Date of Award
Fall 1975
Document Type
Dissertation - Restricted
Degree Name
Doctor of Philosophy (PhD)
Department
Electrical and Computer Engineering
First Advisor
Louis Cartz
Second Advisor
W. Hirthe
Third Advisor
Thomas G. Worlton
Fourth Advisor
Raymond Fournelle
Fifth Advisor
Kenneth S. Mendelson
Abstract
This study concerns the relationship of the anisotropic physical properties of orthorhombic black phosphorus to its crystal structure. Orthorhombic black phosphorus, which will be hereafter referred to as ortho-P, is an interesting solid to investigate because it has a complex structural arrangement, yet is a single element. This study was conducted by (1) measuring the thermal expansion coefficients of a single crystal by x-ray diffractometer techniques and verifying these results by the x-ray diffractometer method on the powder; (2) measuring the compressibility coefficients by neutron time-of-flight (TOF) diffraction and by an x-ray diffraction method; and (3) measuring the integrated intensity of the x-ray and neutron diffraction peaks in order to determine the atomic position parameters, bond lengths, and amplitudes of thermal vibration with respect to temperature and pressure.
It is assumed that the general reader is not familiar with the orthorhombic black phosphorus structure or its properties. Therefore, a review is included of orthorhombic lack phosphorus in Chap. II based for the most part on the two following reviews1: (1) Volume 1, "Phosphorus and Its Compounds", and Volume II, Technology, Biological Functions, and Applications" (1966) by J. R. Van Wazer and (2) Volume VIII, Supplement III on Phosphorus from "Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry", (1971). Chapter III presents the basic theory of x-ray and neutron (TOF) diffraction. The section on technique, Chap. IV. is intended to aid the person unfamiliar with the type of study, reported in this dissertation especially with regards to the single crystal and TOF studies. The results of the various measurements are presented separately in Chap. V with the combined results of the x-ray and neutron diffraction studies discussed in Chap. VI. Chap. VI also compares the results with measurements made by others on similar materials, α-Ås, Ga, α-U and PbO
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1Another review recently published fs "The Structurla Chemistry of Phosphorus by Corbridge. (1