LAUSR

With the emergence of fused ring electron acceptors, the power conversion efficiency of organic solar cells reached 19%. In comparison with the electron donor and acceptor materials progress, the development of cathode interlayers lags. As a result, charge extraction barriers, interfacial trap states, and significant transport resistance may be induced due to the unfavorable cathode interlayer, limiting the device performances. Herein, a hybrid cathode interlayer composed of PNDIT‐F3N and PDIN is adopted to investigate the interaction between the photoexcited acceptor and cathode interlayer. The state of art acceptor Y6 is chosen and blended with PM6 as the active layer. The device with hybrid interlayer, PNDIT‐F3N:PDIN (0.6:0.4, in wt%), attains a power conversion efficiency of 17.4%, outperforming devices with other cathode interlayer such as NDI‐M, PDINO, and Phen‐DPO. It is resulted from enhanced exciton dissociation, reduced trap‐assisted recombination, and smaller transfer resistance. Therefore, the hybrid interlayer strategy is demonstrated as an efficient approach to improve device performance, shedding light on the selection and engineering of cathode interlayers for pairing the increasing number of fused ring electron acceptors.