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Enabling electron-energy-loss spectroscopy at very high energy losses: An opportunity to obtain x-ray absorption spectroscopy–like information using an electron microscope

Sorin Lazar1,*, Peter Tiemeijer1, Claudia S. Schnohr2, Maria Meledina1, Christian Patzig3, Thomas Höche3, Paolo Longo1, and Bert Freitag1

  • *Contact author: sorin.lazar@thermofisher.com
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Phys. Rev. Applied 23, 054095 – Published 30 May, 2025

DOI: https://doi.org/10.1103/PhysRevApplied.23.054095

Abstract

Electron-energy-loss spectroscopy (EELS) with an electron microscope and X-ray absorption spectroscopy (XAS) with a synchrotron are techniques for material characterization, both of which are based on exciting core electrons. Both techniques have a similar energy resolution, but while the spatial resolution of EELS can drop to atomic scales, the spatial resolution of XAS is typically limited to micrometer scales. Yet, XAS is commonly the preferred technique for analysis of the extended fine structure of ionization edges, mainly thanks to the excellent signal-to-noise ratio and the large range of ionization energies (from ∼5 to ∼40 keV) that can be probed at synchrotron end stations. In contrast, EELS is traditionally limited to ionization energies of ≲2 keV because electrons in the beam that lose more than 2 keV will be too distant from the operating energy of the electron microscope. Chromatic effects in the postsample lenses allow only some of such energy-loss electrons to reach the EELS detector, as the latter electrons will either suffer from being strongly defocused or will not make it to the detector at all. In this paper, we present results from our novel Iliad EELS spectrometer, which offers a greatly increased range of ionization energies up to 30 keV. We achieve this vast increase by carefully controlling the optics of our electron microscope and carefully matching the optics of our EELS spectrometer to it, such that all the chromatic effects are removed or compensated. We exemplify its performance by recording EELS near-edge fine structure (ELNES) of the Zr L-edges at 2.3 keV, extended fine structure EELS (EXELFS) of Cu K-edge at ∼9 keV, and EELS of the Mo K-edge at 20 keV and Sb K-edge at ∼30 keV. We benchmark our data against near-edge and extended fine structure X-ray absorption (XANES and EXAFS) data, and we quantitatively analyze the Cu K-edge EXELFS, demonstrating the capability to determine element-specific bond lengths and to distinguish different oxidation states such as metallic Cu, Cu2O, or CuO on a submicrometer scale.

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References (24)

