<i>In-situ</i> Transmission Electron Microscopy Study of Oxygen Vacancy Ordering and Dislocation Annihilation in Undoped and Sm-doped CeO₂ Ceramics During Redox Processes

Ceria (CeO2) based ceramics have been widely used for many applications due to their unique ionic, electronic, and catalytic properties. Here, we report our findings in investigating into the redox processes of undoped and Sm-doped CeO2 ceramics stimulated by high-energy electron beam irradiation within a transmission electron microscope (TEM). The reduced structure with oxygen vacancy ordering has been identified as the CeO1.68 (C-Ce2O3+δ) phase via high-resolution TEM. The reduction of Ce4+ to Ce3+ has been monitored by electron energy-loss spectroscopy. The decreased electronic conductivity of the Sm-doped CeO2 (Sm0.2Ce0.8O1.9, SDC) is revealed by electron holography, as positive electrostatic charges accumulated at the surfaces of SDC grains under electron beam irradiation, but not at CeO2 grains. The formation of the reduced CeO1.68 domains corresponds to lattice expansion compared to the CeO2 matrix. Therefore, the growth of CeO1.68 nuclei builds up strain inside the matrix, causing annihilation of ...