Er^3＋：Y0.5Gd0.5VO4晶体的生长和光谱性质

用液相法合成GdVO4和YVO4多晶原料，提拉法生长出具有高光学质量的Er^3＋：Y0.5Gd0.5VO4混晶。用ICP法分析了晶体中Er^3＋离子的浓度。用x射线粉末衍射法对晶体的晶胞参数进行了测量，分别测量了1．62％（原子分数）Er^3＋：Y0.5Gd0.5VO4晶体的偏振吸收光谱、荧光发射光谱和荧光寿命谱；光谱显示该晶体在382，454，525，656，804，985，1536nm有很强的偏振光吸收峰，且π偏振光（E∥C）吸收远强于σ偏振光（E⊥C）吸收；同时通过偏振吸收光谱，计算了晶体吸收峰的半高宽度和吸收截面；与Er^3＋：YVO4，Er^3＋：GdVO4晶体吸收峰的半高宽度和吸收截面进行了比较。其荧光发射（^4I13/2-^4I15/2跃迁）峰值波长在1．5μm，荧光寿命为4．7ms；光谱特性表明Er^3＋：Y0.5Gd0.5VO4晶体是潜在的高效率激光晶体材料。     

水热法制备近红外发光NaLa(WO4)2∶Ln(Ln=Er, Nd)球形粒子的研究

利用水热法制备了NaLa（WO4）2∶Ln（Ln=Er,Nd）球形粉末,分别用XRD,TEM和发光光谱等对粉末的物相、形貌、发光性质进行研究。XRD和SEM结果表明：制得的NaLa（WO4）2∶Ln（Ln=Er,Nd）粉末为白钨矿晶型,分散性良好,粒度均匀,呈规则的球形,粒径为1μm左右。发光光谱的测试表明：样品的最佳掺杂浓度为1.0%;随着煅烧温度的增加,样品发光强度逐渐增大;700℃下煅烧时最佳煅烧时间是4 h。     

掺三价铈离子四偏磷酸盐NaLn(PO3)4 (Ln=La, Gd)的真空紫外光谱研究

用高温固相法合成了NaLn（PO3）4：1．0％（原子分数）Ce^3＋（Ln=La,Gd）两种粉末发光材料,在合肥国家同步辐射实验室（NSRL）测得两种样品中Ce^3＋的真空紫外光谱。根据真空紫外光谱图,得到了两种稀土偏磷酸盐中所掺Ce^3＋离子5d轨道的能级分裂图。结合NaLa（PO3）4和NaGd（PO3）4的单晶结构数据,发现随着Ln-O平均键长的减小,Ce^3＋离子5d轨道的晶场劈裂（εcfs）、重心位移（εc）和总的红移（total redshilt,D）均增大。根据配体极化模型,计算了两种化合物中掺杂Ce^3＋离子的有效平均键长（Reff）和光谱极化率（αsp）,发现随着平均键长Rav（Ln—O）变短,Ce^3＋离子的光谱极化率（αsp）也随之减小。     

LaAl3(BO3)4的合成及其晶体结构的研究

在研究LnAl3(BO3)(Ln=稀土元素，Y）的合成及发光特性过程中，发现镧铝硼酸盐LaAl3(BO3)4具有一种新的晶体结构。本文用助熔剂法合成了LnAl3(BO3)4(Ln=Gd,La)单晶样品，LaAl3(BO3)4为薄板状，而GdAl3(BO3)4为六方的棒状，用TREOR90程序对LaAl3(BO3)4粉末样品的X射线衍射数据进行了指标化，结果为：LaAl3(BO3)4属正交晶系，晶胞参数为a=0.93586(4)nm,b=0.79904(3)nm,c=0.40626(6)nm,V=0.34595nm^3，在1000℃空气环境下，用硝酸盐热分解法合成了单相LnAl3(BO3)4:E3 （Ln=Gd,La)荧光粉并研究了其发光特性，结果表明：LnAl3(BO3)4:Eu^3 (Ln=Gd,La)是非常有前途的等离子显示器用荧光粉。     

