Planar Benzofuran Inside-Fused Perylenediimide Dimers for High V_OC Fullerene-Free Organic Solar Cells

Bulk heterojunction organic solar cells based on perylenediimide (PDI) derivatives as electron acceptors have afforded high power conversion efficiency (PCE) but still lagged behind fullerene-based analogues. Design of novel molecular structures by adjusting the PDI ring and/or connection mode remains the breakthrough point to improve the photovoltaic performance. After introducing benzofuran at the inside bay positions and being linked with a single bond and a fluorene unit, mandatory planar PDI dimers were achieved and named FDI2 and F-FDI2. Both acceptors show high-lying LUMO energy levels and realize high VOC beyond 1.0 V when using the classic polymer of PBDB-T as an electron donor. However, FDI2 and F-FDI2 gave totally different photovoltaic performance with PCEs of 0.15 and 6.33%, respectively. The central fluorene linkage increased the miscibility of materials and ensured a much higher short-circuit current because of the formation of suitable phase separation. Our results demonstrated that utilizing the mandatory planar skeleton of PDI dimers is a simple and effective strategy to achieve high-performance nonfullerene electron acceptors, and the modulation of central conjugated units is also vital.