Photoexcitation dynamics in polythiophene/fullerene blends for photovoltaic applications

► Localized polarons and excitons are instantaneously photogenerated in D-A blends. ► The generation of delocalized polarons occurs at the expense of excitons. ► The dynamics of localized polarons are unrelated with those of excitons. ► Ultrafast quantum interference anti-resonances are photogenerated.