白光LED用LiBaBO3:Eu2+材料发光特性研究

采用高温固相法制备了LiBaBO₃:Eu²⁺绿色发光材料.测量了Eu²⁺浓度为1mol%时样品的激发与发射光谱,其发射光谱为双峰宽谱,主峰分别为482和507nm,与理论计算值符合很好;监测482nm发射峰时,对应激发光谱的峰值为287和365nm,监测507nm发射峰时,对应的激发峰为365和405nm.研究了Eu²⁺浓度对材料发射光谱的影响,结果显示,随Eu²⁺浓度的增大,蓝、绿发射峰均发生了     

YBO3:Eu3+纳米晶发光特性

用水热法制备了YBO₃:Eu³⁺纳米材料，通过改变其反应条件对纳米颗粒的大小和形貌进行了控制，对其发射光谱进行分析并与体材料进行了比较.在纳米材料中，很大比例的稀土离子微观环境受到表面的影响.这种影响可能使稀土离子的Judd-Ofelt参数Ω₂增大，从而使Eu³⁺的⁵D₀→⁷F₂的发射加强，红色发光材料的色纯度提高.     

掺Bi离子锗铌酸盐红外发光玻璃的研究

用高温熔融法制备了Bi₂O₃掺杂的(0.9-x) GeO₂-xNb₂O₅-0.1BaO (含量x为摩尔分数, x=0, 0.04, 0.07, 0.1)系列玻璃. 测定了玻璃样品的差热分析(DTA)曲线、吸收光谱、发射光谱及X射线光电子能谱(XPS). 从DTA曲线分析得到玻璃的结晶起始温度与软化温度之差(T_x-T_g)达200℃以上. 吸收光谱中可观察到位于500, 700, 808和1000 nm处的吸收峰, 并随着Nb₂O₅含量x的增加吸收边带发生红移. 在波长为808 nm激光激发下, 观察到发光中心位于1300 nm处、荧光光谱半高宽约为200 nm的宽带发光. 荧光强度随Bi₂O₃掺杂量δ的增加先增强后减弱, 当掺杂量δ达到约0.01时, 荧光强度达到最强. 随着Nb₂O₅含量x从0.04增加到0.1时, 荧光强度逐步减弱. 样品的XPS峰分别位于159.6和164.7 eV, 它们介于Bi³⁺与Bi⁵⁺的特征结合能之间, 因此Bi³⁺与Bi⁵⁺可能同时存在于玻璃基质中. 从XPS及Bi离子的发光特性推断, 宽带的荧光发射可能起因于Bi⁵⁺. 随着Nb₂O₅含量x的增加, 荧光强度逐步减弱. 分析认为, Nb₂O₅取代GeO₂后形成了NbGe缺陷, 需要低价Bi离子进行电子补偿, 因而抑制了Bi⁵⁺形成, 致使荧光强度减弱.     

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.     

Eu3+掺杂CaWO4红色荧光粉发光性质的浓度依赖关系研究

采用共沉淀法制备了不同Eu³⁺掺杂浓度的CaWO₄荧光粉材料.通过X射线衍射和场发射扫描电镜技术对样品的结构和形貌进行了表征.测量了各样品的激发光谱、发射光谱和荧光衰减曲线, 计算了各样品的部分Judd-Oflet (J-O)参数和^5D_0 (Eu³⁺)能级量子效率,以及荧光粉的色坐标, 讨论了样品电荷迁移带相对强度、J-O参数、量子效率与掺杂浓度的依赖关系.对Eu³⁺掺杂的CaWO₄ 发光材料的光致发光性质的研究表明,在CaWO₄: Eu³⁺中⁵D₀→⁷F₂跃迁的616~nm 红色发光能被394.5~nm和465~nm的激发光有效激发,具有近紫外(或蓝光)激发效率高和猝灭浓度大的优点, 有潜力成为高效的近紫外(或蓝光)激发白光发光二极管用红色荧光粉材料.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(t=2, 4, 6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

