Eu3+离子在微晶玻璃研究中的探针作用

制备出单掺Eu³⁺离子的氟氧化物玻璃陶瓷系列样品，利用Eu³⁺离子作为荧光探针，通过热处理前后Eu³⁺离子发射光谱中电偶极子跃迁与磁偶极子跃迁强度比值的变化表征在玻璃材料中微晶是否形成，分析了Eu³⁺离子荧光发射谱中电偶极子跃迁与晶体场对称性的关系，进一步表征了稀土离子所处微晶晶格场的变化. 关键词： 微晶玻璃 探针 3+离子')" href="#">Eu³⁺离子     

Zr and Ba edge phenomena in the scintillation intensity of fluorozirconate‐based glass‐ceramic X‐ray detectors

The energy‐dependent scintillation intensity of Eu‐doped fluorozirconate glass‐ceramic X‐ray detectors has been investigated in the energy range from 10 to 40 keV. The experiments were performed at the Advanced Photon Source, Argonne National Laboratory, USA. The glass ceramics are based on Eu‐doped fluorozirconate glasses, which were additionally doped with chlorine to initiate the nucleation of BaCl₂ nanocrystals therein. The X‐ray excited scintillation is mainly due to the 5d–4f transition of Eu²⁺ embedded in the BaCl₂ nanocrystals; Eu²⁺ in the glass does not luminesce. Upon appropriate annealing the nanocrystals grow and undergo a phase transition from a hexagonal to an orthorhombic phase of BaCl₂. The scintillation intensity is investigated as a function of the X‐ray energy, particle size and structure of the embedded nanocrystals. The scintillation intensity versus X‐ray energy dependence shows that the intensity is inversely proportional to the photoelectric absorption of the material, i.e. the more photoelectric absorption the less scintillation. At 18 and 37.4 keV a significant decrease in the scintillation intensity can be observed; this energy corresponds to the K‐edge of Zr and Ba, respectively. The glass matrix as well as the structure and size of the embedded nanocrystals have an influence on the scintillation properties of the glass ceramics.     

Effect of induced crystallization in rare-earth doped lithium borate glass

Rare-earth doped borate glasses and glass ceramics are investigated for their potential as photon converters. Thermal processing of the as-made glass results in the formation of nanocrystals therein. For optical activation, the glasses are doped with Eu³⁺ and Tb³⁺, both enabling an intense emission under ultraviolet excitation. Differential scanning calorimetry and X-ray diffraction are applied to analyze the crystallization behavior. Compared to the undoped glass, the glass transition temperature as well as the crystallization temperature are increased with Eu³⁺ doping. Upon thermal processing of the as-made glasses, the transmittance is significantly reduced. Preliminary photoluminescence quantum efficiency measurements yield lower values for the glass ceramics.     

Synthesis, structure and optical properties of Eu/TiO2 nanocrystals at room temperature

The nanocrystal samples of titanium dioxide doped with europium ion (Eu³⁺/TiO₂ nanocrystal) are synthesized by the sol-gel method with hydrothermal treatment. The Eu³⁺ contents (molar ratio) in the samples are 0, 0.5%, 1%, 2%, 3% and 4%. The X-ray diffraction, UV-Vis spectroscopy data and scanning electron microscope image show that crystallite size is reduced by the doping of Eu³⁺ into TiO₂. Comparing the Raman spectra of TiO₂ with Eu³⁺/TiO₂ (molar ratio Eu³⁺/TiO₂=1%, 2% and 4%) nanocrystals at different annealing temperatures indicates that the anatase-to-rutile phase transformation temperatures of Eu³⁺/TiO₂ nanocrystals are higher than that of TiO₂. This is due to the formation of Eu-O-Ti bonds on the surface of the TiO₂ crystallite, as characterized by the X-ray photoelectron spectroscopy. The photoluminescence spectra of TiO₂ in Eu³⁺/TiO₂ nanocrystals are interpreted by the surface self-trapped and defect-trapped exciton relaxation. The photoluminescence of Eu³⁺ in Eu³⁺/TiO₂ nanocrystals has the strongest emission intensity at 2% of Eu³⁺ concentration.     

