New Insights into Intrinsic Point Defects in V₂VI₃ Thermoelectric Materials

Defects and defect engineering are at the core of many regimes of material research, including the field of thermoelectric study. The 60-year history of V₂VI₃ thermoelectric materials is a prime example of how a class of semiconductor material, considered mature several times, can be rejuvenated by better understanding and manipulation of defects. This review aims to provide a systematic account of the <i>underexplored</i> intrinsic point defects in V₂VI₃ compounds, with regard to (i) their formation and control, and (ii) their interplay with other types of defects towards higher thermoelectric performance. We herein present a convincing case that intrinsic point defects can be actively controlled by extrinsic doping and also via compositional, mechanical, and thermal control at various stages of material synthesis. An up-to-date understanding of intrinsic point defects in V₂VI₃ compounds is summarized in a (χ, r)-model and applied to elucidating the donor-like effect. These new insights not only enable more innovative defect engineering in other thermoelectric materials but also, in a broad context, contribute to rational defect design in advanced functional materials at large.