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Microbeam and
Nanobeam
Analysis
Edited by
D. Benoit, J.-F. Bresse,
L. Van't dack, H. Werner,
J. Wernisch
Mikrochimica Acta
Supplement 13
Springer-Verlag Wien GmbH
Dr. Daniele Benoit
Beauchamp, France
Dr. Jean-Francois Bresse
Department PAP/CDP/CMT, C.N.E.T. France Telecom
Bagneux, France
Luc Van't dack
Department of Chemistry, University of Antwerp (UlA),
Antwerp-Wilri jk, Belgium
Univ.-Prof. Dr. Helmut Wemer
Waalre, The Netherlands
Univ.-Doz. Dr. Johann Wemisch
Institut fiir angewandte und technische Physik,
Technische Universităt, Wien, Austria
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© 1996 Springer-Verlag Wien
Originally published by Springer-Verlag/Wien in 1996
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Die Deutsche Bibliothek -CIP-Einheitsaufnahme
Microbeam and nanobeam analysis / D. Benoit ... (ed.). -Wien
; New York: Springer, 1996
(Mikrochimica acta : Supplementum ; 13)
ISBN 978-3-211-82874-8 ISBN 978-3-7091-6555-3 (eBook)
DOI 10.1007/978-3-7091-6555-3
NE: Benoit, Daniele [Hrsg.]; Mikrochimica acta / Supplementum
ISSN 0026-3672
ISBN 978-3-211-82874-8
Preface
This supplement of Mikrochimica Acta contains selected papers from the Fourth
Workshop of the European Microanalysis Society (EMAS) on "Modern Develop
ments and Applications in Microbeam Analysis" which took place in May 1995 in
Saint Malo (France).
EMAS was founded in 1986 by members from almost all european countries in
order to stimulate research, applications and development of all forms of microbeam
methods. One important EMAS activity is the organisation of biennial workshops for
demonstrating the current status and developing trends of microanalytical techniques.
For this meeting, EMAS chose to highlight the following topics: Monte-Carlo simula
tions, transport calculations and use of soft X-rays for electron probe microanalysis
(EPMA), dynamic secondary ion mass spectrometry (SIMS), detection of small quan
tities using different techniques: synchrotron radiation X-ray fluorescence, particle in
duced X-ray emission (PIXE), cathodoluminescence microscopy (CL). Two new
kinds of instrumental techniques were also presented: atomic probe and scanning
probe microscopy (STM). The aim of the conference is to give introductory lectures
corresponding to the topics of the meeting and to have contributions in the form of po
ster sessions. More than 80 posters were presented. Most of them gave a short oral pre
sentation. The poster subjects were related to the use of microanalytical techniques:
EPMA with wavelength dispersive spectrometry (WDS) and energy dispersive spec
trometry (EDS), Auger electron spectrometry (AES), secondary ion mass spectro
metry (SIMS), scanning electron microscopy and other topographical methods like
scanning tunneling microscopy (STM) or atomic force microscopy (AFM). The field
of applications is very broad: metallurgy, mineralogy, semiconductor, ceramic, glass,
composite, polymer and biological material.
The authors originate from almost all european countries, including eastern euro
pean ones and Russia. One invited lecture was given by a USA speaker.
This issue contains the full texts of the ten introductory lectures and 50 brief arti
cles. These articles are the condensed scientific informations of the poster sessions.
They were subjected to peer-review according to the usual procedure and some of
them were rejected.
Proceedings of previous EMAS workshops were also published, either as a sup
plement to or in a regular issue of Mikrochimica Acta. We hope that these contributi
ons to the field of microbeam techniques will be found to be useful.
