Luminescence studies on SrMgAl10O17:Eu, Dy phosphor crystals

Using urea as fuel, SrMgAl₁₀O₁₇:Eu, Dy phosphor was prepared by a combustion method. Its luminescence properties under ultraviolet (UV) excitation were investigated. Pure SrMgAl₁₀O₁₇ phase was formed by urea-nitrate solution combustion synthesis at 550 °C. The results indicated that the emission spectra of SrMgAl₁₀O₁₇:Eu, Dy has one main peak at 460 nm and one shoulder peak near 516 nm, which are ascribed to two different types of luminescent Eu²⁺ centers existing in the SrMgAl₁₀O₁₇ matrix crystal. The blue luminescence emission of SrMgAl₁₀O₁₇:Eu phosphors was improved under UV excitation by codoping Dy³⁺ ions. The SrMgAl₁₀O₁₇:Eu phosphors showed green afterglow (λ=516 nm) when Dy³⁺ ions were doped. Dy³⁺ ions not only successfully play the role of sensitizer for energy transfer in the system, but also act as trap levels and capture the free holes in the spinel blocks.     

Synthesis and crystal structures and luminescent properties of divalent europium-doped Ba2ZnSi2O7 and BaZn2Si2O7

The monoclinic Ba₂ZnSi₂O₇:Eu²⁺ blue-green-emitting phosphor and the orthorhombic BaZn₂Si₂O₇:Eu²⁺ green-emitting phosphor were prepared by combustion-assisted synthesis method as the fluorescent materials for ultraviolet-light-emitting diodes (UV-LEDs) performed as a light source. The crystallinity and luminescence were investigated using X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Pure monoclinic Ba₂ZnSi₂O₇ and orthorhombic BaZn₂Si₂O₇ crystallize completely at 1100 °C. The doped Eu²⁺ ions did not cause any significant change in the host structure. The emission spectra presented an emission position red shift of up to 16 nm from Ba₂ZnSi₂O₇:Eu²⁺ to BaZn₂Si₂O₇:Eu²⁺. The excitation spectra of Ba₂ZnSi₂O₇:Eu²⁺ and BaZn₂Si₂O₇:Eu²⁺ were broad-banding, extending from 260 to 465 nm, which match the emission of UV-LEDs.     

Enhanced luminescence from transparent Ni-doped MgO–Al2O3–SiO2 glass ceramics by Ga2O3 addition

Transparent Ni²⁺-doped MgO–Al₂O₃–SiO₂ glass ceramics without and with Ga₂O₃ were synthetized. The precipitation of spinel nanocrystals, which was identified as solid solutions in the glass ceramics, could be favored by Ga₂O₃ addition and their sizes were about 7.6 nm in diameter. The luminescent intensity of the Ni²⁺-doped glass ceramics was largely enhanced by Ga₂O₃ addition which could mainly be caused by increasing of Ni²⁺ in the octahedral sites and the reduction of the mean frequency of phonon density of states in the spinel nanocrystals of solid solutions. The full width at half maximum (FWHM) of emissions for the glass ceramics with different Ga₂O₃ content was all more than 200 nm. The emission lifetime increased with the Ga₂O₃ content and the longest lifetime is about 250 μs. The Ni²⁺-doped transparent glass ceramics with Ga₂O₃ addition have potential application as broadband optical amplifier and laser materials.     

Combustion synthesis and luminescent properties of a new material Li2(Ba0.99,Eu0.01)SiO4:B for ultraviolet light emitting diodes

Using urea as fuel and boric as flux, a novel bluish green emitting phosphor Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ has been successfully synthesized using a combustion method. The material has potential application as the fluorescent material for ultraviolet light-emitting diodes (UV-LEDs). The dependence of the properties of Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ phosphors upon urea concentration, boric acid doping and initiating combustion temperature were investigated. The crystallization and particle sizes of Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ have been investigated by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Luminescence measurements showed that the phosphors can be efficiently excited by ultraviolet (UV) to visible region, emitting a bluish green light with peak wavelength of 490 nm. The results showed that the boric acid was effective in improving the luminescence intensity of Li₂(Ba_0.99,Eu_0.01)SiO₄ and the optimum molar ratio of boric acid to barium nitrate was about 0.06. The optimized phosphors Li₂(Ba_0.99,Eu_0.01)SiO₄:B_0.06³⁺ showed 160% improved emission intensity compared with that of the Li₂(Ba_0.99,Eu_0.01)SiO₄ phosphors under UV (λ_ex=350 nm) excitation.     