掺Bi的GeO2-Al2O3-Na2O玻璃的热学和光学性质

 用高温熔融法制备了96GeO-(3-χ)Al₂O₃-χNa₂O-1NaBiO₃ （将χ分别为0，0.5，1.5的玻璃命名为A1，A2，A3）和 96GeO-(3.5-ψ)Al₂O₃-ψχNa₂O-0.5Bi₂O₃（将ψ分别为0，0.5，2的玻璃命名为B1，B2，B3）玻璃。观察到样品在1 220 nm处（800 nm 激光二极管激发）的超宽带发光特性（半高宽约250 nm）。结果表明，以NaBiO₃形式引入Bi⁵⁺到玻璃原料中比以Bi₂O₃形式引入Bi³⁺到原料中得到的玻璃在1 220 nm处的发光强度大4.6倍，且荧光寿命和荧光半高宽也分别从280 μs和195 nm增加到了434 μs和275 nm。从A3，A2和A1的吸收边带的红移可初步推断出A3，A2及A1玻璃中Bi5+的含量逐步增加。总结吸收光谱与发射光谱的变化规律，认为Bi离子近红外高发射强度和宽荧光半高宽是由Bi⁵⁺的发光引起的。在两组玻璃中，热稳定性以及荧光发射截面积与荧光寿命的乘积值和荧光发射截面积与荧光半高宽的乘积值随着Na₂O含量的增加而增加。     

Tm3+掺杂锗酸盐玻璃材料上转换发光的研究

测量了50GeO₂-40PbF₂-9.9WO₃-0.1Tm₂O₃玻璃材料的Raman光谱。确定了Tm³⁺离子在这种材料中¹G₄上转换发射的有效激发波长为650nm,并且观测了在650nm激发下Tm³⁺的¹G₄上转换发光及其斜率效率。采用ASE(Amplified Spontaneous Emission)技术测量了⁴G₄上转换发射的光学增益系数。     

Tm3+/Yb3+共掺氧卤碲酸盐玻璃上转换发光研究

研究了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光光谱，分析了Tm₂O₃含量对Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃上转换发光的影响机理.结果表明：在Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光中，Tm³⁺存在较强的浓度猝灭效应.随Tm₂O₃含量增加，Tm³⁺的上转换蓝光和红光强度先增加，后降低，在0.1mol% Tm₂O₃达到最大.该结果有助于进一步提高Tm³⁺的上转换发光效率.     

退火温度对ZrO2纳米材料中Eu3+离子发光的影响

研究了退火温度对ZrO₂纳米材料中Eu³⁺离子发光性质的影响. 材料的结构、晶粒尺寸和形状以及晶格的排列分别由XRD，TEM表征. 结果表明：用共沉淀法制备的ZrO₂纳米材料具有不随退火温度变化、稳定的四方结构；材料的晶粒尺寸随退火温度的提高而增大；晶格的排列由无序逐渐变为有序；发射光谱表明其主要发射在595 nm和604 nm处；在394 nm的紫外光辐照下得到了不同样品的604 nm荧光发射强度的变化不同. 这种现象与样品中O^2-离子含量和样品表面的表面缺陷有关；另外，电荷迁移带随退火温度的变化而变化.     

Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline

A multi-functional ligand, 5-acryloxyethoxymethyl-8-hydroxyquinoline (Hamq), was synthesized, which contained a polymerizable C=C double bond for the copolymerization with other vinyl monomers and acted as photon antenna able to transfer energy to Eu³⁺ ions effectively. The triplet state energy of Hamq was determined to be 22,370 cm⁻¹ via the phosphorescence spectra of Hamq and its gadolinium complex. The title complex monomer Eu(tta)₂(amq) was prepared by coordination reaction of Hamq with europium isopropoxide and 2-thenoyltrifluoroacetone (Htta) in dry organic solvents under argon atmosphere and characterized by elemental analysis and IR spectrum. The photophysical properties of the complex were studied in detail with UV-vis, luminescence spectra, luminescence lifetime and quantum yield. The complex exhibited nearly monochromatic red emission at 612 nm, a remarkable luminescence quantum yield at room temperature (30.6%) upon ligand excitation and a long ⁵D₀ lifetime (389 μs), which indicated that the ligand Hamq could sensitize the luminescence of Eu(III) ion efficiently in Eu(tta)₂(amq), resulting in a strong luminescence of its copolymer poly[MMA-co-Eu(TTA)₂(amq)] under UV excitation. The excellent luminescence properties of the complex made it not only a promising light-conversion molecular device but also an excellent luminescent monomer.     

