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Organo-halide perovskite solar cells (PSCs) have emerged as next-generation photovoltaics, owing to their high power-conversion efficiency (PCE), lower production cost, and high flexibility. ABX 3 -structured methylammonium lead triiodide (CH 3 NH 3 PbI 3  or MAPbI 3 ) perovskite is a widely studied light-absorbing material in PSCs. Interestingly, a small amount of chlorine incorporation into MAPbI 3  increases charge carrier diffusion lengths (from 129 nm to 1069 nm), which enables planar structured PSCs with high PCEs. However, existence of chloride ions in the final perovskite film is still under debate. Contrastingly, few studies reported a negligible amount or absence of chloride ions in the final film, while others reported detection of chloride ions in the final film. Herein, we observed the microstructure and chlorine content of MAPbI 3−x Cl x  thin films with increasing temperature via an in-situ nano-Auger spectroscopy and in-situ scanning electron microscopic analysis. The relative precipitation of MAPbI 3−x Cl x  films occur at lower temperature and MAPbI 3−x Cl x  grains grow faster than those of MAPbI 3  grains. Local concentrations of chlorine at intragrain and the vicinity of grain boundary were analyzed to understand the behavior and role of the chloride ions during the microstructural evolution of the MAPbI 3−x Cl x  films.

In-Situ Nano-Auger Probe of Chloride-Ions during CH3NH3PbI3−xClx Perovskite Formation