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In early 1987 I was attempting to develop a CVD-based tungsten process for Intel. At every step ofthe development, information that we were collecting had to be analyzed in light of theories and hypotheses from books and papers in many unrelated subjects. Thesesources were so widely different that I came to realize there was no unifying treatment of CVD and its subprocesses. More interestingly, my colleagues in the industry were from many disciplines (a surface chemist, a mechanical engineer, a geologist, and an electrical engineer werein my group). To help us understand the field of CVD and its players, some of us organized the CVD user's group of Northern California in 1988. The idea for writing a book on the subject occurred to me during that time. I had already organized my thoughts for a course I taught at San Jose State University. Later Van Nostrand agreed to publish my book as a text intended for students at the senior/first year graduate level and for process engineers in the microelectronics industry, This book is not intended to be bibliographical, and it does not cover every new material being studied for chemical vapor deposition. On the other hand, it does present the principles of CVD at a fundamental level while uniting them with the needs of the microelectronics industry.
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CHEMICAL VAPOR DEPOSITION
CHEMICAL VAPOR DEPOSITION Thermal and Plasma Deposition of Electronic Materials
S. Sivaram
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SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Copyright © 1995 by Springer Science+Business Media New York Originally published by VanNostrand Reinhold in 1995 I(IJP TM A division of International Thomson Publishing Inc. The ITP logo is a trademark under license.
All rights reserved. No part of this work covered by the copyright hereon may be reproduced or used in any form or by any means- graphic, electronic, or mechanical, including photocopying, recording, taping, or information storage and retrieval systems- without the written permission of the publisher. 1 2 3 4 5 6 7 8 9
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Library of Congress Cataloging-in-Publication Data Sivaram, S. Chemical vapor deposition : thermal and plasma deposition of electronic materials I S. Sivaram. p. cm. Jncludes bibliographical references and index. ISBN 978-1-4757-4753-9 ISBN 978-1-4757-4751-5 (eBook) DOI 10.1007/978-1-4757-4751-5 1. Microelectronics industry. 2. Chemical vapor deposition. 3. Microelectronics-Materials. I. Title TK7836.S54 1994 621.3815'2---dc20
94-39696 CIP
To my family, starting with my father, whose dreams I am living.
Contents
Preface
1. Introduction 1.1 Basic Assumptions 2 1.2 CVD in Microelectronics 1.3 Organization of the Book Reference 7
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2. Thin Film Phenomena 2.1 Early Stages ofThin Film Growth 8 2.2 Steady-State Growth and the Evolution of Order 19 2.3 Properties of Thin Films 25 2.4 Special Property Requirements for Microelectronics 34 2.5 Review 38 References 39 3. Manufacturability 3.1 Quality and Manufacturability of Processes 3.2 Defining the Environment 42 3.3 Process Development Sequence 45 3.4 Metrology 57 3.5 Overview of CVD Processes 58 References 61 4. Chemical Equilibrium and Kinetics 4.1 Thermodynamics versus Kinetics
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Contents 4.2 4.3 4.4 4.5
Equilibrium Thermodynamics of Reactions Chemical Reaction Kinetics 76 Heterogeneaus Reactions 82 Searching for an Overall Mechanism 90 References 93
5. Reactor Design for Thermal CVD 5.1 Classification of Reactors 94 5.2 Pressure and Flow Regimes in CVD Reactors 5.3 Residence Times in Reactors 103 5.4 Gradients in Reactors 107 5.5 Commercial Production CVD Reactors 111 Refere