Structural phase transition and phonon instability in Cu12Sb4S13

May, Andrew F.; Delaire, Olivier A.; Niedziela, Jennifer L.; Lara-Curzio, Edgar; Susner, Michael A.; Abernathy, Douglas L.; Kirkham, Melanie J.; McGuire, Michael A.

doi:10.1103/PhysRevB.93.064104

Title: Structural phase transition and phonon instability in Cu₁₂Sb₄S₁₃

Journal Article · Mon Feb 08 00:00:00 EST 2016 · Physical Review B

DOI:https://doi.org/10.1103/PhysRevB.93.064104· OSTI ID:1238019

May, Andrew F. ^[1]; Delaire, Olivier A. ^[1]; Niedziela, Jennifer L. ^[1]; Lara-Curzio, Edgar ^[1]; Susner, Michael A. ^[1]; Abernathy, Douglas L. ^[1]; Kirkham, Melanie J. ^[1]; McGuire, Michael A. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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.

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Research Organization:: Oak Ridge National Laboratory (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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; SC0001299; SC0001054

OSTI ID:: 1238019

Alternate ID(s):: OSTI ID: 1237391

Journal Information:: Physical Review B, Vol. 93, Issue 6; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 44 works

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