Conduction band engineering of half-Heusler thermoelectrics using orbital chemistry

Abstract

Semiconducting half-Heusler (HH, XYZ) phases are promising thermoelectric materials owing to their versatile electronic properties. Because the valence band of half-Heusler phases benefits from the valence band extrema at several high-symmetry points in the Brillouin zone (BZ), it is possible to engineer better p-type HH materials through band convergence. However, the thermoelectric studies of n-type HH phases have been lagging behind since the conduction band minimum is always at the same high-symmetry point (X) in the BZ, giving the impression that there is little opportunity for band engineering. Here we study the n-type orbital phase diagram of 69 HH compounds, and show that there are two competing conduction bands with very different effective masses actually at the same X point in the BZ, which can be engineered to be converged. The two conduction bands are dominated by the d orbitals of X and Y atoms, respectively. The energy offset between the two bands depends on the difference in the electron configuration and electronegativity of the X and Y atoms. Based on the orbital phase diagram, we provide the strategy to engineer the conduction band convergence by mixing the HH compounds with the reverse band offsets. We demonstrate the strategy by alloying VCoSn and TaCoSn. The V_0.5Ta_0.5CoSn solid solution is predicted to have high conduction band convergence and corresponding significantly larger density-of-states effective mass than either VCoSn or TaCoSn. Our work indicates that analyzing the orbital character of band edges provides new insight into engineering thermoelectric performance of HH compounds.