Thermoelectric Performance of IV–VI Compounds with Octahedral‐Like Coordination: A Chemical‐Bonding Perspective

Abstract Thermoelectric materials provide a challenge for materials design, since they require optimization of apparently conflicting properties. The resulting complexity has favored trial‐and‐error approaches over the development of simple and predictive design rules. In this work, the thermoelectric performance of IV–VI chalcogenides on the tie line between GeSe and GeTe is investigated. From a combination of optical reflectivity and electrical transport measurements, it is experimentally proved that the outstanding performance of IV–VI compounds with octahedral‐like coordination is due to the anisotropy of the effective mass tensor of the relevant charge carriers. Such an anisotropy enables the simultaneous realization of high Seebeck coefficients, due to a large density‐of‐states effective mass, and high electrical conductivity, caused by a small conductivity effective mass. This behavior is associated to a unique bonding mechanism by means of a tight‐binding model, which relates band structure and bond energies; tuning the latter enables tailoring of the effective mass tensor. The model thus provides atomistic design rules for thermoelectric chalcogenides.