D-核糖NIR-SERS光谱及其在金纳米棒表面吸附行为分析

本文采用种子生长法、利用双表面修饰剂制备了金纳米棒,其长径比为3.5:1。该金纳米棒的消光光谱显示:利用该方法制备的金纳米棒有两个表面等离子共振(SPR)峰,分别位于540nm和780nm处。其中780nm处的表面等离子共振峰靠近红外光谱区,可以与文中采用的激发光源(785nm激光)较好的匹配,从而有助于实现共振拉曼散射增强效应。本文以D-核糖(D-Ribose)为探测分子,基于金纳米棒进行了近红外表面拉曼散射(NIR-SERS)活性检测,从而获得了光谱重复性良好的NIR-SERS光谱图。同时,采用密度泛函理论(DFT),以B3LYP/6-31G和6-31G/LanL2DZ为基组函数,分别对D-核糖分子以及D-核糖分子与金原子形成的团簇进行结构优化和普通拉曼光谱(NR)计算,发现理论值和实验值符合较好。此外,文中对D-核糖的NIR-SERS谱带进行了分析和归属,发现当D-核糖分子吸附到金纳米粒棒上时,主要是以羟基上的氧原子(O9)吸附在金原子上而形成金属键。     

金纳米棒二聚体结构的Fano共振

等离激元金属纳米结构中的Fano共振,由于其在超灵敏传感、超材料、光开关和非线性光学器件等方面的潜在应用而引起了广泛的关注。但在单颗粒尺度下单个金属纳米二聚体结构的Fano共振的实验研究仍然很少。本研究基于单颗粒光谱技术从实验上探讨了二聚体结构产生的Fano共振现象。利用种子生长法制备了等离激元共振峰分别在1 060 nm和700 nm的一长一短金纳米棒,通过L-半胱氨酸分子的静电吸附自组装构建首尾相连的金纳米棒二聚体结构,在暗场显微系统中表征了金纳米棒二聚体耦合前后的散射光谱。结果表明,短金纳米棒的明偶极模式与长金纳米棒的暗四极模式间的相消干涉在660 nm处产生了明显的Fano共振谷,同时基于有限差分时域（FDTD）方法的理论模拟散射光谱与实验结果能够较好地符合。这种自组装金纳米棒二聚体在等离激元传感和探测等方面具有广阔的应用前景。     

硫离子修饰的金纳米棒用于汞离子检测

表面修饰硫离子的金纳米棒可与汞发生相互作用,导致体系的共振光散射（RLS）和紫外-可见吸收光谱发生变化。利用这种特殊的选择性结合反应建立了一种采用RLS技术定量检测水溶液中汞离子的新方法。在优化的实验条件下,汞离子分析测定的线性范围为0.1—10.0μm ol.L^-1,检出限为0.096μm o.lL^-1。     

利用聚碳酸酯模板制备的金纳米棒的表面增强Raman散射效应研究

采用聚碳酸酯模板和电化学沉积法制备基于金纳米棒的Raman场增强衬底, 制备的金纳米棒直径大约36 nm, 长约1 μm, 测试结果显示其共振吸收峰的位置约为540 nm. 比较了谐振和非谐振条件下的场增强情况, 并确定了场增益系数, 结果显示谐振激光激发下的增益比非谐振情况下提高了7.36倍. 本研究相对于前人的工作取得了如下进展: 一是讨论了谐振模式与非谐振模式下的金纳米棒的场增益系数, 利用谐振波长的激光激发金纳米棒, 进一步提高了场增益; 二是消除了聚碳酸酯模板分子的荧光背底, 使其在表面增强 Raman 散射方面的应用进一步变得可行.关键词：金纳米棒表面增强Raman散射聚碳酸酯模板     

