Prof Henry Snaith FRS

Abstract:

Many optoelectronic properties have been reported for lead halide perovskite polycrystalline films. However, ambiguities in the evaluation of these properties remain, especially for long-range lateral charge transport, where ionic conduction can complicate interpretation of data. Here we demonstrate a new technique to measure the long-range charge carrier mobility in such materials. We combine quasi-steady-state photo-conductivity measurements (electrical probe) with photo-induced transmission and reflection measurements (optical probe) to simultaneously evaluate the conductivity and charge carrier density. With this knowledge we determine the lateral mobility to be ∼2 cm2 V−1 s−1 for CH3NH3PbI3 (MAPbI3) polycrystalline perovskite films prepared from the acetonitrile/methylamine solvent system. Furthermore, we present significant differences in long-range charge carrier mobilities, from 2.2 to 0.2 cm2 V−1 s−1, between films of contemporary perovskite compositions prepared via different fabrication processes, including solution and vapour phase deposition techniques. Arguably, our work provides the first accurate evaluation of the long-range lateral charge carrier mobility in lead halide perovskite films, with charge carrier density in the range typically achieved under photovoltaic operation.

Abstract:

The last five years have witnessed remarkable progress in the field of lead halide perovskite materials and devices. Examining the existing body of literature reveals staggering inconsistencies in the reported results among different research groups with a particularly wide spread in the photovoltaic performance and stability of devices. In this work we demonstrate that fractional, quite possibly unintentional, deviations in the precursor solution stoichiometry can cause significant changes in the properties of the perovskite layer as well as in the performance and stability of perovskite photovoltaic devices. We show that while the absorbance and morphology of the layers remain largely unaffected, the surface composition and energetics, crystallinity, emission efficiency, energetic disorder and storage stability are all very sensitive to the precise stoichiometry of the precursor solution. Our results elucidate the origin of the irreproducibility and inconsistencies of reported results among different groups as well as the wide spread in device performance even within individual studies. Finally, we propose a simple experimental method to identify the exact stoichiometry of the perovskite layer that researchers can employ to confirm their experiments are performed consistently without unintentional variations in precursor stoichiometry.

Abstract:

An understanding of the factors driving halide segregation in lead mixed-halide perovskites is required for their implementation in tandem solar cells with existing silicon technology. Here we report that the halide segregation dynamics observed in the photoluminescence from CH3NH3Pb(Br0.5I0.5)3 is strongly influenced by the atmospheric environment, and that encapsulation of films with a layer of poly(methyl methacrylate) allows for halide segregation dynamics to be fully reversible and repeatable. We further establish an empirical model directly linking the amount of halide segregation observed in the photoluminescence to the fraction of charge carriers recombining through trap-mediated channels, and the photon flux absorbed. From such quantitative analysis we show that under pulsed illumination, the frequency of the modulation alone has no influence on the segregation dynamics. Additionally, we extrapolate that working CH3NH3Pb(Br0.5I0.5)3 perovskite cells would require a reduction of the trap-related charge carrier recombination rate to ≲105s–1 in order for halide segregation to be sufficiently suppressed.