Eu<SUP>3+</SUP>-Doped Gadolinium Oxide Nanoparticles Synthesized by Chemical Coprecipitation Predicted by Thermodynamic Modeling

Thermodynamic modeling of the Gd(3+)-Eu(3+)-O(2-)-CO3(2-)-Cl- system has been adopted as a rational approach to establish routes to the better synthesis conditions for pure phase Eu(3+)-doped Gd2O3 nanoparticles. Quantitative analyses of the different reaction equilibria involved in the coprecipitation of Gd2(CO3)3 and Eu2(CO3)3 x 3H2O from aqueous solutions have been used to determine the optimum synthesis conditions. The characterization and photoluminescence spectra of Gd2O3 nanoparticles doped with Eu3+ activator ions at the concentrations of 1, 2, 3, 4 and 5 mol% synthesized by urea-based homogeneous coprecipitation are presented. The surface of the as-prepared mixture of Gd2(CO3)3 and Eu2(CO3)3 x 3H2O particles are coated with silica to avoid the agglomeration followed by annealing the carbonate precursors at 800 degrees C for 3 hours. Subsequently, the silica shell is removed with an alkali solution resulting in well-crystallized Eu(3+)-doped Gd2O3 nanoparticles. X-ray diffraction (XRD) results show that all the diffraction peaks are well indexed to the cubic Gd2O3 with high crystallinity. The photoluminescence spectra exhibit a characteristic f-f transition band that corresponds to Eu3+. The sharp red emission at 616 nm corresponds to the transition identified as 5D0 __7F2. Both the emission intensity at 616 nm and asymmetry factor of [I(5D0 --> 7F2)/I(5D0 --> 7F1)] exhibit clearly Eu(3+)-doping concentration-dependent luminescence behaviors. The rather fast decay time is closely correlated to the proper occupation of the Eu3+ activator ions in the C2 sites of the Gd2O3 cage, resulting in strong dependence on small changes of the total electric density and defect density. Thus, the best concentration of Eu3+ activator ions for the maximum brightness are the 3 mol% Eu(3+)-doped Gd2O3 at 5D0 --> 7F2 because it shows the longest decay time and more luminescent intensity than the other doping concentrations.