Structural and spectroscopic characteristics of Eu3+-doped tungsten phosphate glasses

Tungsten based phosphate glasses are interesting non-crystalline materials, commonly known for photochromic and electrochromic effects, but also promising hosts for luminescent trivalent rare earth ions. Despite very few reports in the literature, association of the host́s functionalities with the efficient emissions of the dopant ions in the visible and near-infrared spectra could lead to novel applications. This work reports the preparation and characterization of glasses with the new composition 4(Sb₂O₃)96−x(50WO₃ 50NaPO₃)xEu₂O₃ where x = 0, 0.1, 0.25, 0.5 and 1.0 mol%, obtained by the melt quenching technique. The glasses present large density (∼4.6 g cm⁻³), high glass transition temperature (∼480 °C) and high thermal stability against crystallization. Upon excitation at 464 nm, the characteristic emissions of Eu³⁺ ions in the red spectral region are observed with high intensity. The Judd–Ofelt intensity parameters Ω₂ = 6.86 × 10⁻²⁰, Ω₄ = 3.22 × 10⁻²⁰ and Ω₆ = 8.2 × 10⁻²⁰ cm² were calculated from the emission spectra and found to be higher than those reported for other phosphate glass compositions. An average excited state lifetime value of 1.2 ms, was determined by fitting the luminescence decay curves with single exponential functions and it is comparable or higher than those of other oxide glasses.     

Spectroscopic properties of Sm3+-doped oxy-fluoride powders with various Sm3+ concentration and sintering temperature

Sm³⁺-doped oxy-fluoride (OFSm) powders are prepared by the melt quenching technique and characterized using FE-SEM, optical absorption and emission techniques. Spectroscopic properties of Sm³⁺-doped oxy-fluoride powders with different Sm³⁺ concentration and sintering temperature are presented and discussed by using the absorption, emission measurements. The Judd–Ofelt intensity (J–O) parameters (Ω_λ, where λ = 2, 4 and 6), measured from the experimental oscillator strengths of the absorption spectra, are used to evaluate the radiative parameters of the fluorescence transitions. Intense orange emission can be obtained when excited with 325 nm wavelength by increasing the sintering temperature to 1400 °C. Ratio of fluorescence intensities arising from the two closing lying ⁴F_3/2 and ⁴G_5/2 levels is studied, concentration quenching has been noticed beyond 2 mol% of Sm³⁺ ions concentration. The excellent spectroscopic properties along with the outstanding thermal stability suggest that the OFSm03 powders may become an attractive laser material to exhibit efficient visible lasing emission in the orange spectral region.     

Spectroscopic investigations on Eu3+ ions in Li–K–Zn fluorotellurite glasses

Eu³⁺ ions incorporated Li–K–Zn fluorotellurite glasses, (70 − x)TeO₂ + 10Li₂O + 10K₂O + 10ZnF₂ + xEu₂O₃, (0 ⩽ x ⩽ 2 mol%) were prepared via melt quenching technique. Optical absorption from ⁷F₀ and ⁷F₁ levels of the Eu³⁺-doped glass has been studied to examine the covalent bonding characteristics, energy band gap and Judd–Ofelt intensity parameters. The emission spectra (⁵D₀ → ⁷F_0,1,2,3,4) of the glasses were used to estimate the luminescence enhancement, asymmetric environment in the vicinity of Eu³⁺ ions, stimulated emission cross section and branching ratios. The phonon side band mechanism of ⁵D₂ level of the Eu³⁺ ions in the prepared glass was examined by considering the excitation and Raman spectra. The radiative lifetime calculated using Judd–Ofelt parameters was compared with the experimental lifetime to estimate the quantum efficiency of ⁵D₀ level of Eu³⁺ ions in Li–K–Zn fluorotellurite glass.     

