Accelerat ing t he world's research.

The casa cookbook

Alan Carrick

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TimesFront2c.fm Page i Thursday, July 14, 2005 10:52 AM

The
Casa Cookbook
Part 1: Recipes for XPS
Data Processing

Neal Fairley
and
Alan Carrick
TimesFront2c.fm Page ii Thursday, July 14, 2005 10:52 AM

The Casa Cookbook - Part 1: Recipes for XPS Data Processing

By Neal Fairley and Alan Carrick

Copyright © 2005 Acolyte Science. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system,

or transmitted, in any form or by any means, electronic, mechanical,
photocopying, recording or otherwise, without the prior written permission
of Acolyte Science

Whilst every care and precaution has been taken in the preparation of this
book, the publisher assumes no responsibility for errors or omissions, or
for damages resulting from the use of information contained herein.

The rights of Neal Fairley and Alan Carrick to be identified as authors of this work have been
asserted in accordance with sections 77 & 78 of the Copyright, Designs, and Patents Act, 1988

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library
ISBN: 0-9549533-0-4

Published by Acolyte Science, Kinderton Close, High Legh, Knutsford, Cheshire, WA16 6LZ U.K.
http://www.acolytescience.co.uk

Visit the Casa web site: http://www.casaxps.com

Printed and bound in England by Pelican Press, Manchester, on Cyclus Offset paper
with ISO 14001and NAPM Certificates
CasaCookBook5TOC.fm Page 1 Thursday, July 14, 2005 10:49 AM

Contents

Foreword

Section 1 - Quick Guide

Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3
Getting Started . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Installing CasaXPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Starting CasaXPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
The Program Frame . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
How do I....? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

Section 2 - What CasaXPS Can Do

Chapter 2 Basic Concepts & Case Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
The Main Window and Experiment Frames . . . . . . . . . . . . . . . . . . . . . . . 21
Toolbars and Menus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Case Study 1: Quantification of a survey spectrum . . . . . . . . . . . . . . . . . . . . . 24
Converting the Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Browsing the Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Element Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Quantification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Manual Adjustment of Quantification Regions . . . . . . . . . . . . . . . . . . . . . 26
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Case Study 2: Display of Spectra and Printed Logo . . . . . . . . . . . . . . . . . . . . . 28
Adding a Logo to Printouts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Case Study 3: Satellite Subtraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Case Study 4: Quantification Tables and Areas . . . . . . . . . . . . . . . . . . . . . . . . 34
Facts relating to quantification: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Case Study 5: Displaying Spectra & Saving Display Formats . . . . . . . . . . . . . 38
Mouse and Keyboard Operations: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Toolbar Display Buttons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Saving the Formatting of the Display Tiles . . . . . . . . . . . . . . . . . . . . . . . . 39
Case Study 6: Multiple Experimental Variables and ISO Files . . . . . . . . . . . . 41
Saving and Restoring the Display State from File . . . . . . . . . . . . . . . . . . 43
Case Study 7: Cu Auger Line Curve Fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Construct background subtracted line-shapes from the data. . . . . . . . . . . 45
Define a peak model on the unknown spectrum. . . . . . . . . . . . . . . . . . . . 47
Chapter 3 Using CasaXPS Toolbars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .49
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Contents

Toolbar (upper toolbar, main toolbar) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

First Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Second Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Options Bar (lower toolbar) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
First Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Second Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Third Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Fourth Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Fifth Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Sixth Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Alignment of Blocks in the Browser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Chapter 4 Managing the Display using Inset Tiles . . . . . . . . . . . . . . . . . . . . . . . . . .65
Regular Sets of Display Tiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Inset Tiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
To Create an Inset Tile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Deleting Display and Inset Tiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Peak Fitting Using Inset Tiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Tile Display Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Chapter 5 Qualitative Analysis and the Element Library . . . . . . . . . . . . . . . . . . . . .81
The Element Library File Format . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
The Element Library and Auger Spectra: a General Example . . . . . . . . . . . . . 84
Identifying Peaks Interactively . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Chapter 6 Quantification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .91
Regions Property Page . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Background (BG Type) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Report Specification Property Page . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Constructing Columns of Intensities from Regions and Components . . . 96
Where do the Quantification Item Names come from? . . . . . . . . . . . . . . . 96
Adjusting the Formulae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Preparing a quantification report . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Quantification of Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Quantification of a Survey Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Quantification of High Resolution Spectra . . . . . . . . . . . . . . . . . . . . . . . 103
Quantification with Tags . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Quantification of Depth Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
Manual Creation of Quantification Regions . . . . . . . . . . . . . . . . . . . . . . 105
Relative Sensitivity Factors and Other Corrections . . . . . . . . . . . . . . . . 107
Atomic Concentration Report . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
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Contents

