180 resultados para 3d transition metal complexes


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In this paper the magnetic and magneto-optical properties of amorphous rare earth-transition metal (RE-TM) alloys as well as the magnetic coupling in the multi-layer thin films for high density optical data storage are presented. Using magnetic effect in scanning tunneling microscopy the clusters structure of amorphous RE-TM thin films has been observed and the perpendicular magnetic anisotropy in amorphous RE-TM thin films has been interpreted. Experimental results of quick phase transformation under short pulse laser irradiation of amorphous semiconductor and metallic alloy thin films for phase change optical recording are reported. A step-by-step phase transformation process through metastable states has been observed. The waveform of crystallization propagation in micro-size spot during laser recording in amorphous semiconductor thin films is characterized and quick recording and erasing mechanism for optical data storage with high performance are discussed. The nonlinear optical effects in amorphous alloy thin films have been studied. By photo-thermal effect or third order optical nonlinearity, the optical self-focusing is observed in amorphous mask thin films. The application of amorphous thin films with super-resolution near field structure for high-density optical data storage is performed. (c) 2007 Elsevier B.V. All rights reserved.

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To optimize the performance of longitudinally pumped Yb^(3+):Y2O3 ceramic lasers, cavity parameters such as material length and output coupler transmission at a certain laser output power are calculated numerically using quasi-three-level laser model. The results show great potential of Yb^(3+):Y2O3 ceramics for highly efficient diode-pumped solid-state lasers.

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综述了过渡金属杂质(Cu,Fe)和稀土杂质(Dy,Pr,Sm,Ce)对掺钕磷酸盐激光玻璃吸收损耗及Nd^3+荧光猝灭影响的研究状况。

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The optical loss coefficient at 1053-nm wavelength, influenced by Fe ions in N31-type Nd-doped phosphate laser glass, was determined precisely and analyzed in detail. It is found that the optical loss coefficient per unit of Fe concentration (cm^(-1)/ppmw) increases with Fe concentration in the range of 0---300 ppmw, but it approaches a constant as the Fe concentration is larger than 300 ppmw. Such a concentration effect is due to a shift in the redox equilibrium between Fe3+ and Fe2+ ions in the glass. The effect of oxygen pressure, temperature, and variable valence states of other metal ions in glass samples on the optical loss is also discussed.

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abstract {Silica glass is an attractive host matrix for the emission ions of rare earth and transition metal ions because it has small thermal expansion coefficient, strong thermal resistance, large fracture strength and good chemical durability and so on. However, a major obstacle to using it as the host matrix is a phenomenon of concentration quenching. In this paper, we introduces a novel method to restrain the concentration quenching by using a porous glass with SiO2 content > 95% (in mass) and prepare intense fluorescence high-SiO2 glasses and high-SiO2 laser glass. The porous glass with high-SiO2 content was impregnated with rare-earth and transition metal ions, and consequently sintered into a compact non-porous glass in reduction or oxidization atmospheres. Various intense fluorescence glasses with high emission yields, a vacuum ultraviolet-excited intensely luminescent glass, high silica glass containing high concentration of Er3+ ion, ultrabroad infrared luminescent Bi-doped high silica glass and Nd3+-doped silica microchip laser glass were obtained by this method. The porous glass is also favorable for co-impregnating multi-active-ions. It can bring effective energy transferring between various active ions in the glass and increases luminescent intensity and extend range of excitation spectrum. The luminescent active ions-doped high-SiO2 glasses are potential host materials for high power solid-state lasers and new transparent fluorescence materials.}

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We report on the bluish green upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation. The dependence of the fluorescence intensity on the pump power density of laser indicates that the conversion of infrared irradiation to visible emission is dominated by three-photon excitation process. We suggest that the charge transfer from O-2-to Nb5+ can efficiently contribute to the bluish green emission. The results indicate that transition metal ions without d electrons play an important role in fields of optics when embedded into silicate glass matrix. (C) 2008 Optical Society of America.