Ag nanoparticles enhanced near-IR emission from Er3+ ions doped glasses

Vitreous materials containing rare-earth (RE) ions and metallic nanoparticles (NPs) attract considerable interest because the presence of the NPs may lead to an intensification of luminescence. In this work, the characteristics of 1.54 μm luminescence for the Er³⁺ ions doped bismuthate glasses containing Ag NPs were studied under 980 nm excitation. The surface plasmon resonance (SPR) band of Ag NPs appears from 500 to 1500 nm. Transmission electron microscopic (TEM) image reveals that the Ag NPs are dispersed homogeneously with the size from 2 to 7 nm. The strength parameters Ω_t(t = 2, 4, 6), spontaneous emission probability (A), radiative lifetime (τ) and stimulated emission section (σ_em) of Er³⁺ ions were calculated by the Judd–Ofelt theory. When the glass contains 0.2 wt% AgCl, the 1.54 μm fluorescence intensity of Er³⁺ reaches a maximum value, which is 7.2 times higher than that of glass without Ag NPs. The Ag NPs embedded glasses show significantly fluorescence enhancement of Er³⁺ ions by local field enhancement from SPR.     

Alkaline aluminum phosphate glasses for thermal ion-exchanged optical waveguide

Alkaline aluminum phosphate glasses (NMAP) with excellent chemical durability for thermal ion-exchanged optical waveguide have been designed and investigated. The transition temperature Tg (470 °C) is higher than the ion-exchange temperature (390 °C), which is favorable to sustain the stability of the glass structure for planar waveguide fabrication. The effective diffusion coefficient D_e of K⁺–Na⁺ ion exchange in NMAP glasses is 0.110 μm²/min, indicating that ion exchange can be achieved efficiently in the optical glasses. Single-mode channel waveguide has been fabricated on Er³⁺/Yb³⁺ doped NMAP glass substrate by standard micro-fabrication and K⁺–Na⁺ ion exchange. The mode field diameter is 9.6 μm in the horizontal direction and 6.0 μm in the vertical direction, respectively, indicating an excellent overlap with a standard single-mode fiber. Judd–Ofelt intensity parameter Ω₂ is 5.47 × 10⁻²⁰ cm², implying a strong asymmetrical and covalent environment around Er³⁺ in the optical glasses. The full width at half maximum and maximum stimulated emission cross section of the ⁴I_13/2 → ⁴I_15/2 are 30 nm and 6.80 × 10⁻²¹ cm², respectively, demonstrating that the phosphate glasses are potential glass candidates in developing compact optoelectronic devices. Pr³⁺, Tm³⁺ and Ho³⁺ doped NMAP glasses are promising candidates to fabricate waveguide amplifiers and lasers operating at special telecommunication windows.     

Spectroscopic properties of Tm3+/Al3+ co-doped sol–gel silica glass

Tm³⁺/Al³⁺ co-doped silica glass was prepared by sol–gel method combined with high temperature sintering. Glasses with compositions of xTm₂O₃–15xAl₂O₃–(100 − 16x) SiO₂ (in mol%, x = 0.1, 0.3, 0.5, 0.8 and 1.0) were prepared. The high thulium doped silica glass was realized. Their spectroscopic parameters were calculated and analyzed by Judd–Ofelt theory. Large absorption cross section (4.65 × 10⁻²¹ cm² at 1668 nm) and stimulated emission cross section (6.00 × 10⁻²¹ cm² at 1812 nm), as well as low hydroxyl content (0.180 cm⁻¹), long fluorescence lifetime (834 μs at 1800 nm), large σ_em × τ_rad (30.05 × 10⁻²¹ cm² ms) and large relative intensity ratio of the 1.8 μm (³F₄ → ³H₆) to 1.46 (³H₄ → ³F₄) emissions (90.33) are achieved in this Tm³⁺/Al³⁺ co-doped silica glasses. According to emission characteristics, the optimum thulium doping concentration is around 0.8 mol%. The cross relaxation (CR) between ground and excited states of Tm³⁺ ions was used to explain the optimum thulium doping concentration. These results suggest that the sol–gel method is an effective way to prepare Tm³⁺ doped silica glass with high Tm³⁺ doping and prospective spectroscopic properties.     

