Chemistry of inorganic compounds – Phosphorus or compound thereof
Patent
1982-09-17
1986-11-04
Heller, Gregory A.
Chemistry of inorganic compounds
Phosphorus or compound thereof
423322, 252 623ZB, 252 623E, C01B 2500, C01B 2501, C01B 2502, C04B 3500
Patent
active
046209689
ABSTRACT:
Monoclinic phosphorus is produced in a single source vapor transport apparatus comprising a sealed evacuated ampoule containing a mixture or compound of phosphorus and an alkali metal with the phosphorus to alkali metal ratio being 11 or greater. The charge is heated to 550.degree.-560.degree. C. and the monoclinic phosphorus crystals are formed on the cooler surface at the top of the ampoule over the temperature range of 500.degree.-560.degree. C. The preferred heating temperature is in the neighborhood of 555.degree. C. and the preferred deposition temperature is in the neighborhood of 539.degree. C. Alkali metals that may be employed include sodium, potassium, rubidium and cesium. The monoclinic phosphorus crystals form in two habits. Those formed in the presence of sodium and cesium are in the form of flat square platelets up to 4 mm on a side and 2 mm thick. These platelets may be easily cleaved into thinner platelets, like mica. The other habit formed in the presence of potassium and rubidium is in the form of a truncated pyramid up to 4 mm.times.3 mm.times.2 mm high. This habit is hard to cleave. The crystals are semiconductors with a band gap, indicated by photoluminescence, of about 2.1 eV at room temperature. Powder X-ray diffraction, and differential thermal analysis are consistent with that reported for Hittorf's phosphorus prepared according to the prior art. The crystals are a deep red on transmission and birefringent, rotating the plane of polarization in a polarizing microscope. They contain from 50 to 2000 parts per million of alkali metal and therefore may be utilized as a form of very pure phosphorus as well as for their semiconducting and birefringent qualities and as phosphors.
REFERENCES:
patent: 3127226 (1964-03-01), Rector
patent: 3361591 (1968-01-01), Dill et al.
patent: 3446936 (1969-05-01), Hanson et al.
patent: 3716844 (1973-02-01), Brodsky
patent: 3864717 (1975-02-01), Merrin
patent: 3983542 (1976-09-01), Ovshinsky
patent: 4013756 (1977-03-01), Lowe et al.
patent: 4177473 (1979-12-01), Ovshinsky
patent: 4177474 (1979-12-01), Ovshinsky
patent: 4217374 (1980-08-01), Ovshinsky et al.
patent: 4226898 (1980-10-01), Ovshinsky et al.
patent: 4286545 (1981-09-01), Takagi et al.
J. D. Jensen and R. B. Schoolar, "Surface Charge Transport in PbS.sub.x Se.sub.1-x and Pb.sub.1-y Sn.sub.y Se Epitaxial Films", J. Vac. Sci. Technol, vol. 13, No. 4, p. 920, 1976.
J. Donahue, "Phosphorus", The Structures of the Elements, pp. 289-303, 403-436, 1974.
A. Wold and R. Kaner, "Preparation of Transition Metal Phosphides and Silicides from Metal Fluxes", 181 American Chemical Society Meeting, INOR No. 117, 1980.
cpD. Adler, "Chemistry and Physics of Amorphous Semiconductors", Journal of Chemical Education, vol. 57, No. 8, pp. 560-564, Aug. 1980.
F. Yonezawa, Fundamental Physics of Amorphous Semiconductors, p. 20, Springer-Verlag, 1981, Proceedings of the Kyoto Summer Institute, Kyoto, Japan, Sep. 8-11, 1980.
D. Beecham, "Cadmium/Sulfur Isothermal Source for CdS Deposition", The Review of Scientific Instruments, vol. 41, No. 11, p. 1654, 1970.
K. Shimakawa, Y. Inagaki, S. Nitta, and T. Arizumi, "Dependences of the Resistivity and the Switching on Composition in Chalcogenide Glasses", Japan, J. Appl. Phys. 10, pp. 956-957, 1971.
H. U. Beyeler and S. Veprek, "Radial Distribution Function of Amorphous Phosphorus Prepared by Chemical Transport in a Low Pressure Hydrogen Plasma", Philosophical Magazine B, vol. 41, No. 3, pp. 327-340, 1980, U.K.
D. J. Smith and W. M. Stobbs, "Investigations on the Structure of Amorphous Phosphorus", Inst. Phys. Conf. Ser. No. 52, Chapter 10, pp. 457-460, 1980.
D. J. Braun and W. Jeitschko, "The Synthesis and Crystal Structure of the Polyphosphides La.sub.6 Ni.sub.6 P.sub.17, Ce.sub.6 Ni.sub.6 P.sub.17, and Pr.sub.6 Ni.sub.6 P.sub.17 ", Acta Cryst, B34, pp. 2069-2074, 1978.
W. E. Spear, P. G. Le Comber, S. Veprek and R. Wild, "Electronic Properties of Amorphous Phosphorus Prepared by Chemical Transport in a Glow Discharge", Philosophical Magazine B, vol. 38, No. 4, pp. 349-355, 1978.
M. H. Brodsky, Ed., "Amorphous Semiconductors", pp. 3, 5, 44, 216-218, 224-225, 241-243, Springer-Verlag, 1979.
P. B. Kirby and E. A. Davis, "Photoluminescence from Amorphous Phosphorus", Journal of Non-Crystalline Solids, 35 & 36, pp. 945-950, 1980.