半胱氨酸修饰金纳米棒光学性质的研究

采用种子生长法制备了不同长径比的金纳米棒,并通过金硫键的结合在其表面包覆半胱氨酸分子。利用紫外-可见吸收光谱仪,扫描电子显微镜以及拉曼光谱仪等对样品进行分析和表征。实验结果表明金纳米棒产率较高,且一致性较好。表面修饰后的金纳米棒的纵向吸收峰发生蓝移,表明半胱氨酸分子与金纳米棒的结合有助于溶液分散性的提升。以结晶紫为探针分子,随着金纳米棒长径比的增加其拉曼增强效果变强。进一步分析发现,修饰后的金纳米棒的表面增强拉曼光谱的增强效果并未受到影响。通过金纳米棒与半胱氨酸分子牢固的结合,一方面可以提高金纳米棒溶液的分散性与稳定性;另一方面半胱氨酸分子可为金纳米棒修饰其它有机官能团提供了一个牢固的桥梁,有效地拓展了金纳米棒的应用方向。     

利用表面等离子体共振效应确定金纳米棒的尺寸

金属纳米粒子的尺寸和形状对其物理和化学性质有很大影响,通常利用昂贵的透射电子显微镜和扫描电子显微镜进行其尺寸测量。为了节约测量成本,利用时域有限差分法研究了金纳米棒的尺寸与吸收峰的对应关系得到间接的测量方法。即当金纳米棒的纵横比增大时,横向等离子峰几乎没有变化,纵向等离子峰出现明显的红移,且红移速度随着金纳米棒半径的增大而增大。实际制备了两种不同尺寸的金纳米棒样品,通过理论模拟确定的金纳米棒的尺寸与利用透射电子显微镜测量的金纳米棒的尺寸符合的很好。     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.     

金纳米颗粒光散射提高InAs单量子点荧光提取效率

采用光学方法确定InAs/GaAs单量子点在样品外延面上的位置坐标, 利用AlAs牺牲层把含有量子点的GaAs层剥离并放置在含有金纳米颗粒或平整金膜上, 研究量子点周围环境不同对量子点自发辐射寿命及发光提取效率的影响. 实验结果显示, 剥离前后量子点发光寿命的变化小于13%, 含有金纳米颗粒的量子点发光强度是剥离前的7倍, 含有金属薄膜的量子点发光强度是剥离前的2倍. 分析表明在金纳米颗粒膜上的量子点荧光强度的增加主要来自于金纳米颗粒对量子点荧光的散射效应, 从而提高量子点发光的提取效率.     

金纳米棒表面等离子体共振瑞利散射能量转移光谱测定痕量硼

硼是一种生命体必需的微量元素,但过量的硼对人体以及动植物有害。建立一种高灵敏度,高选择性以及简便的硼检测方法,对于环境和人类健康都具有很重要的意义。本研究的目的是建立一种简便,灵敏,选择性测定硼的金纳米棒等离子体共振瑞利散射能量转移光谱新方法。直径为12 nm, 长度为37 nm的金纳米棒采用种子生长法制备。在pH 5.6的NH₄Ac-HAc的缓冲溶液中和甲亚胺-H存在下,金纳米棒在404 nm处产生较强的共振瑞利散射峰。当体系中存在硼酸时,硼酸与甲亚胺-H形成硼酸-甲亚胺-H配合物。作为散射受体的配合物与散射共振能量转移的给体纳金米棒靠近时,发生瑞利散射共振能量转移,导致瑞利散射信号猝灭。随着硼酸浓度的增加,形成的配合物增加,金纳米棒转移给黄色配合物的散射光能量增大,导致体系404 nm处的瑞利散射强度线性降低。其降低值ΔI_{404 nm}与硼的浓度在10～750 ng·mL-1范围内呈良好的线性关系。考察了共存物质对该法测定2.3×10-7 mol·L-1 B的干扰情况。结果表明该法具有较高的选择性,即4×10-4 mol·L-1的Mn2+,Cd2+,Zn2+,Bi3+,Na+,Al3+,葡萄糖,Hg2+,IO-₃,F-,SO2-₄,SiO2-₃,NO-₃,ClO-₄,过氧化氢等对硼的测定无干扰。据此建立了一个灵敏度高,选择性好,简便快速检测硼的瑞利散射共振能量转移新方法。     

