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Constructing tandem and multi‐blend organic solar cells (OSCs) is an effective way to overcome the absorption limitations of conventional single‐junction devices. However, these methods inevitably require tedious multilayer deposition or complicated morphology‐optimization procedures. Herein, sequential deposition is utilized as an effective and simple method to fabricate multicomponent OSCs with a double‐bulk heterojunction (BHJ) structure of the active layer to further improve photovoltaic performance. Two efficient donor‐acceptor pairs, D18‐Cl:BTP‐eC9 and PM6:L8‐BO, are sequentially deposited to form the D18‐Cl:BTP‐eC9/PM6:L8‐BO double‐BHJ active layer. In these double‐BHJ OSCs, light absorption is significantly improved, and optimal morphology is also retained without requiring a more complicated morphology optimization involved in quaternary blends. Compared to the quaternary blend devices, energy loss (Eloss) is also reduced by rationally matching each donor with an appropriate acceptor. Consequently, the power conversion efficiency (PCE) is improved from 18.25% for D18‐Cl:BTP‐eC9 and 18.69% for PM6:L8‐BO based binary blend OSCs to 19.61% for the double‐BHJ OSCs. In contrast, a D18‐Cl:PM6:L8‐BO:BTP‐eC9 quaternary blend of OSCs exhibited a dramatically reduced PCE of 15.83%. These results demonstrate that a double‐BHJ strategy, with a relatively simple processing procedure, can potentially enhance the device performance of OSCs and lead to more widespread use.
A double‐bulk heterojunction active layer structure for organic solar cell (OSC) is constructed by sequential deposition of a PM6:L8‐BO blend on top of a D18‐Cl:BTP‐eC9 blend, in which the optimal morphology of the two binary blends were retained with a vertical phase separation, resulting in a record PCE of 19.61%.