柠檬酸-凝胶法合成ZnGa_2O_4:Mn~(2+)/Eu~(3+)及其发光性能的研究

ZnGa_2O_4是具有尖晶石结构的复合氧化物,是一种重要的阴极射线发光材料。同时由于它的光透明性和金属导电性,它又可以用作液晶显示和太阳能电池的透明电极。ZnGa_2O_4的能隙大约为4.4ev,作为一种低电压发光材料,它有可能取代以ZnS为基础的低电压阴极射线发光粉而用于新型的真空平板阴极射线管中。文献[1-2]中报导的ZnGa_2O_4以及激活离子掺杂的ZnGa_2O_4大部分由传统的固相法

Bond-charge calculation of electro-optic coefficients of diatomic crystals

A theoretical method has been set up to calculate the electrooptic tensor coefficients r(ijk), based on the Phillips-Van Vechten (PV) dielectric theory and the Levine bond charge model, Starting from the crystal structure data and only introducing the experimentally determined optical permittivity and dielectric constant, the electro-optic tensor coefficients r(ijk) can be quantitatively predicted, The theoretical calculations are in good agreement with experiment in the case of zinc blende and wurtzite crystals, For zinc blende crystals, the effects of covalent radii on the linear electro-optic coefficients are discussed. (C) 1997 Academic Press.

地幔副矿物和硫化物的热（PVT）状态方程研究

矿物PVT状态方程是研究矿物在一定温压条件下的晶胞体积与温度、压力之间的关系，依据这个基本关系，可以了解矿物在高温高压下的密度、弹性、热膨胀等性质。矿物PVT状态方程的研究可以了解矿物在地球深部存在的结构状态，为进一步的理论计算提供基础的数据，其结果也可以与天然和人工地震的地震波反演的结果对比，对地球深部的地质作用过程、物质结构状态和组成进行限制。然而，目前矿物PVT状态方程的研究主要集中在氧化物矿物和上地幔主要矿物（橄榄石和辉石）及其高压相（瓦兹利石、林伍德石、方镁铁矿、Majorite、Mg-Perovskite、Ca-Perovskite）的研究上，对石榴石、尖晶石等地幔常见副矿物和硫化物矿物的PVT状态方程的研究很少。 作者在参与搭建并完善金刚石压腔外加温系统的基础上，利用北京同步辐射X射线衍射实验技术结合金刚石压腔外加温技术对天然铁铝榴石、锰铝榴石、铬尖晶石进行了PVT状态方程的研究，同时对闪锌矿、辰砂、方铅矿、辉钼矿、辉锑矿等硫化物矿物进行了相变及状态方程的研究。结合前人研究成果，讨论了类质同象置换对镁铝－铁铝系列石榴石、锰铝－铁铝系列石榴石、尖晶石和硫化物矿物相变及状态方程的影响。获得了以下研究结果： 1）镁铝－铁铝系列石榴石和锰铝－铁铝系列石榴石的体弹模量都随着铁铝榴石组分的增加而增大。其主要原因是在二价阳离子位置上Fe2+取代了Mg2+、Mn2+。在镁铝－铁铝榴石系列中Mg2+的共价键半径（1.36Å）要大于Fe2+的共价键半径（1.17Å），而Mg2+－O键长（2.270Å）与铁铝榴石中的Fe2+－O（2.299Å）键长基本相当。在锰铝－铁铝榴石系列中， 尽管Mn2+的共价键半径（1.17Å）与铁铝榴石中的Fe2+共价键半径（1.17Å）相等，但是Mn2+－O键长（2.326Å）大于Fe2+－O键长（2.299Å）。较小的键长和共价键半径将会增强离子间的结合力，从而具有较强的抗压缩能力，因此随铁铝榴石组分的增加，镁铝－铁铝榴石系列和锰铝－铁铝榴石系列具有较大的体弹模量。 2）首次获得了铬尖晶石（(Mg0.6766Fe0.2808Na0.0073Ti0.0014)0.9661(Cr1.4874Al0.5367)2.0241O4）的体弹模量的温度导数。结合前人关于其他组分尖晶石的实验结果发现，尖晶石中在四面体位置上发生Fe2+－Mg2+置换对体弹模量的影响要大于在八面体位置上发生Cr3+－Al3+置换对体弹模量的影响。而造成铬尖晶石的体弹模量值比其他组分尖晶石的体弹模量值大的主要原因也是四面体位置上的Fe2+－Mg2+的类质置换。 3）依据获得的尖晶石和石榴石的状态方程计算了不同地幔岩模型（橄榄岩和榴辉岩模型）的密度值在上地幔温压条件下的变化情况。结果表明，在尖晶石二辉橄榄岩模型中尖晶石含量的改变（2％－10％）会引起较大的密度变化（2.2％）；在石榴石二辉橄榄岩（石榴石含量14％－20％）和榴辉岩（石榴石含量37％－45％）模型中石榴石含量的变化几乎未引起其密度值的变化，但石榴石是这两种地幔岩模型中的重要组成矿物。 4）首次获得了辰砂的Cinnabar相、方铅矿的B33相、辉钼矿、辉锑矿体弹模量的温度导数和热膨胀系数。讨论了闪锌矿、辰砂、方铅矿的相变情况。 5）总结了锌的、汞的、铅的硫族化合物发生结构相变的规律。认为造成锌的、汞的、铅的硫族化合物的相变压力随阴离子原子序数的增加（S→Se→Te）而逐渐减小的原因是：元素周期表中相对较大原子序数的原子具有更多的核内电子，引起价电子及导带电子的有效位能相对变弱，引起电离能降低，因此在相对较低的压力下就容易发生结构相变。 6）分析了ZnS中Fe2+替代Zn2+、Sb2S3－Bi2S3、MoS2－WS2以及同族相同结构不同组分的简单硫化物矿物的阴、阳离子对体弹模量值的影响。认为简单硫化物矿物的体弹模量值取决于阴、阳离子的离子半径、电负性以及键长。

