Alkyl‐Chain Branching of Non‐Fullerene Acceptors Flanking Conjugated Side Groups toward Highly Efficient Organic Solar Cells

Abstract Side‐chain modifications of non‐fullerene acceptors (NFAs) are essential for harvesting their full potential in organic solar cells (OSC). Here, an effective alkyl‐chain‐branching approach of the Y‐series NFAs flanking meta‐substituted phenyl side groups at the outer positions is demonstrated. Compared to BTP‐4F‐PC6 with linear m ‐hexylphenyl chains, two new acceptors named BTP‐4F‐P2EH and BTP‐4F‐P3EH are developed with bulkier alkyl chains branched at the β and γ positions, respectively. These branched chains result in altered molecular packing of the NFAs and afford higher open‐circuit voltage of the devices. Despite the blue‐shifted absorption of the branched‐chain NFAs, their blends with PBDB‐T‐2F enable improved short‐circuit current density for the corresponding devices owing to the more suitable phase separation and better exciton dissociation. Consequently, the OSCs based on BTP‐4F‐P2EH and BTP‐4F‐P3EH yield enhanced device performance of 18.22% and 17.57%, respectively, outperforming the BTP‐4F‐PC6‐based ones (17.22%). These results highlight that the side‐chain branching design of NFAs has great potential in optimizing molecular properties and promoting photovoltaic performance.