September 1996 The Editors
Contents
Invited Speakers
Monte Carlo Simulation Techniques for Quantitative X-Ray Microanalysis
L. Reimer ................................ 1
Transport Equation Approach to Electron Microbeam Analysis: Fundamentals
and Applications
W S. M. Werner. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 13
Use of Soft X-Rays in Microanalysis
J.-L. Pouchou ......... . 39
Intensity Measurement of Wavelength Dispersive X-Ray Emission Bands: Ap
plications to the Soft X-Ray Region
G. Remond, C. Gilles, M. Fialin, O. Rouer, R. Marinenko, R. Myklebust,
D. Newbury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
Synchrotron Radiation Induced X-ray Microfluorescence Analysis
K. Janssens, L. Vincze, B. Vekemans, A. Aerts, F. Adams, K. W Jones,
A. KnOchel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Particle-Induced X-Ray Emission - A Quantitative Technique Suitable for
Microanalysis
K. G. Malmqvist. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Cathodoluminescence Microscopy and Spectroscopy of Semiconductors and
Wide Bandgap Insulating Materials
J. F. Bresse, G. Remond, B. Akamatsu . . . . . . . . . . . . . . . . . . . . 135
Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS)
P. Bertrand, L.-T. Weng . . . . . . . . . . . . . . . . . . . . . . . . 167
Three-Dimensional Nanoanalysis with the Tomographic Atom-Probe
D. Blavette, A. Bigot, C. Schmuck, F. Danoix, P. Auger .......... 183
Microanalysis at Atomic Resolution
S. J. Pennycook, D. E. Jesson, N. D. Browning, M. F. Chisholm ...... 195
Contributed Papers
Composition of Vanadium Carbides Formed by Solidification in Fe-V-C-M
Alloys: Influence of Additions (M = AI, Cu, Mo)