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The effects of annealing on the optical properties of InAs/GaAs quantum dots (QDs) grown under different conditions by metalorganic chemical vapor deposition (MOCVD) are studied. A lower QD growth rate leads to an earlier and faster decrease of QD photoluminescence (PL) intensity with increasing annealing temperature. which is proposed to be related to the increased QD two-dimensional (2D)-three-dimensional (3D) transition critical layer thickness at low QD growth rate. High-quality GaAs cap layers grown at high temperature and a low deposition rate are shown to decrease the blueshift of the QDs' emission wavelength significantly during in-situ I h annealing experiments, which is important for the fabrication of long-wavelength InAs/GaAs QD lasers by MOCVD technique. (C) 2009 Elsevier B.V. All rights reserved.

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The magnetic properties of RCo5Ga7 (R = Y, Tb, Dy, Ho and Er) compounds which crystallize in the ScFe6Ga6-type structure have been studied. The compounds with R, Y, Tb, Dy, Ho and Er display behaviour similar to semiconductors. The Co transition metal sublattice is ferrimagnetic with a very low spontaneous magnetization. The ferrimagnetic ordering observed for R = Y, Tb, Dy, Ho and Er is due to the transition metal sublattice with transition temperatures at about 295 K. At low temperatures, the magnetic ordering for R Tb, Dy, Ho and Er is due to the rare-earth sublattice, which is ferromagnetic with a Curie temperature below 5 K. By fitting the linear part of the inverse magnetization, the effective magnetic moment of the R ion is found to be close to its expected theoretical value, with paramagnetic Curie temperatures below 5 K. Due to the paramagnetic nature of the R sublattice above 60 K, the ferrimagnetic ordering temperature of the Co sublattice does not vary with the type of rare-earth ion. The irreversibility of the magnetization of YCo5Ga7, as measured in zero-field cooled (ZFC) and field cooled (FC) states, is attributed to movement of domain walls. Application of a large enough applied field completes the movement of the domain wall from the low-temperature to the high-temperature one at 5 K. With a very low magnetic field 100 Oe, the difference between the ZFC and the FC shrinks. (C) 2004 Elsevier B.V. All rights reserved.

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Atomic force microscopy and photoluminescence spectroscopy (PL) has been used to study asymmetric bilayer InAs quantum dot (QD) structures grow by molecular-beam epitaxy on GaAs (001) substrates. The two InAs layers were separated by a 7-nm-thick GaAs spacer layer and were grown at different substrate temperature. We took advantage of the intrinsic nonuniformity of the molecular beams to grow the seed layer with an average InAs coverage of 2.0 ML. Then the seed layer thickness could be divided into three areas: below, around and above the critical thickness of the 2D-3D transition along the 11101 direction of the substrate. Correspondingly, the nucleation mechanisms of the upper InAs layer (UIL) could be also divided into three areas: temperature-controlled, competition between temperature-controlled and strain-induced, and strain-induced (template-controlled) nucleation. Small quantum dots (QDs) with a large density around 5 x 10(10) cm(-2) are found in the temperature-controlled nucleation area. The QD size distributions undergo a bimodal to a unimodal transition with decreasing QD densities in the strain-induced nucleation area, where the QD densities vary following that of the seed layer (templating effect). The optimum QD density with the UIL thickness fixed at 2.4 ML is shown to be around 1.5 x 10(10) cm(-2), for which the QD size distribution is unimodal and PL emission peaks at the longest wavelength. The QDs in the in-between area exhibit a broad size distribution with small QDs and strain-induced large QDs coexisting.

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Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

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The optical properties of Au nanoparticles deposited on thermochromic thin films of VO2 are investigated using spectroscopy. A localized modification on the transmittance spectrum of VO2 film is formed due to the presence of Au nanoparticles which exhibit localized surface plasmon resonance (LSPR) in the visible-near IR region. The position of the modification wavelength region shows a strong dependence on the Au mass thickness and shifts toward the red as it increases. On the other hand, it was found that the LSPR of Au nanoparticles can be thermally tunable because of the thermochromism of the supporting material of VO2. The LSPR wavelength, lambda(SPR), shifts to the blue with increasing temperature, and shifts back to the red as temperature decreases. A fine tuning is achieved when the temperature is increased in a stepwise manner.

