镱铕共掺硅酸盐玻璃光致发光谱及上转换分析

用烧结法制备了镱铕共掺硅酸盐玻璃系列样品.测量了样品在978nm半导体激光器泵浦时光致发光谱,讨论了上转换机制.结果表明:随着镱、铕离子浓度的增加,铕在694nm红光波段光谱强度增强.镱铕离子之间能量传递主要通过合作上转换完成.     

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd₂O₃:Eu³⁺ (4 mol%) co-doped with Bi³⁺ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800°C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV–Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer’s method and Williamson–Hall plots and are found to be in the ranges 40–60 nm and 30–80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at ～590, 612 and 625 nm, which are due to the transitions ⁵D₀→⁷F₀, ⁵D₀→⁷F₂ and ⁵D₀→⁷F₃ of Eu³⁺, respectively. It is observed that a significant quenching of Eu³⁺ emission was observed under 230 nm excitation when Bi³⁺ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu³⁺ ions was enhanced by incorporation of Bi³⁺ (5 mol%) ions. The introduction of Bi³⁺ ions broadened the excitation band of Eu³⁺ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s²→6s6p transition of Bi³⁺ ions, implying a very efficient energy transfer from Bi³⁺ ions to Eu³⁺ ions. The gamma radiation response of Gd₂O₃:Eu³⁺ exhibited a dosimetrically useful glow peak at 380°C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd₂O₃:Eu³⁺, Bi³⁺ phosphors have promising applications in solid-state lighting.     

Photoluminescence properties and energy transfer of Ca3WO6:Sm3+ co-doped Eu3+

A reddish-orange phosphor, Ca₃WO₆:Sm³⁺, was synthesized by the convenient solid-state reaction method and characterized by X-ray diffraction (XRD). Photoluminescence properties and concentration quenching of Ca₃WO₆:Sm³⁺ phosphor have been discussed in the excitation and emission spectra. Ca₃WO₆:Sm³⁺ phosphor is able to generate a strong excitation peak, which matches the emission wavelength from near-UV LEDs. Energy transfer from Sm³⁺ to Eu³⁺ in Ca₃WO₆ host is observed and investigated in detail. The chromaticity coordinates of Ca₃WO₆:Sm³⁺ can be regulated to approach the NTSC standard values of red phosphor by codoping Eu³⁺ ions. The photoluminescence properties suggest that novel Ca₃WO₆:Sm³⁺, Eu³⁺ phosphor might have a potential application for near-UV LEDs.     

Preparation and photoluminescence properties of the Eu2+, Sm3+ co-doped Li2SrSiO4 phosphors

A series of Eu²⁺ and Sm³⁺ co-doped Li₂SrSiO₄ phosphors are prepared by the high temperature solid-state reaction. The morphology, structure and spectroscopic properties of the prepared samples are characterized by scanning electron microscopy, X-ray diffraction, diffuse reflection spectra, photoluminescence spectra and electron paramagnetic resonance spectra, respectively. The effect of Sm³⁺ doping concentration on the photoluminescence intensity of the prepared samples is also investigated. The results indicate that the crystal structure of Li₂SrSiO₄ is not changed with the Eu²⁺, Sm³⁺ co-doping. The spherical-like particle size of the obtained product is about 20–30 nm in diameter. When the Sm³⁺ concentration is 0.3 mol% and the Eu²⁺ concentration is 0.7 mol%, the phosphors show the maximum emission intensity, which is 50% higher than that of Eu²⁺ doped Li₂SrSiO₄. Excited at 420 nm, the phosphor presents a single broad emission band peaking at 558 nm, which is ascribed to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ and ⁴G_5/2 → ⁶H_5/2 and ⁴G_5/2 → ⁶H_7/2 transitions of Sm³⁺. The Commission International de I′Eclairage chromaticity coordinates of Li₂SrSiO₄:0.7 mol% Eu²⁺, 0.3 mol% Sm³⁺ are x = 0.28, y = 0.28.     

