Self-assembly of biaxial discorectangular lead carbonate nanosheets into stacked ribbons studied by SAXS and HAADF-STEM tomographic tilt series

Abstract

The self-assembling behaviour of 2.6 nm thin PbCO3 nanoplatelets with discorectangular shape and uniform width and thickness occurring after their formation in nonionic water-in-oil microemulsions has been investigated using synchrotron small angle X-ray scattering (SAXS) and (scanning) transmission electron microscopy ((S)TEM). The presence of attractive depletion forces originating from the ubiquitous microemulsion droplets triggers a new type of superstructure at low particle concentration. Instead of the universally observed formation of face-to-face assembled lamellar mesostructures, the nanosheets self-organise into extended ribbon structures, whereby each on top lying sheet is displaced by a constant shift in the length and width directions leading to a so far unprecedented staggered zigzag-type stack assembly with restricted height. This type of stacking gives rise to a complex interference pattern in the isotropic small angle scattering of the stacked ribbon assemblies (SRAs) in reverse micellar solution. Different to the, for lamellar-structured nanosheets typical, diffraction peaks at multiples of the wave vector corresponding to one particular repeat distance, the scattering peaks measured in this study are asymmetric, displaying a shoulder on their low wave vector side. The asymmetric shape of the observed face-to-face correlation peaks indicates that the SRAs do not extend in one direction only. Their scattering behaviour is analysed by expanding the Kratky-Porod structure factor for stacking plates into three dimensions. High-angle annular dark-field (HAADF)-STEM tilt series have complementary been acquired to retrieve three-dimensional structural information on the SRAs in the dry state and to confirm the model used for the refinement of the SAXS data. This journal is