Bismuth-based fluoride nanocrystalline particles have recently attracted much attention as hosts for luminescent ions such as lanthanides (Ln) being proposed for lighting devices and biological applications. However, a comprehensive investigation on the chemical properties of this family of materials, the growth of the nanoparticles, and information about the chemical and thermal stabilities are critical to assess the real potential of nanosystems. In this view, a combined experimental and theoretical approach is employed to investigate the crystalline and electronic structure of BiF3 and NaBiF4. A detailed spectroscopic investigation allows us to measure the exciton peaks of these fluoride compounds for the first time and to design the vacuum referred binding energy level diagram of the lanthanide-doped fluorides with respect to the valence and conduction bands of the hosts in comparison with conventional fluorides. In addition, temperature and water effects on the chemical stability of NaBiF4 were addressed, evidencing detrimental limitations and envisaging possible solutions in view of biological applications.

Rare earth doped materials play a very important role in the development of many photonic devices, such as optical amplifiers and lasers, frequency converters, solar concentrators, up to quantum information storage devices. Among the rare earth ions, ytterbium is certainly one of the most frequently investigated and employed. The absorption and emission properties of Yb3+ ions are related to transitions between the two energy levels 2F7/2 (ground state) and 2F5/2 (excited state), involving photon energies around 1.26 eV (980 nm). Therefore, Yb3+ cannot directly absorb UV or visible light, and it is often used in combination with other rare earth ions like Pr3+, Tm3+, and Tb3+, which act as energy transfer centres. Nevertheless, even in those co-doped materials, the absorption bandwidth can be limited, and the cross section is small. In this paper, we report a broadband and efficient energy transfer process between Ag dimers/multimers and Yb3+ ions, which results in a strong PL emission around 980 nm under UV light excitation. Silica-zirconia (70% SiO2-30% ZrO2) glass-ceramic films doped by 4 mol.% Yb3+ ions and an additional 5 mol.% of Na2O were prepared by sol-gel synthesis followed by a thermal annealing at 1000 °C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 430 °C to induce the migration and aggregation of the metal. The structural, compositional, and optical properties were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag dimers/multimers, which could have important applications in different fields, such as PV solar cells and light-emitting near-infrared (NIR) devices.

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Undoped and heavily doped (K, Y, Zr, Mo) strontium barium niobate Sr0.5Ba0.5Nb2O6 (SBN50) materials have been prepared by co-precipitation. X-ray diffraction shows the formation of a single-phase product and that 10% and 12.5% of the Nb sites can be occupied by Zr and Mo, respectively. K can enter 40% of the Sr sites, while the maximum Y substitution is also around 40%. The starting stoichiometry is effective in driving the substitutions to the desired sites. X-ray Absorption Spectroscopy (XAS) at the Nb-K edge shows the presence of Nb(V) independent of doping. A pre-edge 1s-4d transition surprisingly indicates the hole injection with Y doping and the electron injection with Zr doping. Chemical reduction does not affect the stability of the structure, except for a small decrease of maximum Y solubility, while the Nb(V) oxidation state and the XAS pre-edge feature are unmodified. The oxidized samples are insulators, the reduced samples show electrical conductivity, and doping significantly enhances thermopower and electrical conductivity. The Y doped sample shows a power factor ∼30 times larger than that of the undoped sample.

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