High Thermoelectric Performance in Chalcopyrite CuAgGaTe-ZnTe: Nontrivial Band Structure and Dynamic Doping Effect.

The understanding of thermoelectric properties of ternary I-III-VI type (I = Cu, Ag; III = Ga, In; and VI = Te) chalcopyrites is less well developed. Although their thermal transport properties are relatively well studied, the relationship between the electronic band structure and charge transport properties of chalcopyrites has been rarely discussed. In this study, we reveal the unusual electronic band structure and the dynamic doping effect that could underpin the promising thermoelectric properties of CuAgGaTe compounds. Density functional theory (DFT) calculations and electronic transport measurements suggest that the CuAgGaTe compounds possess an unusual non-parabolic band structure, which is important for obtaining a high Seebeck coefficient. Moreover, a mid-gap impurity level was also observed in CuAgGaTe, which leads to a strong temperature-dependent carrier concentration and is able to regulate the carrier density at the optimized value for a wide temperature region and thus is beneficial to obtaining the high power factor and high average of CuAgGaTe compounds. We also demonstrate a great improvement in the thermoelectric performance of CuAgGaTe by introducing Cu vacancies and ZnTe alloying. The Cu vacancies are effective in increasing the hole density and the electrical conductivity, while ZnTe alloying reduces the thermal conductivity. As a result, a maximum of 1.43 at 850 K and a record-high average of 0.81 for the CuAgGaTe-0.5%ZnTe compound are achieved.