Samarium doped hafnium oxide cubic and monoclinic nanometric powders synthesized by hydrothermal route

Hafnium oxide nanoparticles doped with trivalent samarium (HfO₂:Sm³⁺) were synthesized by hydrothermal route from chloride reagents. Different samarium doping concentrations (0, 0.5, 1, 3, 5 and 10?at% with respect to Hf) and different post-annealing temperatures (200, 400, 600, 800 and 1000?°C) were evaluated. The resulting nanoparticles showed an oval morphology with average sizes below 30?nm. A sensitive relationship between the samarium concentration and the resulting crystal structure of the material was observed by X-Ray diffraction and further evidenced by the cathodoluminescence and photoluminescence spectra. Low concentrations of samarium (0, 0.5 and 1?at%) generated a monoclinic phase, whereas higher concentrations of samarium (5 and 10?at%) generated a metastable cubic phase. The average crystallite sizes calculated by the Scherrer's equation were close to 8?nm and 12?nm for cubic and monoclinic phases, respectively. The luminescent emission corresponded to the characteristic 4f-4f transitions of the samarium ion with a principal peak centered at 610?nm. The best luminescent properties were obtained with the sample doped with samarium at 0.5?at%, annealed at 600?°C.