A site-selective spectroscopy study of Ag nanoclusters dispersed in oxyfluoride glass hosts has been carried out. The nano- to millisecond, essentially non-exponential, luminescence kinetics of Ag nanoclusters has been detected in the spectral range from 450 to 1000 nm, when excited at discrete wavelengths in the range 250 to 450 nm. Based on these experimental observations, the energy level configuration coordinate diagram for the involved ground and excited singlet/triplet states of the Ag nanoclusters has been proposed and confirmed by the density functional theory (DFT). The sites for the Ag nanoclusters are argued to be multiple. The structure/geometry of the involved Ag nanoclusters has been suggested to involve spin-paired dimers Ag²⁺, or tetramers Ag₄²⁺, with a varying elongation/distortion along the tetramer diagonals.

Transparent glass-ceramics have shown interesting optical properties for several photonic applications. In particular, compositions based on oxide glass matrices with fluoride crystals embedded inside, known as oxyfluoride glass-ceramics, have gained increasing interest in the last few decades. Melt-quenching is still the most used method to prepare these materials but sol-gel has been indicated as a suitable alternative. Many papers have been published since the end of the 1990s, when these materials were prepared by sol-gel for the first time, thus a review of the achievements obtained so far is necessary. In the first part of this paper, a review of transparent sol-gel glass-ceramics is made focusing mainly on oxyfluoride compositions. Many interesting optical results have been obtained but very little innovation of synthesis and processing is found with respect to pioneering papers published 20 years ago. In the second part we describe the improvements in synthesis and processing obtained by the authors during the last five years. The main achievements are the preparation of oxyfluoride glass-ceramics with a much higher fluoride crystal fraction, at least double that reported up to now, and the first synthesis of NaGdF₄ glass-ceramics. Moreover, a new SiO₂ precursor was introduced in the synthesis, allowing for a reduction in the treatment temperature and favoring hydroxyl group removal. Interesting optical properties demonstrated the incorporation of dopant ions in the fluoride crystals, thus obtaining crystal-like spectra along with higher efficiencies with respect to xerogels, and hence demonstrating that these materials are a suitable alternative for photonic applications.

Bulk oxyfluoride glasses co-doped with Ag nanoclusters and Yb³⁺ ions have been prepared by a melt quenching technique. When excited in the absorption band of the Ag nanoclusters between 300 to 500 nm, these glasses emit a broad band characteristic of the Ag nanoclusters between 400 to 750 nm as well as an emission band between 900 to 1100 nm, originating from Yb³⁺ ions. The intensity ratio of the Yb³⁺/Ag emission bands increases with the Ag doping level at a fixed concentration of Yb³⁺, indicating the presence of energy transfer mechanism from the Ag nanoclusters to the Yb³⁺ ions. Comparison of time-resolved decay kinetics of the luminescence in the respectively Ag nanocluster-Yb³⁺ co-doped and single Ag nanocluster doped glasses, hints towards an energy transfer from the red and infrared emitting Ag nanoclusters to the Yb³⁺ ions.

95 SiO 2 – 5 LaF 3 sol-gel derived nano-glass-ceramics single doped with 0.1Dy3+ or 0.1Tb3+ mol % and codoped with 0.1Dy3+ and xTb3+ (x=0.1,0.3) mol % were successfully obtained. XRD and HRTEM measurements confirm the precipitation of LaF3 nanocrystals during the ceramming process, with mean size ranging from 10 to 20 nm and increasing with the thermal treatment temperature. About 75% of lanthanide ions are partitioned into LaF3 nanocrystals, as calculated from luminescence decays. The effect of increasing the Tb3+ concentration and also of codoping with Dy3+ in the Tb3+ green emission from the D54 level have been studied. The energy transfer mechanisms between Tb3+ ions and also between Tb3+–Dy3+ ions, which favor the green emission, have been analyzed.