Towards Blue Long-Lasting Luminescence of Eu/Nd-Doped Calcium-Aluminate Nanostructured Platelets via the Molten Salt Route

Abstract

Calcia-alumina binary compounds doped with rare earths and some transition metals cations show persistent luminescence from the visible to the infrared range. Specifically, the blue light can be obtained through the Eu2+ activator center in a potential host, such as dodecacalcium hepta-aluminate (Ca12Al14O33) and monocalcium aluminate (CaAl2O4). By doping with Nd3+, the persistent luminescence can be substantially prolonged; for this reason, the Eu/Nd pair is a potential choice for developing long-lasting blue luminescence. Herein, the phase evolution of the calcia-alumina system via molten salt synthesis is reported as a function of the synthesis temperature and the atmospheric environment. The fraction of CaAl2O4 phase increases when the temperature is higher. Synthesized microparticles of platelet-type morphology represent isolated nanostructured ceramic pieces. Under visible light, the particles are white. This indicates that the followed process solves the dark-gray coloring of phosphor when is synthesized in a reduced atmosphere at high temperature. As regards the synthesis mechanism, which is assisted by the molten flux, the dissolution−diffusion transport process is promoted at the surface of the alumina microparticles. In fact, the emission intensity can be modulated through the phase of the Eu-doped calcium-aluminate discrete platelets synthesized. Consequently, the photoluminescence intensity depends also on the oxidation state of the Eu ion. X-ray absorption near-edge structure and photoluminescence measurements corroborate the Eu reduction and the grain coarsening with the enhancement of the blue emission. The doped phosphors with Eu/Nd show a broad and strong absorption in the region of 320–400 nm and a broad emission band at around 440 nm when they are excited in this absorption range. From a broader perspective, our findings prove that the Ca12Al14O33 and CaAl2O4 phases open new opportunities for research into the design of blue long-lasting emitters for a wide range of fields from ceramic to optoelectronic materials.