X-Ray Spectroscopy for Chemical State Analysis

238 Pages·2022·10.157 MB·English

by  Jun Kawai

Jun Kawai
X-Ray
Spectroscopy
for Chemical
State Analysis
X-Ray Spectroscopy for Chemical State Analysis
Jun Kawai
X-Ray Spectroscopy
for Chemical State Analysis
Jun Kawai
Department of Materials Science
and Engineering
Kyoto University
Kyoto, Japan
ISBN 978-981-19-7360-4 ISBN 978-981-19-7361-1 (eBook)
https://doi.org/10.1007/978-981-19-7361-1
© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
Singapore Pte Ltd. 2023
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Preface
The present book “X-Ray Spectroscopy for Chemical State Analysis” is a book on
methods of materials characterization using X-ray emission, absorption, and photo-
electron spectroscopies. This book is also on various methods of instrumentation of
X-ray measurements, from high-precision double-crystal spectrometers to cheap Si-
PIN or Webcam X-ray detectors. This book treats from synchrotron radiation exper-
iments to crude experiments using discharge X-ray emitters. This book is overall on
the physics and chemistry of X-rays based on my experience from 1978 until 2022.
Chapter 1 is an introductory chapter, treating particle and wave duality of X-
rays for Bragg diffraction, Compton scattering, refraction, polarization, and total
reflection. This chapter contains X-ray physics not widely known to the beginners
of X-ray research.
Chapter 2 treats X-ray spectra from a one-electron picture using molecular-orbital
theory, and Chap. 3 from a many-electron picture of multiple hole states (shake-off,
3d-transition metals, and radiative Auger effect). The theory is explained by some
personification of electrons, which has never been described in the original academic
papers treated in Chap. 3.
Chapters 4–7 treat experimental techniques. Chapter 4 treats pyroelectric X-ray
emission and charge-up phenomena. Chapter 5 treats portable (i) total reflection
X-ray fluorescence, (ii) polarization X-ray fluorescence, and (iii) palm-top EPMA,
where all the instruments are very small, and X-rays are very weak. Chapter 6 treats
synchrotron radiation-related analyses, where X-rays are very strong. Chapter 7
treats various experimental techniques for accurate and precise quantitative chem-
ical analysis, also describing digital signal processors, analog amplifiers, proportional
counters, and crystal spectrometers.
Chapter 8 is the concluding chapter of the present book from the anti-synchrotron
point of view.
All the topics in the present book are more or less related to my own experiences
over 45 years. I met Prof. Yohichi Gohshi in October 1978, when I took Gohshi’s
seminar, “Methodology of Engineering” as a first-year student at the University of
Tokyo. That was a one-semester seminar for about ten students. Gohshi selected
one book for every 2 weeks, such as James Watson’s “The Double Helix”, and we
v
vi Preface
discussed the method of research based on each book. I selected analytical chem-
istry next year as my major among science and engineering, and joined Gohshi’s
Lab (March 1981) 2 years after the seminar and started X-ray spectroscopy. I would
like to list my mentors since then as my acknowledgements: Yohichi Gohshi (School
of Engineering, the University of Tokyo), Chikatoshi Satoko and Keiji Morokuma
(Institute for Molecular Science), Yoshimasa Nihei (Institute of Industrial Science,
the University of Tokyo), Kuniko Maeda and Michio Takami (RIKEN, The Institute
of Physical and Chemical Research), Masayuki Uda (Waseda University), and Hiro-
hiko Adachi and Takeshi Mukoyama (Kyoto University). I also thank all the associate,
assistant professors, and students in my lab, and collaborators from various universi-
ties and institutes, whose names are found in the reference lists of the present book,
but I sometimes refer to these references as one primary author’s name, in place of
the “first author, et al.” for the acknowledgements of his/her primary contribution to
the work. I have enjoyed writing the present book, especially writing my personal
episodes scattered in many chapters. The readers will find that my students have
enjoyed their experiments from various hand-made instruments shown especially in
Chapters 4 and 5, and I hope the readers also enjoy the present book. Finally, I thank
my wife Masako for her support in everything except for research.
Kyoto, Japan Jun Kawai
August 2022
Contents
1 Particle and Wave Duality of X-Rays ............................. 1
1.1 Bragg Diffraction of X-Rays Derived
from the Bohr-Sommerfeld Quantization
Rule ..................................................... 1
1.2 Units of X-Ray Wavelength ................................. 3
1.3 Wave Theory of Bragg Diffraction ........................... 3
1.4 Phasor for X-Ray Diffraction ................................ 3
1.5 Compton Scattering as a Double Doppler Shift ................ 6
1.6 Compton Scattering Interpreted from Particle Picture ........... 9
1.7 X-Ray Linear Polarization from an Electric Dipole Moment ..... 10
1.8 Barkla’s Experiments on X-Ray Polarization .................. 12
1.9 Refractive Index—Phase and Group Velocities of an Electron .... 13
1.10 Brewster’s Angle .......................................... 15
References ..................................................... 17
2 Profile Change of X-Ray Spectra ................................. 21
2.1 Kβ ..................................................... 21
5
2.2 Electric Quadrupole Antenna ................................ 24
