Unexpected high-temperature stability of β-Zn4Sb3 opens the door to enhanced thermoelectric performance.

β-Zn4Sb3 has one of the highest ZT reported for binary compounds, but its practical applications have been hindered by a reported poor stability. Here we report the fabrication of nearly dense single-phase β-Zn4Sb3 and a study of its thermoelectric transport coefficients across a wide temperature range. Around 425 K we find an abrupt decrease of its thermal conductivity. Past this point, Zn atoms can migrate from crystalline sites to interstitial positions; β-Zn4Sb3 becomes metastable and gradually decomposes into Zn(hcp) and ZnSb. However, above 565 K it recovers its stability; in fact, the damage caused by decomposition can be repaired completely. This is key to its excellent thermoelectric performance at high temperature: the maximum ZT reaches 1.4. Molecular dynamics simulations are used to shed light on the microscopic behavior of the material.

[1]  N. Nong,et al.  Low‐Cost High‐Performance Zinc Antimonide Thin Films for Thermoelectric Applications , 2012, Advanced materials.

[2]  B. Iversen,et al.  Thermal Stability of Thermoelectric Zn4Sb3 , 2010 .

[3]  Eric S. Toberer,et al.  Characterization and analysis of thermoelectric transport in n-type Ba_(8)Ga_(16−x)Ge_(30+x) , 2009 .

[4]  Z. Wang,et al.  Atomistic origin of glass-like Zn4Sb3 thermal conductivity , 2013, 1810.10679.

[5]  Matthew J. Rosseinsky,et al.  Physical Review B , 2011 .

[6]  G. J. Snyder,et al.  Predicted electronic and thermodynamic properties of a newly discovered Zn8Sb7 phase. , 2011, Journal of the American Chemical Society.

[7]  Jonathan D'Angelo,et al.  High thermoelectric figure of merit and nanostructuring in bulk p-type Na1-xPbmSbyTem+2. , 2006, Angewandte Chemie.

[8]  M. Dresselhaus,et al.  New Directions for Low‐Dimensional Thermoelectric Materials , 2007 .

[9]  Alexandra O. Pecharsky,et al.  A Promising Thermoelectric Material: Zn4Sb3 or Zn6-δSb5. Its Composition, Structure, Stability, and Polymorphs. Structure and Stability of Zn1-δSb , 2004 .

[10]  G. J. Snyder,et al.  Interstitial Zn atoms do the trick in thermoelectric zinc antimonide, Zn4Sb3: a combined maximum entropy method X-ray electron density and ab initio electronic structure study. , 2004, Chemistry.

[11]  G. J. Snyder,et al.  Entropic stabilization and retrograde solubility in Zn_4Sb_3 , 2010, 1010.4795.

[12]  G. J. Snyder,et al.  Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties , 2004, Nature materials.

[13]  Ali Shakouri,et al.  Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features , 2010, Advanced materials.

[14]  M. P. Walsh,et al.  Quantum Dot Superlattice Thermoelectric Materials and Devices , 2002, Science.

[15]  Rajeev J Ram,et al.  Trend for Thermoelectric Materials and Their Earth Abundance , 2012, Journal of Electronic Materials.

[16]  Siegfried Schmauder,et al.  Comput. Mater. Sci. , 1998 .

[17]  Yang Ren,et al.  Heterogeneous in-situ nanostructure contributes to the thermoelectric performance of Zn4Sb3 , 2013 .

[18]  Terry M. Tritt,et al.  Thermoelectric Materials, Phenomena, and Applications: A Bird’s Eye View , 2006 .

[19]  R. Hermann,et al.  Dumbbell rattling in thermoelectric zinc antimony. , 2007, Physical review letters.

[20]  G. J. Snyder,et al.  Structure, heat capacity, and high-temperature thermal properties of Yb 14Mn 1-xAl xSb 11 , 2009 .

[21]  Steve Plimpton,et al.  Fast parallel algorithms for short-range molecular dynamics , 1993 .

[22]  M. Oh,et al.  Thermoelectric properties of Zn 4Sb 3 prepared by hot pressing , 2011 .

[23]  M. Kanatzidis,et al.  Nanostructures boost the thermoelectric performance of PbS. , 2011, Journal of the American Chemical Society.

[24]  Jean-Pierre Fleurial,et al.  Preparation and thermoelectric properties of semiconducting Zn4Sb3 , 1997 .

[25]  M. Dresselhaus,et al.  High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys , 2008, Science.

[26]  Y. Mozharivskyj,et al.  Zn13Sb10: A Structural and Landau Theoretical Analysis of Its Phase Transitions , 2006 .

[27]  R. Rosenfeld.  Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.

[28]  C. Erk,et al.  Nanoscale zinc antimonides: synthesis and phase stability. , 2006, Inorganic chemistry.

[29]  B. Iversen,et al.  Thermal Stability of High Performance Thermoelectric β-Zn4Sb3 in Argon , 2011 .

[30]  Ctirad Uher,et al.  High performance Na-doped PbTe-PbS thermoelectric materials: electronic density of states modification and shape-controlled nanostructures. , 2011, Journal of the American Chemical Society.

[31]  O. Løvvik,et al.  Self-diffusion in Zn4Sb3 from first-principles molecular dynamics , 2011 .

[32]  M. Kanatzidis,et al.  Cubic AgPbmSbTe2+m: Bulk Thermoelectric Materials with High Figure of Merit , 2004, Science.

[33]  T. Souma,et al.  Low-temperature thermoelectric properties of α- and β-Zn4Sb3 bulk crystals prepared by a gradient freeze method and a spark plasma sintering method , 2002 .

[34]  A. Sievers,et al.  Intrinsic localized modes in anharmonic crystals. , 1988, Physical review letters.

[35]  K. Ito,et al.  Effects of ZnSb and Zn inclusions on the thermoelectric properties of β-Zn4Sb3 , 2003 .

[36]  R. Venkatasubramanian,et al.  Thin-film thermoelectric devices with high room-temperature figures of merit , 2001, Nature.

[37]  P. Zhai,et al.  Molecular Dynamics Study of the Mechanical Behavior of Zn4Sb3 Nanofilms , 2011 .

[38]  John Ziman,et al.  Electrons and Phonons: The Theory of Transport Phenomena in Solids , 2001 .

[39]  S. Haile,et al.  Local structure of interstitial Zn in β‐Zn4Sb3 , 2007 .

[40]  B. Pedersen,et al.  Thermally stable thermoelectric Zn4Sb3 by zone-melting synthesis , 2008 .