Crystal symmetry induced structure and bonding manipulation boosting thermoelectric performance of GeTe

Rock-salt structured GeTe has been reckoned as a promising medium temperature thermoelectric material due to its decent thermal conductivity and multiple electronic valence bands that can be easily modified. However, the applications of GeTe-based thermoelectric materials are strongly impeded by their excessive hole concentration and detrimental phase transition, which deteriorates both thermoelectric performance and mechanical robustness. In this study, we simultaneously solve these two issues by co-doping Ti and Sb in GeTe, achieving an ultrahigh figure-of-merit (ZT) of ~2.2 at 725 K with an average ZT over 2.0 plateauing from 625 to 755 K. Our X-ray spectroscopy analysis and electron microscopy investigation, coupled with first-principle calculation, attribute the extraordinary thermoelectric performance of Ge1-x-yTixSbyTe to the synergetic effects of: a) resonant bonding properties induced by symmetrized crystal lattice; b) high Seebeck coefficient and quality factor due to enhanced band degeneracy and effective mass; c) optimized hole concentration by the aliovalent TiGe and SbGe substitution; and d) minimized thermal conductivity due to the evident frequency-selective phonon scattering by diverse types of defects. Our study indicates that manipulating structure and bonding properties by crystal symmetry modification can explore new-type and high-performance thermoelectric candidates in GeTe and its derivatives, as well as other phase-transition materials. [Display omitted] •Comprehensive synthesis, characterization and modelling for Ti and Sb co-doped GeTe.•Lattice symmetrisation optimizes charge and phonon transport properties in GeTe.•Significant thermoelectric figure-of-merit and efficiency in Ge1-x-yTixSbyTe.•The thermoelectric properties of Ge1-x-yTixSbyTe is rationalized by rigorous first-principle calculation.