We show that oxy-fluoride glass ceramics, with typical composition, 32(SiO2):9(AlO1.5):31.5(CdF2):18.5(PbF2):5.5(ZnF2): 3.5(ErF3) mol % have potential applications in telecommunications. Upon heat treatment, Er3+ nucleates the growth of the nanocrystalline β-PbF2, which acts as its host. Heat treatment at 440 °C for 5 h and at 390 °C for 3 h gave rise to ∼12 and ∼2.5 nm diameter crystals, respectively. The emission band of Er3+ in the 1.54 μm telecommunications window (4I13/2→4I15/2 transition, at the half-height width) was 75 nm in the former and 90 nm in the latter case, while I13/24↔I15/24 absorption and emission bands became wavelength divergent in both cases. Also in the latter case, the spectrum was flat from 1.53 to 1.56 μm. The evolution of spectral behavior is explained by changes in average site geometry of the Er3+ dopant, related to the α→β phase transition of PbF2, which is stimulated by heat treatment.
Bulk oxyfluoride glasses doped with Ag nanoclusters have been prepared using the melt quenching technique. When pumped in the absorption band of Ag nanoclusters between 300 to 500 nm, these glasses emit a very broad luminescence band covering all the visible range with a weak tail extending into the near infrared. The maximum of the luminescence band and its color shifts to the blue with a shortening of the excitation wavelength and an increasing ratio of oxide to fluoride components, resulting in white color luminescence at a particular ratio of oxide to fluoride; with a quantum yield above 20%.
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.
A bright persistent photoluminescence has been observed in Er(3+)-doped nanoparticles prepared by selective dissolution of bulk oxyfluoride nano-glass-ceramics. A 2 orders of magnitude decrease of intensity of the (4)S(3/2)-->(4)I(15/2) green emission band of Er(3+) in these nanoparticles is observed in magnetic fields up to 50 T. This strong luminescence sensitivity to magnetic field can be used for localization and distant optical detection of magnetic field in nanovolumes with a field-resolution of 0.01 T.
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