Probing complex disorder in Ce 1-xGd xO 2-x/2 using the Pair Distribution Function analysis

In this work the first Pair Distribution Function (PDF) study on Ce 1-xGd xO 2-x/2 (CGO) electrolytes for solid oxide fuel cells is presented, aiming to unveil the complex positional disorder induced by gadolinium doping and oxygen vacancies formation in these materials. The whole range of Gd concentration x Gd (0 ≤ x Gd ≤ 1) of the CGO solid solutions was investigated through high resolution synchrotron radiation powder diffraction. The reciprocal space Rietveld analysis revealed in all the solid solutions the presence of positional disorder, which has been explicitly mapped into the real space. The average structural models, as obtained by the Rietveld method, fit well the experimental PDF data only for a spatial range r > ∼10 Å. The same models applied at lower r values fails to reproduce the experimental curves. A clear improvement of the fit quality in the 1.5 < r < ∼6 Å range was obtained for all the CGO samples applying a biphasic model encompassing both a fluorite CeO 2-like and a C-type Gd 2O 3-like phases. This provides evidence that extended defects at local scale exist in the CGO system. Gdrich and Ce-rich droplets coexist in the subnanometric range. © 2012 American Chemical Society