Two-Dimensional-Like Phonons in Three-Dimensional-Structured Rhombohedral GeSe-Based Compounds with Excellent Thermoelectric Performance

The coupling of charge and phonon transport in solids is a long-standing issue for thermoelectric performance enhancement. Herein, two new narrow-gap semiconductors with the same chemical formula of GeSe_0.65Te_0.35 (GST) are rationally designed and synthesized: one with a layered hexagonal structure (H-GST) and the other with a non-layered rhombohedral structure (R-GST). Thanks to the three-dimensional (3D) network structure, R-GST possesses a significantly larger weighted mobility than H-GST. Surprisingly, 3D-structured R-GST displays an extremely low lattice thermal conductivity of ∼0.5 W m^-1 K^-1 at 523 K, which is comparable to that of layered H-GST. The two-dimensional (2D)-like phonon transport in R-GST stems from the unique off-centering Ge atoms that induce ferroelectric instability, yielding soft polar phonons, as demonstrated by the Boson peak detected by the low-temperature specific heat and calculated phonon spectra. Furthermore, 1 mol % doping of Sb is utilized to successfully suppress the undesired phase transition of R-GST toward H-GST at elevated temperatures. Consequently, a peak ZT of 1.1 at 623 K is attained in the rhombohedral Ge_0.99Sb_0.01Se_0.65Te_0.35 sample, which is 1 order of magnitude larger than that of GeSe. This work demonstrates the feasibility of exploring high-performance thermoelectric materials with decoupled charge and phonon transport in off-centering compounds.