Quantification Examples in Detail . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

Quantification using High Resolution Spectra . . . . . . . . . . . . . . . . . . . . 112
Quantification of a survey scan using Tags . . . . . . . . . . . . . . . . . . . . . . . 117
A Multi-layer Depth Profile Example . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Quantification for Depth Profiles including Curve Fitting . . . . . . . . . . . 128
Adjusting Spectra for Comparative Quantification . . . . . . . . . . . . . . . . . 139
Customizing Columns in the Standard Report . . . . . . . . . . . . . . . . . . . . . . . . 143
Chapter 7 Line Shapes and Backgrounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
Peak fits and background choice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
A List of Line-Shapes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Gaussian/Lorentzian Product Form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Gaussian/Lorentzian Sum Form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Exponential Asymmetric Blend Based upon Voigt-type Line-Shapes . . 150
Alternative Asymmetric Line-Shapes . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Doniach Sunjic: A Theoretically Based Asymmetric Line-Shape . . . . . 151
Line-Shapes Based upon Backgrounds . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Line-Shapes Available in CasaXPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Further adjustments to the basic shapes . . . . . . . . . . . . . . . . . . . . . . . . . 153
Asymmetric Line-Shapes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Modifications to the Doniach Sunjic function . . . . . . . . . . . . . . . . . . . . . 155
A New Line-Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Background Subtraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Adjusting the three-parameter universal cross-section . . . . . . . . . . . . . . 162
Simulating Spectra using Custom Tougaard Backgrounds . . . . . . . . . . . 164
Spline Backgrounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
Chapter 8 Peak Fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .169
Peak Fitting and Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Multi-scan Peak Fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
Issues associated with common peak models . . . . . . . . . . . . . . . . . . . . . 179
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
Automatic Fitting of Peaks Across Multiple Spectral Regions . . . . . . . . 181
Peak fits using multiple spectral regions: An example . . . . . . . . . . . . . . . . . . 182
Curve-Fitting using Models Defined from Data . . . . . . . . . . . . . . . . . . . . . . . 186
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Chapter 9 Manipulating Spectra - the Calculator . . . . . . . . . . . . . . . . . . . . . . . . . .189
The Calculator User Interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
Displaying the VAMAS block index: . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Background Subtraction: an example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
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Normalising the Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

Note: Normalising the display of overlaid spectra: . . . . . . . . . . . . . . . . 197
Subtracting the Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
A Note of Caution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
Processing History: a general note . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
Charge Correction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
Energy Calibration Based on Locating a Synthetic Peak . . . . . . . . . . . . 202
Creating the Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Creating the Peak Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
Energy Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
Undo and Retrospective Calibration Adjustments . . . . . . . . . . . . . . . . . 208
Locating a Peak Maximum without Quantification Regions . . . . . . . . . 213
Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
Chapter 10 Batch Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .215
Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Setting-up the .rpt File . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Energy Calibration for Batch Processing . . . . . . . . . . . . . . . . . . . . . . . . 219
Batch Processing, non-printing, with the Default Report File . . . . . . . . 219
Batch Processing with Printing and .rpt File . . . . . . . . . . . . . . . . . . . . . . 222

Section 3 - Mathematical Methods and Image Processing

Chapter 11 Monte Carlo Methods - Uncertainties in Peak Fits . . . . . . . . . . . . . . . .225
Monte Carlo Data Sets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Error Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Monte Carlo: A Simple Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Quantification Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Intensities Determined by Peak-Fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Chapter 12 Principal Component Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .237
Data and Vectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
Co-ordinate Systems, Basis Vectors and PCA . . . . . . . . . . . . . . . . . . . . . . . . 238
Some Cautionary Notes on PCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
A Real Application for PCA: Spectra and Images . . . . . . . . . . . . . . . . . . . . . 248
Chapter 13 PCA Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .255
PCA and Data Smoothing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
Reconstruction of Spectra Using a Reduced Set of Abstract Factors . . . 255
Constructing a Depth Profile using PCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
A Good Dataset . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
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Contents

