In-situ transmission electron microscopy study of oxygen vacancy ordering and dislocation annihilation in undoped and Sm-doped CeO2 ceramics during redox processes

Abstract

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 dislocations inside the grains. By using in-situ high-resolution TEM and a fast OneView camera recording system, we investigated dislocation motion inside both CeO2 and SDC grains under electron beam irradiation. The dislocations prefer to dissociate into Shockley partials bounded by stacking faults. Then, the partials can easily glide in the {111} planes to reach the grain surfaces. Even the Lomer-Cottrell lock can be swept away by the phase change induced strain field. Our results revealed the high mobility of dislocations inside CeO2 and SDC grains during their respective redox processes.