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非相干的超瑞利散射(HRS)技术是20世纪90年代发展起来的用于测定分子发色团一阶超极化率β的有效工具。由于它与惯用的相干二次谐波发生(SHG)和电场诱导二次谐波发生(EFISHG)技术相比较,不受样品的尺寸、取向和/或电荷的限制,因此近四五年来被使用来测定无机纳米粒子的一阶超极化率,并取得了一些重要的结果。文章介绍了HRS技术的一般原理、实验装置及数据处理方法。根据目前报导的实验结果,并结合我们的工作,探讨了纳米粒子超瑞利散射的几种可能机制:表面贡献、类体相贡献、聚集体贡献、共振增强的贡献以及粒子表面静电场和溶剂场的贡献,其中特别强调了表面贡献。指出用HRS技术研究纳米粒子二阶光学非线性这一新的领域正逐步吸引越来越多的科学家的兴趣,将成为非线性光学和纳米科学交叉领域的一个热点。 相似文献
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用硫脲分子表面修饰的CdS纳米粒子的合成和表征 总被引:15,自引:0,他引:15
报道了用硫脲分子进行表面化学修饰的CdS纳米粒子的合成方法,并引入了AOT(磺基琥珀酸双-2-乙基己基酯钠盐)作为平衡反离子,进一步对CdS表面作了修饰,增加了CdS纳米粒子在有机溶剂中的稳定性和可分散性。我们还探讨了温度、浓度、pH等因素对合成的影响,并通过TEM、XRD、FT-IR等手段对产物结构进行了表征。所得微粒粒径为5 nm左右,呈球形,硫脲分子与CdS纳米粒子富Cd2+表面通过形成Cd-S配位键而修饰在粒子表面。这种表面修饰的CdS纳米粒子将在非线性光学及自组装方面具有优 相似文献
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氨基酸桥联手性双卟啉的二阶非线性光学性质研究 总被引:4,自引:0,他引:4
采用半经验量子化学PM3方法对系列氨基酸桥联双卟啉1, 2, 3, 4及其锌配合物进行了几何结构优化, 并用TDHF/PM3方法计算了其静态二阶非线性光学系数. 计算结果表明, L型-氨基酸桥联双卟啉及其锌配合物具有右手螺旋结构特征. 在电偶极近似下, 不同手性氨基酸侧链基团R对分子的总体二阶非线性光学系数β和βHRS的影响不大, 但对二阶非线性光学系数的手性分量βxyz却有显著影响. βxyz与螺旋结构参数r2ζ/L4成正比关系, 符合手性分子二阶非线性光学响应的单电子螺旋模型理论. β张量分析表明, 此类分子表现为以八极为主、 偶极为辅的多极分子, 卟啉环与锌离子的配位有利于增加二阶非线性光学响应的偶极分量和手性分量βxyz. 相似文献
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CdS纳米粒子与半胱氨酸相互作用的研究 总被引:1,自引:0,他引:1
合成了粒径均匀和分散性好的CdS纳米粒子.通过改变CdS纳米粒子及半胱氨酸的浓度、体系的pH值及CdCl2和CH3CSNH2摩尔比等实验条件跟踪监测了CdS纳米粒子光谱性质的变化,探讨了CdS纳米粒子与半胱氨酸之间的相互作用及化学反应机理. 相似文献
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CdS/TiO2复合纳米粒子的光学性质 总被引:5,自引:0,他引:5
在Brij35/正己醇/环己烷/水构成的反相微乳体系中,分别合成了CdS、TiO2纳米粒子和TiO2包覆CdS(CdS/TiO2)的复合纳米粒子.测定了它们的紫外-可见吸收和荧光光谱.结果表明, CdS/TiO2复合纳米粒子在可见光区的吸收比相应的两组分的吸收之和更强.纳米CdS和纳米TiO2均有较强的荧光.而且在相同浓度时纳米TiO2的荧光比纳米CdS的荧光更强.但在CdS/TiO2复合纳米粒子中,TiO2的荧光被淬灭,而CdS的荧光稍有降低. 相似文献
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Optical nonlinearities of semiconductor nanoparticles are of great interest recently. So fartheir third-order nonlinear optical (NLO) properties have been widely studied. However,there are only few studies on second-order NLO properties, because it is believed that thecentrosymmetry or near-centrosymmetry of spherical nanoparticles eliminate their firstorder hyperpolarizability 6 values to'zero or near zero. And for a long time it remains aproblem to directly study the second-order=NLO pro… 相似文献
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CdS and CdS/ZnS core-shell structure nano particles were synthesized in micro emulsion, and characterized by X-ray diffraction(XRD), transmission electron microscopy (TEM), UV absorption spectra and PL. The average diameter of CdS was about 3.3 nm, and CdS/ZnS core-shell structure was confirmed by XRD and UV. Considering the optical properties of CdS/ZnS core-shell structure nanoparticles which have different ZnS shell thickness, the UV absorption edge of CdS/ZnS becomes as lightred-shift with the thickness of ZnS layer increasing, and the absorption of shortwave band is strongly enhanced at the same time. The PL spectra indicate that ZnS shell layer can greatly eliminate surface defects of CdS nanoparticles and make its band-edge directed recombination increased, and the luminous efficiency of CdS is improved greatly when it has appropriate shell thickness. 相似文献
