Manipulation of Charge Delocalization in a Bulk Heterojunction Material Using a Mid-Infrared Push Pulse

[Image: see text] In organic bulk heterojunction materials, charge delocalization has been proposed to play a vital role in the generation of free carriers by effectively reducing the Coulomb attraction via an interfacial charge transfer exciton (CTX). Pump-push-probe (PPP) experiments produced evidence that the excess energy given by a push pulse enhances delocalization, thereby increasing photocurrent. However, previous studies have employed near-infrared push pulses in the range ∼0.4–0.6 eV, which is larger than the binding energy of a typical CTX. This raises the doubt that the push pulse may directly promote dissociation without involving delocalized states. Here, we perform PPP experiments with mid-infrared push pulses at energies that are well below the binding energy of a CTX state (0.12–0.25 eV). We identify three types of CTXs: delocalized, localized, and trapped. The excitation resides over multiple polymer chains in delocalized CTXs, while it is restricted to a single chain (albeit maintaining a degree of intrachain delocalization) in localized CTXs. Trapped CTXs are instead completely localized. The pump pulse generates a “hot” delocalized CTX, which promptly relaxes to a localized CTX and eventually to trapped states. We find that photo-exciting localized CTXs with push pulses resonant to the mid-infrared charge transfer absorption can promote delocalization and, in turn, contribute to the formation of long-lived charge separated states. On the other hand, we found that trapped CTXs are non-responsive to the push pulses. We hypothesize that delocalized states identified in prior studies are only accessible in systems where there is significant interchain electronic coupling or regioregularity that supports either inter- or intrachain polaron delocalization. This, in turn, emphasizes the importance of engineering the micromorphology and energetics of the donor–acceptor interface to exploit the full potential of a material for photovoltaic applications.