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Title: Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}

Abstract

KSb{sub 5}S{sub 8} and its solid solution analogs with Rb and Tl were found to exhibit a reversible and tunable glass{sup {yields}}crystal{sup {yields}}glass phase transition. Selected members of this series were analyzed by differential scanning calorimetry to measure the effect of the substitution on the thermal properties. The solid solutions K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} exhibited clear deviations in melting and crystallization behavior and temperatures from the parent structure. The crystallization process of the glassy KSb{sub 5}S{sub 8} as a function of temperature could clearly be followed with Raman spectroscopy. The thermal conductivity of both glassy and crystalline KSb{sub 5}S{sub 8} at room temperature is {approx}0.40 W/m K, among the lowest known values for any dense solid-state material. Electronic band structure calculations carried out on KSb{sub 5}S{sub 8} and TlSb{sub 5}S{sub 8} show the presence of large indirect band-gaps and confirm the coexistence of covalent Sb-S bonding and predominantly ionic K(Tl)...S bonding. Pair distribution function analyses based on total X-ray scattering data on both crystalline and glassy K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} showed that the basic structure-defining unit is the same and it involves a distorted polyhedron of 'SbS{sub 7}'more » fragment of {approx}7 A diameter. The similarity of local structure between the glassy and crystalline phases accounts for the facile crystallization rate in this system. - Graphical abstract: The KSb{sub 5}S{sub 8} is a good example of a phase-change material with a mixed ionic/covalent bonding. The members of the K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} series exhibit phase-change properties with greater glass forming ability (GFA) than KSb{sub 5}S{sub 8}. The GFA increases with increasing Rb content. In this case, the random alloy disorder in the alkali metal sublattice seems to predominate over the increased degree of ionicity in going from K...S to Rb...S bonding and works to stabilize the glass forms in K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}.« less

Authors:
 [1];  [2];  [3];  [1];  [3];  [1];  [2];  [4];  [5];  [5];  [6]
  1. Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States)
  2. Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)
  3. Department of Physics, Central Michigan University, Mount Pleasant, MI 48859 (United States)
  4. Department of Physics, Michigan State University, East Lansing, MI 48824 (United States)
  5. Institut fuer Physikalische Chemie, Westf. Wilhelms-Universitaet Muenster (Germany)
  6. Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States), E-mail: m-kanatzidis@northwestern.edu
Publication Date:
OSTI Identifier:
21015666
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2006.10.027; PII: S0022-4596(06)00567-6; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIMONY COMPOUNDS; CALORIMETRY; CRYSTALLIZATION; DISTRIBUTION FUNCTIONS; GLASS; MELTING; PHASE CHANGE MATERIALS; POTASSIUM COMPOUNDS; RAMAN SPECTROSCOPY; RUBIDIUM COMPOUNDS; SODIUM COMPOUNDS; SOLID SOLUTIONS; SULFIDES; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0273-0400 K; THERMAL CONDUCTIVITY; X-RAY DIFFRACTION

Citation Formats

Wachter, J.B., Chrissafis, K., Petkov, V., Malliakas, C.D., Bilc, D., Kyratsi, Th., Paraskevopoulos, K.M., Mahanti, S.D., Torbruegge, T., Eckert, H., and Kanatzidis, M.G. Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.10.027.
Wachter, J.B., Chrissafis, K., Petkov, V., Malliakas, C.D., Bilc, D., Kyratsi, Th., Paraskevopoulos, K.M., Mahanti, S.D., Torbruegge, T., Eckert, H., & Kanatzidis, M.G. Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}. United States. doi:10.1016/j.jssc.2006.10.027.
Wachter, J.B., Chrissafis, K., Petkov, V., Malliakas, C.D., Bilc, D., Kyratsi, Th., Paraskevopoulos, K.M., Mahanti, S.D., Torbruegge, T., Eckert, H., and Kanatzidis, M.G. Thu . "Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}". United States. doi:10.1016/j.jssc.2006.10.027.
@article{osti_21015666,
title = {Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}},
author = {Wachter, J.B. and Chrissafis, K. and Petkov, V. and Malliakas, C.D. and Bilc, D. and Kyratsi, Th. and Paraskevopoulos, K.M. and Mahanti, S.D. and Torbruegge, T. and Eckert, H. and Kanatzidis, M.G.},
abstractNote = {KSb{sub 5}S{sub 8} and its solid solution analogs with Rb and Tl were found to exhibit a reversible and tunable glass{sup {yields}}crystal{sup {yields}}glass phase transition. Selected members of this series were analyzed by differential scanning calorimetry to measure the effect of the substitution on the thermal properties. The solid solutions K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} exhibited clear deviations in melting and crystallization behavior and temperatures from the parent structure. The crystallization process of the glassy KSb{sub 5}S{sub 8} as a function of temperature could clearly be followed with Raman spectroscopy. The thermal conductivity of both glassy and crystalline KSb{sub 5}S{sub 8} at room temperature is {approx}0.40 W/m K, among the lowest known values for any dense solid-state material. Electronic band structure calculations carried out on KSb{sub 5}S{sub 8} and TlSb{sub 5}S{sub 8} show the presence of large indirect band-gaps and confirm the coexistence of covalent Sb-S bonding and predominantly ionic K(Tl)...S bonding. Pair distribution function analyses based on total X-ray scattering data on both crystalline and glassy K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} showed that the basic structure-defining unit is the same and it involves a distorted polyhedron of 'SbS{sub 7}' fragment of {approx}7 A diameter. The similarity of local structure between the glassy and crystalline phases accounts for the facile crystallization rate in this system. - Graphical abstract: The KSb{sub 5}S{sub 8} is a good example of a phase-change material with a mixed ionic/covalent bonding. The members of the K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} series exhibit phase-change properties with greater glass forming ability (GFA) than KSb{sub 5}S{sub 8}. The GFA increases with increasing Rb content. In this case, the random alloy disorder in the alkali metal sublattice seems to predominate over the increased degree of ionicity in going from K...S to Rb...S bonding and works to stabilize the glass forms in K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}.},
doi = {10.1016/j.jssc.2006.10.027},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 180,
place = {United States},
year = {Thu Feb 15 00:00:00 EST 2007},
month = {Thu Feb 15 00:00:00 EST 2007}
}