Cysteine-assisted growth of silver on gold nanorods

Au–Ag core–shell (Au@Ag) nanobars could be synthesized from gold nanorod (NR) seeds with cysteine additives by a two-step process of reaction temperatures. The lateral sides of gold NRs surrounded by surfactant bilayers render cysteine additives binding on both ends of the NRs, and restricted silver deposition to their lateral sides at room temperature. Further, silver deposition can take place at first on the pre-formed silver layers on the lateral sides at higher temperatures and finally resulted in the formation of Au@Ag nanobars in which gold NRs are in the corner positions of the nanobars and their longitudinal axes parallel to the longer sides of the nanobars.     

Investigation of the effects of the local environment on the surface-enhanced Raman spectra of striped gold/silver nanorod arrays

The effects of the local environment on surface-enhanced Raman scattering (SERS) spectra utilizing gold, silver, and gold/silver striped nanorod array substrates was investigated. The arrays were fabricated using an electrochemical metal deposition into an anodic aluminum oxide template. The analyte chosen for this study was p-nitroso-N,N-dimethylaniline (p-NDMA), which has an electronic structure that is highly sensitive to its surrounding environment. Changes in the peak positions and peak ratios were used to probe the influence of water and the striping pattern on the SERS signal of p-NDMA. We present the results of the fabrication and characterization of the nanorod array substrates, as well as SERS spectra of p-NDMA in both polar and nonpolar environments and SERS spectra on a variety of striped nanorod arrays. The Raman data suggests that the p-NDMA molecule exists in a more polarized state when bound to the gold as compared to the silver rods. We have attempted to use these differences to determine whether the SERS signal predominantly arises from the tips of the rods or from the interior of the array.     

P3HT/CdS/TiO2/ZnO一维有序核壳式纳米棒阵列的构制及其在杂化太阳电池中的应用研究

采用恒电位法在铟锡氧化物导电玻璃(ITO)上制备了高度有序一维ZnO纳米棒阵列,将ZnO纳米棒阵列在TiO2溶胶中采用提拉法制备出了一维TiO2/ZnO核壳式纳米棒阵列.在一维TiO2/ZnO核壳式纳米棒阵列上电沉积CdS纳米晶得到一维CdS/TiO2/ZnO核壳式纳米棒阵列,然后在一维CdS/TiO2/ZnO核壳式纳米棒阵列上电沉积聚3-己基噻吩(P3HT)薄膜得到P3HT/CdS/TiO2/ZnO核壳式纳米结构薄膜.以该纳米结构薄膜电极为光阳极制备出新型纳米结构杂化太阳电池,研究了该类电池的光电转换性能,初步探讨了该类电池的工作机理.     

Enhancement at the junction of silver nanorods

The enhancement of surface enhanced Raman scattering (SERS) at the junction of linearly joined silver nanorods (31 nm in diameter) deposited in the pores of anodic aluminum oxide templates was studied systematically by excitation with a 632.8 nm laser line. The single and joined silver nanorod arrays showed a similar extinction spectrum when their length was the same. Maximum enhancement was observed from the junction system of two nanorods of the same size with a total length of 62 nm. This length also corresponded to the optimum length of single nanorods for SERS by excitation with a 632.8 nm laser line. The enhancement at the junction was approximately 40 times higher than that of the 31 nm single nanorod, while it was 4 times higher than that of the 62 nm single nanorod. The enhancement factor at the junction after oxide removal was approximately 3.9 x 10 (9).     

基底对电沉积制备ZnO纳米棒阵列的影响

采用恒电位电沉积方法, 在未经修饰的ITO导电玻璃基底上通过控制实验条件制备出不同形貌的纳米ZnO结构, 而在经过ZnO纳米粒子膜修饰后的ITO导电玻璃基底上, 制备出透明、高取向、粒径小于30 nm的ZnO纳米棒阵列. 用扫描电子显微镜(SEM)、X射线衍射(XRD)以及透射光谱对制备出的ZnO纳米棒阵列的结构、形貌和透明性进行了表征. 测试结果表明, ZnO纳米棒阵列的平均直径为21 nm, 粒径分布窄, 约18～25 nm, 择优生长取向为[001]方向, 垂直于基底生长. 当入射光波长大于400 nm时, ZnO纳米棒阵列的透光率大于95%.     

