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HANDBOOK OF CHEMICAL VAPOR DEPOSITION (CVD) Principles, Technology, and Applications Second Edition by Hugh O. Pierson Consultant and Sandia National Laboratories (retired) Albuquerque, New Mexico NOYES PUBLICATIONS Park Ridge, New Jersey, U.S.A. WILLIAM ANDREW PUBLISHING, LLC Norwich, New York, U.S.A.

Copyright © 1999 by Noyes Publications No part of this book may be reproduced or utilized in any form or by any means, elec- tronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without permission in writing from the Publisher. Library of Congress Catalog Card Number: 99-26065 ISBN: 0-8155-1432-8 Printed in the United States Published in the United States of America by Noyes Publications / William Andrew Publishing, LLC Norwich, New York, U.S.A. 10 9 8 7 6 5 4 3 2 1 Library of Congress Cataloging-in-Publication Data Pierson, Hugh O. Handbook of chemical vapor deposition / by Hugh O. Pierson. -- 2nd ed. p . cm. Rev. ed. of: Handbook of chemical vapor deposition (CVD), c1992 Includes bibliographical references. ISBN 0-8155-1432-8 1. Chemical vapor depostion Handbooks, manuals, etc. 2. Vapor -plating Handbook, manuals, etc. I. Pierson, Hugh O. Handbook of chemical vapor deposition (CVD) II. Title. TS695.P52 671.7'35--dc21 1 9 9 9 99-26065 CIP

About the Author Hugh Pierson is presently a private consultant in Chemical Vapor Deposition. He was formerly the head of the Deposition Laboratory at the Sandia National Laboratories and is now retired. Since then, he has been a consultant to the U.S. State Department in South America; Ultramet in Pacoima, California; LOF in Toledo, Ohio; the Gorham Institute in Maine; REI in Whittier, California; TH Goldschmidt AG in Germany; and to many other companies. A graduate of the University of Paris and the French Naval College, Mr. Pierson has published over one hundred technical publications in the field of Chemical Vapor Deposition. He has also been a contributor to a book on Chemically Vapor Deposited Coatings published by the American Ceramic Society, and has authored three books. NOYES PUBLICATIONS WILLIAM ANDREW PUBLISHING, LLC

MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES Series Editors Rointan F. Bunshah, University of California, Los Angeles Gary E. McGuire, Microelectronics Center of North Carolina Stephen M. Rossnagel, IBM Thomas J. Watson Research Center Electronic Materials and Process Technology CHARACTERIZATION OF SEMICONDUCTOR MATERIALS, Volume 1: edited by Gary E. McGuire CHEMICAL VAPOR DEPOSITION FOR MICROELECTRONICS: by Arthur Sherman CHEMICAL VAPOR DEPOSITION OF TUNGSTEN AND TUNGSTEN SILICIDES: by John E. J. Schmitz CHEMISTRY OF SUPERCONDUCTOR MATERIALS: edited by Terrell A. Vanderah CONTACTS TO SEMICONDUCTORS: edited by Leonard J. Brillson DIAMOND CHEMICAL VAPOR DEPOSITION: by Huimin Liu and David S. Dandy DIAMOND FILMS AND COATINGS: edited by Robert F. Davis DIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS: edited by Devendra Gupta and Paul S. Ho ELECTROCHEMISTRY OF SEMICONDUCTORS AND ELECTRONICS: edited by John McHardy and Frank Ludwig ELECTRODEPOSITION: by Jack W. Dini HANDBOOK OF CARBON, GRAPHITE, DIAMONDS AND FULLERENES: by Hugh O. Pierson HANDBOOK OF CHEMICAL VAPOR DEPOSITION, Second Edition: by Hugh O. Pierson HANDBOOK OF COMPOUND SEMICONDUCTORS: edited by Paul H. Holloway and Gary E. McGuire HANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited by Donald L. Tolliver HANDBOOK OF DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS, Second Edition: edited by Rointan F. Bunshah HANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J. Cuomo, Stephen M. Rossnagel, and Harold R. Kaufman HANDBOOK OF MAGNETO-OPTICAL DATA RECORDING: edited by Terry McDaniel and Randall H. Victora HANDBOOK OF MULTILEVEL METALLIZATION FOR INTEGRATED CIRCUITS: edited by Syd R. Wilson, Clarence J. Tracy, and John L. Freeman, Jr. HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M. Rossnagel, Jerome J. Cuomo, and William D. Westwood HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS, 2nd Edition: by James Licari and Laura A. Hughes HANDBOOK OF REFRACTORY CARBIDES AND NITRIDES: by Hugh O. Pierson v

