纳米结构自组装和分子自组装体系

系统地总结并评述了纳主结构和自组装体系和分子自组装体系的最新进展,介绍了纳米结构自组装和分子自组装的基本概念,总结了几类自组和分子自组装体系的合成方法,例举了这类自组装体系的新特性及与下一代纳米结构器件之间的联系。     

基于金纳米棒@二氧化硅表面等离子体共振增强的有机太阳能电池

把包裹SiO₂的金纳米棒（Au NRs@SiO₂）掺杂到有机太阳能电池的活性层中,利用表面等离子体共振效应来增强活性层对光的吸收,从而提高有机太阳能电池的能量转换效率。研究了不同掺杂浓度和不同包裹厚度对电池性能的影响。结果表明,掺杂浓度为1.5%时,器件性能最佳,能量转换效率达到4.02%;SiO₂壳层厚度为3 nm时,转换效率达到4.38%,较标准电池提升了29.2%。     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒（Au nanorods）作为种子,借助形成核/壳结构,诱导了Ag...     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒(Au nanorods)作为种子,借助形成核/壳结构,诱导了Ag, Pd, Pt棒状纳米结构的形成,并实现了对杂化纳米结构光学和催化性能的调控,进一步扩展了贵金属纳米结构的应用范围.作者的研究结果表明,形成杂化纳米结构是性能调控的一种有效方式.     

金纳米粒子自组装薄膜的光谱学研究

采用柠檬酸钠还原氯金酸制备了金胶体，通过静电自组装制备了金纳米粒子薄膜，利用紫外-可见光吸收光谱等对金纳米粒子薄膜进行了光谱学研究，紫外-可见光吸收光谱表明所制备的金溶胶为单分散体系，根据自组装薄膜的X-射线衍射谱，由谢乐公式估算金纳米粒子的粒径约为21nm；X-射线光电子能谱显示氯金酸的还原反应比较完全，金主要以Au^0的价态存在，金胶体粒子通过静电吸引机制组装到PDDA改性的衬底表面；紫外-可见光吸收光谱和表面增强拉曼光谱显示，由于粒子间的电磁耦合，自组装金纳米粒子薄膜表现出协同等离子体共振吸收行为和表面增强拉曼散射效应。     

金纳米棒复合体的消光特性

金属纳米颗粒局域表面等离激元共振时能够产生消光和近场增强效应已经成为国内外研究的热点. 应用时域有限差分法对L形纳米棒与普通纳米棒构成的金纳米棒复合体的消光光谱及其近场增强和电流矢量密度分布进行了研究. 计算结果表明, 普通纳米棒和L形纳米棒二聚体的光谱响应与纳米棒间的间距有关, 而金纳米棒复合体的消光光谱可通过调整L形纳米棒与普通纳米棒间的间距、L形纳米棒的臂长度以及普通纳米棒的长度进行调谐. 此外金纳米棒复合体可以分解成L形纳米棒二聚体和普通纳米棒二聚体两个部分, 通过分别改变L形纳米棒的臂长和普通纳米棒的长度, 对比L形纳米棒二聚体和普通纳米棒二聚体间的共振峰位置变化, 可以更直观地了解金纳米棒复合体消光光谱线型的变化. 这些结果可用于指导金纳米棒复合体纳米光子器件的设计, 以满足其在表面增强拉曼散射和生物传感等方面应用.     

基于自洽场理论两亲高分子自组装的研究

运用扩展的自洽场和密度泛函理论(SCF/DFT),研究ABC蝌蚪形两亲高分子在稀溶剂中的自组装形态,其中蝌蚪形两亲高分子由线形嵌段共聚物链AB嫁接到球形纳米颗粒C上构成.与以往研究的线形ABC两亲高分子相比,蝌蚪形两亲高分子的自组装形态有着很大的不同.在粒子亲溶剂,嵌段共聚物疏溶剂时,各组分间弱分凝条件下,蝌蚪形两亲高分子自组装成胶球状形貌;在强分凝条件下,随着嵌段共聚物疏溶剂性的增强,两亲高分子的自组织态由胶球状转变成四角、三角状形貌,其中嵌段B主要分布在各角上.通过改变各组分间的相互作用,在嵌段A亲溶剂,嵌段B和粒子疏溶剂时,粒子呈平行棒状或小方块状分布在胶球中.     