Multiplesite structure and photoluminescence properties of Eu3+ doped MgO nanocrystals

MgO:Eu³⁺ nanocrystals with average diameter around 15 nm were prepared via a facile combustion method under a weak reductive atmosphere at temperature as low as 300°C. The photoluminescence spectra showed that the MgO:Eu³⁺ nanocrystals emit white light, the hypersensitive transition (⁵ D ₀→⁷ F _j of Eu³⁺) emission was prominent in the emission spectra resulting from the noinversion symmetry local site at which Eu³⁺ ions were located. Two kinds of luminescence sites of Eu³⁺ are identified by means of the fluorescence decay and site-selective spectroscopy. The excitation and absorption spectra indicated that the absorption of surface state decreased with the increase of Eu³⁺ concentration, meaning that the surface defect decreased through Eu³⁺ doping for some of them located at the disordered sites near the surface or absorbed at the surface of MgO host. Meanwhile, absorptivity and CIE chromaticity coordinates of all samples were measured; the results were in accordance with the excitation and absorption spectra and photoluminescence spectra, respectively.     

Luminescence and energy transfer of Eu/Mn co-doped SiO2–Al2O3–ZnO–K2O glass ceramics for white LEDs

Transparent Eu²⁺/Mn²⁺ co-doped new glass ceramics (GC) containing β-Zn₂SiO₄ nanocrystals were prepared under a reduced atmosphere. The optical properties of these samples have been investigated. The emission spectra of Eu²⁺/Mn²⁺ co-doped glass ceramics show two broadband peakings at 458 and 560 nm under ultraviolet radiation, which can be attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺ and ⁴T₁(⁴G)→⁶A₁(⁶S) transition of Mn²⁺, respectively. Energy transfer (ET) from Eu²⁺ to Mn²⁺ is discovered by directly observing significant overlap of the excitation spectrum of Mn²⁺ and the emission spectrum of Eu²⁺. ET from Eu²⁺ to Mn²⁺ in glass ceramics is further confirmed by fluorescence studies performed on the samples with various activator (Mn²⁺) concentrations. The optimal composition generates white light with chromaticity coordinates (0.291, 0.344). The results indicate that Eu²⁺/Mn²⁺ co-doped glass ceramics is potential material for white light-emitting diodes (LEDs).     

Judd–Ofelt analysis and upconversion emission of Er3+–Yb3+ co-doped oxyfluoride glass ceramics containing LaF3 nanocrystals

Er³⁺–Yb³⁺ co-doped glasses and glass ceramics containing LaF₃ nanocrystals were prepared and their absorption spectra obtained. The Judd–Ofelt parameters Ω _t (t?=?2,?4,?6) for f–f transition of Er³⁺, as well as spontaneous emission probabilities, branching ratios and radiative lifetimes for stimulated emission of each band were determined. Addition of Er³⁺ and Yb³⁺ ions into low-phonon energy LaF₃ nanocrystals makes the upconversion emission of Er³⁺–Yb³⁺ co-doped glass ceramic much stronger than that of Er³⁺–Yb³⁺ co-doped glass.     

Fabrication, photoluminescence, and potential application in white light emitting diode of Dy3+–Tm3+ doped transparent glass ceramics containing GdSr2F7 nanocrystals

Dy³⁺–Tm³⁺ doped transparent glass ceramics containing GdSr₂F₇ nanocrystals were fabricated successfully by a melt-quenching method and subsequent heating. X-ray diffraction and transmission electron microscopy analyses show that tetragonal GdSr₂F₇ nanocrystals are homogeneously precipitated among the borosilicate glass matrix. If excited with 354 nm UV light, the photoluminescence spectrum of Dy³⁺ single-doped transparent glass ceramics shows white-light emission. With doping of Tm³⁺, the overall emission color of Tm³⁺–Dy³⁺ co-doped transparent glass ceramics can be tuned from white to blue through energy transfer between Dy³⁺ and Tm³⁺. CIE chromaticity and color temperature measurements show that the resulting TGCS may be a candidate as a white LED material pumped by a UV InGaN chip.     