金纳米棒组装体表面等离子体共振耦合效应的FDTD模拟

贵金属纳米结构的光学性质与其尺寸、形貌、介质环境等因素的相关性是基础研究领域的重要内容.本文利用时域有限差分(FDTD)方法,计算了不同构型二聚体和多聚体的表面等离子体共振(SPR)特性.研究了金纳米棒结构和组装方式对SPR耦合效应的影响,模拟结果与实验规律比较吻合.金纳米棒二聚体的光吸收结果表明:对于肩并肩(S-S)的组装体,随着间隙的减小,金纳米棒的横向SPR(SPRT)峰有较小的红移,而纵向SPR(SPRL)峰显著蓝移.对于端对端(E-E)的组装体,随着组装体间隙的减小,金纳米棒的SPRT峰无明显移动,而SPRL峰显著红移,并在近红外较长波段范围内出现新的共振峰,其强度随着间隙的减小而增强;结合弹簧振子模型和纳米颗粒在外电场作用下的极化,对组装体共振吸收峰的移动和新的耦合共振峰的出现提出了初步的解释.     

电沉积ZnO纳米棒阵列膜制备及其透光性能研究

应用阴极恒电流电沉积法,以ZnC l2水溶液为电解液,在经预处理的ITO导电玻璃上制备ZnO纳米棒阵列,扫描电子显微镜(SEM)、X射线衍射(XRD)及透射光谱等测试表明,ZnO纳米棒阵列具有c轴高度择优取向,呈六方纤锌矿结构.当入射光波长大于380 nm时,ZnO纳米棒阵列的透光率大于95%,并且禁带宽度变窄.     

Fast and slow deposition of silver nanorods on planar surfaces: application to metal-enhanced fluorescence

Two methods have been considered for the deposition of silver nanorods onto conventional glass substrates. In the first method, silver nanorods were deposited onto 3-(aminopropyl)triethoxysilane-coated glass substrates simply by immersing the substrates into the silver nanorod solution. In the second method, spherical silver seeds that were chemically attached to the surface were subsequently converted and grown into silver nanorods in the presence of a cationic surfactant and silver ions. The size of the silver nanorods was controlled by sequential immersion of silver seed-coated glass substrates into a growth solution and by the duration of immersion, ranging from tens of nanometers to a few micrometers. Atomic force microscopy and optical density measurements were used to characterize the silver nanorods deposited onto the surface of the glass substrates. The application of these new surfaces is for metal-enhanced fluorescence (MEF), whereby the close proximity of silver nanostructures can alter the radiative decay rate of fluorophores, producing enhanced signal intensities and an increased fluorophore photostability. In this paper, it is indeed shown that irregularly shaped silver nanorod-coated surfaces are much better MEF surfaces as compared to traditional silver island or colloid films. Subsequently, these new silver nanorod preparation procedures are likely to find a common place in MEF, as they are a quicker and much cheaper alternative as compared to surfaces fabricated by traditional nanolithographic techniques.     

金纳米棒组装体表面等离子体共振耦合效应的FDTD模拟

贵金属纳米结构的光学性质与其尺寸、形貌、介质环境等因素的相关性是基础研究领域的重要内容. 本文利用时域有限差分（FDTD）方法,计算了不同构型二聚体和多聚体的表面等离子体共振（SPR）特性. 研究了金纳米棒结构和组装方式对SPR耦合效应的影响,模拟结果与实验规律比较吻合. 金纳米棒二聚体的光吸收结果表明：对于肩并肩（S-S）的组装体,随着间隙的减小,金纳米棒的横向SPR（SPR_T）峰有较小的红移,而纵向SPR（SPR_L）峰显著蓝移. 对于端对端（E-E）的组装体,随着组装体间隙的减小,金纳米棒的SPR_T峰无明显移动,而SPR_L峰显著红移,并在近红外较长波段范围内出现新的共振峰,其强度随着间隙的减小而增强;结合弹簧振子模型和纳米颗粒在外电场作用下的极化,对组装体共振吸收峰的移动和新的耦合共振峰的出现提出了初步的解释.     

