The ultrafast dynamics of non-equilibrium photoexcitations govern the initial energy and charge transport in photovoltaic (PV) materials. Hence, they may strongly influence device operation. Such ultrafast dynamics depend, in turn, on the details of the electronic system and its coupling to the nuclear degrees of freedom. Here we discuss a few examples showing how ultrafast two-dimensional electronic spectroscopy can provide detailed new insight into light-induced charge transfer processes in technologically-relevant PV materials. Specifically, we discuss the role of vibronic couplings and conical intersections for the light-initiated intermolecular dynamics in efficient organic PV thin films, and ultrafast charge carrier relaxation and exciton dynamics in inorganic halide perovskites crystals. Our results suggest potential new strategies to control coherent energy and charge transport in PV materials by tailoring electron-phonon couplings.
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