Defect Migration in Supercrystalline Nanocomposites

Supercrystalline nanocomposites (SCNCs) are nanostructured hybrid materials with a variety of unique functional properties. Given their periodically arranged building blocks, they also offer interesting parallels with crystalline materials. They can be processed in multiple forms and at different scales, and cross-linking their organic ligands via heat treatment leads to a boost of their mechanical properties. This study shows, via X-ray and in situ scanning transmission electron microscopy (STEM) analyses, how each of these processing steps plays a distinct role in the generation, migration, interaction, and healing of supercrystalline defects. Pressing of SCNCs into bulk pellets leads to a distortion of the otherwise <i>fcc</i> superlattice, while emulsion-templated self-assembly yields supraparticles (SPs) with stacking faults and size-dependent symmetries. Heat treatment at the same temperatures as those applied for the organic cross-linking has significant effects on planar defects. Stacking faults migrate and get healed, as also confirmed via molecular dynamics simulations, and intersupercrystalline "grain" boundaries migrate via anisotropic motion of disconnections. These rearrangements of defects at the supercrystalline scale (tens of nanometers) in nanocomposites with high mechanical properties (compressive strength of 100-500 MPa) provide insights into the formation and evolution of ordered assemblies of functionalized nanoparticles.