Ti基ZnO纳米棒阵列的制备及其光催化性能研究

采用两电极体系中恒电流电沉积在Ti基底上制得较均一的ZnO纳米棒阵列,利用SEM和XRD观察表征样品,研究Zn(NO₃)₂浓度及电流密度对ZnO纳米棒阵列微观形貌的影响. 以甲基橙为目标降解物,考察该电极光催化性能. 结果表明,Zn(NO₃)₂浓度和电流密度对纳米棒阵列的形貌有显著影响;与ITO玻璃等其他基底相比,在Ti基底上也可沉积较好均一取向的ZnO纳米棒阵列;紫外灯照射下,ZnO/Ti电极对甲基橙（10 mg·L^-1）模拟印染废水降解2.5 h,降解率达到83.3%,光催化活性较佳;无光照时ZnO纳米棒的降解率仅7%.     

Chemical growth of ZnO nanorod arrays on textured nanoparticle nanoribbons and its second-harmonic generation performance

On the basis of the highly oriented ZnO nanoparticle nanoribbons as the growth seed layer (GSL) and solution growth technique, we have synthesized vertical ZnO nanorod arrays with high density over a large area and multi-teeth brush nanostructure, respectively, according to the density degree of the arrangement of nanoparticle nanoribbons GSL on the glass substrate. This controllable and convenient technique opens the possibility of creating nanostructured film for industrial fabrication and may represent a facile way to get similar structures of other compounds by using highly oriented GSL to promote the vertical arrays growth. The growth mechanism of the formation of the ordered nanorod arrays is also discussed. The second-order nonlinear optical coefficient d₃₁ of the vertical ZnO nanorod arrays measured by the Maker fringes technique is 11.3 times as large as that of d₃₆ KH₂PO₄ (KDP).     

Structure, bonding, and linear optical properties of a series of silver and gold nanorod clusters: DFT/TDDFT studies

DFT/TDDFT calculations have been carried out for a series of silver and gold nanorod clusters (Ag(n), Au(n), n = 12-120) whose structures are of cigar-type. Pentagonal Ag(n) clusters with n = 49-121 and hexagonal Au(n) clusters with n = 14-74 were also calculated for comparison. Metal-metal distances, binding energies per atom, ionization potentials, and electron affinities were determined, and their trends with cluster size were examined. The TDDFT calculated excitation energies and oscillator strengths were fit by a Lorentz line shape modification, which gives rise to the simulated absorption spectra. The significant features of the experimental spectra for actual silver and gold nanorod particles are well reproduced by the calculations on the clusters. The calculated spectral patterns are also in agreement with previous theoretical results on different-type Ag(n) clusters. Many differences in the calculated properties are found between the Ag(n) and Au(n) clusters, which can be explained by relativistic effects.     

Shape and size effects in the optical properties of metallic nanorods

The influence of size and geometrical shape on the optical properties of randomly oriented metallic nanorods is investigated using the discrete dipole approximation (DDA). Our calculations provide a benchmark for an accurate characterisation of nanorod suspensions by frequently used optical spectroscopic techniques. Our DDA results confirm the longitudinal plasmon resonance to be primarily affected by the nanorod aspect ratio, and also verify that the quasi-static (dipole) approximation for ellipsoidal particles is only valid for very small sizes. For prolate ellipsoidal and cylindrical nanorods with an identical aspect ratio, the latter exhibit a longitudinal resonance at significantly longer wavelengths. The importance of phase retardation and multipole contributions for larger nanorod dimensions is discussed. Also, we investigate the influence on the optical spectra of electron surface scattering, which arises from the limited size of the nanorods in comparison to the electron mean free path.     

氧化锌纳米棒微结构光电极的制备

通过两步法,即首先热分解醋酸锌制备氧化锌晶种层,在晶种的诱导下,再采用低温水热法在氟掺杂的SnO₂导电玻璃(fluorine-doped tin oxide, FTO)基底导电面上成功制备出高取向性的氧化锌纳米棒阵列光电极。系统研究了前驱液浓度、溶液pH值、反应时间等实验条件对光电极微结构的影响。实验结果表明在一定变化范围内,随着前驱液浓度和溶液pH值的增大,纳米棒的直径增大;随着反应时间的延长,纳米棒的长度增长。将氧化锌纳米棒阵列薄膜制作成染料敏化太阳电池(dye-sensitized solar cell, DSSC)的光电极,并对电池的I-V特性进行了表征。     

Effect of seed layer on the growth and the consequent gas sensing characteristics of ZnO nanorod arrays using aqueous chemical growth

