Edited by Gernot Friedbacher and Henning Bubert Surface and Thin Film Analysis Related Titles Watts, J. F., Wolstenholme, J. An Introduction to SIMS for Surface and Thin Film Analysis 2011 ISBN: 978-0-470-09132-6 Guo, J. (ed.). X-Rays in Nanoscience Spectroscopy, Spectromicroscopy, and Scattering Techniques 2010 ISBN: 978-3-527-32288-6 Birkholz, M. Thin Film Analysis by X-Ray Scattering 2006 ISBN: 978-3-527-31052-4 Bordo, V. G., Rubahn, H.-G. Optics and Spectroscopy at Surfaces and Interfaces 2005 ISBN: 978-3-527-40560-2 Edited by Gernot Friedbacher and Henning Bubert Surface and Thin Film Analysis A Compendium of Principles, Instrumentation, and Applications Second, Completely Revised and Enlarged Edition The Editors All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Prof. Dr. Gernot Friedbacher publisher do not warrant the information Institute of Chemical Technology contained in these books, including this book, to and Analytics be free of errors. Readers are advised to keep in Getreidemarkt 9 /164 mind that statements, data, illustrations, 1060 Vienna procedural details or other items may Austria inadvertently be inaccurate. Dr. Henning Bubert Library of Congress Card No.: applied for Augsburger Weg 51 59439 Holzwickede British Library Cataloguing-in-Publication Data Germany A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>. © 2011 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfi lm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifi cally marked as such, are not to be considered unprotected by law. Composition Toppan Best-set Premedia Ltd., Hong Kong Printing and Binding Cover Design Adam Design, Weinheim Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-32047-9 V Contents Preface to the First Edition XVII Preface to the Second Edition XIX List of Contributors XXI 1 Introduction 1 John C. Rivière and Henning Bubert Part One Electron Detection 7 2 X-Ray Photoelectron Spectroscopy (XPS) 9 Henning Bubert, John C. Rivière, and Wolfgang S.M. Werner 2.1 Principles 9 2.2 Instrumentation 12 2.2.1 Vacuum Requirements 12 2.2.2 X-Ray Sources 13 2.2.3 Synchrotron Radiation 16 2.2.4 Electron Energy Analyzers 16 2.2.5 Spatial Resolution 18 2.3 Spectral Information and Chemical Shifts 19 2.4 Quantifi cation, Depth Profi ling, and Imaging 21 2.4.1 Quantifi cation 21 2.4.2 Depth Profi ling 23 2.4.3 Imaging 26 2.5 The Auger Parameter 27 2.6 Applications 28 2.6.1 Catalysis 28 2.6.2 Polymers 30 2.6.3 Corrosion and Passivation 31 2.6.4 Adhesion 32 2.6.5 Superconductors 34 2.6.6 Semiconductors 35 VI Contents 2.7 Ultraviolet Photoelectron Spectroscopy (UPS) 38 References 39 3 Auger Electron Spectroscopy (AES) 43 Henning Bubert, John C. Rivière, and Wolfgang S.M. Werner 3.1 Principles 43 3.2 Instrumentation 44 3.2.1 Vacuum Requirements 44 3.2.2 Electron Sources 44 3.2.3 Electron-Energy Analyzers 45 3.3 Spectral Information 47 3.4 Quantifi cation and Depth Profi ling 51 3.4.1 Quantifi cation 51 3.4.2 Depth Profi ling 53 3.5 Applications 54 3.5.1 Grain Boundary Segregation 54 3.5.2 Semiconductor Technology 56 3.5.3 Thin Films and Interfaces 58 3.5.4 Surface Segregation 58 3.6 Scanning Auger Microscopy (SAM) 61 References 64 4 Electron Energy-Loss Spectroscopy (EELS) and