CaO-SiO2-B2O3:Sm2O3玻璃的合成及Sm3+发光性质研究

用常规的高温合成法合成了CaO-SiO2-B2O3Sm2O3玻璃, 探讨了玻璃的最佳合成温度、玻璃的吸收光谱, 并研究了其发光性质. 在CaO-SiO2-B2O3Sm2O3玻璃体系中观察到了Sm3+的发射光谱. 样品的发射光谱有3个主要荧光发射峰, 峰值波长分别为568, 605, 650 nm, 其中最强峰为605 nm,可见发射起源于Sm3+离子4f电子的f-f跃迁. 其中568 nm对应于4G5/2→6H5/2跃迁、 605 nm对应于4G5/2→6H7/2跃迁、 650 nm对应于4G5/2→6H9/2跃迁, 光谱性质表明这种玻璃体系能够把太阳光中的紫外光转换成红光, 从而增强红光的发射强度. 可以利用这些玻璃的发光性质来制备农用转光玻璃.     

Sm3+杂CaO-SiO2-B2O3发光玻璃的制备、表征及性质

用高温固相法合制备了以CaO-SiO2-B2O3为基质,Sm3+为激活离子的发光玻璃.对Sm3+的淬灭浓度、基质中的硼硅比例、其他稀土离子的敏化作用以及基质组成等因素对玻璃发光特性的影响进行了探讨,并用红外和X-衍射分析对样品的结构进行了表征.结果表明:当Sm3+掺杂的物质的量分数为1.2%,激发波长λ=404 nm时,玻璃体60CaO-20SiO2-20B2O3:1.2Sm3+的发光强度为4838 A.U.(λ=606 nm);这种发光玻璃具有将紫外及近紫外光转换为橙红色光的特点.少量的Eu3+的掺入,对玻璃体的发光起敏化作用;玻璃体中的组分CaO可被ZnO替代.     

Er3+掺杂Li2O-CdO-Al2O3-SiO2玻璃的合成及光谱分析

合成了Er^3 掺杂Li2O—CdO—Al2O3-SiO2玻璃，对其吸收光谱、红外及上转换荧光光谱进行了测试和分析。根据吸收光谱和Judd—Ofelt理论计算了该玻璃中Er^3 离子在不同能级间的实验与理论振子强度、辐射跃迁几率、荧光分支比和寿命等光谱强度参数，在798和975nm激光激发下，观察到强的1．53μm红外发射及绿色上转换发光现象，对其形成机制进行了分析。探讨了这种玻璃作为新的激光材料及上转换实用功能材料的可能性。     

Ce/Tb/Sm共掺杂CaO-B2O3-SiO2发光玻璃的白光发射及其发光颜色调控

用高温熔融法制备了Ce/Tb/Sm三元共掺杂的CaO-B2O3-SiO2发光玻璃材料,并使用荧光分光光度计和CIE色度坐标对其光谱学和发光特性进行了研究.结果表明:在374nm激发下,在Ce/Tb/Sm三元共掺杂发光玻璃的发射光谱中同时观测到了蓝光、绿光和红橙光的发射带,这些发射带的混合实现了白光的全色发射显示.此外,Ce/Tb/Sm三元共掺杂发光玻璃的发光颜色随着Tb4O7含量的减小从绿光逐渐过渡到白光,显示出发光颜色的可调节性,极大地扩展了其在白光发光二极管中的应用.     

掺杂Eu2O3的SrTiO3及SnO2光致发光

用具有大能隙的本征半导体(SrTiO₃及SnO₂)粉末作本体,分别掺杂1%(原子百分数)的Eu₂O₃;所得物质表现出Eu³⁺离子的线发射光谱特性,但相对发光强度及光谱形状有相当大的变化。X射线衍射结构分析显示Eu³⁺在SrTiO₃晶格里是处在间隙位置,而它在SnO₂晶格里则形成新物相Eu₂Sn₂O₇。     

