Linear and non-linear optics and FTIR characteristics of borosilicate glasses doped with gadolinium ions

Borosilicate glasses have been prepared using the high-temperature melt components of ingredients Gd₂O₃ doped borosilicate glasses. FTIR spectra were measured in the wavenumber range (4000–400 cm⁻¹) to explore the state and influence of Gd³⁺ ions in the structure of the glasses. Data indicated that B₂O₃ is acting as dual network formers (BO₃) and (BO₄) structural units whereas the gadolinium ions playing the role of network modifier in these glasses. Optical transmission spectra were recorded in the range 190–2500 nm and different optical parameters such as the direct and the indirect optical band gap, Urbach energy, refractive index and optical dielectric constant, have been determined. The molar refraction, electronic polarizability and the optical basicity results have been determined using the measured glass refractive indices. Gadolinium-doped borosilicate glasses are found to be characterized by different optical parameters.     

Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass–ceramics

This paper reports the fabrication and characterization of Eu³⁺/Nd³⁺ co-doped phosphate (PNE) glasses and glass–ceramics as a function of Eu³⁺ concentration. The precursor glasses were prepared by the conventional melt quenching technique and the opaque glass–ceramics were obtained by heating the precursor glasses at 450 °C for 30 h. The structural and optical properties of the glass and glass–ceramics were analyzed by means of X-ray diffraction, Raman spectroscopy, UV–VIS–IR absorption spectroscopy, photoluminescence spectra and lifetimes. The amorphous and crystalline structures of the precursor glass and opaque glass–ceramic were confirmed by X-ray diffraction respectively. The Raman spectra showed that the maximum phonon energy decreased from 1317 cm⁻¹ to 1277 cm⁻¹ with the thermal treatment. The luminescence spectra of the glass and glass–ceramic samples were studied under 396 nm and 806 nm excitation. The emission intensity of the bands observed in opaque glass–ceramic is stronger than that of the precursor glass. The luminescence spectra show strong dependence on the Eu³⁺ ion concentration in the Nd³⁺ ion photoluminescence (PL) intensity, which suggest the presence of energy transfer (ET) and cross-relaxation (CR) processes. The lifetimes of the ⁴F_3/2 state of Nd³⁺ ion in Eu³⁺/Nd³⁺ co-doped phosphate glasses and glass–ceramics under 806 nm excitation were measured. It was observed that the lifetimes of the ⁴F_3/2 level of Nd³⁺ of both glasses and glass–ceramics decrease with the increasing Eu³⁺ concentration. However in the case of opaque glass–ceramics the lifetimes decrease only 16%.     

Thermal stability and annealing behavior of photoluminescence from Eu doped YAG

Eu₂O₃ doped Y₃Al₅O₁₂ (YAG) crystals have been grown using a floating zone technique and evaluated thermal stability and annealing behavior of PL for a fluorescence thermo-sensor application. Color of the crystals grown varies from deep purple to colorless with O₂ concentration of the growth atmosphere and annealing in air. Photoluminescence (PL) peaking at λ = 590, 607, 624, 647 and 709 nm due to Eu³⁺ ions are observed from the crystals under UV excitation. Anomalous temperature dependence of PL intensity, which is observed in as-grown crystals, is improved greatly by annealing through the heat cycle. From annealing behavior of optical absorption spectra, residual Eu²⁺ ions are suggested to be responsible for the de-coloration and the improvement of anomalous temperature dependence of Eu doped YAG crystals.     

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.     

Luminescence and energy transfer in Er3+/Nd3+ ion-codoped Ge–In–S–CsBr chalcohalide glasses

This study investigates the emission properties of the Er³⁺/Nd³⁺ ions codoped 70GeS₂–10In₂S₃–20CsBr chalcohalide glasses. The vacuumed melt-quenching technique is employed to synthesize the glasses. The absorption spectra, upconversion and near-IR emission spectra as well as fluorescence decay curves are collected. With the increasing concentration of Er³⁺ ions, the lifetimes at 1073 nm for Nd³⁺ ions decrease from 538 to 420 μs under 808 nm excitation. Meanwhile, the lifetimes at 1540 nm for Er³⁺ ions decrease from 245 to 214 μs with the increasing concentration of Nd³⁺ ions. The emission spectra and lifetimes show that energy transfer exists between the Nd³⁺ and Er³⁺ ions. The luminescence and detailed energy transfer mechanisms are schematically proposed.     

