Luminescence behaviors of the Eu2+ ions in the GeS2-Ga2S3-CsCl chalcohalide glasses

In the paper, we report the luminescence behaviors of Eu²⁺-doped chalcohalide glasses. Composition of glass matrix is 37.5GeS₂-22.5Ga₂S₃-40CsCl (mol%) with the concentration of Eu²⁺ in the range of 0.1–0.25 (mol%). The optimal Eu²⁺ doping concentration was 0.15 mol% at which the glass exhibited an enhanced emission peaking at 434 nm with a full width at half maximum (FWHM) about 80 nm with the excitation at 395 nm.     

Luminescence properties and energy transfer of Eu/Tb ions codoped aluminoborosilicate glasses

Eu/Tb codoped aluminoborosilicate glasses were fabricated by high temperature melting-quenched technique and their luminescence properties were investigated by excitation and emission spectra. Under 376 nm excitation, blue, green and red emission bands were simultaneously observed at 425 nm, 485 nm, 540 nm and 611 nm, respectively. The broad blue emission band centered at 425 nm was originated from the reduced Eu²⁺ ions, which were reduced from Eu³⁺ ions at high temperature in an ambient atmosphere and the reduction process may be related with the optical basicity of glass matrix. A complex bright white light emission was obtained for 0.5 mol% Eu₂O₃, 0.5 mol% Tb₂O₃ codoped aluminoborosilicate glass with CIE-X = 0.31 and CIE-Y = 0.33. The energy transfer among Eu³⁺, Eu²⁺ and Tb³⁺ ions was also discussed.     

Optical properties of Er3+-doped alkali fluorophosphate glasses

A systematic study of the optical absorption and luminescence spectra of Er³⁺-doped alkali fluorophosphate glasses (RTFP) 50(NaPO₃)–10TeO₂–20AlF₃–19RF–1Er₂O₃ (R = Li, Na and K) has been performed. The phenomenological Judd–Ofelt intensity parameters have been determined from the spectral intensities of the absorption bands in order to calculate the radiative transition probabilities, radiative lifetimes and branching ratios for various excited luminescent states. Using the visible and near infrared emission spectra, full width at half maximum (FWHM), emission cross-sections (σ_e) and figure of merit (FOM) were evaluated and compared with other hosts. Especially, the numerical values of these parameters indicate that the emission transition ⁴I_13/2 → ⁴I_15/2 transition at 1.534 μm in Er³⁺-doped fluorophosphate glasses may be highly useful in optical communication. The decay characteristic of ⁴S_3/2 excited level has also been recorded and analyzed. The calculated and experimental lifetimes were compared in terms of quantum efficiencies and multiphonon relaxation rates.     

Synthesis and photoluminescence of Eu3+-doped ZnO–Ga2O3–SiO2 nano-glass-ceramics

Transparent rare-earth Eu³⁺-doped ZnO–Ga₂O₃–SiO₂ nano-glass-ceramics were obtained by a sol–gel method. X-ray diffraction and transmission electron microscopy were used to characterize the as-synthesized materials. Results showed that ZnGa₂O₄ nanocrystals with the size of 5 nm were precipitated from ZnO–Ga₂O₃–SiO₂ system and dispersed in the SiO₂-based glass when the heat-treatment temperature was up to 800 °C. Photoluminescence characterization of Eu³⁺-doped ZnO–Ga₂O₃–SiO₂ nano-glass-ceramics was carried out and the results show that the as-synthesized material display intense emission at 615 nm belonging to ⁵D₀ → ⁷F₂ transition.     

Intense luminescence of amorphous Eu2O3 prepared by aqueous sol–gel method

Amorphous Eu₂O₃ was prepared by an aqueous sol–gel method. Emission due to the ⁵D₀ → ⁷F_J (J = 0, 1, 2) transitions of Eu³⁺ ions were observed. The dominant transition was the ⁵D₀ → ⁷F₂ red emission of Eu³⁺. The properties of the as-prepared samples were different with changes in the annealing temperature. To investigate the luminescence properties of the amorphous Eu₂O₃, the temperature-dependent photoluminescence (PL) spectra of samples annealed at 600 °C were measured in the temperature range 77–300 K. PL peak positions were unchanged with the change of temperature.     