2.3 Pre-edge in K-XANES ..................................... 25
2.4 Toxicity of Chromium and the Pre-edge ...................... 26
2.5 Historical Review of Kβ ................................... 26
5
2.6 Stigler’s Law of Eponymy .................................. 31
2.7 Nomenclature of X-Ray Emission Lines of Diagram Lines ...... 31
2.8 X-Ray Emission or X-Ray Fluorescence ...................... 36
2.9 K and L Edges ............................................ 37
2.10 Satellites ................................................. 39
2.11 Urch-Manne Method ....................................... 40
2.12 Calculation of SO 2− SKβ Spectra .......................... 45
4
2.13 Local Structure and Group Theory ........................... 46
2.14 History of the Xα Method .................................. 48
2.15 The DV-Xα Method ....................................... 50
vii
viii Contents
2.16 ΔSCF or the Slater’s Transition State Method? ................ 50
2.17 Calculation of Carbon Kα Spectra ........................... 53
2.18 Electronic Structure Information Known Only
from the Comparison of Measured Data ...................... 55
References ..................................................... 56
3 Chemical Effects of Multiply Ionized Satellites .................... 63
3.1 Shake-up and Shake-off Satellites in XPS ..................... 63
3.2 Charge-Transfer Satellites of XPS ........................... 65
3.3 Asada Theory of XPS Satellite .............................. 70
3.4 Shake-off and Coster-Kronig ................................ 73
3.5 Linewidth Satellite ........................................ 78
3.6 Urch-Benka-Hartmann Theory for F Kα ...................... 82
3.7 Kα Line Shape of Transition-Metal Compounds ............... 84
3.8 Radiative Auger Effect and X-Ray Raman .................... 88
3.9 Plasmon Satellites ......................................... 94
3.10 Summary of Chapters 2 and 3 ............................... 97
References ..................................................... 99
4 Pyroelectric X-Ray Emission .................................... 107
4.1 Principle ................................................. 107
4.2 A Personal Experience of Charge-Up X-Ray Emission .......... 114
4.3 Quantitative Elemental Analysis by Pyroelectric X-Ray
Generator ................................................ 124
4.4 Extended Applications of Pyroelectric Crystal
and Concluding Remarks ................................... 127
References ..................................................... 129
5 Small-Size and Low-Power X-Ray Instruments ................... 135
5.1 3D Printer ................................................ 135
5.2 TXRF (Total Reflection X-Ray Fluorescence) Spectrometer ..... 137
5.3 X-Ray Reflectometer ...................................... 143
5.4 Polarization X-Ray Fluorescence Spectrometer ................ 152
References ..................................................... 158
6 Synchrotron Radiation Experiments ............................. 163
6.1 Total Reflection X-Ray Photoelectron Spectroscopy
(TRXPS) ................................................. 163
6.2 Total Electron Yield (TEY) XAFS for Powder Analysis ......... 171
6.3 Simultaneous Measurement of SR-XRF and SEM-EDX ........ 178
6.4 X-Ray Photoelectron Diffraction (XPED) and X-Ray
Fluorescence Holography (XFH) ............................ 180
References ..................................................... 182
Contents ix
7 Quantitative Analysis Using XRF and SEM ....................... 189
7.1 Black-Body Radiation ..................................... 189
7.2 Energy-θ Conversion ...................................... 195
7.3 Crystal Reflectivity and Spectrometer Window ................ 200
7.4 Precision and Sample Amount .............................. 203
7.5 Precision of Synchrotron Radiation XRF ...................... 206
7.6 Detection Limit of Selective Excitation for SR-XRF ............ 208
7.7 High Resolution X-Ray Fluorescence Spectrometers ........... 209
7.8 EPMA and SEM–EDX ..................................... 212
7.9 Artificial Peaks in X-Ray Spectra ............................ 217
References ..................................................... 224
8 Conclusions .................................................... 231
8.1 Keeping Distance from the Synchrotron Radiation ............. 231
8.2 Still We Have Many Open Problems ......................... 232
References ..................................................... 233
Chapter 1
Particle and Wave Duality of X-Rays
1.1 Bragg Diffraction of X-Rays Derived
from the Bohr-Sommerfeld Quantization Rule
The early quantum mechanics was based on the Bohr-Sommerfeld quantization rule
[1]:
∫
pdq = nh, (1.1)
where p and q are the momentum and position, respectively, n is a positive integer,
and h is Planck’s constant: h = 6.626 070 15 ×10−34 Js becomes the exact value
since 2018 or 2019 [2]. The Bohr-Sommerfeld quantization rule began the discussion
at the 1st Solvay Conference in 1911 [3].
If an X-ray photon with the momentum p = hν/c is reflected by a single crystal at
an angle θ as shown in Fig. 1.1,thez component changes from +hν sinθ to −hν sinθ.
c c
Duane [4] recognized that the Bohr-Sommerfeld quantization rule (1.1) becomes
∫ d
p dz = nh (1.2)
z
0
for the Bragg diffraction because the crystal is the repeat by d spacing. Integrating
Eq. (1.2) yields
p d = nh. (1.3)
z
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 1
J. Kawai, X-Ray Spectroscopy for Chemical State Analysis,
https://doi.org/10.1007/978-981-19-7361-1_1