Establishing Co‐Continuous Network of Conjugated Polymers and Elastomers for High‐Performance Polymer Solar Cells with Extreme Stretchability

Abstract High power conversion efficiency (PCE) and mechanical robustness are prerequisites for wearable applications of organic solar cells (OSCs). However, stretchability of present active systems (i.e., crack‐onset strain (COS) < 30%) should be improved. While introducing elastomers into active systems is considered a simple method for improving stretchability, the inclusion of elastomers typically results in a decrease in PCE of the OSC with a limited enhancement in the stretchability due to lack of interconnected electrical and mechanical pathways. In this study, it is developed efficient and intrinsically stretchable (IS)‐OSCs with exceptional mechanical robustness, by constructing co‐continuous networks of conjugated polymers (D18) and elastomers (SEBS) within active layers. It is demonstrated that the blend film with a specific ratio (40:60 w/w) of D18:SEBS is crucial for forming co‐continuous structures, establishing well‐connected mechanical and electrical channels. Consequently, D18_0.4:SEBS_0.6/L8‐BO OSCs achieve 16‐times higher stretchability (COS = 126%) than the OSCs based on D18/L8‐BO (COS = 8%), while achieving 4‐times higher PCE (12.13%) compared to the OSCs based on SEBS‐rich active layers (D18_0.2:SEBS_0.8/L8‐BO, PCE = 3.15%). Furthermore, D18_0.4:SEBS_0.6‐based IS‐OSCs preserve 86 and 90% of original PCEs at 50% strain and after 200 stretching/releasing cycles with 15% strain, respectively, demonstrating the highest mechanical robustness among reported IS‐OSCs.