Mechanically Robust Supercrystals from Antisolvent-Induced Assembly of Perovskite Nanocrystals

Ordered arrays of nanocrystals, called supercrystals, have attracted significant attention owing to the collective quantum effects arising from the coupling between neighboring nanocrystals. In particular, lead halide perovskite nanocrystals are widely used because of the combination of the optical properties and faceted cubic shape, which enables the formation of highly ordered supercrystals. The most frequently used method for the fabrication of perovskite supercrystals is based on the self-assembly of nanocrystals from solution via slow evaporation of the solvent. However, the supercrystals produced with this technique grow in random positions on the substrate. Moreover, they are mechanically soft due to the presence of organic ligands around the individual nanocrystals. Therefore, such supercrystals cannot be easily manipulated with microgrippers, which hinders their use in applications. In this work, we synthesize mechanically robust supercrystals built from cubic lead halide perovskite nanocrystals by a two-layer phase diffusion self-assembly with acetonitrile as the antisolvent. This method yields highly faceted thick supercrystals, which are robust enough to be picked up and relocated by microgrippers. We employed X-ray nanodiffraction together with high-resolution scanning electron microscopy and atomic force microscopy to reveal the structure of CsPbBr₃, CsPbBr₂Cl, and CsPbCl₃ supercrystals assembled using the two-layer phase diffusion technique and explain their unusual mechanical robustness. Our findings are crucial for further experiments and applications in which supercrystals need to be placed in a precise location, for example, between the electrodes in an electro-optical modulator.