共沉淀法合成的（Y，Gd）BxV1-xO4-x：Eu荧光粉的光谱特性研究

采用共沉淀反应软化学法合成了体色洁白的（Y，Gd）BxV1-xO4-x：Eu^3＋荧光粉。在147nm真空紫外线的激发下，（Y，Gd）BxV1-xO4-x：Eu^3＋荧光粉的发射主峰位于619nm，红色色纯度优于PDP用商品（Y，Gd）BxV1-xO4-x：Eu^3＋荧光粉，但其相对发光亮度只有商品粉的90％，是一种有前途的PDP用和荧光灯用的红色荧光粉。     

GdF3∶Er^3＋,Yb^3＋的合成和上转换发光特性

采用水热法制备了Er^3＋离子浓度为3%,Yb^3＋离子浓度分别为10%,20%的GdF3∶Er^3＋,Yb^3＋。XRD结果表明：合成的样品均为正交结构的GdF3,Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品的晶粒尺寸分别为28和26nm。研究了980nm红外光激发的上转换发射光谱。结果表明：红光和绿光发射分别来自于Er^3＋离子的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁。样品的绿光发射强度较红光发射强。但绿光和红光发射的相对强度比例与Yb^3＋离子浓度有关。对Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品中可能的上转换发光机制进行了讨论。     

Ce3+在LnOX(Ln=La,Gd或Y;X=Cl,Br或I)中的发光

以激发光谱和发光光谱研究了Ce³⁺在LnOX中的发光。光谱表明当X相同而Ln不同时,谱图上Ce³⁺峰的位置只有较小的移动;而X不同时Ce³⁺峰的位置有明显和有规律地移动,即按照Cl——Br——I次序往长波方向移动,这个次序与X的电负性减小的次序是一致的。还可以看到Ln=La时与Ln=Gd或Y时有差别,而且Ln=La时stokes位移较大,从离子半径角度对这些进行了讨论。     

Ce~(3+)在LnOX(Ln=La,Gd或Y;X=Cl,Br或I)中的发光

以激发光谱和发光光谱研究了Ce~(3+)在LnOX中的发光。光谱表明当X相同而Ln不同时,谱图上Ce~(3+)峰的位置只有较小的移动;而X不同时Ce~(3+)峰的位置有明显和有规律地移动,即按照Cl——Br——I次序往长波方向移动,这个次序与X的电负性减小的次序是一致的。还可以看到Ln=La时与Ln=Gd或Y时有差别,而且Ln=La时stokes位移较大,从离子半径角度对这些进行了讨论。     

ZnO-P2O5:Tb3+玻璃的热释光研究

采用高温熔融法制备了ZnO-P2O5：Tb^3＋玻璃,并以热释光为手段,研究了基质组成、Tb^3＋掺杂浓度、熔制气氛、Tb^3＋与其他稀土离子共掺等因素对ZnO-P2O5：Tb^3＋玻璃的发光中心、陷阱浓度及陷阱能级分布的影响。结果表明：ZnO含量的增加,使得与Zn^2＋配位的氧空位的数量增多,导致50-150℃低温区对应的陷阱浓度增加;还原气氛下,Tb^3＋掺杂后,一方面形成发光中心使得热释光强度提高,另一方面,可能由于不等价取代基质中的Zn^2＋离子产生新的缺陷使得陷阱能级加深;空气气氛下,大部分Tb^3＋被氧化成Tb^4＋,发光中心浓度降低;Ce^3＋,Eu^3＋,Dy^3＋,Nd^3＋,Pr^3＋和Er^3＋与Tb^3＋共掺时,陷阱能级深度与陷阱中心的电荷密度发生了不同程度的变化。     

RbLn2F7的水热合成及RbLn2F7:Eu3+(Ln=Gd,Y)的VUV光谱

利用水热方法合成出RbLn2F7（Ln=Gd，Y，Er，Yb和Lu），均为六方RbEr2F7型结构。掺杂Eu^3＋离子样品的光谱表明水热产物中氧杂质含量极低。在RbGd2F7：Eu^3＋（0．5mol％）的激发光谱中只观测到Gd^3＋离子f-f跃迁，Eu^3＋离子的激发跃迁很弱。激发Gd^3＋离子到^6IJ能级后，观测到Eu^3＋离子的特征发射，Gd^3＋离子与Eu^3＋离子之间存在能量传递过程。Eu^3＋离子的^5D0→^7F1和^5D0→F2跃迁发射较强，表明稀土离子在六方HbLn2F7中处于非中心对称的格位。     

