Reversible solvent vapor-mediated phase changes in nanocrystal superlattices.

Colloidal nanocrystals are being explored for use in a variety of applications, from solar cells to transistors to medical diagnostics and therapy. Ordered assemblies of nanocrystals, or superlattices, are one particularly interesting class of these materials, in which the nanocrystals serve as modular building blocks to construct nanostructures by self-assembly with spatial and temporal complexity and unique properties. From a fundamental perspective, the nanocrystals are simple molecular models that can be manipulated and studied to test statistical mechanical and thermodynamic models of crystallization and disorder. An article by Bian et al. in this issue of ACS Nano reports surprising new phase behavior in semiconductor nanocrystal superlattices: reversible transitions between non-close-packed body-centered cubic (bcc) and body-centered tetragonal (bct) structures, and close-packed face-centered cubic (fcc) structures, observed by real-time in situ grazing incidence small-angle X-ray scattering (GISAXS) measurements, upon solvent vapor exposure and increased interparticle separation. These studies offer new insight and raise new questions about superlattice structure and the forces that control self-assembly. Accompanying computer simulations show that ligand-ligand interactions are important. Furthermore, it appears that ligand-coated nanocrystals have more in common with soft microphase-separated materials, like diblock copolymers and surfactant assemblies, than previously realized.