Polarized spectral properties of Sm3+:LiLuF4 crystal for visible laser application

A Sm³⁺-doped LiLuF₄ single crystal was grown by the vertical Bridgman–Stockbarge technique. Polarized absorption spectra, polarized fluorescence spectra, and fluorescence lifetime of the Sm³⁺:LiLuF₄ crystal were recorded at room temperature. Based on the Judd–Ofelt theory, spectral parameters of the Sm³⁺:LiLuF₄ crystal were calculated. Emission cross sections for the ⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) transitions with special interest for visible laser application were obtained by the Füchtbauer–Ladenburg formula. The results indicate that the Sm³⁺:LiLuF₄ crystal may be a potential laser gain medium operating in visible region pumped by diode lasers around 401 nm.     

Spectroscopic analysis of a novel Nd3+-activated barium borate glass for broadband laser amplification

Spectroscopic parameters of a novel Nd³⁺-activated barium borate (BBONd) glass have been analyzed for broadband laser amplification. The Judd–Ofelt (JO) intensity parameters were determined through a systematic analysis of the absorption spectrum of Nd³⁺ ions in the BBONd glass. High values of the JO intensity parameters reveal a great centro-symmetrical loss of the Nd³⁺ sites and high covalency degree of the ligand field. The very high Ω₆ intensity parameter value makes evident both a great structural distortion of the Nd³⁺ sites and a strong electron–phonon coupling between Nd³⁺ and free OH⁻ ions, which is consistent with the phonon energy maximum (3442.1 cm⁻¹) recorded by Raman spectroscopy. This strong electron–phonon coupling favors high effective bandwidth and gain bandwidth values of the laser emission (⁴F_3/2 → ⁴I_11/2) of Nd³⁺ ions. The electric-dipole oscillator strengths of all the Nd³⁺ absorption transitions, and in particular that of the hypersensitive transition (⁴I_9/2 → ⁴G_5/2), are enhanced by this great structural distortion of the host. Broadband laser amplification of the ⁴F_3/2 → ⁴I_11/2 emission (1062 nm) of Nd³⁺ ions in the BBONd glass pumped at 805 nm (⁴I_9/2 → ⁴F_5/2 + ²H_9/2) is evaluated through the main fluorescent parameters in competition with non-radiative processes. In general, the BBONd glass exhibits spectroscopic parameters comparable with those reported in the literature for broadband laser amplification into the IR region.     

Optical properties of Nd3+ and Er3+ ions in TeO2–WO3–PbO–La2O3 glasses

Multicomponent telluride-tungstate glasses containing Nd³⁺ and Er³⁺ ions were studied experimentally at 77 and 293 K using spectroscopic methods. The Judd–Ofelt intensity parameters were derived from the absorption spectra and used to calculate the radiative lifetimes and branching ratios. The quantum efficiency η = 0.95 of the ⁴F_3/2 level of Nd³⁺ ion is higher than the typical value of other tellurite-based glasses. For low concentration of Er³⁺ ions, the luminescence decay of the ⁴S_3/2 and ⁴I_11/2 levels is governed by radiative transitions and multiphonon relaxation involving the Te-O highest energy vibrations.     

Synthesis,crystal structure refinement,electrical and magnetic properties of BaV13O18 and SrV13O18

Polycrystalline samples of BaV₁₃O₁₈ and SrV₁₃O₁₈ were prepared by solid-state reaction of BaCO₃, SrCO₃, V₂O₅ and V at 1773–2073 K in flowing Ar. The crystal structures of BaV₁₃O₁₈ (R-3, a_h=12.6293(10) Å, c_h=7.0121(4) Å) and SrV₁₃O₁₈ (a_h=12.5491(7) Å, c_h=6.9878(3) Å) were refined by the Rietveld method using X-ray diffraction data. BaV₁₃O₁₈ exhibited semiconducting behavior with electrical resistivity from 5.8×10⁻³ to 2.7×10⁻³ Ω cm at 100–300 K. Electrical resistivity of SrV₁₃O₁₈ ranged from 1.5×10⁻³ to 1.8×10⁻³ Ω cm, and it increased slightly up to around 250 K and decreased above 250 K with increasing temperature. Negative Seebeck coefficients of both compounds at 100–300 K indicated that electron was the dominant carrier. BaV₁₃O₁₈ and SrV₁₃O₁₈ showed paramagnetism with the effective magnetic moment of 0.11μ_B and 0.15μ_B, respectively, at 10–100 K.     

