Preparation and luminescence properties of ormosil hybrid materials doped with Tb(Tfacac)(3)phen complex via a sol-gel process

In this paper, silica-based transparent organic-inorganic hybrid materials were prepared via the sol-gel process. Tetraethoxysilane (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) were used as the inorganic and organic precursors, respectively. The terbium complex, Tb(Tfacac)(3)phen (Tfacac = 1,1,1-trifluoroacetylacetone, phen = 1, 10-phenanthroline) was successfully doped into organically modified silicate (ormosil) matrix derived from TEOS and GPTMS, and the luminescent properties of the resultant ormosil composite phosphors [ormosil/Th(Tfacac)(3)phen] were investigated compared with those of the Tb(Tfacac)(3)phen incorporated into SiO2 derived from TEOS (labeled as silica/Tb(Tfacac)(3)phen). Both kinds of the materials show the characteristic green emission of Tb3+ ion. The luminescence behavior of the resultant composite products was dependent on the matrix composition. The optimized lanthanide complex concentration in the ormosil/Tb(Tfacac)(3)phen was increased compared with in silica/Tb(Tfacac)(3)phen. Furthermore, the lifetime of Tb3+ in Tb(Tfacac)(3)phen, silica/Tb(Tfacac)(3)phen and ormosil/Tb(Tfacac)(3)phen follows the sequence: onmosil/Tb(Tfacac)(3)phen>silica/Tb(Tfacac)(3)phen>pure Tb(Tfacac)(3)phen.

Preparation and characterization of a layered transparent luminescent thin film of silica-CTAB-Tb(acac)(3) composite with mesostructure

A layered luminescent mesostructured thin film of silica-CTAB-Tb(acac)(3) composite has been synthesized by a dip-coating process through an in situ sol-gel method. The terbium (Tb3+) ion and beta-diketone organic ligand acetylacetone (acac) were introduced into the precursor solution, respectively. The as-synthesized composite film was transparent, colorless and possessed a layered structure. After the composite film was dried at 50 degreesC for a few minutes Tb(acac)(3) complex was synthesized in the mesostructured thin film, which can be indicated by the luminescence of the composite film under the UV lamp. The properties of the samples were characterized by XRD, absorption, Fourier transform infrared spectroscopy, and luminescent spectra.

VUV excitation properties of LnAl(3)B(4)O(12): Re (Ln = Y, Gd; Re=Eu, Tb)

Vacuum ultraviolet excitation spectra of LnAl(3)B(4)O(12):Re (Ln = Y, Gd; Re = Eu, To), along with X-ray photoelectron spectra, were measured. The spectra are tentatively interpreted in terms of the optical properties of the rare earth ions and the band structure. It was found that there is an energy transfer from the hosts to the rare earth ions. It was also found that the top of the valence band in the Gd compound is mainly formed by the 2p levels of O2- and the 4f levels of Gd3+, and in the Y compound mainly by the 2p levels of O2-. (C) 2000 Elsevier Science Ltd. All rights reserved.

Electroluminescent properties of the Tris-(acetylsalicylate)-terbium (Tb(AS)(3))

The solubility of [Tris-(acetylsalicylate)-terbium] [Tb(AS)(3)] is improved to a greater extent than [Tris-(salicylate)-terbium] [Tb(Sal)(3)] following introduction of a flexible acetyl group. Th3+ binds with acetylsalicylate in solution at low pH value and the resultant Tb(AS)(3) has good solubility in chloroform. A Green EL device with the structure ITO/PVK/PVB:PBD: Tb(AS)(3)/ PBD/Al has been fabricated based on soluble Tb(AS)(3), in which Tb(AS)(3) was first used as an emissive center doped with PVK and PBD. The hole-transporting layer and the emissive layer were formed by spin coating. The device exhibited a highly pure characteristic green light of Tb3+. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis and luminescence characteristics of LiMgAlF6:Ln(3+) (Ln = Ce, Eu, Tb)

By solid state reaction, LiMgAlF6 and LiMgAlF6:Ln(3+) are synthetized with the ratio 120/100/110 of LiF/MgF2/AlF3, at 1008 K, in high-purity Ar stream. Their crystal structure which belongs to hexagonal system are determined by X-Ray-Diffraction (XRD). Luminescence characteristics of Ce3+, Eu3+, Tb3+ and sensitization of Ce3+ to Tb3+ in LiMgAlF6 are studied. It is shown that the sensitization of Ce3+ to Tb3+ is efficient and a bright green emission is observed.

Luminescent properties of Ba-3(PO4)(2):Eu, Tb phosphors

Luminescence of europium (III), europium(II) and terbium(III) has been observed in Ba-3(PO4)(2):Eu, Tb phosphors which are synthesized in air atmosphere. The valence state of europium is influenced by amount of terbium. It is notable that the relative intensity of the emission spectra peaks corresponding to Eu2+ is increased if the amount of Tb3+ is increased. These phenomena can be explained by an electron transfer mechanism. We predict a new kind of two-rare-earth codoped trichromatic phosphors in Ba-3(PO4)(2) matrix.

