Organic Macromolecular materials for Efficient Transport Properties in Light-Energy Conversion Applications. Final Report

Abstract

We are grateful for the Department of Energy for support of this research related to the improvement of power conversion efficiency of organic photovoltaic architectures over the years. As we noted at the beginning and now, the fundamental photophysical pathways that connect the absorption of light to the production of charge carriers remain elusive in spite of continuing experimental and theoretical efforts. Our investigations were directed toward gaining information about the mechanism of this ultrafast, long-range charge separation in photovoltaic systems with non-fullerene acceptors. This problem is still of high importance for the organic photovoltaics because solving this problem will allow us to minimize the contribution of the geminate recombination and trapping the charges in bound charge transfer states. Extremely low charge separation driving energy specific to non-fullerene acceptor systems reduces the energy loss in organic photovoltaic cells making them competitive with inorganic and perovskite photovoltaic systems. A major accomplishment of this study was to detail the long-range ballistic charge separation in donor-non-fullerene acceptor photovoltaic systems. We have successfully probed the spatial structure of ultrafast long-range (~40nm) ballistic charge separation in donor-non-fullerene acceptor photovoltaic system. We performed a systematic investigation of the delocalized states in their connection to the efficient long-range charge separation using the pulse pair interferometric near-field microscopy method. This method possesses unique capability of detecting coherent effects with spatial resolution of few tens of nanometers. These measurements allowed us the determination of delocalized excitations locally in a thin film photovoltaic system and to be connected to the long-range charge separation and the power conversion efficiency. We also investigated long-lived coupled triplet pairs in a singlet fission process for the possibility of concerted extraction of two electrons from triplet entangled states. New experimental and theoretical approaches of the concerted double electron extraction were carried out. The impact of this work is the development of important structure-property relationships to the design criteria of more efficient organic photovoltaic cells in accordance with the BES mission.