Unraveling Morphological Recoverability and Dynamics in Intrinsically Stretchable Organic Photovoltaics

The future of self‐powered wearable electronics is dependent on the development of energy sources that are not only stretchable but also durable under the cyclic strains of real‐world use. While intrinsically stretchable organic photovoltaics (IS‐OPVs) hold great promise, their adoption is hindered by a limited understanding of their mechanical recovery dynamics, the ability to restore function after deformation. Although initial stretchability has been prioritized in research, recovery behavior is recognized as the true determinant of long‐term durability. In this study, morphological recoverability is introduced as a critical design parameter for IS‐OPVs. By employing in situ grazing‐incidence X‐ray scattering complemented by optical and nanomechanical probes, how acceptor material type (small‐molecule, polymerized small‐molecule, and polymer) governs deformation mechanisms and structural restoration pathways is systematically unraveled. It is demonstrated that molecular architecture and blend morphology dictate not only material alignment under strain but also its intrinsic capacity for recovery. Homogeneous, entangled all‐polymer networks are identified to exhibit superior, viscoelastic recovery, which translates to exceptional device stability. Through the establishment of a definitive link between nanoscale morphology, recovery dynamics, and operational endurance, a clear guideline is provided for engineering mechanically resilient photoactive layers, paving the way for durable and reliable next‐generation wearable power sources.