Spectral analysis of a novel Eu2+ activated SiO2–BaO glass ceramics phosphor under UV-LED excitation

A novel Eu²⁺ activated 60SiO₂–40BaO (mol%) glass ceramics phosphor was prepared and the optical properties were investigated. X-ray diffraction (XRD) and Raman spectra confirmed the formation of Ba₂Si₃O₈ nano-crystals in the glass matrix. The Eu²⁺ activated glass ceramics exhibited broad emission band centered at 518 nm due to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. Compared with the glass, the emission intensity of Eu²⁺ activated glass ceramics was much stronger, and the peak wavelength shifted toward shorter wavelength. The photoluminescence excitation (PLE) spectra of the glass ceramics showed an overlap with the main emission region of an ultraviolet light-emitting diode (UV-LED). According to the photoluminescence (PL) spectra, the CIE chromaticity coordinates of the Eu²⁺ activated glass and glass ceramics were calculated. The results indicated that the Eu²⁺ activated glass ceramics containing Ba₂Si₃O₈ nano-crystals can be used as a potential green emitting phosphor under UV-LED excitation.     

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.     

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.     

On the limitation of quantitative measurements using transmission electron microscopy

This work discussed the limitation of (scanning) transmission electron microscopy (TEM/STEM) techniques in quantitative measurements in electron-beam-sensitive silicate glasses and glass ceramics. Electron beam induced damages in the silicate glasses containing Na and the glass ceramics containing fluorite nanocrystals were demonstrated. The damages were mainly caused by preferentially removing Na and decomposing CaF₂ into Ca. All the damage phenomena were observed under electron beam intensities, which were much weaker than the intensities used in the conventional high-resolution electron microscopy (HREM) and microanalysis in STEM. Therefore, although the advanced TEM/STEM techniques are very promising in the precise measurement of local composition at ultra-high spatial resolution in some materials, they may not be applicable to Na-containing silicate glasses and glass ceramics containing fluorite nanocrystals.     

(Y,Gd)2O3:Eu闪烁体材料的研究进展

阐述了闪烁体的研究现状,主要介绍了(Y,Gd)2O3:Eu (简称YGO)陶瓷闪烁体材料的性能特点,特别对YGO的晶体结构和发光性能的研究进行了总结;并对YGO粉体材料的制备及烧结方法进行了叙述.展望了YGO闪烁体材料未来的研究前景及研究重点.     

The effect of PbF2 content on the microstructure and upconversion luminescence of Er-doped SiO2-PbF2-PbO glass ceramics

The Er³⁺ doped transparent oxyfluoride glass ceramics were obtained by appropriate heat treatment of the precursor glasses with composition (mol%) 50SiO₂-xPbF₂-(50 − x)PbO-0.5ErF₃. The microstructure and optical properties of the glasses and glass ceramics were determined by differential scanning calorimetry (DSC), X-ray diffraction (XRD), absorption spectra and luminescence spectra. The intensity of upconversion luminescence significantly increased in glass ceramics compared to that in precursor glass. The emission bands centered around 660 nm (⁴F_9/2 → ⁴I_15/2) and 410 nm (²H_9/2 → ⁴I_15/2) were simultaneously observed in glass ceramics but cannot be seen in the corresponding precursor glass. The influence of different PbF₂ content on the microstructure and upconversion luminescence of the samples was analyzed in detail. The results indicated that with the increase of PbF₂ content, the Ω₂ was almost the same and the ratios of red to green upconversion luminescence decreased in glass ceramics.     

Stimulated emission of Co2+-doped glass–ceramics

Pump–probe spectroscopy studies on cobalt-doped spinel-based aluminosilicate glass–ceramics of various compositions have been made in the visible part of the spectrum. Stimulated emission from the ⁴T₁(⁴P) state to the ⁴A₂ one of tetrahedral Co²⁺ ion has been observed for all glass–ceramic materials. The peak values of effective stimulated emission cross-sections for Co²⁺ ions are estimated to be 4–5 × 10⁻¹⁹ cm² depending on glass–ceramics composition and are found to be higher than in spinel single crystals.     

