Preparation and characterisation of Langmuir–Blodgett films of 4‐(4‐(N‐octadecyl‐N‐methylamino) phenylazo)benzoic acid

Langmuir films of the title compound have been spread on an aqueous subphase at various values of pH at 10, 15 and 20°C. Increasing pH and increasing temperature favour stable films, but at the higher subphase pH and temperature values the pressure–area isotherms exhibit a transition to aggregated forms. Tilt angles between the alkyl chains and the normal to the subphase increase with increasing subphase pH and temperature. The area per molecule for films deposited at 15 °C decreased steadily with time at a fixed surface pressure, except at the highest pH, indicating poor stability. Langmuir–Blodgett films deposited at a surface pressure of 30 mN m⁻¹ and a subphase temperature of 15 °C were of Y‐type and showed transfer ratios above unity for the lower subphase pH values. UV/visible spectra of the LB films showed features characteristic of the formation of H aggregates for deposition at the higher subphase pH values. Over long periods of time the spectra for high pH showed evidence of increasing aggregation. Small‐angle X‐ray diffraction confirmed molecular tilts larger than those deduced in the floating monolayer. Reflection–absorption infrared spectroscopy of the LB films showed differences from the bulk also indicative of significant tilt, as did surface‐enhanced Raman spectroscopy. The LB films showed weak second‐harmonic generation from 1064 nm radiation consistent with a polar film structure parallel to the substrate. Copyright © 1999 John Wiley & Sons, Ltd.     

Induced SER‐Activity in Nanostructured Ag–Silica–Au Supports via Long‐Range Plasmon Coupling

A novel Ag–silica–Au hybrid device is developed that displays a long‐range plasmon transfer of Ag to Au leading to enhanced Raman scattering of molecules largely separated from the optically excited Ag surface. A nanoscopically rough Ag surface is coated by a silica spacer of variable thickness from ～1 to 21 nm and a thin Au film of ～25 nm thickness. The outer Au surface is further functionalized by a self‐assembled monolayer (SAM) for electrostatic binding of the heme protein cytochrome c (Cyt c) that serves as a Raman probe and model enzyme. High‐quality surface‐enhanced resonance Raman (SERR) spectra are obtained with 413 nm excitation, demonstrating that the enhancement results exclusively from excitation of Ag surface plasmons. The enhancement factor is estimated to be 2 × 10⁴–8 × 10³ for a separation of Cyt c from the Ag surface by 28–47 nm, corresponding to an attenuation of the enhancement by a factor of only 2–6 compared to Cyt c adsorbed directly on a SAM‐coated Ag electrode. Upon immobilization of Cyt c on the functionalized Ag–silica–Au device, the native structure and redox properties are preserved as demonstrated by time‐ and potential‐dependent SERR spectroscopy.     

脉冲激光改性金属纳米薄膜的等离子体特性

在室温环境下,实验采用Nd\:YAG光纤脉冲激光器辐照银(Ag)、铜(Cu)、铝(Al)三种光滑连续的金属薄膜,制备出了对应的三种金属纳米颗粒薄膜。通过调节激光扫描速率可以实现三种金属纳米颗粒薄膜的局域表面等离子体共振(LSPR)波长和强度的调谐。其中,Ag纳米颗粒薄膜在可见光波段的等离子体吸收峰的波长和强度均表现出较宽的调谐范围,Cu纳米颗粒薄膜在可见光波段的等离子体吸收峰的波长和强度均表现较小的调谐范围,Al纳米颗粒薄膜在紫外光波段的等离子体吸收峰窄而尖锐,且LSPR波长调谐范围也较小。与激光辐照前的三种金属薄膜相比,激光辐照后生成的三种金属纳米颗粒薄膜出现了更强的表面增强拉曼散射信号。有限差分时域仿真模拟出的样品的电场强度分布与实验得到的表面增强拉曼散射结果一致。     

Ultrasonication‐Induced Self‐Assembled Fixed Nanogap Arrays of Monomeric Plasmonic Nanoparticles inside Nanopores

