Toward Efficient Polymer Solar Cells Processed by a Solution‐Processed Layer‐By‐Layer Approach

The solution‐processed layer‐by‐layer (LBL) method has potential to achieve high‐performance polymer solar cells (PSCs) due to its advantage of enriching donors near the anode and acceptors near the cathode. However, power conversion efficiencies (PCEs) of the LBL‐PSCs are still significantly lower than those of conventional one‐step‐processed PSCs (OS‐PSCs). A method to solve the critical problems in LBL‐PSCs is reported here. By employing a specific mixed solvent (o‐dichlorobenzene [o‐DCB]/tetrahydrofuran) to spin‐coat the small‐molecular acceptor IT‐4F onto a layer of the newly designed polymer donor (PBDB‐TFS1), appropriate interdiffusion between the PBDB‐TFS1 and the IT‐4F can critically be controlled, and then an ideal phase separation of the active layer and large donor/acceptor interface area can be realized with a certain amount of o‐DCB. The PSCs based on the LBL method exhibit PCEs as high as 13.0%, higher than that of the counterpart (11.8%) made by the conventional OS solution method. This preliminary work reveals that the LBL method is a promising approach to the promotion of the photovoltaic performance of polymer solar cells.