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Measurement and Calculation of X-Ray Production Efficiencies for Copper, Zirconium, and Tungsten

Published online by Cambridge University Press:  12 September 2022

Mathias Procop*
Affiliation:
Division 6.1 Surface Analysis and Interfacial Chemistry, Federal Institute for Materials Research and Testing (BAM), Berlin 12205, Germany
Ralf Terborg
Affiliation:
Bruker Nano GmbH, Am Studio 2D, Berlin 12489, Germany
*
*Corresponding author: Mathias Procop, E-mail: [email protected]
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Abstract

Electron probe microanalysis (EPMA) is based on physical relations between measured X-ray intensities of characteristic lines and their X-ray production efficiency, which depends on the specimen composition. The quality of the analysis results relies on how realistically the physical relations describe the generation and emission of X-rays. Special experiments are necessary to measure X-ray production efficiencies. A challenge in these experiments is the determination of the detection efficiency of the spectrometer as a function of the photon energy. An energy-dispersive spectrometer was used in this work, for which the efficiency was determined at metrological synchrotron beamlines with an accuracy of ±2%. X-ray production efficiencies for the L series and the Kα series of copper and zirconium and for the M and L series of tungsten were determined at energies up to 30 keV in a scanning electron microscope. These experimental values were compared with calculated X-ray production efficiencies using physical relations and material constants applied in EPMA. The objective of the comparison is the further improvement of EPMA algorithms as well as extending the available database for X-ray production efficiencies. Experimental data for the X-ray production efficiency are also useful for the assessment of spectrum simulation software.

Type
Materials Science Applications
Copyright
Copyright © The Author(s), 2022. Published by Cambridge University Press on behalf of the Microscopy Society of America

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Footnotes

Retired.

