Anchored Ligands Facilitate Efficient B‑Site Doping in Metal Halide Perovskites

Metal halide perovskites exhibit outstanding optoelectronic properties: superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX₃, where A is a monovalent cation (e.g., methylammonium (MA⁺), Cs⁺), B is the divalent metal ion(s) (e.g., Pb²⁺, Sn²⁺), and X is the halide group (e.g., Cl^–, Br^–, or I^–), the isovalent exchange of A- and X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancy-mediated diffusion of B-site cations are much higher than those for A- and X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn²⁺, Zn²⁺, Bi³⁺) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in three-dimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.