Creating Line-Shapes using PCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Chapter 14 SVD Sorting: Images, Spectra and Information Combing . . . . . . . . . .267
Theoretical Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
A Synthetic Data Set . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Vector Spaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
SVD Sorting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Image Processing with SVD sort - a practical example . . . . . . . . . . . . . . . . . 275
SVD Sort and PCA Noise Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
Image Processing Dialog Window: A Quick Summary of Features . . . . . . . 281
Chapter 15 More Numerical Methods - Savitzky-Golay and Linear Analysis . . . .285
Savitzky-Golay Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Linear Analysis of Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
What is Linear Analysis? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292

Section 4 - The CasaXPS System and some background to XPS

Chapter 16 Converting File Formats - using different systems . . . . . . . . . . . . . . . .293
PHI MultiPak files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
MultiPak Binary files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
MultiPak ASCII files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
VG Eclipse Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
VG Avantage Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
Kratos Vision 1.x/2.x ASCII files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
“Dayta” System Files (University of Bristol IAC) . . . . . . . . . . . . . . . . . . . . . 298
VGX900 (Ron Unwin) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
SSI M-Probe Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
RDB Text Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Kratos DS800 Binary Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Scienta DOS Binary Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Scienta IGOR .pxt files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Specs SpecsLab I .exp files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
X/Y Column Data Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Chapter 17 Auger Considerations and Casa Auger Features . . . . . . . . . . . . . . . . . .303
Auger Imaging and the Advantages of Spectra at Pixels . . . . . . . . . . . . . . . . 303
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Contents

Analysis of Auger Images in CasaXPS . . . . . . . . . . . . . . . . . . . . . . . . . . 304

Ordering the Images using the Experimental Variable . . . . . . . . . . . . . . 305
Converting Images to Differentiated Spectra . . . . . . . . . . . . . . . . . . . . . 307
Quantifying the Spectra at Pixels to Produce Images . . . . . . . . . . . . . . . 308
Converting AES Direct Spectra to Differential Form . . . . . . . . . . . . . . . . . . 310
Linear Least Squares Analysis of Chemical States . . . . . . . . . . . . . . . . . . . . 311
Quantifying Spectra Using Peak-to-Peak . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
Quantification: An Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Chapter 18 The CasaXPS File System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .317
Help Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
Default Settings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
ParameterFile.txt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
PrintFootNote.txt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
ComponentQuantTable.txt and RegionQuantTable.txt . . . . . . . . . . . . . . 320
Element Library Files . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
Chapter 19 Background to the XPS Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . .321
The Nature of X-ray Photoelectron Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 321
Photoelectric Peaks, Auger Peaks and Energy Scales . . . . . . . . . . . . . . . 322
Satellite Peaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Backgrounds and Plasmon Peaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Spikes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
XPS Instrumentation - an overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Energy Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Small Area Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335

Section 5 - Appendices
Appendix 1: ISO 14976 format files annotated . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Appendix 2: ISO 14976 and the World Wide Web . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Appendix 3: Definitions and Formulae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Appendix 4: References and other Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Appendix 5: Some Questions and Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Appendix 6: CasaXPS Installation Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358

Index

Recipe

Colophon
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Section0 Page ii Monday, June 13, 2005 4:10 PM
Foreword.fm Page 3 Tuesday, July 12, 2005 11:34 AM

