The role of Pb oxidation state of the precursor in the formation of 2D perovskite microplates

Abstract

Two-dimensional (2D) lead halide perovskites are an exciting class of materials currently being extensively explored for photovoltaics and other optoelectronic applications. Their ionic nature makes them ideal candidates for solution processing into both thin films and nanostructured crystals. Understanding how 2D lead halide perovskite crystals form is key towards full control over their physical properties, which may enable new physical phenomena and devices. Here, we investigate the effects of the Pb oxidation state of the initial inorganic precursor on the growth of pure-phase (n = 1) – Popper 2D perovskite BA₂PbI₄ in single-step synthesis. We examine the different crystallisation routes in exposing PbO₂ and PbI₂ powders to a BAI : IPA organo-halide solution, by combining in situ optical microscopy, UV–VIS spectroscopy and time-resolved high performance liquid chromatography. So far, works using PbO₂ to synthesise 3D LHPs introduce a preceding step to reduce PbO₂ into either PbO or PbI₂. In this work, we find that BA₂PbI₄ is directly formed when exposing PbO₂ to BAI : IPA without the need for an external reducing agent. We explain this phenomenon by the spontaneous reduction/oxidation of PbO₂/BAI that occurs under iodine-rich conditions. We observe differences in the final morphology (rectangles vs. octagons) and nanocrystal growth rate, which we explain through the different chemistry and iodoplumbate complexes involved in each case. As such, this work spans the horizon of usable lead precursors and offers a new turning knob to control crystal growth in single-step LHP synthesis.