Exploring Intrinsic and Extrinsic p‑Type Dopability of Atomically Thin β‑TeO₂ from First Principles

Two-dimensional (2D) β-TeO₂ has gained attention as a promising material for optoelectronic and power device applications, thanks to its transparency and high hole mobility. However, the mechanisms driving its p-type conductivity and dopability remain elusive. In this study, we investigate the intrinsic and extrinsic point defects in monolayer and bilayer β-TeO₂, the latter of which has been experimentally synthesized, using the Heyd–Scuseria–Ernzerhof (HSE) + D3 hybrid functional. Our results reveal that most intrinsic defects are unlikely to contribute to p-type doping in 2D β-TeO₂. Moreover, Si and H contamination could further impair p-type conductivity. Since the point defects do not contribute to p-type conductivity, we suggest two possible mechanisms for hole conduction: hopping conduction via localized impurity states, and substrate effects. We also explored substitutional p-type doping in 2D β-TeO₂ with 10 trivalent elements. Among these, the Bi dopant is found to exhibit a relatively shallow acceptor transition level. However, all the dopants introduce deep localized states, where hole polarons are trapped by the lone pairs of Te atoms. Interestingly, monolayer β-TeO₂ shows potential advantages over bilayers due to reduced self-compensation effects for p-type dopants. These findings provide valuable insights into defect engineering strategies for future electronic applications involving 2D β-TeO₂.