Imaging how thermal capillary waves and anisotropic interfacial stiffness shape nanoparticle supracrystals.

Development of the surface morphology and shape of crystalline nanostructures governs the functionality of various materials, ranging from phonon transport to biocompatibility. However, the kinetic pathways, following which such development occurs, have been largely unexplored due to the lack of real-space imaging at single particle resolution. Here, we use colloidal nanoparticles assembling into supracrystals as a model system, and pinpoint the key role of surface fluctuation in shaping supracrystals. Utilizing liquid-phase transmission electron microscopy, we map the spatiotemporal surface profiles of supracrystals, which follow a capillary wave theory. Based on this theory, we measure otherwise elusive interfacial properties such as interfacial stiffness and mobility, the former of which demonstrates a remarkable dependence on the exposed facet of the supracrystal. The facet of lower surface energy is favored, consistent with the Wulff construction rule. Our imaging–analysis framework can be applicable to other phenomena, such as electrodeposition, nucleation, and membrane deformation. Interfacial fluctuations at the nanoscale, such as shape evolution of a growing crystal, are prohibitively difficult to study experimentally. Here, the authors are able to map the kinetic and thermodynamic parameters involved in shaping of nanoparticle supracrystals by directly imaging the fluctuating crystal surface by liquid-phase TEM, and analyzing it in the context of capillary wave theory.