Zn4B6O13∶ Ce3+, Tb3+ 的合成与发光

高温固相扩散方法首次合成了Zn4B6O13:Ce^3 ,Tb^3 光致光材料。通过XRD分析获得晶胞参数：α=0.7472nm,V=0.4172nm^3,为立方晶系，研究Ce^3 和Ce^3 ,Tb^3 在Zm4B6O13中的激发和发射光谱，发现Ce^3 在Zn4B6O13中的激发和发射带比Ce^3 在其他基质中红移2.38-4.94KK,Ce^3 的发射带与Tb^3 与^7F6→^5G2,^5D1,^5H7吸收带有很好的重叠，使Ce^3 对Tb^3 有良好的敏化作用。Ce^3 ,Tb^3 在基质中的能量传递机理为：Ce^3 →Ce^3 和Ce^3 →Tb^3 之间的偶极子－－偶极子的电多级相互作用的共振传递机理，色坐标为：x=0.281,y=0.619。SEM摄取产物晶貌，颗粒均匀，平均粒度为0.23μm，接近纳米级。     

Er^3＋掺杂TeO2-WO3-ZnO—ZnF2玻璃的光谱性质

制备了Er^3 离子掺杂的TeO2-WO3-ZnO-ZnF2(TWZOF)玻璃，测试了样品的吸收光谱和970nmLD激发下样品中Er^3 离子的荧光光谱与荧光寿命，计算了Er^3 离子的J—O强度参数Ωt(t=2，4，6)和1．5μm波段的吸收截面与发射截面，研究了Er^3 离子1．5μm发射强度、荧光寿命和发射带宽与玻璃中ZnF2含量的关系。实验得到Er^3 离子在TWZOF玻璃中1．5μm发射的最大荧光半高宽(TwHm)为83nm；随着ZnF2含量的增加，Er^3 离子1．5μm发射强度、荧光寿命均增加。     

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。     

Eu^2＋和Mn^2＋在Sr3MgSi2O8中的光致发光研究

研究了Ｅｕ＾２＋和Ｍｎ＾２＋共激活的Ｓｒ３ＭｇＳｉ２Ｏ８的荧光性质。Ｅｕ＾２＋和Ｍｎ＾２＋在４６０ｎｍ和６９０ｎｍ的发射峰分别由Ｅｕ＾２＋的５ｄ→４ｆ跃迁和Ｍｎ＾２＋的＾４Ｔ１（＾４Ｇ）→＾６Ａ１ｇ（＾６Ｓ）跃迁产生。未观察到单掺杂Ｍｎ＾２＋的Ｓｒ３ＭｇＳｉ２Ｏ８的荧光发射，而掺入Ｅｕ＾２＋后则出现了Ｍｎ＾２＋的６９０ｎｍ光致发光峰，表明Ｅｕ＾２＋对Ｍｎ＾２＋有敏化作用。Ｅｕ＾２＋的荧光寿命也受Ｍ     

甲烷氧化偶联CaF2／Sm2O3催化剂的研究

甲烷氧化偶联ＣａＦ_２／Ｓｍ_２Ｏ_３催化剂的研究周水琴，龙瑞强，黄亚萍，万惠霖，蔡启瑞（厦门大学化学系，固体表面物理化学国家重点实验室，厦门，３６１００５）关键词甲烷氧化偶联，氟化钙，三氧化二钐，离子交换，氧物种甲烷氧化偶联制乙烯是催化领域中最活跃的?..     

Er3+和Ce3+/Ce4+掺杂β-BaB2O4纳米棒的制备、结构与发光性质

以Ba(NO3)2、NaBH4、Er2O3和CeO2为原料, 在十六烷基三甲基溴化铵(CTAB)表面活性剂辅助下, 采用水热法制备了β-BaB2O4 (β-BBO)纳米棒, 稀土离子Er3+单掺杂的β-BBO(β-BBO:Er3+)及Er3+和Ce3+/Ce4+共掺杂的β-BBO(β-BBO:Er3+/Ce3+/Ce4+)纳米棒. 通过X射线粉末衍射(XRD)、傅里叶变换红外(FTIR)光谱、拉曼光谱、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和光致发光(PL)光谱分别对样品的物相、结构、形貌、成分及光致发光性质进行了表征. 研究结果表明: 微量稀土离子掺杂并不改变β-BBO的结构, 制得的纳米棒尺寸均匀, 长度在200-500 nm 之间, 直径在10-20 nm 之间; β-BBO:Er3+和β-BBO:Er3+/Ce3+/Ce4+纳米棒在400nm光激发下, 在可见光范围内都观察到中心波长为515和542 nm的绿光. 对发光机理的初步研究表明: 发光分别对应于Er3+的2H11/2→4I15/2, 4S3/2→4I15/2跃迁, 铈离子以Ce3+和Ce4+两种形式存在于体系中, Ce3+对Er3+起敏化作用, 可以显著增强β-BBO:Er3+/Ce3+/Ce4+纳米棒的发光强度, 存在Ce3+→Er3+的能量传递过程.     