LUMINESCENCE OF BI(3+) AND THE ENERGY-TRANSFER FROM BI(3+) TO R(3+) (R=EU,DY,SM,TB) IN ALKALINE-EARTH BORATES

At room temperature, the Bi3+ ion shows broad band characters of its luminescence in Ca2B2O5, M3B2O6 ( M=Ca,Sr ) and SrB4O7. The maxima of the Bi3+ S-1(0)-->P-3(1) absorption bands are located in the range of 240-300nm, but the energy variation of the corresponding P-3(1)-->S-1(0) emissions is very large. The maxima of these emission bands change from 350nm in Ca3B2O6;Bi3+ to 586nm in SrB4O7:Bi3+. The Stokes shift of the Bi3+ luminescence increases from 6118 cm-1, in Ca2B2O5:Bi3+, to 24439 cm-1, in SrB4O7:Bi3+. The emission intensity of the Bi3+ luminescence increases with the decreasing Stokes shift. It has been found that in Ca2B2O5, the Bi3+ ion could transfer its excitation energy to the R3+ ions ( R=Eu, Dy, Sm, Tb ) , but in, Ca3B2O6 and Sr3B2O6, only Bi3+-->Eu3+ was observed. No energy transfer from Bi3+ to R3+ was detected in SrB4O7.

YVO_4∶RE~(3+)(RE∶Pr、Sm、Tb、Es、Dy)晶体的研究

本文探讨了助熔剂法生长 YVO_4:RE~(3+)(RE:Pr,Sm,Tb,Er,Dy)晶体的工艺。讨论了助熔剂 V_2O_5,Pb_2P_2O_7和温度对晶体生长习性和缺陷的影响。测定了晶体的结构参数和光谱。Y_(0.9)Sm_(0.1)VO_4和 Y_(0.95)Dy_(0.05)VO_4晶体具有很好的光谱特性。

Growth of (10(1)over-bar(3)over-bar) semipolar GaN on m-plane sapphire by hydride vapor phase epitaxy

The crystalline, surface, and optical properties of the (10 (1) over bar(3) over bar) semipolar GaN directly grown on m-plane sapphire substrates by hydride vapor phase epitaxy (HVPE) were investigated. It was found that the increase of V/III ratio led to high quality (10 (1) over bar(3) over bar) oriented GaN epilayers with a morphology that may have been produced by step-flow growth and with minor evidence of anisotropic crystalline structure. After etching in the mixed acids, the inclined pyramids dominated the GaN surface with a density of 2 X 10(5) cm(-2), revealing the N-polarity characteristic. In the low-temperature PL spectra, weak BSF-related emission at 3.44eV could be observed as a shoulder of donor-bound exciton lines for the epilayer at high V/III ratio, which was indicative of obvious reduction of BSFs density. In comparison with other defect related emissions, a different quenching behavior was found for the 3.29 eV emission, characterized by the temperature-dependent PL measurement. (C) 2009 Elsevier B.V. All rights reserved.

Mossbauer spectroscopy study of Fe-57 in R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

Fe-57 Mossbauer spectra for the Fe atoms in the R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb, Dy; T=V, Cr) compounds were collected at 4.2 K. The analysis of Mossbauer spectra was based on the results of magnetization and neutron powder diffraction measurements. The average Fe magnetic moments at 4.2 K, deduced from our data, are in accord with magnetization measurements. The average hyperfine field of Tb3Fe29-xCrx (x=1.0, 1.5, 2.0, and 3.0) decreases with increasing Cr concentration, which is also in accordance with the variation of the average Fe magnetic moment in the Tb3Fe29-xCrx compounds.

Structural and magnetic properties of hydrides R3Fe29-xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and intrinsic magnetic properties of the hydrides R3Fe29 - xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed in this work. The lattice constants a, b, and c and the unit cell volume of R3Fe29 - xVxHy decrease with increasing rare-earth atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in regular anisotropic expansions along the a-, b-, and c-axes in this series of hydrides. Abnormal crystallographic and magnetic properties of Ce3Fe27.5V1.5H6.5, like Ce3Fe27.5V1.5, suggest that the Ce ion is non-triply ionized. Hydrogenation leads to the increase in both Curie temperature for all the compounds and in the saturation magnetization at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Sm, Gd, and Dy, except for Tb. Hydrogenation also leads to a decrease in the anisotropy field at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Gd, Tb, and Dy, except for Sm. The Ce3Fe27.5V1.5 and Gd3Fe28.4V0.6 show the larger storage of hydrogen with y = 6.5 and 6.9 in these hydrides. (C) 1998 Elsevier Science B.V. All rights reserved.

