Photoluminescence, γ-irradiation and X-ray induced luminescence studies of Sm3+-doped oxyfluorosilicate glasses and glass-ceramics

Sm³⁺-doped oxyfluorosilicate glasses were fabricated through traditional melt quenching technique. After the heat treatment of the prepared glass, transparent SrF₂ nanocrystalline glass-ceramics (GC) were obtained. The amorphous nature of the prepared glasses and crystalline phase (SrF₂) of the GC were confirmed by XRD analysis. Abbe number was calculated for all the prepared glasses by measuring refractive index at different wavelengths. In the framework of Judd-Ofelt (JO) theory, the JO intensity parameters were obtained from the absorption spectra of 1.0 mol% Sm₂O₃-doped glass. The photoluminescence spectrum was recorded with 401 nm excitation. From the analysis of optical spectra and JO parameters, the radiative properties like radiative transition probabilities, branching ratios and radiative lifetimes for the fluorescent levels of Sm³⁺ ions were determined. The effect of γ-irradiation on luminescence properties and X-ray induced luminescence properties were also studied. The emission intensity was increased for GC where as it decreases with increase of γ-irradiation dosages. There are no noticeable changes in the position as well as intensity in photoluminescence and X-ray induced luminescence spectra for GC sample but after the γ-irradiation, the emission intensity was decreased moderately. The luminescence decay profiles for ⁴G_5/2 level were recorded and it is changed from exponential to non-exponential nature for higher Sm³⁺ ion concentrations. The decay profiles which exhibit non-exponential nature are well fitted to the Inokuti-Hirayama model and determined the energy transfer parameters. By using the integrating sphere, the quantum yield values were obtained for all the prepared glasses. The detailed study of the present glasses reveals that these glasses could be useful for radiation shielding and scintillation applications.     

Structure and optical properties of transparent Er3+-doped CaF2–silica glass ceramic prepared by controllable sol–gel method

Transparent Er³⁺-doped CaF₂–silica glass ceramics were prepared by the direct physical introduction of Er³⁺ doped CaF₂ nanocrystals into acid-catalyzed sol–gel silica glass. The physical methods of ball milling, ultrasonic baths, and stirring were investigated to disperse Er³⁺ doped CaF₂ nanocrystals in the silica sols. The CaF₂–silica sol mixture went through gelation and heat-treatment to form Er³⁺-doped CaF₂–silica glass ceramics. The morphology of Er³⁺ doped CaF₂ in silica glass did not change after heat-treatment at 600 °C for 10 h. The experimental results showed that Er³⁺ doped CaF₂ in the glass ceramic prepared with the assistance of ball milling possesses the best dispersity and homogeneity. The highest in-line transmittance of the glass ceramic reached up to 85% in visible region. Glass ceramic exhibits efficient up-conversion emissions corresponding to the Er³⁺:⁴F_9/2→⁴I_15/2 transition and long lifetime of ⁴F_9/2 level (1.73 ms) under 980 nm excitation.     

Near-infrared long-lasting phosphorescence in transparent glass ceramics embedding Cr3+-doped LiGa5O8 nanocrystals

Cr³⁺ doped transparent glass ceramics of SiO₂–Ga₂O₃–Li₂O were fabricated by melt-quenching and subsequent crystallization. X-ray diffraction and transmission electron microscopy analyses evidenced that cubic LiGa₅O₈ nanocrystals were homogeneously precipitated among the silicate glass matrix. The incorporation of Cr³⁺ ions into LiGa₅O₈ nanocrystals was evidenced by absorption, emission and time-resolved luminescence spectra. Impressively, the present Cr³⁺ doped glass ceramics were demonstrated to be a new near-infrared (∼720 nm) long-lasting bulk phosphor whose luminescence can last for more than 2 h after stoppage of UV (250–350 nm) irradiation. The occurring of Cr³⁺ long-lasting phosphorescence in the glass ceramics was confirmed to be mainly due to the precipitation of Cr³⁺:LiGa₅O₈ nanocrystals from glass matrix. The filling/releasing of electrons into/from the intrinsic traps of LiGa₅O₈ nanocrystals through the conduction band of host were proposed to be responsible for the realization of the long-lasting phosphorescence of the investigated Cr³⁺ doped glass ceramics.     