基于金纳米棒组装的半胱氨基酸分子同手性识别

摘要:本文通过半胱氨酸分子诱导金纳米棒自组装形成一维线性链状结构,利用停留装置观察了不同手性的半胱氨酸分子（L/D-半胱氨酸）诱导金纳米棒自组装的动力学过程。通过调控CTAB浓度,首次发现在组装速率很快的情况下,L-半胱氨酸分子诱导金纳米棒自组装的组装速率慢于D-半胱氨酸分子。而在组装速率较慢的情况下,这种情况不存在。通过分析揭示了为什么在慢速动力学和快速动力学会出现这种差异。并对在快速动力学下不同手性分子在诱导纳米颗粒组装上不同动力学行为作出讨论。这一工作可能为进一步解释生命的单一手性现象提供线索。     

金纳米棒三聚体中的等离激元诱导透明

基于金纳米棒构成的三聚体微元结构模型,详细地研究了等离激元诱导透明(plasmon induced transparency,PIT)现象产生的物理过程.研究发现,三聚体的吸收谱线随着其耦合距离以及尺寸的变化,竖直金纳米棒所对应的偶极明模在平行双长条金纳米棒对应的暗模作用下会产生分裂.依据这一结果提出了一个新的物理解释,PIT现象的产生主要来自于竖直金纳米棒中偶极振荡的模式分裂后的相干叠加.同时,考虑到两个振子之间的耦合会伴随着一定的相位关联性,进而引入了耦合相位因子修正了洛伦兹振子耦合模型,解析地研究了耦合相位因子对吸收谱的调控作用和分裂明模之间的相干叠加效应对PIT效应的影响.这为在纳米尺寸范围设计人造原子、光开关、慢光效应等方面的应用提供了理论参考.     

金纳米球壳对的局域表面等离激元共振特性分析

应用有限元方法, 研究金纳米球壳对的几何结构参数及物理参量对其表面等离激元共振的散射及消光光谱的影响, 并根据等离激元杂化理论进行了理论分析. 结果表明, 随着金壳厚度的增加, 金纳米球壳对的散射及消光共振峰先发生蓝移而后红移, 而随着金纳米球壳间隙的减小, 或者随着金纳米球壳的内核尺寸或内核介质折射率的增大, 散射及消光共振峰均发生红移; 随着金壳厚度或内核尺寸减小, 或者随着内核介质折射率增大, 金纳米球壳对的散射与消光共振强度减弱, 而随着金壳间隙的减小, 金纳米球壳对的散射共振强度先增强后减弱, 而消光共振强度逐渐增强, 数值模拟与理论分析一致.     

Kinetic Monte Carlo simulations of optimization of self-assembly quantum rings growth strategy based on substrate engineering

In this paper, the kinetic Monte Carlo simulations of the self-assembly quantum rings (QRs) based on the substrate engineering, which is related to the eventual shape of the formed quantum ring, are implemented. According to the simulation results, the availability of the QR with tunable size and the formation of smooth shape on the ideal flat substrate are checked. Through designing the substrate engineering, i.e., changing the depth, the separation and the ratio between the radius and the height of the embedded inclusions, the position and size of QR can be controlled and eventually the growth strategy of optimizing the self-assembly QRs is accomplished.     

一步水热法在Al掺杂ZnO纳米盘上可控自组装合成ZnO纳米棒阵列

通过简单的水热合成路线,在没有模板、表面活性剂的作用和未处理的基底上合成出铝掺杂ZnO 纳米盘,并以纳米盘为基底自组装合成了ZnO纳米棒阵列.扫描电镜(SEM)观察到铝掺杂ZnO纳米盘的厚度为 200 nm,纳米盘的尺寸约为2 μm;纳米棒的直径约为150 nm,长约1.5 μm.通过不同生长阶段的形貌变化探讨了ZnO纳米结构的形成机理,表明自组装过程存在两个成核阶段.另外, 研究了铝离子掺杂对样品光致发光性质的影响.     

Preparation of monodisperse bimetallic nanorods with gold nanorod core and silver shell and their plasmonic property and SERS efficiency

