Supramolecular Polyurethane “Ligaments” Enabling Room‐Temperature Self‐Healing Flexible Perovskite Solar Cells and Mini‐Modules

Abstract Flexible perovskite solar cells (F‐PSCs) have emerged as promising alternatives to conventional silicon solar cells for applications in portable and wearable electronics. However, the mechanical stability of inherently brittle perovskite, due to residual lattice stress and ductile fracture formation, poses significant challenges to the long‐term photovoltaic performance and device lifetime. In this paper, to address this issue, a dynamic “ligament” composed of supramolecular poly(dimethylsiloxane) polyurethane (DSSP‐PPU) is introduced into the grain boundaries of the PSCs, facilitating the release of residual stress and softening of the grain boundaries. Remarkably, this dynamic “ligament” exhibits excellent self‐healing properties and enables the healing of cracks in perovskite films at room temperature. The obtained PSCs have achieved power conversion efficiencies of 23.73% and 22.24% for rigid substrates and flexible substrates, respectively, also 17.32% for flexible mini‐modules. Notably, the F‐PSCs retain nearly 80% of their initial efficiency even after subjecting the F‐PSCs to 8000 bending cycles (r = 2 mm), which can further recover to almost 90% of the initial efficiency through the self‐healing process. This remarkable improvement in device stability and longevity holds great promise for extending the overall lifetime of F‐PSCs.