Interpretation of the photoluminescence decay kinetics in metal halide perovskite nanocrystals and thin polycrystalline films

In this paper we present critical analysis of different points of view on interpretation of the photoluminescence (PL) decay kinetics in lead halide perovskites prepared in the form of well passivated nanocrystals (PNCs) or thin polycrystalline layers. In addition to the literature data, our own measurements are also considered. For PNCs, a strong dependence of the PL lifetimes on the type of passivating ligand was observed with a consistently high PL quantum yield. It is shown that such ligand effects, as well as a decrease in the PL lifetime with decreasing temperature, are well qualitatively explained by the phenomenological model of thermally activated delayed luminescence, in which the extension of the PL decay time with temperature occurs due to the participation of shallow non-quenching traps. In the case of thin perovskite layers, we conclude that the PL kinetics under sufficiently low excitation intensity is determined by the excitation quenching on the layer surfaces. We demonstrate that a large variety of possible PL decay kinetics for thin polycrystalline perovskite films can be modelled by means of one-dimensional diffusion equation with use of the diffusion coefficient D and surface recombination velocity S as parameters and conclude that long-lived PL kinetics are formed in case of low D and/or S values.