Impact of Eu3+ Ions on Physical and Optical Properties of Li2O-Na2O-B2O3 Glass

The lithium sodium borate glasses doped with Eu³⁺ ion are prepared using melt quenching technique, their structural and optical properties have been evaluated. The density of prepared glasses exhibits an inverse behavior to the molar volume ranging from 2.26 g/cm³ to 2.43 g/cm³ and 26.95 cm³ /mol to 26.20 cm³ /mol, respectively. The absence of sharp peaks in XRD patterns confirms the amorphous nature of the prepared glasses. The absorption spectra yield four transitions centered at 391 nm (⁷F₀→⁵L₆), 463 nm (⁷F₀→⁵D₂), 531 nm (⁷F₀→⁵D₁), and 582 nm (⁷F₀→⁵D₀). The most intense red luminescence is observed at 612 nm corresponding to ⁵D₀→⁷F₂ transition under 390 nm laser excitations.     

BaO-Al2O3-B2O3系密封玻璃的结构与性质

The BaO-Al₂O₃-B₂O₃ glasses manufactured for solid oxide fuel cell(SOFC) sealing were studied. The effect of different n_BaO/n_B2O3 on crystal, thermal properties, density and infrared spectra of this system has been discussed. The results show that the trends of crystallization, glass transformation temperature, dilatometric softening temperature and density increase with n_BaO/n_B2O3 values. But a typical property deviation occurs when n_BaO/n_B2O3 is 0.875, and its coefficient of thermal expansion has the maximum at this point. The changes of properties can attribute to the conversion of boron from tetrahedral coordination to trigonal, breakage of the local glass network and interaction between the network modifiers. These can be proved by infrared spectra of glasses. Thermal properties of some studied samples are suitable for the sealing of SOFC using Sm doped ceria electrolyte and operating at 400～600 ℃.     

Sm3+掺杂CaO-SiO2-B2O3发光玻璃的制备、表征及性质

用高温固相法合制备了以CaO-SiO₂-B₂O₃为基质，Sm³⁺为激活离子的发光玻璃。对Sm³⁺的淬灭浓度、基质中的硼硅比例、其他稀土离子的敏化作用以及基质组成等因素对玻璃发光特性的影响进行了探讨，并用红外和X-衍射分析对样品的结构进行了表征。结果表明：当Sm^3＋掺杂的物质的量分数为1.2%,激发波长λ ＝ 404 nm时,玻璃体60CaO-20SiO₂-20B₂O₃∶1.2Sm^3＋的发光强度为4 838 A.U.( λ ＝ 606 nm );这种发光玻璃具有将紫外及近紫外光转换为橙红色光的特点。少量的Eu^3＋的掺入，对玻璃体的发光起敏化作用；玻璃体中的组分CaO可被ZnO替代。     

Photoluminescence of samarium-doped TiO2 nanotubes

Samarium (Sm)-modified TiO₂ nanotubes (TNTs) were synthesized by low-temperature soft chemical processing. X-ray powder diffraction analyses of the synthesized Sm-doped and non-doped TNTs show a broad peak near 2θ=10°, which is typical of TNTs. The binding energy of Sm ³d_5/2 for 10 mol% Sm-doped TNT (1088.3 eV) was chemically shifted from that of Sm₂O₃ (1087.5 eV), showing that Sm existed in the TiO₂ lattice. Sm-doped TNTs clearly exhibited red fluorescence, corresponding to the doped Sm³⁺ ion in the TNT lattice. The Sm-doped TNT excitation spectrum exhibited a broad curve, which was similar to the UV–vis optical absorption spectrum. Thus, it was considered that the photoluminescence emission of Sm³⁺-doped TNT with UV-light irradiation was caused by the energy transfer from the TNT matrix via the band-to-band excitation of TiO₂ to the Sm³⁺ ion.     

