Realizing over 18% Efficiency for M‐Series Acceptor‐Based Polymer Solar Cells by Improving Light Utilization.

M‐series molecules are one kind of promising acceptor‐donor‐acceptor (A‐D‐A)‐type acceptors for constructing high‐performance organic solar cells (OSCs). However, their power conversion efficiencies (PCEs) are lagging behind that of current state‐of‐the‐art OSCs, limited by the relatively low fill factor (FF) and photocurrent. Herein, combined strategies of layer‐by‐layer (LBL) deposition and interface engineering are conducted to systematically improve light utilization and thus PCEs for M36‐based OSCs. Through choosing a proper processing solvent, a PCE of 17.3% with an FF of 77.9% is achieved for the resulting LBL devices, much higher than those (15.9%/74.0%) from the blend‐casting devices. The improvement is assigned to the favorable morphological evolution that facilitates carrier generation and transport as well as reduces charge recombination. More importantly, light‐harvesting of the active layers can be enhanced upon employing a self‐assembled monolayer of (2‐(9H‐carbazol‐9‐yl)ethyl)phosphonic acid (2PACz) instead of the widely used PEDOT:PSS as the hole‐selecting layer, due to the decreased parasitic absorption of the former. Consequently, 2PACz‐based LBL devices exhibit significantly increased photocurrent, affording a PCE up to 18.2%, which is the highest among the reported A‐D‐A‐type acceptor‐based OSCs. These results deliver important strategies to enhance the performance of OSCs and thus highlight the great potential of M‐series acceptors for practical applications. [ABSTRACT FROM AUTHOR]