Convergence of separate orbits for enhanced thermoelectric performance of layered ZrS2

Abstract

Minimizing the band splitting energy to approach orbital degeneracy has been shown as a route to improved thermoelectric performance. This represents an open opportunity in some promising layered materials where there is a separation of p orbitals at the valence band edge due to the crystal field splitting. In this work, using ab initio calculations and semiclassical Boltzmann transport theory, we try to figure out how orbital degeneracy influences the thermoelectric properties of layered transition-metal dichalcogenide ZrS2. We tune the splitting energy by applying compressive biaxial strain, and find out that near-degeneration at the point can be achieved for around 3% strain. As expected, the enhanced density-of-states effective mass results in an increased power factor. Interestingly, we also find a marked decline in the lattice thermal conductivity due to the effect of strain on phonon velocities and scattering. The two effects synergetically enhance the figure of merit. Our results highlight the convenience of exploring this optimization route in layered thermoelectric materials with band structures similar to that of ZrS2.