Surface-ligand-induced crystallographic disorder–order transition in oriented attachment for the tuneable assembly of mesocrystals

In the crystallisation of nanomaterials, an assembly-based mechanism termed ‘oriented attachment’ (OA) has recently been recognised as an alternative mechanism of crystal growth that cannot be explained by the classical theory. However, attachment alignment during OA is not currently tuneable because its mechanism is poorly understood. Here, we identify the crystallographic disorder-order transitions in the OA of magnetite (Fe₃O₄) mesocrystals depending on the types of organic surface ligands on the building blocks, which produce different grain structures. We find that alignment variations induced by different surface ligands are guided by surface energy anisotropy reduction and surface deformation. Further, we determine the effects of alignment-dependent magnetic interactions between building blocks on the global magnetic properties of mesocrystals and their chains. These results revisit the driving force of OA and provide an approach for chemically controlling the crystallographic order in colloidal nanocrystalline materials directly related to grain engineering.