General Rules for the Impact of Energetic Disorder and Mobility on Nongeminate Recombination in Phase-Separated Organic Solar Cells

Abstract: State of the art organic solar cells exhibit power conversion efficiencies of 18 % and above. These devices benefit from the suppression of free charge recombination with regard to the Langevin-limit of charge encounter in a homogeneous medium. It has been recognized that the main cause of suppressed free charge recombination is the reformation and resplitting of charge transfer states at the interface between donor and acceptor domains. Here, we use kinetic Monte Carlo simulations to understand the interplay between free charge motion and recombination in an energetically-disordered phase-separated donor-acceptor blend. We identify conditions for encounter-dominated and resplitting-dominated recombination. In the former regime, recombination is proportional to mobility for all parameters tested and only slightly reduced with respect to the Langevin limit. In contrast, mobility is not the decisive parameter determining the non-geminate recombination coefficient k_2in the latter case where k_2 is a sole function of the morphology, CT and CS energetics and CT states decay properties. Our simulations also show that free charge encounter in the phase-separated disordered blend is determined by the average mobility of all carriers, while CT reformation and resplitting involves mostly states near the transport energy. Therefore, charge encounter is more affected by increased disorder than the resplitting of the CT state. As a consequence, for a given mobility, larger energetic disorder in combination with a higher hopping rate is preferred. These findings have important implications for the understanding of suppressed recombination in solar cells with non-fullerene acceptors which are known to exhibit lower energetic disorder than fullerenes.