Effect of concentration on the luminescence of Eu ions in nanocrystalline La2O3

Nanocrystalline powders with various Eu³⁺ concentration (from 1 to 10 mol %) doped La₂O₃ were prepared via a combustion route. Their structure and morphology were characterized using X-ray diffraction (XRD) and High-resolution transmission electron microscopy. The emission spectra of the as-synthesized samples show that the strongest emission position is centered at 626 nm corresponding to ⁵D₀→⁷F₂ transition of Eu³⁺ ions and the intensity change of 626 nm emission is considered as a function of ultraviolet (240 nm) irradiation time. The excitation spectra at 626 nm monitoring indicate that the charge transfer state band is varies with different Eu³⁺ ion concentration. These results are attributed to the surface defects of the nanocrystals.     

Influence of nanoenvironment on luminescence of Euactivated SnO2 nanocrystals

The emission intensity of the peak at 612 nm (⁵D₀→⁷F₂) of the Eu³⁺ ions activated SnO₂ nanocrystals (doped and coated) is found to be sensitive to the nanoenvironment. We have compared the luminescence efficiencies of the nanocrystals of SnO₂ doped by Eu₂O₃ with those of SnO₂ coated by Eu₂O₃ and we found that the intensities are significantly higher in coated nanocrystals. Furthermore, it is clear from luminescence intensity measurements that Eu³⁺ ions occupy low symmetry sites in the Eu₂O₃ coated SnO₂ nanocrystal. The analysis suggests that the radiative relaxation rate is higher in Eu₂O₃ coated SnO₂ nanocrystals than Eu₂O₃ doped SnO₂ nanocrystals due to the asymmetric environment of Eu³⁺ ions in coated samples.     

Enhanced luminescence in transparent glass ceramics containing BaYF5: Ce3+ nanocrystals

Ce³⁺ doped transparent glass ceramics containing BaYF₅ nanocrystals were prepared by controlled heat treatment of 45SiO₂–15Al₂O₃–10Na₂O–24BaF₂–6Y₂O₃–0.5Ce₂O₃ (mol%) glass. X-ray diffraction and transmission electron microscopy data have revealed the formation of BaYF₅ nanocrystals. Both photoluminescence and X-ray excited luminescence spectra have shown a blue-shift of the emission band of Ce³⁺ on ceramization, which is consistent with the Ce³⁺ environment evolving from a glassy oxide to a fluoride phase. The luminescent intensity of Ce³⁺ ions in the transparent glass ceramics is greatly enhanced compared with the precursor glass under ultraviolet and X-ray excitation. This could be attributed to the Ce³⁺ ions present in the BaYF₅ crystalline phase.     

X-ray photoelectron spectroscopy of Sm-doped CaO-MgO-Al2O3-SiO2 glasses and glass ceramics

Sm³⁺ doped CaO-MgO-Al₂O₃-SiO₂ glass and glass ceramics have been prepared. The diopside crystal (CaMgSi₂O₆) was identified in the glass ceramics by X-ray diffraction analysis. X-ray photoelectron spectra of the glass and glass ceramics were measured by a monochromatised Al-Kα XPS instrument. Sm 3d core level spectra for the Sm doped samples showed that Sm ions are predominantly in the Sm (III) state in glass and glass ceramics. The O 1s core spectra could be fitted by summing the contributions from bridging oxygen (BO) and non bridging oxygen (NBO) for samarium undoped glass, BO, NBO and Si-O-Sm for the doped glass. The O 1s XPS spectrum of undoped glass ceramics was curve fitted with BO and NBO in glass phase, as well as SiOSi, SiOMg and SiOCa in diopside. In addition to the five components above mentioned, SiOSm in diopside also appeared in O 1s XPS spectra of samarium doped glass ceramics. According to the fitting results, we demonstrate that the Sm₂O₃ exist in glass network as a glass modifier. After heat treatment, nearly all the Sm³⁺ existed in diopside phase as the substitution for Ca²⁺.     