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Method of chemical precipitation from aqueous solutions was used to cover the surface of polycrystalline ZnO nanotubes with a nanostructured CdS layer. The thus synthesized CdS/ZnO composite material was studied by the methods of X-ray diffraction analysis, electron microscopy, and optical spectroscopy. The fundamental time-related aspects of the process of CdS formation on the ZnO surface were examined. It was found that the amount of deposited CdS nanoparticles is independent of the deposition duration. The morphological specific features of ZnO nanotubes are preserved upon a prolonged keeping of ZnO in solution. The photocatalytic activity of CdS/ZnO under visible and UV light was examined in the reaction of hydroquinone oxidation. A possible mechanism of how the CdS/ZnO composite is formed in an aqueous solution in the course of growth of a layer constituted by CdS nanoparticles on the surface of ZnO nanotubes is suggested on the basis of the experimental data. It is demonstrated that the chemical-precipitation method can be used to obtain surface-active composite materials that are photoactive in the visible spectral range. 相似文献
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Yang Y Nogami M Shi J Chen H Ma G Tang S 《The journal of physical chemistry. B》2005,109(11):4865-4871
The composite nanoparticles of Au-core capped by CdS shells of different thickness were prepared and assembled into densely packed 3-dimensional films by the layer-by-layer self-assembly (LBL) technique. These films exhibited the 3-dimensional structure of densely packed Au@CdS composite nanoparticles and the shell thickness was tunable by changing the concentration of Cd2+-thiourea complexes. These multilayer films exhibited enhanced third-order optical nonlinear responses and ultrafast response times (several picoseconds). The third-order nonlinear optical susceptibility of the film with the CdS shell thickness of 4.4 nm was estimated to be 1.48 x 10(-9) esu and the value decreases with the increase of the CdS shell thickness. The enhancement of the optical nonlinearity was explained based on the calculation according to the electrostatic approximation by the solution of Laplace's equation under the boundary conditions appropriate to the model of core-shell nanoparticles, and mainly attributed to localized electric field effects in the CdS shell region. Additionally, the nonlinearity was optimized by determination of the values of the dielectric constant and thickness of the different shell. 相似文献
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Study on the behavior of hyper-rayleigh scattering for silver nanoparticles with aggregation effects
The absorption spectra as well as the Hyper-Rayleigh scattering (HRS) signals of a highly monodisperse 10.5-nm diameter silver colloids with the addition of KNO(3) and pyridine have been measured. Strongly enhanced HRS signals are observed by 15x and 6x, respectively. Through size distribution and TEM measurements, the morphology of aggregated silver nanoparticles has been observed as a chainlike aggregation. The dramatically enhanced second-order nonlinearity was explained by the enhanced electromagnetic (EM) field near the surface of the silver nanoparticles as they approached. The different enhancement between these two kinds of aggregates was considered with the diversity of separated distance between silver nanoparticles. The experimental results reveal that there is an optimum size for the aggregates to yield the maximum HRS response. 相似文献
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Yu ZHANG Xin WANG Ming MA De Gang FU Ning GU Ju Zheng LIU Zu Hong LU Ling XU Jun XU Kun Ji CHENNational Laboratory of Solid State Microstructures Department of Physics Nanjing University Nanjing National Laboratory of Molecular Biomolecular Electronics Southeast University Nanjing 《中国化学快报》2003,14(9):948-951