References

Acosta, E, Llovet, X, Coleoni, E, Riveros, JA & Salvat, F (1998). Monte Carlo simulation of X-ray emission by kilovolt electron bombardment. J Appl Phys 83, 60386049.CrossRefGoogle Scholar
Alvisi, M, Blome, M, Griepentrog, M, Hodoroaba, V-D, Karduck, P, Mostert, M, Nacchuchi, M, Procop, M, Rohde, M, Scholze, F, Statham, P, Terborg, R & Thiot, J-F (2006). The determination of the efficiency of energy dispersive X-ray spectrometers by a new reference material. Microsc Microanal 12, 406415.CrossRefGoogle ScholarPubMed
Bastin, GF, Dijkstra, JM & Heijligers, JM (1998). PROZA96: An improved matrix correction program for electron probe microanalysis, based on a double Gaussian ϕ(ρz) approach. X-Ray Spectrom 27, 310.3.0.CO;2-L>CrossRefGoogle Scholar
Bethe, H (1930). Zur Theorie des Durchganges schneller Korpuskularstrahlen durch Materie. Annalen Physik 5 (Folge 5), 325400.CrossRefGoogle Scholar
Bethe, H & Ashkin, J (1953). Passage of radiation through matter. Exp Nucl Phys 1, 252254.Google Scholar
Bote, D, Llovet, X & Salvat, F (2008). Monte Carlo simulation of characteristic X-ray emission from thick samples bombarded by kiloelectronvolt electrons. J Phys D Appl Phys 41, 19.CrossRefGoogle Scholar
Bote, D & Salvat, F (2008). Calculations of inner shell ionization by electron impact with the distorted-wave and plane-wave born approximation. Phys Rev A 77, 042701-1042701-24.CrossRefGoogle Scholar
Bote, D, Salvat, F, Jablonski, A & Powell, CJ (2009). Cross sections for ionization of K, L and M shells of atoms by impact of electrons and positrons with energies up to 1 GeV: Analytical formulas. At Data Nucl Data Tables 95, 871909.CrossRefGoogle Scholar
Casnati, E, Tartari, A & Baraldi, C (1982). An empirical approach to K-shell ionisation cross section by electrons. J Phys B 15, 155167.CrossRefGoogle Scholar
Elam, WT, Ravel, BD & Sieber, JR (2002). A new atomic database for X-ray spectroscopic calculations. Radiat Phys Chem 63, 121128. Available at https://www.nist.gov/mml/csd/inorganic-measurement-science/resources/xrf-downloadsCrossRefGoogle Scholar
Gauvin, R, Lifshin, E, Demers, H, Horny, P & Campbell, H (2003). Win X-ray, The Monte Carlo program for X-ray microanalysis in the scanning electron microscope. Microsc Microanal 9(S02), 3233.CrossRefGoogle Scholar
Green, M & Cosslett, VE (1968). Measurements of K, L and M shell X-ray production efficiencies. Br J Appl Phys (J Phys D) Ser 2 1, 425436.CrossRefGoogle Scholar
Henke, BL, Gullikson, EM & Davis, JC (1993). X-ray interactions: Photoabsorption, scattering, transmission, and reflection at E=50-30000 eV, Z=1−92. At Data Nucl Data Tables 54, 181342. Available at https://henke.lbl.gov/optical_constants/CrossRefGoogle Scholar
Jablonski, A, Tanuma, S & Powel, JC (2008). Modified predictive formula for the electron stopping power. J Appl Phys 103, 063708-1063708-11.CrossRefGoogle Scholar
Joy, DC (1995). A database on electron-solid interactions. Scanning 17, 270275.CrossRefGoogle Scholar
Joy, DC (1998). The efficiency of X-ray production at low energies. J Microsc 191, 7482.CrossRefGoogle ScholarPubMed
Joy, DC & Luo, S (1989). An empirical stopping power relationship for low-energy electrons. Scanning 11, 176180.CrossRefGoogle Scholar
Kolbe, M, Hönicke, P, Müller, M & Beckhoff, B (2012). L-subshell fluorescence yields and Coster-Kronig transition probabilities with a reliable uncertainty budget for selected high- and medium-Z elements. Phys Rev A 86, 042512-1042512-12.CrossRefGoogle Scholar
Kramers, HA (1923). On the theory of X-ray absorption and of the continuous X-ray spectrum. Philos Mag 46, 836871.CrossRefGoogle Scholar
Krause, MO (1979). Atomic radiative and radiationless yields for K and L shells. J Phys Chem Ref Data 8, 307327.CrossRefGoogle Scholar
Lépy, MC, Plagnard, J, Stemmler, P, Ban, G, Beck, L & Dhez, P (1997). Si(Li) detector efficiency and peak shape calibration in the low energy range using synchrotron radiation. X-Ray Spectrom 26, 195202.3.0.CO;2-5>CrossRefGoogle Scholar
Lifshin, EC (1980). New measurements of the voltage dependence of absolute X-ray yields. In Proceedings. 8th ICXOM, Beaman DO (Ed.), pp. 141–148. Midland, MI: Pendell Publishers.Google Scholar
Llovet, X, Moy, A, Pinard, P, & Fournell, T & H, J (2021). Electron probe microanalysis: A review of recent developments and applications in materials science and engineering. Prog Mater Sci 116, 100673-1100673-90.CrossRefGoogle Scholar
Llovet, X, Powell, CJ, Salvat, F & Jablonsky, A (2014). Cross sections for inner-shell ionization by electron impact. J Phys Chem Ref Data 43, 013102-1013102-105.CrossRefGoogle Scholar
Maenhaut, W & Raemdonck, H (1984). Accurate calibration of a Si(Li) detector for PIXE analysis. Nucl Instrum Methods B 1, 123136.CrossRefGoogle Scholar
Ménesguen, Y, Gerlach, M, Pollakowski, B, Unterumsberger, R, Haschke, M, Beckhoff, B & Lépy, M-C (2016). High accuracy experimental determination of copper and zinc mass attenuation coefficients in the 100 eV to 30 keV photon energy range. Metrologia 53, 717.CrossRefGoogle Scholar
