Shallow halogen vacancies in halide optoelectronic materials
Halogen vacancies (V H ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep V H contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH 3 NH 3 PbI 3 and TlBr. Both CH 3 NH 3 PbI 3 and TlBr have been found to have shallow V H , in contrast to commonly seen deep V H in halides. In this paper, several halide optoelectronic materials, i.e., CH 3 NH 3 PbI 3 , CH 3 NH 3 SnI 3 (photovoltaic materials), TlBr, and CsPbBr 3 , (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether V H is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns 2 ions both play important roles in creating shallow V H in halides such as CH 3 NH 3 PbI 3 , CH 3 NH 3 SnI 3 , and TlBr. The key to identifying halides with shallow V H is to find the right crystal structures and compounds that suppress cation orbital hybridization at V H , such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at V H . Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow V H as good electronic and optoelectronic materials.