Molecularly Engineered Self‐Healing Scaffold With Customized Dynamic Bonds Enable Stable and Scalable Flexible Perovskite Solar Cells and Modules

ABSTRACT Organometallic halide perovskites hold great promise as materials for high‐performance flexible perovskite solar cells (f‐PSCs). However, achieving uniform, highly crystalline, and mechanically robust perovskite films remains a critical challenge for f‐PSCs. Here, a tandem dynamic bond‐based monomer (ADM) was incorporated into a perovskite film, where it cross‐links in situ to control nucleation and crystallization. This enables multi‐modal passivation via Lewis‐base coordination and hydrogen bonding between ADM and the perovskite lattice. The tandem dynamic bonds within the cross‐linked network, preferentially residing at grain boundaries, endow the flexible perovskite films with an instantaneous self‐curing capability under mild treating conditions (40°C for 30 min). As a result, champion devices deliver a power conversion efficiency (PCE) of 27.12% (certified 26.80%) for small‐area rigid PSCs and 20.00% for a flexible minimodule (10.24 cm 2 ), while a large‐area inverted perovskite submodule with an active area of 655.2 cm 2 achieves a record‐breaking PCE of 21.60% and a certified efficiency of 20.37%, demonstrating excellent scalability. Critically, the intrinsic self‐healing capability underpins exceptional mechanical endurance, allowing the devices to maintain more than 91% of their original PCE after 10 000 bending cycles.