Green Printing for Scalable Organic Photovoltaic Modules by Controlling the Gradient Marangoni Flow

Abstract Despite the rapid development in the performances of organic solar cells (OSCs), high‐performance OSC modules based on green printing are still limited. The severe Coffee‐ring effect (CRE) is considered to be the primary reason for the nonuniform distribution of active layer films. To solve this key printing problem, the cosolvent strategy is presented to deposit the active layer films. The guest solvent Mesitylene with a higher boiling point and a lower surface tension is incorporated into the host solvent o‐XY to optimize the rheological properties, such as surface tension and viscosity of the active layer solutions. And the synergistic effect of inward Marangoni flow generation and solution thickening caused by the cosolvent strategy can effectively restrain CRE, resulting in highly homogeneous large‐area active layer films. In addition, the optimized crystallization and phase separation of active layer films effectively accelerate the charge transport and exciton dissociation of devices. Consequently, based on PM6:BTP‐eC9 system, the device prepared with the co‐solvent strategy shows the a power conversion efficiency of 17.80%. Moreover, as the effective area scales to 1 and 16.94 cm², the recorded performances are altered to 16.71% and 14.58%. This study provides a universal pathway for the development of green‐printed high‐efficiency organic photovoltaics.