Direct monitoring of gold nanorod growth

The seed-mediated growth of gold nanorods is shown to be strongly dependent on the reaction time and chemical environment of the reaction solution. The versatile seed-mediated approach in aqueous surfactant solutions has been used in this study for the synthesis of gold nanorods. Changes in the aspect ratio of gold nanorods were reflected in shifts of the plasmon resonance peaks and were monitored using UV-Visible absorption spectroscopy (UV-Vis) to follow the different stages of gold nanorod formation as a function of time and varying amounts of silver ion. Unlike the use of strong reducing agents to make spherical gold nanoparticles, the growth of gold nanorods requires weak reducing conditions, leading to an unknown degree of gold reduction. Therefore, cyclic voltammetry was used to electrochemically interrogate the entire reaction from gold seed to gold nanorod as a function of time. Data obtained revealed that time-dependent gold species are involved in gold nanorod formation.     

球形串型二维表面等离子体光栅光吸收器

本文设计了一种球形串型二维表面等离子体光栅光吸收器,采用二维时域有限差分法(2D-FDTD)分析了该吸收器的几何结构参数对其吸收特性的影响.结果表明,通过调整小球的半径、球形串之间的中心距离以及球形串上小球的层数,可以有效地降低反射率,从而提高对光的吸收率.从中心位置向左右两边使球形串之间的中心距离线性减小,可明显改善其吸收效果.当球形串上小球的层数超过50层时,基本达到了饱和吸收的状态.这种光吸收器在薄膜太阳能电池中具有一定的应用前景.     

金纳米棒状微粒的胶囊模型及吸收光谱

提出了金纳米棒状微粒的胶囊模型,用Waterman发展的T矩阵方法计算了金纳米棒状微粒的吸收光谱.计算谱和实验谱基本符合,520nm左右处的吸收峰对应于金纳米棒的横向表面等离体子共振（横模）,长波长处的吸收峰对应于金纳米棒的纵向表面等离体子共振（纵模）.随着金纳米棒纵横比的增加,纵模吸收峰表现出显著的红移,横模吸收峰则微弱地蓝移.此外,计算结果表明,金纳米棒状微粒外部介质的介电常数必须随着金纳米棒纵横比的增大非线性地减小.     

Origin of the surface recombination centers in ZnO nanorods arrays by X-ray photoelectron spectroscopy

The surface composition of as-grown and annealed ZnO nanorods arrays (ZNAs) grown by a two-step chemical bath deposition method has been investigated by X-ray photoelectron spectroscopy (XPS). XPS confirms the presence of OH bonds and specific chemisorbed oxygen on the surface of ZNAs, as well as H bonds on surfaces which has been first time observed in the XPS spectra. The experimental results indicated that the OH and H bonds play the dominant role in facilitating surface recombination but specific chemisorbed oxygen also likely affect the surface recombination. Annealing can largely remove the OH and H bonds and transform the composition of the other chemisorbed oxygen at the surface to more closely resemble that of high temperature grown ZNAs, all of which suppresses surface recombination according to time-resolved photoluminescence measurements.     

Tailoring the optical and hydrophobic property of zinc oxide nanorod by coating with amorphous graphene

Zinc oxide (ZnO) nanorods were synthesized at room temperature on potassium permanganate activated silicon and glass substrate by simple chemical method using zinc acetate as precursor.To modify the surface energy of the as prepared ZnO thin films the samples were coated with amorphous graphene (a-G) synthesized by un-zipping of chemically synthesized amorphous carbon nanotubes (a-CNTs). All the pure and coated samples were characterized by x-ray diffraction, field emission scanning electron microscope, Raman spectroscopy, and Fourier transformed infrared spectroscopy. The roughness analysis of the as prepared samples was done by atomic force microscopic analysis. The detail optical properties of all the samples were studied with the help of a UV-Visible spectrophotometer.The surface energy of the as prepared pure and coated samples was calculated by measuring the contact angle of two different liquids. It is seen that the water repellence of ZnO nanorods got increased after they are being coated with a-Gs. Also even after UV irradiation the contact angle remain same unlike the case for the uncoated sample where the contact angle gets decreased significantly after UV irradiation. Existing Cassie-Wenzel model has been employed along with the Owen's approach to determine the different components of surface energy.     