Photoluminescence and structural characteristics of double tungstates A(M1−X PrX)W2O8 (A = Li,Cs, M = Al,Sc, La)

In this article, photoluminescence of Pr³⁺ ions in the double tungstate A(M_1?X Pr_X)W₂O₈ (A = Li, Cs, M = Al, Sc, La; 0.0 ≤ X ≤ 0.1) are characterised. By varying ion radius in A and M sites the crystal structure was modified and even in crystals with similar structural characteristics three distinctive types of luminescence are observed. When the substitution ions in both A and M sites are relatively small the host lattice exhibits luminescence dominantly. With the small A site ion (Li⁺) and the large M site ion (La³⁺, 1.03 Å) the Pr³⁺ ion exhibits prominent luminescence. With the very large A site ion (Cs⁺, 1.67 Å) and relatively small M site ion (Sc³⁺, 0.75 Å) the Pr³⁺ exhibits both the 4f²–4f5d excitation and the ³P_J manifold excitations in the absorption spectrum. These excitation levels lead to two strong emissions from the Pr³⁺. PL characteristics are discussed with respect to crystal structural criteria.     

Upconversion emission of ZrO2 nanoparticles doped with erbium (Er3+) and ytterbium (Yb3+), synthesized by hydrothermal route

This paper reports the luminescent response upconversion of zirconium oxide (ZrO₂) nanoparticles doped with erbium (Er³⁺) and ytterbium (Yb³⁺) ions, synthesized by hydrothermal route. X ray diffraction (DRX) showed that the synthesized material presents the face centered cubic (FCC) structure. High resolution transmission electron microscopy (HRTEM) showed the presence of crystals size smaller than 10 nm. The photoluminescent analysis allowed to observe an intense upconversion luminescence emission of the samples doped with both ions Er³⁺ and Yb³⁺, when these are excited with 910 nm laser source, showing the electronic transitions ⁴F_9/2 → ⁴I_5/2; ²H_11/2 → ⁴I_5/2; ⁴S_3/2 → ⁴I_15/2 of Er³⁺. Two decay times were observed, whose behavior can be associated to the average distance between erbium ions within the nanocrystals.     

Preparation and mid-infrared 2.7 µm luminescence property of high content Er3+-doped (Y0.9La0.1)2O3 transparent ceramics pumped at 980 nm

High content Er³⁺ doped (Y_0.9La_0.1)₂O₃ transparent ceramics have been prepared by conventional ceramic process. Absorption spectra, mid-infrared, up-conversion and near-infrared emission spectra of Er³⁺ pumped at 980 nm have been investigated. The mechanisms of energy transfer processes have been discussed. Large values of Judd–Ofelt parameter Ω₂ (5.73 × 10^–20 cm²) and spectral quality factor X (3.71) have been obtained. The greatly enhanced green up-conversion emission in the high Er³⁺ doped sample is considered important for the applications in up-converters. The much enhanced mid-infrared 2.7 µm and up-conversion emissions, as well as the depressed near-infrared 1.5 µm emission demonstrate the efficient population inversion of Er³⁺:⁴I_11/2 → ⁴I_13/2 in high Er³⁺-doped ceramics for the 2.7 µm emission. These results suggest that high Er³⁺-doped (Y_0.9La_0.1)₂O₃ transparent ceramics are promising host materials for the applications of mid-infrared lasers and infrared-to-visible up-converters.     