J. Brunner, M. Thuler, S. Veprek and R. Wild, "X-Ray Photoelectron Study of Amorphous Phosphorus Prepared by Plasma Chemical Transport, Comparison with Crystalline Polymorphs", J. Phys. Chem. Solids, vol. 40, pp. 967-971, 1979, U.K.
V. I. Kosyakov and I. G. Vasil'eva, "Phosphorus Rings, Clusters, Chains, and Layers", Russian Chemical Reviews, 48(2), pp. 153-161, 1979; [translated from Uspekhi Khimii, 48, pp. 280-296 (1979)].
A. Catalano and R. B. Hall, "Defect Dominated Conductivity in Zn.sub.3 P.sub.2 ", J. Phys. Chem. Solids, vol. 41, pp. 635-640, 1980.
V. Kosyakov and I. Vasilyeva, "Relation [Correlation] Between the Structure and Properties of Polyphosphides", Poluprovdn. Materialy i Ikh. Primenenie Voronezh, pp. 143-153, 1977, USSR.
D. E. C. Corbridge, Phosphorus, An Outline of Its Chemistry, Biochemistry and Technology (2nd Edition), "Studies in Inorganic Chemistry 2", Chapter 2, Phosphides and Single Compounds, Elsevier Scientific Publishing Co., 1980.
V. Kosyakov and I. Vasilyeva, "Structural Classification of Polyphosphides", Poluch. svoistra i primenenie Fosfidov, pp. 17-22, 1977, USSR.
D. E. C. Corbridge, Structural Chemistry of Phosphorus, Elsevier Scientific Publishing Co., Amsterdam, Chapter 2, "Phosphorus: The Element", pp. 13-24, 42-44, 46-47, 56-58, 61-63, 1974.
H. Krebs and Th. Ludwig, "About Crystallized Metal Polyphosphides, III, The Structure of the Metal Phosphides of the Type HgPbP.sub.14 ", Z. Anorg, Allg. Chem. 294, pp. 257-266, 1958, Germany.
V. L. Dalal, B. N. Baron and T. W. F. Russell, "Technology Considerations for Thin Solar Cells", American Section International Solar Energy Society, Jun. 2-6, 1980, U.S.
H. Krebs, I. Pakulla, and G. Zurn, "About Crystallized Metal Polyphosphides. I", Z. Anorg. Allg. Chem. 278, pp. 274-286, 1955, Germany.
E. A. Davis, "Review of Group-V Amorphous Semiconductors", Journal De Physique, Colloque C4, supplement au No. 10, Tome 42, Oct./1981, pp. 855-864.
J. S. Lannin and B. V. Shanabrook, "Raman Scattering and Infrared Absorption in Bulk Amorphous Red Phosphorus", Solid State Communications, vol. 28, pp. 497-500, 1978, U.K.
Encyclopaedia Britannica, "Semiconductor Devices", and Solid State of Matter, vol. 16, pp. 512-529, 1032-1043, (1974), William Benton, publisher, U.S.
T. S. Moss, "Photoconductivity in the Elements", Proc. Phys. Soc., vol. 64A, pp. 590-591, 1951.
E. A. Fagen, "Optical Properties of Zn.sub.3 P.sub.2 ", J. Appl. Phys., vol. 50, No. 10, pp. 6505-6515, 1979.
F. Grandjean, A. Gerard, U. Krieger, C. Heiden, D. J. Braun and W. Jeitschko, "A Mossbauer Investigation of Diamagnetic, Semiconducting Alpha-FeP.sub.4 ", Solid State Communications, vol. 33, pp. 261-264, 1980.
K. E. Pachali, W. Ott, and H. Thurn, "The Crystal Structure of ZnSnP.sub.14 And Its Relationship to Hittorf Phosphorus And Other Polyphosphides:, Acta Cryst. A31, Suppl. 3, p. 69, 1976, Germany.
G. Haacke and G. A. Castellion, "Preparation and Semiconducting Properties of Cd.sub.3 P.sub.2 ", J. Appl. Phys., vol. 35, No. 8, pp. 2484-2487, 1964.
K. E. Petersen, D. Adler, and M. P. Shaw, "Amorphous-Crystalline Heterojunction Transistors", IEEE Transactions on Electron Devices, vol. ED-23, No. 4, pp. 471-477, Apr./1976, U.S.
Y. Hamakawa, "Amorphous Semiconductor Technologies & Devices", North Holland Publishing Company, Introductory pages, Preface, Table of Contents, Chapter 1, 1982, (Copyright 1981) Japan.
H. Richter and L. Ley, "Optical Properties and Transport in Microcrystalline Silicon Prepared at Temperatures Below 400.degree. C.", J. Appl. Phys., 52(12), Dec./1981, U.S.
W. Honle, "Uber Niedere Phosphide, Arsenide und Antimonide der Alkalimetalle", Dissertation University of Munster, 1975, Germany.
W. L. Roth, T. W. DeWitt and A. J. Smith, "Polymorphism of Red Phosphorus", J. Am. Che
Baumann John A.
Kuck Mark A.
Michel Christian G.
Raccah Paul M.
Schachter Rozalie
Davis IV F. Eugene
Heller Gregory A.
Stauffer Chemical Company
LandOfFree
Monoclinic phosphorus formed from vapor in the presence of an al does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Monoclinic phosphorus formed from vapor in the presence of an al, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Monoclinic phosphorus formed from vapor in the presence of an al will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-696417