub.2Cl.sub.2 are provided in a container resembling the shape of a gas cylinder. In one aspect of this embodiment, the container has a height to diameter ratio at least 2/1. In one aspect of this embodiment, the container has a height to diameter ratio at least 3/1. In one aspect of this embodiment, the container has a height to diameter ratio at least 4/1. In one aspect of this embodiment, the container has a height to diameter ratio at least 5/1. In a further aspect of this embodiment, the container is equipped (or can be equipped) with at least one valve and an inlet tube for filling molten ultra-pure MoO.sub.2Cl.sub.2, where the inlet tube resides in the headspace above filled material.
EXAMPLES
[0093] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. The examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.
[0094] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter, including the descriptions provided by the following examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.
Methods
.SUP.1.H NMR Analysis:
[0095] Proton NMR is used as an analytical method for detecting low levels (i.e., 0.1 wt % or lower) of moisture and residual hydrogen atoms in the ultra-pure MoO.sub.2Cl.sub.2. In this methodology, the moisture and total proton content in an ultra-pure MoO.sub.2Cl.sub.2 sample were measured by integration of the water peak of a 5 wt. % ultra-pure MoO.sub.2Cl.sub.2 solution in CD.sub.3CN using ethylene carbonate as an internal standard and blank subtraction.
[0096] A 5 mm Wilmad low pressure/vacuum NMR tube was charged with ethylene carbonate (0.008 g) and CD.sub.3CN (1.000 g) under an N.sub.2 atmosphere. The .sup.1H NMR spectrum was collected using 512 scans with a 1 second relaxation delay on a Bruker Ascend 500 MHZ NMR. Then, MoO.sub.2Cl.sub.2 (0.050 g) was dissolved into the solution under an N.sub.2 atmosphere. Again, the .sup.1H NMR spectrum was collected under identical conditions as the previous run.
[0097] MestReNova software was used to integrate the peak at 4.45 ppm corresponding to the CH.sub.2 groups in ethylene carbonate and the peak at 2.13 ppm corresponding to H.sub.2O in the blank. In the MoO.sub.2Cl.sub.2 sample, the internal standard at 4.45 ppm and the broad ultra-pure MoO.sub.2Cl.sub.2.Math.xH.sub.2O peak at 5.24 ppm were integrated and blank subtraction was utilized to determine the moisture content in the ultra-pure MoO.sub.2Cl.sub.2 sample. The method detection limit by this method is estimated to be 10 ppm of H.sub.2O in ultra-pure MoO.sub.2Cl.sub.2 which is equivalent to 1.1 ppm of total protons in MoO.sub.2Cl.sub.2.
[0098] This analysis was used on all ultra-pure MoO.sub.2Cl.sub.2 samples prepared by the processed disclosed and claimed herein.
Example 1: Preparation of Ultra-Pure MoO.SUB.2.Cl.SUB.2
[0099] A low purity MoO.sub.2Cl.sub.2 sample having low bulk density and high moisture content was analyzed by .sup.1H NMR method as described above. Moisture in the sample was 709 ppm (equivalent to 78.8 ppm of total residual protons in the low purity MoO.sub.2Cl.sub.2) and the bulk density was 0.3 g/cm3. The low purity MoO.sub.2Cl.sub.2 (5.7 kg) was charged into a 21 L C-22 Hastelloy vessel and heated to 200? C. to completely melt MoO.sub.2Cl.sub.2. The vessel was heated at 200? C. for 24 hours to decompose residual hydrate and to release hydrogen chloride. Thereafter, the vessel was cooled to room temperature and the residual gases were removed under nitrogen purge. An additional 5.0 kg of the low purity MoO.sub.2Cl.sub.2 was then charged on top of the solidified MoO.sub.2Cl.sub.2 melt in the 21 L C-22 Hastelloy vessel and heated to 200? C. to completely melt the low purity MoO.sub.2Cl.sub.2. The vessel was heated at 200? C. for 24 hours to decompose residual hydrate and to release hydrogen chloride. The above steps were repeated two additional times to fill the 21 L container with 20.6 kg of ultra-pure MoO.sub.2Cl.sub.2.
