AbstractIn organic solar cells (OSCs), cathode interfacial materials are generally designed with highly polar groups to increase the capability of lowering the work function of cathode. However, the strong polar group could result in a high surface energy and poor physical contact at the active layer surface, posing a challenge for interlayer engineering to address the trade-off between device stability and efficiency. Herein, we report a hydrogen-bonding interfacial material, aliphatic amine-functionalized perylene-diimide (PDINN), which simultaneously down-shifts the work function of the air stable cathodes (silver and copper), and maintains good interfacial contact with the active layer. The OSCs based on PDINN engineered silver-cathode demonstrate a high power conversion efficiency of 17.23% (certified value 16.77% by NREL) and high stability. Our results indicate that PDINN is an effective cathode interfacial material and interlayer engineering via suitable intermolecular interactions is a feasible approach to improve device performance of OSCs.