Ce~（3＋）,Tb~（3＋）激活的Ln（BO_3,PO_4）绿色荧光粉的合成与真空紫外光谱特性

针对目前PDP用商品绿粉余辉时间较长,以及合成稀土硼酸盐与稀土磷酸盐工序长、能耗高等缺点,本研究以自制的磷酸硼（BPO4）和稀土氧化物为原料,采用一步烧成法合成了结晶良好的Ce3＋、Tb3＋激活的Ln（BO3,PO4）（Ln=La,Y,Gd）绿色荧光粉,并对其在147 nm激发下的光谱性质进行了研究。结果表明：Ln（BO3,PO4）：Ce3＋、Tb3＋（Ln=Y,La,Gd）激发光谱是由来自BO33-和PO43-基质敏化带的120~175 nm和来自Tb3＋离子的4f→5d跃迁的多宽带的175~300 nm组成;改变基质稀土离子,发射光谱中的荧光分支比和色坐标也随之改变,其中以Gd（BO3,PO4）：Ce3＋、Tb3＋荧光粉的荧光分支比为最高;拟合Gd（BO3,PO4）：Ce3＋、Tb3＋荧光粉的衰减曲线后,得出其荧光寿命为2.92 ms,10%的余辉为6.7 ms,优于Zn2SiO4∶Mn2＋商品粉,能够满足PDP器件的要求。     

（Y，Bi，Sc）VO4：Eu^3＋的制备及其发光特性

用高温固相法在900℃，保温6h的条件下制备了YVO4单相粉末样品。在紫外光254nm激发下，YVO4：Eu^3＋的激发光谱由VO4^3＋的吸收带和Eu^3＋的电荷迁移带组成。发射光谱为Eu^3＋的^5D0→^7Fj（J=1,2，4）跃迁。在Eu^3＋含量一定的情况下掺杂Bi^3＋和sc^3＋，随着Bi^3＋浓度的增加，激发光谱宽化，但发射强度变弱；SC^3＋浓度的增加则使YVo4：Eu^3＋的发射强度先增加后降低。在147nm激发下，（Y,Bi，Sc）VO4：Eu^3＋的发射光谱相对于YVO4：Eu^3＋有降低趋势。     

M3Gd（PO4）3：Tm^3＋（M=Mg，Ca，Sr，Ba）真空紫外发光特性

研究了M3Gd（PO4）3：Tm^3＋（M=Mg，Ca，Sr，Ba）样品的结构特性、发光特性。M3Gd（PO4）3：Tm^3＋属于立方晶系。基质掺入铥离子后其结构没有明显变化。M3Gd（PO4）3：Tm^3＋在166nm和210nm附近有强烈的吸收峰。位于166nm附近的强烈吸收峰归因于基质的强烈吸收，210nm附近的吸收峰则归因于Gd^3＋的^8S7/2-^6GJ的能级跃迁。在166nm真空紫外光激发下，样品在453nm及363nm处有较强的发射峰，发射主峰位于453nm。随着样品中阳离子的变化，M3Gd（PO4）3：Tm^3＋的激发峰发生强烈变化，从而导致其发射光谱有了较大变化。     

Y2-x-yGdxEuyO3纳米材料制备过程中的固溶行为及其发光性能术

用柠檬酸螯合法制备Y2-x-yGdxEuyO3纳米粉体（x＋y≤2）,通过FTIR,XRD和SEM分析了制备过程中的物相变化以及pH值对粉体形貌的影响．测试了Y2-x-yGdxEuyO3晶格常数和晶胞体积,分析了Gd与Eu在Y2O3中的固溶行为及其发光性能．结果表明：在pH〈3的体系中制备Y2-x-yGdxEuyO3粉体较为适合,经900℃煅烧2h可完全合成出立方相的Y2-x-yGdxEuyO3;在pH=1时,加入少量乙二醇（5％,体积分数）时得到粉体形貌最佳,粒径约90nm,近球形．样品的发光性能和Y,Gd的配比以及Eu的含量有关,当化学配比为Y0.2Gd1.65Eu0.15O3时样品发光强度最高,y值超过0．15会发生浓度猝灭,导致发光强度降低．     

