Anion Exchange of Ruddlesden–Popper Lead Halide Perovskites Produces Stable Lateral Heterostructures

Heterostructures of three-dimensional (3D) halide perovskites are unstable because of facile anion interdiffusion at halide interfaces. Two-dimensional (2D) Ruddlesden–Popper halide perovskites (RPPs) show suppressed and anisotropic ion diffusion that could enable stable RPP heterostructures, yet the direct and general growth of lateral RPP heterostructures remains challenging. Here, we show that halide miscibility in RPPs decreases with perovskite layer thickness (n), enabling the formation of sharp halide lateral heterostructures from n = 1 and 2 RP lead iodide microplates via anion exchange with hydrogen bromide vapor. In contrast, RPPs with n ≥ 3 form more diffuse lateral heterojunctions, more similar to those in 3D perovskites. The anion exchange behaviors are further modulated by the spacer and A-site cations in the RPP structures. These new insights, and kinetic studies of the exchange reactions, enable the preparation of lateral heterostructures from various n = 2 RPPs that are more stable against anion interdiffusion and degradation for potential optoelectronic device applications.