Regulated Charge Transfer in Donor‐Acceptor Metal‐Organic Frameworks for Highly‐Sensitive Photodetectors

Abstract In photo‐induced charge separation, organic thin films with donor and acceptor chromophores are vital for uses such as artificial photosynthesis and photodetection. The main challenges include optimizing charge separation efficiency and identifying the ideal acceptor/donor ratio. Achieving this is difficult due to the variability in molecular configurations within these typically amorphous organic aggregates. Metal–organic frameworks (MOFs) provide a structured solution by enabling systematic design of donor/acceptor blends with adjustable ratios within a crystalline lattice. We demonstrate this approach by incorporating donor and acceptor naphthalenediimide (NDI) chromophores as linkers in a highly oriented, monolithic MOF thin film. By adjusting the NDI acceptor linker concentration during the layer‐by‐layer assembly of surface‐anchored MOF thin films (SURMOFs), we significantly enhanced charge separation efficiency. Surprisingly, the optimum acceptor concentration was only 3 %, achieving a forty‐fold increase in photodetection efficiency compared to baseline NDI donor‐based SURMOFs. This unexpected behaviour was clarified through theoretical analysis enabled by the well‐defined crystalline structure of the SURMOFs. Using density functional theory and kinetic Monte Carlo simulations, we identified two opposing effects from acceptors: the positive effect of suppressing undesirable charge carrier recombination is offset at high concentrations by a reduction in charge‐carrier mobility.