Gd1-xAlO3：Eux^3＋梯度材料芯片制备及发光性能

将组合材料芯片技术中梯度组合法应用于新型发光材料Gd1-xAlO3：Eux^3＋（发光峰丰峰位置为615nm，对应Eu^5D0→^7F2电子跃迁）的激活剂掺杂晕优化。获得如下的研究结果：在紫外激发T（254nm）Gd1-xAlO3：Eux^3＋材料中的x值为0．09；Pr共掺杂时会降低发光强度（n（Pr）：n（Eu）〈1：10）。光谱分析表明：Pr，Eu间卢子支持的共振能量传递，是Pr降低Gd1-xAlO3：Eux^3＋（简写为：GAP：Eu）发光强度的丰要原因。优化的结果与柠檬酸盐硝酸盐溶胶凝胶法制备粉体掺杂萤优化实验结果一致。实验结果表明组合法在发光材料开发中具有高效性。     

LaMgAl11O19：Tb的助熔剂法制备及其发光特性

以H3BO3作助熔剂,用高温固相法在1400℃、保温4 h的条件下成功制备了LaMgAl11O19：Tb单相粉末样品并研究了其紫外光、真空紫外光激发下的一系列发光特性.在紫外光（254 nm）、真空紫外光（147 nm）激发下,观察到Tb^3＋很强的^5D4→^7FJ（=6,5,4,3）的跃迁发光.分析了LaMgAl11O19：Tb^3＋的发光强度与Tb^3＋掺杂浓度的关系.     

Eu0.12Y1.88-xMxO3-δ（M=Mg,Ca）纳米晶的制备及光致发光性能

在超声波作用下以均匀沉淀法制备Eu0.12Y1.88-xMxO3-δ（M=Mg,Ca）纳米晶荧光粉,用X射线衍射仪（XRD）、透射电镜（TEM）、荧光光谱对其进行表征,研究掺杂Mg2＋、Ca2＋对Y2O3：Eu3＋纳米晶光致发光（PL）性能的影响。结果表明,掺杂Mg2＋后,Y2O3：Eu3＋的PL发射强度减弱,而掺杂Ca2＋后Y2O3：Eu3＋的PL发射强度得到明显增强,掺杂浓度高至15%（摩尔分数）后仍具有优良的发光性能,大大提高掺杂Y2O3：Eu3＋纳米晶的猝灭浓度。样品Eu0.12Y1.78Ca0.10O3-δ具有最佳PL发射强度,是未掺杂Y2O3：Eu3＋的2.4倍,且色纯度显著提高。掺杂样品PL性能的增强可归因于Eu3＋的电荷迁移带（CTS）与接近Y（4d＋5s）导带处缺陷态的叠加,与掺杂离子的电负性及掺杂离子后样品的晶粒尺寸、结构对称性有关。     

Syntheses and cofluorescence of complexes of Eu（Ⅲ）/Y（Ⅲ） with terephthalic acid, 2-thenoyltrifluoroacetone and trioctylphosphine oxide

A series of Eu（ Ⅲ）/Y（Ⅲ） complexes of terephthalic acid（TPA） with 2-thenoyltrifluoroacetone（HTTA） and trioctylphosphine oxide（TPPO） were synthesized. Compositions of these complexes are revealed to be Eu2（1-x）Y2x（TPA）（TTA）4- （TPPO）4 or EU1-xYx（TPA）（TTA）（TPPO）2. Their 1R spectra, fluorescent spectra and the thermal and optical stability were studied. The fluorescent excitation spectra of these complexes show more broad excitation bands than those of Eu2（TPA）3（TPPO）4 and Eu（TTA）3（TPPO）2 corresponding to their formations. In addition, both the binuclear complex EuY（TPA）（TTA）4（TPPO）4 and the chain complex EU0.4Y0.6（TPA）（TTA）（TPPO）2 present higher thermal stability and better optical stability than the mononuclear complex Eu（TTA）3（TPPO）2 does. And their thermal and optical stabilities are preferably interpreted from the binuclear structure together with the chain polynuclear structure of the complexes. The fluorescence enhancement of cofluorescence Y^3＋ ions to the Eu（Ⅲ） complexes is clear. The optimum content of Y^3＋ is 0.6 （molar fraction） for the chain complexes Eu1-xYx（TPA）（TTA）- （TPPO）2 and 0.5 for the binuclear complexes Eu^2（1-x）Y2x（TPA）（TTA）4（TPPO）4. The formation of polynuclear structure of the complex Eu1-xYx（TPA）（TTA）（TPPO）2 appears to be responsible for the good cofluorescence effect of Y^3＋ ions.     

