Spectroscopic study of the 4f (n-1)5d transitions of LaPO4 doped with Pr3+ or co-doped with Pr3+ and Gd3+ in the vacuum ultra violet region

摘要

The energy of f-d transitions depends on the crystalline field in which the lanthanide ion is inserted. Depending on the experimental setup, these transitions could occur at high energy, so several studies regarding theoretical data have been conducted. Here, we present the experimental determination of the energy of interconfigurational 4f ( n ) -> 4f ( n-1)5d (f-d) transitions from Pr3+ ions to the lanthanum orthophosphate LaPO4 matrix; we have also determined the bandgap value for this host. The experiments were carried out at the Synchrotron setup of the Brazilian LNLS laboratory. Specifically, we synthesized LaPO4:Pr3+ and LaPO4:Pr3+/Gd3+ by the hydrothermal method under different pH conditions or by spray pyrolysis. The particles resulting from hydrothermal synthesis had different morphologies and the influence of pH value was showed: the reaction medium was controlled along the process, which changed the surface potential. On the basis of Raman spectroscopy and x-ray diffraction analyses, we found that the crystalline phase was monoclinic monazite for all the samples. We studied the 4f5d level and bandgap transitions at high energy by absorption analysis in the VUV range. The experimental results were 7.5 eV (LaPO4 bandgap) and 5 eV (4f ( n ) -> 4f ( n-1)5d transition of the Pr3+ ion), which were close to the theoretical values reported in the literature for this ion and this matrix.