Herein, two diketopyrrolopyrrole (DPP)-based, small-molecule isomers, o- and p-DPP-PhCN, were introduced as acceptors in ternary organic solar cells (OSCs). The isomers have the same molecular backbone but differ in the positions of the cyanide (CN) substituents (ortho and para), which greatly affects their packing behavior. Ternary solar cells composed of poly(3-hexylthiophene) (P3HT):DPP-PhCN:phenyl-C61-butyric acid methyl ester (PCBM) were fabricated, and the effects of the different packing behaviors of the third component on the device performance and the working mechanism of the ternary cells were investigated. The addition of o-DPP-PhCN with a relatively high-lying lowest unoccupied molecular orbital energy level resulted in an increase in the open-circuit voltage (VOC) in the ternary devices, demonstrating the alloy-like structure of the two acceptors (o-DPP-PhCN and PCBM) in the ternary system. However, the p-DPP-PhCN-based ternary cells exhibited VOC values similar to that of a P3HT:PCBM binary cell, irrespective of the addition of p-DPP-PhCN, indicating a cascade energy-level structure in the ternary system and an effective charge transfer from the P3HT to the PCBM. Importantly, by increasing the addition of p-DPP-PhCN, the short-circuit current density increased substantially, resulting in pronounced shoulder peaks in the external quantum efficiency responses in the long-wavelength region, corresponding to the contribution of the photocurrent generated by the light absorption of p-DPP-PhCN. Despite sharing the same molecular backbone, the two DPP-PhCNs exhibited substantially different packing behaviors according to the position of their CN substituents, which also greatly affected the working mechanism of the ternary devices fabricated using the DPP-PhCNs as the third component.
Terminal group engineering for small-molecule donors boosts the performance of nonfullerene organic solar cells