MATERIALS SCIENCE MONOGRAPHS, 73 APPLICATIONS OF DIAMOND FILMS AND RELATED MATERIALS Proceedings of the First International Conference on the Applications of Diamond Films and Related Materials - ADC '91 Auburn, Alabama, U.S.A., August 17-22, 1991 Edited by Y. TZENG Department of Electrical Engineering Auburn University Auburn, Alabama, U.S.A. M. YOSHIKAWA Tokyo Institute of Technology Tokyo, Japan M. MURAKAWA Nippon Institute of Technology Saitama, Japan A. FELDMAN National Institute of Standards and Technology Gaithersburg, Maryland, U.S.A. ELSEVIER Amsterdam - Oxford - New York - Tokyo 1991 ELSEVIER SCIENCE PUBLISHERS B.V. Sara Burgerhartstraat 25 P.O. Box 211, 1000 AE Amsterdam, The Netherlands Distributors for the U.S.A. and Canada: ELSEVIER SCIENCE PUBLISHING COMPANY, INC. 655 Avenue of the Americas New York, N.Y. 10010, U.S.A. Library of Congress Cataloglng-ln-PublIcatton Data International Conference on the Applications of Diamond Films and Related Materials (1st : 1991 : Auburn, Ala.) Applications of diamond films and related materials ·. proceedings of the First International Conference on the Applications of Diamond Films and Related Materials : ADC '91, Auburn, Alabama, U.S.A., August 17-22, 1991 / edited by Y. Tzeng ... [et al.], p. cm. — (Materials science monographs ; 73) Includes indexes. ISBN 0-444-89162-5 1. Diamonds, Artifical—Congresses. 2. Diamond thin films- -Congresses. I. Tzeng, Y. (Yonhua) II. Title. III. Series. TP873.5.D3I58 1991 666'.88—dc20 91-21719 CIP ISBN: 0 444 89162 5 © ELSEVIER SCIENCE PUBLISHERS B.V., 1991 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science Publishers B.V. / Academic Publishing Division, P.O. Box 103, 1000 AC Amsterdam, The Netherlands. Special regulations for readers in the U.S.A. - This publication has been registered with the Copyright Clearance Center Inc. (CCC), Salem, Massachusetts. Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the U.S.A. All other copyright questions, including photocopying outside of the U.S.A., should be referred to the copyright owner, unless otherwise specified. No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. This book is printed in acid-free paper. Printed in The Netherlands ν FOREWORD These are the Proceedings of the first conference emphasizing the applications of diamond films and related wide bandgap semiconductors and superhard materials. These materials are rapidly becoming economically significant. Due to their combination of superior properties- great hardness, high thermal conductivity, chemical inertness, high stiffness, high carrier mobilities, etc, these materials are attracting considerable interest. Initial commercial products employing the new diamond technology are already on the market. These include diamond loudspeakers, diamond x-ray windows, diamond bonders, diamond cutting tools, and heads for magnetic disks coated with diamond-like carbon. Other potential products include heat dissipating electronic substrates, hard infrared windows and coatings, electroluminescent devices, high power active electronics, etc. These products will be important not only in terms of their own markets, but, also because they are expected to enable a wide range of other new products and production methods. An intensifying interest by the scientific, technical, and industrial community in the new diamond technology can be attested to by an examination of the technical calendar which shows an ever increasing number of conferences devoted to these exciting materials. In view of the competition for attendees, the great interest expressed in this conference attests to the growing importance of applications of the new diamond. Alternating with the International Conference on the New Diamond Science and Technology, the Applied Diamond Conference is planned to be held every other year, with ADC '91 being held in the United States and ADC '93 in Japan. We thank all of the sponsors, attendees, contributors, committee members, and session chairs who have made this conference a success. Albert Feldman, Chairman Manasori Yoshikawa, Chairman