Physical and optical properties of Co2+, Ni2+ doped 20ZnO + xLi2O + (30 − x)K2O + 50B2O3 (5 ≤ x ≤ 25) glasses: Observation of mixed alkali effect

Co²⁺ and Ni²⁺ ions doped 20ZnO + xLi₂O + (30 ? x) K₂O + 50B₂O₃ (5 ≤ x ≤ 25) mol% glasses are prepared using melt quenching technique. Structural changes of the prepared glasses by addition of transition metal oxides, CoO and NiO are investigated by UV–vis–NIR, FT-IR spectroscopy and XRD. The XRD pattern indicates the amorphous nature of prepared glasses. FT-IR measurements of the all glasses revealed that the network structure of the glasses are mainly based on BO₃ and BO₄ units placed in different structural groups in which the BO₃ units being dominant. The optical absorption spectra suggest the site symmetry of Co²⁺ and Ni²⁺ ions in the glasses are near octahedral. Crystal field and inter-electronic repulsion parameters are also evaluated. The optical band gap and Urbach energies exhibited the mixed alkali effect. Various physical parameters such as density, refractive index, optical dielectric constant, polaron radius, electronic polarizability and inter-ionic distance are also determined.     

CaAlSiN3:Eu2+ phosphors bonding with bismuth borate glass for high power light excitation

The CaAlSiN₃:Eu²⁺ red phosphor-in-glass was prepared using bismuth borate glass as the binder for high power light excitation. B₂O₃–Bi₂O₃–Al₂O₃–ZnO glass powder showed good sintering behavior with CaAlSiN₃:Eu²⁺ phosphors at around 550 °C. The phosphor-in-glass has flat surface with a thickness of about 100 μm. From the images of FE-SEM and confocal laser scanning microscope, the uniform distribution of phosphor particles inside the phosphor-in-glass was vividly and clearly observed. And the luminescent property of phosphors was not greatly affected by glasses, as shown in fluorescence spectra. When the volume radio of CaAlSiN₃:Eu²⁺ phosphors was 50%, the sample exhibited low thermal quenching and high flexural strength of 28.5 MPa. Compared YAG:Ce³⁺ phosphor-in-glass with CaAlSiN₃:Eu²⁺ phosphor-in-glass, we found bismuth borate glass had better wettability on YAG:Ce³⁺ particles, which caused a higher flexural strength of the YAG:Ce³⁺ phosphor-in-glass.     

Synthesis and spectroscopic characterization of the K4BaSi3O9:Eu3+

K₄BaSi₃O₉:Eu³⁺ polycrystals were synthesized by solid state method. X-ray powder diffraction measurements confirmed structure of the samples. The excitation and the emission spectra of orthorhombic K₄BaSi₃O₉ doped with Eu³⁺ were investigated. The excitation spectrum exhibits a broad band with maximum at 220 nm corresponding to the charge transfer (CT) transition between O²⁻ and Eu³⁺ ions and smaller 4f–4f transitions. The emission of investigated phosphor was excited at 395 nm and has quantum efficiency (QE) equal 27%. The emission maximum at 616.5 nm was assigned to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The luminescence decay profiles as well as the thermal quenching were measured and analyzed. K₄BaSi₃O₉:Eu³⁺has high temperature quenching of the emission T_0.5 = 335 °C.     

