Understanding the local structure of Eu3+- and Y3+-stabilized zirconia: insights from luminescence and X-ray absorption spectroscopic investigations

This study combines bulk structural and spectroscopic investigations of Eu$^{3+}$- or Y$^{3+}$/Eu$^{3+}$ co-doped tetragonal and cubic zirconia polymorphs to gain an indepth understanding of the solid solution formation process. Our bulk structural characterizations show that the dopant is homogenously distributed in the ZrO$_{2}$ host structure resulting in an increase of the bulk symmetry with increasing dopant substitution (from 8 to 26 mol%). The local site symmetry around the Eu$^{3+}$ dopant, however, determined with luminescence spectroscopy (TRLFS), remains low in all samples. Results obtained with X-ray pair distribution function and X-ray absorption spectroscopy show that the average coordination environment in the stabilized zirconia structures remains practically unchanged. Despite this very constant average dopant environment, siteselective TRLFS data show the presence of three nonequivalent Eu$^{3+}$ environments in the ZrO$_{2}$ solid structures. These Eu$^{3+}$ environments are assumed to arise from Eu$^{3+}$ incorporation at superficial sites, which increase in abundance as the size of the crystallites decrease, and incorporation on two bulk sites differing in the location of the oxygen vacancies with respect to the dopant cation.