[0100] Analysis: The bulk density of the ultra-pure MoO.sub.2Cl.sub.2 was 2.6 g/cm.sup.3 as determined by measurement of void volume of the container. A representative sample from the container was analyzed by .sup.1H NMR as described above and showed the residual moisture in the ultra-pure MoO.sub.2Cl.sub.2 was 126 ppm (equivalent to 14 ppm of total residual protons in the ultra-pure MoO.sub.2Cl.sub.2).
Example 2: Bulk density of Ultra-Pure MoO.SUB.2.Cl.SUB.2
[0101] Low purity MoO.sub.2Cl.sub.2 powder (4.2 g) was charged into a SS316 tube with 10 mm ID. The tube with the low purity MoO.sub.2Cl.sub.2 powder was capped with SS316 VCR caps and heated to 185? C. for 22 hours. The tube was cooled to room temperature and the residual gases were removed with nitrogen purge. The ultra-pure MoO.sub.2Cl.sub.2 formed a solid block at the bottom of the vessel with a 10 mm diameter and 19 mm height. The bulk density of the ultra-pure MoO.sub.2Cl.sub.2 was 2.8 g/cm3. By comparison, the bulk density of the low purity MoO.sub.2Cl.sub.2 described in WO Publication No. 2020/021786 is reported to be around 0.8-1.2 g/cm.sup.3.
Example 3: Container/Vaporizer with High Packing Density of MoO.SUB.2.Cl.SUB.2
[0102] A container with 20 kg of low purity MoO.sub.2Cl.sub.2 prepared as demonstrated in Example 1 was heated at 200? C. to completely melt the low purity MoO.sub.2Cl.sub.2. The molten liquid was transferred into a container/vaporizer having external diameter 9.2 inches and 51-inch height (aspect ratio of 5.5), equipped with a valve and an inlet tube. The transfer was repeated at least one time to fill 40 kg of the MoO.sub.2Cl.sub.2 in a 44 L container. During cool down, the container/vaporizer was vented to release excess pressure from hydrogen chloride formed from decomposition of proton-containing species initially present in the low purity MoO.sub.2Cl.sub.2 powder. The samples of ultra-pure MoO.sub.2Cl.sub.2 from the container/vaporizer were collected by vaporization of MoO.sub.2Cl.sub.2 at 160? C.-180? C. and condensing it on a cold surface. The samples were analyzed by .sup.1H NMR as described above. Residual moisture in the ultra-pure MoO.sub.2Cl.sub.2 was less than about 20 ppm (equivalent to less than about 2.2 ppm of total residual protons in the ultra-pure MoO.sub.2Cl.sub.2).
Example 4: Preparation of Ultra-Pure MoO.SUB.2.Cl.SUB.2
[0103] A low purity MoO.sub.2Cl.sub.2 sample having low bulk density and high moisture content was analyzed by .sup.1H NMR method as described above. Moisture in the sample was 1074 ppm (equivalent to 119.4 ppm of total residual protons in the low purity MoO.sub.2Cl.sub.2) and the bulk density was 0.3 g/cm3. The low purity MoO.sub.2Cl.sub.2 (6.4 kg) was charged into a 21 L C-22 Hastelloy vessel and heated to 200? C. to completely melt MoO.sub.2Cl.sub.2. The vessel was heated at 200? C. for 12 hours to decompose residual hydrate and to release hydrogen chloride. Thereafter, the vessel was cooled to room temperature and the residual gases were removed under nitrogen purge. An additional 4.0 kg of the low purity MoO.sub.2Cl.sub.2 was then charged on top of the solidified MoO.sub.2Cl.sub.2 melt in the 21 L C-22 Hastelloy vessel and heated to 200? C. to completely melt the low purity MoO.sub.2Cl.sub.2. The vessel was heated at 200? C. for 12 hours to decompose residual hydrate and to release hydrogen chloride. After cooling this 21 L container now contained 10.4 kg of ultra-pure MoO.sub.2Cl.sub.2.
[0104] Analysis: The bulk density of the ultra-pure MoO.sub.2Cl.sub.2 was 3.0 g/cm3 as determined by measurement of void volume of the container. A representative sample from the container was analyzed by .sup.1H NMR as described above and showed the residual moisture in the ultra-pure MoO.sub.2Cl.sub.2 was <15 ppm (equivalent to <2 ppm of total residual protons in the ultra-pure MoO.sub.2Cl.sub.2).
