Facet-Dependent Photoelectrochemistry on Single Crystal Organic–Inorganic Halide Perovskite Electrodes

[Image: see text] Organometallic halide perovskites have garnered significant attention in various fields of material science, particularly solar energy conversion, due to their desirable optoelectronic properties and compatibility with scalable fabrication techniques. It is often unclear, however, how carrier generation and transport within complex polycrystalline films are influenced by variations in local structure. Elucidating how distinct structural motifs within these heterogeneous systems affect behavior could help guide the continued improvement of perovskite-based solar cells. Here, we present studies applying scanning electron microscopy (SECCM) to map solar energy harvesting within well-defined model systems of organometallic halide perovskites. Methylammonium lead bromide (MAPbBr(3)) single crystals were prepared via a low-temperature solution-based route, and their photoelectrochemical properties were mapped via SECCM using p-benzoquinone (BQ) in dichloromethane as a redox mediator. Correlated SECCM mapping and electron microscopy studies enabled facet-to-facet variations in photoelectrochemical performance to be revealed and carrier transport lengths to be evaluated. The photoelectrochemical behavior observed within individual single crystals was quite heterogeneous, attributable to local variations in crystal structure/orientations, intrafacet junctions, and the presence of other structural defects. These observations underscore the significance of controlling the microstructure of single perovskite crystals, presenting a promising avenue for further enhancement of perovskite-based solar cells.