Tuning assembly structures of hard shapes in confinement via interface curvature.

Assembly in confinement is a problem of great interest in colloidal structure design, plasmonics, photonics, and industrial packaging. Along with the range of design choices provided by particle shape and attraction or repulsion, confined systems add an additional layer of complexity through the interactions between particles and the container holding them. The range of possible behaviors produced by these systems remains largely unexplored, yet has profound consequences on the resultant assembled structure. Here, we address this problem by exploring how the assembly of hard tetrahedral particles is affected by a spherical container. We simulate particle assemblies in containers holding 4 to 10 000 particles and analyze the range of resultant structures. We find that the presence of a curved wall causes organization into distinct concentric shells in containers holding up to thousands of particles. In addition, we see that wall curvature affects structural motifs in systems as large as 10 000 particles, promoting local environments that maximally conform to the wall and providing a seed for the propagation of these motifs into the interior of the container. Through this work, we show how confining interfaces can be used to promote the assembly of structures markedly distinct from those seen in the more commonly studied bulk systems.

Multiscale hierarchical structures from a nanocluster mesophase.

Spontaneous hierarchical self-organization of nanometre-scale subunits into higher-level complex structures is ubiquitous in nature. The creation of synthetic nanomaterials that mimic the self-organization of complex superstructures commonly seen in biomolecules has proved challenging due to the lack of biomolecule-like building blocks that feature versatile, programmable interactions to render structural complexity. In this study, highly aligned structures are obtained from an organic-inorganic mesophase composed of monodisperse Cd37S18 magic-size cluster building blocks. Impressively, structural alignment spans over six orders of magnitude in length scale: nanoscale magic-size clusters arrange into a hexagonal geometry organized inside micrometre-sized filaments; self-assembly of these filaments leads to fibres that then organize into uniform arrays of centimetre-scale bands with well-defined surface periodicity. Enhanced patterning can be achieved by controlling processing conditions, resulting in bullseye and 'zigzag' stacking patterns with periodicity in two directions. Overall, we demonstrate that colloidal nanomaterials can exhibit a high level of self-organization behaviour at macroscopic-length scales.