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本论文共合成了两种类型12个稀土金属配合物和一个硅化合物,分别对它们进行了红外、核磁等表征,对其中的9个配合物进行了晶体结构的测定。考察了配体结构和反应条件对所生成的配合物结构的影响,研究了稀土单烷基配合物的反应性,以及稀土双烷基配合物在烷基铝和有机硼盐的共同作用下对丁二烯聚合的催化活性和选择性。主要工作内容和结论如下: (1) 合成了噻吩苯胺配体(HL1),该配体与(Lu,Y)稀土三烷基化合物反应,通过C–H活化和烷基消除反应制备了稀土(Lu,Y)单烷基配合物1和2,配体以少见的C,N模式配位,S原子并不参与配位。配体(HL1)与Sc三烷基化合物反应制备了配体分别以C, N和N, S配位的双配的Sc配合物5。 (2) 通过改变反应时间和溶剂体系,HL1与稀土钇三烷基化合物反应可得到罕见的由稀土烷基化物和胺化物两部分组成的配合物3,它们通过噻吩环上活化的C原子连接在一起。HL1和Lu(CH2SiMe3)2(THF)2LiCH2SiMe3在甲苯和正己烷溶剂中反应可得到以L12Lu(CH2SiMe3)2为阴离子,Li(THF)4为阳离子的离子对4。 (3) 研究配合物1和2的反应性。1和2与过量的PhSiH3反应得到中心金属与Si元素交换的Si化合物。 (4) 合成了噻吩苯基膦胺配体(HL2-4)和苯基膦胺配体(HL5)配体。HL2-5与稀土(Y, Lu和Sc)三烷基化合物反应制备了稀土双烷基配合物6,7,8,9,10,11和12。进一步研究了稀土金属双烷基配合物6–12对丁二烯的催化特性,发现该系列催化剂具有独特的催化性质,能够催化丁二烯高反1,4-聚合(91.3%),得到的聚合物分子量在1到2万之间,分子量分布较窄(1.4–1.6)。 (5) 研究了金属钇(Y),镥(Lu),钪(Sc)三种中心金属对丁二烯聚合活性和反式1,4选择性的影响,发现催化剂对丁二烯聚合活性和反1,4选择性取决于配合物的中心金属原子,其中选择性最高为钪配合物,催化活性最佳的为钇配合物。 (6) 研究了配体HL2-4的N-芳环上的取代基分别为甲基,乙基,异丙基时催化体系对丁二烯反式1,4聚合活性和选择性的影响,发现随着N-芳环上取代基空间位阻的增大,催化剂活性逐渐下降,选择性逐渐增加,但当其取代基为异丙基时,过大的空间位阻导致活性和选择性同时有明显的下降。我们通过改变噻吩基为苯基,比较了相同聚合条件下含噻吩基的稀土双烷基配合物和含苯基的稀土双烷基配合物对丁二烯聚合活性和选择性的影响,发现噻吩环的存在对催化剂的活性和选择性有较大的影响。 (7) 在相同催化剂条件下,研究了不同聚合条件(不同类型的AlR3,不同类型的Borate,Al/Ln比等)对丁二烯反1,4聚合活性和选择性的影响。 我们发现,在AlR3和Borate这两种影响因素中,以烷基铝的类型对催化剂催化活性和选择性的影响最大,而有机硼盐的影响则比较轻微,其中以烷基铝为AliBu3,Borate为[B(C6F5)4][Me2NHPh]时,反1,4选择性为最佳。Al/Ln增大并不能够显著增加催化剂的活性,对选择性的影响也并不明显,相反,随着铝比的增加,聚合过程中的链转移增加,导致分子量下降,对于该系列稀土烷基催化剂,最佳Ln/Al 为10。