Crystallographic and magnetic properties of R3Fe29-xVxN4 (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and magnetic properties of nitride R3Fe29-xVxN4 (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Nitrogenation leads to a relative volume expansion of about 6%. The lattice constants and unit cell volume decrease with increasing rare-earth atomic number from Nd to Dy, reflecting the lanthanide contraction. On average, the Curie temperature increases due to the nitrogenation to about 200 K compared with its parent compound. Generally speaking, nitrogenation also results in a remarkable improvement of the saturation magnetization and anisotropy fields at 4.2 K and room temperature for R3Fe29-xVxN4 compared with their parent compounds. The transition temperature indicates the spin reorientations of R3Fe29-xVxN4 for R = Nd and Sm are at around 375 and 370 K which are higher than that of R3Fe29-xVx, for R = Nd and Sm 145 and 140 K, respectively. The magnetohistory effects of R3Fe29-xVxN4 (R = Ce, Nd, and Sm) are observed in low fields of 0.04 T. After nitrogenation the easy magnetization direction of Sm3Fe26.7V2.3 is changed from an easy-cone structure to the b-axis. As a preliminary result, a maximum remanence B-r of 0.94 T, an intrinsic coercivity mu(0)H(C) of 0.75 T, and a maximum energy product (B H)(max) of 108.5 kJ m(-3) for the nitride magnet Sm3Fe26.7V2.3N4 are achieved by ball-milling at 293 K.

Hydride Vapor Phase Epitaxy Growth of Semipolar, 10(1)over-bar(3)over-barGaN on Patterned m-Plane Sapphire

We have investigated the hydride vapor-phase epitaxy growth of (10 (1) over bar(3) over bar)-oriented GaN thick films on patterned sapphire substrates (PSSs) (10 (1) over bar0). From characterization by atomic force microscopy, scanning electron microscopy, double-crystal X-ray diffraction, and photoluminescence (PL), it is determined that the crystalline and optical qualities of (10 (1) over bar(3) over bar) GaN epilayers grown on the cylindrical PSS are better than those on the flat sapphire. However, two main crystalline orientations (10 (1) over bar(3) over bar) and (11 (2) over bar2) dominate the GaN epilayers grown on the pyramidal PSS, demonstrating poor quality. After etching in the mixed acids, these (10 (1) over bar(3) over bar) GaN films are dotted with oblique pyramids, concurrently lining along the < 30 (3) over bar2 > direction, indicative of a typical N-polarity characteristic. Defect-related optical transitions of the (10 (1) over bar(3) over bar) GaN epilayers are identified and detailedly discussed in virtue of the temperature-dependent PL. In particular, an anomalous blueshift-redshift transition appears with an increase in temperature for the broad blue luminescence due to the thermal activation of the shallow level.

P_(507)萃取分离Gd、Tb、Dy三出口工艺及多元稀土萃取分离数学模拟的研究

溶剂分馏萃取是分离、提纯、富集物质的有效方法之一，由于它具有分离效果好，易于操作等优点。因此，在稀土萃取分离工艺中得到了广泛的应用。但是，每个分馏萃取工艺只能分离两个组份，若要分离所有稀土元素，流程较长。为改进生产，本工作提出了一种三出口萃取分离工艺流程。这种工艺流程可视为由两个萃取段和两个洗涤段组成，由于在两个洗涤段中，两相稀土浓度较高、稀土交换量较大，故可使级数减少。采用此工艺流程进行了P_(507)萃取分离Gd、Tb、Dy三组元素的串级模拟实验，得到了纯度大于99.99％的La－Gd，纯度大于99.8％的Dy－Lu和含量高于65％的Tb_4O_2富集物。Tb的收率大于95％。串级总级数为38级。通过对P_(507)萃取实际体系中稀土元素行为的研究，建立了多元体系中稀土在两相分配的经验模型。Z＝C_1H~(C2)×T~(C_3)e~(c_4X(Tb)+C_5X(Dy))和具有一定物理意义的半热力学半经验模型。YT=(Z/H)~3[Σ from i=1 to m of CiXi + Co]根据氨化P_(507)萃取工艺中稀土总浓度在两相的分布规律，提出了一种适合氨化P_(507)萃取分离多元混合稀土工艺的串级计算方法，并用FORTRAN语言编写 了计算程序。使用自编的计算程序进行了氨化P_(507)萃取分离Gd、Tb、Dy三出口工艺的串级模拟计算，计算结果与实验值基本一致。同时，对文献中报导的中间某级开设出口的一分三工艺也进行了串级计算，根据计算结果讨论了两种工艺的优缺点。对恒定混合萃取比的多元稀土萃取分离工艺，进行了在不同串级条件下分界元素在各级的积累及易萃组份和难萃取份的有效分离系数在各级变化规律的计算。结果表明，有效分离系数在级体中出现一极小值β~*，并且β~*值的大小与其出现在级体中的位置随条件不同而改变。对同一萃取体系，当出口产品较纯时，用线性回归分析法关联计算数据得到了β~*与出口产品组成和总萃取比的经验关系式，在萃取段有（A、B与C分离的工艺）β~*/β_B~C=C1+C2EM+C_3ln (A1)/(B1)引入有效分离系数后，进行了环烷酸萃取分离钇与镧系元素的串级模拟计算，计算结果与实验值基本吻合。