A light-induced photoluminescence (PL) enhancement in surface-deposited methylammonium lead iodide (CH₃NH₃PbI₃) perovskites was investigated in detail using time-resolved luminescence microscopy. We found the PL intensity to increase up to three orders of magnitude upon light illumination with an excitation power density of 0.01–1 W cm⁻². The PL enhancement is accompanied by an increase of the PL lifetime from several nanoseconds to several hundred nanoseconds and also by an increase of the initial amplitude of the PL decay. The latter suggests excited state quenching at the subpicosecond timescale. We propose a model where the trapping sites responsible for non-radiative charge recombination can be de-activated by a photochemical reaction involving oxygen. The reaction zone is spatially limited by the excitation light-penetration depth and diffusion length of the charge carriers. The latter increases in the course of the light-curing process making the reaction zone spreading from the surface towards the interior of the crystal. The PL enhancement can be reversed by switching on/off the excitation light or switching the atmosphere between oxygen and nitrogen. Slow diffusion of the reactants and products and equilibrium between the active and “cured” trapping sites are proposed to be the reasons for peculiar responses of PL to such varied experimental conditions.

Due to the complex core–shell structure and variety of surface functional groups, the photoluminescence (PL) mechanism of carbon dots (CDs) remain unclear. o-Phenylenediamine (oPD), as one of the most common precursors for preparing red emissive CDs, has been extensively studied. Interestingly, most of the red emission CDs based on oPD have similar PL emission characteristics. Herein, we prepared six different oPD-based CDs and found that they had almost the same PL emission and absorption spectra after purification. Structural and spectral characterization indicated that they had similar carbon core structures but different surface polymer shells. Furthermore, single-molecule PL spectroscopy confirmed that the multi-modal emission of those CDs originated from the transitions of different vibrational energy levels of the same PL center in the carbon core. In addition, the phenomenon of “spectral splitting” of single-particle CDs was observed at low temperature, which confirmed these oPD-based CDs were unique materials with properties of both organic molecules and quantum dots. Finally, theoretical calculations revealed their potential polymerization mode and carbon core structure. Moreover, we proposed the PL mechanism of red-emitting CDs based on oPD precursors; that is, the carbon core regulates the PL emission, and the polymer shell regulates the PL intensity. Our work resolves the controversy on the PL mechanism of oPD-based red CDs. These findings provide a general guide for the mechanism exploration and structural analysis of other types of CDs.