Oxyfluorotellurite glasses doped by dysprosium ions. Thermal and optical properties

The paper shows results of investigation of thermal and optical properties of oxyfluorotellurite (65 − x)TeO₂–20ZnF₂–12Pb₂O₅–3Nb₂O₅–xDy₂O₃ (x = 0.5, 2 and 5) glass systems. Thermal stability and the onset of crystallization of the materials were monitored by differential thermal analysis (DTA). It was found that characteristic parameters, namely glass transition temperatures (T_g), onset of crystallization temperatures (T_c) and thermal stability criteria ΔT and H’ increased with increasing Dy₂O₃ content indicating that the incorporation of dysprosium ions improves substantially thermal stability of glass system under study.Optical absorption and emission spectra of Dy³⁺ ions in oxyfluorotellurite glass were investigated at room temperature in the visible (VIS) and near-infrared (NIR) region. Oscillator strengths, phenomenological Judd–Ofelt (JO) intensity parameters Ω_2,4,6, radiative transition probabilities, branching ratios and radiative lifetimes of luminescent levels were determined. Decay curves of the ⁴F_9/2 luminescence of incorporated Dy³⁺ ions were recorded and analysed. Lifetimes and the luminescence dynamics were studied as a function of the Dy₂O₃ concentration. It was concluded that good thermal stability combined with desirable spectroscopic parameters of investigated dysprosium-doped oxyfluorotellurite glass point at the suitability of this material for the design of UV-excited visible phosphors.     

Influence of W5+ ions on the optical properties of doped Bi12TiO20

There have been studied single crystals of undoped and doped Bi₁₂TiO₂₀ with two concentrations of W⁵⁺ (2.62 × 10¹⁷ cm⁻³ and 2.62 × 10¹⁸ cm⁻³). There have been obtained absorption spectra in the energy range of 10,482–15,408 cm⁻¹ by classical measurements. There have been determined the cross-section (σ_a) of the impurity absorption and the oscillator strength of d–d transitions. There have been calculated the refractive index of doped crystals and the concentration of Ti³⁺ ions in an undoped sample through an experiment.     

Synthesis and dc conductivity of Nd2/3TiO2.988

The A-site deficient perovskite Nd_2/3TiO_3 − δ was synthesized under an H₂–CO₂ gas mixture. The sample was found to have slight oxygen deficiency of δ∼0.012. The crystal structure was assigned to a double perovskite structure with orthorhombic space group Pmmm, as in the case of La_2/3TiO_3 − δ. Electrical conductivity measurement has also been performed. The temperature dependence of conductivity shows that electronic transport in Nd_2/3TiO_2.988 is well described by Emin–Holstein adiabatic small polaron model. The polaron density extracted from the conductivity measurement is ∼1.96 × 10²⁰ cm^− 3. This result agrees well with nominal polaron density for Nd_2/3TiO_2.988, ∼2.1 × 10²⁰cm^− 3. We have also derived important quantities for transport in Nd_2/3TiO_2.988.     