Synthesis,characterization and luminescence of Sr3Al2O6 phosphor with trivalent rare earth dopant

The luminescent properties of Sr₃Al₂O₆ doped and co-doped with the rare earths (Ln³⁺ = Eu³⁺, Dy³⁺, Eu³⁺ and Dy³⁺) have been studied. The material was synthesized by reflux method and fired up to 900 °C for 16 h. The X-ray diffraction pattern confirms that the synthesized material consists of Sr₃Al₂O₆ as main phase. The photoluminescence study gives a clear evidence of europium stabilizing in trivalent form and surprisingly with no presence of europium in the divalent state. The addition of Dy³⁺ as co-dopant in the Sr₃Al₂O₆:Eu³⁺ matrix shows the quenching effect in the photoluminescence (PL) spectra. The photoluminescence intensity of Eu³⁺ falls gradually on increasing the concentration of the co-dopant in the range from 0.1 mole% to 2.0 mole%. The significantly intense thermoluminescence (TL) glow peak was obtained for Sr₃Al₂O₆:Eu³⁺, Dy³⁺ (1% and 0.1%) at around 194 °C when irradiated with 10 kGy dose from Sr-90 β source.     

The effect of Eu3+ concentration on the Y2O3 host lattice obtained from citrate precursors

This work presents a thermal decomposition study of the precursor resin prepared from the citrate precursor along with structural features and optical properties materials composed by Y₂O₃ and Eu³⁺ containing Y₂O₃ in 0.5, 3, 5 and 7 mol%. The microcrystallite sizes were estimated from the Scherrer equation. The structural and optical properties revealed that the addition of 5 mol% of Eu³⁺ to the Y₂O₃ matrix gave rise to the highest relative emission intensity which was evidenced by the luminescence intensity. The lifetime of the 0.5 mol% Eu³⁺-doped sample suggested two different symmetry sites for Eu³⁺ ions because two different lifetime values were acquired for this sample, while for phosphors doped with 3 or 5 mol% of Eu³⁺ ions only one similar lifetime was observed. When the concentration of Eu³⁺ is 0.5 and 3 mol%, the luminescence intensity is weak due to the low probability of the O^2? - Eu³⁺ charge transfer transition. On the other hand, when the concentration of the Eu³⁺ ions is 7 mol%, a quenching effect is evidenced.     

Synthesis and photoluminescence study of La1.8Eu0.2O3 coating on nanometric α-Al2O3

In this work the La_1.8Eu_0.2O₃ coating on nanometric alpha-alumina, α-Al₂O₃@La_1.8Eu_0.2O₃, was prepared for the first time by a soft chemical method. The powder was heat-treated at 100, 400, 800 and 1200 °C for 2 h. X-ray powder diffraction patterns (XRD), transmission electronic microscopy (TEM), emission and excitation spectra, as well as Eu³⁺ lifetime were used to characterize the material and to follow the changes in structure as the heating temperature increases. The Eu³⁺ luminescence data revealed the characteristic transitions ⁵D₀ → ⁷F_J (J = 0, 1 and 3) of Eu³⁺ at around 580, 591 and 613 nm, respectively, when the powders were excited by 393 nm. The red color of the samples changed to yellow when the powder was annealed at 1200 °C. The decrease in the (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) ratio from around 5.0 for samples heated at lower temperatures to 3.1 for samples annealed at 1200 °C is consistent with a higher symmetry of the Eu³⁺ at higher temperature. The excitation spectra of the samples also confirms this change by the presence of a more intense and broad band at around 317 nm, instead of the presence of the characteristic peak at 393 nm, which corresponds to the ⁷F₀ → ⁵L₆ transition of the Eu³⁺. The lifetimes of the ⁵D₀ → ⁷F₂ transition of Eu³⁺ for the samples heat-treated at 100, 400, 800 and 1200 °C was evaluated as 0.57, 0.72, 0.43 and 0.31 ms, respectively.     

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.     

Luminescence concentration quenching and site-occupancy of Eu2+ ions in Na2Ca2Si3O9 phosphors derived from 45S5 glass-ceramics

The phosphors of Na₂Ca_2-2xEu_2xSi₃O₉ (x = 0, 0.03, 0.05, 0.07, 0.09) were first synthesized by sol-gel method. The crystal phase formations of the phosphors were detected by X-ray powder diffraction (XRD) measurements and the structure refinement. The photoluminescence spectra, the concentration quenching, the luminescence decay curves and the luminescence color chromaticity were measured, respectively. The excitation spectra indicate that the phosphors can be effectively excited by near UV-LED chips. Two kinds of Eu²⁺ sites centered at 545 nm and 505 nm were discussed by analyzing the spectra, concentration-dependent luminescence intensity and lifetimes. This is a potential tool for monitoring the bioactivity of 45S5 glass-ceramics in situ.     

