Vacuum‐Free, All‐Solution, and All‐Air Processed Organic Photovoltaics with over 11% Efficiency and Promoted Stability Using Layer‐by‐Layer Codoped Polymeric Electrodes

Abstract

Nonfullerene organic photovoltaics (OPVs) have achieved a breakthrough in pushing the efficiency beyond 15%. Although this sheds light on OPV commercialization, the high cost associated with the scalable device fabrications remains a giant challenge. Herein, a vacuum‐free, all‐solution and all‐air processed OPV is reported that yields 11.12% efficiency with a fill factor of 0.725, due to the usages of high‐merit polymeric electrodes and modified active blends. The design principle toward the high‐merit electrodes is to induce heavy acid doping into the matrices for a raised carrier concentration and mobility, make a large removal of insulating components in the whole matrices rather than surfaces, and restrain the formation of large‐domain aggregates. A unique layer‐by‐layer doping is developed to enable the polymeric electrodes with record‐high trade‐offs between optical transmittance and electrical conductivity. Moreover, solvent vapor annealing is proposed to boost device efficiency and it has the advantages of finely adjusting the active blend morphology and raising the electron mobility. The resulting devices are highly efficient and most (≈91%) of the initial efficiency are maintained in 30 day storage. This work indicates bright future for making cost‐effective all‐solution processed OPVs in air.