Suppressing Charged Cation Antisites via Se Vapor Annealing Enables p‐Type Dopability in AgBiSe₂–SnSe Thermoelectrics

Abstract Cation disordering is commonly found in multinary cubic compounds, but its effect on electronic properties has been neglected because of difficulties in determining the ordered structure and defect energetics. An absence of rational understanding of the point defects present has led to poor reproducibility and uncontrolled conduction type. AgBiSe₂ is a representative compound that suffers from poor reproducibility of thermoelectric properties, while the origins of its intrinsic n‐type conductivity remain speculative. Here, it is demonstrated that cation disordering is facilitated by Bi_Ag charged antisite defects in cubic AgBiSe₂ which also act as a principal donor defect that greatly controls the electronic properties. Using density functional theory calculations and in situ Raman spectroscopy, how saturation annealing with selenium vapor can stabilize p‐type conductivity in cubic AgBiSe₂ alloyed with SnSe at high temperatures is elucidated. With stable and controlled hole concentration, a peak is observed in the weighted mobility and the density‐of‐states effective mass in AgBiSnSe₃, implying an increased valley degeneracy in this system. These findings corroborate the importance of considering the defect energetics for exploring the dopability of ternary thermoelectric chalcogenides and engineering electronic bands by controlling self‐doping.