High Thermoelectric Performance in Rhombohedral GeSe-LiBiTe 2 .

GeSe, an analogue of SnSe, shows promise in exhibiting exceptional thermoelectric performance in the Pnma phase. The constraints on its dopability, however, pose challenges in attaining optimal carrier concentrations and improving ZT values. This study demonstrates a crystal structure evolution strategy for achieving highly doped samples and promising ZT s in GeSe via LiBiTe 2 alloying. A rhombohedral phase ( R 3 m ) can be stabilized in the GeSe-LiBiTe 2 system, further evolving into a cubic ( Fm 3 ̅m ) phase with a rising temperature. The band structures of GeSe-LiBiTe 2 in the rhombohedral and cubic phases feature a similar multiple-valley energy-converged valence band of L and Σ bands. The observed high carrier concentration (∼10 20 cm -3 ) reflects the effective convergence of these bands, enabling a high density-of-states effective mass and an enhanced power factor. Moreover, a very low lattice thermal conductivity of 0.6-0.5 W m -1 K -1 from 300 to 723 K is achieved in 0.9GeSe-0.1LiBiTe 2 , approaching the amorphous limit value. This remarkably low lattice thermal conductivity is related to phonon scattering from point defects, planar vacancies, and ferroelectric instability-induced low-energy Einstein oscillators. Finally, a maximum ZT value of 1.1 to 1.3 at 723 K is obtained, with a high average ZT value of over 0.8 (400-723 K) in 0.9GeSe-0.1LiBiTe 2 samples. This study establishes a viable route for tailoring crystal structures to significantly improve the performance of GeSe-related compounds.