Luminescence studies of thallium co-doped KBr:Eu2+ powder phosphors

In this study, photoluminescence (PL) and photostimulated luminescence (PSL) properties in KBr:Eu²⁺, Tl⁺ powder phosphors are reported. PL emission spectra of these Tl⁺ co-doped KBr:Eu²⁺ phosphors show four overlapping bands around 310, 325, 360 and 375 nm in addition to the characteristic of Eu²⁺ ions at 420 nm. These additional short wavelength bands were attributed to centres involving Tl⁺ ions. The decrease in PSL intensity of γ-irradiated KBr:Eu²⁺, Tl⁺ powder phosphors with Tl⁺ concentration and the absence of thallium emission bands in PSL were attributed to the efficient electron trapping by Tl⁺ ions during irradiation.     

纳米Gd2O3中两种格位Eu3+的电荷迁移态激发跃迁

观测了粒径分别为15,23,135m的立方相Gd2O3：Eu^3 的选择激发光谱、发射光谱和激发光谱。受强量子限域效应的影响,纳米Gd2O3：Eu^3 的激发光谱的强度表现出对颗粒尺寸的明显依赖性。用Jorgensen公式计算电荷迁移带的位置,与实验测得激发光谱中位置相一致。通过电荷迁移带不同位置的选择激发光谱可以分辨出立方相Gd2O3：Eu^3 中C2和S6格位Eu^3 的发光,从选择激发的发射光谱和激发光谱结果计算出C2和S6格位电荷迁移带的激发光谱,与实验结果相符合。     

用于白光LED的单一基质白光荧光粉Ca2SiO3Cl2:Eu2+,Mn2+的发光性质

用高温固相法合成了Eu2+,Mn2+共激活的Ca2SiO3Cl2高亮度白色发光材料,并对其发光性质进行了研究.该荧光粉在近紫外光激发下发出强的白色荧光,Eu2+中心形成峰值为419 nm和498 nm的特征宽带,通过Eu2+中心向Mn2+中心的能量传递导致了峰值为578 nm的发射,三个谱带叠加从而在单一基质中得到了白光.激发光谱均分布在250-415 nm的波长范围,红绿蓝三个发射带的激发谱峰值分别位于385 nm,412 nm,370 nm和396 nm处,可以被InGaN管芯产生的紫外辐射有效激发.Ca2SiO3Cl2:Eu2+,Mn2+是一种很有前途的单一基质白光LED荧光粉.     

Synthesis,characterization and photoluminescence of Eu3+, Ce3+ co-doped CaLaAl3O7 phosphors

Powder phosphors of CaLa_{1? x} Eu _x Al₃O₇, CaLa_{1? x} Ce _x Al₃O₇ and CaLa_{0.99? x} Eu _x Ce_0.01Al₃O₇, where x = 0.01, 0.03, 0.05 and 0.07, were prepared by a combustion method. The powders were well characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence techniques. Emission spectra of Eu³⁺-doped powder phosphors showed strong red emission at 613 nm (⁵D₀ → ⁷F₂); no concentration quenching was observed. Generally, Ce³⁺ acts as an efficient sensitizer when doped with other trivalent lanthanide ions. However, interestingly, in the CaLaAl₃O₇ powder phosphors, the addition of Ce³⁺ with Eu³⁺ exhibited an adverse effect–decreased photoluminescence intensity. The reasons for this behavior are discussed.     

Energy transfer between Eu3+ ions in a lattice with two different crystallographic sites: Y2O3:Eu3+, Gd2O3:Eu3+ and Eu2O3

The Eu³⁺ ion occupies two different crystallographic sites in (Y_1−xEu_x)₂O₃ and (Gd_1−xEu_x)₂O₃, with site symmetry S₆ and C₂. Energy transfer over more than 7 Å occurs from Eu³⁺ (S₆) ions to Eu³⁺ (C₂) ions. This is shown to be a direct one-phonon assisted process, in combination with a one-site resonant two-phonon assisted process at higher temperatures. For x = 1 there is energy migration over the Eu³⁺ (C₂) sublattice to quenching impurities. The presence of cooperative absorption points to superexchange interaction between the Eu³⁺ ions.     

