Publication date: 15th December 2025
Lead halide perovskites exhibit a unique combination of defect tolerance, long carrier lifetimes, and solution processability, enabling rapid advances in photovoltaic and optoelectronic device performance. Yet, despite power conversion efficiencies now exceeding 26%, fundamental questions remain regarding the role of doping and defect-mediated electronic processes in these materials. A particularly intriguing but underexplored phenomenon is photodoping—the illumination-induced imbalance of electron and hole populations caused by preferential trapping of one carrier type in shallow, localized states. While early studies proposed photodoping as a key feature of halide perovskites, its quantification has been hindered by the difficulty of experimentally distinguishing electron and hole densities, as most optical probes are sensitive only to their sum or product. In this work, we demonstrate that both steady-state and transient photoluminescence (PL) provide accessible, powerful routes to identifying and characterizing photodoping in perovskite thin films. We show that the excitation-intensity dependence of steady-state PL directly reflects changes in charge neutrality conditions and yields modified ideality factors, including extended regions where nid ≈ 1.5—behavior not captured by classical trap-assisted recombination models. By incorporating photodoping into recombination frameworks, we connect these optical signatures to the presence and density of shallow traps that may contribute simultaneously to defect tolerance and recombination asymmetries. Complementarily, we use high dynamic range transient PL measurements, enabled by ultra-low repetition rate excitation and gated CCD detection, to probe power-law decay dynamics spanning microseconds to beyond 100 μs [1]. By using particularly low repetition rates, we extract decay times over a large range of injection conditions, providing an increased amount of confidence in the inferred defect parameters.
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