Organizing Committee Program Committee Masao Murakawa, Co-Chairman Yonhua Tzeng, Co-Chairman Organizing Committee Program Committee and Secretary, Organizing Committee APPLIED DIAMOND CONFERENCE 1991 ORGANIZING COMMUTEE Masao Murakawa, Co-Chairman Albert Feldman, Chairman Nippon Institute of Technology National Institute of Standards and Technology Saitama, Japan Gaithersburg, MD USA Yonhua Tzeng, Secretary Shojiro Miyake, Assistant Secretary Nippon Institute of Technology Auburn University Saitama, Japan Auburn, AL USA S. Holly Louis Κ. Bigelow Rocket-Dyne Norton Company Canoga Park, CA USA Northboro, MA USA Alan H. Lettington J.E. Butler Royal Signals & Radar Establishment Naval Research Laboratory Great Malvern, Worcs. United Kingdom Washington, DC USA William D. Partlow Mark A. Cappelli Westinghouse Science & Technology Center Stanford University Pittsburgh, PA USA Stanford, CA USA J. Michael Pinneo Yves Catherine Crystallume UMR C.N.R.S. Nantes Cedex, France Menlo Park, CA USA Junichi Sato Francis G. Celii Showa Denko KK Texas Instruments Tokyo, Japan Dallas, TX USA Mats E. Sjostrand Robert E. Clausing AB Sandvik, Coromant Oak Ridge National Laboratory Lekrogsva gen, Sweden Oak Ridge, TN USA Sokichi Takatsu R. N. Dewitt Toshiba Tungaloy Co. Naval Surface Warfare Center Kanagawa, Japan Silver Spring, MD USA Ichiro Tokumitsu Rainer Doehl-Oelze Idemitsu Petrochemical VDI Technology Center Tokyo, Japan Dusseldorf, FRG K. Wu Y. Fujiwara SDIO/IST Mitsubishi Metal Corporation Tokyo, Japan Washington, DC USA Osamu Fukunaga Shuji Yazu Tokyo Institute of Technology Sumitomo Electric Ind. Ltd. Tokyo, Japan Hyogo, Japan Max N. Yoder Alfred Grill Office of Naval Research IBM, T.J. Watson Research Center Arlington, VA USA Yorktown Heights, NY USA Masanori Yoshikawa D. Harris Tokyo Institute of Technology Office of Naval Technology Tokyo, Japan China Lake, CA USA Akio Hiraki Osaka University Osaka, Japan viii INTERNATIONAL ADVISORS John C Angus Michael Seal Case Western Reserve University Sigillum, B.V. Cleveland, OH USA Amsterdam, The Netherlands N. Setaka Thomas R. Anthony NIRHVi GE Corporation Schenectady, NY USA Ibaraki, Japan M. Kamo B.V. Spitsyn Institute of Physical Chemistry NERIM Moscow, USSR Ibaraki, Japan Benno Lux Technische Universitat Vienna Vienna, Austria PROGRAM COMMITTEE Yonhua Tzeng, Co-Chairman Masanori Yoshikawa, Chairman Auburn University Tokyo Institute of Technology Auburn, AL USA Tokyo, Japan Alan H. Lettington Naoji Fujimori Royal Signals & Radar Establishment Sumitomo Electric Ind. Ltd. Great Malvern, Worcs. United Kingdom Hyogo, Japan Masao Murakawa Paul D. Gigl Nippon Institute of Technology GE Superabrasives Saitama, Japan Worthington, OH USA K. Shibuki Yoichi Hirose Toshiba Tungaloy Co., Ltd. Nippon Institute of Technology Kanagawa, Japan Saitama, Japan Stafifen Soderberg David S. Hoover Sandvik, Materials & Processes Diamonex, Inc. Lekrogsva gen, Sweden Allentown, PA USA Hitoshi Tokura Moribund M. Kikuchi Tokyo Institute of Technology Mitsubishi Metal Corporation Tokyo, Japan Saitama, Japan Charles B. Willingham Claus-Peter Klages Raytheon Company Fraunhofer-Institut Lexington, MA USA Hamburg, FRG Walter A. Yarbrough Kunio KomaJri Pennsylvania State University Showa Denko KK Center University Park, PA USA Tokyo, Japan Max N. Yoder Office of Naval Research Arlington, VA USA ix LOCAL ARRANGEMENTS Anthony K. Hyder, Chairman Thaddus RoppeL Co-Chairman Auburn University Auburn University Auburn, AL USA Auburn, AL USA Charles Ellis, Exhibit Chairman R. Ramesham Auburn University Auburn University Auburn, AL USA Auburn, AL USA Calvin Cutshaw James R. Wilbanks Auburn University Auburn University Auburn, AL USA Auburn, AL USA J. Fred O'Brien, Jr. Ann Crance Auburn University Auburn University Auburn, AL USA Auburn, AL USA Debra Alexander Auburn University Auburn, AL USA ORAL SESSION CHAIRS M. Anschel P. Klocek IBM Texas Instruments Hopewell Junction, NY USA Dallas, TX USA J. Butler K. Kurihara Naval Research Laboratory Fujitsu Labs. Ltd. Washington, DC USA Atsugi, Japan M. Cappelli J. Larsen-Basse Stanford