Cambridge University Press
052184875X - Electron Microprobe Analysis and Scanning Electron Microscopy in Geology - by S. J. B. Reed
Frontmatter/Prelims
This book describes electron microprobe analysis (EMPA) and scanning electron microscopy (SEM) specifically from a geological viewpoint. No prior knowledge is assumed and unnecessary technical detail is avoided, in order to keep the book easily accessible to new users of these techniques.
The principles of electron–specimen interactions and instrumentation are covered in the first part of the book. The mechanisms involved in SEM (secondary and backscattered electron) image formation are then explained, with full consideration of digital imaging techniques. The operating principles of energy- and wavelength-dispersive X-ray spectrometers are described, as well as ancillary techniques including cathodoluminescence (CL) and electron backscatter diffraction (EBSD). Procedures for qualitative and quantitative X-ray analysis (using either electron microprobe or SEM instruments) are described in detail. The production of X-ray ‘maps’ showing element distributions is also described, with examples. Finally the subject of specimen preparation is discussed. There is an emphasis throughout on specifically geological aspects not covered in books aimed at a more general readership.
This updated version of the first (1996) edition takes full account of recent developments and is intended for geological graduate students and postdoctoral workers, as well as those in commercial laboratories. It is also an invaluable accompaniment to courses for geological EMPA and SEM users.
DR REED is affiliated to the Department of Earth Sciences at the University of Cambridge. After studying physics at Southampton University, he gained a Ph.D. from the University of Cambridge in 1964 for research in using EMPA to analyse iron meteorites. He went on to be a Scientific Officer at the Natural History Museum, London from 1965 until 1970 before his appointment as Senior Research Fellow at the Australian National University, Canberra in 1970, where he implemented a new system for quantitative ED analysis. From 1974 until his retirement in 2002, Dr Reed was at the Department of Earth Sciences, University of Cambridge with research interests including ion and electron microprobe analysis and developing simulation software. In 1981 he was awarded the Microbeam Analysis Society Presidential Award for his outstanding scientific contribution to the theory and practice of microbeam analysis, followed in 1984 by honorary life membership. He has written, and contributed to, several books on the subject, including Electron Microprobe Analysis (Cambridge University Press, first edn 1975, second edn 1993).
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© S. J. B. Reed 2005
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Preface | page ix | ||||||
Acknowledgment | xiii | ||||||
1 | Introduction | 1 | |||||
1.1 | Electron microprobe analysis | 1 | |||||
1.2 | Scanning electron microscopy | 1 | |||||
1.2.1 | Use of SEM for analysis | 2 | |||||
1.3 | Geological applications of SEM and EMPA | 2 | |||||
1.4 | Related techniques | 4 | |||||
1.4.1 | Analytical electron microscopy | 4 | |||||
1.4.2 | Proton-induced X-ray emission | 4 | |||||
1.4.3 | X-ray fluorescence analysis | 5 | |||||
1.4.4 | Auger analysis | 5 | |||||
1.4.5 | Ion microprobe analysis | 6 | |||||
1.4.6 | Laser microprobe methods | 6 | |||||
2 | Electron–specimen interactions | 7 | |||||
2.1 | Introduction | 7 | |||||