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本文以调控发光颜色、提高发光效率为目的,通过改变配体、中心金属离子、取代基等进行颜色调节;通过引入电子或空穴传输单元,实现发光分子的功能化进而改善载流子传输提高发光效率。文中主要以有机小分子和金属配合物为研究对象,它们本身都具有良好的发光性质。工作集中围绕以下几个问题展开:1、PPV齐聚物是一类高效发光的分子体系,如果在其中嵌入8一取代的哇琳单元对发光会有什么影响?2、使用含噁二唑(具有电子传输功能)的配体得到的金属配合物是否能同时拥有双重功能,即高效发光(金属配合物的特点)和优良的电子传输?3、由N2O-双齿配体转变成N,N-双齿配体,配合物的发光又会如何?4、稀土配合物具有高的光致发光效率,但电致发光效率非常低,能否通过咔哇或呛二吟功能化来改善载流子传输,提高电致发光效率?主要工作及取得的结果概述如下:1、经由Knoevenagel缩合反应合成了一系列共骊的2,21-(1,4-芳二乙烯基)双-8-取代喹啉。单晶X-射线衍射研究表明固态下存在分子间,π…π堆积相互作用,这对于载流子传输是比较有利的。喹啉8-位于的取代基的变化对发光影响不大,表明刚性共扼骨架对发光起主要贡献。改变中心的芳核,明显可以调控发光颜色。当存在分子内电荷转移时,与不存在的相比,发光显著红移。电致发光性质表明这些含双喳琳的PPV齐聚物是良好的发光和电子传输材料。2、存在分子内氢键的化合物2-(2-羟基苯基)-5-苯基-1,3,4-噁二唑(HOXD),具有激发态分子内质子转移(ESIPT)特性。在室温下,用365脚的紫外灯照射时表现强的兰色荧光。室温和低温(77K)下的磷光光谱表明它在固态下具有较强的磷光发射,与理论预测完全一致。多层电致发光器件ITO加PB/HOXD/BCP/Alq3/Mg:Ag最大亮度达到656cd/m2,电流效率为0.37cd/A。当把HoxD掺在cBP中时,亮度和效率都有一定程度的提高,达到870cd/m2和0.82cd/A。3、合成了含有德二哩配体(HOXD)的碱金属配合物MOxD(M=Li,Na,K)。我们发现配合物的发光颜色取决于中心金属离子,LiOXD是一个优良的蓝光材料,半峰宽是65nm,发射峰位在478nm,它也可以作为界面材料使用,起到和LIF相同的作用,即改善电子注入。同时作者首次报道了钠和钾的配合物可以用作发光材料。电致发光性质表明这些配合物是优良的蓝/绿色发光和电子注入/传输材料。4、使用从N双齿配体代替N,O-双齿配体(比如8-羟基喹啉),合成了含有2-(2-羟基喹啉)苯并咪唑的锌、铍和硼配合物。用硼配合物作为发光层的三层器件ITO/NPB/boron-complex/Alq3/LiF/A1所得到的光谱覆盖了从400到750nm的区域,表明获得了一个很好的白色发光。白光分别源于激子和激基复合物发光,由三种成分构成:来自于硼配合物的兰色发光(490nm);来自于Alq3的发光(535nln);NPB和BPh2(Pybm)界面形成的激基复合物发光(610nm)。器件最大亮度是110cd/m2最大效率是0.8cd/A。5、设计、合成了咔唑、噁二唑功能化的稀土馆配合物,期望通过改善空穴和电子传输来提高发光效率。含咔哇的配合物的双层器件发光光谱较宽,包括三价铺的特征发射和一个宽峰,可能是咔唑的发光。当使用TPD做空穴传输层时,噁二唑铺配合物的电致发光器件得到纯正明亮的红色发光,器件结构为ITO/TPD(40nm)/(OXD-PyBM)Eu(DBM)3(SOnm)/LiF(Inm)/Al(200m),启动电压为7.8V,在21v时达到最大亮度322cd/m2。亮度为57cd/m2和13.sv时电流效率最大,为1.9cd/A,对应外量子效率是1.7%。高的效率表明通过引入噁二唑基团,配合物的电子传输能力得到明显改善。6、初步研究了三线态发光的铱的金属有机配合物,得到了高亮度、高效率的绿色发光;对8-羟基喹啉锌配合物的高分子化也做了初步探讨。