Merlet, C & Llovet, X (2006). Absolute determination of characteristic X-ray yields with a wavelength-dispersive spectrometer. Microchim Acta 155, 199204.CrossRefGoogle Scholar
Merlet, C, Llovet, X & Salvat, F (2004). Measurements of absolute K-shell ionization cross sections and L-shell x-ray production cross sections of Ge by electron impact. Phys Rev A 69, 032708-1032708-8.CrossRefGoogle Scholar
Moy, A & Fournelle, J (2021). Φ(ρz) distributions in bulk and thin film samples for EPMA. Part 1: A modified Φ(ρz) distribution for bulk materials, including characteristic and bremsstrahlung fluorescence. Microsc Microanal 27, 266283.CrossRefGoogle ScholarPubMed
Moy, A, Merlet, C & Dugne, O (2015). Standardless quantification of heavy elements by electron probe microanalysis. Anal Chem 87, 77797786.CrossRefGoogle ScholarPubMed
Nasir, MJ (1976). X-ray analysis without the need for standards. J Microsc 108(Pt. 1), 7987.CrossRefGoogle Scholar
Nuclear Energy Agency (2019). PENELOPE 2018: A Code System for Monte Carlo Simulation of Electron and Photon Transport. Barcelona, Spain: OECD Publishing. doi:10.1787/32da5043-enGoogle Scholar
Pinard, PT, Protheroe, A, Holland, J, Burgess, S & Statham, PJ (2020). Development and validation of standardless and standard-based X-ray microanalysis. IOP Conf Series 891, 112.Google Scholar
Pouchou, J-L (1994). Standardless X-ray analysis of bulk specimens. Mikrochim Acta 114/115, 3352.CrossRefGoogle Scholar
Pouchou, JL & Pichoir, F (1991). Quantitative analysis of homogeneous or stratified microvolumes applying the model “PAP”. In Electron Probe Quantitation, Heinrich, KF & Newbury, DE (Eds.), pp. 3165. New York: Plenum Press.CrossRefGoogle Scholar
Powell, CJ (1976). Cross sections for ionization of inner-shell electrons by electron impact. J Vac Sci Technol 13, 219220.CrossRefGoogle Scholar
Procop, M (2004). Measurement of X-ray emission efficiency for K-lines. Microsc Microanal 10, 481490.CrossRefGoogle ScholarPubMed
Procop, M & Hodoroaba, V-D (2008). X-ray fluorescence as an additional analytical method for a scanning electron microscope. Microchim Acta 161, 413419.CrossRefGoogle Scholar
Procop, M & Scholze, F (2004). Synchrotron radiation for the characterization of energy dispersive X-ray spectrometers. Microsc Microanal 10(Suppl 2), 9899 .CrossRefGoogle Scholar
Procop, M & Scholze, F (2008). Calibration of the detection efficiency of energy dispersive X-ray spectrometers for absolute intensity measurements and for establishing a basis for a more rigorous quantitation procedure. Microsc Microanal 14(Suppl 2), 11581159.CrossRefGoogle Scholar
Rabus, H, Scholze, F, Thornagel, R & Ulm, G (1996). Detector calibration at the PTB radiometry laboratory at BESSY. Nucl Instrum Methods A 377, 209216.CrossRefGoogle Scholar
Reed, SJ (1993). Electron Microprobe Analysis, 2nd ed. Cambridge, UK: Cambridge University Press.Google Scholar
Ritchie, NW (2009). Spectrum simulation in DTSA-II. Microsc Microanal 15, 454468.CrossRefGoogle ScholarPubMed
Röhrbacher, K, Andrae, MV & Wernisch, J (1998). Efficiency calibration of a Si(Li) detector by EPMA. In Modern Development and Application in Microbeam Analysis, 15, Love, G, Nicholson, WA & Armigliato, A (Eds.), pp. 2128. Microchimica Acta. Vienna: SpringerCrossRefGoogle Scholar
Scholze, F, Krumrey, M, Müller, P & Fuchs, D (1994). Plane grating monochromator beamline for VUV radiometry. Rev Sci Instrum 65, 32293232.CrossRefGoogle Scholar
Scholze, F & Procop, M (2001). Measurement of detection efficiency and response functions for an Si(Li) X-ray spectrometer in the range 0.1–5 keV. X-Ray Spectrom 30, 6976.CrossRefGoogle Scholar
Schwinger, J (1949). On the classical radiation of accelerated electrons. Phys Rev 75, 19121925.CrossRefGoogle Scholar
Shima, K, Okuda, E, Suzuki, T, Tsubota, T & Mikumo, T (1983). Lα X-ray production efficiency from Z = 50−82 thick target elements by electron impact from threshold energy to 30 keV. J Appl Phys 54, 12021208.CrossRefGoogle Scholar
Statham, P (2009). Prospects for single standard quantitative analysis with SDD. Microsc Microanal 15(Suppl 2), 528529.CrossRefGoogle Scholar
Subbotin, AN, Gaganov, VV, Kalutzsky, AV, Pindyurin, VF, Nazmov, VP, Nikolenko, AD & Krasnov, AK (2000). Absolute calibration of X-ray semiconductor detectors against synchrotron radiation of the VEPP-3 storage ring. Metrologia 37, 497500.CrossRefGoogle Scholar
Tanuma, S, Powell, CJ & Penn, DR (1994). Calculation of electron inelastic mean free paths V. Surf Interface Anal 21, 165176.CrossRefGoogle Scholar
Wernisch, J (1985). Quantitative electron microprobe analysis without standard samples. X-Ray Spectrom 14, 109119.CrossRefGoogle Scholar
Yadav, N, Bhatt, P, Singh, R, Llovet, X & Shanker, R (2011). Study of K-line radiation of thick titanium produced in collisions of keV electrons. Appl Radiat Isot 69, 13801384.CrossRefGoogle ScholarPubMed
Yadav, N, Bhatt, P, Singh, R, Llovet, X & Shanker, R (2012). Total M-shell X-ray yields from a thick Pt target irradiated by 10–25 keV electrons. J Electron Spectrosc Relat Phenom 185, 2326.CrossRefGoogle Scholar