Solution‐Processed Organic–Inorganic Hybrid Anode Interface Layer for High‐Performance Organic Photodiodes

The solution‐processing technology of organic photodiodes (OPDs) stands as a core advantage distinguishing them from conventional silicon‐based devices, offering several design opportunities for macroscopic structural innovations such as special‐shaped, large‐area, and flexible architectures. The anode interface layer (AIL), an indispensable component in OPD, is highly desired for processing techniques and physicochemical compatibility to meet the demands of high‐performance devices. However, viable alternatives to the commercial material PEDOT:PSS remain scarce, with the narrow selection pool of solution‐processed AIL materials. Here, a novel solution‐processed organic–inorganic hybrid AIL (D149:Cu) is developed with tunable physicochemical properties, which combines the stability/high carrier mobility of inorganic components with the biocompatibility/flexibility of organic counterparts. The D149:Cu layer optimizes interfacial contact and energy level alignment, effectively enhancing photo‐generated hole transport while suppressing dark‐state electron injection from external circuit, thereby enabling OPDs with lower dark current (4.96 × 10 −9 vs 1.19 × 10 −7 A cm −2 ) and higher specific detectivity (9.09 × 10 12 vs 1.62 × 10 12 Jones) compared to PEDOT:PSS counterparts. Moreover, flexible D149:Cu‐based OPD (≈51 µm‐thick) is demonstrated, showing exceptional operational stability under mechanical flexing of 1500 bending cycles. This work alleviates the selection limitations of AILs in optoelectronic devices.