Temporal Evolution of Superlattice Contraction and Defect-Induced Strain Anisotropy in Mesocrystals during Nanocube Self-Assembly

[Image: see text] Understanding and controlling defect formation during the assembly of nanoparticles is crucial for fabrication of self-assembled nanostructured materials with predictable properties. Here, time-resolved small-angle X-ray scattering was used to probe the temporal evolution of strain and lattice contraction during evaporation-induced self-assembly of oleate-capped iron oxide nanocubes in a levitating drop. We show that the evolution of the strain and structure of the growing mesocrystals is related to the formation of defects as the solvent evaporated and the assembly process progressed. Superlattice contraction during the mesocrystal growth stage is responsible for the rapidly increasing isotropic strain and the introduction of point defects. The crystal strain, quantified by the Williamson–Hall analysis, became more anisotropic due to the formation of stress-relieving dislocations as the mesocrystal growth was approaching completion. Understanding the formation of the transformation of defects in mesocrystals and superlattices could assist in the development of optimized assembly processes of nanoparticles with multifunctional properties.