Construction of Linear Tetramer‐type Acceptors for High‐efficiency and High‐stability Organic Solar Cells

The photovoltaic conversion efficiency (PCE) of organic solar cells (OSCs) has exceeded 20%, which has met the requirements for commercialisation. In the current stage, the main focus is to balance the performance and stability. It has been shown that all‐polymer formulation can improve device stability, however, PCE is not in satifsfaction, and the batch‐to‐batch variation leads to quality control issues. In this work, we constructed monodispersed tetramer NFA materials named G‐1 and G‐2, to best integrate the merits of small molecule and polymer. It was revealed that different connecting units at the centre could significantly affect the molecular planarity and thin film morphology. The alkene‐bonded tetramer G‐1 had a more regioregular structure, leading to better molecular planarity, and more ordered packing in thin film. More importantly, the oligomeration induced a favourable face‐on orientation, achieved a lower binding energy and a higher photoluminescence yield. As a result, the exciton and charge carrier kinetics was optimized with reduced non‐radiative energy loss. The OSC based on PM6:G‐1 achieved a PCE of 19.6%, which is the highest PCE reported so far for oligomer‐based binary OSC. In addition, the device stability was largely improved, showing a lifetime over 10000 hours in the inverted OSC device.