稀土配合物掺杂的中孔杂化发光材料的制备及其表征

稀土配合物由于具有优良的窄带发光性能和较长的荧光寿命，因而在光电学领域比如激光材料或者荧光标记上引起了广泛的兴趣和应用。吸附在固体表面的稀土配合物的发光性质得到了广泛的研究。MCM-48中孔材料是M41S家族中的一种，具有直径20-30A三维结构的中孔孔道，比MCM-41的一维结构孔道更有优势，比如它可以最大可能的避免客体分子的堆积现象。因此本论文中我们研究了将稀土（Eu3+）β-二酮（DBM＝dibenzoylmethane）配合物掺杂到纯硅MCM-48以及三种有机基团嫁接的有机－无机杂化MCM-48的孔道中去，得到了各种不同的杂化中孔发光材料。首先烧结后的MCM-48被装载稀土Eu（OBM）3'2H2O配合物之后。XRD结果说明稀土配合物被组装到了MCM-48中，其有序结构因为稀土配合物的进入而受到一定的影响，但是样品仍保持了MCM-48的立方相结构。分别通过吸收光谱和热失重的方法计算了掺杂后的发光MCM-48样品进行洗涤后留在MCM一48中配合物的量。固体漫反射光谱在紫外区有一个OBM配体的Sn基态能级（π）到S1激发态能级份＊）的电子跃迁形成的吸收宽带。可见区还观察到E护”离子的4f-4畴征吸收线。与稀土配合物中的OBM配体相比，掺杂MCM-48样品的Sn-S1吸收带均发生蓝移，反映了S1能级向高能方向移动。然后采用了室温两步合成法合成MCM-48，模板剂的去除采用了溶剂萃取法。最佳掺杂浓度为6.98×10-3 mol/l；同时最佳掺杂时间为24小时。在同样的掺杂条件下，稀土配合物在基质中的掺杂量MCM-48＞MCM-41＞＞SiO2。萃取之后的MCM-48在外形上近乎于球形，粒子的直径在0.7-1.2μm之间。粒子显现出多孔的海绵状表面形态，并且具有晶体结构外形，呈菱形十二面体被削去顶端立方体的结构。而且在粒子的表面观察到了类似螺旋结构的孔道，我们认为这是MCM一48所特有的双螺旋型三维孔道结构，这是到目前为止首次报道利用扫描电镜观察到中孔分子筛的孔道结构。荧光光谱结果观察到了激发峰的最大值由于纳米粒子效应出现的蓝移现象。不同基质中的发射系数QZ和04比较可知配合物在三种基质SiO2、MCM-41和MCM-48中环境的极性相差不大。掺杂到中孔MCM-48材料中的稀土配合物的热稳定性比在MCM-41中强，这是由于MCM-48的三维孔道对配合物的保护作用。室温条件下合成的MCM-48分子筛利用后合成嫁接的方法[post-synthesis grajng（PSG）]进行表面修饰，修饰剂选用了带有功能性乙烯基的VTES，链长最短的MTES以及带有氨基的长链NTSED。稀土Eu（DBM）3'2H2O配合物被组装到杂化中孔分子筛材料中。红外光谱与2951核磁共振光谱表明MCM-48的表面被成功的接枝上了有机M下任S，盯任s，N丁s任D基团。与MCM-48相比，MCM-48-R的表面积、孔体积和孔径的减少有以下NTSED＞VTES＞MTES的顺序。这也许是修饰的有机基团不同的链的长度不同的原因。稀土配合物在这三种有机一无机杂化基质环境的极性比纯硅MCM-48要增大。同时配合物在三种基质的中的QZ的值及发光效率的顺序为：MCM-48-MTES＜MCM-48-VTES＜MCM-48-NTSED，说明MCM-48经过三种有机硅氧烷修饰之后孔道极性也遵循同样的顺序，可以认为这是由于三种有机基团的链长的不同造成的，链长越长则修饰之后孔道极性增大的就越多。最后通过溶胶一凝胶过程利用提拉法（Dip-coating method）制备了具有中孔结构的SiO2-CTAB-Tb（acac）3透明发光薄膜（Mesostructed Iuminescence thin film，略为MLTF），稀土配合物利用原位合成（In-situ）的办法掺入到透明薄膜中。对薄膜进行热处理过程表明薄膜中的稀土配合物在50℃的时候开始形成。XRO结果表明稀土离子及有机配体的掺入对薄膜中孔相的结构没有太大的影响，荧光薄膜仍保持层状结构。红外光谱结果说明制备的中孔薄膜是由CTAB和硅氧烷聚合物组成的复合薄膜。荧光薄膜的发射光谱给出了Th3+离子的特征发射峰，荧光薄膜中有机配体与丁b离子之间发生了能量传递现象。因为在热处理过程中有机配体逐渐代替了开始与Tb离子配位的OH基团，使得二者间的能量传递更加有效，从而导致了荧光的增强。