Energy-Filtering Transmission Electron Microscopy (EFTEM) 67 Reinhard Schneider 4.1 Principles 68 4.2 Instrumentation 70 4.3 Qualitative Spectral Information 72 4.3.1 Low-Loss Excitations 74 4.3.2 Ionization Losses 77 4.3.3 Fine Structures 79 4.4 Quantifi cation 83 4.5 Imaging of Element Distribution 85 4.6 Summary 88 References 89 5 Low-Energy Electron Diffraction (LEED) 93 Georg Held 5.1 Principles and History 93 5.2 Instrumentation 94 5.3 Qualitative Information 96 5.3.1 LEED Pattern 96 5.3.2 Spot Profi le Analysis 100 5.3.3 Applications and Restrictions 100 5.4 Quantitative Structural Information 101 Contents VII 5.4.1 Principles 101 5.4.2 Experimental Techniques 102 5.4.3 Computer Programs 104 5.4.4 Applications and Restrictions 105 5.5 Low-Energy Electron Microscopy 106 5.5.1 Principles of Operation 106 5.5.2 Applications and Restrictions 108 References 108 6 Other Electron-Detecting Techniques 111 John C. Rivière 6.1 Ion (Excited) Auger Electron Spectroscopy (IAES) 111 6.2 Ion Neutralization Spectroscopy (INS) 111 6.3 Inelastic Electron Tunneling Spectroscopy (IETS) 112 Reference 113 Part Two Ion Detection 115 7 Static Secondary Ion Mass Spectrometry (SSIMS) 117 Heinrich F. Arlinghaus 7.1 Principles 117 7.2 Instrumentation 119 7.2.1 Ion Sources 119 7.2.2 Mass Analyzers 120 7.2.2.1 Quadrupole Mass Spectrometers 120 7.2.2.2 Time-of-Flight Mass Spectrometry (TOF-MS) 121 7.3 Quantifi cation 123 7.4 Spectral Information 125 7.5 Applications 127 7.5.1 Oxide Films 128 7.5.2 Interfaces 128 7.5.3 Polymers 131 7.5.4 Biosensors 133 7.5.5 Surface Reactions 134 7.5.6 Imaging 135 7.5.7 Ultra-Shallow Depth Profi ling 137 References 138 8 Dynamic Secondary Ion Mass Spectrometry (SIMS) 141 Herbert Hutter 8.1 Principles 141 8.1.1 Compensation of Preferential Sputtering 141 8.1.2 Atomic Mixing 142 8.1.3 Implantation of Primary Ions 142 VIII Contents 8.1.4 Crater Bottom Roughening 142 8.1.5 Sputter-Induced Roughness 142 8.1.6 Charging Effects 142 8.2 Instrumentation 143 8.2.1 Ion Sources 143 8.2.1.1 Duoplasmatron 144 8.2.2 Mass Analyzer 144 8.2.2.1 Magnetic Sector Field 144 8.2.2.2 Detector 145 8.3 Spectral Information 146 8.4 Quantifi cation 147 8.4.1 Relative Sensitivity Factors 147 8.4.2 Implantation Standards 147 8.4.3 Metal Ceside (MCs+) Ions 148 8.4.4 Theoretical Models 148 8.4.4.1 Electron Tunneling Model 148 8.4.4.2 Broken Bond Model 148 8.4.4.3 Local Thermodynamic Equilibrium LTE 148 8.5 Mass Spectra 149 8.6 Depth Profi les 149 8.6.1 Dual-Beam Technique for TOF-SIMS Instruments 152 8.6.2 Molecular Depth Profi les 152 8.7 Imaging 152 8.7.1 Scanning SIMS 152 8.7.2 Direct Imaging Mode 153 8.8 Three-Dimensional (3-D)-SIMS 154 8.9 Applications 156 8.9.1 Implantation Profi les 156 8.9.2 Layer Analysis 157 8.9.3 3-D Trace Element Distribution 158 References 159 9 Electron-Impact (EI) Secondary Neutral Mass Spectrometry (SNMS) 161 Michael Kopnarski and Holger Jenett 9.1 Introduction 161 9.2 General Principles of SNMS 162 9.2.1 Postionization via Electron Impact 163 9.2.2 Suppression of Residual Gas and Secondary Ions 164 9.3 Instrumentation and Methods 166 9.3.1 Electron Beam SNMS 166 9.3.2 Plasma SNMS 167 9.4 Spectral Information and Quantifi cation 170 9.5 Element Depth Profi ling 172