2.2 | Inelastic scattering | 7 | |||||
2.2.1 | Electron range | 8 | |||||
2.3 | Elastic scattering | 8 | |||||
2.3.1 | Backscattering | 9 | |||||
2.4 | Secondary-electron emissiontd | 11 | |||||
2.5 | X-ray production | 11 | |||||
2.5.1 | The continuous X-ray spectrum | 12 | |||||
2.5.2 | Characteristic X-ray spectra | 12 | |||||
2.6 | X-ray absorption | 16 | |||||
2.7 | The Auger effect and fluorescence yield | 17 | |||||
2.8 | Cathodoluminescence | 17 | |||||
2.9 | Specimen heating | 19 | |||||
3 | Instrumentation | 21 | |||||
3.1 | Introduction | 21 | |||||
3.2 | The electron gun | 21 | |||||
3.2.1 | High-brightness electron sources | 23 | |||||
3.3 | Electron lenses | 23 | |||||
3.3.1 | Aberrations | 25 | |||||
3.3.2 | Apertures | 27 | |||||
3.4 | Beam diameter and current | 27 | |||||
3.5 | Column alignment | 27 | |||||
3.6 | Beam current monitoring | 28 | |||||
3.7 | Beam scanning | 29 | |||||
3.8 | The specimen stage | 30 | |||||
3.9 | The optical microscope | 32 | |||||
3.10 | Vacuum systems | 33 | |||||
3.10.1 | Contamination | 34 | |||||
3.10.2 | Low-vacuum or environmental SEM | 34 | |||||
3.11 | Electron detectors | 35 | |||||
3.11.1 | Secondary-electron detectors | 35 | |||||
3.11.2 | Backscattered-electron detectors | 36 | |||||
3.12 | Detection of other types of signal | 37 | |||||
3.12.1 | Auger electrons | 37 | |||||
3.12.2 | Cathodoluminescence | 38 | |||||
3.12.3 | Electron backscatter diffraction | 40 | |||||
4 | Scanning electron microscopy | 41 | |||||
4.1 | Introduction | 41 | |||||
4.2 | Magnification and resolution | 41 | |||||
4.3 | Focussing | 42 | |||||
4.3.1 | Working distance | 42 | |||||
4.4 | Topographic images | 43 | |||||
4.4.1 | Secondary-electron images | 43 | |||||
4.4.2 | Topographic contrast in BSE images | 45 | |||||
4.4.3 | Spatial resolution | 49 | |||||
4.4.4 | Depth of focus | 52 | |||||
4.4.5 | Stereoscopic images | 52 | |||||
4.4.6 | Environmental SEM | 53 | |||||
4.5 | Compositional images | 53 | |||||
4.5.1 | Atomic-number discrimination in BSE images | 55 | |||||
4.5.2 | Spatial resolution in BSE images | 61 | |||||
4.5.3 | The application of etching | 61 | |||||
4.6 | Image defects | 61 | |||||
4.6.1 | Statistical noise | 61 | |||||
4.6.2 | Specimen charging | 62 | |||||
4.6.3 | Stray field and vibration | 63 | |||||
4.6.4 | Astigmatism | 63 | |||||
4.6.5 | Coating artefacts | 64 | |||||
4.7 | Image enhancement | 64 | |||||
4.7.1 | Digital image processing | 64 | |||||
4.7.2 | False colours | 67 | |||||
4.8 | Other types of image | 68 | |||||
4.8.1 | Absorbed-current images | 68 | |||||
4.8.2 | Magnetic-contrast images | 70 | |||||
4.8.3 | Electron backscatter diffraction images | 70 | |||||
4.8.4 | Cathodoluminescence images | 73 | |||||
4.8.5 | Charge-contrast images | 77 | |||||
4.8.6 | Scanning Auger images | 77 | |||||
5 | X-ray spectrometers | 78 | |||||
5.1 | Introduction | 78 | |||||
5.2 | Energy-dispersive spectrometers | 78 | |||||
5.2.1 | Solid-state X-ray detectors | 78 | |||||
5.2.2 | Energy resolution | 80 | |||||
5.2.3 | Detection efficiency | 81 | |||||
5.2.4 | Pulse processing and dead-time | 82 | |||||
5.2.5 | Spectrum display | 84 | |||||
5.2.6 | Artefacts in ED spectra | 86 | |||||
5.3 | Wavelength-dispersive spectrometers | 88 | |||||
5.3.1 | Bragg reflection | 88 | |||||
5.3.2 | Focussing geometry | 90 | |||||
5.3.3 | Design of WD spectrometers | 92 | |||||
5.3.4 | Proportional counters | 94 | |||||
5.3.5 | Pulse counting and dead-time | 96 | |||||
5.4 | Comparison between ED and WD spectrometers | 97 | |||||
6 | Element mapping | 99 | |||||