University National Science Foundation Stanford, CA USA Washington, DC USA R.N. Dewitt A. Lettington Naval Surface Warfare Center Royal Signals & Radar Establishment Silver Spring, MD USA Great Malvern, Worcs. UK A. Feldman B. Lux National Institute of Standards Technical University of Vienna and Technology Vienna, Austria Gaithersburg, MD USA M. Mirtich N. Fujimori NASA Lewis Research Center Sumitomo Electric Ind. Ltd. Cleveland, OH USA Hyogo, Japan M Murakawa O. Fukunaga Nippon Institute of Technology Tokyo Institute of Technology Saitama, Japan Tokyo, Japan H. Tokura P. Gigle Tokyo Institute of Technology G.E. Superabrasive Tokyo, Japan Worthington, OH USA R.C Woodin IvLN. Gardos Norton Company Hughes Aircraft Northboro, MA USA El Segundo, CA USA K. Wu D. Harris SDIO/IST Office of Naval Technology Washington, DC USA China Lake, CA USA MN. Yoder Y.Hirose Office of Naval Research Nippon Institute of Technology Arlington, VA USA Saitama Japan M. Yoshikawa GA Kim Tokyo Institute of Technology Edge Technologies, Inc. Tokyo, Japan Indianapolis, IN USA ACKNOWLEDGMENT APPLIED DIAMOND CONFERENCE 1991 Sponsored by: Auburn University Alabama Advanced Manufacturing Technology Center Alabama Microelectronics Science and Technology Center Space Power Institute Center for Commercial Development of Space Center for Advanced Technology Japan New Diamond Forum National Aeronautics and Space Administration National Institute of Standards and Technology National Science Foundation Norton Company Office of Naval Technology Raytheon Company Westinghouse Electric Corporation In Cooperation with: American Carbon Society American Vacuum Society American Society for Metallurgy French Optical Society IEEE - Electron Devices Society International Society for Hybrid Microelectronics Japan Society for Precision Engineering SPLE - The International Society for Optical Engineering TMS - Minerals, Metals, and Materials Society The Surface Finishing Society of Japan Applications of Diamond Films and Related Materials Y. Tzeng, M. Yoshikawa, M. Murakawa, A. Feldman (Editors) © Elsevier Science Publishers B.V., 1991 3 Applications of Bulk and Thin-Film Diamonds M. Seal Sigillum B.V., P.O. Box 7129, 1007 JC Amsterdam, The Netherlands Abstract The applications of bulk diamond are mainly in the jewelry and abrasive industries. Other applications which use substantial quantities of diamond include turning tools and wire drawing dies, whereas more specialised uses are as thermally conducting substrates, optical components, surgical knives, etc. Thin-film diamonds are clearly unsuited for jewelry or as abrasives, but may be deposited as hard coatings on a variety of softer materials to act as cutting tools or knives, thus in effect forming abrasion resistant layers which allow the sharp edges to remain sharp. They also may act as abrasion resistant layers on optical surfaces such as those of spectacle lenses, as thermally conducting layers on electronic device substrates ("heat sinks"), or as chemically resistant layers. 1- BULK DIAMOND Bulk diamond is to-day, in 1991, a major industry. Bulk diamond comprises both natural (mined) diamond and high pressure synthesised diamond. Estimates from a variety of sources put 1990 world natural diamond production at about 100 million carats (or 20 tons). The major producers are Australia (about 7 tons). West and Central Africa (about 6 tons), Botswana (about 3 tons), U.S.S.R. (about 2 tons), and South Africa (about 1\ tons). The U.S.S.R. and total figures exclude diamonds mined in the U.S.S.R. and consumed there, the 2 ton figure being an estimate only of the total of Soviet rough diamonds exported to the West. The total value of the 20 tons was probably in excess of $ 5 billion, giving an average value of $ 50.00 per carat. This figure conceals, however, an enormous variation in the value of individual diamonds which can range from under $ 2.00 per carat for the lowest industrial boart qualities to over $ 10,000.00 per carat for the finest large white gem stones. This means that the money values of the production from the different