Correlative Analysis of the Dimensional Properties of Bipyramidal Titania Nanoparticles by Complementing Electron Microscopy with Other Methods

In this paper, the accurate determination of the size and size distribution of bipyramidal anatase nanoparticles (NPs) after deposition as single particles on a silicon substrate by correlative Scanning Electron Microscopy (SEM) with Atomic Force Microscopy (AFM) analysis is described as a new measurement procedure for metrological purposes. The knowledge of the exact orientation of the NPs is a crucial step in extracting the real 3D dimensions of the particles. Two approaches are proposed to determine the geometrical orientation of individual nano-bipyramides: (i) AFM profiling along the long bipyramid axis and (ii) stage tilting followed by SEM imaging. Furthermore, a recently developed method, Transmission Kikuchi Diffraction (TKD), which needs preparation of the crystalline NPs on electron-transparent substrates such as TEM grids, has been tested with respect to its capability of identifying the geometrical orientation of the individual NPs. With the NPs prepared homogeneously on a TEM grid, the transmission mode in a SEM, i.e., STEM-in-SEM (or T-SEM), can be also applied to extract accurate projection dimensions of the nanoparticles from the same sample area as that analysed by SEM, TKD and possibly AFM. Finally, Small Angle X-ray Scattering (SAXS) can be used as an ensemble technique able to measure the NPs in liquid suspension and, with ab-initio knowledge of the NP shape from the descriptive imaging techniques, to provide traceable NP size distribution and particle concentration.