The second-order optical nonlinearity of CdS nanoparticles with different diameters of 28.0, 30.0, 31.5, 50.0, and 91.0 A was studied by hyper-Rayleigh scattering technique. Results show that the first-order hyperpolarizability P value per CdS partiele decreases as size is reduced to diameter of 31.5 A; however, as CdS size further decreases, this trend is reversed and (J value increases. Substantially, the normalized P value per CdS formula unit, β0, exhibits systematic enhancement with decreasing size. This phenomenon is interpreted in terms of a so-called surfaee contribution mechanism. 相似文献
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Swapnil B. Ambade Rajaram S. Mane Anil V. Ghule Go-Woon Lee Ramphal Sharma Oh-shim Joo Rohan B. Ambade Soo-Hyoung Lee Sung-Hwan Han 《Journal of photochemistry and photobiology. A, Chemistry》2011,217(1):267-270
Enhanced photosensitization in presence of CdS nanoparticles is achieved in electrochemically deposited ZnO nanoplates and N3 loaded dye-sensitized solar cells. Chemically embedded CdS nanoparticles act as a sandwiching layer between ZnO nanoplates and dye molecules by overcoming current limiting serious Zn2+/dye insulating complex formation and CdS photo-corrosion issues. The X-ray diffraction and the scanning electron microscopy confirm the ZnO with vertically aligned nanoplates, perpendicular to the substrate surface. Amorphous CdS is monitored using electron dispersive X-ray analysis. The low and high resolution transmission electron microscope images confirm the presence of CdS nanoparticles over ZnO nanoplates which later is supported by an increase in optical absorbance and shift in band edge. About 400% increase in solar conversion efficiency with this cascade arrangement is achieved when compared with without CdS which could be fascinating while designing solid state solar cells in presence of suitable p-type layer. 相似文献
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Shi‐Zhao Kang Yikai Yang Zhizhen Xu 《Journal of Dispersion Science and Technology》2013,34(4):521-524
CdS nanoparticles were formed on the surface of silica microspheres by the improved layer‐by‐layer self‐assembled technique. High‐resolution electron microscope (HRTEM) image and energy dispersive x‐ray analysis (EDX) confirmed formation of a quasi‐continuous CdS nanoparticles film on the silica microspheres. The results of UV‐vis and fluorescence spectra display that the spherical silica surface has a great effect on the photoluminescence of the loaded CdS nanoparticles. In contrast to the CdS nanoparticles powder, the composite can exhibit the emission ascribed to the band gap transition when the CdS nanoparticles film is relatively thick. This phenomenon is probably due to an enhancement of the crystallinity of CdS nanoparticles induced by the silica spheres. 相似文献
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水溶性CdSe/CdS量子点的合成及其与牛血清蛋白的共轭作用 总被引:4,自引:0,他引:4
用巯基乙酸(TGA)作为稳定剂,合成了水溶性的CdSe和核壳结构的CdSe/CdS半导体量子点。吸收光谱和荧光光谱研究表明,核壳结构的CdSe/CdS半导体量子点比单一的CdSe量子点具有更优异的发光特性。用TEM、电子衍射(ED)和XPS分别表征了CdSe和CdSe/CdS纳米微粒的结构、形貌及分散性。红外光谱和核磁共振谱证实了巯基乙酸分子中的硫原子和氧原子与纳米微粒表面的金属离子发生了配位作用。在pH值为7.4的条件下,将合成的CdSe和CdSe/CdS量子点直接与牛血清白蛋白(BSA)相互作用。实验发现,两种量子点均对BSA的荧光产生较强的静态猝灭作用;而BSA对两种量子点的荧光则具有显著的荧光增敏作用,存在BSA时CdSe/CdS量子点的荧光增强是不存在BSA时体系荧光强度的3倍。 相似文献
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We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface. 相似文献