Over 18.8% Efficiency of Layer‐By‐Layer Organic Photovoltaics Enabled by Ameliorating Exciton Utilization in Acceptor Layer

The layer‐by‐layer (LbL) organic photovoltaics (OPVs) are constructed with wide‐bandgap donor PM1 and narrow‐bandgap acceptor L8‐BO. The exciton utilization near cathode is still challenging considering restricted diffusion distance of excitons and inability for transferring energy from L8‐BO to PM1. Herein, donor incorporation into acceptor layer (DIA) strategy is employed to improve exciton utilization near cathode. The efficiency of LbL OPVs can be improved from 18.02% to 18.81% by incorporating 10 wt% PM1 into L8‐BO layer, which is closely associated with efficient exciton separation into L8‐BO layer originated from more adequate donor/acceptor interface for faster charge transfer, as evidenced by magneto‐photocurrent and transient absorption results. The in situ test and morphological characterization clarify that molecular packing property can be improved benefited from prolonged aggregation and nucleation time of acceptor layer assisted by DIA strategy, contributing to more efficient charge transport and inhibited charge recombination in active layers. The thickness insensitive property of LbL OPVs can be also improved induced by DIA strategy, indicated by PCE retention value (82.2% vs. 74.0%) for PM1/L8‐BO:PM1 and PM1/L8‐BO OPVs when acceptor layer thickness increased to ≈180 nm. This work demonstrates the effectiveness of DIA strategy in improving efficiency and thickness tolerance of LbL OPVs. The exciton utilization near the cathode of LbL OPVs is still challenging due to the restricted diffusion distance of excitons. By incorporating less PM1 into the L8‐BO layer, an optimal PCE of 18.81% can be achieved benefiting from more efficient exciton separation in the L8‐BO layer near the cathode, as well as more ordered molecular arrangement for charge transport and collection.