Direct Observation of Inherent Atomic-Scale Defect Disorders responsible for High-Performance Ti_{1− x}Hf_xNiSn_{1− y}Sb_y Half-Heusler Thermoelectric Alloys

Structural defects often dominate the electronic- and thermal-transport properties of thermoelectric (TE) materials and are thus a central ingredient for improving their performance. However, understanding the relationship between TE performance and the disordered atomic defects that are generally inherent in nanostructured alloys remains a challenge. Herein, the use of scanning transmission electron microscopy to visualize atomic defects directly is described and disordered atomic-scale defects are demonstrated to be responsible for the enhancement of TE performance in nanostructured Ti_{1− x}Hf_xNiSn_{1− y}Sb_y half-Heusler alloys. The disordered defects at all atomic sites induce a local composition fluctuation, effectively scattering phonons and improving the power factor. It is observed that the Ni interstitial and Ti,Hf/Sn antisite defects are collectively formed, leading to significant atomic disorder that causes the additional reduction of lattice thermal conductivity. The Ti_{1− x}Hf_xNiSn_{1− y}Sb_y alloys containing inherent atomic-scale defect disorders are produced in one hour by a newly developed process of temperature-regulated rapid solidification followed by sintering. The collective atomic-scale defect disorder improves the zT to 1.09 ± 0.12 at 800 K for the Ti_0.5Hf_0.5NiSn_0.98Sb_0.02 alloy. These results provide a promising avenue for improving the TE performance of state-of-the-art materials.