Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States

Organic-inorganic perovskites are attracting increasing attention for their use in high-performance solar cells. Nevertheless, a detailed understanding of charge generation, interplay of excitons and free charge carriers, and recombination pathways, crucial for further device improvement, remains incomplete. Here, we present an analytical model describing both equilibrium properties of free charge carriers and excitons in the presence of electronic subgap trap states and their time evolution after photoexcitation in CH3NH3PbI3-xClx. At low fluences the charge-trapping pathways limit the photoluminescence quantum efficiency, whereas at high fluences the traps are predominantly filled and recombination of the photogenerated species is dominated by efficient radiative processes. We show experimentally that the photoluminescence quantum efficiency approaches 100% at low temperatures and at high fluences, as predicted by our model. Our approach provides a theoretical framework to understand the fundamental physics of perovskite semiconductors and to help in designing and enhancing the material for improved optoelectronic device operation.