  1. D. E. Sayers, E. A. Stern, and F. W. Lytle, New technique for investigating noncrystalline structures: Fourier analysis of the extended x-ray—absorption fine structure, Phys. Rev. Lett. 27, 1204 (1971).
  2. S. Calvin, XAFS for Everyone (CRC Press, Taylor & Francis Group, Boca Raton, 2013).
  3. A. J. Craven, H. Sawada, S. McFadzean, and I. MacLaren, Getting the most out of a post-column EELS spectrometer on a TEM/STEM by optimizing the optical coupling, Ultramicroscopy 180, 66 (2017).
  4. I. MacLaren, K. J. Annand, C. Black, and A. J. Craven, EELS at very high energy losses, Microscopy 6 (Issue suppl_1), i78 (2018).
  5. I. MacLaren, R. B. Cummings, F. Gordon, E. Frutos-Myro, S. McFadzean, A. P. Brown, and A. J. Craven, Performing EELS at higher energy losses at both 80 and 200 kV, Adv. Imaging Electron Phys. 210, 345 (2019).
  6. J. L. Hart, A. C. Lang, S. Shahrezaei, D. D. Alix-Williams, M. L. Falk, S. N. Mathaudhu, A. I. Frenkel, and M. L. Taheri, Revealing local order via high energy EELS, Mater. Today Nano 21, 100298 (2023).
  7. D. Bach, R. Schneider, D. Gerthsen, J. Verbeeck, and W. Sigle, EELS of niobium and stoichiometric niobium-oxide phases-part I: plasmon and near-edges fine structure, Microsc. Microanal. 15, 505 (2009).
  8. C. Patzig, T. Höche, M. Dittmer, and C. Rüssel, Temporal evolution of crystallization in MgO–Al2O3–SiO2–ZrO2 glass ceramics, Cryst. Growth Des. 12, 2059 (2012).
  9. S. Seidel, C. Patzig, T. Höche, M. Krause, M. Ebert, Y. Hu, L. Zuin, A. Gawronski, and C. Rüssel, The crystallization of MgO–Al2O3–SiO2–ZrO2 glass-ceramics with and without the addition of Y2O3 – a combined STEM/XANES study, RSC Adv. 6, 62934 (2016).
  10. C. Patzig, T. Höche, Y. Hu, H. Ikeno, M. Krause, M. Dittmer, A. Gawronski, C. Rüssel, I. Tanaka, and G. S. Henderson, Zr coordination change during crystallization of MgO–Al2O3–SiO2–ZrO2 glass ceramics, J. Non-Cryst. Solids 384, 47 (2014).
  11. R. C. Garvie, Stabilization of the tetragonal structure in zirconia microcrystals, J. Phys. Chem. 69, 1238 (1965).
  12. A. G. Evans and R. M. Cannon, Toughening of ceramics by martensitic transformations, Acta Metall. 34, 761 (1986).
  13. R. J. Brook, in Advances in Ceramics: Science and Technology of Zirconia, edited by A. H. Heuer, and L. W. Hobbs (American Ceramic Society, Columbus, Ohio, 1981), Vol. 3.
  14. B. Ravel and M. Newville, ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT, J. Synchrotron Radiat. 12, 537 (2005).
  15. https://bruceravel.github.io/demeter/documents/Athena/index.html
  16. E. Welter, R. Chernikov, M. Herrmann, and R. Nemausat, A beamline for bulk sample x-ray absorption spectroscopy at the high brilliance storage ring PETRA III, AIP Conf. Proc. 2054, 040002 (2019).
  17. J. J. Rehr, J. J. Kas, F. D. Vila, M. P. Prange, and K. Jorissen, Parameter-free calculations of x-ray spectra with FEFF9, Phys. Chem. Chem. Phys. 12, 5503 (2010).
  18. M. E. Straumanis and L. S. Yu, Lattice parameters, densities, expansion coefficients and perfection of structure of Cu and of Cu–In α phase, Acta Crystallogr., Sect. A 25, 676 (1969).
  19. B. K. Meyer, A. Polity, D. Reppin, M. Becker, P. Hering, P. J. Klar, Th. Sander, C. Reindl, J. Benz, M. Eickhoff, et al., Binary copper oxide semiconductors: From materials towards devices, Phys. Status Solidi B 249, 1487 (2012).
  20. S. Åsbrink and L.-J. Norrby, A refinement of the crystal structure of copper (II) oxide with a discussion of some exceptional E.s.d.’s, Acta Crystallogr., Sect. B 26, 8 (1970).
  21. Crystal Structures, 2nd ed. (Interscience Publishers, New York, New York., 1963), Vol. 1, pp.7–83.
  22. E. Ghorbani, M. Schiller, H. H. Falk, L. A. Wägele, S. Eckner, F. d’Acapito, R. Scheer, K. Albe, and C. S. Schnohr, Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations, J. Phys. Energy 5, 035003 (2023).
  23. XAFS Database, Materials Data Repository (MDR), National Institute for Materials Science (NIMS), Japan. https://doi.org/10.48505/nims.2052
  24. XAFS Database, Materials Data Repository (MDR), National Institute for Materials Science (NIMS), Japan. https://doi.org/10.48505/nims.2617

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Phys. Rev. Applied 23, 054095– Published 30 May, 2025
  • Received 6 November 2024
  • Accepted 10 February 2025
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