Spectroscopic characterization, conductivity and relaxation anomalies in the Li2O-MgO-B2O3 glass system: Effect of nickel ions

Glass samples of the system, Li₂O-MgO-B₂O₃ containing different concentrations of nickel oxide (ranging from 0 to 1.0 mol%) were prepared by using the melt quenching technique. The optical absorption studies indicate that the nickel ions occupy both tetrahedral and octahedral positions in the glass network. However, the octahedral positions seem to be dominant when the concentration of nickel oxide is ?0.4 mol% in the glass matrix. When in the octahedral positions, nickel ions occupy the network modifying positions. This has a tremendous effect on the thermoluminescence, electrical conductivity and magnetic susceptibility studies. Electrical measurements were carried out as a function of frequency and temperature over the frequency range of 10-10⁶ Hz and a temperature range of 303-523 K. The electric modulus formalism was applied to study the relaxation behavior by using the impedance data for all the samples at 403 K, and also for analyzing the relaxation behavior of the highest conducting sample (0.4 mol% of nickel oxide) at different temperatures. An attempt has been made to relate the measured properties to the structural modifications in the glass network due to the modifying effect of octahedral Ni²⁺ ions.     

Microstructural, dielectric and spectroscopic properties of Li2O-Nb2O5-ZrO2-SiO2 glass system crystallized with V2O5

Li₂O-Nb₂O₅-ZrO₂-SiO₂ glasses mixed with different concentrations of V₂O₅ were crystallized. The samples were characterized by XRD, SEM and DTA techniques. The SEM pictures indicated that the samples contain well defined and randomly distributed crystal grains. The X-ray diffraction studies have revealed the presence of several crystalline phases in these samples. Optical absorption, ESR and photoluminescence spectral studies on these samples have indicated that a considerable proportion of vanadium ions do exist in V⁴⁺ state in addition to V⁵⁺ state and the redox ratio seems to be increasing with increase in the concentration of crystallizing agent V₂O₅. The infrared spectral studies have pointed out the existence of conventional SiO₄, ZrO₄, NbO₆, VO structural units in the glass ceramic network. The study of dielectric properties suggested a decrease in the insulating character of the glass ceramics with increase in the crystallizing agent. A.C. conductivity in the high temperature region seems to be connected mainly with the polarons involved in the process of transfer from V⁴⁺↔V⁵⁺ ions.     

Thermoluminescence studies of LiBa2B5O10:RE (RE=Dy, Tb and Tm)

LiBa₂B₅O₁₀:RE³⁺ (RE=Dy, Tb and Tm) was synthesized by the method of high-temperature solid-state reaction and the thermoluminescence (TL) properties of the samples under the irradiation of the γ-ray were studied. The result showed that Dy³⁺ ion was the most efficient activator. When the concentration of Dy³⁺ was 2 mol%, LiBa₂B₅O₁₀:Dy³⁺ exhibited a maximum TL output. The kinetic parameter of LiBa₂B₅O₁₀:0.02Dy was estimated by the peak shape method, for which the average activation energy was 0.757 eV and the frequency factor was 1.50×10⁷ s⁻¹. By the three-dimensional (3D) TL spectrum, the TL of the sample was contributed to the characteristic f-f transition of Dy³⁺. The dose-response of LiBa₂B₅O₁₀:0.02Dy to γ-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of LiBa₂B₅O₁₀:0.02Dy was also investigated.     

Enhanced photoluminescence properties of Sm ions in Cu and Sn co-doped P2O5:BaO glass

Luminescent glasses activated with Sm³⁺ ions are of current interest given their potential for a wide range of photonic applications. In this work, Sm³⁺-containing P₂O₅:BaO glasses are prepared by a simple melt-quench method, and the influence of CuO and SnO co-doping on Sm³⁺ photoluminescence (PL) is investigated. Optical absorption, solid-state ³¹P nuclear magnetic resonance spectroscopy, and PL spectroscopy are employed in the assessment of material optical and structural properties. The data indicates that monovalent copper ions and twofold-coordinated Sn centers are successfully stabilized in the matrix and both species can enhance the orange–red emission of Sm³⁺ ions. The optical properties of the material after heat treatment have been also assessed. Results indicate the chemical reduction of ionic copper via Sn²⁺ ultimately producing Cu nanoparticles as evidenced by the surface plasmon resonance. As a result, Sm³⁺ PL diminishes consistent with an excitation energy transfer to plasmonic Cu particles, i.e. the “plasmonic diluent” effect prevails.     