geographical areas are not directly correlated with the tonnage figures. Australia, for example, has a large production of very low quality industrial grades and only very limited numbers of the fancy pink gemstones for which it has become famous. Namibia on the other hand has a small production consisting almost entirely of gem quality diamonds. An even more extreme case was the Letseng-la-Terae mine in Lesotho (now closed) which relied financially on the production of a very few, very large gem diamonds each year. There have been claims of successful synthesis of diamond dating back to the 19th century. The experiments of Moissan and of Hannay are pre- 4 eminent amongst this early work, and their results have been reviewed by Seal [1] amongst others. They realised the need for high pressures though it is unlikely that they achieved pressures which were sufficiently high for diamond stability. Their work was discounted after true high pressure synthesis was achieved in the 1950's by ASEA, General Electric, and De Beers. Paradoxically with the proven possibility of low pressure CVD diamond growth it now seems more likely or at least less unlikely that Hannay and/or Moissan may in fact have grown a few small diamonds. The theoretical basis of modern high pressure diamond synthesis rests on calculations of the graphite-diamond equilibrium line in a pressure- temperature phase diagram. The first calculation to give the general picture of graphite stability at normal pressures and diamond stability at elevated pressures was that of Miething [2] whilst the first in which one could have reasonable confidence as to its accuracy was that of the famous Berman-Simon line in 1955 [3]. The practical basis of modern high pressure diamond synthesis rests on the pioneering work of P.W. Bridgman [4] and of the engineering teams at ASEA, General Electric, and De Beers. Since the 1950's growth of the diamond abrasive business has followed a curve which looks almost exponential. In 1950 consumption of diamond abrasive grit in the non-communist world was about 20 million carats (4 tons). By 1960 the consumption had risen to 6 tons. The latest estimate for consumption in 1990 is between 70 and 80 tons. These figures are taken from a publication by Martin [5] who also states that about 90% of the present abrasive grit total is synthetic. Extrapolation of these numbers would suggest that about 8 tons of natural diamond grit and about 75 tons of synthetic diamond grit will be used in 1991, again excluding consumption in the U.S.S.R. and other countries for which data are not available. The value of the 1990 diamond and CBN grit market was given as about $ 500 million. This corresponds to an average price of $ 1.25 to $ 1.40 per carat. There is also a market amounting to about $ 100 million per year in polycrystalline diamond (PCD) and polycrystalline CBN blanks for cutting tool applications in the engineering and woodworking industries and for drills for the oil, gas, and mining industries. In short, the major application for bulk natural diamonds is jewelry, and for bulk high pressure synthetics it is in abrasive products, cutting tools and drills. Other applications of bulk diamond include single point turning tools, wire drawing dies, styli, bearings, etc., together with the newer applications such as heat sinks, anvils, optical components, surgical blades and cleaving knives. These last have been described in a variety of publications, to which reference is made for further details [6-9]. In total these newer markets are fairly small at least as regards present diamond consumption, but they are ones which are capable of great expansion. 2. THIN FILM DIAMOND The application of this material is the theme of the present conference. Looking at the program one can see a tremendous range of possibilities, the most exciting of which seem to be in active electronics, and the most immediate as tool coatings and as heat sinks or other passive substrates for electronic circuitry. If one considers the
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