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Title: Structural phase transition and phonon instability in Cu12Sb4S13

Abstract

In this study, a structural phase transition has been discovered in the synthetic tetrahedrite Cu12Sb4S13 at approximately 88 K. Upon cooling, the material transforms from its known cubic symmetry to a tetragonal unit cell that is characterized by an in-plane ordering that leads to a doubling of the unit cell volume. Specific heat capacity measurements demonstrate a hysteresis of more than two degrees in the associated anomaly. A similar hysteresis was observed in powder x-ray diffraction measurements, which also indicate a coexistence of the two phases, and together these results suggest a first-order transition. This structural transition coincides with a recently-reported metal-insulator transition, and the structural instability is related to the very low thermal conductivity κ in these materials. Inelastic neutron scattering was used to measure the phonon density of states in Cu12Sb4S13 and Cu10Zn2Sb4S13, both of which possess a localized, low-energy phonon mode associated with strongly anharmonic copper displacements that suppress κ. In Cu12Sb4S13, signatures of the phase transition are observed in the temperature dependence of the localized mode, which disappears at the structural transition. In contrast, in the cubic Zn-doped material, the mode is at slightly higher-energy but observable for all temperatures, though it softens upon cooling.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC); Energy Frontier Research Centers (EFRC) (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1238019
Alternate Identifier(s):
OSTI ID: 1237391
Grant/Contract Number:  
AC05-00OR22725; SC0001299; SC0001054
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 93; Journal Issue: 6; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

May, Andrew F., Delaire, Olivier A., Niedziela, Jennifer L., Lara-Curzio, Edgar, Susner, Michael A., Abernathy, Douglas L., Kirkham, Melanie J., and McGuire, Michael A. Structural phase transition and phonon instability in Cu12Sb4S13. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.93.064104.
May, Andrew F., Delaire, Olivier A., Niedziela, Jennifer L., Lara-Curzio, Edgar, Susner, Michael A., Abernathy, Douglas L., Kirkham, Melanie J., & McGuire, Michael A. Structural phase transition and phonon instability in Cu12Sb4S13. United States. doi:10.1103/PhysRevB.93.064104.
May, Andrew F., Delaire, Olivier A., Niedziela, Jennifer L., Lara-Curzio, Edgar, Susner, Michael A., Abernathy, Douglas L., Kirkham, Melanie J., and McGuire, Michael A. Mon . "Structural phase transition and phonon instability in Cu12Sb4S13". United States. doi:10.1103/PhysRevB.93.064104. https://www.osti.gov/servlets/purl/1238019.
@article{osti_1238019,
title = {Structural phase transition and phonon instability in Cu12Sb4S13},
author = {May, Andrew F. and Delaire, Olivier A. and Niedziela, Jennifer L. and Lara-Curzio, Edgar and Susner, Michael A. and Abernathy, Douglas L. and Kirkham, Melanie J. and McGuire, Michael A.},
abstractNote = {In this study, a structural phase transition has been discovered in the synthetic tetrahedrite Cu12Sb4S13 at approximately 88 K. Upon cooling, the material transforms from its known cubic symmetry to a tetragonal unit cell that is characterized by an in-plane ordering that leads to a doubling of the unit cell volume. Specific heat capacity measurements demonstrate a hysteresis of more than two degrees in the associated anomaly. A similar hysteresis was observed in powder x-ray diffraction measurements, which also indicate a coexistence of the two phases, and together these results suggest a first-order transition. This structural transition coincides with a recently-reported metal-insulator transition, and the structural instability is related to the very low thermal conductivity κ in these materials. Inelastic neutron scattering was used to measure the phonon density of states in Cu12Sb4S13 and Cu10Zn2Sb4S13, both of which possess a localized, low-energy phonon mode associated with strongly anharmonic copper displacements that suppress κ. In Cu12Sb4S13, signatures of the phase transition are observed in the temperature dependence of the localized mode, which disappears at the structural transition. In contrast, in the cubic Zn-doped material, the mode is at slightly higher-energy but observable for all temperatures, though it softens upon cooling.},
doi = {10.1103/PhysRevB.93.064104},
journal = {Physical Review B},
number = 6,
volume = 93,
place = {United States},
year = {2016},
month = {2}
}

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