The ZnO nanorod arrays are grown on the sol–gel-derived seed layer through aqueous chemical growth, and then assembled as gas sensors for detecting carbon monoxide (CO). It is found that the structural and photoluminescent properties of the ZnO nanorod arrays are different as they are grown on seed layers annealed at different temperature (300–700 °C), which is ascribed to distinct growth kinetics of nanorods on the annealed seed layer. Moreover, the correlation between the exposed surface area and the defect density of those ZnO nanorod arrays points out the intrinsic (interior) defects can dominate the green emission instead of surface defects in the present study. Furthermore, the quantities of chemisorbed oxygen on ZnO nanorod arrays can be estimated through XPS analysis. Consequently, the influence of intrinsic defects and chemisorbed oxygen on the electrical properties and gas sensitivities of ZnO nanorod arrays has been clearly elucidated. It is demonstrated that the more adsorbed oxygen and an appropriate amount of intrinsic defects is advantageous to obtain superior CO gas sensitivity for ZnO nanorod arrays.     

Solvent-induced hot spot switch on silver nanorod enhanced Raman spectroscopy

An extremely simple and sensitive approach using solvent-induced hot spot switch on silver nanorod enhanced Raman spectroscopy has been found and experimentally demonstrated, which can be used for detection and identification analyte molecules.     

Controllable growth of silver nanostructures by a simple replacement reaction and their SERS studies

Hierarchical silver nanostructures, consisting of dendritic (symmetric branched) and fractal patterns (randomly ramified), were synthesized very easily by dropping a droplet of AgNO₃-HF solution on silicon wafers. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and open circuit potential-time (Ocp-t) measurement demonstrated that the two nanostructures converted with the reaction composition. The structural evolution was tentatively explained with the theory that oriented growth was determined by the anisotropy of the solid–liquid interfacial energy and the oriented attachment-based aggregation mechanism. Results on surface-enhanced Raman scattering (SERS) signals of the silver films with hierarchical nanostructures demonstrate that SERS is sensitive to silver nanostructures.     

Large‐Area Plasmonic Substrate of Silver‐Coated Iron Oxide Nanorod Arrays for Plasmon‐Enhanced Spectroscopy

One‐dimensional iron oxide materials fabricated on conducting glass substrates and their unique properties make these nanostructures promising candidates for a wide range of applications. Herein, vertically oriented α‐Fe₂O₃ nanorod arrays synthesized under hydrothermal conditions over a large area are described, as an active platform for surface‐enhanced resonance Raman scattering (SERRS) and surface‐enhanced fluorescence (SEF). From scanning electron microscopy images the formation of a homogeneous distribution of vertically oriented rods in a large area is confirmed. For activating the localized surface plasmon resonances, which are responsible for SERRS and SEF, a 6 nm layer of Ag is deposited onto the α‐Fe₂O₃ nanorod arrays by physical vapor deposition to form Ag islands.     

Bio-inspired fabrication of well-oriented ZnO nanorod arrays film and its superhydrophobicity and superhydrophilicity

A highly oriented ZnO nanorod array film was fabricated on glass substrate by combinations of Sol–Gel and hydrothermal. The film exhibits perfect superhydrophobicity with a contact angle of 155° and a glide angle of 4° after being surface modified by fluoroalkylsilane, which is similar with wings’ property and structures of large yellow spots mosquitoes. Interestingly, the ZnO nanorods film were converted from superhydrophobicity into superhydrophilicity under ultraviolet light for 2 h due to the decomposition of fluoroalkyl chain of fluoroalkylsilane and the photosensitivity of ZnO surface. The transition mechanisms of wettability are discussed on the basis of correlated theories.     

ZnO纳米棒阵列在TiO2介孔薄膜上的生长及其表征

通过低温水热法成功地将ZnO纳米棒阵列定向生长在了介孔锐钛矿TiO2纳米晶薄膜上,并主要利用X射线衍射、场发射扫描电子显微镜和光致发光光谱等对其进行了表征。所制备的纳米棒具有六边形的端面,纳米棒的尺寸及端面边长分布范围窄,并且沿c轴方向(002)表现出了明显的择优化生长。此外,相比于玻璃基底或TiO2纳米颗粒薄膜,生长在介孔TiO2薄膜上的ZnO纳米棒阵列表现出了较好的取向生长,表明基底的表面结构和组成对ZnO纳米棒阵列的生长有显著的影响。根据基底有序的多孔结构,讨论了纳米棒阵列可能的生长机理。所得到的ZnO纳米棒阵列在室温下分别表现出了以370 nm为中心的强近紫外光和以530 nm为中心的弱绿光两条荧光谱带。