Fano effect on shot noise through a Kondo-correlated quantum dot

Transport in a semiopen Kondo- correlated quantum dot is mediated through more than one quantum state. Using the Keldysh technique and the equation of motion method, we study the shot noise S for a wide range of source- drain voltages V-sd within a model incorporating the additional states as a background continuum, demonstrating the importance of the Fano interference. In the absence of the interference, the noise is revealed to be a probe of the second moment of the local density of states, and our theory reproduces the well- known peak structure around the Kondo temperature in the S-V-sd curve. More significantly, it is found that taking account of the background transmission, the voltage dependence of the noise exhibits rich peak- dip line shapes, indicating the presence of the Fano effect. We further demonstrate that due to its two- particle nature, the noise is more sensitive to the quantum interference effect than the simple current.

长江口南汇潮滩湿地污水处理系统的净化功能

2002年8月～12月对长江口南汇潮滩湿地处理系统对污水净化效果进行了研究,分析了潮滩沉积物中N、P含量变化及其与功能细菌含量间的关系,以及芦苇对污染物质的直接去除作用。结果表明:潮滩湿地对污水的净化效果显著,对TN、TP和COD的去除率分别达到94.06%,76.82%和92.47%;沉积物中N、P含量随样点与排污口间距离增大呈下降趋势;沉积物中NH4+—N、NO3-—N、DIP含量与功能细菌数量间呈良好的正相关;收割芦苇去除的N、P量分别只占全年排入湿地总量的2.201×10-5%、4.552×10-4%。潮滩湿地对污染物的去除主要通过:潮汐稀释转移,沉降,滩面沉积物吸附等物理过程和微生物分解等生物过程的综合作用,而潮滩植物的直接去除作用仅占很小部分。

Model analysis of dissolved inorganic phosphorus exports from the Yangtze river to the estuary

In this paper, we estimate the inputs of phosphorus (P) to the Yangtze River Basin and exports of dissolved inorganic phosphorus (DIP) from the river to the estuary for the period 1970-2003, by using the global NEWS-DIP model. Modeled DIP yields range from 2.5 kg P km(-2) yr(-1) in 1970 to 4.6 kg P km(-2) yr(-1) in 1985, and then dramatically increase to 14.1 kg P km(-2) yr(-1) in 2003. No significant difference between the modeled and measured values at the level of P = 0.05 is observed. The study also demonstrates variable source contributions of P to the modeled DIP during the period 1970-2003. Point sewage P input accounted for approximately 100% in the period 1970-1985 and substantially decreased to 24.8% in 2003. Chemical fertilizer contributed 25.4% of DIP yields in 1986 and increased continuously to 50.3% in 2003, while a stable trend in manure P contribution averaging 22.9% of DIP yields was shown in the same period. The study concludes that P inputs to the Yangtze River Basin and the river DIP export to the estuary have substantially increased during the study period consequence to human pressure.

