The exciton diffusion length (L _D) and fluid mechanics were effectively optimized by modulating the polymer aggregation structure. The printing PPHJ flexible OPVs exhibits more than 18% efficiency, and the flexible device maintained 90.4% of the initial PCE after 2000 bending cycles, showing excellent mechanical stability. Meanwhile, the rigid device exhibits 20% efficiency (certified19.68%, the highest value for the eco-friendly solvent system). Notably, the fabricated 23.60 cm² large-area module was 15.60% PCE.

Abstract

The performance of flexible all-polymer organic photovoltaics (OPVs) constrained by low short-circuit current density (J _SC) and fill factor (FF), resulting in diminished power conversion efficiency (PCE) and compromised mechanical stability. Enhancing the exciton diffusion length (L _D) is pivotal for improving device parameters, including PCE. However, the underlying mechanisms governing exciton diffusion dynamics, influenced by the aggregation structure of conjugated polymers, remain insufficiently understood. This study employs molecular dynamics simulations to calculate the interchain free energy distribution [ΔG(r)] and strategically modulates the aggregation behavior of the polymer donor PM6 by controlling its molecular weight (MW). Medium-MW PM6 demonstrates optimized aggregation behavior, leading to extended L _D and precisely tuned fluid mechanics, which facilitate the formation of a pseudo-planar heterojunction (PPHJ) active layer. These advancements enable PPHJ-based all-polymer flexible devices to achieve a PCE of 18.01%, with notable improvements in J _SC and FF, and retain 90.4% of their initial efficiency after 2000 bending cycles. Encouraged by these advantages, a record-breaking efficiency of 20.0% (certified 19.68%) was achieved for eco-friendly, printed OPVs (PM6//L8-BO) with small-area devices (0.0621 cm²), whereas large-area modules (23.60 cm²) reached an efficiency of 15.60%.