Luminescence variations in hydroxyapatites doped with Eu2+ and Eu3+ ions

We present a detailed analysis of the luminescence behavior of europium-doped hydroxyapatite (HAp) and calcium-deficient hydroxyapatite (Ca-D HAp) nanopowders. The results show that, while both powders are similar in crystallite size, particle size, and morphology, the luminescence behavior differs significantly. For the HAp:Eu powders, the emission is clearly from Eu(3+) ions and corresponds to typical (5)D(0) --> (7)F(J) emissions, whereas for the Ca-D HAp:Eu powders, we also see a broad emission with two peaks at 420 and 445 nm, corresponding to the 4f(6)5d(1) --> 4f(7) ((8)S(7/2)) transition of Eu(2+). The powders are weakly luminescent in the as-synthesized state, as expected for combustion-synthesized materials and have higher emission intensities as the heat treatment temperature is increased. Luminescence spectra obtained using an excitation wavelength of 254 nm are weak for all samples. Excitation wavelengths of 305, 337, and 359 nm, are better at promoting the Eu(3+) and Eu(2+) emissions in hydroxyapatites. We propose that fluorescence measurements are an excellent way of qualitatively determining the phase composition of europium-doped hydroxyapatite powders, since powders that exhibit a blue emission contain substantial amounts of Ca-D HAp, allowing the determination of the presence of this phase in mixed-phase hydroxyapatites.