A Strain Relaxation Modulation for Printing High‐performance Flexible Pseudo‐Planar Heterojunction Organic Solar Cells

The rational toughening of photosensitive films is crucial for the development of robust and flexible organic solar cells (F-OSCs), which are always influenced by mechanical strain and thermodynamic relaxation within the films. Nevertheless, the potential determinants of these properties and quantitative metrics modulating the overall performance of flexible devices have not been thoroughly defined. Herein, a fine-grain strengthening strategy is demonstrated for mitigating the excessive aggregation or crystallization in small-molecule acceptor films, the secondary thermal relaxation of side chains in polyethylene oxide (PEO) local motion restricts the free fluctuation volume through hydrogen-bonding interactions, thereby suppressing the non-ideal thermodynamic behavior and residual-enriched state. These contribute to an increase in yield strength and a reduction in microcracks while enhancing the fracture energy at the donor/acceptor interface. Finally, the optimal F-OSCs demonstrate champion PCEs of 19.12% (0.04 cm²) and 16.92% (1.00 cm²), and maintain 80% of their initial efficiency after heating at 85 °C for 2600 h. Besides, the flexibility and mechanical robustness of devices are also optimized, the elastic modulus and stiffness are decreased by 50.68% and 5.71%. This work provides interesting references for the synergistic enhancement of efficiency, mechanical and environmental stability in flexible organic photovoltaics.