Features of the local structural disorder in Li2O-CaF2-P2O5 glass-ceramics with Cr2O3 as nucleating agent

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of Cr₂O₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy (EDS), differential thermal analysis and conventional spectroscopic techniques. The X-ray diffraction and scanning electron microscopic studies reveal the presence of lithium phosphate, calcium phosphate and chromium phosphate (complexes of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions) crystal phases. The study on DTA suggests that the crystallization is predominantly due to the surface crystallization when the concentration of nucleating agent Cr₂O₃ is around 0.8 mol%. The IR and Raman spectral studies of these samples indicate that the sample crystallized with 0.8 mol% Cr₂O₃ is more compact and possesses high rigidity due to the presence of chromium ions largely in tetrahedral positions.     

Optical absorption spectrum of Cu2O-CaO-P2O5 glasses

Homogeneous CaO-P₂O₅ and Cu₂O-CaO-P₂O₅ glasses were prepared using a melt-quenched method under controlled conditions. The binary glasses were found to be colourless and transparent while the ternary glasses changed from light green to dark green as the Cu₂O content increased. From the absorption edge studies, the values of the optical band gap, E_opt and Urbach energy, ΔE were evaluated. The position of the absorption edge and hence the optical band gap were found to depend on the glass composition. Analysis of the optical band gap shows that for the binary glasses, the value increases as the content of CaO decreases, while for the ternary glasses, the value of the optical band gap increases as the content of the Cu₂O decreases. The density of the glasses was also measured and was found to increase with the increase in CaO and Cu₂O contents.     

The photoluminescent properties of Eu in MgO-Ga2O3-SiO2 nanocrystalline glass-ceramic

The MgO-Ga₂O₃-SiO₂ glass-ceramic (GC) containing MgGa₂O₄ nanocrystals and glasses doped with Eu³⁺ ions were prepared by the sol-gel method. The down-conversion and up-conversion luminescence (UCL) properties were studied. The results indicated that the relative intensity of f-f transitions of Eu³⁺ decreased in contrast with that of charge transfer (CT) absorption with the increase in heating temperature. Using a Xe lamp and 800 nm femtosecond (fs) laser excitation, strong red luminescence of Eu³⁺ in MgO-Ga₂O₃-SiO₂ glasses and GC was observed.     

Preparation and luminescent properties of BaCa2Si3O9:Eu

A blue emitting phosphor of the triclinic BaCa₂Si₃O₉:Eu²⁺ was prepared by the combustion-assisted synthesis method and an efficient blue emission ranging from the ultraviolet to visible was observed. The luminescence and crystallinity were investigated using luminescence spectrometry and X-ray diffractometry (XRD), respectively. The emission spectrum shows a single intensive band centered at 445 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The excitation spectrum is a broad extending from 260 to 450 nm, which matches the emission of ultraviolet light-emitting diodes (UV-LEDs). The critical quenching concentration of Eu²⁺ in BaCa₂Si₃O₉:Eu²⁺ phosphor is about 0.05 mol. The corresponding concentration quenching mechanism is verified to be a dipole-dipole interaction. The CIE of the optimized sample Ba_0.95Ca₂Si₃O₉:Eu_0.05²⁺ was (x, y)=(0.164, 0.111). The result indicates that BaCa₂Si₃O₉:Eu²⁺ can be potentially useful as a UV radiation-converting phosphor for white light-emitting diodes (LEDs).     

Emission analysis of Tb:MgAl2O4 powder phosphor

This paper reports the emission analysis of green-emitting Tb³⁺-doped MgAl₂O₄ phosphors. Uniformity of the phase of the Tb³⁺-doped MgAl₂O₄ phosphor has been checked by X-ray diffraction (XRD) technique and show common bands existing in the results of Fourier transform infrared (FT-IR). This phosphor exhibits weak blue, orange emissions and a strong emission at λ_exci=350 nm. The blue and green-orange emissions are ascribed to ⁵D₃→⁷F_J and ⁵D₄→⁷F_J (where J=3-6) transitions of Tb³⁺ ions, respectively. These phosphors have shown a strong, more prominent green emission from ⁵D₄→⁷F₅ at 543 nm. The results have indicated that MgAl₂O₄:Tb³⁺ could be a potential candidate as agreen-emitting powder phosphor.     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis

Spherical-shaped Li₄Ti₅O₁₂ anode powders with a mean size of 1.5 μm were prepared by spray pyrolysis. The precursor powders obtained by spray pyrolysis had no peaks of crystal structure of Li₄Ti₅O₁₂. The powders post-treated at temperatures of 800 and 900 °C had the single phase of spinel Li₄Ti₅O₁₂. The powders post-treated at a temperature of 1000 °C had main peaks of the Li₄Ti₅O₁₂ phase and small impurity peaks of Li₂Ti₃O₇. The spherical shape of the precursor powders was maintained after post-treatment at temperatures below 800 °C. The Brunauer-Emmett-Teller (BET) surface areas of the Li₄Ti₅O₁₂ anode powders post-treated at temperatures of 700, 800 and 900 °C were 4.9, 1.6 and 1.5 m²/g, respectively. The initial discharge capacities of Li₄Ti₅O₁₂ powders were changed from 108 to 175 mAh/g when the post-treatment temperatures were changed from 700 to 1000 °C. The maximum initial discharge capacity of the Li₄Ti₅O₁₂ powders was obtained at a post-treatment temperature of 800 °C, which had good cycle properties below current densities of 0.7 C.     