Optical absorption and emission from irradiated RbMgF3:Eu2+ and KMgF3:Eu2+

The optical properties of irradiated RbMgF₃:Eu²⁺ and KMgF₃:Eu²⁺ have been investigated. Previous research has shown that Eu²⁺ ions in unirradiated RbMgF₃ give rise to broad band absorption around 250 nm and sharp intense line emission at 360 nm. When this material is irradiated little or no change occurs in the 250 nm absorption, but the lifetime of the Eu²⁺ 360 nm transition is reduced. In addition, new emission is observed at 680 nm. In the case of irradiated KMgF₃:Eu²⁺ two new emission bands are observed at 600 and 800 nm. All of these transitions have short lifetimes and are not due to Eu³⁺ ions.     

Eu2+在磷酸镧中的发光及Ce3+→Eu2+的能量传递

采用高温固相反应合成了LaPO₄:Eu²⁺和LaPO₄:Ce³⁺,Eu²⁺样品,报道了Eu²⁺在LaPO₄中的发光性质和Ce³⁺→Eu²⁺的能量传递现象。文中探讨了Ce³⁺→Eu²⁺的能量传递机理,根据Dexter电多极相互作用的理论证明其为偶极子偶极子相互作用的共振能量传递。     

Eu3+ luminescence and Gd3+-Eu3+ energy transfer in K5Li2GdF10:Eu3+

Polycrystalline samples of europium-doped K₅Li₂GdF₁₀ have been obtained by a slow cooling of melted compound and investigated using spectroscopy methods. Luminescence from the ⁵ D ₂ level of Eu³⁺ is found to be weak. Intense visible emission upon excitation into the ⁵ D ₂ or higher energy levels has been attributed to overlapping transitions from long-lived ⁵ D ₁ and ⁵ D ₀ levels. A strong increase of the ⁵ D ₀ emission at the expense of the ⁵ D ₁ emission occurs between 5 K and 25 K without significant change of the ⁵ D ₁ lifetime. To account for this, it is supposed that both the radiative and the nonradiative transition rates are temperature-dependent. Efficient energy transfer from the ⁶ G _J levels of Gd³⁺ to Eu³⁺ ions has been evidenced by excitation spectra in the VUV region and VUV-excited luminescence. It has been concluded that the cross relaxation contributes to the energy-transfer process. Received: 8 May 2001 / Accepted: 11 May 2001 / Published online: 25 July 2001     

KMgF3:Eu2+晶体中Eu2+的受激发射研究

二价铕离子(Eu2 )在KMgF3晶体中产生窄带线状发射,峰值位于360 nm.依据自身建立的激发态能量损耗模型,预测了4f7(6P7/2)→4f7(8S7/2)跃迁实现受激发射的可能性.采用ASE技术测得了KMgF3:Eu2 晶体360 nm发射的光学增益,得到净光学增益系数g=(11.4±3.2)cm-1,实验证实了理论预测.晶体退火或掺杂敏化离子Gd3 或Ce3 可以改善Eu2 的增益效果.     

