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Semiconductor Clathrates: In Situ Studies of Their High Pressure, Variable Temperature and Synthesis Behavior

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The Physics and Chemistry of Inorganic Clathrates

Part of the book series: Springer Series in Materials Science ((SSMATERIALS,volume 199))

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Abstract

In situ studies have provided valuable new information on the synthesis mechanisms, low temperature properties and high pressure behavior of semiconductor clathrates. Here we review work using synchrotron and laboratory X-ray diffraction and Raman scattering used to study mainly Si-based clathrates under a variety of conditions. During synthesis of the Type I clathrate Na8Si46 by metastable thermal decomposition from NaSi in vacuum, we observe an unusual quasi-epitaxial process where the clathrate structure appears to nucleate and grow directly from the Na-deficient Zintl phase surface. Low temperature X-ray studies of the guest-free Type II clathrate framework Si136 reveal a region of negative thermal expansion behavior as predicted theoretically and analogous to that observed for diamond-structured Si. High pressure studies of Si136 lead to metastable production of the β-Sn structured Si-II phase as well as perhaps other metastable crystalline materials. High pressure investigations of Type I clathrates show evidence for a new class of apparently isostructural densification transformations followed by amorphization in certain cases.

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Authors and Affiliations

  1. Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon, 69622, Villeurbanne Cedex, France

    D. Machon & A. San-Miguel

  2. Christopher Ingold Laboratories, Department of Chemistry and Materials Chemistry Centre, University College London, 20 Gordon Street, London, WC1H 0AJ, UK

    P. F. McMillan

  3. Dept. Crystallography, School of Biological Sciences, Birkbeck College, Malet Street, London, WC1E 7HX, UK

    P. Barnes

  4. Infineum Business and Technology Centre, Infineum UK Ltd., P.O. Box 1, Milton Hill, Abingdon, OX13 6AE, UK

    P. T. Hutchins

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  1. D. Machon
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  1. Dept. of Physics, ISA 2019, University of South Florida, Tampa, Florida, USA

    George S. Nolas

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Machon, D., McMillan, P.F., San-Miguel, A., Barnes, P., Hutchins, P.T. (2014). Semiconductor Clathrates: In Situ Studies of Their High Pressure, Variable Temperature and Synthesis Behavior. In: Nolas, G. (eds) The Physics and Chemistry of Inorganic Clathrates. Springer Series in Materials Science, vol 199. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-9127-4_4

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