Monomeric gold (Au) and silver (Ag) nanoparticle (NP) arrays are self‐assembled uniformly into anodized aluminium oxide (AAO) nanopores with a high homogeneity of greater than 95%, using ultrasonication. The monomeric metal NP array exhibits asymmetric plasmonic absorption due to Fano‐like resonance as interpreted by finite‐difference time‐domain (FDTD) simulation for the numbers up to 127 AuNPs. To examine gap distance‐dependent collective‐plasmonic resonance, the different dimensions of S, M, and L arrays of the AuNP diameters/the gap distances of ≈36 nm/≈66 nm, ≈45 nm/≈56 nm, and ≈77 nm/≈12 nm, respectively, are prepared. Metal NP arrays with an invariable nanogap of ≈50 nm can provide consistent surface‐enhanced Raman scattering (SERS) intensities for Rhodamine 6G (Rh6G) with a relative standard deviation (RSD) of 3.8–5.4%. Monomeric arrays can provide an effective platform for 2D hot‐electron excitation, as evidenced by the SERS peak‐changes of 4‐nitrobenzenethiol (4‐NBT) adsorbed on AgNP arrays with a power density of ≈0.25 mW µm^‐2 at 514 and 633 nm. For practical purposes, the bacteria captured by 4‐mercaptophenylboronic acid are found to be easily destroyed under visible laser excitation at 514 nm with a power density of ≈14 mW µm^‐2 for 60 min using Ag due to efficient plasmonic‐electron transfer.     

Template‐Confined Dewetting Process to Surface Nanopatterns: Fabrication,Structural Tunability,and Structure‐Related Properties

Metallic surface nanopatterns are prepared by a template‐confined dewetting process with multiple structural controllabilities. The morphology of the building blocks is homogeneous throughout the surface nanopatterns, as the dewetting process proceeds separately in each bowl. The features of the building units in the surface patterns are highly dependent on the annealing temperature. Importantly, the size and composition of the nanoparticles in the surface nanopatterns can be pre‐calculated and designed by manipulating the thickness of the evaporated metallic films. The heating temperature and composition of the building units influence the surface‐enhanced Raman scattering (SERS) and plasmonic properties, thus tuning the localized surface plasmon resonance peaks over a broad range (from visible to near infrared). The introduction of silver in the gold surface nanopatterns enhances the SERS performance dramatically. This work not only provides a powerful route to fabricate surface nanopatterns, but also supplies a platform to study the mechanism of the complicated dewetting processes of metals.     

Langmuir–Blodgett films of a benzothiazolium dye containing a crown ether ring

The structure of Langmuir–Blodget (LB) films built up from a novel benzothiazolium steryl dye containing a 1, 10-dithia-18-crown-6 ether group has been investigated using ellipsometry and polarised absorption spectroscopy. The Y-type deposition results in a uniaxial film with a thickness of 2.18 ± 0.08 nm per monolayer and an index of refraction of 1.57 ± 0.03. the chromophore parts of the moelcule exhibit an in-Plane orientation. The influence of mercury vapouron the LB films has been investigated using the technique of surface plasmon resonance.     

Facile Fabrication of High‐Density Sub‐1‐nm Gaps from Au Nanoparticle Monolayers as Reproducible SERS Substrates

The fabrication of ultrasmall nanogaps (sub‐1 nm) with high density is of significant interest and importance in physics, chemistry, life science, materials science, surface science, nanotechnology, and environmental engineering. However, it remains a challenge to generate uncovered and clean sub‐1‐nm gaps with high density and uniform reproducibility. Here, a facile and low‐cost approach is demonstrated for the fabrication of high‐density sub‐1‐nm gaps from Au nanoparticle monolayers as reproducible surface‐enhanced Raman scattering (SERS) substrates. Au nanoparticles with larger diameters possess lower surface charge, thus the obtained large‐area nanoparticle monolayer generates a high‐density of sub‐1‐nm gaps. In addition, a remarkable SERS performance with a 10¹¹ magnitude for the Raman enhancement is achieved for 120 nm Au nanoparticle monolayers due to the dramatic increase in the electromagnetic field enhancement when the obtained gap is smaller than 0.5 nm. The Au nanoparticle monolayer is also transferred onto a stretchable PDMS substrate and the structural stability and reproducibility of the high‐density sub‐1‐nm gaps in Au monolayer films are illustrated. The resultant Au nanoparticle monolayer substrates with an increasing particle diameter exhibit tunable plasmonic properties, which control the plasmon‐enhanced photocatalytic efficiency for the dimerization of p‐aminothiophenol. The findings reported here offer a new opportunity for expanding the SERS application.     

