Defect Engineering of Bi ₂ SeO ₂ Thermoelectrics

Abstract Bi 2 SeO 2 is a promising n ‐type semiconductor to pair with p ‐type BiCuSeO in a thermoelectric (TE) device. The TE figure of merit zT and, therefore, the device efficiency must be optimized by tuning the carrier concentration. However, electron concentrations in self‐doped n ‐type Bi 2 SeO 2 span several orders of magnitude, even in samples with the same nominal compositions. Such unsystematic variations in the electron concentration have a thermodynamic origin related to the variations in native defect concentrations. In this study, first‐principles calculations are used to show that the selenium vacancy, which is the source of n ‐type conductivity in Bi 2 SeO 2 , varies by 1–2 orders of magnitude depending on the thermodynamic conditions. It is predicted that the electron concentration can be enhanced by synthesizing under more Se‐poor conditions and/or at higher solid‐state reaction temperatures ( T SSR ), which promote the formation of selenium vacancies without introducing extrinsic dopants. The computational predictions are validated through solid‐state synthesis of Bi 2 SeO 2 . More than two orders of magnitude increase are observed in the electron concentration simply by adjusting the synthesis conditions. Additionally, a significant effect of grain boundary scattering on the electron mobility in Bi 2 SeO 2 is revealed, which can also be controlled by adjusting T SSR . By simultaneously optimizing the electron concentration and mobility, a zT of ≈0.2 is achieved at 773 K for self‐doped n ‐type Bi 2 SeO 2 . The study highlights the need for careful control of thermodynamic growth conditions and demonstrates TE performance improvement by varying synthesis parameters according to thermodynamic guidelines.