• Energy Research

Structural secrets of hybrid perovskites The optoelectronic and photovoltaic applications of polycrystalline hybrid metal halide perovskite films are notable because grain boundaries in most materials cause scattering of charge carriers that decreases performance. Electron microscopy studies of these materials have been hindered by their rapid structural degradation under intense electron beams. Rothmann et al. now present an atomic crystallographic structure of formamidinium lead triiodide (FAPbI 3 ) polycrystalline thin films obtained by low-electron-dose scanning transmission electron microscopy with advanced image processing. The crystal structure sustains substoichiometry in the A-site cation, has a nearly perfect crystallographic alignment between PbI 2 impurity phases and the FAPbI 3 perovskite, and has atomically clean grain boundaries between polycrystalline domains. These features help to explain the films' surprising regenerative ability, their benign grain boundaries where strain and dislocations appear mostly absent, and why excess lead-iodide precursor can be counterintuitively beneficial. Science , this issue p. eabb5940

AbstractMixed‐halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution‐processed triple‐cation mixed‐halide (Cs0.06MA0.15FA0.79)Pb(Br0.4I0.6)3 perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar‐equivalent illumination. It is found that the illumination leads to localized surface sites of iodide‐rich perovskite intermixed with passivating PbI2 material. Time‐ and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide‐rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed‐halide mixed‐cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.