Short-lived charge-transfer excitons in organic photovoltaic cells studied by high-field magneto-photocurrent

The main route of charge photogeneration in efficient organic photovoltaic cells based on bulk hetero-junction donor–acceptor blends involves short-lived charge-transfer excitons at the donor–acceptor interfaces. The cell efficiency is critically affected by the charge-transfer exciton recombination and dissociation processes. By measuring the magneto-photocurrent under ambient conditions at room temperature, we show here that magnetic field-induced spin-mixing among the charge-transfer exciton spin sublevels occurs in fields up to at least 8.5 Tesla. The resulting magneto-photocurrent increases at high fields showing non-saturating behaviour up to the highest applied field. We attribute the observed high-field spin-mixing mechanism to the difference in the donor–acceptor g-factors. The non-saturating magneto-photocurrent response at high field indicates that there exist charge-transfer excitons with lifetime in the sub-nanosecond time domain. The non-Lorentzian high-field magneto-photocurrent response indicates a dispersive decay mechanism that originates due to a broad distribution of charge-transfer exciton lifetimes.