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.

Preparation, structural characterization, semiconductor and photoluminescent properties of zinc oxide nanoparticles in a phosphonium-based ionic liquid

A convenient microwave method in preparation of zinc oxide nanoparticles (ZnONPs) using an ionic liquid, trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}-imide, [P-66614][NTf2], as a green solvent is described in this paper. To the best of our knowledge, there is no report for synthesizing any nanoparticle using this ionic liquid. Trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}-imide has low interface tension and thus it can enhance the nucleation rate, which is favorable to the formation of smaller ZnONPs. The fabricated ZnONPs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis spectroscopy. The XRD pattern reveals that the ZnONPs have hexagonal wurtzite structure. The strong intensity and narrow width of ZnO diffraction peaks indicate that the resulting nanoparticles are of high crystallinity. The synthesized ZnONPs show direct band gap of 3.43 eV. The UV-vis absorption spectrum of ZnONPs dispersed in ethylene glycol at room temperature revealed a blue-shifted onset of absorption. (C) 2011 Elsevier Ltd. All rights reserved.

Sonochemical synthesis and measurement of optical properties of zinc sulfide quantum dots

A facile sonochemical method has been developed to prepare very small zinc sulfide nanoparticles (ZnS NPs) of extremely small size about 1. nm in diameter using a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the NPs were determined in depth with X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), Fourier transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS) analysis, and UV-vis absorption spectroscopy. The energy band gap measurements of ZnS NPs were calculated by UV-vis absorption spectroscopy. One of the interesting features of the present work is that the wide band gap semiconductor ZnS nanocrystals were prepared which are used in the fabrication of photonic devices.

One-step synthesis of ZnO nanosheets: a blue-white fluorophore

Zinc oxide is synthesised at low temperature (80A degrees C) in nanosheet geometry using a substrate-free, single-step, wet-chemical method and is found to act as a blue-white fluorophore. Investigation by atomic force microscopy, electron microscopy, and X-ray diffraction confirms zinc oxide material of nanosheet morphology where the individual nanosheets are polycrystalline in nature with the crystalline structure being of wurtzite character. Raman spectroscopy indicates the presence of various defects, while photoluminescence measurements show intense green (centre wavelength approximately 515 nm) blue (approximately 450 nm), and less dominant red (approximately 640 nm) emissions due to a variety of vacancy and interstitial defects, mostly associated with surfaces or grain boundaries. The resulting colour coordinate on the CIE-1931 standard is (0.23, 0.33), demonstrating potential for use as a blue-white fluorescent coating in conjunction with ultraviolet emitting LEDs. Although the defects are often treated as draw-backs of ZnO, here we demonstrate useful broadband visible fluorescence properties in as-prepared ZnO. 

