Self-Doping for Synergistically Tuning the Electronic and Thermal Transport Coefficients in n-Type Half-Heuslers

Ternary intermetallic half-Heusler (HH) compounds (XYZ) with 18 valence electron count, namely, ZrCoSb, ZrNiSn, and ZrPdSn, have revealed promising thermoelectric properties. Exemplarily, it has been experimentally observed that a slight change in the content of Y site atoms (by ∼3-12.5% i.e., m = 0.03 and 0.125 in ZrY₁₊Z) leads to a drastic decrease in lattice thermal conductivity κ_L by more than 65-80% in many of these compounds. The present work aims at exploring the possibility of maximizing the electronic transport scenario after achieving the low κ_L limit in these compounds. By taking into account the full anharmonicity of the lattice dynamics, Boltzmann transport calculations are performed under the framework of density functional theory. Our results show that these excess atoms present in the vacant lattice site induce scattering either by acting as a rattling mode or by hybridizing with the acoustic modes of the host depending upon their mass and bonding chemistry, respectively. Furthermore, the introduction of these scattering centers may lead either to the formation of a defect midgap state in the electronic band structure (detrimental for electronic transport) or to light doping of the host compound. The latter is found to be particularly conducive for attaining synergy in both thermal and electronic transport.