HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY Edited by William C. O'Mara Rose Associates Los Altos, California Robert B. Herring Thermco Systems San Jose, California Lee P. Hunt Hunt Associates Edmond, Oklahoma NOYES PUBLICATIONS I "P I Park Ridge, New Jersey. USA. Copyright @ 1990 by Noyes Publications No part of this book may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any informa- tion storage and retrieval system, without permission in writing from the Publisher. Library of Congress Catalog Card Number: 89-77167 ISBN: 0-8155-1237-6 Printed in the United States Published in the United States of America by Noyes Publications Mill Road, Park Ridge, New Jersey 07656 109876 543 Library of Congress Cataloging-in-Publication Data Handbook of semiconductor silicon technology I edited by William C. O'Mara, Robert E. Herring, Lee Philip Hunt. p. cm. Includes bibliographical references. ISBN 0-8155-1237-6: 1. Semiconductors--Handbooks, manuals, etc. 2. Silicon crystals- -Handbooks, manuals, etc. I. O'Mara, William C. II. Herring, Robert E. 111. Hunt, Lee Philip. TK7871.85.H334 1990 621.381'52--d~20 89-77167 CIP Contributors W. Murray Bullis H. Ming Liaw Siltec Corporation Motorola, Inc. Mountain View, CA Phoenix, AZ Robert B. Herring William C. O’Mara Thermco Systems Rose Associates San Jose, CA Los Altos, CA Lee P. Hunt Leo C. Rogers Hunt Associates Polycrystalline Silicon Technology Edmond, OK Corporation Mesa, AZ Theodore D. Kamins Hewlett Packard Company Dieter K. Schroder Palo Alto, CA Arizona State University Tempe, AZ Richard L. Lane Rochester Institute of Richard A. Seilheimer Technology Thermco Systems Rochester, NY San Jose, CA vii NOTICE To the best of our knowledge the informa- tion in this publication is accurate; however the Publisher does not assume any responsi- bility or liability for the accuracy or com- pleteness of, or consequences arising from, such information. 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 contem- plated 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 pro- cedures for semiconductor silicon technol- ogy mentioned in this publication should satisfy himself as to such suitability, and that he can meet all applicable safety and health standards. We strongly recommend that users seek and adhere to the manu- facturer’s or supplier’s current instructions for handling each material they use. viii MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES Editors Rointan F. Bunshah, University of California, Los Angeles (Materials Science and Process Technology) Gary E. McGuire, Microelectronics Center of North Carolina (€lectronic Mate- rials and Process Technology) DEPOSITION TECHNOLOGIES FOR FILMSANDCOATINGS: by Rointan F. Bunshahetal CHEMICAL VAPOR DEPOSITION IN MICROELECTRONICS: by Arthur Sherman SEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by Gary E. McGuire SOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICS AND SPECIALTY SHAPES: edited by Lisa A. Klein HYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK: by James J. Licari and Leonard R. Enlo w HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited by Klaus K. Schuegraf IONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori Takagi DIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS: edited by Devendra Gupta and Paul S. Ho SHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E. Murr HANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited by Donald L. Tolliver HANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J. Cuomo, Stephen M. Rossnagel, and Harold R. Kaufman FRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J. Blau CHARACTERIZATION OF SEMICONDUCTOR MATERIALS-Volume 1: edited by Gary E. McGuire SPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G.K. Bhat HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M. Ross- nagel, Jerome J. Cuomo, and William D. Westwood FIBER REINFORCED CERAMIC COMPOSITES: edited by K.S. Mazdiyasni HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C. O’Mara, Robert B. Herring, and Lee P. Hunt HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS: by James J. Licari and Laura A. Hughes Related Titles ADHESIVES TECHNOLOGY HANDBOOK: by Arthur H. Landrock HANDBOOK OF THERMOSET PLASTICS: edited by Sidney H. Goodman SURFACE PREPARATION TECHNIQUES FOR ADHESIVE BONDING: by Raymond F. Wegman Preface Semiconductor silicon has become the most important and characteristic material of our age-the silicon age. It has achieved this distinction with a rather modest volume of production as compared to that of other basic industrial ma- terials. For example, in 1989, about 