Heterostructures via a Solution‐Based Anion Exchange in Microcrystalline 2D Layered Metal‐Halide Perovskites

Abstract Layered perovskites consist of stacks of inorganic semiconducting metal‐halide octahedra lattices sandwiched between organic layers with typically dielectric behavior. The in‐plane confinement of electrical carriers in such two‐dimensional metal halide perovskites drives a large range of appealing electronic properties, such as strong exciton binding, anisotropic charge diffusion, and polarization‐directionality. Heterostructures provide additional control on carrier diffusion and localization, and in‐plane heterojunctions are interesting because of the associated high charge mobility. Here, this work demonstrates a versatile solution‐based approach to fabricate in‐plane heterostructures with different halide composition in two‐dimensional lead‐halide perovskite microcrystals. This leads to spatially separated halide phases with different band gap and light emission. Interestingly, the composition of the exchanged phase and the morphology of the phase boundary depends on the exchange route, which can be related to the preferred localization of the halides at the equatorial or axial octahedra positions that either leads to dissolution and recrystallization of the octahedra lattice (for bromide to iodide), or allows for ion diffusion within the lattice (for iodide to bromide). These detailed insights on the ion exchange processes in layered perovskites will stimulate the development of heterostructures that can be tailored for different applications such as photocatalysis, energy storage, and light emission.