铈掺杂对BaFBr:Eu2+光激励发光性能的影响

采用一步反应法制备了BaFBr:Eu2+,Ce3+X射线影像存储材料.通过荧光光谱和光激励发光谱研究了材料的光致发光及其经X射线辐照后的光激励发光性质.结果发现,Ce离子的掺入使得BaFBr:Eu2+的发光性能明显增强,存在Ce3+离子向Eu2+离子的能量传递,Ce离子的掺杂浓度为0.7%(摩尔分数)左右时可得到较高的光致发光及光激励发光强度.且掺入Ce3+后,可以有效的形成能稳定存储的较低能级的电子陷阱,使得在信息读出过程中所需激励光能量降低,从而使得读出光的能量与价廉、便携的长波激光器的读出波长匹配得更好.     

CaAl12O19基质中Eu2+-Cr3+的能量传递与发光性质

在还原气氛下高温固相法合成了CaAl12O19:Eu2+,Cr3+荧光粉.样品光谱显示:Eu2+发射带与Cr3+吸收带有重叠,具备Eu2+-Cr3+之间发生能量传递必要条件.在290 nm近紫外光激发下,单掺杂Eu2+和Cr3+时样品均无691 nm发射,仅在Eu2+,Cr3+共掺时才出现691 nm发射,这证明Eu2+和Cr3+之间发生了能量传递,且监测691 nm时样品的激发光谱也证实了这一点.CaAl12O19:1%Eu2+,x%Cr3+样品组的发射光谱研究表明:增大x能提高Cr3+红光与Eu2+蓝紫光发射强度之比及Eu2+-Cr3+之间能量传递效率.CaAl12O19:2%Cr3+,x%Eu2+样品组的激发光谱分析表明:x>2时,Cr3+在415 nm处的吸收效率相对于565 nm有显著提高.还对样品CaAl12O19:1%Eu2+,1%Cr3+荧光寿命和能量传递速率进行了简单分析.     

Enhanced red light emission from LaBSiO5:Eu3+,R3+ (R=Bi or Sm) phosphors

Polycrystalline LaBSiO5:Eu3+,R3+ (R=Bi or Sm) phosphors have been synthesized by a facile sol-gel method. The phosphors have been characterized by thermogravimetric analysis/different scanning calorimeter, scanning electron microscopy, X-ray diffractometer and fluorescence measurements. It was found that the emission intensity of LaBSiO5:Eu phosphors increases clearly and reaches a maximum at 30 mol% with increasing of Eu3+ concentration. The incorporation of Bi3+ ions and/or Sm3+ ions have greatly enhanced the emission intensity of Eu3+ upon excitation with 391 nm light. The possible sensitization mechanisms of Sm3+ and/or Bi3+ on Eu3+ emission intensity have been investigated and discussed. The high brightness and short luminescence decay times make it promising red-emitting candidates for white light-emitting diodes.     

掺杂铕和铽的卤硼酸盐荧光体的制备及光谱特征

采用高温固相法在空气中合成了一系列掺杂稀土离子的卤硼酸盐荧光体, 研究了其发光性质和基质组成对稀土离子共掺杂的荧光体发光性质的影响. 研究结果表明, 在Eu3+和Tb3+共掺杂的体系中存在电子转移, 因此出现了Eu3+, Eu2+和 Tb3+共存于同一基质共同发射的现象. Ce3+对Eu2+和Tb3+具有敏化作用, 可增强其发射强度. 基质的组成对稀土离子的发射峰位和发射强度有明显影响.     