Effect of Bi2O3 content on physical and optical properties of 15Li2O-15K2O-xBi2O3-(65−x) B2O3: 5V2O5 glass system

Multi-component bismuth borate glasses doped with vanadium ions 15Li₂O-15K₂O-xBi₂O₃-(65−x) B₂O₃: 5V₂O_5, (x=3, 5, 7, 10, 12 and 15) have been prepared using conventional melt quench technique. Characterization of the prepared glasses has been done using X-ray diffraction, differential scanning calorimetry and density measurements. The effect of Bi₂O₃ content on the optical properties of the present glass system is studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The origin of the Urbach energy is associated with the phonon-assisted indirect transitions. The density and molar volume studies indicate that Bi₂O₃ in these glasses is acting partly as network modifier and partly as network former. The variations in the optical band gap energies, density and molar volume with Bi₂O₃ content have been discussed in terms of changes in the glass structure. Values of the theoretical optical basicity, average crosslink density and the average electronic polarizability are also reported.     

Crystal field parameters and energy level structure of the MnO4 tetroxo anion in Li3PO4, Ca2PO4Cl and Sr5(PO4)3Cl crystals

A comparative study concerning the electronic structure of the Mn⁵⁺ ion in the Li₃PO₄, Ca₂PO₄Cl, Sr₅(PO₄)₃Cl host lattices has been carried out in the framework of the exchange charge model. The crystal field parameters have been evaluated using the structural data as the only input information. The 10 K absorption spectra of the investigated compounds have been measured in order to verify the correspondence between experimental and calculated energy levels. A systematic trend of the crystal field splitting of the most intense transitions has been evidenced and discussed by considering the symmetry properties of the coordination polyhedra around Mn⁵⁺.     

Phase formation and characterization of Sr3Y2Ge3O12, Sr3In2Ge3O12, and Ca3Ga2Ge3O12 doped by trivalent europium

This work reports on the phase formation during a solid-state reaction of Eu³⁺-doped garnets with the general formula A₃B₂Ge₃O₁₂ (A=Ca, Sr and B=Ga, In, Y) and their luminescent properties. It is shown by XRD and DTA/TG experiments that the garnet-phase formation is completed at 1100-1200 °C. Moreover, it turned out that the position of the oxygen to europium charge-transfer band and the intensity of the forbidden 4f-4f transitions of Eu³⁺ is dependent on the covalent interaction between the Eu³⁺ activator and the surrounding oxygen anions. The investigated red-emitting luminescent materials show high lumen equivalents and deep red emission at the same time, which makes them attractive for the application in LEDs (light emitting diodes), in particular for near UV-emitting LEDs.     

Electrical behaviour of Li2O-ZnO-SiO2 glass and glass-ceramics system

Sealing quality lithium zinc silicate (LZS) glasses of compositions (wt.%) (a) LZSL- Li₂O: 12.65, ZnO: 1.85, SiO₂: 74.4, Al₂O₃: 3.8, K₂O: 2.95, P₂O₅: 3.15, B₂O₃: 1.2 (low ZnO), and (b) LZSH- Li₂O: 8.9, ZnO: 24.03, SiO₂: 53.7, Na₂O: 5.42, P₂O₅: 2.95, B₂O₃: 5 (high ZnO) were prepared by conventional melt-quench technique and converted to glass-ceramics by controlled crystallization process. The electrical properties of these samples were measured using ac impedance spectroscopy technique over a frequency range of 10 Hz-15 MHz at several temperatures in the range of 323-673 K. The ac conductivity, dc conductivity, dielectric constant and loss factor were obtained from these measurements. The dc conductivity (σ_dc) follows the Arrhenius behaviour with temperature. It is observed that σ_dc in LZSL glass is significantly higher than in the LSZH glass and the activation energies for σ_dc for LZSL and LZSH glasses are 0.59 and 1.08 eV, respectively. It further observed that the conductivity value decreases nearly one order of magnitude on conversion to glass-ceramics. The behaviour is explained on the basis of distributions and nature of alkali ions and network structures in these samples.     

Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.