Perovskite Excitonics: Primary Exciton Creation and Crossover from Free Carriers to a Secondary Exciton Phase

Abstract Understanding exciton formation is of fundamental importance for emerging optoelectronic materials, like hybrid organic–inorganic perovskites, as excitons are the lowest‐energy photoexcitations in semiconductors, are electrically neutral, and do not directly contribute to charge transport, but can emit light more efficiently than free carriers. However, despite the increasing attention toward these materials, experimental results on the processes of formation of an exciton population in perovskites are still elusive. Here, an ultrafast differential photoluminescence technique is presented that is able to track the kinetics of exciton formation and dissociation in CH₃NH₃PbBr₃. Data show the presence of geminate excitons, i.e., primary excitons directly created upon photon absorption, and their dissociation into free electron–hole pairs. The formation is demonstrated of a secondary exciton phase through pairing of the initial population of free carriers. The analysis of the generation of secondary excitons provides an estimate of the Langevin factor, the parameter governing the charge‐pairing rate. Understanding and controlling the formation of a bright exciton population instead of a highly conductive free carrier population may help to design new hybrid perovskite materials with tailored optoelectronic functionalities.