Eu3+掺杂SiO2-B2O3-NaF玻璃的制备及发光性质

The Eu-doped SiO₂-B₂O₃-NaF glass was prepared by sol-gel process, using tetraethoxy Silicane, boric acid and sodium fluoride as starting materials, 0.10 mol·L^-1 EuCl₃ solution as the dopant. The luminescent properties of Eu³⁺ doped SiO₂-B₂O₃-NaF phosphors were investigated. The phosphors showed prominent luminescence in pink, the strong emission of Eu³⁺ comes from electronic transition of ⁵D₀- ⁷F₁（591 nm）and ⁵D₀- ⁷F₂（615 nm）,which derived from two transition modes of magnetic-dipole and electric-dipole .The peak intensity of 591nm in SiO₂-B₂O₃-NaF matrix is much stronger than it in the other matrixes, it means that SiO₂-B₂O₃-NaF has sensitization on the transition of ⁵D₀- ⁷F₁ (Eu³⁺). If there are broad bonds in the range of 275～380 nm in the excitation spectrum of Eu³⁺ -doped SiO₂-B₂O₃-NaF glass, the emission peak intensity should be intensified. It is because the electron migration CT band of O^2--Eu³⁺. For all Eu³⁺ concentrations used, the investigation found that when the mass of fraction got to 29.19×10^-3, the luminescence intensity reached the summit. And there is a phenomenon of concentration quenching. Investigation with the same concentration of Eu³⁺ at different annealed temperature, we found that the sample annealed at 400 ℃, the luminescence intensity achieved its maximum value, and Eu³⁺ in this matrix had a phenomenon of temperature quenching. The structural characterization of these luminescent materials was carried by used XRD and TEM. The result showed that the phosphor was in amorphous phase.     

Crystal structure and electrical properties of the mixed valent titanium oxysulfide Sm2Ti2S2O4.5

A new phase Sm₂Ti₂S₂O_4.5 was synthesized and its crystal structure was solved by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system (C2/m) with lattice constants a=17.9987(11) Å, b=3.71607(14) Å, c=12.6172(8) Å and β=133.645(4)°. The structure is built up from double chains of Ti-centered octahedra between which Sm-polyhedra develop. In spite of very close formulations, the structure of Sm₂Ti₂S₂O_4.5 differs completely from that of the defect Ruddelsden-Popper phase Sm₂Ti₂S₂O₅ previously reported. The title compound presents a mixed valence for titanium with Ti(III) (d¹) and Ti(IV) (d⁰) located in different crystallographic sites. However, conductivity measurements show that this compound is non-metallic.     

Sm2NiSn4: The intermediate structure type between ZrSi2 and CeNiSi2

A new rare earth nickel stannide, Sm₂NiSn₄, has been prepared by reacting the pure elements at high temperature in welded tantalum tubes. Its crystal structure was established by single crystal X-ray diffraction studies. Sm₂NiSn₄ crystallizes in the orthorhombic space group Pnma (No. 62) with cell parameters of a=16.878(2) Å, b=4.4490(7) Å, c=8.915(1) Å, and Z=4. Its structure can be viewed as the intermediate type between ZrSi₂ and CeNiSi₂. Sm₂NiSn₄ features two-dimensional (2D) corrugated [NiSn₄]⁶⁻ layers in which the 1D Sn zigzag chains and the 2D Sn square sheets are bridged by Ni atoms. The Sm³⁺ cations are located at the interlayer space. Results of both resistivity measurements and extended-Hückel tight-binding band structure calculations indicate that Sm₂NiSn₄ is metallic.     

Photoluminescence and energy transfer in Tb/Mn co-doped ZnAl2O4 glass ceramics

We report on Tb³⁺ as efficient sensitizer for red photoemission from Mn²⁺-centers in ZnO-B₂O₃-Al₂O₃-Si₂O-Na₂O-SrO glasses and corresponding gahnite glass ceramics. In comparison to singly or co-doped glasses, the glass ceramics exhibit significantly increased emission intensity. Structural considerations, ESR, and dynamic luminescence spectroscopy indicate partial incorporation of Mn²⁺ as well as Tb³⁺ into the crystalline phase, the former on octahedral Zn²⁺-sites. Interionic distance and charge transfer probability between both species depend on crystallization conditions. This enables control of the energy transfer process and, hence, tunability of the color of photoemission by simultaneous emission from Tb³⁺ and Mn²⁺ centers. Concentration quenching in Mn²⁺-singly doped materials was found at a critical dopant concentration of about 1.0 mol%. The energy transfer process was studied in detail by dynamic as well as static luminescence spectroscopy. Spectroscopic results suggest the application of the studied materials as single or dual-mode emitting phosphor for luminescent lighting.