Hydrothermal-assisted ion exchange synthesis and photoluminescence of Li+ and Eu3+ co-doped NaLa(WO4)2 as near-UV type red phosphors

A series of Li⁺ and Eu³⁺ co-doped double tungstate NaLa(WO₄)₂ (NLW) red phosphors have been successfully synthesized by an ion exchange method under a hydrothermal condition. The effects of Li⁺ doping concentration on the crystal structure, morphology and photoluminescence properties were investigated using the XRD, TEM and photoluminescence (PL) measurements. The results reveal that the samples have phase-pure scheelite structure and adopt spherical particle morphology. Furthermore, room temperature PL spectrum shows that the optical brightness is highly dependent on the concentration of doping Li⁺, which is determined by ion exchange duration and the precursor concentration of LiNO₃. As 5% Li⁺ ions was introduced into the crystal lattice, the emission intensity was enhanced by more than 10-fold as compared with the pristine one. Moreover, the co-doping of Li⁺ can substantially improve the effective excitation of the NaLa(WO₄)₂:Eu³⁺ phosphors under near-UV region.     

Cathodoluminescence of Eu2+ in EuGa2S4 and Ga2S3:Eu2O3

We present the results of an investigation of the cathodoluminescence of the Eu²⁺ ion in gallium chalcogenides (Ga₂S₃) and europium thiogallate (EuGa₂S₄). We show that the intense wide-band radiation of these compounds is due to the 4f-5d transitions of the Eu²⁺ ions. With increase in the Eu²⁺ percent composition from 0.1 to 5.0 mol.% the luminescence brightness increases and then decreases. Translated from Zhurnal Prikladnoi Spektrskopii, Vol. 67, No. 2, pp. 268–270, March–April, 2000.     

基于 Eu~(3 +)还原制备 Eu~(3 +)-Eu~(2 +)共存发光材料的研究进展

稀土Eu元素因其优良的光学特性常被作为激活离子广泛应用于无机发光材料中。激活离子的发光性质由自身的价态决定,同时受基质晶体结构影响。不同价态的Eu离子呈现不同的光学特性,当二者共存时有可能得到单一基质的白光。本文主要综述近几年Eu~(3+)-Eu~(2+)共存于铝酸盐、磷酸盐、硅酸盐及硼酸盐基质中的荧光性能、Eu~(3+)的还原条件及还原机理。     

Photoluminescence characteristics and energy transfer between Bi3+ and Eu3+ in Gd2O3: Eu3+, Bi3+ nanophosphors

Bi³⁺ and Eu³⁺ codoped cubic Gd₂O₃ nanocrystals were prepared by the Pechini sol-gel method. Their photoluminescent properties were investigated under ultraviolet light excitation. The introduction of Bi³⁺ ions broadened the excitation band of Eu³⁺ emission, of which a new strong band occurred ranging from 320 to 380 nm due to the 6s²→6s6p transition of Bi³⁺ ions, implying a very efficient energy transfer from Bi³⁺ ions to Eu³⁺ ions. Upon 325 and 355 nm light excitation, the luminescent intensity of Eu³⁺ ions was remarkably improved by the incorporation of Bi³⁺ ions. But a significant quenching of Eu³⁺ emission was observed under 266 nm light excitation when Bi³⁺ was codoped. The possible energy transfer processes between Bi³⁺ and Eu³⁺ were discussed. The decay curves of Eu³⁺ emission under the excitation of 266 nm pulsed laser were measured and gave further evidence for our discussion.     

Yb3+,Er3+掺杂的SrAl2O4:Eu2+,Dy3+长余辉材料的发光特性

根据Dorenbos能级模型的推论,利用掺杂Yb3+和Er3+对典型的长余辉材料SrAl2O4:Eu2+,Dy3+(简称SAO:ED)的发光特性(发光强度和余辉时间)进行调制.在发光特性分析中,发展并使用了一种简便易行的解析模型,而不是常用的多项e指数衰减函数的经验模型.研究发现,正如Dorenbos所预言的,Yb+3掺杂确实能够提高SAO:ED的发光强度;但进一步研究发现,Yb3+不完全是发光中心,而是一种辅助激发中心.Er3+掺杂效果也和Dorenbos的预言相同,即它是一种俘获中心;但是当Er3+和Yb3+共掺杂时,Er3+却有一种脱俘作用,使得初始发光强度增强,衰减常数变小,但蓄光能力变化不大.