Molten salt synthesis and optical properties of Eu3+, Dy3+or Nd3+ doped NiNb2O6 columbite-type phosphors

Pure, Eu³⁺, Dy³⁺ or Nd³⁺-doped NiNb₂O₆ powders have been prepared by a molten salt synthesis method by using Li₂SO₄–Na₂SO₄ salt mixture as a flux at relatively low temperatures as compared to the solid state reaction method. X-ray diffraction patterns of pure NiNb₂O₆ samples indicated an orthorhombic single phase. For Eu³⁺-doped NiNb₂O₆ samples, the luminescence of Eu³⁺ was observed at 615 nm as red emission while Dy³⁺-doped NiNb₂O₆ showed yellow emission at 577 nm and Nd³⁺ doped sample exhibited a typical emission at 1064 nm varying with the Eu³⁺ or Nd³⁺ doping concentrations. These luminescence characteristics of the doped samples may be attributed to the energy transfer between rare earth ions and NiO₆ octahedral groups in the columbite structure.     

Composition and poling-induced modulation on photoluminescence properties for NBT-xBT: Pr3+ ceramics

In this work, the modulation of photoluminescence (PL) properties, which was realized by the composition and poling-induced structural evolution, for the Pr³⁺ doped (1-x)(Na_1/2Bi_1/2)TiO₃-xBaTiO₃ (NBT-xBT: Pr³⁺) piezoelectric ceramics was systematically investigated. Based on the Rietveld refinement structural analysis, there were two distinct composition ranges characterized by different structural features for NBT-xBT: Pr³⁺ ceramics at room temperature: (i) rhombohedral R3c + monoclinic Cc phases for the compositions of x ≤ 0.03, and (ii) tetragonal P4bm + monoclinic Cc phases for 0.04 ≤ x ≤ 0.07. It was interesting to notice that the PL emission intensity is positively correlated with the phase fraction of Cc, which is closely related to the crystal symmetry of NBT-xBT: Pr³⁺ ceramics. The compositions with x ≤ 0.06 underwent an irreversible phase transformation on the application of electric field. The dielectric and Raman measurement revealed a transition from a relaxor state to a normal ferroelectric for the x ≤ 0.06 compositions under an applied poling electric field, with not only the reduction in the in-phase octahedral tilting disorder but also the establishment of long-range ordering. These electric field-induced structural changes were responsible for poling-induced PL quenching behaviors as a result of the increased local structure symmetry around doped Pr³⁺ ions in the poled ceramics.     

Perfectly transparent pore-free Nd3+-doped Sr9GdF21 polycrystalline ceramics elaborated from single-crystal ceramization

An Nd³⁺-doped Sr₉GdF₂₁ (SGF) transparent pore-free polycrystalline ceramic is produced by the ceramization of single crystals. The average transmittance (T_A) of the Nd³⁺-doped SGF ceramic (8-mm thick) is about 90.6% in the visible region and more than 92% in the near-IR region. The fracture toughness of the Nd³⁺-doped SGF ceramic is up to 1.28 MPa m^1/2, which is significantly higher than that of similar types of ceramics. Gd³⁺ ions, acting as both buffer ions and pinning ions, effectively improve the optical and mechanical properties of the SGF ceramic, implying that the sample is a promising candidate for high-power lasers. Moreover, the SGF ceramic shows a high mid- and far-infrared (up to 9 μm) transmittance, low phonon energy, and high density (ρ = 4.8466 g/cm³), which pave the way for a wide range of applications such as infrared windows, mid- and far-infrared lasers, scintillators, and in photonics.     

Fatigue-resistant,temperature-insensitive strain behavior and strong red photoluminescence in Pr-modified 0.92(Bi0.5Na0.5)TiO3–0.08(Ba0.90Ca0.10)(Ti0.92Sn0.08)O3 lead-free ceramics

