Cs4PbBr6 is a member of the extended halide perovskite family that is built from isolated (zero-dimensional) PbBr64- octahedra with Cs+ counter ions. The material exhibits anomalous optoelectronic properties: optical absorption and weak emission in the deep ultraviolet (310-375 nm) with efficient luminescence in the green region (∼540 nm). Several hypotheses have been proposed to explain the giant Stokes shift including: (i) phase impurities; (ii) self-trapped exciton; (iii) defect emission. We explore, using first-principles theory and self-consistent Fermi level analysis, the unusual defect chemistry and physics of Cs4PbBr6. We find a heavily compensated system where the room-temperature carrier concentrations (<109 cm-3) are more than one million times lower than the defect concentrations. We show that the low-energy Br-on-Cs antisite results in the formation of a polybromide (Br3) species that can exist in a range of charge states. We further demonstrate from excited-state calculations that tribromide moieties are photoresponsive and can contribute to the observed green luminescence. Photoactivity of polyhalide molecules is expected to be present in other halide perovskite-related compounds where they can influence light absorption and emission.
Bibliographical noteFunding Information:
The authors thank S. D. Stranks and M. V. Kovalenko for useful discussions. This research was supported by Young Researcher Program and Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (2018R1C1B6008728 and 2018M3D1A1058536). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). JC acknowledges the Generalitat Valenciana for the APOSTD/2017/081 fellowship.
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)