Ag2Se is a narrow band gap n-type semiconductor with high carrier mobility and low lattice thermal conductivity. It has high thermoelectric performance near room temperature. However, there is a noticeable data discrepancy for thermoelectric performance in the reported literature studies, which greatly hinders the rational understanding and potential application of this material. In this work, we comprehensively studied the homogeneity, reproducibility, and thermal stability of bulk Ag2Se prepared by melting and mechanical alloying methods followed by spark plasma sintering. By virtue of the atom probe topology technique, we revealed nanosized Ag- or Se-rich precipitates and micropores with Se-aggregated interfaces that have not been detected previously. The samples prepared by melting and spark plasma sintering exhibit the best homogeneity and repeatability in thermoelectric properties despite abundant nanoprecipitates. Moreover, the thermoelectric performance of Ag2Se is greatly improved by introducing a slight amount of excess selenium. The average zT can steadily reach 0.8–0.9 in the range of 300–380 K, which is among the highest values reported for Ag2Se-based materials. This work will rationalize the evaluation of the thermoelectric performance of Ag2Se.

The amalgamation of multi-subjects often elicits novel materials, new concepts and unexpected applications. Recently, Ge 2 Sb 2 Te 5 , as the most established phasechange material, has been found to exhibit decent thermoelectric performance in its stable, hexagonal phase. The challenge for higher figure of merit (zT) values lies in reducing the hole carrier concentration and enhancing the Seebeck coefficient, which, however, can be hardly realized by conventional doping. Here in this work, we report that the electrical properties of Ge 2 Sb 2 Te 5 can be readily optimized by anion-site modulation. Specifically, Se/S substitution for Te induces stronger and more ionic bonding, lowering the hole density. Furthermore, an increase in electronic density of state is introduced by Se substitution, contributing to a large increase in Seebeck coefficient. Combined with the reduced thermal conductivity, maximum zT values above 0.7 at 800 K have been achieved in Se/S-alloyed materials, which is * 30% higher than that in the pristine Ge 2 Sb 2 Te 5 .