Cathodoluminescence of epitaxial GaN and ZnO thin films for scintillator applications

A comparative study of cathodoluminescence ultraviolet photon yields and decay times of large area GaN and zinc oxide (ZnO) layers grown for scintillator applications by metalorganic vapor phase epitaxy is presented. Silicon-doped GaN and non-intentionally-doped ZnO yield up to 1.4±0.2 photons/kVe⁻ and 1.3±0.2 photons/kVe^– at room-temperature, respectively. For GaN the decay times scatter between 0.4 and 0.9 ns, and for ZnO between 2.5 and 3.0 ns. The GaN and the ZnO absorption coefficients, α, internal efficiencies, η_i, and radiative constants, B, are determined. The characteristics of thin-film scintillators based on these materials are compared with commercially available granular scintillators.     

Characterization of BGO glass–ceramic materials

Glass–ceramics of the compositions Bi₄Ge₃O₁₂ (BGO) and Bi₂O₃–GeO₂ have been obtained by pouring molten materials onto graphite plates heated below and above the glass transition temperatures. Glass transitions temperatures have been measured by DSC. T_g is lower in the case of BGO than with the Bi₂O₃–GeO₂ glass ceramics material. Crystallization is evaluated by X-ray diffraction and microscopic observations. The XRD measurements confirm the amorphous structure of the samples cast below T_g. The Hruby factor, which measures the stability of the glass–ceramics, is about 0.21 in the case of BGO glass ceramics suggesting a rather stable glass. The fluorescence under U.V. excitation is larger by one order of magnitude in the case of BGO glass–ceramics by comparison to the Bi₂O₃–GeO₂ glasses, suggesting it is a good candidate for scintillation materials. The images obtained under U.V. excitation shows structured luminescent centers in the case of BGO glass–ceramics.     

A new transparent oxyfluoride glass ceramic with improved luminescence

A new type of glass ceramic containing BaF₂ nano-crystals was prepared by melt quenching. Differential scanning calorimetry, X-ray diffraction and transmission electron microscopy were used to study its thermal behaviors and structural characteristics. Based on Judd-Ofelt theory, the spectroscopic properties of the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ in glass ceramic were evaluated. Notably, it is found that the fluorescence lifetime in the present system is much longer than that in most other glasses and glass ceramics. A comparative study on luminescence performance suggests that the obtained glass ceramic is a promising material for Er³⁺ doped fiber amplifiers.     

Crystallization behavior of Dy3+-doped selenide glasses

Rare earth (RE)-doped chalcogenide glasses are an important promising material for active photonic devices, including mid-infrared (mid-IR) fiber lasers and amplifiers. Here we report on dysprosium ion (Dy³⁺)-doped GeAsGaSe chalcogenide glasses based on 10 atomic (at.) % Ga. A series of Dy³⁺-doped GeAsGaSe glasses, with increasing levels of Dy³⁺ dopant from 0 ppm to 2000 ppm added to the Ge_16.5As₉Ga₁₀Se_64.5 (at. %) base glass, is synthesized and characterized using: Fourier transform infrared spectrometry; X-ray diffraction (XRD); imaging and analysis using a high resolution transmission electron microscope, with selected area electron diffraction (HRTEM-SAED), and energy dispersive X-ray spectroscopy (HRTEM-EDX) and an environmental scanning electron microscope with energy dispersive X-ray spectroscopy (ESEM-EDX) and with secondary electron mapping. At the higher levels of Dy³⁺ doping, the glasses exhibit bulk crystallization; XRD, HRTEM-EDX and ESEM-EDX indicate the crystals are predominantly a modified, face centered cubic α-Ga₂Se₃, with some substitution of Ge. In addition, features on the bulk glass surface are shown to comprise Dy³⁺, sometimes accompanied by Si and [O] which, it is suggested, are due to contamination from the silica glass melting ampoule.     