Spectroscopic properties of B2O3–PbO–Bi2O3–GeO2 glass doped with Sm3+ and gold nanoparticles

Heavy metal oxide B₂O₃–PbO–Bi₂O₃–GeO₂ transparent glass doped with Sm³⁺ was synthesized and implanted with Au⁺ using energy of 300 keV and fluence of 1 × 10¹⁶ cm⁻². The annealing of the implanted glass at moderate temperature below the glass transition temperature induced the nucleation of gold nanoparticles, confirmed by the characteristic absorption band in the visible range and by transmission electron microscopy. Using Miés and Doylés theories for the surface plasmon resonance, the average size of the gold nanoparticles was about 4.6 nm, similar to the values observed by transmission electron microscopy. It was also observed the crystallization of a thin layer of the glass at the implanted surface after annealing, detected by X-ray diffraction and scanning electron microscope. Visible and near-infrared emission of Sm³⁺ was enhanced after annealing of the glass implanted with gold. Judd–Ofelt parameters and radiative parameters were calculated for the glass doped with Sm³⁺ with and without gold nanoparticles.     

Investigation of traps in AlGaN/GaN HEMTs by current transient spectroscopy

Deep levels in AlGaN/GaN HEMTs on Si substrate are known to be responsible for trapping processes like: threshold voltage shift, leakage current, degradation in saturation current and hysteresis effect. The related deep levels are directly characterized by Conductance Deep Level Transient Spectroscopy (CDLTS) method. Hereby we have detected four carrier traps with activation energy of 0.83, 0.50, 0.20 and 0.07 eV and capture cross-section respectively of σ = 3.14 × 10^− 14 cm², σ = 2.57 × 10^− 15 cm², σ = 3.03 × 10^− 17 cm² and σ = 2.65 × 10^− 15 cm². All these traps are located between the substrate and the two-dimensional electron gas (2DEG) channel.     

Erbium doped tellurite glasses with improved thermal properties as promising candidates for laser action and amplification

The influence of composition on the thermal stability of tellurite glasses was investigated by using differential scanning calorimetry (DSC). The studied glasses were synthesized by conventional melting quenching method. The best thermal stability and poor crystallization tendency were obtained for the glass composed of 65TeO₂–15ZnO–10Na₂O–5BaO–3La₂O₃ doped with Er₂O₃ (2 mol %). This glass will be referred, in this article, as TZNBL: Er³⁺ glass.The spectroscopic properties of the above glass are investigated based on the Judd–Ofelt and McCumber theories.The calculated intensity parameters (Ω_2,4,6) are compared to those obtained for Er³⁺ in other glasses. The radiative emission rate has been calculated for the different Er³⁺emitting levels. The high values of Ω₄ and Ω₆ confirm the results of the DSC experiment concerning the rigidity of the studied glass.Absorption, emission and gain cross section of the ⁴I_13/2 ↔ ⁴I_15/2 (Er³⁺) transition in the studied glass are reported and the results are compared to those of other glasses.The ⁴I_13/2 ↔ ⁴I_15/2 (Er³⁺) absorption and emission cross sections derived by the application of the Mc Cumber’s theory corroborate the Judd–Ofelt results.The whole of results demonstrate that the new composition leads to good thermal and mechanical properties as well efficient Er³⁺ absorption, emission cross sections, which make this glass as a promising candidate for laser action and amplification.     

Coupled substitutions in In2O3: New transparent conductors In2−xM2x/3Sbx/3O3 (M = Cu,Zn)

Two solid solutions In_2−xM_2x/3Sb_x/3O₃ (M = Cu, Zn) with the bixbyite structure have been synthesized in air at 1300 °C. The homogeneity range is larger for Zn (x = 0.42) than for Cu (x = 0.20) and the cationic distribution of the Cu/Sb and Zn/Sb couples is weakly ordered. These new oxides appear to be transparent conductors. Even fully deprived of tin, they have good potential properties. These oxides are either semiconductors with a small band gap (Cu/Sb) or semimetals (Zn/Sb) with σ = 3 × 10² (Ω cm)⁻¹ at room temperature. These materials are more efficient than bulk ITO prepared under the same experimental conditions, i.e. without reducing treatment (σ = 50 (Ω cm)⁻¹).     