Synthesis and luminescent properties of novel RENbO4:Ln3+ (RE = Y, Gd, Lu; Ln = Eu, Tb) micro-crystalline phosphors

Using rare earth coordination polymers with aromatic carboxylic acids as the precursors of rare earth oxide components, with polyethylene glycol (PEG) as the dispersing media, micro-crystalline phosphors RENbO₄:Ln³⁺ (RE = Y, Gd, Lu; Ln = Eu, Tb) have been synthesized by an in situ co-precipitation method. Both X-ray diffraction and scanning electron microscopy have shown that the resultant samples present are crystalline with ‘rice glue ball’ micro-morphology and crystalline grain sizes in the range of 1–2 μm. The luminescent properties of these phosphors have been studied, which show that the best photoluminescent performance is achieved for GdNbO₄:Tb³⁺ or Eu³⁺. This was because Gd³⁺ plays an important role to enhance the luminescence of Tb³⁺ or Eu³⁺ in an energy transfer process. In addition, the influence of the doping concentration on the fluorescence behaviors has been examined. With increase of the doping concentration from 1 mol% to 5 mol%, both the red emission intensity of Eu³⁺ and the green emission intensity of Tb³⁺ increase.     

Energy transfer from Bi3+ sensitizing the luminescence of Eu3+ in clusters embedded into sol–gel silica glasses

Y³⁺(La³⁺), Eu³⁺ and Bi³⁺ ions co-doped sol–gel silica glasses were synthesized. Photoluminescence spectra show that there is energy transfer from Bi³⁺ ions to the emission band of Eu³⁺ ions. The co-dopants Y³⁺ or La³⁺ have strong effects on the local structure and luminescence of Eu³⁺ ions. For 0.5 mol% Eu³⁺ ions doped glasses, the co-doping of 1 mol% Bi³⁺ and 1 mol% Y³⁺ is the most appropriate for the sensitization from Bi³⁺ to Eu³⁺. The sensitization effectiveness from Bi³⁺ ions to Eu³⁺ ions was studied by changing the amount of Bi³⁺ and Y³⁺, and clusters containing rare earth ions and Bi³⁺ ions dominate the energy transfer processes. The comparison of luminescent R-values (the intensity ratio of ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁ in Eu³⁺ ions) between glasses containing La³⁺ and containing Y³⁺ verifies the formation of clusters in sol–gel glasses. As a favorable configuration for energy transfer, the accurate design and synthesis of clusters-contained glasses may provide a new kind of luminescent materials.     

Reduction and luminescence of europium ions in glass ceramics containing SrF2 nanocrystals

Reduction of Eu³⁺ → Eu²⁺ and luminescence of europium (Eu) ions in glass ceramics containing SrF₂ nanocrystals have been investigated. The formation of SrF₂ nanocrystals in glass ceramics was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Blue luminescence of the Eu²⁺ ions was observed in the Eu doped glass ceramics which were prepared by the heat treatment of the glass in air atmosphere. The double-exponential decay curves of ⁵D₀ state of Eu³⁺ in the Eu doped glass ceramics indicated that there were two different surroundings of the Eu ions in the glass ceramics.     

Preparation and luminescent properties of Eu-doped transparent glass-ceramics containing SrF2 nanocrystals