Phase separation, crystallization and leaching of microporous glass ceramics in the CaO-TiO2-P2O5 system

Microporous glass ceramics belonging to the CaO-TiO₂-P₂O₅ system were prepared with the assumption of a 2:1 mole ratio for β-Ca₃(PO₄)₂:CaTi₄(PO₄)₆, the anticipated crystalline phases in the end product. The glasses formulated according to the above composition were melted and cast onto a steel mold and were crystallized to glass ceramics containing the above phases. Dilatometric/differential thermal analysis (DTA) techniques were utilized to determine the appropriate phase separation-nucleation and crystallization temperatures. The crystalline products and resulting microstructures in various stages of process were determined and observed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). By leaching the resulting glass ceramics in HCl, β-Ca₃(PO₄)₂ was dissolved out leaving a porous skeleton of CaTi₄(PO₄)₆. It was found that the volume porosity, specific surface area and mean pore diameter of microporous glass ceramics can be managed through the proper selection of heat treatment conditions. In the optimized conditions for fabricating glass ceramics of minimum mean pore size the values of 41 ± 4%, 26 ± 3 m²/g and 14.3 ± 2 nm were obtained for porosity, surface area and pore diameter respectively.     

Erbium activated HfO2 based glass–ceramics waveguides for photonics

(100 − x)SiO₂ − xHfO₂ (x = 10, 20, 30 mol) glass–ceramics planar waveguides activated by 0.3 mol% Er³⁺ ions were prepared by sol–gel route, using dip-coating deposition on v-SiO₂ substrates. High resolution transmission electron microscopy has shown that after an adapted heat treatment, the resulting materials show nanocrystalline structures. The glass–ceramics waveguides were characterized by m-line, Raman, losses measurements, and photoluminescence spectroscopy. Photoluminescence spectroscopy has demonstrated the embedding of erbium ions in the nanocrystals. The results are discussed with the aim of assessing the role of hafnia on the structural, optical and spectroscopic properties of erbium doped silica hafnia glass–ceramics planar waveguides.     

Erbium- and chlorine-doped fluorozirconate-based glasses for up-converted fluorescence

A series of glass ceramics was prepared and the structure–property relationships evaluated. The base composition of the series was comprised of fluorozirconate (FZ) and fluorochlorozirconate (FCZ) glass ceramics. Thermal processing of as-made FCZ-based glass ceramics produced sharp peaks in X-ray diffraction patterns, which was attributed to BaCl₂ nanocrystals formed in the material; this was not observed in the FZ glass. Up-conversion fluorescence experiments were carried out for both the FZ and FCZ samples doped with erbium. The fact that an increase in the up-conversion efficiency was not observed indicates that erbium ions were not embedded in the BaCl₂ nanocrystals. A comparison is made between this series and a similar series that was doped with neodymium.     

Luminescence properties of Tb3+/Sm3+ co-doped 38B2O3―31Al2O3―31SrO glasses and glass ceramics

In this paper, Tb³⁺/Sm³⁺ co-doped 38B₂O₃―31Al₂O₃―31SrO glass was successfully prepared. After heat treatment, single crystal phase SrAl₂B₂O₇ was precipitated from the parent glass. DTA data showed the glass transition temperature at 625 °C and a sharp exothermic peak at 860 °C. XRD patterns demonstrated a regular evolution from glass to glass ceramics with higher treatment temperature and longer treatment time. From the XRD patterns, we supposed that Tb³⁺/Sm³⁺ ions can be most likely contained in the crystal phase. The photoluminescence spectra showed that the crystallization can enhance the emission intensity significantly and there could be an optimum crystallization degree to get the strongest luminescence in glass ceramics. The light scattering of devitrification sample can vary the intensity ratio of Sm³⁺ and Tb³⁺ emission. Therefore, as a potential route, rare earth ions doped glass ceramics could be a further research direction of luminescence glasses for white light emitting diodes application.     