The 1.53 μm spectroscopic properties of Er3+/Ce3+/Yb3+ tri-doped tellurite glasses containing silver nanoparticles

The metallic silver nanoparticles (NPs) was introduced into the Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glasses with composition TeO₂–ZnO–La₂O₃ to improve the 1.53 μm band fluorescence. The UV/Vis/NIR absorption spectra, 1.53 μm band fluorescence spectra, fluorescence lifetimes, X-ray diffraction (XRD) curves, differential scanning calorimeter (DSC) curves and transmission electron microscopy (TEM) image of tri-doped tellurite glasses were measured, together with the Judd–Ofelt intensity parameters, emission cross-sections, absorption cross-sections and radiative quantum efficiencies were calculated to investigate the effects of silver NPs on the 1.53 μm band spectroscopic properties of Er³⁺ ions, structural nature and thermal stability of glass hosts. It is shown that Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glasses can emit intense 1.53 μm band fluorescence through the combined energy transfer (ET) processes from Yb³⁺ to Er³⁺ ions and Er³⁺ to Ce³⁺ ions under the 980 nm excitation. At the same time, the introduction of an appropriate amount of silver NPs can further improve the 1.53 μm band fluorescence owing to the enhanced local electric field effect induced by localized surface Plasmon resonance (LSPR) of silver NPs and the possible energy transfer from silver NPs to Er³⁺ ions, and an improvement by about 120% of fluorescence intensity is found in the studied Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glass containing 0.5 mol% amount of silver NPs with average diameter of ∼15 nm. The energy transfer mechanisms from Yb³⁺ to Er³⁺ ions and Er³⁺ to Ce³⁺ ions were also quantitatively investigated by calculating energy transfer microparameters and phonon contribution ratios. Furthermore, the thermal stability of glass host increases slightly with the introduction of silver NPs while the glass structure maintains the amorphous nature. The results indicate that the prepared Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glass with an appropriate amount of silver NPs is an excellent gain medium applied for 1.53 μm band EDFA pumped with a 980 nm laser diode (LD).     

New phospho-tellurite glasses with optimization of transition temperature and refractive index for hybrid microstructured optical fibers

The glass formation and compositional dependences of glass thermal properties and optical properties were investigated in TeO₂–ZnO–Na₂O–P₂O₅ system. The refractive index at 1.55 μm and glass transition temperature varied in a wide range from 1.513 to 2.036 and from 265 °C to 376 °C by controlling of the TeO₂/P₂O₅ and ZnO/Na₂O content, respectively. These properties enable phospho-tellurite glasses with large freedom in designing and fabrication of hybrid microstructured optical fiber. The structures of glasses were investigated by Raman spectra to understand their dependence of structure on composition. Using the present glasses, some hybrid microstructured optical fibers with various dispersion profiles were designed.     

A facile preparation and the luminescent properties of Eu3+-doped Y2O2SO4 nanopieces

The europium(III)-doped yttrium oxysulfate (Y₂O₂SO₄:Eu³⁺) nanopieces have been prepared via electrospinning followed by calcination at 1000 °C in mixed gas of sulfur dioxide and air. Based on the experimental results, a possible formation mechanism for the nanopieces is that the nanopieces are determined by the directing template of electrospun nanoribbons and the multilayer crystal structure of Y₂O₂SO₄. Besides, the nanopieces show excellent luminescent properties with emissions at 581, 589, 597, 653, 619, and 697 nm resulting from the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transition of Eu³⁺. The peaks of charge transfer and ⁵D₀ → ⁷F₂ transition of Eu³⁺ obviously have red shifts comparing to those of both Y₂O₃:Eu³⁺ nanoribbons and commercial Y₂O₃:Eu³⁺. Moreover, the nanopieces exhibit stronger intensities than the Y₂O₃:Eu³⁺ in excitation and emission spectra. Concentration quenching in the nanopieces occurs when Eu³⁺ concentration is 11 mol%, indicating that the nanopieces have an optimum luminescent intensity under this doping concentration.     