Structure and magnetism in Pr3RuO7

The crystal structure of the ordered fluorite, Pr₃RuO₇, was refined from powder neutron diffraction data in Cmcm. An interesting structural feature is the presence of relatively well separated zig-zag chains of corner sharing RuO₆ octahedra, Ru–Ru interchain distance 6.61 Å vs. Ru–Ru intrachain distance of 3.76 Å. Magnetic susceptibility data show a Curie–Weiss behavior for T>225 K with C=5.96(4) emu K mol⁻¹ and θ_c=+11(2) K. In an attempt to separate the contributions of Pr(3+) and Ru(5+), the properties of isostructural Pr₃TaO₇ were also measured, yielding C=4.63(3) emu K mol⁻¹. Thus, the contribution of Ru(5+), 4d³, S=3/2, to the measured Curie constant is estimated to be 1.33 emu K mol⁻¹, not far from the spin-only value of 1.87 emu K mol⁻¹. This supports the view that the Ru 4d electrons are localized and magnetic, not itinerant. A susceptibility maximum at about 50 K is attributed to long-range magnetic order and this is substantiated by neutron diffraction data. There is little evidence for one-dimensional antiferromagnetic correlations in this material but behavior characteristic of short-range ferromagnetic correlations attributed to Pr–Ru exchange interactions are found in the temperature range 50–200 K, consistent with the positive θ_c.     

The rock salt oxide Li2MgTiO4: Type I dielectric and ionic conductor

The exploration of the Li–Ti–Mg–O system, using both sol–gel technique and solid state reaction method, allowed a new phase, Li₂MgTiO₄, with disordered rock salt structure (a = 4.159 Å) to be synthesized. The latter is shown to be a good type I dielectric material, with a relative constant of 15 at high frequency and low dielectric loss (tanδ < 10⁻³) over the temperature range −60 to 160 °C. It is also observed that the sintering temperature of this phase is strongly lowered by adopting the sol–gel technique compared to solid state reaction (1150 °C instead of 1300 °C). Finally we show that this phase exhibits cationic conductivity above 400 °C (σ_600 °C = 9 × 10⁻⁵ S cm⁻¹).     

Negative thermal expansion in silicalite-1 and zirconium silicalite-1 having MFI structure

In situ high temperature X-ray diffraction (HTXRD) studies on monoclinic silicalite-1 (S-1, silica polymorph of ZSM-5) and an orthorhombic metallosilicate molecular sieve, zirconium silicalite-1 (ZrS-1) with MFI structure (Si/Zr = 50) have been carried out using a laboratory X-ray diffractometer with an Anton Parr HTK 1600 attachment. While the structure of the S-1 collapsed at 1123 K forming α-cristobalite. S-1 and ZrS-1 showed a complex thermal expansion behavior in the temperature range 298–1023 K, ZrS-1 was stable. Powder X-ray diffraction (PXRD) data taken in this region have shown strong negative lattice thermal expansion coefficient, α_V = −6.75 × 10⁻⁶ and −17.92 × 10⁻⁶ K⁻¹ in the temperature range 298–1023 K⁻¹ for S-1 and ZrS-1 samples, respectively. The thermal expansion behavior of S-1 and ZrS-1 is anisotropic, with the relative strength of contraction along a axis is more than that along b and c axes. Three different thermal expansion regions could be identified in the overall temperature range (298–1023 K) studied, corroborating with the three steps of weight loss in the TG curve of ZrS-1 sample. While the region between 298 and 423 K, displays positive thermal expansion coefficient with α_V = 2.647 × 10⁻⁶ and 4.24 × 10⁻⁶ K⁻¹, the second region between 423 and 873 K shows strong negative thermal expansion (NTE) coefficient α_V = −7.602 × 10⁻⁶ and −15.04 × 10⁻⁶ K⁻¹, respectively, for S-1 and ZrS-1 samples. The region between 873 and 1023 K, shows a very strong NTE coefficient with α_V = −12.08 × 10⁻⁶ and −45.622 × 10⁻⁶ K⁻¹ for S-1 and ZrS-1, respectively, which is the highest in the whole temperature range studied. NTE seen over a temperature range 298–1023 K could be associated with transverse vibrations of bridging oxygen atoms in the structure which results in an apparent shortening of the Si–O distances.