Reversible Nanopatterning on Self-Assembled Monolayers on Gold

The reversible fabrication of positive and negative nanopatterns on 1-hexadecanethiol (HDT) self-assembled monolayers (SAMs) on Au(111) was realized by bias-assisted atomic force microscopy (AFM) nanolithography using an ethanol-ink tip. The formation of positive and negative nanopatterns via the bias-assisted nanolithography depends solely on the polarity of the applied bias, and their writing speeds can reach 800,um/s and go beyond 1000 mu m/s, respectively. The composition of the positive nanopatterns is gold oxide and the nanometer-scale gold oxide can be reduced by ethanol to gold, as proved by X-ray photoelectron spectroscopy (XPS) analysis, forming the negative nanopatterns which can be refilled with HDT to recover the SAMs.

Synthesis of Ruthenium Dioxide Nanoparticles by a Two-Phase Route and Their Electrochemical Properties

Dissolvable, size- and shape-controlled ruthenium dioxide nanoparticles are successfully achieved through a two-phase route. The influence of reaction time, temperature, and monomer concentration and the nature of capping agents on the morphologies of nanoparticles are studied through transmission electron microscopy (TEM). A possible mechanism for the formation and growth of nanoparticles is also involved. X-ray powder diffraction (XRD) confirms the amorphous structure for as-prepared ruthenium dioxide nanoparticles. Samples are immobilized by simple dip-coating on a current collector, and the cyclic voltammetry measurement is utilized to investigate their electrochemical properties. The specific capacitance of one sample can teach as high as 840 F g(-1), which reveals the promising application potential to electrochemical capacitors.

Manipulations of atoms and molecules by scanning probe microscopyk

Scanning probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), has become a powerful tool in building nanoscale structures required by modern industry. In this article, the use of SPM for the manipulation of atoms and molecules for patterning nanostructures for opt-electronic and biomedical applications is reviewed. The principles and procedures of manipulation using STM and AFM-based technologies are presented with an emphasis on their ability to create a wide variety of nanostructures for different applications. The interaction among the atoms/molecules, surface, and tip are discussed. The approaches for positioning the atom/molecule from and to the desired locations and for precisely controlling its movement are elaborated for each specific manipulation technique. As an AFM-based technique, the dip-pen nanolithography is also included. Finally, concluding remarks on technological improvement and future research is provided.

Sol-ogel deposition and luminescence properties of lanthanide ion-doped Y2(1-x)Gd2xSiWO8 (0 <= x <= 1) phosphor films

Y2(1-x) Gd2xSiWO8 : A ( 0 <= x <= 1; A= Eu3+, Dy3+, Sm3+, Er3+) phosphor films have been prepared on silica glass substrates through the sol - gel dip-coating process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscope (AFM), scanning electron microscopy (SEM) and photoluminescence spectra as well as lifetimes were used to characterize the resulting films. The results of the XRD indicated that the films began to crystallize at 800 degrees C and crystallized completely at 1000 degrees C. The AFM and SEM study revealed that the phosphor films, which mainly consisted of closely packed grains with an average size of 90 - 120 nm with a thickness of 660 nm, were uniform and crack free. Owing to an efficient energy transfer from the WO42- groups to the activators, the doped lanthanide ion ( A) showed its characteristic f - f transition emissions in crystalline Y2(1-x) Gd2xSiWO8 (0 <= x <= 1) films. The optimum concentrations for Eu3+, Dy3+, Sm3+, Er3+ were determined to be 21, 5, 3 and 7 mol% of Y3+ in Y2SiWO8 films, respectively.

Effects R3+ on the photoluminescent properties of Ca2R8(SiO4)(6)O-2 : A (R = Y, La, Gd; A= Eu3+, Tb3+) phosphor films prepared by the sol-gel process

Using CaCO3, metal oxides (all dissolved by nitric acid) and tetraethoxysilane Si(OC2H5)(4) (TEOS) as the main starting materials, Ca2R8(SiO4)(6)O-2:A (R = Y, La, Gd; A = EU3+, Tb3+) phosphor films have been dip-coated on quartz glass substrates through the sol-gel process. X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the 1000 degreesC annealed films are isomorphous and crystallize with the silicate oxyapatite structure. AFM and SEM studies revealed that the phosphor films consisted of homogeneous particles ranging from 30 to 90 nm, with an average thickness of 1.30 mum. The Eu3+ and Tb3+ show similar spectral properties independent of R 3, in the films due to their isomorphous crystal structures. However, both the emission intensity and lifetimes of Eu3+ and Tb3+ in Ca2R8(SiO4)(6)O-2 (R = Y, La, Gd) films decrease in the sequence of R = Gd > R = Y > R = La, which have been explained in accordance with the crystal structures.