Transient Polymorphism in NaCl

We introduce a new, collective variable (CV) that can be used to increase the frequency with which nucleation events are observed in biased atomistic simulations. This CV forces the ions to aggregate into clusters but does not force the ions to order themselves in a particular pattern. We perform metadynamics simulations using this CV in order to examine nucleation in a solution of sodium chloride and find that for small cluster sizes the usual bulk rocksalt structure is less stable than a structure that resembles wurtzite.

Factors affecting the photoelectrochemical fixation of carbon dioxide with semiconductor colloids

Carbon dioxide was reduced photocatalytically using aqueous CdS or ZnS colloids containing tetramethylammonium chloride to give the dimeric and tetrameric products namely, oxalate, glyoxylate, glycolate and tartrate. A model is presented to explain the role of the tetramethylammonium ions. Studies were also performed using ZnO, SiC, BaTiO₃ and Sr TiO₃, which in the absence of tetramethylammonium ions produced formate and formaldehyde. The relative quantum efficiencies of the six semiconductors were related to their band gaps and conduction band potentials. The role and effectiveness of several 'hole acceptor' (electron donor) compounds in this process is shown to be related to their redox potentials.

Photoreduction of carbon dioxide on zinc sulfide to give four-carbon and two-carbon acids

Aqueous solutions of CO₂ containing tetramethylammonium chloride were photolysed with visible light in the presence of colloidal ZnS to yield tartaric acid, glyoxylic acid, oxalic acid, formic acid and formaldehyde.

Performance of polarisation functionals for linear and nonlinear optical properties of bulk zinc chalcogenides ZnX (X=S,Se,Te).

We calculated the frequency dependent macroscopic dielectric function and second-harmonic generation of cubic ZnS, ZnSe and ZnTe within time-dependent density-polarisation functional theory. The macroscopic dielectric function is calculated in a linear response framework, and second-harmonic generation in a real-time framework. The macroscopic exchange–correlation electric field that enters the time-dependent Kohn–Sham equations and accounts for long range correlation is approximated as a simple polarisation functional αP, where P is the macroscopic polarisation. Expressions for α are taken from the recent literature. The performance of the resulting approximations for the exchange–correlation electric field is analysed by comparing the theoretical spectra with experimental results and results obtained at the levels of the independent particle approximation and the random-phase approximation. For the dielectric function we also compare with state-of-the art calculations at the level of the Bethe–Salpeter equation.

Métodos químicos de modificação superficial de nanomateriais

O objectivo geral desta tese foi investigar diversas estratégias de síntese de nanocompósitos híbridos de matriz polimérica, contendo nanopartículas inorgânicas com funcionalidades diversas. O interesse nestes nanocompósitos multifuncionais consiste no enorme potencial que apresentam para novas aplicações tecnológicas, tais como em optoelectrónica ou em medicina. No capítulo introdutório, apresenta-se uma revisão das propriedades de nanopartículas inorgânicas e nanoestruturas obtidas a partir destas, métodos de preparação e de modificação química superficial, incluindo a formação de nanocompósitos poliméricos, bem como a aplicação destas nanoestruturas em medicina e biologia. O estudo das propriedades de nanopartículas de ouro é um importante tema em Nanociência e Nanotecnologia. As propriedades singulares destas NPs apresentam uma estreita relação com o tamanho, morfologia, arranjo espacial e propriedades dieléctricas do meio circundante. No capítulo 2, é reportada a preparação de nanocompósitos utilizando miniemulsões de poli-estireno (PS) e poli-acrilato de butilo (PBA) contendo nanopartículas de ouro revestidas com moléculas orgânicas. As propriedades ópticas destas estruturas híbridas são dominadas por efeitos plasmónicos e dependem de uma forma crítica na morfologia final dos nanocompósitos. Em particular, demonstra-se aqui a possibilidade de ajustar a resposta óptica, na região do visível do espectro, através do arranjo das nanopartículas na matriz polimérica, e consequentemente o acoplamento plasmónico, utilizando nanopartículas resultantes da mesma síntese. Na generalidade, é reportada aqui uma estratégia alternativa para modificar a resposta óptica de nanocompósitos, através do controlo da morfologia do compósito final face à estratégia mais comum que envolve o controlo das características morfológicas das partículas metálicas utilizadas como materiais de partida. No Capítulo 3 apresentam-se os resultados da preparação de vários compósitos poliméricos com propriedades magnéticas de interesse prático. Em particular discute-se a síntese e propriedades magnéticas de nanopartículas de ligas metálicas de cobalto-platina (CoPt3) e ferro-platina (FePt3), assim como de óxidos de ferro (magnetite Fe3O4 e maguemite g-Fe2O3) e respectivos nanocompósitos poliméricos. A estratégia aqui descrita constitui uma via interessante de desenvolver materiais nanocompósitos com potencial aplicação em ensaios de análise de entidades biológicas in vitro, que pode ser estendido a outros materiais magnéticos. Como prova de conceito, demonstrase a bioconjugação de nanocompósitos de CoPt3/PtBA com anticorpos IgG de bovino. No capítulo 4 é descrita a preparação e propriedades ópticas de pontos quânticos (“quantum dots”, QDs) de CdSe/ZnS assim como dos seus materiais nanocompósitos poliméricos, CdSe/ZnS-PBA. Como resultado das suas propriedades ópticas singulares, os QDs têm sido extensivamente investigados como materiais inorgânicos para aplicações em dispositivos ópticos. A incorporação de QDs em matrizes poliméricas é de particular interesse, nomeadamente devido ao comportamento óptico do nanocompósito final parecer estar dependente do tipo de polímero utilizado. As propriedades ópticas dos nanocompósitos foram estudadas sistematicamente por medidas de fotoluminescência. Os nanocompósitos apresentam propriedades interessantes para potenciais aplicações biológicas em diagnóstico in vitro, funcionando como sondas biológicas luminescentes.