An electric-field-induced large strain and strong photoluminescence was achieved by introducing trivalent Pr³⁺ as the activator into 0.92(Bi_0.5Na_0.5)TiO₃ − 0.08(Ba_0.90Ca_0.10)(Ti_0.92Sn_0.08)O₃ (BNT−8BCST) ceramics. Around a critical composition of 0.4 mol% Pr³⁺, a large strain of ∼0.39% with a relatively small hysteresis compared with existing lead-free Bi-perovskite ceramics was obtained. In particular, the strain is very resistant to field cycling and thermal shock, giving the materials attractive for its exceptionally good fatigue resistance and high temperature stability. Besides the excellent electrical properties, Pr³⁺-modified BNT−8BCST host exhibits a strong photoluminescence with a bright red emission at 610 nm assigned to ¹D₂ → ³H₄ transitions of the Pr³⁺ ions upon a blue light excitation of 400–500 nm. The photoluminescence can be enhanced through poling treatment of the samples. Moreover, samples have a superior water resistance property which almost maintaining the same photoluminescence intensity after 40 h water immersion time. These results suggest the material may have potential application as a multifunctional device such as “on-off” actuator and electric field-controlled photoluminescence devices by integrating its excellent luminescence and electrical properties.     

Spectroscopic and energy transfer mechanism of Er3+, Pr3+-codoped ZBYA glass

Absorption spectra, emission spectra and the rate parameters of the energy-exchange processes relevant to the ⁴I_11/2→⁴I_13/2 laser transition in Er³⁺/Pr³⁺- codoped ZBYA(ZrF₄–BaF₂–AlF₃–YF₃) glass were presented. Intensive 2.7 μm emission was obtained in the codoped glass and the optimized concentration ratio of Pr³⁺ to Er³⁺ was found to be 0.1:1. With the presence of Pr³⁺ ions, the intensities of the green and near-infrared emission were dramatically reduced to 1/15 and 1/21, respectively. The Er³⁺/Pr³⁺-codoped sample was found to have higher predicted spontaneous transition probability (16.57%) along with larger calculated emission cross section (14.6×10⁻²¹ cm²). These results suggest that the 2.7 μm emission of Er³⁺ ions could be achieved in ZBYA glass and codoping with Pr³⁺ could greatly improve the mid-infrared emission performance.     

Er3+-Yb3+ ions doped fluoro-aluminosilicate glass-ceramics as a temperature-sensing material

The transparent Er³⁺-Yb³⁺-doped fluoro-aluminosilicate glass-ceramic (GC) was prepared by melt-quenching. The crystal phase, morphology, and up-conversion (UC) luminescence of as-produced GC were characterized by X-ray diffraction, scanning electron microscopy, and fluorescence spectrophotometry, respectively. The results show that BaYF₅ nanocrystals were uniformly distributed in the glass matrix of the as-produced GC. When the as-produced GC was subjected to heat treatment, the crystallinity was increased, but the crystal identity remains unchanged. Such heat-treatment doubled the intensity of the UC luminescence, and this enhancement was ascribed to the increased incorporation of both Er³⁺ and Yb³⁺ ions into the lower phonon energy environment of BaYF₅ nanocrystals. Furthermore, the heat-treated GC was stable against further crystallization, and consequently its UC luminescence was stable at the application temperature. The heat-treated GC was found to possess an outstanding temperature-sensing capability.     

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er³⁺, Nd³⁺, Yb³⁺, Sm³⁺, Pr³⁺) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)₃phen–M41 and Pr(tfnb)₃phen–M41; Ln = Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate) were characterized by powder X-ray diffraction, N₂ adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er³⁺, Nd³⁺, Yb³⁺, Sm³⁺, Pr³⁺) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.     

Photoluminescence properties of Pr3+ ion-doped YInGe2O7 phosphor under an ultraviolet irradiation

Pr³⁺ ion-doped YinGe₂O₇ phosphors are synthesized by a vibrating milled solid state reaction. There is a red shift for the excitation peak for the charge transfer transition between In³⁺ and O^2- ion because the numbers of oxygen vacancies change the structure, which leads to a change in the crystal field. The results indicate that the emission spectra for the YinGe₂O₇:Pr samples under an excitation of 263 nm exhibit two dominant peaks at 486 and 604 nm, which are respectively assigned to the ³P₀→³H₄ and ¹D₂→³H₄ transitions. The chromaticity coordinate for (Y_1?xPr_x)InGe₂O₇ phosphors varies with the Pr³⁺ doping concentration, from white, to greenish, to blueish. This has a potential application as a white light emitting phosphor for ultraviolet light-emitting diodes.     

