稀土配合物的配体PNIPAM塌缩诱导配位键断裂（英文）

通过一系列化学反应合成得到了Eu(ally-DBM)3-2TPPO和PNIPAM形成的大分子水溶性发光配合物.本文通过TGA、GPC、HNMR表征复合物的结构,并研究了配合物在水溶液中的荧光热响应性.研究发现,PNIPAM在低临界溶解温度以上塌缩引起配位键断裂,导致Eu~(3+)的荧光减弱和配体荧光增强.当温度降低时,发现Eu~(3+)的荧光增强,配体荧光相应减弱.推断当温度降低时配体再次与铕离子重新配位,并通过红外光谱进一步证实了.这种配合物的荧光热响应性具有可逆性,可用作分子探针应用在生物成像方面和研究PNIPAM塌缩.     

Eu(TTFA)3掺杂SiO2杂化胶体球的合成及特性

采用改进的碱催化法和种子法分别制得了稀土配合物Eu(TTFA)₃掺杂的SiO₂杂化胶体球,并用透射电子显微镜和荧光分光光度计对其显微形貌和荧光光谱特性进行了详细地研究.结果表明,两种方法都可以获得单分散性的、稀土配合物掺杂SiO₂杂化胶体球,且都具有Eu³⁺离子典型的荧光光谱特性.Eu(TTFA)₃掺杂入SiO₂胶体球中后,有机配体TTFA在短波长处的吸收明显增强了,最大的吸收峰位也向短波长方向移动大约20～30 nm,Eu³⁺离子5D0→7F2发射跃迁仍然具有良好的窄线发光特征,同时荧光峰值的形态和位置受SiO₂基体的影响发生轻微的变化.     

光谱探针法确定Eu3+:ThO2的格位对称性及选择激发下样品的光致发光研究

测量和分析了不同温度下Eu³⁺:ThO₂的激发光谱、发射光谱和荧光 衰减曲线.Eu³⁺:ThO₂晶体是用熔融法生长的.通过12K下格位选择激 发下的发射光谱测量,利用晶场理论,确定了Eu³⁺在ThO₂占据Oh和C_3v两种格位.列表给出了两种格位Eu³⁺离子的晶场能 级和室温及12K下的荧光寿命.讨论了温度对能     

超声喷雾共沉淀法制备的Lu3Al5O12∶Eu3+ 纳米粉体发光特性

采用新型超声喷雾共沉淀法技术,以Lu₂O₃、Eu₂O₃、Al(NO₃)₃·9H₂O为原料,制备了不同浓度Eu³⁺离子掺杂的Lu₃Al₅O₁₂纳米粉体.用X射线粉末衍射表征了获得纳米粉体的相,用扫描电镜观察了纳米粒子的形貌.测定了粉体的激发光谱、⁷F₀-⁵D₂声子边带谱与发射光谱.研究了不同高温烧结温度与Eu³⁺掺杂浓度对纳米粒子的发光强度与粒子形貌的影响规律.研究表明,当烧结温度高于900 ℃时,粉体发光强度明显增强,并且随着煅烧温度的增加,发光强度有所增强.Eu³⁺离子的最佳掺杂浓度为5~7 mol%.根据稀土离子Eu³⁺光学跃起矩阵元的特点,从发射光谱获得Eu³⁺光学跃起的J-O参量Ω₂与Ω₄.在Eu³⁺掺杂浓度均为5 mol%时,其强度参量达最小,电-声子耦合最强.然后随着掺杂浓度的进一步提高,强度参量略有增加,电-声子耦合减弱.说明Eu-O键强增加,共价性增强,Eu³⁺的局域环境对称性降低.Ω₂值低于Eu³⁺在玻璃与晶体基质中的情况,这是由于纳米粒子中存在着大量的缺陷以及晶体的结构畸变导致纳米粒子的对称性下降所致.     

掺杂浓度和烧结温度对CaWO4:Eu3+发光性能的影响

采用微乳液法合成掺杂浓度不同和烧结温度不同的CaWO₄:Eu³⁺系列荧光体, 这些荧光体都具有Eu³⁺离子的特征荧光发射. 在不同温度烧结后, 高浓度掺杂的样品(Eu³⁺掺杂30或50 mol%)可获得最大的发光强度, 低浓度掺杂的样品(掺杂0.5—2 mol%)在800 ℃烧结时也可获得优异的发光强度. 实验结果表明, Eu³⁺离子高浓度掺杂的CaWO₄:Eu³⁺在紫外光激发下可成为高效发光的荧光粉.     

