Atomic-level chemical reaction promoting external quantum efficiency of organic photomultiplication photodetector exceeding 10⁸% for weak-light detection

Low-cost, solution-processed photomultiplication organic photodetectors (PM-OPDs) with external quantum efficiency (EQE) above unity have attracted enormous attention. However, their weak-light detection is unpleasant because the anode Ohmic contact causes exacerbation in dark current. Here, we introduce atomic-level chemical reaction in PM-OPDs which can simultaneously suppress dark current and increase EQE via depositing a 0.8 nm thick Al₂O₃ by the atomic layer deposition. Suppression in dark current mainly originates from the built-in anode Schottky junction as a result of work function decrease of hole-transporting layer of which the chemical groups can react chemically with the bottom surface of Al₂O₃ layer at the atomic-level. Such strategy of suppressing dark current is not adverse to charge injection under illumination; instead, responsivity enhancement is realized because charge injection can shift from cathode to anode, of which the neighborhood possesses increased photogenerated carriers. Consequently, weak-light detection limit of the forwardly-biased PM-OPD with Al₂O₃ treatment reaches a remarkable level of 2.5 nW cm⁻², while that of the reversely-biased control is 25 times inferior. Meanwhile, the PM-OPD yields a record high EQE and responsivity of 4.31 × 10⁸% and 1.85 × 10⁶ A W⁻¹, respectively, outperforming all other polymer-based PM-OPDs.