Manipulating the Ge Vacancies and Ge Precipitates through Cr Doping for Realizing the High‐Performance GeTe Thermoelectric Material

GeTe alloy is a promising medium‐temperature thermoelectric material but with highly intrinsic hole carrier concentration by thermodynamics, making this system to be intrinsically off‐stoichiometric with Ge vacancies and Ge precipitations. Generally, an intentional increase of formation energy of Ge vacancy by element substitution will lead to an effective dissolution of Ge precipitates for reduction in hole concentration. Here, an opposite direction of decreasing the formation energy of Ge vacancies is demonstrated by substituting Cr at Ge site. This strategy produces more but nearly homogenously distributed Ge precipitations and Ge vacancies, which provides enhanced phonon scattering and effectively reduces the lattice thermal conductivity. Furthermore, Cr atom carries one more electron than Ge and serves as an electron donor for decreasing the hole carrier concentrations. Further optimization incorporates the effect of Bi substitution for facilitating band convergence. A maximum figure of merit (ZT) of 2.0 at 600 K with average ZT of over 1.2 is achieved in the sample of Ge_0.92Cr_0.03Bi_0.05Te, making it one of the best thermoelectric materials for medium‐temperature application.