Decreasing the Carrier Concentration of ZrNiSn: An Opposite Way to the Best N‐Type Half‐Heusler Thermoelectrics

Abstract N‐type ZrNiSn‐based alloys reach a record thermoelectric figure of merit zT ≈1.2 by increasing the carrier concentration to 4–5 × 10 20 cm −3 . In this work, It is reported that a comparable zT can also be realized in trace Ru‐doped ZrNiSn‐based alloy at even lower temperature by decreasing the carrier concentration. Compared to the previously reported Co doping, the doping of Ru results in a more effective reduction in carrier concentration, and thus higher Seebeck coefficient, lower electronic thermal conductivity, and enhanced thermoelectric performance. The electronic specific heat coefficient of the ZrNi 1‐ x Ru x Sn sample remains constant with increasing Ru content, indicating no obvious change in the density of states effective mass. Theoretical calculations show that the doping of Ru has negligible effect on the bottom of conduction band. The lattice thermal conductivity is further reduced by alloying Ti and Hf at the Zr site, and the bipolar diffusion is suppressed by doping of 0.5 at.% Sb. As a result, Ti 0.25 Zr 0.5 Hf 0.25 Ni 0.99 Ru 0.01 Sn 0.995 Sb 0.005 reaches not only a zT value of 1.1 at 773 K but also a record average zT value of 0.8 in 300 to 873 K, demonstrating the effectiveness of trace Ru doping on boosting the thermoelectric performance of ZrNiSn‐based alloys.