Eu3+掺杂SiO2-Al2O3-B2O3玻璃制备及光谱性能研究

高温溶制了Eu^3＋掺杂SiO2-Al2O3-B2O3-MxOy（M=Li^＋,Na^＋,K^＋,Mg^2＋,Ca^2＋,Sr^2＋,RE^3＋）硼硅酸盐玻璃,测试了玻璃样品的发射光谱、激发光谱和透射光谱,研究了不同碱金属离子、碱土金属离子对该系统荧光性能的影响。利用发射光谱计算了Ω2,Ω4以及^5D0到^7F2,^7F4的自发辐射几率和振子强度f（^5D0→^7F2）,f（^5D0→^7F4）。结果表明,材料的发射能级为^5D0→^7F1（590nm）,^5D0→^7F2（617nm）,^5D0→^7F4（698nm）,而且材料的结构对称性越差,跃迁戒律打破地越彻底,荧光发射越强。     

Eu3+在SrZnP2O7中的发光性能和Eu3+, Bi3+间的能量传递

采用高温固相法合成了SrZnP2O7：Eu^3＋荧光粉,该荧光粉的激发主峰值位于400nm,适用于UVLED管芯的激发;在紫外激发下的发射峰由位于591和597nm（^5D0～^7F1）,616,624和629nm（^5D0～^7F2）,656nm（^5D0～^7F3）及688nm（^5D0～^7F4）4组线状峰构成,对应Eu^3＋的特征跃迁,呈现橙红色发光。分析了Eu^3＋离子浓度对样品发光效率的影响,随着浓度增加,其发射一直增强,但其发光效率已经开始减弱。Bi^3＋的加入使发光强度得到很大提高,并讨论了在SrZnP2O7基质中Bi^3＋对Eu^3＋的能量传递和敏化作用。     

SrZnO2:Eu3+, Li+长波紫外激发红光荧光体的合成及发光性能研究

采用高温固相法合成了一种长波紫外激发的SrZnO2：Eu^3＋, Li^＋发光材料, 用X射线衍射谱、荧光光谱对样品进行了表征. 结果表明, Eu^3＋离子在SrZnO2基质中主要占据Sr^2＋离子不对称性格位, 发射来源于5D0→7F2 612 nm为主的红光. 加入电荷补偿剂Li^＋离子能显著提高发光强度, 350～400 nm内的激发峰也有明显提高, 同时观察到来自Eu^3＋离子高能级5D1→7FJ（J=0～2）的跃迁发射, 并对其产生机制进行了初步探讨. 实验结果表明, SrZnO2：Eu^3＋, Li^＋是一种有发展前途的长波紫外激发红光荧光体.     

Eu:GGG纳米荧光粉体制备及其光学特性

采用液相共沉淀方法并在不同烧结温度下制得了Eu：GGG荧光粉体。用X射线衍射分析了样品的结构，计算了其晶格常数，为1．2371nm。室温下，测量了Eu：GGG的光致发射光谱、激发光谱和荧光衰减曲线。激发光谱在波长240～287nm的谱带内和393。。处有强的激发，分别来自于Eu^3＋O2^-间的电荷迁移态吸收和Eu“的^7F0→^5L6的跃迁吸收，同时在274nm处也出现了Gd^3＋的^8S7/2→^6I1的特征吸收。393nm激发下，591nm处的发射峰最强，对应Eu^3＋的^5D0→^7F1的磁偶极跃迁，可能由于部分Eu^3＋处于反演中心对称格位所致。随着烧结温度升高，Eu：GGG的发光强度增强，这可能由于随着烧结温度升高，样品晶粒尺寸变大，单位体积内被激发的Eu^3＋离子数增加引起，而591nm发光的荧光寿命变短，可能是由Eu^3＋离子的能量共振传递过程中发光被陷阱捕获所致。     