Foreword

CasaXPS is designed to take data from a wide range of instruments and their data
systems using native file formats wherever possible, convert these formats to the
ISO 14976 (“VAMAS”) format and provide a single environment in which to proc-
ess XPS and AES data. For many analysts problem solving using multiple tech-
niques is common-place and while the origins of CasaXPS are clearly XPS the
expansion of the system to cover AES (and, in Part II of this Series, SIMS) is both
natural and desirable. In addition, XPS image processing has also become increas-
ingly important, and to fulfil the potential of the modern imaging instruments, new
features and new algorithms have been added to CasaXPS.
Many of the capabilities of CasaXPS require an understanding of why as well as
how an operation is performed and therefore a large part of this CasaXPS manual is
devoted to explaining the context for a sequence of data reduction steps. Procedures
for these steps are addressed within sections describing specific examples, but the
essential functions of CasaXPS routines and options and the overall structure of the
program are presented in separate reference chapters. The practical examples are
necessarily wordy and to compensate to some degree the reference section is picto-
rial in essence.
Seasoned Auger and XPS practitioners may wonder at the apparent omission of sep-
arate chapters dealing with topics such as “Depth Profiling”. The approach is delib-
erate as it is felt more appropriate to cover issues of quantitation vs depth in relation
to the (more fundamental) processing mechanisms of peak fitting, PCA, SVD, and
the like. It is hoped that the index will provide an adequate guide to specific appli-
cations orientated questions in this regard.
It is also important to note that Chapter 19 does not intend to supplant existing ex-
cellent books which deal in detail with all aspects of XPS as an analytical technique
(some of which are listed in the Bibliography), but simply to provide a convenient
introduction to the basics for those from disciplines such as biochemistry, earth sci-
ences, and so on who may not otherwise have easy access to this information.

Acknowledgement
CasaXPS wishes to thank all those connected with the production of this manual and
the software system it describes.
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Section 1 - Quick Summary

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Chap01Intro.fm Page 3 Tuesday, July 12, 2005 11:54 AM

CHAPTER 1 Introduction

Computer Aided Surface Analysis for X-ray Photoelectron Spec-

troscopy (CasaXPS) has been designed and written for analysts and
research scientists who use XPS for surface characterisation.

In contrast to the special purpose control systems that form part of commercial XPS
instruments, CasaXPS offers a compact, portable, efficient and user-friendly
processing system to anyone with an IBM compatible (Pentium) PC running Micro-
soft Windows 95 (or later) or a suitable emulator1. It incorporates much of - and in
most cases more than - the processing functionality of the instrument-linked pack-
ages without recourse to unfamiliar operating systems or hardware or proprietary
file formats. It is designed from the outset on the basis of the ISO 14976 Surface
Chemical Analysis Standard Data Transfer Format and so by design has a universal,
manufacturer-independent, “cross platform” approach, relying on nothing other than
a reasonable adherence to the ISO standard. Spectra collected in the standard format
may be selected, viewed and processed in a simple yet powerful way and the results
of CasaXPS data reduction, presented in a variety of graphical and tabular formats,
are available for incorporation into and use as data by other popular Microsoft pack-

1. Microsoft XP systems are the most likely platform (in 2005) for CasaXPS, but in these
days of affordable high performance systems, such as the Macintosh G5, emulators such
as Virtual PC (for Mac OS X) should be seriously considered

3
Chap01Intro.fm Page 4 Tuesday, July 12, 2005 11:54 AM

CHAPTER 1: Introduction

ages such as “Word” or “Excel”. Additional spectrum input filters for other commer-
cial file formats are also provided, supplementing the ISO standard and broadening
its usefulness.

Casa XPS has been written entirely in native C++ using the Microsoft Developers
Studio programming environment. It employs Microsoft Foundation Class (MFC)
libraries to provide a standard graphical user interface as well as much of the data
management required by the system.
The software suite as a whole may be regarded as being structured from five inter-
acting components:
• Data display and browser (an “experiment window”)
• Element library (a “dialog window” as are the others)
• Graph annotation
• Data processing
• Quantification.
This publication provides a detailed description of the system, its operation, com-
mand and function set, and its use in practice in “real life” analytical applications.

The CasaXPS Cookbook’s objectives are to provide both a guide to the software and
its use and some background to the techniques of surface analysis as well as the prin-
ciple behind the mathematics used in the evaluation of the analytical data.

CasaXPS is more than “just another data system”: it is hoped that, similarly, this
“Cookbook” provides more than just “recipes”, provoking serious thought about
procedures and possibilities in one of the most challenging of experimental disci-
plines.

Getting Started
Installing CasaXPS
You must install the application from the CasaXPS CD onto your hard disk. “Drag
and Drop” installation is all that is required for Windows XP or ‘98. Instructions are
available, if required, in the “Read Me” file on the installation CD and some further
details in “Appendix 6: CasaXPS Installation Notes” on page 358. Make sure that
you have your serial number to hand when you install the application, or else the
package will revert to “Demonstration Mode” and will not allow you to save the re-
sults of your work. The serial number is available from your registration documents
(which may be e-mailed to you or included with the CD). You can “validate” a reg-
istration at any time after installation, turning a “demo” version into a fully licensed
product, by using the “About” button in the Toolbar.

4
Chap01Intro.fm Page 5 Tuesday, July 12, 2005 11:54 AM

Getting Started

CasaXPS - Organisation, work flow, and information

remote,
via network
use standard
experiment file on disk linking tools
acquired by spectrometer

local

ISO 14976
Monte Carlo (Appendix 1)
Chapter 11 p. 339 Proprietary format
PCA Chapter 16
Chapter 12
p. 293
spectra (convert)

SVD
images Chapter 14
Display (Plot)

Chapter 4
p. 65
(tiles)
profiles
Chapter 17
p. 303
(AES)

Chapter 9 Quantitate
p. 189 Process
(calculator) Chapter 6
p. 91 Chapter 8
(spectra)
p.104 p. 169
(profiles) (peak fit)
p. 275
(images) Chapter 9
p. 189
(calculator)

Chapter 10
p. 215
(batch)

5
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CHAPTER 1: Introduction

If you are using an emulator package on a processor other than an Intel Pentium, en-
sure that you obey the emulator’s instructions for installation of applications pack-
ages, that you understand the limitations (if any - e.g. mouse button availability) of
the system, and that you have sufficient space and processing power for the conven-
ient use of CasaXPS.
There is further, more detailed, information on program installation (and removal)
in “Appendix 6: CasaXPS Installation Notes” on page 358

Starting CasaXPS
Simply click on the desktop short-cut (if, as recommended, you installed one) or
double click on the programme icon in “Windows Explorer”. Ensure that you have
stored your ISO 14976 data files in an easily accessible directory (or have the demo
data on the installation CD available) Ensure also that you have an appropriate ele-
ment library available (one needs to be installed before the first use of “Library” sys-
tem - see “Element Library Files” on page 320 - a simple “generic” version is
available on the installation disk, but check with your instrument operator which is
the most appropriate file for the data acquired by that particular instrument). At some
point you may wish to install and use the on-line “help” files (see note on your CD
inlay) and you should have a “.def” directory prepared if you wish to store configu-
ration files for future use (see e.g. p. 79, p. 143).

Terminology
CasaXPS components and windows appear on screen as shown in Figure 1•1, where
the annotation defines their names as used throughout this book.
It is assumed always that the user is familiar with the “normal” IBM PC and Micro-
soft Windows operation and terminology.
The following section should be used as a “hands on” introduction to CasaXPS to
provide an overview of key features. Subsequent sections enlarge briefly on the role
of the system modules, and the remaining chapters deal in depth with specific topics
and applications.

The Program Frame

1. The program frame contains experiment frame windows.
2. Each experiment frame is divided into to two splitter windows.
3. The left-hand-side displays the spectra while the right-hand-side offers a data
array (data browser) showing the logical structure of the experiment.

6
Chap01Intro.fm Page 7 Tuesday, July 12, 2005 11:54 AM

How do I....?

CasaXPS (Program Frame)

Toolbar

Options Bar
Experiment
Frames
SIMS Bar

data blocks

Block
display tiles Window

(Browser)

a Dialog
Window scrolled list
Display slider Splitter bar
Window

FIGURE 1•1 A Windows XP™ screen showing CasaXPS in operation

How do I....?
(These commands are cross referenced to fuller descriptions in Chapter 3 starting
on page 49: U = Upper (main) Toolbar, L = Lower (Options Bar) , 2•3 indicates 3rd
button in 2nd group, and so on)

Display spectra
L 1•1-5 (page 58)
Select spectrum block(s) in right-hand-side splitter window (browser - Figure 1•1)
• Press a toolbar button