节能灯用BaMgAl10O17:Eu2+,Mn2+荧光粉的劣化机理研究

对节能灯用BaMgAl₁₀O₁₇: Eu²⁺,Mn²⁺荧光粉的热劣化和紫外辐照劣化机理进行了对比研究. 发现热处理和紫外辐照处理均对BaMgAl₁₀O₁₇: Eu²⁺,Mn²⁺产生明显的发光劣化作用. 研究结果表明：热劣化主要涉及到Eu²⁺ 的氧化及其格位偏移, 而紫外辐照劣化与上述过程无关. 紫外辐照劣化主要源自高能紫外辐照使Eu²⁺ 处于更加不稳定的状态, 从而降低Eu²⁺ 的直接吸收和发射强度.     

BaZr(BO3)2:Eu的合成及发光性能研究

用硝酸盐热分解法成功制备了BaZr(BO₃)₂:Eu(Eu³⁺的掺杂量为摩尔分数5％)荧光材料，并研究了其在254及147nm光束激发下的发光特性.254nm光束激发下的发射主峰位于612nm处，归属于Eu³⁺的⁵D₀—⁷F₂的电偶极跃迁，但在147nm光束激发下的发射主峰位于592nm处，归属于Eu³⁺的相似文献   

NaGdF4:Eu3+和GdBaB9O16的VUV荧光性质

在真空紫外光激发下,六万结构的NaGdF₄:Eu³⁺中的Gd³⁺离子吸收一个光子,将能量分两步传递给Eu³⁺离子,发生红色双光子发射.立方结构的NaGdF₄:Eu³⁺中存在一定量的氧离子取代缺陷,使Gd³⁺离子4f-5d跃迁移到177nm附近,这与惰性气体放电产生的VUV光波长一致,并且其荧光色纯度较高.在VUV激发下,GdBaB₉O₁₆中的Gd³⁺离子发生双光子(紫外和红色或远红外)发射.     

Eu2+, Cr3+共掺杂的MAl12O19 (M=Ca, Sr, Ba) 的发光性质及能量传递

三基色荧光粉中, 红色荧光粉性能较差, 为获得性能优良的红色荧光粉, 本文采用高温固相法合成了Eu²⁺, Cr³⁺单掺杂及共掺杂的碱土金属多铝酸盐MAl₁₂O₁₉ (M =Ca, Sr, Ba) 发光体. 实验表明, 在以上三种基质中均存在Eu²⁺→Cr³⁺的能量传递, 利用能量传递可以有效将Eu²⁺的蓝光或绿光转换为红光. 三种碱土金属多铝酸盐基质的晶体结构相似,但Eu²⁺, Cr³⁺发光受晶体场影响,导致在不同的基质中Eu²⁺, Cr³⁺间能量传递效率不同.通过光谱分析及能量传递效率计算发现, 相同掺杂浓度下,CaAl₁₂O₁₉中Eu²⁺→Cr³⁺的能量传递效率最高,SrAl₁₂O₁₉次之, BaAl₁₂O₁₉最低.红光转换率在CaAl₁₂O₁₉中最高.     

La2Zr2O7:Eu3+纳米棒的合成、表征及其荧光性能

采用传统固相法和水热法成功地制备出棒状La₂Zr₂O₇:Eu³⁺荧光粉. 利用X射线粉末衍射仪、透射电镜和荧光光谱仪等分析了产物的结构、形貌和发光特性. 结果表明红色荧光粉La₂Zr₂O₇:Eu³⁺有良好的晶相,属于立方结构,空间点群为Fd3m; 其形貌主要为纳米棒, 平均直径约47 nm, 长度为50～700 nm. 并对纳米棒的生长机理进行了探讨. 在466 nm蓝光激发下,La₂Zr₂O₇:Eu³⁺荧光粉能发射出Eu³⁺的特征红色荧光,发射主峰位于616 nm处,归属于Eu³⁺的⁵DO_→⁷F2_{超灵敏电偶极跃迁.此外,在产物的发射光谱中能够观察到⁵D}1_→⁷FJ _{(J=0, 1, 2)跃迁和⁵D}1_→⁷FJ _{(J=1, 2, 4)跃迁的劈裂峰,这说明Eu³⁺处在低对称性的晶体场格位中.}     