Ln(III)-cored complexes based on 2-thenoyltrifluoroacetone ligand for near infrared emission: Energy transfer pathway and transient absorption behavior

Lanthanide(III)-cored complexes based on 2-thenoyltrifluoroacetone (TTA) ligand for near infrared (NIR) emission have been developed to investigate the energy transfer pathway from the antenna ligand to the Ln³⁺ ion. Their photophysical studies indicate the sensitization of Ln³⁺ luminescence by energy transfer through the excited triplet state of β-diketone ligand. Nanosecond (ns) transient absorption behavior of Ln³⁺-[TTA]₃(terpy) complexes at room temperature is explored. The triplet-triplet absorption spectrum for Gd³⁺-[TTA]₃(terpy) is observed under degassed condition, whereas it is hardly observed in Er³⁺-[TTA]₃(terpy) complex. The sensitizing process in Er³⁺-[TTA]₃(terpy), through the triplet state of TTA ligand to Er³⁺ ion, is also independent on the presence of oxygen. It indicates that the energy transfer rate through the excited triplet state of β-diketone ligand to Er³⁺ ion occurs approximately faster than that of the oxygen quenching rate.     

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.     

Preparation, Crystal Structures and Luminescent Properties of Terbium and Europium Complexes with a New Amino-Alkenone Type Ligand

Solid complexes of terbium and europium nitrates with an amino-alkenone type ligand, 1-[2-(6-methylpyridin-2-ylamino)-5,6-dihydro-4H-pyran-3-yl]ethanone (L) have been prepared and characterized by elemental analysis, conductivity measurements, and IR spectra. The crystal and molecular structures of the complexes [TbL₂(NO₃)₃(H₂O)]·CHCl₃ (1) and [EuL₂(NO₃)₃(H₂O)]·CH₃CO₂C₂H₅ (2) have been determined by single crystal X-ray diffraction. And the coordination spheres of the complexes are similar. At the same time, the luminescent properties of the Tb³⁺ complex in solid state and in solvents were investigated at room temperature. Under the excitation of UV light, Tb(III) complex exhibited characteristic emissions but not for the Eu(III) complex. The lowest triplet state energy level of the ligand in the complex matches better to the resonance level of Tb(III) than Eu(III) ion.     

Luminescent europium(III) and terbium(III) nicotinate complexes covalently linked to a 1,10-phenanthroline functionalised sol-gel glass

Sol-gel glasses with covalently linked lanthanide complexes are luminescent materials which can be processed at ambient temperatures, which have a good solubility and uniform distribution of the complexes in the host matrix. In this study, a luminescent terbium(III) complex was covalently coupled to an organic-inorganic hybrid material prepared by the sol-gel process. This was realised by use of nicotinate groups as the ligands for the terbium(III) ion. The [Tb(C₅H₄NCO₂)₃(phen)(H₂O)₂] complex was immobilised on the sol-gel glass matrix and showed a green photoluminescence upon irradiation with ultraviolet light. The nicotinate groups act as an antenna to absorb the incident light and channel the excitation energy to the terbium(III) ion. The sol-gel glass was also prepared for the corresponding europium(III) complex. In this case, excitation of the europium(III) ion was possible via both the nicotinate ligands and the 1,10-phenanthroline ligands. High-resolution luminescence and excitation spectra were recorded and the radiative lifetimes were measured.     

Sensitivized photoluminescence of manganese in calcium sulfate phosphors

Although the sensitivization mechanism of the excitation of manganese in calcium sulfate phosphors is considered to be the most probable [1] it has not been sufficiently confirmed by direct luminescence measurements, and in certain cases, the results of these measurements contradict each other. In [4] the sensitivizing action of the WO ₄ ^?2 group on the luminescence of the Mn²⁺ ion was established for mixed phosphors based on calcium sulfate and tungstenate, but this effect was not studied in detail. Previously, we observed lattice-defect sensitivization of the radioluminescence of Mn²⁺ in radioactive CaSO₄·Mn phosphors [5]. On the other hand, the work of Rudolph and Ruffer [2] on the cerium sensitivization of Mn²⁺ luminescence is not confirmed by other researchers [3]. In the same work it was shown that Pb, Sn, and Bi also sensitivize Mn²⁺ luminescence in CaSO₄.     