In this study, monodisperse bimetallic nanorods with gold (Au) nanorod core and silver (Ag) shell (Au@AgNRs) were synthesized through seed‐mediated growth process by reduction of AgNO₃ using Au nanorods with narrow size and shape distribution as seeds. With increasing the used amount of AgNO₃, the Ag shell thickness of their lateral facets is raised faster than that of their two tips, leading to a decrease of their aspect ratios. Four plasmon bands are observable on the extinction spectra of Au@AgNRs, which are attributed to the longitudinal dipolar plasmon mode, transverse dipolar plasmon mode, and octupolar plasmon mode of the core‐shell structured bimetallic nanorods, respectively. As their Ag shell thickness increases, their longitudinal plasmon band blue‐shifts notably with the transverse plasmon band blue‐shifting and the two octupolar plasmon bands red‐shifting slightly, due to the decrease of their aspect ratios and enhancement of Ag plasmon resonance contribution. When used as surface‐enhanced Raman scattering (SERS) substrate for probing minute amounts of 4‐mercaptobenzoic acid in aqueous solution, Au@AgNRs have much stronger SERS activity than Au nanorods, and the obtained Raman signals are highly reproducible arising from their excellent monodispersity. Their SERS activity is remarkably increased with their Ag shell thickness thanks to the enhancing surface electric field and the chemical enhancement associated with electronic ligand effect. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface-enhanced Raman scattering properties of highly ordered self-assemblies of gold nanorods with different aspect ratios

Gold nanorods with aspect ratios of from 1 (particles) to 31.6 were synthesized by the seed-mediated method and packed in a highly ordered structure on a large scale on silicon substrates through capillary force induced self-assembly behaviour during solvent evaporation.The gold nanorod surface exhibits a strong enhancing effect on Raman scattering spectroscopy.The enhancement of Raman scattering for two model molecules (2-naphthalenethiol and rhodamine 6G) is about 5-6 orders of magnitude.By changing the aspect ratio of the Au nanorods,we found that the enhancement factors decreased with the increase of aspect ratios.The observed Raman scattering enhancement is strong and should be ascribed to the surface plasmon coupling between closely packed nanorods,which may result in huge local electromagnetic field enhancements in those confined junctions.     

Molecular simulations of self-assembly processes of amphiphiles in dilute solutions: the challenge for quantitative modelling

We report on two recent developments in molecular simulations of self-assembly processes of amphiphilic solutions. We focus on the determination of micelle formation of ionic surfactants which exhibit the archetype of self-assembling compounds in solution. The first approach is centred on the challenge in predicting micellisation properties through explicit solvent molecular dynamics simulations. Even with a coarse-grained (CG) approach and the use of highly optimised software packages run on graphics processing unit hardware, it remains in many cases computationally infeasible to directly extract the critical micelle concentration (cmc). However, combined with a recently presented theoretical mean-field model this task becomes resolved. An alternative approach to study self-assembly is through implicit solvent modelling of the surfactants. Here we review some latest results and present new ones regarding capabilities of such a modelling approach in determining the cmc, and the aggregate structures in the dilute regime, that is currently not accessible through explicit solvent simulations, neither through atomistic nor through CG approaches. A special focus is put on surfactant concentration effects and surfactant correlations quantified by scattering intensities that are compared to recently published small-angle X-ray scattering data.     

A study of transition from n-to p-type based on hexagonal WO3 nanorods sensor

Hexagonal WO3 nanorods are fabricated by a facile hydrothermal process at 180 ℃ using sodium tungstate and sodium chloride as starting materials. The morphology, structure, and composition of the prepared nanorods are studied by scanning electron microscopy, X-ray diffraction spectroscopy, and energy dispersive spectroscopy. It is found that the agglomeration of the nanorods is strongly dependent on the PH value of the reaction solution. Uniform and isolated WO3 nanorods with diameters ranging from 100 nm-150 nm and lengths up to several micrometers are obtained at PH = 2.5 and the nanorods are identified as being hexagonal in phase structure. The sensing characteristics of the WO3 nanorod sensor are obtained by measuring the dynamic response to NO2 with concentrations in the range 0.5 ppm-5 ppm and at working temperatures in the range 25 ℃-250 ℃. The obtained WO3 nanorods sensors are found to exhibit opposite sensing behaviors, depending on the working temperature. When being exposed to oxidizing NO2 gas, the WO3 nanorod sensor behaves as an n-type semiconductor as expected when the working temperature is higher than 50 ℃, whereas, it behaves as a p-type semiconductor below 50 ℃. The origin of the n- to p-type transition is correlated with the formation of an inversion layer at the surface of the WO3 nanorod at room temperature. This finding is useful for making new room temperature NO2 sensors based on hexagonal WO3 nanorods.     

Effects of Kinetic Decoupling on Relic Density with Sommerfeld Enhancement

We investigate the effect of kinetic decoupling on the relic density of the non-relativistic particles whose annihilation rate is increased by Sommerfeld enhancement. We discuss the effect of kinetic decoupling both for the Sommerfeld enhanced s-wave annihilation and p-wave anihilation cross sections. We find after kientic decoupling Sommerfeld enhanced annihilations continue to change the particle abundance until the matter domination begins or
the Sommerfeld effect cuts off. We provide analytic estimates of this effect.