High resolution 29Si NMR study of the structure and devitrification of lead-silicate glasses

High speed magic-angle rotation of glass samples in the strong polarizing field of a superconducting magnet yields high-resolution ²⁹Si NMR spectra. Using this technique glasses of various composition, PbO·SiO₂, (PbO)₂·SiO₂, and (PbO)₄·SiO₂ were studied and the influence of thermal treatment followed. Crystallization of PbO·SiO₂ glass has been found to be a complex process leading to a structure identical with that of the mineral alamosite. The ²⁹Si NMR spectrum of crystalline alamosite consists of three lines in agreement with the structure determined by X-ray diffraction.     

Eu2+/Dy3+ co-doped white light emission glass ceramics under UV light excitation

In the present work, transparent Eu²⁺/Dy³⁺ co-doped white light-emitting glass ceramics containing CaF₂ were successfully prepared under reducing atmosphere. Their luminescence properties have been studied by excitation and emission spectra. A combination of blue, yellow and red emissions has emerged in Eu²⁺/Dy³⁺ co-doped glass and glass ceramics, which allows the observation of bright white light when the samples are excited by the ultraviolet light. Energy transfer (ET) from Eu²⁺ to Dy³⁺ is discovered by directly observing the luminescence intensity of Dy³⁺ in the Eu²⁺/Dy³⁺ co-doped glass which is much stronger than that in the Dy³⁺-doped glass. ET from Eu²⁺ to Dy³⁺ in glass is further confirmed by fluorescence studies performed on the samples with various activator (Dy³⁺) concentrations. The color of luminescence could be adjusted by varying the proportions of europium and dysprosium. The optimal composition generates white light with chromaticity coordinates (0.296, 0.311). The results indicate that Eu²⁺/Dy³⁺ co-doped glass ceramics containing CaF₂ nano-crystals is a potential material for white LED.     

Structural changes during the crystallization of the Bi4Ge3O12 glasses

Bismuth-germanate glass ceramics with the composition 40% Bi₂O₃-60% GeO₂ (in molar percents) were prepared through controlled crystallization of melt-quenched glass. The Raman and FTIR spectra recorded in the as-made glasses show broad bands at 240, 400, 780 cm^− 1 and 400, 745 cm^− 1 have been assigned Ge-O bonds which appear right after preparation. X-ray diffraction has shown that the as-made glasses are amorphous, but after annealing above the crystallization temperature at 558 °C, BGO nano-crystallites with a size of about 50 nm precipitate in the glass matrix. The Raman and FTIR spectra reveal sharp peaks associated to the “internal” and “external vibrations” of GeO₄ tetrahedral groups inside the BGO nano-crystallites. In the glass ceramic sample the transparency region is shifted at longer wavelengths compared to as-made glass, due to the Rayleigh scattering on the BGO nano-crystallites.     

Preparation and third-order optical nonlinearity of glass ceramics based on GeS2–Ga2S3–CsCl pseudo-ternary system

Chalcohalide glass-ceramics based on GeS₂–Ga₂S₃–CsCl pseudo-ternary system were prepared by heat treatment method. X-ray diffraction and scanning electron microscope studies confirmed the formations of Ga₂S₃ and GeS₂ phase grains with sizes of 2–5 and 80 nm, respectively. Z-scan technology was employed to investigate the third-order nonlinear optical characteristics of both precursor glass and its glass ceramics at 800 nm. The results show that nonlinear refractive index n₂ as well as nonlinear absorption coefficient β increase after heat treatment, which is due to quantum effects, and the largest n₂ of the glass ceramics is 4.3 × 10^? 11 esu which is 4 times larger than that of the host.     

Nanophase separation and effects on properties of Ge–As–Se chalcogenide glasses

Nanophase separation in the bulk Ge–As–Se chalcogenide glasses was observed by SEM and supported by XRD and IR measurements. Effects of nanophase separation on glass transition temperature (T_g), microhardness (H_v), optical band gap (E_opt) and thermal expansion coefficient (α) were investigated in terms of glass rigidity transitions. According to the correlations between the properties and average coordination number Z, it is established that nanophase separation becomes more intensive when Z is larger than 2.64.