L. Adnane, R. Kesri, S. Hamar-Thibault .................. 209
VIII Contents
Electron Transmission Coefficient for Oblique Angle of Incidence
M. Andrae, P. Klein, K. Rohrbacher, J. Wernisch .... . . . . . . . 217
Depth Distribution Function for Oblique Angle of Incidence
M. Andrae, K. Rohrbacher, P. Klein, J. Wernisch . . . . . . . . . . 225
Simulation of EDS Spectra Using X-RES Software
M. Aouine, C. Esnouf, T. Epicier ...... . 233
On the Use of the GeLa Line in Thin Film X-Ray Microanalysis of Si1_x Gex lSi
Heterostructures
A. Armigliato, T. Lews, R. Rosa. . . . . . . . . . . . . . . . . . . . . . . . 241
Computer Simulations ofthe X-Ray Intensity Distribution from Submicron Par
ticles Embedded in a Matrix
A. Berner, I. Levin .............................. 251
Determination of Rare Earth Elements in Biological and Mineral Apatite by
EPMA and LAMP-ICP-MS
S. Chenery, T. Williams, T. A. Elliott, P. L. Forey, L. Werdelin . . . . . . 259
Quantitative Analysis of the Compound Layer of Plasma Nitrided Pure Iron
J. D'Haen, M. D'Olieslaeger, L. De Schepper, L. M. Stals. . . . . . . . . . 271
Correction of the Edge Effect in Auger Electron Microscopy
L. Frank, F. Matejka. . . . . . . . . . . . . . . . .. .......... 279
Low Energy Imaging of N onconductive Surfaces in SEM
L. Frank, M. ZadraZil, I. Miillerova. . . . . . . . . . 289
Investigation of the Bonding Mechanism of Glass Ceramic Layers on Metal
Alloys
M. Frigge, G. Volksch . . . . . . . . . . . . . . . . . . . . . . . . . .. 299
Monte Carlo Method for Quantitative Analysis of Bulk and Layered Samples
O. Gedeon, V. Hui(nskj, K. Jurek, M. Simeekova ............. 307
SIMS Linescan Profiling of Chemically Bevelled Semiconductors: a Method of
Overcoming Ion Beam Induced Segregation in Depth Profiling
c.-M. Hsu, D. S. McPhail .......................... 317
Experimental Verification of Theoretical Models Simulating the Temperature
Increase in EPMA of Glass
V. Hui(nskj, K. Jurek, O. Gedeon ...................... 325
Quantitation of Mineral Elements of Different Fruit Pollen Grains
M. J. Bucsek, J. Nytki, Z. Szabo, A. Kadar. . . . . . . . . . . . . . . . . . 333
Electron Beam Induced Migration of Alkaline Ions in Silica Glass
K. Jurek, V. Hui(nskj, O. Gedeon .............. . 339
Application of the Boltzmann Transport Equation in the Thickness Determination
of Thin Films
G. Kaltsas, N. Glezos, E. Valamontes, A. G. Nassiopoulos. . . . . . . . . . 349
Contents IX
Characterisation of the Shape of Microparticles via Fractal and Fourier Analyses
of Scanning Electron Microscope Images
V. V. Kindratenko, P. J. M. Van Espen, B. A. Treiger, R. E. Van Grieken 355
Calculation ofthe Surface Ionisation Using Analytical Models of Electron Back
scattering
P. Klein, M. Andrae, K. Rohrbacher, J. Wernisch 363
Thickness Determination of Thin Insulating Layers
P. Klein, K. Rohrbacher, M. Andrae, J. Wernisch 377
High Energy and Angular Resolution Dynamic Secondary Ion Mass Spectro
metry
A. A. Kosyachkov 391
EPMA and Mass Spectrometry of Soil and Grass Containing Radioactivity from
the Nuclear Accident at Chernobyl
0. Lejevre, M. Betti, L. Koch, C. T. Walker. . . . . . . . . . . . . . . . . . 399
Application of a New Monte Carlo Simulation Algorithm to Electron Probe
Microanalysis
X. Llovet, A. Riveros, F. Salvat . . . . . . . . . . 409
Topography Development on Single Crystal MgO Under Ion Beam Bom-
bardment
N. J. Montgomery, D. S. McPhail ........ 419
Determination of SPM TIP Shape Using Polystyrene Latex Balls
P. Nagy, G. 1. Mark, E. Baldzs . . . . . . . . . . . . . . .. ....... 425
Combined Characterization of Nanostructures by AEM and STM
V. P. Oleshko, R. H. Gijbels, W A. Jacob, M. V. Alfimov 435
Study of Quasi-Fractal Many-Particle-Systems and Percolation Networks by
Zero-Loss Spectroscopic Imaging, Electron Energy-Loss Spectroscopy and
Digital Image Analysis
V. P. Oleshko, V. V. Kindratenko, R. H. Gijbels, P. J. M. Van Espen, W A.
Jacob 443
Calculation of Bremsstrahlung Spectra for Multilayer Samples
A. Pfeiffer, C. Schiebl, J. Wernisch . . . . . . . . . . . . . 453
Thickness Measurement of Thin Films by EPMA - Influence of ¢(O), MAC's and
Substrate
P. Polt, B. StOckl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
A Simple Procedure to Check the Spectral Response of an EDX Detector
M. Pro cop .................................. 473
Virtual WDS
S. J. B. Reed, A. Buckley 479
Monte Carlo Simulation Program with a Free Configuration of Specimen and
Detector Geometries
L. Reimer, M. Kiissens, L. Wiese 485
X Contents
Barriers to Energy Dispersive Spectrometry with Low Energy X-Rays
D. G. Rickerby . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
Measurements of Gal_xAlxAs Layers on GaAs with EDS
K. Rohrbacher, P. Klein, M. Andrae, 1. Wernisch .. 501