vi Series HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C. O’Mara, Robert B. Herring, and Lee P. Hunt HANDBOOK OF SEMICONDUCTOR WAFER CLEANING TECHNOLOGY: edited by Werner Kern HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa and Shigeru Hayakawa HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited by Klaus K. Schuegraf HANDBOOK OF VACUUM ARC SCIENCE AND TECHNOLOGY: edited by Raymond L. Boxman, Philip J. Martin, and David M. Sanders HANDBOOK OF VLSI MICROLITHOGRAPHY: edited by William B. Glendinning and John N. Helbert HIGH DENSITY PLASMA SOURCES: edited by Oleg A. Popov HYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK, Second Edition: by James J. Licari and Leonard R. Enlow IONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori Takagi MOLECULAR BEAM EPITAXY: edited by Robin F. C. Farrow SEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by Gary E. McGuire ULTRA-FINE PARTICLES: edited by Chikara Hayashi, R. Ueda and A. Tasaki Ceramic and Other Materials—Processing and Technology ADVANCED CERAMIC PROCESSING AND TECHNOLOGY, Volume 1: edited by Jon G. P. Binner CEMENTED TUNGSTEN CARBIDES: by Gopal S. Upadhyaya CERAMIC CUTTING TOOLS: edited by E. Dow Whitney CERAMIC FILMS AND COATINGS: edited by John B. Wachtman and Richard A. Haber CORROSION OF GLASS, CERAMICS AND CERAMIC SUPERCONDUCTORS: edited by David E. Clark and Bruce K. Zoitos FIBER REINFORCED CERAMIC COMPOSITES: edited by K. S. Mazdiyasni FRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J. Blau HANDBOOK OF CERAMIC GRINDING AND POLISHING: edited by Ioan D. Mavinescu, Hans K. Tonshoff, and Ichiro Inasaki HANDBOOK OF INDUSTRIAL REFRACTORIES TECHNOLOGY: by Stephen C. Carniglia and Gordon L. Barna SHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E. Murr SOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICS AND SPECIALTY SHAPES: edited by Lisa C. Klein SOL-GEL SILICA: by Larry L. Hench SPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G. K. Bhat SUPERCRITICAL FLUID CLEANING: edited by John McHardy and Samuel P. Sawan

Preface to the First Edition Chemical vapor deposition (CVD) has grown very rapidly in the last twenty years and applications of this fabrication process are now key elements in many industrial products, such as semiconductors, optoelectronics, optics, cutting tools, refractory fibers, filters and many others. CVD is no longer a laboratory curiosity but a major technology on par with other major technological disciplines such as electrodepo- sition, powder metallurgy, or conventional ceramic processing. The estimated market for CVD products is very large and predicted to reach almost three billion dollars in 1993, in the U.S. alone. The rapid development of the technology and the expansion of the market are expected to continue in the foreseeable future. The reasons for the success of CVD are simple: • CVD is a relatively uncomplicated and flexible tech- nology which can accommodate many variations. • With CVD, it is possible to coat almost any shape of almost any size. • Unlike other thin film techniques such as sputtering CVD can also be used to produce fibers, monoliths, foams and powders. • CVD is economically competitive. viii

Preface to the First Edition ix Still the technology faces many challenges and a large research and development effort is under way in most major laboratories in the U.S., Japan and Europe, particularly in the semiconductor and tool industries. The general outlook is one of constant change as new designs, new products and new materials are continuously being introduced. Generally CVD is a captive operation and an integral part of a fabrication process, particularly in microelectronics where most manu- facturers have their own CVD facilities. It is also an international business, and, while the U.S. is still in the lead, a great deal of work is under way, mostly in Japan and Europe. A significant trend is the internationalization of the CVD industry, with many multi-national ventures. Several books have recently been published on the subject of CVD, each dealing with a specific aspect of the technology, such as CVD for microelectronics or metallo-organic CVD. With many of his colleagues, the author has felt the need for a general, systematic, objective, and balanced review solely devoted to CVD, which would cover all its scientific, engineering, and applications aspects, coordi- nate the divergent trends found today in the CVD business, promote interaction and sharpen the focus of research and development. To fill this need is the purpose of this book, which should be useful to students, scientists, and engineers, as well as production and marketing managers and suppliers of materials, equipment and ser- vices. The author is fortunate to have the opportunity, as a consultant, to review and study CVD processes, equipment, materials and appli- cations for a wide cross-section of the industry, in the fields of optics, optoelectronics, metallurgy and others. He is in a position to retain an overall viewpoint difficult to obtain otherwise. The book is divided into three major parts. The first covers a theoretical examination of the CVD process, a description of the major chemical reactions and a review of the CVD systems and equipment used in research and production, including the advanced subprocesses such as plasma, laser, and photon CVD.

x Preface to the First Edition The second part is a review of the materials deposited by CVD, i.e., metals, non-metallic elements, ceramics and semiconductors, and the reactions used in their deposition. The third part identifies and describes the present and potential applications of CVD in semiconductors and electronics, in optics and optoelectronics, in the coating of tools, bearings and other wear- and corrosion-resistant products, and in the automobile, aerospace, and other major industries. The author is indebted to Dr. Jacob Stiglich and other members of the staff at Ultramet for their cooperation, and to an old friend, Dr. John M. Blocher Jr., for his many ideas, comments and thorough review of the manuscript. He is also grateful to George Narita, Executive Editor of Noyes Publications, for his help and patience in the preparation of this book. February 1992 Albuquerque, New Mexico Hugh Pierson NOTICE To the best of our knowledge the information in this publication is accurate; however the Publisher does not assume any responsibility or liability for the accuracy or completeness of, or consequences arising from, such information. This book is intended for informational purposes only. Mention of trade names or commercial products does not constitute endorsement or recommendation for use by the Publisher. Final determination of the suitability of any information or product for use contemplated by any user, and the manner of that use, is the sole responsibility of the user. We recommend that anyone intending to rely on any recommendation of materials or procedures mentioned in this publication should satisfy himself as to such suitability, and that he can meet all applicable safety and health standards.

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