Microanalysis of Solids Microanalysis of Solids Edited by B.G. Yacobi EMT ECH Toronto, Ontario, Canada D.B. Holt Imperial College London, England and L.L. Kazmerski National Renewable Energy Laboratory Golden, Colorado Springer Science+Business Media, LLC L1brarv of Congress Catalog1ng-1n-Pub11cat1on Data M1croanalys1s of sol1ds I ed1ted by 6.G. Yacob1, D.6. Holt, and L.L. Kazmersk1. p. em. Includes b1bl1ograph1cal references and 1ndex. ISBN 978-1-4899-1494-1 ISBN 978-1-4899-1492-7 (eBook) DOI 10.1007/978-1-4899-1492-7 1. M1crochem1stry. 2. Sol1ds--Analys1s. I. Yacob1, 6. G. II. Holt, D. 6. III. Kazmersk1, Lawrence L. OD79.M5M53 1994 543' .081--dc20 93-40984 CIP ISBN 978-1-4899-1494-1 © 1994 Springer Science+B usiness Media New York Originally published by Plenum Press, New York in 1994 Softcover reprint of the hardcover 1st edition 1994 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher Contributors S. E. Asher, National Renewable Energy Laboratory, Golden, Colorado 80401 G. A. D. Briggs, Department ofMaterials, University of Oxford, Oxford OX1 3PH, England R. F. Cohn, 51-5 Jacqueline Road, Waltham, Massachusetts 02154 A. J. Garratt-Reed, Center for Materials Science and Engineering, Massa chusetts Institute of Technology, Cambridge, Massachusetts 02139 D. A. Grigg, Digital Instruments, Santa Barbara, California 93117 D. B. Holt, Department of Materials, Imperial College, London SW7 2BP, England J. J. Hren, Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 L. L. Kazmerski, National Renewable Energy Laboratory, Golden, Colorado 80401 J. Li, Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853. Present address: Intel Corporation, Santa Clara, California 95052 J. Liu, Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 A. G. Michette, Department of Physics, King's College, London WC2R 2LS, England P. Mutti, Dipartimento di Ingegneria Nucleare Politecnico di Milano, Milano, Italy 20133 v vi Contributors A. J. Nelson, National Renewable Energy Laboratory, Golden, Colorado 80401 R. W. Odom, Charles Evans & Associates, Redwood City, California 94063 A. W. Potts, Department of Physics, King's College, London WC2R 2LS, England F. Radicati di Brozolo, Charles Evans & Associates, Redwood City, California 94063 P. Revesz, Department of Materials Science and Engineering, Cornell Uni versity, Ithaca, New York 14853 P. E. Russell, Department of Materials Science and Engineering, North Car olina State University, Raleigh, North Carolina 27695 T. Wilson, Department of Engineering Science, University of Oxford, Oxford OX1 3PJ, England B. G. Yacobi, EMTECH, Toronto, Ontario, Canada Preface The main objective of this book is to systematically describe the basic principles of the most widely used techniques for the analysis of physical, structural, and compositional properties of solids with a spatial resolution of approxi mately 1 ~m or less. Many books and reviews on a wide variety of microanalysis techniques have appeared in recent years, and the purpose of this book is not to replace them. Rather, the motivation for combining the descriptions of various mi croanalysis techniques in one comprehensive volume is the need for a reference source to help identify microanalysis techniques, and their capabilities, for obtaining particular information on solid-state materials. In principle, there are several possible ways to group the various micro analysis techniques. They can be distinguished by the means of excitation, or the emitted species, or whether they are surface or bulk-sensitive techniques, or on the basis of the information obtained. We have chosen to group them according to the means of excitation. Thus, the major parts of the book are: Electron Beam Techniques, Ion Beam Techniques, Photon Beam Techniques, Acoustic Wave Excitation, and Tunneling of Electrons and Scanning Probe Microscopies. We hope that this book will be useful to students (final year undergrad uates and graduates) and researchers, such as physicists, material scientists, electrical engineers, and chemists, working in a wide variety of fields in solid state sciences. B. G. Yacobi D. B. Holt L. L. Kazmerski Toronto, London, and Denver vii Contents PART I. INTRODUCTION 1. An Introduction to Microanalysis of Solids B. G. Yacobi and D. B. Holt 1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2. Electron Beam Techniques . . . . . . . . . . . . . . . . . . . . . . . . 6 1.3. Ion Beam Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.4. Photon Beam Techniques . . . . . . . . . . . . . . . . . . . . . . . . . 