Example 5: Bulk Density of Ultra-Pure MoO.SUB.2.Cl.SUB.2
[0105] Low purity MoO.sub.2Cl.sub.2 powder (10.4 kg) was charged into a 21L C-22 Hastelloy vessel and heated to 200? C. to completely melt MoO.sub.2Cl.sub.2. While at 200? C., 9.8 kg liquid MoO.sub.2Cl.sub.2 was then transferred into an 8.8L C-22 Hastelloy vessel. The 8.8 L vessel was gradually cooled to room temperature by first cooling the bottom and over a period of 4 hours cooling the top of the vessel until the vessel was at ambient temperature. At ambient temperature, the residual gases were removed with vacuum. The ultra-pure MoO.sub.2Cl.sub.2 formed a solid block at the bottom of the vessel with a 222 mm diameter and 85.6 mm height. The bulk density of the ultra-pure MoO.sub.2Cl.sub.2 was 2.96 g/cm.sup.3. By comparison, the bulk density of the low purity MoO.sub.2Cl.sub.2 described in WO Publication No. 2020/021786 is reported to be around 0.8-1.2 g/cm.sup.3.
Comparative Example 6: MoO.SUB.2.Cl.SUB.2 .Collected from Low Purity MoO.SUB.2.Cl.SUB.2
[0106] In this comparative example, the MoO.sub.2Cl.sub.2 was neither purified nor packaged by the disclosed methods. A container with 5.7 kg of low purity MoO.sub.2Cl.sub.2 with a moisture level of 390 ppm (equivalent to 43.4 ppm of total residual protons in the low purity MoO.sub.2Cl.sub.2) was prepared as demonstrated in Example 1 and heated to 150? C., below the melting point of MoO.sub.2Cl.sub.2. A small portion of the hot solid was vapor transferred into an evacuated container with ambient internal surface temperatures over the duration of 30 seconds. The low purity MoO.sub.2Cl.sub.2 at 150? C. was allowed to re-equilibrate for 1.5 hours. A second 30 second vapor transfer was done into the same evacuated container. This 30 second transfer with 1.5-hour re-equilibration holds was repeated 4 more times for a total of 6 hot vapor transfers. Both vessels were cooled to ambient temperature. The material collected in the evacuated receiver, 135 g, had a moisture level of 373 ppm (equivalent to less than about 41.5 ppm of total residual protons in the ultra-pure MoO.sub.2Cl.sub.2). This example demonstrated that Mo202Cl.sub.2 collected from low purity material contained significant amount of moisture (373 ppm) in contrast to Mo.sub.2O.sub.2Cl.sub.2 collected from ultra-pure MoO.sub.2Cl.sub.2 (<20 ppm).
Example 7: Measurement of HCl Concentration in MoO.SUB.2.Cl.SUB.2 .Vapor
[0107] A Hastelloy C22 vessel was filled with MoO.sub.2Cl.sub.2. The vessel was connected to Hastelloy pneumatic valve and SS vacuum manifold. The vessel with MoO.sub.2Cl.sub.2 was heated to 190? C. to melt MoO.sub.2Cl.sub.2 and to release traces of residual HCl into the vapor phase. Residual HCl was purged from the headspace above MoO.sub.2Cl.sub.2 with purified N.sub.2 to obtain ultra-pure MoO.sub.2Cl.sub.2. During the purge N.sub.2 carrier gas containing MoO.sub.2Cl.sub.2 vapor was flowing via 5.33-meter IR cell of the FT-IR spectrometer (MKS Multigas 2030) heated to 150? C. The absorbance of 2799 cm.sup.?1 HCl peak in MoO.sub.2Cl.sub.2 reduced from 0.0088 to at least 7.4?10.sup.?4 Absorbance Units/meter HCl at 0.5 cm.sup.?1 resolution.
SUMMARY
[0108] It has been demonstrated that ultra-pure MoO.sub.2Cl.sub.2 can be prepared at purity levels that are nearly 100-fold greater than has previously been reported and that this ultra-pure MoO.sub.2Cl.sub.2 has unexpected properties providing exceptionally high-density packaged forms thereof.
[0109] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.