6,000 metric tons of polysilicon were pro- duced worldwide for silicon crystal growth, resulting in 3,000 tons of crystal produced in the United States, Japan, and Europe. This silicon crystal was con- verted to approximately 1,500 million square inches of wafer, or about 90 million individual wafers used for integrated circuit and discrete device pro- duction. For comparison, the annual worldwide production of steel and alumi- num amounts to hundreds of thousands of tons. In spite of its relatively small volume, the impact of silicon production is multiplied manyfold by the devices and electronic systems that are based on its properties. There have been many attempts to find improved materials with ‘better’ properties than silicon, but candidates such as sapphire, silicon carbide, diamond and 111-V materials all lack some essential ingredient for manufactur- ing in quantity. Examples of these missing ingredients include: ease of growing large perfect crystals, freedom from extended and point defects, existence of a native oxide, or other essential properties, many of which are discussed in this book. Basic information about silicon-how it is made, and its important physi- cal, chemical and mechanical properties- is hard to find, and one of the motives for this volume is to make fundamental information available in handbook form. This also absolves the authors from having to include the relevant papers in their field that were published in the last twenty-four hours. Early work in silicon science and technology was excellent, as evidenced by the fact that the original crystal growth process is still used in manufactur- ing today. That process was developed at Bell Laboratories by Teal and Buehler, following the original crystal growth process developed for germanium by Teal and Little. This initial work was done in spite of device engineers who were V vi Preface convinced that polycrystalline material would be adequate for transistor manu- facture. In the past, there has been only one book on semiconductor silicon tech- nology, by Walt Runyan, formerly with Texas Instruments. Following his lead and inspiration, we have undertaken to produce a work of similar utility, since his original volume has gone out of print. Today it requires ten people to do what he was able to do by himself. In part this is testimony to the development that has occurred in all of these areas, and each chapter of the original work is now a separate discipline. We are fortunate to have excellent contributors for each of the topics discussed here, but we wish to salute Dr. Runyan for his original and enduring contribution to the field. Los Altos, California William C. O’Mara January 1990 Contents 1 . SILICON PRECURSORS: THEIR MANUFACTURE AND PROPERTIES ........................................ 1 Lee P . Hunt 1.0 Introduction ................................. 1 2.0 Precursor Manufacture ........................... 2 2.1 Metallurgical-Grade Silicon (MG-Si) ..............2 2.2 Trichlorosilane ............................ 3 2.3 Silicon Tetrachloride ........................ 5 2.4 Dichlorosilane ............................. 7 2.5 Silane .................................. 7 3.0 Physical Properties and Critical Constants ..............9 3.1 Non-Temperature Sensitive Properties and Constants ................................ 9 3.2 Vapor Pressure ............................ 9 3.3 Density (Liquid) .......................... 10 3.4 Heat Capacity (Liquid) ...................... 11 3.5 Heat Capacity (Gas)........................ 12 3.6 Free Energy, Standard Enthalpy, and Standard Entropy of Formation ...................... 14 3.7 Enthalpy of Vaporization .................... 19 3.8 Surface Tension .......................... 20 3.9 Viscosity (Gas) ........................... 21 3.10 Viscosity (Liquid) ......................... 21 3.11 Thermal Conductivity (Gas) ..................22 3.12 Thermal Conductivity (Liquid) ................24 4.0 Safety ..................................... 24 4.1 Health Hazards ........................... 24 4.2 Fire and Explosion Hazards ...................25 4.3 Materials of Construction .................... 26 ix x Contents Appendix ....................................... 28 References ...................................... 28 2 . POLYSILICON PREPARATION ........................... 33 Leo C. Rogers 1.0 The Technical History of Polycrystalline Silicon .........33 1.1 Early and Present Polysilicon Manufacturers ........33 1.2 Semiconductor-Grade Polycrystalline Silicon Precursors .............................. 35 1.2.1 Silica (SiO,) ........................ 36