The influence of tip performance on scanning probe lithography

Scanning probe lithography (SPL), employing the tip of an atomic force microscope to mechanically pattern various materials in nanoscale region has provided a simple but significant method for making nanostructures. We use this technique for the lithography of several kinds of substrate surfaces. The tip performance has been found to be a crucial factor in the lithographic process. Four types of cantilevers are employed in nanolithography, including standard silicon nitride (DNP), tapping mode(TM) etched silicon (TESP(W)), uncoated silicon cantilever (NSC21/50) and conductive platinum/iridium-coated probe. Results demonstrate that tips with smaller spring constants can not be used for physically scribing and nanomanipulating in our experiment. The possible mechanism of our experiment is discussed.

Optical intensity gradient by colloidal photonic crystals with a graded thickness distribution

Gradient colloidal crystals with a thickness gradient were prepared by the vertical deposition technique with vertically graded concentration suspensions. The thickness of the gradient colloidal crystal gradually changes at different positions along the specific gradient direction of the crystal. The thickness gradient was determined by the concentration gradient, depending on the initial colloidal concentration and the settling time. The optical transmission intensity at the dip wavelength can be tuned by changing the thickness of the colloidal crystals. The gradient colloidal crystals lead to a gradient of optical intensity at the dip in transmission light. The gradient of optical intensity at the dip increases as the thickness gradient of the colloidal crystal increases.

Photoluminescent properties of sol-gel derived (La, Gd)MgB5O10 : Ce3+/Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped (La,Gd)MgB5O10 nanocrystalline thin films were deposited on silica glass substrates by a sol-gel dip-coating process using triethyl borate B(OC2H5)(3) as the boron source. The results of XRD indicated that the films have fully crystallized after annealing at 800 degrees C. The films are transparent, uniform and crack free with a thickness of about 300 nm, consisting of particles with an average grain size of 50 nm. The luminescence and energy transfer properties of Ce3+ and Tb3+ have been studied in the films. It is confirmed that the excitation energy of Ce3+ transfers to the Gd3+, migrates over the Gd3+ sublattices, trapped by the Tb3+ and resulted in its characteristic green emission (D-5(4)-F-7(5) at 543 nm) in GdMgB5O10 nanocrystalline films as in the powder phosphors.

Fabrication of arrays of silver nanoparticle aggregates by microcontact printing and block copolymer nanoreactors

A combination of microcontact printing and block copolymer nanoreactors succeeded in fabricating arrays of silver nanoparticle aggregates. A complex solution of polystyrene-block-poly(4-vinylpyridine) micelles and silver salt was used as an ink to form thin films or droplets on polydimethylsiloxane stamp protrusions. After these complex aggregates were printed onto silicon substrates under controlled conditions, highly ordered arrays of disklike, dishlike, and dotlike complex aggregates were obtained. A Subsequent oxygen reactive ion etching treatment yielded arrays of silver nanoparticle aggregates.

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.

Photochromic behavior and luminescent properties of novel hybrid organic-inorganic film doped with Preyssler's heteropoly acid H-12[EuP5W30O110] and polyvinylpyrrolidone

A novel hybrid photochromic composite film composed of Preyssler's heteropoly acid H-12[EuP5W30O110] (EuP5W30) and polyvinylpyrrolidone (PVP) was prepared by dip-coating method. Atomic force microscopy (AFM) was used to investigate the surface topography. The change of characteristic peak in the infrared spectra (IR) was investigated. The TG curve showed three steps of weight loss and approximately revealed the composition of the hybrid film. Ultraviolet-visible adsorption spectra (UV-VIS) and electron resonance spectrum (ESR) were used to investigate the photochromic behavior and mechanism of hybrid film. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(o)-F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent thin film with polyoxometalates (POMs).