Interaction of lanthanide and actinide with BaHfO3 perovskite: A case study with cerium and uranium

Speciation of actinide (An) and lanthanide (Ln) in technologically important ceramics is very important from both fundamental as well as technological aspects. The intrinsic structural flexibility of perovskite containing AO(6) and BO12 polyhedra makes them suitable and rich hosts for An and Ln. In this work, emphasis was given to deciphering information such as oxidation state, local dopant site, charge compensating defects, excited state kinetics, and so forth in BaHfO3 (BHO) related to dopant uranium (BHO-U) and cerium (BHO-Ce). Several spectroscopic techniques namely, time-resolved photoluminescence (TRPL), positron annihilation lifetime spectra (PALS), and thermoluminescence (TL) spectroscopy coupled with density functional theory (DFT) were employed to probe the same. Ce and U though are distributed at both Ba and Hf sites, Ce prefers the former, while U prefers the latter site. Uranium on the other hand stabilizes as U6+ in the form of octahedral uranate ion giving green emission. PALS suggested the formation of defects in BHO-Ce and BHO-U with oxygen vacancies predominating in the former whereas BHO-U perovskites are loaded with cation vacancies and vacancy clusters. These cation vacancies are responsible for lower TL output in BHO-U. TL measurements also suggested cerium doping leads to a higher density of deeper traps in BHO-Ce compared to uranium doping in BHO-U which is in concurrence with DFT results and may have implications in designing afterglow phosphors based on perovskite. We believe this work would have a long-term impact on exploring the potential of perovskite for nuclear waste host and afterglow phosphors applications.