The physical and chemical properties of nanophase materials rely on their crystal and surface structures. Transmission electron microscopy (TEM) is a powerful and unique technique for structure characterization. The most important application of TEM is the atomic-resolution real-space imaging of nanoparticles. This article introduces the fundamentals of TEM and its applications in structural determination of shape-controlled nanocrystals and their assemblies. By forming a nanometer size electron probe, TEM is unique in identifying and quantifying the chemical and electronic structure of individual nanocrystals. Electron energy-loss spectroscopy analysis of the solid-state effects and mapping the valence states are even more attractive. In situ TEM is demonstrated for characterizing and measuring the thermodynamic, electric, and mechanical properties of individual nanostructures, from which the structure−property relationship can be registered with a specific nanoparticle/structure.
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