In Situ Electron Microscopy Imaging and Quantitative Structural Modulation of Nanoparticle Superlattices.

We use liquid-phase transmission electron microscopy (LP-TEM) to characterize the structure and dynamics of a solution-phase superlattice assembled from gold nanoprisms at the single particle level. The lamellar structure of the superlattice, determined by a balance of interprism interactions, is maintained and resolved under low-dose imaging conditions typically reserved for biomolecular imaging. In this dose range, we capture dynamic structural changes in the superlattice in real time, where contraction and smaller steady-state lattice constants are observed at higher electron dose rates. Quantitative analysis of the contraction mechanism based on a combination of direct LP-TEM imaging, ensemble small-angle X-ray scattering, and theoretical modeling allows us to elucidate: (1) the superlattice contraction in LP-TEM results from the screening of electrostatic repulsion due to as much as a 6-fold increase in the effective ionic strength in the solution upon electron beam illumination; and (2) the lattice constant serves as a means to understand the mechanism of the in situ interaction modulation and precisely calibrate electron dose rates with the effective ionic strength of the system. These results demonstrate that low-dose LP-TEM is a powerful tool for obtaining structural and kinetic properties of nanoassemblies in liquid conditions that closely resemble real experiments. We anticipate that this technique will be especially advantageous for those structures with heterogeneity or disorder that cannot be easily probed by ensemble methods and will provide important insight that will aid in the rational design of sophisticated reconfigurable nanomaterials.