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STATUS AND APPLICATIONS OF DIAMOND AND DIAMOND-LIKE MATERIALS: AN EMERGING TECHNOLOGY Report of the Committee on Superhard Materials NATIONAL MATERIALS ADVISORY BOARD Commission on Engineering and Technical Systems National Research Council NMAB-445 National Academy Press 1990
NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. This report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of the chaner granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Frank Press is president of the National Academy of Sciences. The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous) in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsiblity for advising the federal government. The National Academy of Engineering also sponsors engineering programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. Robert M. White is president of the National Academy of Engineering. The Institute of Medicine was established in 1970 by the National Academy of Sciences to secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the responsibility given to the National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Samuel O. Thier is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy's purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Frank Press and Dr. Robert M. White are chairman and vice chairman, respectively, of the National Research Council. This study by the National Materials Advisory Board was conducted under Contract No. MDA-903-89-K-0078 with the Department of Defense and the National Aeronautics and Space Administration. Library of Congress Card Number 90-60384. International Standard Book Number 0-309-04196-1. This report is available from the Defense Technical Information Center, Cameron Station, Alexandria, VA 22304-6148. S100. Coyer: Small single crystal diamonds produced by APCI filament assisted COD process ( Courtesy o f A ir Prod acts and Chemical s. Inc. ) Frontispiece: Continuous polycrystallirze diamond coating produced by APCI filament assisted CAD process (Courtesy of Air Products and Chemicals, Inc.) Printed in the United States of America. First Printing, June 1990 Second Paining, November 1990 lbird Pnnung, July 1991 Fourth Pnnung, January 1992
ABSTRACT Recent discoveries that make possible the growth of crystalline diamond by chemical vapor deposition offer the potential for a wide variety of new applications. This report takes a broad look at the state of the technology following from these discoveries in relation to other allied materials, such as high-pressure diamond and cubic boron nitride. Most of the potential defense, space, and commercial applications are related to diamond's hardness, but some utilize other aspects such as optical or electronic properties. The growth processes are reviewed, and techniques for characterizing the resulting materials' properties are discussed. Crystalline diamond is emphasized, but other diamond-like materials (silicon carbide, amorphous carbon containing hydrogen) are also examined. Scientific, technical, and economic problem areas that could impede the rapid exploitation of these materials are identified. Recommendations are presented covering broad areas of research and development. · ~ ~
ACKNOWLEDGMENTS Valuable briefings were presented to the committee by Professor Robert Davis, North Carolina State University, who discussed epitaxy, doping, and characterization of nanocrystalline ,B SiC thin films, and Dr. John W. Coburn, IBM, who spoke on mechanistic aspects of diamond film deposition. The committee acknowledges their assistance with thanks. v
COMMITTEE ON SUPERHARD MATERIALS CHAIRMAN JOHN D. VENABLES, Corporate Scientist, Martin Marietta Laboratories, Baltimore, Maryland VICE CHAIRMAN JACK H. WERNICK, Manager, Division of Materials Science, Bell Communications Research, II1C., Red Bank, New Jersey MEMBERS JOHN C. ANGUS, Professor of Engineering, Chemical Engineering Department, Case Western Reserve University, Cleveland, Ohio PETER M. BELL, Vice President, Corporate Technology, Norton Company, Worcester, Massachusetts JEROME J. CUOMO, Manager, CCS Materials Laboratory, IBM, Thomas J. Watson Research Center, Yorktown Heights, New York ROBERT C. DEVRIES, General Electric Company (Retired), Burnt Hills, New York ALBERT FELDMAN, Leader, Optical Materials Group, National Institute of Standards and Technology, Gaithersburg, Maryland MICHAEL W. GEIS, Staff Member, M.I.T. Lincoln Laboratories, Lexington, Massachusetts DAVID S. HOOVER, Manager, Inorganic Materials, Air Products and Chemicals, Inc., Allentown, Pennsylvania RUSSELL MESSIER, Associate Professor, Engineering Science and Mechanics, Pennsylvania State University, University Park LIAISON REPRESENTATIVES JEROME PERSH, Department of Defense (OUSDR&E), Washington, DeC. T. W. MASS, Air Force Wright Aeronautical Laboratories, Wright-Patterson Air Force Base, Ohio e ~ V11
ROBERT KATZ, Army Materials Technology Laboratory, Watertown, Massachusetts MAX N. YODER, Office of Naval Research, Arlington, Virginia ROBERT POHANKA, Office of Naval Research, Arlington, Virginia BEN A. WILCOX, Defense Advanced Research Projects Agency, Arlington, Virginia ROBERT FUSARO, NASA Lewis Research Center, Cleveland, Ohio NMAB STAFF JOSEPH R. LANE, Senior Program Officer JUDITH A. AMRI, Senior Secretary CATHRYN SUMMERS, Senior Secretary . . . vail
1 CONTENTS SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS 1 Conclusions and Recommendations 3 CHAPTER 1: CHAPTER 2: INTRODUCTION 5 Scope 5 Nomenclature 7 Background ~ Vapor Growth of Diamond Diamond-Like Materials 11 Applications 1 2 International Activities 14 Research and Development Issues References 1 5 GROWTH PROCESSES 19 10 14 Generic and Fundamental Issues 20 High-Pressure, High-Temperature Processes 21 Chemical Vapor Deposition Processes 28 Physical Vapor Deposition Processes 43 Other Deposition Processes 55 Other Superhard Materials 55 References 56 CHAPTER 3: CHARACTERIZATION TECHNIQUES RELEVANT TO SUPERHARD MATERIALS 61 Structure Studies 61 Elemental Composition 65 Fundamental Mechanical Measurements Thermal Conductivity 67 Electrical and Optical Characterization 69 References 70 1X _.