Ca2Gd8（SiO4）6O2：Tb^3＋薄膜的制备及其发光性能研究

用溶胶-凝胶法制备了Ca2Gd8（SiO4）6O2：Tb^3＋薄膜，用X射线衍射（XRD）、原子力显微镜（AFM）、扫描电子显微镜（SEM）和荧光光谱仪对所得发光薄膜进行了表征。XRD的结果表明薄膜在1000℃完全结晶，并且与标准卡片符合得很好。AFM和SEM的结果表明薄膜表面均匀，没有裂痕，粒子排列紧密，平均直径为90nm，薄膜的厚度为1-3μm。当用233nm激发时，Tb^3＋的发射光谱由蓝光发射和绿光发射两部分组成，前者对应^5D3-^7FJ（J=6，5，4，其峰值分别位于376，418，440nm）；后者对应^5D4-^7FJ（J=6，5，4，3，其峰值分别位于490，544，587，623nm）。在Ca2Gd8（SiO4）6O2薄膜基质中，Tb^3＋的最佳掺杂浓度为Gd^3＋的9mol％。     

含铕稀土无机转光剂的制备与荧光性能

以铕(Eu2 )为中心发光离子,掺杂钇(Y3 )或铜(Cu ),分别制备出的Y2O3xEu2 及CaSxEu2 ,yCu 系列稀土无机转光剂,研究并比较了两个系列稀土转光剂的荧光性能.结果表明,Y2O3xEu2 系列稀土无机转光剂具有紫外转红及绿光转红功能,发射的红光峰位在611nm左右,为Eu2 离子5D0→7F7/2的电子跃迁所致;Eu2 和Y3 的摩尔比会影响稀土无机化合物的发光强度,当EuY摩尔比为0.150.85时,其荧光强度最佳.在CaS系列无机转光剂中,Eu2 的掺入使转光剂具有绿光转红光的功能,Cu 的掺入使转光剂具有紫外转红及紫外转蓝的功能,同时掺入Eu2 和Cu 时,则转光剂可同时具备以上功能,且其激发与发射峰皆呈宽峰形状,有利于日光利用及叶绿素吸收与Y2O3xEu2 系列相比,CaS系列转光剂的发射红光峰位650nm更接近叶绿素光合作用的吸收峰位.     

Acid-base behavior of cryptand 1, 4, 7, 10, 13, 16, 21, 24-octaaza-bicyclo [8, 8, 8] hexacosan-3, 8, 12, 17, 20, 25-hexone and complex formation

The bicyclic cryptand I, 4, 7, 10, 13, 16, 21,24-octaaza-bigcyclo [8, 8, 8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-endo conformation. Three identical branches formed by I, 2-diaminoethane link the two tertiary amine groups. The protonation reactions ofcryptand (COBH) and its complex formation with copper (II) were investigated by potentiometry in water and in a DMSO/water (80: 20 in mass ratio) mixture as solvents. The cryptand acts as a bis-base through its two Nbridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (ΔpK≈5.0 ). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (II) leads to several binuclear complex proton contents.     

Acid-base behavior of cryptand 1, 4, 7, 10, 13, 16, 21, 24-octaaza-bicycio[8, 8, 8] hexacosan-3, 8, 12, 17, 20, 25-hexone and complex formation

The bicyclic cryptand 1,4, 7, 10, 13, 16, 21, 24-octaaza-bigcyclo [8, 8, 8] hexacosan-3, 8, 12, 17, 20, 25-hexone (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-endo conformation. Three identical branches formed by 1, 2-diaminoethane link the two tertiary amine groups. The protonation reactions ofcryptand (COBH) and its complex formation with copper (Ⅱ) were investigated by potentiometry in water and in a DMSO/water (80: 20 in mass ratio) mixture as solvents. The cryptand acts as a bis-base through its two Nbridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (pK 5.0 ). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (Ⅱ) leads to several binuclear complex proton contents.     

Supplemental Literature Review of Binary Phase Diagrams: Cs-In, Cs-K, Cs-Rb, Eu-In, Ho-Mn, K-Rb, Li-Mg, Mg-Nd, Mg-Zn, Mn-Sm, O-Sb, and Si-Sr

Recent literature on Cs-In, Cs-K, Cs-Rb, Eu-In, Ho-Mn, K-Rb, Li-Mg, Mg-Nd, Mg-Zn, Mn-Sm, O-Sb, and Si-Sr phase diagrams is reviewed in this article in order to update the 1990 compilation Binary Alloy Phase Diagrams, 2nd edition, by T.B. Massalski, et al. For some systems reaction tables and crystal structure data have been included, as well. Diagrams have been checked for consistency with rules for phase diagram construction and modified when necessary. In addition, diagrams needing more work have been identified.