Vacancy Suppression Induced Synergetic Optimization of Thermoelectric Performance in Sb-Doped GeTe Evidenced by...

Synergetic optimization of the electrical and thermal transport performance of GeTe has been achieved through Sb doping in this work, resulting in a high thermoelectric figure of merit ZT of 2.2 at 723 K. Positron annihilation measurements provided clear evidence that Sb doping in GeTe can effectively suppress the Ge vacancies, and the decrease of vacancy concentration coincides well with the change of hole carrier concentration after Sb doping. The decreased scattering by hole carriers and vacancies causes notable increase in carrier mobility. Despite this, the density of states effective mass is not enhanced by Sb doping, a maximum power factor of 4562 μW m^-1 K^-2 at 723 K is obtained for Ge_0.94Sb_0.06Te with an optimized carrier concentration of ∼3.65 × 10²⁰ cm^-3. Meanwhile, the electronic thermal conductivity κ_e is reduced because of the decreased electrical conductivity σ with the increase of the Sb doping amount. In addition, the lattice thermal conductivity κ_L is also suppressed due to multiple phonon scattering mechanism, such as the large mass and strain fluctuations by the substitution of Sb for Ge atoms, and also the unique microstructure including grain boundary, nano-pore, and dislocation in the samples. In conclusion, a maximum ZT of 2.2 is gained at 723 K, which contributes to preferable TE property for GeTe-based materials.