Vacuum Ultraviolet Excited Photoluminescence Properties of Y202S:Eu3+,Bi3+ Phosphor

As an Hg-free lamp using phosphor,the Bi3+ and Eu3+ co-doped Y2O2S phosphors were prepared and their luminescence properties under vacuum uitraviolet(VUV) excitation were investigated.The VUV photolumineseent intensity of Y2O2S:Eu3+ was weak,however,considerably stronger red emission at 626 nm with good color purity was observed in Y2O2S:Eu3+,Bi3+ systems.Investigation on the photoluminescence reveals that the strong VUV luminescence of Y2O2S:Eu3+,Bi3+ at 147 nm is mainly because the Bi3+ acts as a medium and effectively performs the energy transfer process: Y3+-O2→Bi3+→Eu3+,while the intense emission band at 172 nm is attributed to the absorption of the characteristic 1So-1P1 transition of Bi3+ and the direct energy transfer from Bi3+ to Eu3+.The Y2O2S:Eu3+,Bi3+ shows excellent VUV optical properties compared with the commercial (Y,Gd)BO3:Eu3+.Thus,the Y2O2S:Eu3+,Bi3+ can be a potential red VUV-excited candidate applied in Hg-free lamps for backlight of liquid crystal display.     

YF3:Eu3+纳米纤维/高分子复合纳米纤维的制备与表征

采用静电纺丝技术制备了Y2O3:Eu3+纳米纤维,使用NH4HF2为氟化剂,经双坩埚法氟化和脱氨后得到YF3:Eu3+纳米纤维,再采用静电纺丝技术制备了YF3:Eu3+纳米纤维/PVP复合纳米纤维. XRD分析表明,立方相的Y2O3:Eu3+氟化后,得到了正交相的YF3:Eu3+纳米纤维,空间群为Pnma;YF3:Eu3+纳米纤维/PVP复合纳米纤维具有明显的YF3:Eu3+的衍射峰. SEM分析表明,YF3:Eu3+纳米纤维与YF3:Eu3+纳米纤维/PVP复合纳米纤维的直径分别为91±11 nm、319±43 nm,表面光滑. 用Shapiro-Wilk方法检验,纤维直径属于正态分布. 荧光光谱分析表明,YF3:Eu3+纳米纤维和YF3:Eu3+纳米纤维/PVP复合纳米纤维的最强发射峰均位于588 nm和595 nm,属于Eu3+的5D0→7F1跃迁,表明Eu3+占据YF3基质中Y3+晶格点的C2对称格位. PVP对YF3:Eu3+发光峰位没有影响,但发光强度降低;YF3:Eu3+的含量与YF3:Eu3+纳米纤维/PVP复合纳米纤维的发光强度成线性关系.     

X-Ray storage luminescence of BaFCl:Eu2+ single crystals

Temperature behaviors of X-ray luminescence (XL), photoluminescence (PL), photostimulated luminescence, and thermoluminescence (TL) were studied in BaFCl:Eu2+ single crystals from room temperature to liquid nitrogen temperature. Six emissions at 275, 315, 365, 385, 435, and 500 nm were observed in the XL spectra and are attributed to Cl excitons, V(k)(Cl2-), the 4f65d1 (2e(g)) --> 4f7 (8S(7/2)) transition of Eu2+, and oxygen vacancies, respectively. Three emission peaks at 315, 365, and 390 nm were observed in the PL and TL measurements. These three emissions are from the transitions of 4f7(6I(7/2)) --> 4f7(8S(7/2)), 4f7(6P(7/2)) --> 4f7(8S(7/2)), and 4f65d1 (2e(g)) --> 4f7(8S(7/2)) of Eu2+, respectively. In our measurements, we observed that the emission of Eu2+ increases in intensity upon beta-irradiation and did not see any signals related to Eu3+ ions, which indicates that Eu2+ ions might not be oxidized to Eu3+ upon X-ray or beta-irradiation. Instead, the color centers, Cl excitons, and oxygen defects are created and are stable at room temperature, and they might play a key role in the storage luminescence.     

橙红色荧光粉BaZnP2O7∶Eu3+的制备与发光特性

采用高温固相法合成了BaZnP2O7∶Eu3+荧光粉, 并对其发光性质进行了研究.     

