Poor Photovoltaic Performance of Cs₃Bi₂I₉: An Insight through First-Principles Calculations

Bismuth-based halide perovskite derivatives have now attracted huge attention for photovoltaic (PV) applications after the unparalleled success of lead-based halide perovskites. However, the performances of PV devices based on these compounds are poor, despite theoretical predictions. In this Article, we have investigated the electronic structure and defect formation energies of Cs₃Bi₂I₉ using density functional theory (DFT) calculations. The calculated electronic bandstructure indicates an indirect bandgap and high carrier effective masses. Our calculations reveal a large stability region for this compound; however, deep level defects are quite prominent. Even the varying chemical potentials from the stoichiometric region do not eliminate the presence of deep defects, ultimately limiting photovoltaic efficiencies

Rb as an Alternative Cation for Templating Inorganic Lead-Free Perovskites for Solution Processed Photovoltaics

Even though perovskite solar cells have reached 22% efficiency within a very short span, the presence of lead is a major bottleneck to its commercial application. Tin and germanium based perovskites failed to be viable replacements due to the instability of their +2 oxidation states. Antimony could be a possible replacement, forming perovskites with structure A₃M₂X₉. However, solution processing of Cs, organic ammonium based Sb perovskites result in the formation of the dimer phase with poor charge transport properties. Here we demonstrate that Rb can template the formation of the desired layered phase irrespective of processing methodologies, enabling the demonstration of efficient lead-free perovskite solar cells