Engineering Thermoelectric Performance of α‐GeTe by Ferroelectric Distortion

Abstract

The rhombohedral α‐GeTe can be approximated as a slightly distorted rock‐salt structure along its [1 1 1] direction and possesses superb thermoelectric performance. However, the role of such a ferroelectric‐like structural distortion on its transport properties remains unclear. Herein, we performed a systematic study on the crystal structure and electronic band structure evolutions of Ge1‐xSnxTe alloys where the degree of ferroelectric distortion is continuously tuned. It is revealed that the band gap is maximized while multiple valence bands are converged at x = 0.6, where the ferroelectric distortion is the least but still works. Once undistorted, the band gap is considerably reduced, and the valence bands are largely separated again. Moreover, near the ferro‐to‐paraelectric phase transition Curie temperature, the lattice thermal conductivity reaches its minima because of significant lattice softening enabled by ferroelectric instability. We predict a peak ZT value of 2.6 at 673 K in α‐GeTe by use of proper dopants which are powerful in suppressing the excess hole concentrations but meanwhile exert little influence on the ferroelectric distortion.