Transforming Ionene Polymers into Efficient Cathode Interlayers with Pendent Fullerenes

A new and highly efficient cathode interlayer material for organic photovoltaics (OPVs) was produced by integrating C60 fullerene monomers into ionene polymers. The power of these novel “C60‐ionenes” for interface modification enables the use of numerous high work‐function metals (e.g., silver, copper, and gold) as the cathode in efficient OPV devices. C60‐ionene boosted power conversion efficiencies (PCEs) of solar cells, fabricated with silver cathodes, from 2.79 % to 10.51 % for devices with a fullerene acceptor in the active layer, and from 3.89 % to 11.04 % for devices with a non‐fullerene acceptor in the active layer, demonstrating the versatility of this interfacial layer. The introduction of fullerene moieties dramatically improved the conductivity of ionene polymers, affording devices with high efficiency by reducing charge accumulation at the cathode/active layer interface. The power of C60‐ionene to improve electron injection and extraction between metal electrodes and organic semiconductors highlights its promise to overcome energy barriers at the hard‐soft materials interface to the benefit of organic electronics. C60‐containing ionene polymers reduce energy barriers between common high‐work‐function metal electrodes and organic semiconductors. These interfacial layers enable an efficient use of high‐work‐function metal cathodes, affording high efficiency solar cells, containing either fullerene‐ or non‐fullerene‐ active layers, over a wide range of interlayer thickness.