Unusual thermoelectric transport anisotropy in quasi-2D, rhombohedral GeTe

Abstract

In this study, we calculate the $T$=300 K scattering and thermoelectric transport properties of rhombohedral GeTe using first-principles modeling. The room-temperature phase of GeTe has a layered structure, with cross-plane and in-plane directions oriented parallel and perpendicular to [111], respectively. Based on rigorous electron-phonon scattering, our transport calculations reveal unusual anisotropic properties; n-type GeTe has a cross-plane electrical conductivity that is roughly 3$\times$ larger than in-plane. p-type GeTe, however, displays opposite anisotropy with in-plane conducting roughly 2$\times$ more than cross-plane, as is expected in quasi-2D materials. The power factor shows the same anisotropy as the electrical conductivity, since the Seebeck coefficient is relatively isotropic. Interestingly, cross-plane n-GeTe shows the largest mobility and power factor approaching 500 cm$^2$/V-s and 32 $μ$W/cm-K$^2$, respectively. The thermoelectric figure-of-merit, $zT$, is enhanced as a result of this unusual anisotropy in n-GeTe since the lattice thermal conductivity is minimized along cross-plane. This decouples the preferred transport directions of electrons and phonons, leading to a threefold increase in $zT$ along cross-plane compared to in-plane. The n-type anisotropy results from high-velocity electron states formed by Ge p-orbitals that span across the interstitial region. This surprising behavior, that would allow the preferential conduction direction to be controlled by doping, could be observed in other quasi-2D materials and exploited to achieve higher-performance thermoelectrics.