Regulating solution aggregation and entanglement for efficient <?A3B2 pi6?>self-powered all-polymer photodiodes in water quality monitoring

The solution aggregation structures of conjugated polymers are pivotal in determining their film morphology and optoelectronic properties, yet the relationship between solution aggregation and device performance remains elusive in organic photodiode (OPD) systems. Herein, we introduce the first examination of solution aggregation structures of all-polymer OPD blends, with a focus on how molecular entanglement modulates aggregation behavior and subsequent photodiode performance of low-cost poly(3-pentylthiophene). Using small-angle neutron scattering and freeze-dried imaging, we provide a comprehensive analysis of the solution-state aggregation behavior of poly(3-pentylthiophene) and its evolution in the blend, revealing profound impacts on film morphology and device performance. With finely optimized aggregation, the resulting all-polymer OPD achieves a record-high specific detectivity of ~4×1013 Jones at zero bias, outperforming all bulk heterojunction (BHJ)-type self-powered OPDs reported to date. This device also demonstrates remarkable thermal stability, with negligible performance degradation after over 800 h of thermal annealing at 85 °C. Furthermore, the self-powered OPD exhibits excellent performance across a broad spectral range, enabling its application in both water quality monitoring and biosensing. This work offers new insights into the solution aggregation behavior of conjugated polymers in OPDs and highlights the importance of resolving solution aggregation in optimizing device function.