High Thermoelectric Performance in Phonon-Glass Electron-Crystal Like AgSbTe2.

Achieving glass-like ultra-low thermal conductivity in crystalline solids with high electrical conductivity, a crucial requirement for high-performance thermoelectrics , continues to be a formidable challenge. A careful balance between electrical and thermal transport is essential for optimizing the thermoelectric performance. Despite this inherent trade-off, the experimental realization of an ideal thermoelectric material with a phonon-glass electron-crystal (PGEC) nature has rarely been achieved. Here, PGEC-like AgSbTe2 is demonstrated by tuning the atomic disorder upon Yb doping, which results in an outstanding thermoelectric performance with figure of merit, zT ≈ 2.4 at 573 K. Yb-doping-induced enhanced atomic ordering decreases the overlap between the hole and phonon mean free paths and consequently leads to a PGEC-like transport behavior in AgSbTe2 . A twofold increase in electrical mobility is observed while keeping the position of the Fermi level (EF ) nearly unchanged and corroborates the enhanced crystalline nature of the AgSbTe2 lattice upon Yb doping for electrical transport. The cation-ordered domains, lead to the formation of nanoscale superstructures (≈2 to 4 nm) that strongly scatter heat-carrying phonons, resulting in a temperature-independent glass-like thermal conductivity. The strategy paves the way for realizing high thermoelectric performance in various disordered crystals by making them amorphous to phonons while favoring crystal-like electrical transport.

Chemical Bonding Tuned Lattice Anharmonicity Leads to a High Thermoelectric Performance in Cubic AgSnSbTe3.

Comprehension of chemical bonding and its intertwined relation with charge carriers and heat propagation through a crystal lattice is imperative to design compounds for thermoelectric energy conversion. Here, we report the synthesis of large single crystal of new p-type cubic AgSnSbTe3 which shows an innately ultra-low lattice thermal conductivity (κlat ) of 0.47-0.27 Wm-1  K-1 and a high electrical conductivity (1238 - 800 S cm-1 ) in the temperature range 294-723 K. We investigated the origin of the low κlat by analysing the nature of the chemical bonding and its crystal structure. The interaction between Sn(5 s)/Ag(4d) and Te(5p) orbitals was found to generate antibonding states just below the Fermi level in the electronic band structure, resulting in a softening of the lattice in AgSnSbTe3 . Furthermore, the compound exhibits metavalent bonding which provides highly polarizable bonds with a strong lattice anharmonicity while maintaining the superior electrical conductivity. The electronic band structure exhibits nearly degenerate valence-band maxima that help to achieve a high Seebeck coefficient throughout the measured temperature range and, as a result, the maximum thermoelectric figure of merit reaches to ≈1.2 at 661 K in pristine single crystal of AgSnSbTe3 .