6.1 | Introduction | 99 | |||||
6.2 | Digital mapping | 99 | |||||
6.3 | EDS mapping | 100 | |||||
6.4 | WDS mapping | 102 | |||||
6.5 | Quantitative mapping | 102 | |||||
6.6 | Statistics and noise in maps | 104 | |||||
6.7 | Colour maps | 104 | |||||
6.8 | Modal analysis | 105 | |||||
6.9 | Line scans | 109 | |||||
6.10 | Three-dimensional maps | 109 | |||||
7 | X-ray analysis (1) | 110 | |||||
7.1 | Introduction | 110 | |||||
7.2 | Pure-element X-ray spectra | 110 | |||||
7.3 | Element identification | 113 | |||||
7.4 | Mineral identification | 115 | |||||
7.5 | Quantitative WD analysis | 115 | |||||
7.5.1 | Background corrections | 117 | |||||
7.5.2 | Overlap corrections | 117 | |||||
7.5.3 | Uncorrected concentrations | 118 | |||||
7.6 | Quantitative ED analysis | 120 | |||||
7.6.1 | Background corrections in ED analysis | 120 | |||||
7.6.2 | Measuring peak intensities in ED analysis | 121 | |||||
7.6.3 | Comparison between ED and WD analysis | 121 | |||||
7.7 | Matrix corrections | 122 | |||||
7.7.1 | Atomic-number corrections | 122 | |||||
7.7.2 | Absorption corrections | 123 | |||||
7.7.3 | Fluorescence corrections | 124 | |||||
7.7.4 | Alpha coefficients | 126 | |||||
7.7.5 | The accuracy of matrix corrections | 126 | |||||
7.8 | Correction programs | 127 | |||||
7.8.1 | Unanalysed elements | 127 | |||||
7.9 | Treatment of results | 128 | |||||
7.9.1 | Polyvalency | 129 | |||||
7.9.2 | Mineral formulae | 130 | |||||
7.9.3 | Data presentation | 131 | |||||
7.10 | Standards | 131 | |||||
7.10.1 | Standardless analysis | 135 | |||||
8 | X-ray analysis (2) | 136 | |||||
8.1 | Light-element analysis | 136 | |||||
8.1.1 | Chemical bonding effects | 137 | |||||
8.1.2 | Absorption corrections for light elements | 138 | |||||
8.1.3 | Application of multilayers | 138 | |||||
8.2 | Low-voltage analysis | 139 | |||||
8.3 | Choice of conditions for quantitative analysis | 139 | |||||
8.4 | Counting statistics | 140 | |||||
8.4.1 | Homogeneity | 141 | |||||
8.5 | Detection limits | 142 | |||||
8.6 | The effect of the conductive coating | 142 | |||||
8.7 | Beam damage | 143 | |||||
8.7.1 | Heating | 143 | |||||
8.7.2 | Migration of alkalies etc. | 144 | |||||
8.8 | Boundary effects | 146 | |||||
8.9 | Special cases | 146 | |||||
8.9.1 | Tilted specimens | 147 | |||||
8.9.2 | Broad-beam analysis | 147 | |||||
8.9.3 | Particles | 148 | |||||
8.9.4 | Rough and porous specimens | 149 | |||||
8.9.5 | Thin specimens | 149 | |||||
8.9.6 | Fluid inclusions | 150 | |||||
8.9.7 | Analysis in low vacuum | 151 | |||||
9 | Sample preparation | 152 | |||||
9.1 | Initial preparation of samples | 152 | |||||
9.1.1 | Cleaning | 152 | |||||
9.1.2 | Drying | 152 | |||||
9.1.3 | Impregnation | 153 | |||||
9.1.4 | Replicas and casts | 153 | |||||
9.1.5 | Cutting rock samples | 154 | |||||
9.2 | Mounting | 155 | |||||
9.2.1 | The SEM ‘stub’ | 155 | |||||
9.2.2 | Embedding | 155 | |||||
9.2.3 | Thin sections | 156 | |||||
9.2.4 | Grain mounts | 156 | |||||
9.2.5 | Standards | 157 | |||||
9.3 | Polishing | 158 | |||||
9.4 | Etching | 158 | |||||
9.5 | Coating | 159 | |||||
9.5.1 | Carbon coating | 160 | |||||
9.5.2 | Metal evaporation | 161 | |||||
9.5.3 | Sputter coating | 161 | |||||
9.5.4 | Removing coatings | 162 | |||||
9.6 | Marking specimens | 163 | |||||
9.6.1 | Specimen ‘maps’ | 163 | |||||
9.7 | Specimen handling and storage | 164 | |||||
Appendix | 165 | ||||||
References | 182 | ||||||
Index | 190 | ||||||
The colour plates are situated between pages 96 and 97. |
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