Luminescence properties and water coordination of Eu3+ in the binary solvent mixture water/1-butyl-3-methylimidazolium chloride

The effect of relative water content on the luminescence properties and speciation of Eu3+ ions in solutions of EuCl3 in the binary solvent mixture water/[BMI]Cl is presented, where [BMI]Cl is the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride. Using luminescence techniques, the binding properties of water to Eu3+ are determined for samples with mole ratios of water-to-IL ranging from 0 to 5. Very little water binds to Eu3+ at mole ratios of water-to-IL less than 1, above which binding increases rapidly with increasing water concentration. It is shown that only certain hydration numbers for Eu3+ complexes are stable in the water/IL solutions. The data presented suggest that the Eu3+ species present are [EuClx]3-x, [EuCly(H2O)3-4]3-y, [EuClz(H2O)6]3-z, and [Eu(H2O)8-9]3+ (where x > y > z). Comparison of the positions of the 5D0<--7F0 transitions of the Eu3+ complexes in IL solution with those of model crystal systems provides insight into the extent of Cl- complexation. This study suggests that [BMI]Cl is a promising medium for luminescent lanthanide (Ln) compounds due to the low-energy phonon environment of the [LnClx]3-x complex and to the fact that moderate water contamination does not result in direct binding of water to Ln3+, which would result in luminescence quenching.     

稀土掺杂氟化镁钾纳米晶的合成及其光谱特性

采用微乳液法合成了Eu²⁺,Ce³⁺单掺和双掺KMgF₃纳米晶,分析了样品的结构与形态. 结果表明,所合成的样品均为单相,颗粒粒度分布均匀. 讨论了光谱特性并与高温固相法合成的产物作了对比. 研究发现,在KMgF₃纳米晶双掺体系中,由于Eu²⁺和Ce³⁺竞争吸收激发能,只能观察到Ce³⁺的发射带; 而在KMgF3多晶共掺体系中,因为存在Ce³⁺→Eu²⁺能量传递过程,只能观察到Eu²⁺的发射峰.     

Vacuum Ultraviolet Excited Photoluminescence Properties of Y2O2S：Eu^3＋,Bi^3＋ Phosphor

As an Hg-free lamp using phosphor, the Bi3+ and Eu3+ co-doped Y2O2S phosphors were prepared and their luminescence properties under vacuum ultraviolet(VUV) excitation were investigated. The VUV photoluminescent intensity of Y2O2S:Eu3+ was weak, however, considerably stronger red emission at 626 nm with good color purity was observed in Y2O2S:Eu3+,Bi3+ systems. Investigation on the photoluminescence reveals that the strong VUV luminescence of Y2O2S:Eu3+,Bi3+ at 147 nm is mainly because the Bi3+ acts as a med...     

Preparation, characterization and photoluminescence properties of BaB2O4: Eu3+ red phosphor

A new red emitting BaB2O4: Eu3+ phosphor was synthesized by solid-state reaction method. X-ray powder diffraction (XRD) analysis confirmed the monoclinic formation of BaB2O4. Field-emission scanning electron-microscopy (FE-SEM) observation indicated that the microstructure of the phosphor consisted of irregular grains with heavy agglomerate phenomena. Upon excitation with 394 nm light, the BaB2O4: Eu3+ phosphor shows bright red emissions with the highest photoluminescence (PL) intensity at 611 nm due to 5D0→7F2 transitions of Eu3+ ions. The CIE chromaticity coordinates are calculated from the emission spectrum to be x=0.64, y=0.35. The effects of the Eu3+ concentration on the PL were investigated. The results showed that the optimum concentration of Eu3+ in BaB2O4 host is 6 mol% and the dipole-dipole interaction plays the major role in the mechanism of concentration quenching of Eu3+ in BaB2O4: Eu3+ phosphor. The effect of charge compensation on the emission intensity was also studied. The charge compensations of Li+, Na+ and K+ anions all increased the luminescent intensity of BaB2O4: Eu3+. K+ anion gave the best improvement to enhance the intensity of the emission, indicating K+ is the optimal charge compensator. All properties show that this phosphor could serve as a potential candidate for application as a red phosphor for NUV chip LED.     