Ln3UO6Cl3 (Ln=La,Pr, Nd) -. Die ersten Oxochlorouranate der Seltenen Erden

Ln₃UO₆Cl₃ (Ln=La, Pr, Nd) — The First Oxochlorouranates of the Rare Earths . The new compounds Ln₃UO₆Cl₃ (Ln=La, Pr, Nd) were prepared by heating stoichiometric amounts of LnOCl/Ln₂O₃/U₃O₈ (7 : 1 : 1) (Ln=La, Nd) and PrOCl/Pr₆O₁₁/U₃O₈ (12 : 1 : 2) in silica ampoules (5 d, 1000°C, Ln=La; 9 d 800°C, Ln=Pr, Nd) in the presence of an excess of chlorine [p(Cl₂, 25°C)=1 atm]. Single crystals were obtained by chemical transport reactions using chlorine [p(Cl₂, 25°C)=1 atm] as transport agent [T₂=1000°C→T₁=900°C (Ln=La); T₂=840°C→T₁=780°C (Ln=Pr, Nd)]. Crystals of Ln₃UO₆Cl₃ (Ln=La, Pr, Nd) were investigated by X-ray diffraction methods and La₃UO₆Cl₃ additionally by high resolution electron microscopy. The compounds Ln₃UO₆Cl₃ crystallize in the hexagonal spacegroup P6₃/m (No. 176) with Z=2 formula units per unit cell. Isotypical structure refinements resulted in R=3.04% respectively R_w=1.91% (Ln=La), R=4.72% respectively R_w=3.80% (Ln=Pr) and R=3.99% respectively R_w=2.49% (Ln=Nd). Uranium is coordinated with six oxygen atoms forming a trigonal prism. Lanthanide ions are 10-coordinated (6 oxygen atoms, 4 chlorine atoms).     

Interaction in Systems Ln2O3-CsPO3 and Ln2O3- UO3-CPO3

Abstract

The systems Ln₂O₃-CsPO₃ and Ln₂O₃-UO₃-CsPO₃ were investigated and three sets of compounds A, B, C were isolated.     

钙钛矿型氧化物Ln0.5Sr0.5CoO3的制备与电输运性能

采用固相反应法合成钙钛矿氧化物材料Ln0.5Sr0.5CoO3（h=La，Pr，Nd，Sm，Eu）的超细粉体，研究了不同稀土元素掺杂时的晶体结构和电输运性能，分析了该钙钛矿体系结构的形成过程。实验表明，当烧结温度达到1200℃时，通过固相反应法可以形成稳定的单一的钙钛矿相。样品电导率在700℃附近出现最大值，低温段的导电行为符合小极化子导电机制，La0.5Sr0.5CoO3材料的电导率在中温范围内最大，适合作为中温固体燃料电池的阴极材料。     

Microwave synthesis and photoluminescent properties of Sr2CeO4/Ln3+ (Ln = Er, Ho, Tm)

Sr₂CeO₄/Ln³⁺ (Ln = Er, Ho, Tm) phosphors were synthesized with the microwave radiation method for the first time. The luminescent properties of the samples were investigated and the up-conversion luminescence of Er³⁺, Ho³⁺ and Tm³⁺ doped Sr₂CeO₄ phosphors was observed. The spectra indicate that the energy transfer takes place from the triplet excited state of MLCT (metal-to-ligand charge transfer) state for Sr₂CeO₄ (sensitizer) to the rare earth ions (activator). __________ Translated from Journal of Hebei Normal University (Natural Science Edition), 2007, 31(2): 212–216 [译自: 河北师范大学学报 (自然科学版)]     

Synthesis and Characteristics of Self-Assembled Multifunctional Ln3+-DNA Hybrid Coordination Polymers

