Band engineering in Mg_3Sb_2 by alloying with Mg_3Bi_2 for enhanced thermoelectric performance

Mg_3Sb_2–Mg_3Bi_2 alloys show excellent thermoelectric properties. The benefit of alloying has been attributed to the reduction in lattice thermal conductivity. However, Mg_3Bi_2-alloying may also be expected to significantly change the electronic structure. By comparatively modeling the transport properties of n- and p-type Mg_3Sb_2–Mg_3Bi_2 and also Mg_3Bi_2-alloyed and non-alloyed samples, we elucidate the origin of the highest zT composition where electronic properties account for about 50% of the improvement. We find that Mg_3Bi_2 alloying increases the weighted mobility while reducing the band gap. The reduced band gap is found not to compromise the thermoelectric performance for a small amount of Mg_3Bi_2 because the peak zT in unalloyed Mg_3Sb_2 is at a temperature higher than the stable range for the material. By quantifying the electronic influence of Mg_3Bi_2 alloying, we model the optimum Mg_3Bi_2 content for thermoelectrics to be in the range of 20–30%, consistent with the most commonly reported composition Mg_3Sb_(1.5)Bi_(0.5)