Polarity switching via defect engineering in Cu doped SnSe0.75S0.25 solid solution for mid-temperature thermoelectric applications

Solid solution SnSe0.75S0.25 has potential to improve thermoelectric performance via ultra-low thermal conductivity as compared to the pristine SnSe which originates from phonon scattering due to disordered atoms of selenium (Se) and sulfur (S). SnSe0.75S0.25 and Cu-doped SnSe0.75S0.25 compounds were prepared via high energy ball milling and pelletized by a spark plasma sintering (SPS) process. Dislocation and point defects were successfully introduced by SnSe0.75S0.25. The existence of S in the Se site induced mass fluctuation which favors high-frequency phonon scattering. This leads to an impressively ultra-low thermal conductivity (kappa T) value of 0.258 W mK(-1) at 753 K for SnSe0.75S0.25. Next, the Cu dopant was selected to enhance the electrical conductivity, which improved from 514.44 S m(-1) (SnSe0.75S0.25) to 725.08 S m(-1) for Sn0.98Cu0.02Se0.75S0.25 at 738 K. Interestingly, the Cu dopant induced nanoprecipitates of Cu2Se inside the grains, which further strengthens the phonon scattering. The Cu2Se nanoprecipitates and various defects at the grain boundaries contributed to a lower kappa T of 0.295 W mK(-1) at 753 K for a Sn0.94Cu0.06Se0.75S0.25 sample. Moreover, the maximum figure of merit of (ZT) similar to 0.19 at 738 K was attained for the Sn0.98Cu0.02Se0.75S0.25 sample.

Automated summary

The solid solution of SnSe0.75S0.25 has the potential to improve thermoelectric performance through ultra-low thermal conductivity, achieved by introducing disordered atoms of selenium and sulfur. High energy ball milling and spark plasma sintering were used to prepare SnSe0.75S0.25 and Cu-doped SnSe0.75S0.25 compounds. The presence of S in the Se site induced mass fluctuation, resulting in high-frequency phonon scattering and a remarkably low thermal conductivity value at 753 K. Cu dopant was selected to enhance the electrical conductivity and induce nanoprecipitates of Cu2Se inside the grains, further strengthening phonon scattering and lowering the thermal conductivity.