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

Oriented attachment is a non-classical growth mechanism of nanomaterials that can lead to tunable properties and functionalities. Here the authors show that the crystallographic alignment between magnetite mesocrystal building-blocks can be tuned by the surface ligands, influencing the resulting magnetic properties. 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.

Automated summary

This study investigates the control of crystallographic alignment in nanomaterials through the influence of surface ligands on magnetite mesocrystals. The authors found that different surface ligands can lead to different alignment variations, which are guided by surface energy reduction and surface deformation. The alignment-dependent magnetic interactions between building blocks also affect the overall magnetic properties of mesocrystals and their chains.