Impurity Band Formation as a Route to Thermoelectric Power Factor Enhancement in n‐type XNiSn Half‐Heuslers

Bandstructure engineering is a key route for thermoelectric performance enhancement. Here, 20–50% Seebeck (S) enhancement is reported for XNiCuySn half‐Heusler samples based on X = Ti. This novel electronic effect is attributed to the emergence of impurity bands of finite extent, due to the Cu dopants. Depending on the dispersion, extent, and offset with respect to the parent material, these bands are shown to enhance S to different degrees. Experimentally, this effect is controllable by the Ti content of the samples, with the addition of Zr/Hf gradually removing the enhancement. At the same time, the mobility remains largely intact, enabling power factors ≥3 mW m−1 K−2 near room temperature, increasing to ≥5 mW m−1 K−2 at high temperature. Combined with reduced thermal conductivity due to the Cu interstitials, this enables high average zT = 0.67–0.72 between 320 and 793 K for XNiCuySn compositions with ≥70% Ti. This work reveals the existence of a new route for electronic performance enhancement in n‐type XNiSn materials that are normally limited by their single carrier pocket. In principle, impurity bands can be applied to other materials and provide a new direction for further development.