Synthesis, characterization and fluorescence studies of a novel europium complex based sensor

A novel europium(III) complex was synthesized using TTA (α-thenoyltrifluoroacetone) as the first ligand and H₂bpdc (2,2′-bipyridine-3,3′-dicarboxylate) as the second ligand. Elemental analysis, thermal analysis, IR and UV–vis spectrum and fluorescence spectrum of the europium(III) complex were carried out. A characteristic Eu³⁺ fluorescence emission was observed in ethanol–water (1:1) solution, indicating that the complex is stable in solution and the emission of Eu(III) ions was not influenced by the water molecules. The fluorescence emission of the complex was quenched completely by the Co²⁺ and Fe³⁺ ions, but the quenched emission was recovered in the presence of glycine. Moreover, the Eu³⁺ emission was very sensitive to pH, so the complex can be used as pH-dependent fluorescence probe or chemosensors.     

Luminescent Properties of a Polymer Photoluminescent Composite Containing the Binuclear (EU,TB) Complex as an Emitter

Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu³⁺) to terbium (III) (Tb³⁺) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)₃Phen and Eu_0.5Tb_0.5(AA)₃Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)₃Phen and TCA/Eu_0.5Tb_0.5(AA)₃Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu_0.5Tb_0.5(AA)₃Phen composites the introduced Tb³⁺ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb³⁺ion→Eu³⁺ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu_0.5Tb_0.5(AA)₃Phen composites was noticeably stronger than that of the TCA/Eu(AA)₃Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu_0.5Tb_0.5(AA)₃Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.     

Ligand-sensitized fluorescence of Eu using naphthalene carboxylic acids as ligands

Fluorescence enhancement of Eu³⁺ in its complexes with 1-naphthoic acid (NA) and 2,6-naphthalenedicarboxylic acid (NDA) has been studied. These ligands enhance the fluorescence of Eu³⁺ by about two to three orders of magnitude. The fluorescence of Eu³⁺ in these complexes is further enhanced by more than two orders of magnitude when these complexes are treated with trioctylphosphineoxide (TOPO) and a surfactant. The enhancement due to TOPO is accompanied by an increase in the lifetimes of Eu³⁺ emission in these complexes, compared with the emission in uncomplexed Eu³⁺. The fluorescence of Eu³⁺ in the Eu³⁺-NDA-TOPO/surfactant complex is further enhanced by the addition of Tb³⁺, leading to the possibility of detecting Eu³⁺ at levels of 10⁻¹⁰ M. This ligand gives one of the best limits of detection for Eu³⁺ of all the carboxylic acid ligands that we have studied thus far.     

Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

Fluorescence properties of divalent and trivalent europium ions in CdWO4 single crystals grown by Bridgman method

Optical absorption, excitation, and fluorescence were investigated in Eu ion-doped CdWO₄ single crystal grown by a modified Bridgman method. The results indicate that Eu²⁺ and Eu³⁺ ions coexist in CdWO₄ crystal and an energy transfer occurs between these Eu²⁺ and Eu³⁺ ions. When the crystal is excited by 266-nm light, the energy corresponding to the 4f⁶5d to ⁸S_7/2 transition of Eu²⁺ ions results in the excitation of the Eu³⁺ ions to the ⁵D_J level. The effect on fluorescence of annealing in oxygen at various temperatures was investigated. The excitation intensity of Eu²⁺ ions at 266 nm decreases as annealing temperature increases from 300 K to 1073 K, but it remains at a certain equilibrium level when the annealing temperature is further increased.     

Calcination temperature optimization,energy transfer mechanism and fluorescence temperature dependence of KLa(MoO4)2:Eu3+ phosphors

The optimum calcination temperature for KLa(MoO₄)₂:Eu³⁺ phosphor was confirmed to be 1000 °C via checking the XRD patterns, SEM images and fluorescence spectra for the samples derived from solid state reaction. The energy transfer behavior between Eu³⁺ ions was studied. It was found that electric dipole–dipole interaction is responsible for the fluorescence quenching of ⁵D₂ and ⁵D₁ levels, but exchange interaction is in charge of ⁵D₀ fluorescence quenching. It was also observed that color coordinates of the studied phosphor can be tuned when the doping concentration is relatively low. The fluorescence thermal quenching process was investigated. It was found the thermal quenching followed well crossover model. Judd–Ofelt parameters of Eu³⁺ in KLa(MoO₄)₂ were obtained, and the optical transition properties were further discussed.     