Luminescence and scintillation of Eu2+‐doped high silica glass

High silica glass doped with Eu²⁺ ions was prepared as a scintillating material by impregnation of Eu ions into a porous silica glass followed by reduction sintering in CO atmosphere. A dominant emission band of the Eu²⁺ 5d–4f transition peaking around 430 nm was observed in the luminescence spectrum with the excitation peak around 280 nm and no emission from Eu³⁺ was present. Photoluminescence decay kinetics was governed by decay times of a few microseconds. The Eu²⁺‐doped high silica glass exhibited comparable energy resolution and slightly higher photoelectron yield with respect to the Bi₄Ge₃O₁₂ crystal in the pulse height spectra for X‐ray photon energies within 22–60 keV. Furthermore, a factor of 1.2 higher radioluminescence intensity was observed as well. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical investigation of the emission lines for Eu and Tb ions in the GaN powder host

Gallium nitride (GaN) doped by Eu³⁺ and Tb³⁺ ions have been synthesized using powder technology. The emission and absorption spectra have been obtained by using photoluminesence technique and correlated with the local structural environments. The room temperature yellow emission from GaN grains as well as from Eu³⁺ and Tb³⁺ ions has been observed for nano- as well as for microGaN grains. Additionally, for GaN:1%Eu³ micrograins the blue emission from GaN nanocrystals has been observed.     

Luminescence properties of Pr3+-doped transparent oxyfluoride glass–ceramics containing BaYF5 nanocrystals

Transparent oxyfluoride glass–ceramics containing BaYF₅ nanocrystals were successfully synthesized by appropriate heat-treatment on the SiO₂–Al₂O₃–Na₂O–BaF₂–Y₂O₃–Pr₆O₁₁ precursor glass. The structure and luminescence properties of the precursor glass and glass–ceramics were investigated by DSC, XRD, TEM, optical transmission, photoluminescence, decay time and radioluminescence spectra. The XRD results indicate that the BaYF₅ nanocrystals can percitated in the precursor glass and the sharper emission peaks of Pr³⁺ in glass ceramic suggests that Pr³⁺ ions are incorporated into the BaYF₅ nanocrystals. The higher the heat-treatment temperature is, the more the Pr³⁺ ions are centered into BaYF₅ nanocrystals, which results in the optimal concentration of Pr³⁺ in glass ceramic changes on heat-treatment temperature. It is notable that the emission intensity of both photoluminescence and radioluminescence for 0.1 mol% Pr³⁺ in the glass ceramic (GC665) are stronger than those in the precursor glass. The mechanism of enhanced luminescence is also discussed.     

Spectroscopic properties of Co2+: ZnAl2O4 nanocrystals in sol–gel derived glass–ceramics

Transparent glass–ceramics containing zinc–aluminum spinel (ZnAl₂O₄) nanocrystals doped with tetrahedrally coordinated Co²⁺ ions were obtained by the sol–gel method for the first time. The gels of composition SiO₂–Al₂O₃–ZnO–CoO were prepared at room temperature and heat-treated at temperature ranging 800–950 °C. When the gel samples were heated up to 900 °C, ZnAl₂O₄ nanocrystals were precipitated. Co²⁺ ions were located in tetrahedral sites in ZnAl₂O₄ nanocrystals. X-ray diffraction analysis shows that the crystallite sizes of ZnAl₂O₄ crystal become large with the heat-treatment temperature and time, and the crystallite diameter is in the range of 10–15 nm. The dependence of the absorption and emission spectra of the samples on heat-treatment temperature were presented. The difference in the luminescence between Co²⁺ doped glass–ceramic and Co²⁺ doped bulk crystal was analysed. The crystal field parameter D_q of 423 cm⁻¹ and the Racah parameters B of 773 cm⁻¹ and C of 3478.5 cm⁻¹ were calculated for tetrahedral Co²⁺ ions.     