Red-emitting enhancement of Bi4Si3O12:Sm3+ phosphor by Pr3+ co-doping for White LEDs application

In this account, Bi₄Si₃O₁₂:Sm³⁺ and (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) red phosphors were prepared by solution combustion method fueled by citric acid at 900 °C for 1 h. The effects of co-doping Pr³⁺ ions on red emission properties of Bi₄Si₃O₁₂:Sm³⁺ phosphors, as well as the mechanism of interaction between Sm³⁺ and Pr³⁺ ions were investigated by various methods. X-ray diffraction (XRD) and Scanning electron microscopy (SEM) revealed that smaller amounts of doped rare earth ions did not change the crystal structure and particle morphology of the phosphors. The photoluminescence spectroscopy (PL) indicated that shape and position of the emission peaks of (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) phosphors excited at λ_ex=403 nm were similar to those of Bi₄Si₃O₁₂:Sm³⁺ phosphors. The strongest emission peak was recorded at 607 nm, which was attributed to the ⁴G_5/2→⁶H_7/2 transition of the Sm³⁺ ion. The photoluminescence intensities of Bi₄Si₃O₁₂:Sm³⁺ phosphors were significantly improved by co-doping with Pr³⁺ ions and were maximized at Sm³⁺ and Pr³⁺ ions doping concentrations of 4 mol% and 0.1 mol%, respectively. The characteristic peaks of Sm³⁺ ions were displayed in the emission spectra of (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) phosphors excited at respectively λ_ex=443 nm and λ_ex=481 nm (Pr:³H₄→³P₂, ³H₄→³P₀). This indicated the existence of Pr³⁺→Sm³⁺ energy transfer in (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) phosphors.     

Experimental and theoretical studies on NIR luminescence of titanate-germanate glasses doped with Pr3+ and Tm3+ ions

Near-infrared (NIR) luminescence of Pr³⁺ and Tm³⁺ ions in titanate-germanate glasses has been studied for laser and fiber amplifier applications. The effect of the molar ratio GeO₂:TiO₂ (from 5:1 to 1:5) on spectroscopic properties of glass systems was studied by absorption, luminescence measurements, and theoretical calculations using the Judd–Ofelt theory. It was found that independent of the TiO₂ concentration, intense NIR emissions at 1.5 and 1.8 μm were observed for glasses doped with Pr³⁺ and Tm³⁺ ions, respectively. Moreover, several spectroscopic and NIR laser parameters for Pr³⁺ and Tm³⁺ ions, such as emission bandwidth, stimulated emission cross-section, quantum efficiency, gain bandwidth, and figure of merit, were determined. The results were discussed in detail and compared to the different laser glasses. Systematic investigations indicate that Pr³⁺-doped system with GeO₂:TiO₂ = 2:1 and Tm³⁺-doped glass with GeO₂:TiO₂ = 1:2 present profit laser parameters and could be successfully applied to NIR lasers and broadband optical amplifiers.     

A simple non-destructive method to indicate the spallation and damage degree of the double-ceramic-layer thermal barrier coating of La2(Zr0.7Ce0.3)2O7 and 8YSZ:Eu

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and Eu³⁺-doped zirconia, which was partially stabilised by 8 wt% yttria (8YSZ:Eu), were prepared by atmospheric plasma spraying. A thermal cycling test was carried out. The 8YSZ:Eu sublayer exposed during thermal cycling could produce visible luminescence under ultraviolet (UV) illumination, providing an indication of the spallation and damage degree of the coating. The result shows that the application of a Eu³⁺-doped luminescence sublayer can be a very simple and useful non-destructive technique to indicate the spallation and damage degree of DCL coatings.     

