Abstract

The fabrication of multifunctional electronic devices based on the intriguing natures of organic semiconductors is crucial for organic electronics. Ultranarrow-bandgap materials are in urgent demand for fabricating high-performance organic photovoltaic (OPV) cells and highly sensitive near-infrared organic photodetectors (OPDs). By combining alkoxy modification and an asymmetric strategy, three narrow-bandgap electronic acceptors (BTP-4F, DO-4F, and QO-4F) were synthesized with finely tuned molecular electrostatic potential (ESP) distributions. Through the careful modulation of electronic configurations, the optical absorption onsets of DO-4F and QO-4F exceeded 1 μm. The experimental and theoretical results suggest that the small ESP of QO-4F is beneficial for achieving a low nonradiative voltage loss, while the large ESP of BTP-4F can help obtain high exciton dissociation efficiency. By contrast, the asymmetric acceptor DO-4F with a moderate ESP possesses balanced voltage loss and exciton dissociation, yielding the best power conversion efficiency of 13.6% in the OPV cells. OPDs were also fabricated based on the combination of PBDB-T:DO-4F, and the as-fabricated device outputs a high shot-noise-limited specific detectivity of 3.05 × 1013 Jones at 850 nm, which is a very good result for near-infrared OPDs. This work is anticipated to provide a rational way of designing high-performance ultranarrow-bandgap organic semiconductors by modulating the molecular ESP.

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