CHAPTER 4: CHAPTER 5: APPLICATIONS 73 Mechanical Applications 75 Electronics 78 Optics and Optoelectronics 83 References SS RESEARCH AND DEVELOPMENT ISSUES AND OPPORTUNITIES 91 Growth Processes 92 Materials Characterization 93 Applications 93 Beyond Diamond: Other Materials and Issues 94 References 95 APPENDIX: BIOGRAPHICAL SKETCHES OF COMMITTEE MEMBERS 97 x
TABLES AND FIGURES Table 1-1 Table 1-2 Table 2-1 Table 2-2 Table 2-3 Table 4-1 Table 4-2 Table 4-3 Table 4-4 Table 4-5 Figure 1-1 Figure 1-2 Figure 1-3 Figure 1-4 Figure 2-1 Figure 2-2 Figure 2-3 Nomenclature for Diamond-Like Materials 7 Some Properties of Natural Type IIA Diamond and Vapor- Grown Diamond 12 Plasma-Enhanced Chemical Vapor Deposition (PECVD) Processes for Diamond Film Growth 30 Nonplasma Deposition Processes for Diamond Film Growth 33 Deposition Data for DLC, BN, and Related Composites 45-46 Mechanical and Thermal Applications of Superhard Materials 73 Potential Electronic Applications of Superhard Materials 74 Optical and Optoelectronic Applications of Superhard Materials 75 Relative Figures of Merit for Electronics 78 Figures of Merit for Thermal Stress Resistance 84 Number of papers published in scientific journals on low-pressure growth of diamond and diamond-like materials 6 Hard materials in the composition tetrahedron C-B-N-Si 6 Microhardness versus atomic number density ~ Equilibrium phase diagram for the carbon system 9 The Hall ~belt" apparatus 23 Cell design for growth of large crystals of diamond or cubic EN using a temperature gradient between carbon source and the seed crystal 25 Morphology of diamond from metal solutions as a function of pressure and temperature 26 X1
Figure 2-4 Figure 2-5 Figure 2-6 Figure 2-7 Figure 2-8 Figure 2-9 Figure 2-10 Figure 2-1 1 Figure 2-12 Figure 2-13 Figure 2-14 Figure 2-15 Figure 2-16 Figure 2-17 Figure 2-1 8 Figure 3-1 Figure 3-2 Figure 3-3 Schematic representation of the four principal types of diamond in terms of the systems B-C and C-N 27 Schematic diagrams of various plasma-enhanceci CVD techniques for diamond growth 31 Statistics of abstracts published at the meetings of the Japanese Applied Physics Society on different preparation methods for diamond thin films 32 Schematic diagrams of two different nonplasma approaches for diamond growth 33 Ratio of diamond to graphite nucleation velocity as a function of supersaturation 37 Relative growth and etch rates of diamond and graphite in the presence of a hydrocarbon (CH4) and atomic hydrogen 38 CH4 (open squares) and C2H2 (solid circles) mole fractions at the growing diamond surface as a function of distance between substrate and filament 39 Processes for growing carbon films from hydrocarbon gases 44 Processes for growing carbon films using solid carbon 44 Ton plating configuration 49 RF plasma configuration 50 Direct ion beam deposition from solid precursor onfiguration 50 Direct ion beam deposition from gaseous precursor configuration 51 Dual ion beam deposition configuration 52 Ion beam sputtering with ion beam assist configuration 52 Raman spectra of diamond, graphite, and microcrystalline graphite 62 Atom number density versus atom fraction hydrogen 66 The thermal conductivity of various materials as a function of temperature 67 X11
