Time-resolved imaging of non-diffusive carrier transport in long-lifetime halide perovskite thin films

Owing to their exceptional semiconducting properties, hybrid inorganic-organic perovskites show great promise as photovoltaic absorbers. In these materials, long-range diffusion of charge carriers allows for most of the photogenerated carriers to contribute to the photovoltaic efficiency. Here, time-resolved photoluminescence (PL) microscopy is used to directly probe ambipolar carrier diffusion and recombination kinetics in hybrid perovskites. This technique is applied to thin films of methylammonium lead tri-iodide MAPbI$_3$ obtained with two different fabrication routes, methylammonium lead tribromide (MAPbBr$_3$), and an alloy of formamidinium lead tri-iodide (FAPbI$_3$) and methylammonium lead bromide FA$_{0.85}$MA$_{0.15}$Pb(I$_{0.85}$Br_${0.15}$)$_3$. Average diffusion coefficients in the films leading to the highest device efficiencies and longest lifetimes, i.e., in FA$_{0.85}$MA$_{0.15}$Pb(I$_{0.85}$Br$_{0.15}$)$_3$ and acetonitrile-processed MAPbI$_3$, are found to be several orders of magnitude lower than in the other films. Further examination of the time-dependence shows strong evidence for non-diffusive transport. In particular, acetonitrile-processed MAPbI$_3$ shows distinct diffusion regimes on short and long timescales with an effective diffusion constant varying over 2 orders of magnitude. Our results also highlight the fact that increases in carrier lifetime in this class of materials are not necessarily concomitant with increased diffusion lengths and that the PL quantum efficiency under solar cell operating conditions is a greater indication of material, and ultimately device, quality.