Doping by Design: Enhanced Thermoelectric Performance of GeSe Alloys Through Metavalent Bonding

Abstract Doping is usually the first step to tailor thermoelectrics. It enables precise control of the charge‐carrier concentration and concomitant transport properties. Doping should also turn GeSe, which features an intrinsically a low carrier concentration, into a competitive thermoelectric. Yet, elemental doping fails to improve the carrier concentration. In contrast, alloying with Ag–V–VI 2 compounds causes a remarkable enhancement of thermoelectric performance. This advance is closely related to a transition in the bonding mechanism, as evidenced by sudden changes in the optical dielectric constant ε ∞ , the Born effective charge, the maximum of the optical absorption ε 2 (ω), and the bond‐breaking behavior. These property changes are indicative of the formation of metavalent bonding (MVB), leading to an octahedral‐like atomic arrangement. MVB is accompanied by a thermoelectric‐favorable band structure featuring anisotropic bands with small effective masses and a large degeneracy. A quantum‐mechanical map, which distinguishes different types of chemical bonding, reveals that orthorhombic GeSe employs covalent bonding, while rhombohedral and cubic GeSe utilize MVB. The transition from covalent to MVB goes along with a pronounced improvement in thermoelectric performance. The failure or success of different dopants can be explained by this concept, which redefines doping rules and provides a “treasure map” to tailor p‐bonded chalcogenides.