Structural,optical, and spectroscopic properties of Er3+-doped TeO2–ZnO–ZnF2 glass-ceramics

Transparent fluorotellurite glass-ceramics have been obtained by heat treatment of precursor Er-doped TeO₂–ZnO–ZnF₂ glasses. ErF₃ nanocrystals nucleated in the glass-ceramics have a typical size of 45 ± 10 nm. Based on the Judd-Ofelt theory, the main radiative parameters for the ⁴I_13/2 → ⁴I_15/2 transition have been obtained. The split of the absorption and emission bands and the reduction of the Ω₂ parameter, as compared to the glass, confirm the presence of Er³⁺ ions in a crystalline environment in glass-ceramic samples. The analysis of the ⁴I_13/2 decays suggests that a fraction of Er³⁺ ions remains in a glass environment while the rest forms nanocrystals. For the glass-ceramics, intense red and green upconversion emissions were observed with an enhancement of the ⁴F_9/2 → ⁴I_15/2 red one compared to the glass sample. The temporal evolution of the red emission together with the excitation upconversion spectra suggests that energy transfer processes are responsible for the enhancement of the red emission.     

Synthesis and luminescence characterization of Pr3+, Gd3+ co-doped SrF2 transparent ceramics

Pr³⁺, Gd³⁺ co-doped SrF₂ transparent ceramic, as the potential material for visible luminescent applications, was prepared by hot-pressing of precursor nanopowders. The microstructure, phase compositions, and in-line transmittance, as well as the photoluminescence properties were investigated systematically. Highly optical quality Pr,Gd:SrF₂ transparent ceramic with nearly pore-free microstructure was obtained at 800°C for 1.5 hours. The average in-line transmittance of the x at.% Pr, 6 at.% Gd:SrF₂ (x = 0.2, 0.5, 1.0, 2.0) transparent ceramics reached to 87.3 % in the infrared region. The photoluminescence spectra presented intense visible light emissions under the excitation of 444 nm, the main intrinsic emission bands located at 483 and 605 nm, which were attributed to the transitions of Pr³⁺: ³P₀ → ³H₄ and ¹D₂ → ³H₄, respectively. With the co-doping of Gd³⁺ ions, the emission intensity of the Pr:SrF₂ transparent ceramic was greatly enhanced. All the emission bands of x at.% Pr, 6 at.% Gd:SrF₂ transparent ceramics exhibited the highest luminescence intensity with the 1.0 at.% Pr³⁺ doping concentrations, whereas the lifetimes decreased dramatically with the Pr³⁺ doping contents increasing from 0.2 to 2.0 at.% due to its intense concentration quenching effect. The 1 at.% Pr, 6 at.% Gd:SrF₂ transparent ceramic is a promising material for visible luminescent device applications.     

Energy transfer,tunable emission and optical thermometry in Tb3+/Eu3+ co-doped transparent NaCaPO4 glass ceramics

Tb³⁺/Eu³⁺ co-doped glass ceramics containing NaCaPO₄ nanocrystals were successfully synthesized via traditional melt-quenching route with further heat-treatment and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectroscopy. The energy transfer process of Tb³⁺→Eu³⁺ was confirmed by excitation and emission spectra and luminescence decay curves, and the energy transfer efficiency was also estimated. The results indicated that the efficient emission of Eu³⁺ was sensitized by Tb³⁺ under the excitation of 378 nm, realizing tunable emission in the transparent bulk glass ceramics containing NaCaPO₄ nanocrystals. Furthermore, optical thermometry was achieved by the fluorescence intensity ratio between Tb³⁺:⁵D₄→⁷F₅ (~542 nm) and Eu³⁺:⁵D₀→⁷F₂ (~612 nm). The maximum absolute sensitivity of 4.55% K⁻¹ at 293 K and the maximal relative sensitivity of 0.66% K⁻¹ at T=573 K for Tb³⁺/Eu³⁺ co-doped transparent NaCaPO₄ glass ceramic are obtained. It is expected that the investigated transparent NaCaPO₄ glass ceramics doped with Tb³⁺/Eu³⁺ have prospective applications in display technology and optical thermometry.