Recently, the efficiencies of nonfullerene organic photovoltaics (OPVs) have surpassed 18%. The realization of these high-efficiency OPVs is based on the use of push-pull type conjugated polymer donors, which are costly and not scalable. In contrast, polythiophenes (PTs) hold great promises in cost and scalability, rendering them alternatives to the push-pull type donors for commercial applications. Here, we reveal the crucial role of miscibility and crystallinity in determining the performance of PT:nonfullerene systems. Our study underscores the need for nonfullerene acceptors with much lower miscibility in matching PTs and provides design rules for higher efficiency PT:nonfullerene solar cells.
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