Owing to the unique catalytic, optical and magnetic properties, lanthanides (Ln) as multicomponent biomarkers, are widely used in the field of optical sensing, mass spectrometry and magnetic resonance imaging. As ligands, DNA molecules have good biocompatibility, high stability, cost efficiency, programmability and biodegradability. Based on the coordination-driven self-assembly between Ln ions (Ln³⁺) and DNA molecules, a multifunctional Ln³⁺-DNA hybrid coordination polymers (CPs) were synthesized. Not only a series of different Ln³⁺ (single Ln³⁺) and DNA hybrid CPs were synthesized, but one hybrid CP contains two kinds of Ln³⁺ was obtained. Besides, the synthetic CPs in cell fluorescence imaging and miRNA sensing also exhibited high performance. This work provides a novel idea for the synthesis of DNA based nanomaterials, which is promising for biologically-related applications.     

镧系离子(Ln3+)配合物近红外发光

本文阐述了镧系离子(Ln3+)配合物近红外发光机理及特点，同时就其研究进展及应用情况作了简要介绍。     

Synthesis and characterization of heterodinuclear Ln(3+)-Fe3+ and Ln(3+)-Co3+ complexes,bridged by cyanide ligand (Ln3+ = lanthanide ions). Nature of the magnetic interaction in the Ln(3+)-Fe3+ complexes

The reaction of Ln(NO3)3.aq with K3[Fe(CN)6] or K3[Co(CN)6] in N,N'-dimethylformamide (DMF) led to 25 heterodinuclear [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O and [Ln(DMF)4(H2O)3(mu-CN)Co(CN)5].nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr(3+)-Fe3+), (Tm(3+)-Fe3+), (Ce(3+)-Co3+), (Sm(3+)-Co3+), and (Yb(3+)-Co3+) have been structurally characterized; they crystallize in the equivalent monoclinic space groups P21/c or P21/n. Structural studies of these two families show that they are isomorphous. This relationship in conjunction with the diamagnetism of the Co3+ allows an approximation to the nature of coupling between the iron(III) and the lanthanide(III) ions in the [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O complexes. The Ln(3+)-Fe3+ interaction is antiferromagnetic for Ln = Ce, Nd, Gd, and Dy and ferromagnetic for Ln = Tb, Ho, and Tm. For Ln = Pr, Eu, Er, Sm, and Yb, there is no sign of any significant interaction. The isotropic nature of Gd3+ helps to evaluate the value of the exchange interaction.     

Phase diagrams of the Ln2S3-EuS (Ln = La-Gd) systems

The phase diagrams of the Ln₂S₃-EuS (Ln = La-Gd) systems were studied. In these systems, continuous series of solid solutions form between γ-Ln₂S₃ and EuLn₂S₄ (Th₃P₄ structural type), and also eutectics between EuLa₂S₄ and a solid solution based on EuS form at the following coordinates: 71.5 mol % EuS, 2280 K; 66.5 mol % EuS, 2240 K; and 63.5 mol % EuS, 2100 K. The characteristics of the forming compounds are the following: EuLa₂S₄: a = 0.8759 nm, T _melt = 2420 K, and H = 2380 MPa; EuNd₂S₄: a = 0.8615 nm, T _melt = 2380 K, and H = 2530 MPa; and EuGd₂S₄: a = 0.8507 nm, T _melt = 2300 K, and H = 2670 MPa.     

Phase diagrams of the systems Ln2S3-Ln2O3 (Ln = Gd, Dy)

For the first time, the phase diagrams of the systems Gd₂S₃-Gd₂O₃ and Dy₂S₃-Dy₂O₃ were constructed within the temperature range from 870 K to the melting point. In the systems, compounds Gd₂O₂S and Dy₂O₂S form in hexagonal symmetry with the unit cell parameters a = 0.3858 nm, c = 0.6667 nm and a = 0.3802 nm, c = 0.6591 nm, respectively. The compounds melt congruently at 2430 and 2370 K, respectively. Their microhardnesses are 4900 and 5150 MPa, respectively. The coordinates of eutectics are the following: 21 mol % Gd₂O₃, T _eu = 1875 K; 83 mol % Gd₂O₃, T _eu = 2270 K; 20 mol % Dy₂O₃, T _eu = 1780 K; and 81 mol % Dy₂O₃, T _eu = 2220 K.