On the extinction multipole plasmons in gold nanorods

On the basis of the T-matrix formalism and numerical simulations, we derive an explicit rule for partial multipole contributions to the plasmon resonances of gold nanorods at a fixed or random orientation. The parity of a given spectral resonance number n coincides with the parity of their multipole contributions l, where l is equal to or greater than n, and the total resonance magnitude is determined by the lowest multipole contribution. We also investigate the dependence of multipole plasmons on the size, shape, and orientation of nanorods with respect to the polarized incident light. It is shown that the multipole resonance wavelengths as a function of the aspect ratio divided by the resonance number collapse onto one linear scaling curve. This scaling is explained by using the plasmon standing wave concept introduced by Schider et al. [Plasmon dispersion relation of Au and Ag nanowires. Phys Rev B 2003;68:155427].     

Surface plasmon resonance based fiber optic sensor utilizing indium oxide

A highly sensitive surface plasmon resonance (SPR) based fiber optic sensor with indium oxide (In₂O₃) layer coated on the core of the optical fiber is presented and theoretically analyzed. The sensitivity of the SPR based fiber optic sensor has been evaluated numerically. It is shown that the proposed SPR based fiber optic sensor with In₂O₃ layer possesses high sensitivity in the near infrared region of spectrum, which needs attention to many environmental and security applications and offers more accurate and highly reproducible measurements. In addition, the sensitivity of the SPR based fiber optic sensor decreases with the increase in the thickness of In₂O₃ layer. With sensitivity as high as 4600 nm/RIU, the 170 nm thick In₂O₃ layer based fiber optic SPR sensor demonstrates better performance.     

Investigation of the surface properties of gold nanowire arrays

Gold nanowire arrays with diameters ranging from 45 to 200 nm were obtained via electrochemical deposition within the ion-track templates. The morphology of gold nanowires was imaged by scanning electron microscopy (SEM). The surface properties were investigated by surface plasmon resonance (SPR) and X-ray photoelectron spectroscopy (XPS). The SPR peaks were observed as the gold nanowire arrays embedded in the templates and their intensity decreased after the sample exposed to the air for a certain time due to the formation of chemisorbed oxygen on nanowire surface. The positive binding energy shifts in Au core level was found when the gold nanowire arrays embodied in template and the initial- and finial-state effects were introduced to explain this phenomenon.     

Light transport in laser irradiated turbid media, application in medicine and image processing

Much effort is being made in the study of light propagation in human tissue due to the development and wide use of lasers for surgical and therapeutic applications. When a picosecond light pulse is incident on biological tissue, part of the light is reflected back owing to specular surface reflection and the rest of the light penetrates the tissue and encounters multiple scattering and absorption processes. An analysis has been presented for modeling of light distribution in human tissue. The influence of the refractive index, scattering phase function and scattering albedo on light distribution in laser irradiated tissue has been demonstrated.     

Experimental measurement and analysis of the optical trapping force acting on a yeast cell with a lensed optical fiber probe

Based on an optical trapping system with a single-lensed fiber probe inserted at an angle, the sub-picoNewton trapping force acting on a yeast cell as a function of the displacement is measured experimentally by the static and dynamic methods, respectively, whose measurement processes are presented in detail. The measured maximum trapping efficiency is 0.07 in our experiment, which is an order of magnitude lower than that of the optical tweezers. The characteristics of the trapping force in the various horizontal directions are discussed. Finally, the analysis of the measurement error shows the factors and their magnitude which cause error, and offers a way to reduce the error in future.