新型铕双β-二酮红光材料的合成与发光性质

通过分子设计,合成了一种新颖的双β-二酮有机配体9-乙基-3,6-二（乙酰基-3-苯甲酰基）咔唑（H2L）及其铕配合物,红外光谱和电子光谱表明Eu^3＋与H2L发生配位。配合物的溶液荧光光谱不仅有613 nm处的中心离子Eu^3＋的特征红光,属^5D0→^7F2跃迁带,还有445nm处配体的宽带蓝色发光,属H2L^＊→H2L跃迁带,而配合物的光致发光光谱只有611 nm处为中心离子Eu^3＋的特征红光,属^5D0→^7F2跃迁带,峰形尖锐,半峰宽仅7 nm,单色性好,表明该固体铕双β-二酮配合物是一种潜在的红色发光材料。     

硼离子对铕掺杂SiO2干凝胶发光性能的影响

采用溶胶-凝胶法制备了Al单掺和B，Al共掺的Eu掺杂SiO2干凝胶。利用荧光光谱、IR，XRD，DSC，TG／DTG等技术研究了硼离子、退火温度对样品发光性质的影响。经500℃以上退火处理用248nm激发的样品，产生Eu^3＋离子^5D0→^7FJ的特征发射，^5D0→^7F1的跃迁分裂为两个峰。比较615nm处的发光强度，掺硼酸样品的发光强度是不加硼酸发光强度的3．3倍。这是因为B离子的加入，在材料中形成了Si—O—B键，破坏了网络的对称性，加强了Eu^3＋的红光发射。当退火温度上升到850℃用350nm激发时，样品有很强的Eu^2＋蓝光发射。Al单掺的发射中心在437nm处，发射半峰宽约为70nm，而B，Al共掺样品的发光中心蓝移到425nm处，单掺样品的蓝光强度几乎是共掺样品强度的2倍。这是由于硼酸的加入改变了基质的网络结构，从而导致单掺和共掺样品发射峰位和强度的改变。     

三种方法制备CaGdAlO4:Eu3+荧光粉及其发光性质研究

分别采用柠檬酸溶胶-凝胶法、半干半湿法和高温固相法制备了CaGdAlO4：Eu^3＋荧光粉，并用X线衍射（XRD）分析、场发射扫描电镜（FE—SEM）观察和荧光光谱分析研究了不同制备方法和制备条件对CaGdAlO4：Eu^3＋形貌、粒径和发光性质的影响。XRD结果表明，柠檬酸溶胶-胶法、半干半湿法和固相法制备CaGdAlO4：Eu^3＋生成纯相的温度分别为900，1200和1400℃。FE—SEM照片显示CCaGdAlO4：Eu^3＋颗粒粒径随温度的升高而增大，在同一烧结温度下，粒径大小为柠檬酸溶胶-凝胶法最小，半干半湿法居中，高温固相法最大而且团聚现象严重。以280nm近紫外光激发，CaGdAlO4：Eu^3＋发出明亮的橙红色荧光，以Eu^3＋的^5D0→^7F2跃迁为主，发光强度随烧结温度的升高而增加，在1400℃烧结温度下，以半干半湿法得到的样品发光最强。室温和低温发射谱中Eu^3＋的^5D0→^7Fj，发射峰的数目都表明：Eu^3＋在CaGdAlO4中只占据偏离反演中心的一种格位。     

Eu^3+和Eu^3+在LnBaB~9O~16是的紫外和真空卜外发光性质

研究了Tb^3+和En^3+在LnBaB~9O~16(Lu=La,Gd,Y,Lu)中的卜外和真空紫外光谱性质。X射线粉未衍射数据脂标化结果表明,LnBaB~9O~16(Lu=La,Gd,Y,Lu)系列化合物属于三方晶系。Eu^3+的荧光光谱结果表明,LnBaB~9O~16和GdBaB~9O~16中稀土离子占据非是心对称的格位,Eu^3+在其中的特征发射5D0→7F2电偶极跃迁为主;而在YBaB9O16和LuBaB9O16中稀土离子占据中心对称性的格位,Eu3^+在其中的特征发射以5D0→7F1磁偶极跃迁为主.     

