Lu‑, Sm‑, and Gd-Doped Ceria: A Comparative Approach to Their Structural Properties

A room temperature structural study has been performed through the whole compositional range of the (Ce_1–xLu_x)­O_2–x/2 system by synchrotron X-ray diffraction and μ-Raman spectroscopy. Samples were synthesized by thermal treatment in air at 1373 K of coprecipitated mixed oxalates. A CeO₂-based solid solution with a fluorite-type structure (F) was found to be stable up to x = 0.4, while at higher Lu content a (F + C) biphasic region was observed, with C being the cubic atomic arrangement typical of sesquioxides of the heaviest rare earths. A comparative approach including also results deriving from other (Ce_1–xRE_x)­O_2–x/2 systems (RE  Gd and Sm) allowed us to conclude that the compositional extent of the F solid solution is a complex function of RE³⁺ size and RE compressibility. On this basis, the dependence of ionic conductivity on the RE identity was interpreted as related both to the Ce⁴⁺/RE³⁺ size closeness and to RE compressibility. Ce⁴⁺/RE³⁺ dimensional issues were also revealed to rule the appearance of the hybrid structure observed in the two aforementioned systems, consisting of the intimate intergrowth of C microdomains within the F-based host lattice. Moreover, a more extended definition of F-based solid solution, including also the hybrid structure, is formulated; the latter is meant as a modification of the former, occurring when mainly RE–vacancy aggregates are incorporated into the host lattice in spite of isolated RE ions. By μ-Raman spectroscopy it was possible to demonstrate that the mechanism of oxygen vacancy formation is common to all the systems studied, provided that the structure of the F-based solid solution, also including the hybrid structure, is retained.