SrMgB6O11:Eu3+纳米材料的水热法制备及发光性能研究

采用水热法制备了Eu3+掺杂SrMgB6O11纳米发光材料.利用X射线粉末衍射仪(XRD)、场发射扫描电子显微镜(FESEM)和荧光光谱对SrMgB6O11:Eu3+样品进行表征.结果表明:采用水热法可以成功地合成粒度均匀、结晶完好的SrMgB6O11:Eu3+纳米发光粉.深入研究了反应温度和pH值对SrMgB6O11:Eu3+纳米材料的晶体结构及形貌的影响.结果表明,在120℃时形成了尖锐且强度最强的衍射峰,同时FESEM也表明此时所得材料为纳米棒组成的规则扇形形貌,此后随着温度的升高,XRD图中衍射峰的位置和强度发生变化,说明荧光粉的晶体结构发生变化,FESEM也表明该荧光粉已变为球形颗粒.归属了发射光谱和激发光谱中各激发峰所对应的能级跃迁.荧光光谱也显示:反应温度和pH值影响着Eu3+在晶格中的对称性,且反应温度为120℃及pH值为9时,Eu3+在晶格中的对称性较好.另外,还初步探讨了纳米粒子的生长机制.     

Optical energy storage properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript>,R<Superscript>3+</Superscript> persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr₂MgSi₂O₇:Eu²⁺,R³⁺ materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr₂MgSi₂O₇:Eu²⁺,R³⁺ material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 °C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr₂MgSi₂O₇:Eu²⁺,R³⁺ materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R³⁺ co-dopants.     

Photoluminescence properties and analysis of spectral structure of Eu3+-doped SrY2O4

The aim of this work is to report on the luminescence properties of SrY2O4 activated by Eu3+ ion. Powder samples were prepared by solid-state reaction. X-ray diffraction powder data, photoluminescence, and high-resolution spectroscopy were carried out. Results revealed that the Eu3+ ions occupied three nonequivalent sites, with one at the Sr site, one at the Y(1) site, and another at the Y(2) site. Their spectra wavelengths for the 7F0-5D0 transition are located at 578.49, 581.86, and 580.63 nm, respectively. The corresponding charge-transfer transitions are located at 248, 257, and 270 nm, respectively, which are also confirmed by theoretical analysis.     

CaF_2微晶玻璃的一步法制备及Eu~(3+)离子探针特性

以组成为n(SiO_2)∶n(Al2O3)∶n(CaO)∶n(CaF_2)∶n(NaF)∶n(B_2O_3)=40∶20∶10∶10∶15∶5的微晶发光玻璃为基质,采用一步析晶法制备了CaF_2析晶相.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、X射线能量散射谱仪(EDS)和荧光分光光度计等对样品结构、组成及光谱性能进行分析,探讨了Eu3+掺杂浓度和析晶温度对微晶玻璃发光性能的影响.实验结果表明,在850℃下处理可获得分布均匀、粒径尺寸为200 nm的CaF_2析晶相,微晶玻璃的发光强度是基质玻璃的1.7倍.微晶玻璃的发射光谱在590,614,652和700 nm出现发射峰,分别对应Eu3+的5D0-7FJ(J=1,2,3,4)跃迁.通过对5D0-7F1和5D0-7F2跃迁强度的分析以及Judd-Ofelt理论参数Ω2值的计算可知Eu3+周围晶体场在析晶前后对称性发生变化.机理分析表明,析晶处理后Eu3+从高声子能量的Si-O环境进入低声子能量的Ca-F环境中,说明Eu3+可作为荧光探针研究微晶玻璃晶体结构的变化.     

