Simultaneous Optimization of Carrier Concentration and Alloy Scattering for Ultrahigh Performance GeTe Thermoelectrics

In order to locate the optimal carrier concentrations for peaking the thermoelectric performance in p‐type group IV monotellurides, existing efforts focus on aliovalent doping, either to increase (in PbTe) or to decrease (in SnTe and GeTe) the hole concentration. The limited solubility of aliovalent dopants usually introduces insufficient phonon scattering for thermoelectric performance maximization. With a decrease in the size of cation, the concentration of holes, induced by cation vacancies in intrinsic compounds, increases rapidly from ≈10(18) cm(−3) in PbTe to ≈10(20) cm(−3) in SnTe and then to ≈10(21) cm(−3) in GeTe. This motivates a strategy here for reducing the carrier concentration in GeTe, by increasing the mean size of cations and vice‐versa decreasing the average size of anions through isovalent substitutions for increased formation energy of cation vacancy. A combination of the simultaneously resulting strong phonon scattering due to the high solubility of isovalent impurities, an ultrahigh thermoelectric figure of merit, zT of 2.2 is achieved in GeTe–PbSe alloys. This corresponds to a 300% enhancement in average zT as compared to pristine GeTe. This work not only demonstrates GeTe as a promising thermoelectric material but also paves the way for enhancing the thermoelectric performance in similar materials.