Bio-synthesis of nanosized semiconductors using mine wastes as material sources

This work describes the synthesis of nanosized metal sulfides and respective SiO2 and/or TiO2 composites in high yield via a straightforward process, under ambient conditions (temperature and pressure), by adding to aqueous metals a nutrient solution containing biologically generated sulfide from sulfate-reducing bacteria (SRB). The nanoparticles‘ (NPs) morphological properties were shown not to be markedly altered by the SRB growth media composition neither by the presence of bacterial cells. We further extended the work carried out, using the effluent of a bioremediation system previously established. The process results in the synthesis of added value products obtained from metal rich effluents, such as Acid Mine Drainage (AMD), when associated with the bioremediation process. Precipitation of metals using sulfide allows for the possibility of selective recovery, as different metal sulfides possess different solubilities. We have evaluated the selective precipitation of CuS, ZnS and FeS as nanosized metal sulfides. Again, we have also tested the precipitation of these metal sulfides in the presence of support structures, such as SiO2. Studies were carried out using both artificial and real solutions in a continuous bioremediation system. We found that this method allowed for a highly selective precipitation of copper and a lower selectivity in the precipitation of zinc and iron, though all metals were efficiently removed (>93% removal). This research has also demonstrated the potential of ZnS-TiO2 nanocomposites as catalysts in the photodegradation of organic pollutants using the cationic dye, Safranin-T, as a model contaminant. The influence of the catalyst amount, initial pH and dye concentration were also evaluated. Finally, the efficiency of the precipitates as catalysts in sunlight mediated photodegradation was investigated, using different volumes of dye-contaminated water (150 mL and 10 L). This work demonstrates that all tested composites have the potential to be used as photocatalysts for the degradation of Safranin-T.

Growth and characterization of Cu2ZnSn(S,Se)4 thin films for solar cells

Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) with their band gap energies around 1.45 eV and 1.0 eV, respectively, can be used as the absorber layer in thin film solar cells. By using a mixture of both compounds, Cu2ZnSn(S,Se)4 (CZTSSe), a band gap tuning may be possible. The latter material has already shown promising results such as solar cell efficiencies up to 10.1%. In this work, CZTSSe thin films were grown in order to study its structure and to establish the best growth precursors. SEM micrographs reveal an open columnar structure for most samples and EDS composition profiling of the cross sections show different selenium gradients. X-ray diffractograms show different shifts of the kesterite/stannite (1 1 2) peak, which indicate the presence of CZTSSe. From Raman scattering analysis, it was concluded that all samples had traces of CZTS and CZTSSe. The composition of the CZTSSe layer was estimated using X-ray diffraction and Raman scattering and both results were compared. It was concluded that Se diffused more easily in precursors with ternary Cu–Sn–S phases and metallic Zn than in precursors with ZnS and/or CZTS already formed. It was also showed that a combination of X-ray diffraction and Raman scattering can be used to estimate the ratio of S per Se in CZTSSe samples.

Quantum dots: synthesis, functionalization and bioconjugation for biological applications

Dissertation presented to obtain the Ph.D degree in Engineering Sciences and Technology