Controlling electron trap depth to enhance optical properties of persistent luminescence nanoparticles for in vivo imaging

Focusing on the use of nanophosphors for in vivo imaging and diagnosis applications, we used thermally stimulated luminescence (TSL) measurements to study the influence of trivalent lanthanide Ln(3+) (Ln = Dy, Pr, Ce, Nd) electron traps on the optical properties of Mn(2+)-doped diopside-based persistent luminescence nanoparticles. This work reveals that Pr(3+) is the most suitable Ln(3+) electron trap in the diopside lattice, providing optimal trap depth for room temperature afterglow and resulting in the most intense luminescence decay curve after X-ray irradiation. This luminescence dependency toward the electron trap is maintained through additional doping with Eu(2+), allowing UV-light excitation, critical for bioimaging applications in living animals. We finally identify a novel composition (CaMgSi(2)O(6):Eu(2+),Mn(2+),Pr(3+)) for in vivo imaging, displaying a strong near-infrared afterglow centered on 685 nm, and present evidence that intravenous injection of such persistent luminescence nanoparticles in mice allows not only improved but highly sensitive detection through living tissues.     

Monodisperse and core-shell-structured SiO2@YBO3:Eu3+ spherical particles: synthesis and characterization

Y0.9Eu0.1BO3 phosphor layers were deposited on monodisperse SiO2 particles of different sizes (300, 570, 900, and 1200 nm) via a sol-gel process, resulting in the formation of core-shell-structured SiO2@Y0.9Eu0.1BO3 particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence (CL) spectra as well as lifetimes were employed to characterize the resulting composite particles. The results of XRD, FE-SEM, and TEM indicate that the 800 degrees C annealed sample consists of crystalline YBO3 shells and amorphous SiO2 cores, in spherical shape with a narrow size distribution. Under UV (240 nm) and VUV (172 nm) light or electron beam (1-6 kV) excitation, these particles show the characteristic 5D0-7F1-4 orange-red emission lines of Eu3+ with a quantum yield ranging from 36% (one-layer Y0.9Eu0.1BO3 on SiO2) to 54% (four-layer Y0.9Eu0.1BO3 on SiO2). The luminescence properties (emission intensity and color coordinates) of Eu3+ ions in the core-shell particles can be tuned by the coating number of Y0.9Eu0.1BO3 layers and SiO2 core particle size to some extent, pointing out the great potential for these particles applied in displaying and lightening fields.     

混合价态Eu(+2,+3)离子激活的单一组分发光材料:设计合成、发光性质及机理

作为绿色照明光源的典型代表,白光发光二极管(LED)被誉为21世纪的新一代照明光源。而作为白光LED重要组成部分的荧光粉,对其性能要求也不断被提升。Eu~(2+)和Eu~(3+)由于其电子结构上的差别导致其截然不同的发光性质。其中,Eu~(2+)的特征发射为4f–4f跃迁,而Eu~(3+)离子的特征发射为4f–5d跃迁。为了结合两者各自的发光特性,近年来对于混合价态Eu离子的研究成为热点。混合价态Eu离子掺杂荧光粉结合了Eu~(2+)和Eu3+离子各自的发光特点,具有颜色灵活可调的优良性质。本文主要从Eu~(2+)、Eu~(3+)各自性质出发,从不等价取代、晶场调控等三个方面综述了混合价态Eu(+2,+3)离子激活的单一基质发光材料近年来的研究进展。此外,对不同方法制备的混合价态Eu离子掺杂荧光粉的发光性能及发光机理也进行了归纳总结,为无机荧光材料的发展提供了新的思路。     

Enhanced luminescence of SiO2:Eu3+ by energy transfer from ZnO nanoparticles

ZnO nanoparticles embedded into SiO(2) by an ex situ method were shown to result in stable green emission with a peak at 510 nm compared to the normal peak at 495 nm from micron-sized ZnO powders. Green emission from ZnO nanoparticles was completely suppressed when they were embedded in SiO2 doped with Eu3+. Instead, the f-f emissions from Eu3+ were enhanced 5-10 times by energy transfer from the embedded ZnO nanoparticles to Eu3+. The Eu3+ luminescence increased as the Eu3+ concentration increased from 1 vs 5 mole % (for 10 mole % ZnO). In addition, the intensity increased as the embedded ZnO nanoparticles concentration increased up to 10 mole % (for 5 mole % Eu3+). The effects of phonon mediated energy transfer, quenching by activator interactions between Eu3+ ions, and energy back-transfer from Eu3+ ions to ZnO nanoparticles were discussed.