Supported Faceted Gold Nanoparticles with Tunable Surface Plasmon Resonance for NIR‐SERS

A novel dry plasma methodology for fabricating directly stabilized substrate‐supported gold nanoparticle (NP) ensembles for near infrared surface enhanced Raman scattering (NIR SERS) is presented. This maskless stepwise growth exploits Au‐sulfide seeds by plasma sulfidization of gold nuclei to produce highly faceted Au NPs with a multiple plasmon resonance that can be tuned from the visible to the near infrared, down to 1400 nm. The role of Au sulfidization in modifying the dynamics of Au NPs and of the corresponding plasmon resonance is discussed. The tunability of the plasmon resonance in a broad range is shown and the effectiveness as substrates for NIR SERS is demonstrated. The SERS response is investigated by using different laser sources operating both in the visible and in the NIR. SERS mapping of the SERS enhancement factor is carried out in order to evaluate their effectiveness, stability, and reproducibility as NIR SERS substrates, also in comparison with gold NPs fabricated by conventional sputtering and with the state‐of‐the‐art in the current literature.     

3D Hexagonal (R‐3m) Mesostructured Nanocrystalline Titania Thin Films: Synthesis and Characterization

A straightforward and reproducible synthesis of crack‐free large‐area thin films of 3D hexagonal (R‐3m) mesostructured nanocrystalline titania (meso‐nc‐TiO₂) using a Pluronic triblock copolymer (P123)/1‐butanol templating system is described. The characterization of the films is achieved using a combination of electron microscopy (high‐resolution scanning electron microscopy and scanning transmission electron microscopy), grazing‐incidence small‐angle X‐ray scattering, in situ high‐temperature X‐ray diffraction, and variable‐angle spectroscopic ellipsometry. The mesostructure of the obtained films is found to be based upon a 3D periodic array of large elliptically shaped cages with diameters around 20 nm interconnected by windows of about 5 nm in size. The mesopores of the film calcined at 300 °C are very highly ordered, and the titania framework of the film has a crystallinity of 40 % being composed of 5.8 nm sized anatase crystallites. The film displays high thermal stability in that the collapse of the pore architecture is incomplete even at 600 °C. The accessible surface area of 3D hexagonal meso‐nc‐TiO₂ estimated by the absorption of methylene blue is nearly twice as large as that of 2D hexagonal meso‐nc‐TiO₂ at the same annealing temperature.     

Stimulated Raman Scattering in Nanorod Silicon Carbide Films

When the film is excited by a very low excitation energy, the spontaneous Raman scattering emerges. The intensity of Raman scattering is proportional to the excitation power below the threshold excitation. When the excited power reaches the excitation threshold, the intensity of Stokes light strongly increases. Meanwhile an anti Stokes light at 495 nm and multiple order but small Stokes peaks occur. The intensity of Stokes light is much larger than that of anti Stokes. The full width of half maximum (FWHM) of Stokes peak is reduced from 0.4 nm to less than 0.2 nm, the scattering angle between both Stokes and incident lights becomes less than 1°, and the angle between the Stokes and anti Stokes lights is about 3°. When the exciting power is in excess of the threshold, anti Stokes and multiple Raman scattering peaks reappear. These experiments can be unlimitedly repeated. From this experiment, we can exclude the possibility of spontaneous Raman scattering. It is suggested that the nanorods are a quantum line dimension having a large surface. There will be Raman differential scattering section so long as the nanorod films become very strong scattering media; the surface enhanced Raman scattering will be produced, the nanorod films of SiC will form a strong multiple scattering resonance cavities so as to form the stimulated Raman scattering oscillation.     

