Thermal transition of OSCs constituent materials are often insufficiently researched, resulting in trial-and-error rather than rational approaches to post-casting processing strategies to improve aggregation to enhance the power conversion efficiency. Despite the potential utility, little is known about the thermal transitions of the high-performance acceptors. Here, by using an optical method, we discover that the acceptor N3 has a clear solid-state aggregation transition at 82 °C. The transition informs and enables a double-annealing method that can fine‐tune aggregation and the device morphology. Compared with 16.6% efficiency for the control devices, higher efficiency of 17.6% is obtained through the improved protocol. Design of high-performance acceptors with yet lower aggregation transitions might be required to successfully transition to low thermal budget industrial processing methods where annealing temperatures on plastic substrates have to be kept low.
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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