Design and Synthesis of a Terbium(III) Complex-Based Luminescence Probe for Time-Gated Luminescence Detection of Mercury(II) Ions

Time-gated luminescence detection technique using lanthanide complexes as luminescent probes is a useful and highly sensitive method. However, the effective application of this technique is limited by the lack of the target-responsive luminescent lanthanide complexes that can specifically recognize various analytes in aqueous solutions. In this work, a dual-functional ligand that can form a stable complex with Tb³⁺ and specifically recognize Hg²⁺ ions in aqueous solutions, N,N,N ¹ ,N ¹ -{[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-[N,N-bis(3″,6″-dithiaoctyl)-aminomethyl]- pyridine]} tetrakis(acetic acid) (BBAPTA), has been designed and synthesized. The luminescence of its Tb³⁺ complex is weak, but can be effectively enhanced upon reaction with Hg²⁺ ions in aqueous solutions. The luminescence response investigations of BBAPTA-Tb³⁺ to various metal ions indicate that the complex has a good luminescence sensing selectivity for Hg²⁺ ions, but not for other metal ions. Thus a highly sensitive time-gated luminescence detection method for Hg²⁺ ions was developed by using BBAPTA-Tb³⁺ as a luminescent probe. The dose-dependent luminescence enhancement of the probe shows a good linearity with a detection limit of 17 nM for Hg²⁺ ions. These results demonstrated the efficacy and advantages of the new Tb³⁺ complex-based luminescence probe for the sensitive and selective detection of Hg²⁺ ions.     

Preparation, Characterization and Photophysical Properties of Highly Luminescent Terbium Complexes Incorporated Into SiO2/Polymer Hybrid Material

Two new highly luminescent Tb(III) coordination complexes of beta-diketone ligands, [TbL(capital I, Ukrainian)(NO(3))(3)(H(2)O)] 1 [L(capital I, Ukrainian)=N-(2-pyridinyl)ketoacetamide] and [TbL(capital I, Ukrainiancapital I, Ukrainian) (2)(NO(3))(2)(C(3)H(6)O)][TbL(capital I, Ukrainiancapital I, Ukrainian)(NO(3))(4)] 2 [L(capital I, Ukrainiancapital I, Ukrainian)=N-(6-(4-methylpyridinyl))ketoacetamide], were synthesized and characterized by single crystal X-ray diffraction, and incorporated into SiO(2)/polymer hybrid material by sol-gel method resulting in a novel ternary molecular hybrid material. The Tb(III) complexes display characteristic metal-centered luminescence while the ligands emission are completely quenched, showing that efficient ligand-to-metal energy transfer (antenna effect) occurs. The gels can exhibit the characteristic emission bands of terbium ion. In addition, terbium ions present longer fluorescence lifetime in gels than in the corresponding pure complexes powders. Compared with the complexes, the unit mass luminescence intensities of the gels are enhanced. And the increase extent of luminescence intensity of the gel is influenced by the substituent of the ligands. At the same time, concentration effects on the luminescence intensity were investigated. The photo stabilities of the gels under UV radiation are much better than those of the pure terbium complexes.     

A luminescent dinuclear Eu(III) complex based on 2,8-bis(4′,4′,4′,-trifluoro-1′,3′-dioxobutyl)-dibenzothiophene for light-emitting diodes

A dinuclear Eu (III) complex Eu₂(dbt)₃·4H₂O was synthesized, where H₂dbt was 2,8-bis(4′,4′,4′,-trifluoro-1′,3′-dioxobutyl)-dibenzothiophene. The complex emits the characteristic red luminescence of Eu³⁺ ion due to the ⁵D₀→⁷F_J(J=0-4) transitions under 395 nm-light excitation with a luminescent quantum efficiency of 17%. The complex is thermally stable up to 280 °C. It was found that the complex can be effectively excited by a 395 nm-emitting InGaN chip. Bright red light was obtained using the complex as light color-conversion material.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.