Thermodynamically and Kinetically Controlled Nucleation and Growth of Halide Perovskite Single Crystals

Halide perovskites are ideal for next‐generation optical devices and photovoltaics. Although perovskite single‐crystals show reproducible optoelectronic properties, significant variations in the crystal size, anisotropy, density, defects, photoluminescence (PL), and carrier lifetime affect the sample properties and device performances. Homogenous size and shape FA/MAPbBr3 single microcrystals (MCs) with controlled edge lengths, crystal densities, PL lifetimes, and PL intensities are prepared by thermodynamically controlling and kinetically separating the crystal nucleation‐growth processes using optimum N‐cyclohexyl‐2‐pyrrolidone (CHP) concentration. The crystal growth kinetics at different CHP concentrations and temperatures are estimated spectroscopically by measuring the concentration of Pb (II). High‐density cubic MCs with a homogenous size distribution, high PL intensities, and long PL lifetimes are obtained within minutes at high temperatures by the controlled addition of the pyrrolidone derivative. Conversely, the crystal size nonlinearly increases with time at low temperatures. The isotropically grown high‐density single crystals at controlled nucleation‐growth rates at 190 °C with 20% CHP show the highest PL intensity and the longest PL lifetimes. This method offers thermodynamic and kinetic control of perovskite single‐crystal growth with shape control. Halide perovskite) single crystals are promising for electro‐optical and photovoltaic devices. The challenging size‐ and shape‐controlled single‐crystal synthesis is demonstrated by separating and optimizing the crystal nucleation‐growth processe . The cuboid single‐crystals with controlled size show optimal photoluminescence and minimal defects. This method offers a route to synthesize high‐quality perovskite single crystals with size‐ and shape‐control for devices.