Fluorescence lifetime and quantum efficiency for 5d → 4f transitions in Eu2+ doped chloride and fluoride crystals

An investigation of the relevant parameters for broadly tunable lasers utilizing the efficient, broad-band 5d → 4f emission in a number of Eu²⁺ doped metal fluorides, chlorides, and fluoro-chlorides has been performed. Results of measurements of absorption and emission spectra, quantum efficiencies, and fluorescence lifetimes in MF₂ and MCl₂ (M = Ca, Ba, Sr) and MFCl (M = Ba, Sr) are presented. A calculation of the pump energy threshold for laser action in CaF₂ : Eu²⁺ based on our spectroscopic data is made. Although the estimation indicated that laser threshold in CaF₂ : Eu can be easily achieved, strong excited-state absorption in this system was found to prohibit laser oscillation.     

Photon down-shifting by energy transfer from Sm3+ to Eu3+ ions in sol-gel SiO2-LaF3 nano-glass-ceramics for photovoltaics

95SiO₂?C5LaF₃ sol-gel derived nano-glass-ceramics single doped with Eu³⁺ or Sm³⁺ and codoped with both of them were successfully obtained. XRD measurements confirm the precipitation of LaF₃ nanocrystals after the ceramming process, with mean size ranging from 10 to 20?nm which increases with the thermal treatment temperature. The incorporation of rare-earth ions into precipitated LaF₃ nanocrystals was confirmed from luminescence spectra. Intense yellow-red emissions were detected under UV and blue light excitation in single and codoped samples. The effect of codoping with Eu³⁺ and Sm³⁺ ions and the energy transfer mechanism between them have been analyzed in order to increase the yellow-red emissions.     

Blue light emission from Eu ions in sol-gel-derived Al2O3-SiO2 glasses

Blue light-emitting glasses were successfully prepared by doping Eu²⁺ ions in the system Al₂O₃-SiO₂. The Al₂O₃-SiO₂ glasses doped with Eu³⁺ ions were synthesized using a sol-gel method, followed by heating in hydrogen gas atmosphere to reduce into the Eu²⁺ ions. The obtained glasses exhibited emission spectra with peak at ∼450 nm due to 4f⁶5d→4f⁷ (⁸S_7/2) transition, the intensities of which strongly changed depending on their glass composition and heating conditions. The emission quantum efficiency of 48% was achieved by heating the glass with the ratio of Al³⁺ to Eu³⁺ at about 6 at 1000 °C in hydrogen gas atmosphere. It was found that the Al₂O₃-SiO₂ glasses were appropriate not only for homogeneously doping the Eu³⁺ ions in glass structure but also reducing to Eu²⁺ ions, resulting in enhanced blue light-emission properties.     

Luminescence Properties of Dual Valence Eu Doped Nano-crystalline BaF2 Embedded Glass-ceramics and Observation of Eu2+ → Eu3+ Energy Transfer

Europium doped glass-ceramics containing BaF₂ nano-crystals have been prepared by using the controlled crystallization of melt-quenched glasses. X-ray diffraction and transmission electron microscopy have confirmed the presence of cubic BaF₂ nano-crystalline phase in glass matrix in the ceramized samples. Incorporation of rare earth ions into the formed crystalline phase having low phonon energy of 346 cm⁻¹ has been demonstrated from the emission spectra of Eu³⁺ ions showing the transitions from upper excitation states ⁵D_J (J = 1, 2, and 3) to ground states for the glass-ceramics samples. The presence of divalent europium ions in glass and glass-ceramics samples is confirmed from the dominant blue emission corresponding to its 5d-4f transition under an excitation of 300 nm. Increase in the reduction of trivalent europium (Eu³⁺) ions to divalent (Eu²⁺) with the extent of ceramization is explained by charge compensation model based on substitution defect mechanisms. Further, the phenomenon of energy transfer from Eu²⁺ to Eu³⁺ ion by radiative trapping or re-absorption is evidenced which increases with the degree of ceramization. For the first time, the reduction of Eu³⁺ to Eu²⁺ under normal air atmospheric condition has been observed in a BaF₂ containing oxyfluoride glass-ceramics system.