Defect Physics of Pseudo-cubic Mixed Halide Lead Perovskites from First Principles

Abstract

Owing to the increasing popularity of lead-based hybrid perovskites for photovoltaic (PV) applications, it is crucial to understand their defect physics and its influence on their optoelectronic properties. In this work, we simulate various point defects in pseudo-cubic structures of mixed iodide-bromide and bromide-chloride methylammonium lead perovskites with the general formula MAPbI_{3-y}Br_{y} or MAPbBr_{3-y}Cl_{y} (where y is between 0 and 3), and use first principles based density functional theory computations to study their relative formation energies and charge transition levels. We identify vacancy defects and Pb on MA anti-site defect as the lowest energy native defects in each perovskite. We observe that while the low energy defects in all MAPbI_{3-y}Br_{y} systems only create shallow transition levels, the Br or Cl vacancy defects in the Cl-containing pervoskites have low energy and form deep levels which become deeper for higher Cl content. Further, we study extrinsic substitution by different elements at the Pb site in MAPbBr_{3}, MAPbCl_{3} and the 50-50 mixed halide perovskite, MAPbBr_{1.5}Cl_{1.5}, and identify some transition metals that create lower energy defects than the dominant intrinsic defects and also create mid-gap charge transition levels.