Intermolecular energy transfer from UO2+2 to Eu3+ in solutions

The quenching constants for the UO²⁺₂ ion fluorescence by the Eu³⁺ ion in H₂O, D₂O, potassium formate and acetic acid media were determined by measuring the decrease in intensity of the 5050 Å fluorescence peak and the lifetime of the UO²⁺₂ ion fluorescence. The energy transferred to the Eu³⁺ ion was found to be a small fraction of the energy lost by the UO²⁺₂ ion by the non-radiative processes. The variations of the quenching constants of the UO²⁺₂ ion and the fluorescence lifetimes were determined for different concentrations of potassium formate and acetic acid. These results indicate that the UO²⁺₂ ion forms inner sphere complexes with the two ligands mentioned.     

A study of the luminescence properties of Eu -doped borate crystal and glass

Eu³⁺-doped La₂O₃-3B₂O₃ crystal and glass were prepared by solid state reaction under different calcination temperature. The emission spectrum, phonon sideband (PSB), charge transfer band (C.T.B.) and lifetime of the Eu³⁺ ion in the two materials, with the same composition but with different phase, were investigated. With excitation at 394 nm light, the glass presented intense 618 nm red luminescence; however, the crystal gave 696 nm red luminescence. This difference is ascribed to the discrepancy of the local structure around the Eu³⁺ ion in the crystal and glass. To clarify the discrepancy, the coordination of Eu³⁺ in the borate glass and crystal was investigated. The results show that Eu³⁺ ions formed a complex Eu³⁺-O²⁻-B³⁺ bond in glass; however, in the crystal, it formed a complex Eu³⁺-O²⁻-La³⁺ bond. The lifetime of Eu³⁺ ions in the crystal and the glass is 3.08 ms and 1.98 ms, respectively. This indicates that the discrepancy in the local structure around the Eu³⁺ ions between the crystal and the glass leads to different fluorescence properties.     

Radiative and Nonradiative Transitions of Eu3+ in Binary Solvent Systems

The fluorescence efficiency of the rare-earth ions in solution increases upon deuteration of the solvent^(1–3) and is dependent upon the presence in the solvent molecule of such groups as etc. Lower fluorescence quantum yields observed for Eu³⁺ and Tb³⁺ in protic solvents were accounted for, at least qualitatively, by electronic excitation energy transfer from the excited rare-earth ion to some of the vibrational modes in the solvent molecule. The fluorescence quantum yield of Dy³⁺ in solution is also lower in the presence of groups.⁽⁷⁾ Furthermore, significant fluorescence enhancement and long fluorescence lifetimes were observed for both Sm³⁺ and Eu³⁺ in such aprotic solvents as POCl₃:SnCl₄, POCl₃:ZrCl₄ and POCl₃:TiCl₄, where both the fluorescence intensities and lifetimes were enhanced by a factor of 1000 and 300, respectively, relative to those in aqueous solutions.^(8,9) The fluorescence efficiency of Sm³⁺ and Eu³⁺ was also found to depend upon the composition of the primary solvation sphere of the ion.^(8,9) The low fluorescence quenching efficiency of these aprotic solvents was further emphasized by the observation of fluorescence emission arising from the ⁵D₃-state of Tb³⁺ in POCl₃:SnCl₄.⁽¹⁰⁾ The significance of the composition of the solvent and its effect upon the pertinent transition probabilities were also demonstrated in solutions of Eu³⁺ in DMSO.^(6,11) Results obtained in spectroscopic studies of Eu³⁺ in binary solvent systems in which only one of the components is the solvating species will be reported here.     

Structural and spectroscopic studies of Lu2O3/Eu nanocrystallites embedded in SiO2 sol-gel ceramics

Preparation and optical properties of Lu₂O₃/Eu³⁺ nanocrystals embedded in silica gel glass are described. The structure of the obtained ceramics was determined by XRD and transmission electron microscopy. It was found that with increasing sintering temperature the Lu₂O₃/Eu³⁺ nanocrystallites underwent transformation into monoclinic Lu₂Si₂O₇ nanocrystallites. The fluorescence properties were investigated as a function of thermal treatment of the samples. It was found that after sintering at 1250 °C the fluorescence lifetime increased to 1.5 ms at room temperature. The material studied in this work exhibits a very high intensity of fluorescence with potentials for display application.