Achieving band convergence by tuning the bonding ionicity in n-type Mg₃ Sb₂

Identifying strategies for beneficial band engineering is crucial for the optimization of thermoelectric (TE) materials. In this study, we demonstrate the beneficial effects of ionic dopants on n-type Mg₃ Sb₂ . Using the band-resolved projected crystal orbital Hamilton population, the covalent characters of the bonding between Mg atoms at different sites are observed. By partially substituting the Mg at the octahedral sites with more ionic dopants, such as Ca and Yb, the conduction band minimum (CBM) of Mg₃ Sb₂ is altered to be more anisotropic with an enhanced band degeneracy of 7. The CBM density of states of doped Mg₃ Sb₂ with these dopants is significantly enlarged by band engineering. The improved Seebeck coefficients and power factors, together with the reduced lattice thermal conductivities, imply that the partial introduction of more ionic dopants in Mg₃ Sb₂ is a general solution for its n-type TE performance. © 2019 Wiley Periodicals, Inc.