Achieving band convergence by tuning the bonding ionicity in n‐type Mg 3 Sb 2

• Published in: Journal of computational chemistry Vol. 40; no. 18; pp. 1693 - 1700
• Main Authors: Sun, Xin, Li, Xin, Yang, Jiong, Xi, Jinyang, Nelson, Ryky, Ertural, Christina, Dronskowski, Richard, Liu, Weishu, Snyder, Gerald J., Singh, David J., Zhang, Wenqing
• Format: Journal Article
• Language: English
• Published: United States Wiley Blackwell (John Wiley & Sons) 05.07.2019
• Subjects: band engineering; band-resolved COHP; Mg3Sb2; thermoelectric; bonding ionicity
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.25822

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 Mg 3 Sb 2 . 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 Mg 3 Sb 2 is altered to be more anisotropic with an enhanced band degeneracy of 7. The CBM density of states of doped Mg 3 Sb 2 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 Mg 3 Sb 2 is a general solution for its n‐type TE performance. © 2019 Wiley Periodicals, Inc.