All‐Green Solvent‐Processed Planar Heterojunction Organic Solar Cells with Outstanding Power Conversion Efficiency of 16%

Abstract Device engineering is an effective way to improve the photovoltaic performance of organic solar cells (OSCs). Currently, the widely used bulk heterojunction (BHJ) structure has problems such as material solubility limitations and the emerging pseudoplanar heterojunction (PPHJ) structure is also troubled by printing technology requirements. However, these issues can be solved by the reasonable application of traditional planar heterojunction (PHJ) structure. Herein, PM6:BO‐4F system is selected to prepare PHJ devices by combining sequential spin‐coating and orthogonal solvent strategy. In view of the good solubility of PM6 and BO‐4F in commonly used high‐boiling solvent chlorobenzene (CB) and green solvent tetrahydrofuran (THF), respectively, the PHJ devices are successfully prepared by using these two orthogonal solvents, achieving a power conversion efficiency (PCE) of 15.6%. On this basis, green nonhalogen reagent o ‐xylene (O‐XY) is further used to process PM6. Due to the large polarity difference between O‐XY and THF, all‐green solvent‐processed PHJ devices are successfully fabricated and obtain an astonishing PCE of 16%. As far as it is known, it is the highest efficiency for PHJ OSCs. The results prove the huge research potential of PHJ structure and point out new direction for solving OSC materials compatibility, long‐term stability, and future commercial applications.