10 1.5. Acoustic Wave Excitation . . . . . . . . . . . . . . . . . . . . . . . . . 14 1.6. Tunneling of Electrons and Scanning Probe Microscopies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 1.7. Emerging Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 PART II. ELECTRON BEAM TECHNIQUES 2. Scanning Electron Microscopy B. G. Yacobi and D. B. Holt 2.1. Introduction to Basic Principles . . . . . . . . . . . . . . . . . . . . 25 2.2. Interaction of Electrons with Solids . . . . . . . . . . . . . . . . . 29 2.3. The Emissive Mode ............................. . 36 2.4. Transmitted Electrons ........................... . 42 2.5. The X-ray Mode ............................... . 44 2.6. Cathodoluminescence Mode ...................... . 45 2.7. The Charge-Collection Mode ..................... . 51 2.8. The Electron Acoustic Mode ...................... . 57 2.9. Scanning Deep-Level Transient Spectroscopy ........ . 57 2.10. Conclusions ................................... . 60 Bibliography ................................... . 60 References .................................... . 61 ix X Contents 3. Transmission Electron Microscopy A. J. Garratt-Reed 3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 3.2. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.3. Interaction of Electrons with Matter, and Contrast . . . . . 67 3.4. Construction Details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 3.5. Microanalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 3.6. Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 3.7. Final Comments and Future Trends . . . . . . . . . . . . . . . . . 95 3.8. Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 4. Auger Electron Spectroscopy L. L. Kazmerski 4.1. Introduction and Background . . . . . . . . . . . . . . . . . . . . . . 99 4.2. Fundamental Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 4.3. Experimental Methods and Instrumentation . . . . . . . . . . Ill 4.4. Scanning Auger Electron Spectroscopy . . . . . . . . . . . . . . . 120 4.5. Chemical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 4.6. Sputtering and Depth Profiles . . . . . . . . . . . . . . . . . . . . . . 129 4.7. Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135 4.8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142 PART III. ION BEAM TECHNIQUES 5. Secondary Ion Mass Spectrometry S. E. Asher 5 .1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2. Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150 5.3. Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159 5.4. Sensitivity and Resolution . . . . . . . . . . . . . . . . . . . . . . . . . 162 5.5. Experimental Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . 166 5.6. Related Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169 5.7. Future Trends .................................. 173 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . l 7 5 Contents xi 6. Applications ofMegaelectron-Volt Ion Beams in Materials Analysis P. Revesz and J. Li 6.1. Introduction to Rutherford Backscattering . . . . . . . . . . . . 179 6.2. Physical Principles of Backscattering . . . . . . . . . . . . . . . . 181 6.3. Forward Recoil Elastic Scattering . . . . . . . . . . . . . . . . . . . 197 6.4. Channeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199 6.5. Elastic Resonances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 6.6. Particle-Induced X-ray Emission . . . . . . . . . . . . . . . . . . . 211 6.7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215 PART IV. PHOTON BEAM TECHNIQUES 7. Confocal Microscopy T. Wilson 7.1. Introduction ................................... . 219 7.2. The Confocal Optical System ..................... . 220 7.3. Alternative Forms of Detector ..................... . 226 7.4. Conclusions ................................... . 230 References 231 8. X-ray Microscopy A. G. Michette and A. W Potts 8.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233 8.2. X-ray Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 8.3. X-ray Optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236 8.4. X-ray Microscopes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237 8.5. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240 8.6. The Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245 9. X-ray Photoemission Spectroscopy A. J. Nelson 9.1. Introduction and Background . . . . . . . . . . . . . . . . . . . . . . 247 9.2. Fundamental Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . 248