Revealing the Intrinsic Electronic Structure of 3D Half‐Heusler Thermoelectric Materials by Angle‐Resolved Photoemission Spectroscopy

Accurate determination of the intrinsic electronic structure of thermoelectric materials is a prerequisite for utilizing an electronic band engineering strategy to improve their thermoelectric performance. Herein, with high-resolution angle-resolved photoemission spectroscopy (ARPES), the intrinsic electronic structure of the 3D half-Heusler thermoelectric material ZrNiSn is revealed. An unexpectedly large intrinsic bandgap is directly observed by ARPES and is further confirmed by electrical and optical measurements and first-principles calculations. Moreover, a large anisotropic conduction band with an anisotropic factor of 6 is identified by ARPES and attributed to be one of the most important reasons leading to the high thermoelectric performance of ZrNiSn. These successful findings rely on the grown high-quality single crystals, which have fewer Ni interstitial defects and negligible in-gap states on the electronic structure. This work demonstrates a realistic paradigm to investigate the electronic structure of 3D solid materials by using ARPES and provides new insights into the intrinsic electronic structure of the half-Heusler system benefiting further optimization of thermoelectric performance.