Enhancing the Thermoelectric Properties via Modulation of Defects in P‐Type MNiSn‐Based (M = Hf, Zr, Ti) Half‐Heusler Materials

Abstract The thermoelectric figure‐of‐merit (zT) of p‐type MNiSn (M = Ti, Zr, or Hf) half‐Heusler compounds is lower than their n‐type counterparts due to the presence of a donor in‐gap state caused by Ni occupying tetrahedral interstitials. While ZrNiSn and TiNiSn, have been extensively studied, HfNiSn remains unexplored. Herein, this study reports an improved thermoelectric property in p‐type HfNi_1−xCo_xSn. By doping 5 at% Co at the Ni sites, the Seebeck coefficient becomes reaching a peak value exceeding 200 µV K⁻¹ that breaks the record of previous reports. A maximum power factor of ≈2.2 mW m⁻¹ K⁻² at 973 K is achieved by optimizing the carrier concentration. The enhanced p‐type transport is ascribed to the reduced content of Ni defects, supported by first principle calculations and diffraction pattern refinement. Concomitantly, Co doping also softens the lattice and scatters phonons, resulting in a minimum lattice thermal conductivity of ≈1.8 W m⁻¹ K⁻¹. This leads to a peak zT of 0.55 at 973 K is realized, surpassing the best performing p‐type MNiSn by 100%. This approach offers a new method to manipulate the intrinsic atomic disorder in half‐Heusler materials, facilitating further optimization of their electronic and thermal properties.