Colloidal Nanocrystals of Lead-Free Double-Perovskite (Elpasolite) Semiconductors: Synthesis and Anion Exchange To Access New Materials.

Concerns about the toxicity and instability of lead-halide perovskites have driven a recent surge in research toward alternative lead-free perovskite materials, including lead-free double perovskites with the elpasolite structure and visible bandgaps. Synthetic approaches to this class of materials remain limited, however, and no examples of heterometallic elpasolites as nanomaterials have been reported. Here, we report the synthesis and characterization of colloidal nanocrystals of Cs2AgBiX6 (X = Cl, Br) elpasolites using a hot-injection approach. We further show that postsynthetic modification through anion exchange and cation extraction can be used to convert these nanocrystals to new materials including Cs2AgBiI6, which was previously unknown experimentally. Nanocrystals of Cs2AgBiI6, synthesized via a novel anion-exchange protocol using trimethylsilyl iodide, have strong absorption throughout the visible region, confirming theoretical predictions that this material could be a promising photovoltaic absorber. The synthetic methodologies presented here are expected to be broadly generalizable. This work demonstrates that nanocrystal ion-exchange reactivity can be used to discover and develop new lead-free halide perovskite materials that may be difficult or impossible to access through direct synthesis.