The Relative Intensity Factor for La Radiation Considering the Different Mass
Absorption of La and Lf3 Radiation
K. Rohrbacher, M. Andrae, P. Klein, 1. Wernisch .............. 507
Determination of the Solubility of Cerium in BaTi0 by Quantitative WDS Elec
3
tron Probe Microanalysis
Z. Samardiija, M. Ceh, D. Makovec, D. Kolar. . . . . . . . . . . . . 517
Simulation of X-Ray Diffraction Profiles of Gradually Relaxed Epilayers
A. Sanz-Hervas, E. 1. Abril, M. Aguilar, G. de Benito, C. Llorente, M.
Lopez .................................... 525
Monte Carlo Simulation of Electron Scattering for Arbitrary 2D Structures Using
a Modified Quadtree Geometry Discretization
C. 0. Schiebl, A. Pfeiffer, H. W Wagner, W s. M. Werner, H. Stippel 533
Chemical-Bond Characterization of Nanostructures by EELS
R. Schneider, 1. Woltersdorf, A. Roder . . . . . . . . . . 545
Local Determination of Carbon by Combining Beta-Autoradiography and Elec
tron Microprobe Analysis
V. G. Sen in, S. N. Shilobreeva ........................ 553
The Check of the Elastic Scattering Model in Monte-Carlo Simulation
V. Stary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .... 559
True Colour X-Ray Vision for Electron Microscopy and Microanalysis
P. 1. Statham. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
Determination of the Oxidation States of Nb by Auger Electron Spectroscopy
Z. Tass, G. Horvath. . . . . . . . . . . . . . . . . . . . . . . . . . .. . 581
Study by SIMS of the 54Cr and 180 Diffusion in Cr2 0 3 and in Cr203 Scales
S. C. Tsai, A. M. Huntz, C. Dolin, C. Monty .............. 587
Comparison of Back- Foil Scanning X -Ray Microftuorescence and Electron Probe
X-Ray Microanalysis for the Elemental Characterisation of Thin Coatings
E. Valamontes, A. G. Nassiopoulos. . . . . . . . . . . . . . . . . . . . . . 597
Electron Probe X-Ray Microanalysis of Coatings
E. Valamontes, A. G. Nassiopoulos. . . . . . 605
Analysis of Layers: X-Ray Maps of Change in Thickness Obtained by Electron
Macroprobe
D. Viale, G. Petitgand ............................ 611
Comparison of Simulated and Experimental Auger Intensities of Au, Pt, Ni and Si
in Absolute Units
H. W Wagner, C. O. Schiebl, W S. M. Werner . . . . . . . . . . . . . . . . 623
Practical Aspects and Applications of EPMA at Low Electron Energies
P Willich, R. Bethke. . . . . . . . . . . . . . . . . . . . . . . .. .... 631
Oxidation and Reduction Processes of Be/BeO Induced by Electrons
P Zanel, H. Hammer ............................ 639
Listed in Current Contents
Mikrochim. Acta [Supp!.] 13, 1-12 (1996)
© Springer-Verlag 1996
Monte Carlo Simulation Techniques
for Quantitative X-Ray Microanalysis
Ludwig Reimer
Physikalisches Institut, Universitat Munster, Wilhelm-Klemm Str. 10, D-48149 Munster, Federal
Republic of Germany
Abstract. Monte Carlo simulations of electron diffusion become of increasing
interest for scanning electron microscopy (SEM), X-ray microanalysis (XRMA)
and Auger electron spectroscopy (AES) due to the increasing speed and storage
capability of modern PCs. Depth distribution functions can be calculated in less
than a minute also for complex specimen structures. To apply Monte Carlo
simulations in the energy range of0.1-50keV it is necessary to use a data base
of Mott elastic cross-sections calculated by the partial-wave method. For most
applications it is sufficient to consider inelastic scattering by the Bethe
continous-slowing-down approximation and inner-shell ionisations with energy
losses larger than 100-200eV by the Gryzinski cross-section. In future,
energy-loss functions obtained by a Kramers-Kronig analysis of experimental
electron energy-loss spectra (EELS) will become of interest for a better
consideration of straggling effects during the slowing-down.
Key words: Monte Carlo simulation, electron scattering, X-ray microanalysis,
scanning electron microscopy.
We need for the X-ray microanalysis (XRMA) with 1-50 ke V electrons the depth
distribution functions lI>(pz) of ionizing the corresponding inner atomic shells to
calculate the ratio
(1)
of X-ray counts from an element (a) in the specimen and a pure-element or
compound standard (s) with the ZAF factors for atomic mumber, absorption and
fluorescence correction, respectively. This allows to calculate the fraction calc of
s
mass concentrations from the measured ratio NaiNs of X-ray counts.
The depth distribution function is strongly influenced by the electron diffusion
which can be described by a Boltzmann transport equation but not by an analytical
solution. In case of plane surfaces and multilayers on substrates the transport
equation can be simplified because the number of orginally 7 coordinates reduces
to 3, one z coordinate (depth below surface), one angle 8 relative to the surface
z
