The size of dopant-rich nanodomains was assessed in four samples of Ce1−μ Yμ O2−μ/2 through systematic pair distribution function (PDF) refinements. Experimental G(r) curves were fitted by different structural models with the aim of finding a description which balanced precise structure parameterization and reasonable number of parameters. The most reliable model was a single Y2O3-like phase, which best accommodated to the close relationship between the fluorite (CeO2-like) and C-type (Y2O3-like) structures. In this model, a refined cation coordinate, x(M2), measured the relative occurrence in the G(r) of the chemical environment of Y and Ce at any value of r. The r-value at which x(M2) vanished, i.e. at which the refined C-type cell becomes a redundant, low-symmetry description of a fluorite cell, was assumed as the size of a C-type domain. Subtle features in G(r) could be attributed to the fluorite or C-type phase up to ~500 Å thanks to the narrow instrumental resolution function of the ID31 beamline (now ID22) at the ESRF, which allows us to get high resolution PDF data.

The ordered structures in different doping levels (x = 0.1, 0.15, 0.2, 0.25, 0.3) of yttrium doped ceria (YDC, Ce(1−x)YxO2−δ) electrolytes were investigated by electron diffraction, high-resolution transmission electron microscopy (TEM), scanning TEM, and electron energy loss spectroscopy. Oxygen vacancy ordering was experimentally confirmed within the ordered structures. With increasing the doping level, the concentration of trivalent Ce cations was increased in YDC samples and such trivalent Ce cations were supposed to mainly exist in the ordered structures. Based on our electron microscopic observation and microanalysis, a crystal model for the ordered structures is proposed.