Eu^3+和Eu^3+在LnBaB~9O~16是的紫外和真空卜外发光性质

研究了Tb^3+和En^3+在LnBaB~9O~16(Lu=La,Gd,Y,Lu)中的卜外和真空紫外光谱性质。X射线粉未衍射数据脂标化结果表明,LnBaB~9O~16(Lu=La,Gd,Y,Lu)系列化合物属于三方晶系。Eu^3+的荧光光谱结果表明,LnBaB~9O~16和GdBaB~9O~16中稀土离子占据非是心对称的格位,Eu^3+在其中的特征发射5D0→7F2电偶极跃迁为主;而在YBaB9O16和LuBaB9O16中稀土离子占据中心对称性的格位,Eu3^+在其中的特征发射以5D0→7F1磁偶极跃迁为主.     

Preparation and Luminescence Behavior of CaSiO3：Eu^3＋（Bi^3＋）

CaSiO3：Eu0.08^3＋Bi0.002^3＋ with a monoclinic perovskite structure was synthesized by using sol-gel method, and its luminescence characteristics were investigated. From the excitation spectrum, it can be seen that the main peaks located at 238,396,415,437 and 359 nm correspond to the charge-transfer band of Eu^3＋-O^2- , the absorption transitions of ^7F0.1→^3L6, ^7F0→^5D3, ^7F1→^5D3 of Eu^3＋ ions, and ^3P1→^1S0 of Bi^3＋ ions, respectively. When the samples were excited with a light of wavelength 359 or 395 nm, it can be seen from the emission spectrum that the electronic dipole transition located at 609 nm corresponding to ^5D0→^7F2 of Eu^3＋ ions was stronger than the magnetic dipole transition located at 587 nm corresponding to ^5D0→^7F1 of Eu^3＋ ions, which shows that more Eu^3＋ ions were located in nonreversion center lattices. The energy transfer from Bi^3＋ ions to Eu^3＋ ions in the phosphor was also discussed. The results show that Eu^3＋ ions could be well sensitized by ^3＋ions, and the energy-transfer pattern between Bi^3＋ ions and Eu^3＋ ions was resonance energy transfer.     

Structures of gas-phase C2F 7 + ions

In an ion cyclotron resonance spectrometer, less than 96% of the C₇F ₇ ⁺ cation formed on electron ionization of perfluorotoluene reacts with hexamethyldisilazane. In contrast, the C₇F ₇ ⁺ from perfluoronorbornadiene or perfluorobicyclo[3.2.O]hepta-2,6-diene is nonreactive with hexamethyldisilazane. Collision-induced dissociation results support this dichotomy, although the evidence is not as clear-cut. The reactive ion is assigned the benzyl structure and the nonreactive ion the tropyl structure, on the basis of analogy with the protio cases. By AM1 calculations, the perfluorobenzyl ion is 25 kcal/mol more stable than the perfluorotropyl ion, the opposite of the situation for the protio analogs (? 12 kcal/mol). Ab initio calculations at the 3–21G level agree with the semiempirical energy difference to within 0.4 kcal/mol; at the more appropriate 6–31G*/MP2 level, the perfluorobenzyl cation is 9.7 kcal/mol more stable than the perfluorotropyl cation.     

Structure of Na2Fe2F7 and structural relations in the family of weberites Na2MIIMIIIF7

The mixed valence compound Na₂Fe₂F₇ crystallizes in the monoclinic weberite structure of the Na₂CuFeF₇-II type (M-II), space group C2/c, Z = 16, a = 12.676, b = 7.422, c = 24.710 Å, β = 99.97°. Refinement on F² led to wR(F²) = 0.117 for all 2 645 reflections, R = 0.057 for 1 258 refl. with F_o > 4σ(F). On the basis of this and other recent single crystal investigations the structures of weberites Na₂M^IIM^IIIF₇ are classified in four main structure types: O-I is the ‘classical’ orthorhombic weberite type (S.G. Imma) encountered e.g. in the mineral Na₂MgAlF₇, from which two lower symmetric variants O-II (Na₂CuCrF₇ type) and O-III (Na₂NiInF₇) are deriving. The second M-I and third M-II basic type are monoclinic (e. g. Na₂CuFeF₇-I and -II), the fourth type T is trigonal (Na₂MnFeF₇). The structural relations within the weberite family are discussed and the connections established, which allow to regard these weberites as well as the pyrochlores as subtraction derivatives of the fluorite type.     