Transparent glass-ceramics containing SrF₂ nanocrystals were fabricated by melt-quenching and subsequent heating of glass with a composition of 50SiO₂–10Al₂O₃–20ZnF₂–20SrF₂. X-ray diffractometry, transmission electron microscopy, and energy dispersive spectroscopy were used to investigated the microstructure of the SrF₂ glass-ceramics. Results show that SrF₂ nanocrystals were homogeneously precipitated among the aluminosilicate glass matrix, and the mean size of the SrF₂ nanocrystals was about 20 nm, and Eu³⁺ ions partition mainly into the precipitated SrF₂ nanocrystals after crystallization. The glass-ceramics exhibited intense red emission corresponding to the ⁵D₀ → ⁷F_J (J = 0–4) transitions of Eu³⁺ ions under 393 nm excitation. A significant Eu³⁺ luminescence enhancement by a factor of about nine times was observed after crystallization. Besides, the obvious stark splitting emissions, the low forced electric dipole ⁵D₀ → ⁷ F₂ transition, and the long decay lifetimes of Eu³⁺ ions also revealed the partition of Eu³⁺ ions into low phonon energy SrF₂ nanocrystals. Our results indicate the SrF₂ based fluorosilicate glass-ceramics is an excellent host for trivalent lanthanide ion doping and may find applications in photonics.     

Spectroscopy and crystal-field analysis of Cr4+-doped transparent silicate glass-ceramics

We report transparent Cr⁴⁺-doped SiO₂–Al₂O₃–ZnO–Li₂O–K₂O glass-ceramics with broadband infrared luminescence. After heart-treatment, Li₂ZnSiO₄ crystallite was precipitated in the glasses, and its average size increased with increasing heat-treatment temperature. Racah parameters of Cr⁴⁺–Li₂ZnSiO₄ glass-ceramics have been calculated, and it was confirmed from absorption spectra that the energy levels of Cr⁴⁺-doped glass-ceramics are close to the cross point ¹E and ³T states. No infrared emission was detected in the as-made glass samples, but the broadband infrared emission centered at 1210 nm with the full width at half maximum (FWHM) of more than 250 nm was observed by exciting the glass-ceramics with excitation of an 808 nm laser diode. In order to analyze the located crystal field of Cr⁴⁺ ions, the emission spectra are fitted by multi-peak Gauss fitting. It is seen that the fluorescence spectra are fitted into two Gaussian bands at around 1195 and 1263 nm with band widths of 208 and 278 nm, respectively. The two Gaussian bands at around 1195 and 1263 nm have about the same decay rate, and hence they would probably originate from the same luminescent centers. The observed infrared emission could be attributed to Cr⁴⁺ ions at low-field sites in Li₂ZnSiO₄ glass-ceramics.     

Effect of annealing and gamma irradiation on undoped and Eu3+-doped Y2SiO5 single crystals

The absorption spectra of the undoped Y₂SiO₅ and Eu³⁺-doped Y₂SiO₅ crystals grown by the Czochralski technique were compared before and after annealing and, similarly, the unannealed and annealed crystals after γ-ray irradiation. The absorption bands of Eu²⁺ ions with peaks at 300 and 390 nm were observed in the as-grown Y₂SiO₅:Eu³⁺ crystal. These peaks were more intense in H₂-annealed and irradiated Y₂SiO₅:Eu³⁺ crystals. The additional absorption peaks at 260 and 320-330 nm which were attributed to F color centers and O⁻ hole centers were observed in irradiated undoped Y₂SiO₅ and Y₂SiO₅:Eu³⁺ crystals, respectively.     

Characterization of Eu3+-doped fluorophosphate glasses for red emission

Fluorescence spectra and decay curves of the ⁵D₀ level for different concentrations of Eu³⁺ (4f⁶) ions in K–Ba–Al fluorophosphate glasses have been measured at room temperature and are analyzed. The Judd–Ofelt intensity parameters Ω₂ and Ω₄ have been determined from the intensity ratios of emission peaks corresponding to ⁵D₀ → ⁷F_J (J = 2 and 4) to ⁵D₀ → ⁷F₁ transitions for 1.0 mol% glass. The intensity parameters thus obtained are in turn used to calculate the radiative properties of the fluorescent levels of Eu³⁺ ions. Second and fourth rank crystal-field parameters have been evaluated by assuming a C_2V site symmetry for the local environment of Eu³⁺ ions to estimate the crystal-field strength experienced by Eu³⁺ ions in the present host. The decay profiles of the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions in the present glasses are found to be single exponential for all the studied Eu³⁺ ion concentrations. A marginal increase in lifetime of the ⁵D₀ level has been noticed with Eu³⁺ ion concentration up to 2.0 mol% and then the lifetime marginally decreases for higher Eu³⁺ ion concentrations.     

Highly enhanced f–f transitions of Eu3+ in La2O3 phosphor via citric acid and poly (ethylene glycol) precursor route

The luminescent material europium-activated La₂O₃ have been prepared by the citric acid and poly (ethylene glycol) (PEG) precursor route. Their structures and optical properties were characterized by FT-IR spectrum, X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), UV–vis spectroscopy, and photoluminescence (PL) spectra, respectively. The results show considerable enhancement of the photoluminescence, especially the Eu³⁺ f–f transition excitation lines and the charge transfer band (CT). The samples can exhibit strong red emission centered at 626 nm excited at either the CT band (300 nm) or the Eu³⁺ f–f transition (396 nm), suggesting the potential application as the red phosphors for ultraviolet light-emitting diodes (LEDs), which can be attributed to the ⁵D₀→⁷F₂ transition of Eu³⁺. The remarkable enhancement of color purity of red emission and the concentration quenching of Eu³⁺ in La₂O₃ were also observed with increasing Eu³⁺ doped concentration.     

Site selective spectroscopy of Eu3+ in heavy-metal oxide glasses

In this work, we report time-resolved line-narrowed fluorescence spectra of the ⁵D₀ → ⁷F₀₋₆ transitions of Eu³⁺-doped 40Bi₂O₃–40PbO–10Ga₂O₃–10GeO₂ and 60GeO₂–25PbO–15Nb₂O₅ glasses obtained at 10 K by using different resonant excitation wavelengths along the ⁷F₀ → ⁵D₀ transition. The wavelength dependence of the ⁷F₁ splitting in both glasses suggests the existence of a broad distribution of Eu³⁺ centres possessing a variety of local field environments. The influence of the local coordination ions on the optical properties of Eu³⁺ has been studied by analysing the dependence of the crystal field (CF) parameters on the excitation energy along the ⁷F₀ → ⁵D₀ transition.     

Ultraviolet to near-infrared spectral modification in Ce3+ and Yb3+ codoped phosphate glasses

The ultraviolet to near-infrared spectral modification in Ce³⁺ and Yb³⁺ codoped phosphate glasses was realized through the energy transfer from Ce³⁺ to Yb³⁺. The absorption spectra, fluorescence excitation and emission spectra, luminescence decay curves, and time-resolved emission spectra were measured and analyzed. The energy transfer efficiency and concentration quenching efficiency were calculated based on the decay curves of Ce³⁺ 340 nm emission and Yb³⁺ 976 nm emission. The calculated and experimental NIR emission intensities on the Yb³⁺ concentrations were compared and discussed.     

Time-resolved fluorescence measurements on Eu3+- and Eu2+-doped glasses

Various fluoride, phosphate and borosilicate glasses with known properties and global structure have been doped with Eu³⁺ (4f⁶) at doping concentrations between 10¹⁸ and 10²¹ cm^?3. By applying reductive melting conditions Eu³⁺ could partially be transformed to Eu²⁺ (4f⁷). Four fluoroaluminate glasses with varying phosphate content between 0 and 20 mol% (FPx), a pure phosphate glass (P100) and two borosilicate glasses with low (DURAN^®-like) and high optical basicity (NBS1) have been used for these investigations. The time-resolved fluorescence in the visible range has been studied for both ions. Although static and dynamic fluorescence of Eu³⁺ and Eu²⁺ are dramatically different (f–f-transitions for Eu³⁺; d–f-transitions for Eu²⁺), glass structure changes have a similar influence on the dynamic fluorescence behavior of both ions. A strongly ionic surrounding due to fluorine ligands as in fluoroaluminate glass samples provides the longest fluorescence lifetime (about 7 ms for Eu³⁺; about 1.3 μs for Eu²⁺). Increasing phosphate content decreases the fluorescence lifetime due to more oxygen ligands. Interesting differences have been found for the two borosilicate glasses due to the difference in their optical basicity (Na₂O/B₂O₃ ratio). Measurements indicate a homogeneous distribution of europium ions in most FP samples. NBS1 measurements suggest that two different local europium sites are formed. For Duran-like samples only one specific europium site was found, although these samples show phase separation at high doping concentrations into a SiO₂-rich phase and borate- and europium-rich droplets. Fluorescence quenching due to energy transfer from Eu²⁺ to Eu³⁺ could be found for co-doped samples; Eu³⁺-doped samples show no fluorescence quenching.     

Bismuth-activated luminescent materials for broadband optical amplifier in WDM system

New broadband near infrared luminescence covering the whole work windows (1260–1625 nm) of the current wavelength division multiplexing (WDM) system was found from bismuth-activated M₂O–Al₂O₃–SiO₂ (M = Li, Na) and Li₂O–Ta₂O₅–SiO₂ glasses at room temperature in the case of 808 nm-laser excitation. But the near infrared luminescence mechanism of the bismuth-activated glasses is not well understood up to now. The figure-of-merits of bandwidth and gain of the glasses are better than those of Er³⁺-doped silicate glasses and Ti³⁺ doped sapphire, implying they are the promising gain-medium candidates for the broadband amplifiers and the widely tunable laser sources.     

Luminescence properties of Y3Al5O12:Eu3+-coated submicron SiO2 particles

Silica submicron spherical particles coated with an yttrium aluminum garnet (Y₃Al₅O₁₂, YAG) layer doped with Eu³⁺ were prepared by the sol–gel method. The structure and morphology of samples determined by the X-ray powder diffraction measurements and transmission electron microscope images, respectively, indicated that well-crystallized garnet nanocrystallites were formed with successive coating cycles. Similar trends were deduced from the evolution of the luminescence spectra. The ratio of integrated intensities of the ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁ transitions was used to analyze the structural variations in the surroundings of the Eu³⁺ ion. The effect of coating was analyzed by comparing the luminescence properties of the Y₃Al₅O₁₂:Eu³⁺ nanocrystalline powders and composite Y₃Al₅O₁₂:Eu³⁺/SiO₂ materials.     

Spectroscopic characterization of signal gain and pump ESA in short-lengths of RE-doped tellurite fibers

We report the results of emission and amplification in Tm³⁺- and Er³⁺-fibers for signal gain in the 1460–1600 nm region, which covers a large part of S-, C- and L-bands of silica fiber optical communication networks. The paper explains the mechanism for alleviating the pump-excited absorption in Er³⁺-doped and Tm³⁺-doped tellurite fibers for maximizing the pump inversion efficiency at 980 nm using the co-dopants and via the structural modification of TeO₂ glass by incorporating a high phonon energy oxide namely, B₂O₃. The spectroscopic data and gain bandwidth of Er-doped fibers are reported in the C- and L-bands. To date the measured maximum relative gain in short fibers of 5–10 cm in length in C- and L-bands are: 30 dB and 15 dB, respectively. By comparison the internal gain in a 20 cm long Tm/Yb ion co-doped fiber pumped with a 980 nm source was 7 dB.     

Enhanced luminescent properties of Tb3+ ions in transparent glass ceramics containing BaGdF5 nanocrystals

Tb³⁺ doped transparent oxyfluoride glass ceramics containing BaGdF₅ nanocrystals were prepared. The transmission spectra, photoluminescence spectra, decay time and X-ray excited luminescence spectra of the Tb³⁺-doped glass and glass ceramics were investigated. Energy transfer from Gd³⁺ to Tb³⁺ has been observed in the glass and glass ceramics. The emission intensity of green band (⁵D₄ → ⁷F_J) of the Tb³⁺-doped glass ceramics is enhanced compared with that of the glass under ultraviolet and X-rays, which could be attributed to that the generation of BaGdF₅ nanocrystals with low phonon energy reduces the non-radiative transitions.