Robot-Accelerated Perovskite Investigation and Discovery: Copper Halide Perovskitoids

Metal halide perovskitoids are a compositionally and structurally diverse class of materials with many applications. High-throughput experimentation is a valuable tool for exploratory synthesis of these materials, particularly as part of the search for environmentally friendly lead-free perovskitoids. Herein, we describe an automated, high-throughput approach for metal halide perovskite single crystal discovery based on antisolvent vapor diffusion (ASVD) to rapidly identify and optimize synthesis conditions for the formation of high-quality single crystals. Using this automated approach, a total of 315 copper iodide/chloride perovskite synthesis reactions were conducted using five organoammonium cations, resulting in nine new phases. The nature of the crystalline products is controlled primarily by CuCl2 concentration in the mother liquor, and secondarily by the shape and non-covalent interactions of the organoammonium cation. This approach is generalizable to other metal and halide compositions, as well as the wide array of