Luminescence study of Eu3+: KGd2F7

A spectroscopic investigation of the host matrix KGd₂F₇ is performed using Eu³⁺ as local probe. Its crystal structure derives from the fluorite-type by an ordering of the cations and anions. On powdered samples with different europium concentrations, the luminescence spectra of Eu³⁺:KGd₂F₇ allowed an identification of a multisite behaviour for the Eu³⁺ ions, leading to a lifetime distribution for the ⁵D₀ emitting level.     

Zur Thermischen Zersetzung von CaOP3F · 2 H2O

On the Thermal Decomposition of CaPO₃F · 2H₂O . The thermal decomposition of CaPO₃F · 2H₂O was investigated by thermogravimetry under inert conditions. A parallel mass spectrometric analysis of gases produced is made. Using an effusion cell a quasi equilibrium evaporation in the nearness of the ion source of the spectrometer is achieved. The results are comparable with the thermogravimetric analysis under normal pressure. During first state of thermal decomposition one mole H₂O is lost. Then the further course is determined by release of HF and POF₃. The several steps of decomposition leading to α-Ca₂P₂O₇ at temperatures above 360° C are discussed.     

Ba7Fe6F32 · 2H2O: Original isolated trimers [Fe3F16]7− in a new defective jarlite-type compound

Ba₇Fe₆F₃₂ · 2H₂O was prepared from HF aqueous solution in a teflon bomb (Berghof) at 180°C. A partial exchange F^?/OH^? can be realized in more diluted HF medium and leads to Ba₇Fe₆F_32–x(OH)_x · 2H₂O. The compounds crystallize in the monoclinic system, space group C2/m (Z = 2) with a = 17.023(1) Å, b = 11.482(1) Å, c = 7.624(1) Å, β = 101.13(1)° for x = 0 and a = 17.036(2) Å, b = 11.489(1) Å, c = 7.620(2) Å, β = 101.48(1)° for x ≈? 5.3. The structures were determined from 2 256 and 1 343 independent reflections for x = 0 and x ≈? 5.3 respectively, collected with a Siemens AED2 four-circle diffractometer with the MoKα radiation (R = 0.0235 and R_w = 0.0240 for x = 0 and R = 0.0324 and R_w = 0.0335 for x ≈? 5.3). The structure, closely related to that of the Jarlite-type, is built up from isolated octahedra trimers [Fe₃F₁₆]^7?, connected together by Ba²⁺-cations. The location of anions and water molecules is discussed from bond valence calculations. Magnetic and Mössbauer studies are reported and discussed.     

Crystal structure of Ni3[(UO2)2F7]2 · 18H2O

Journal of Structural Chemistry -     

A hexa­gonal 2a,c superstructure of Ba7F12Cl2

Hydro­thermal synthesis yielded crystals of hepta­barium dodeca­fluoride dichloride, Ba₇F₁₂Cl₂, displaying a new 2a,c hexa­gonal superstructure with P symmetry. The superstructure results from the disorder of Ba²⁺ cations over two adjacent tricapped trigonal prismatic sites located in channels parallel to the c axis.     

Gas phase reactions of CF3, C2F5, and n-C3F7 with carbon tetrachloride

The reactions of some perfluoroalkyl radicals with carbon tetrachloride have been studied using the photolysis of the corresponding perfluoroalkyl iodide as the free radical source. The Arrhenius parameters, based on the value of 2.3 × 10¹³ cm³ mol^?1 s^?1 for the self-combination rate constant of all radicals are: