Developing a Multiband Electronic Band Structure Model and Predictive Maps for Bismuth-Rich Mg₃(Sb_1–xBi_x)₂ Thermoelectric Materials

In recent years, bismuth-rich Mg 3 (Sb 1– x Bi x ) 2 ( x = 0.5–0.8) compositions have generated significant interest due to their excellent thermoelectric (TE) performance near room temperature, making them potential applicants for recovery of low-grade waste heat. The superior performance in these materials is due to its complex electronic band structure (EBS) with presence of multiple near degenerate bands close to the conduction band edge. The position and curvature of these bands strongly depend on the alloy composition, doping amount as well as temperature. Thus, identifying optimal material compositions to get the best TE performance depends on an understanding of the temperature dynamics of EBS and forms the objective of this work. Mg 3 Sb 0.6 Bi 1.4 ( x = 0.7) is chosen for this study due to its reported high near room temperature performance, and compositions with varying doping concentrations (Te used as dopant) have been synthesized. EBS parameters like effective mass and deformation potential of bands, interband separation and band gap values have been estimated using a recently developed refinement approach. Refinement results indicate that the interband separation between conduction bands to be a function of both temperature and doping concentration. Further, thermal conductivity (κ) was estimated for all of the compositions. Utilizing the EBS and κ information, predictive 3D maps indicating the variation in zT (TE figure of merit) with doping concentration and temperature have been generated. The 3D maps reveal an interesting surface topography with a broad peak zT region. This observation explains why these materials have high TE performance and are less sensitive to doping inhomogeneities. Our results provide detailed EBS information and fundamental insights on the TE properties of Mg 3 Sb 0.6 Bi 1.4 . Further, the proposed technique can be utilized to probe other Mg 3 (Sb 1– x Bi x ) 2 compositions and TE materials.