Luminescence properties of nanocrystalline YVO4:Eu3+ under UV and VUV excitation

Single phase of Eu³⁺-doped YVO₄ nanophosphors at different pH values were synthesized by a mild hydrothermal method. Their photoluminescence were evaluated under UV and VUV region, respectively. Monitoring by 619 nm emission, broad bands at around 143 nm, 200 nm, 260 nm were observed in the excitation spectrum of YVO₄:5 mol%Eu³⁺. These peaks could be assigned to host absorption, the overlap of the VO₄³⁻ host absorption and charge transfer transition between Eu³⁺ and O²⁻, respectively. Both 254 nm and 147 nm excitations, the emission spectra were identical, they were all composed of Eu³⁺ emission transitions arising mainly from the ⁵D₀ level to the ⁷F_J (J = 1, 2, 3, 4) manifolds. With the pH values ranging from 7 to 11, the relative intensity of the emission spectra were decreasing, and the position of the predominant peak (⁵D₀ → ⁷F₂) was changed from 619 nm to 615 nm when the pH values changed from 7 to 11.     

Formation and spectral probing of transparent oxyfluoride glass-ceramics containing (Eu2+, Eu3+:BaGdF5) nano-crystals

In the present study, we report the formation of transparent glass-ceramics containing BaGdF₅ nanocrystals under optimum ceramization of SiO₂–BaF₂–K₂O–Sb₂O₃–GdF₃–Eu₂O₃ based oxyfluoride glass and the energy transfer mechanisms in Eu²⁺ → Eu³⁺ and Gd³⁺ → Eu³⁺ has been interpreted through luminescence study. The modification of local environment surrounding dopant ion in glass and glass ceramics has been studied using Eu³⁺ ion as spectral probe. The optimum ceramization temperature was determined from the differential scanning calorimetry (DSC) thermogram which revealed that the glass transition temperature (T_g), the crystallization onset temperature (T_x), and crystallization peak temperature (T_p) are 563 °C, 607 °C and 641 °C, respectively. X-ray diffraction pattern of the glass-ceramics sample displayed the presence of cubic BaGdF₅ phase (JCPDS code: 24-0098). Transmission electron microscopy image of the glass-ceramics samples revealed homogeneous distribution of spherical fluoride nanocrystals ranging 5–15 nm in size. The emission transitions from the higher excited sates (⁵D_J, J = 1, 2, and 3) as well as lowered asymmetry ratio of the ⁵D₀ → ⁷F₂ transition (forced electric dipole transition) to that of the ⁵D₀ → ⁷F₁ transition (magnetic dipole) of Eu³⁺ in the glass-ceramics when compared to glass sample demonstrated the incorporation of dopant Eu³⁺ ions into the cubic BaGdF₅ nanocrystals with higher local symmetry with enhanced ionic nature. The presence of absorption bands of Eu²⁺ ions and Gd³⁺ ions present in the glass matrix or fluoride nanocrystals in the excitation spectra of Eu³⁺ by monitoring emission at 614 nm indicated energy transfer from (Eu²⁺ → Eu³⁺) and (Gd³⁺ → Eu³⁺) in both glass and glass-ceramics samples.     

A novel blue-emitting Ca2B5O9Br:Eu2+ phosphor prepared by a microwave calcination route

A blue-emitting Ca₂B₅O₉Br:Eu²⁺ phosphor for white light-emitting diodes was synthesized via a microwave calcination route. The phosphor powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectrophotometer, respectively. The obtained results revealed that the Ca₂B₅O₉Br:Eu²⁺ phosphor prepared by the microwave calcination route possessed a rod-like morphology with the single phase orthorhombic structure. Based on the photoluminescence analysis, it was found that Ca₂B₅O₉Br:Eu²⁺ phosphor exhibited a broad excitation band chiefly in the near ultraviolet region (270–420 nm) and a blue broad emission band of main peak at 452 nm under the strongest excitation of 411 nm. Further investigation on concentration-dependent emission spectra indicated that Ca₂B₅O₉Br:0.03Eu²⁺ phosphor exhibited the strongest luminescent intensity, and the concentration quenching for the two Eu-site emission centers was caused by dipole–dipole interactions.