多元等离子体共振纳米结构的飞秒激光加工与拉曼检测应用

以多元金属纳米薄膜(金、银)为基底,利用飞秒激光加工技术制备得到多元等离子体纳米结构,并研究了其局域表面等离子体共振效应(Local Surface Plasmon Resonance,LSPR)和表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)性能。利用时域有限差分(Finite Difference Time Domain,FDTD)软件模拟了不同情况下(单层金膜、金银双层金属薄膜的平面以及阵列结构)的电场分布情况。根据仿真结果,相较于平面金属膜来说,飞秒激光制备的微纳结构阵列附近区域产生电磁场增强,集中在结构边缘处,且其强度变化与预期结果基本保持一致。此外,使用浓度为10-4 M和10-6 M的罗丹明(R6G)溶液进行SERS性能测试。测试的结果表明,单层平面金膜基本没有SERS峰值信号出现,而单层金膜上制备的等离子体纳米结构附近出现峰值信号,双层金属薄膜上制备的等离子体纳米结构展现出更高的SERS峰值信号。多元金属等离子体纳米结构展示出更强的局域表面等离子体共振效应,从而在表面增强拉曼散射、光催化、生物传感等领域具有广泛的应用。     

Confocal Raman Spectroscopy of α‐Sexithiophene: From Bulk Crystals to Field‐Effect Transistors

We report confocal micro‐Raman spectra of the organic semiconductor α‐sexithiophene (T6) on bulk crystals and on thin films grown on technologically relevant substrates and devices. We show that the two polymorphs, which are clearly identified by their lattice phonon spectra, may coexist as physical impurities of one inside the other in the same crystallite. Spatial distribution of the two phases is monitored by Raman phonon mapping of crystals grown upon different conditions. Raman microscopy has then been extended to T6 thin films grown on silicon oxide wafers. We identify the crystal phase in thin films whose thickness is just 18 nm. The most intense total‐symmetric Raman vibration is still detectable for a two‐monolayer thick film. Comparative analysis between micro‐Raman and AFM of T6 thin films grown on field effect transistors shows that electrode‐channel steps favour the nucleation and growth of T6 molecules on the substrate, at least below 50 nm.     

激光能量对沉积纳米Si薄膜晶粒尺寸的影响

为了制备纳米硅薄膜,采用脉冲激光沉积系统,保持靶材和衬底间距不变,在不同激光能量条件下,得到一系列纳米Si薄膜。利用喇曼散射光谱和X射线衍射谱对晶粒尺寸进行了计算和分析,取得了几组数据。结果表明,改变脉冲激光能量时,纳米Si晶粒平均尺寸均随能量的增强先增大后减小;在单脉冲能量为300mJ时制备的纳米Si晶粒平均尺寸最大,为8.58nm。这一结果对纳米硅薄膜制备的研究有积极意义。     

Hierarchically Ordered Arrays of Noncircular Silicon Nanowires Featured by Holographic Lithography Toward a High‐Fidelity Sensing Platform

A novel, highly uniform and tunable hybrid plasmonic array is created via ion‐milling, catalytic wet‐etching and electron‐beam evaporation, using a holographically featured structure as a milling mask. A simple and low‐cost prism holographic lithography (HL) technique is applied to create an unprecedentedly coordinated array of elliptic gold (Au) holes, which act as the silicon (Si) etching catalyst in the reaction solution used to fabricate an elliptic silicon nanowire (SiNW) array; here, the SiNWs are arrayed hierarchically in such a way that three SiNWs are triangularly coordinated, and the triangles are arranged hexagonally. After removing the polymeric mask and metal thin film, the highly anisotropic thick Au film is deposited on the SiNW arrays. This hybrid substrate shows tunable optical properties in the near‐infrared (NIR) region from 875 nm to 1030 nm and surface‐enhanced Raman scattering (SERS) activities; these characteristics depend on the catalytic wet etching time, which changes the size of the vertical gap between the Au thick films deposited separately on the SiNWs. In addition, lateral interparticle coupling induces highly intensified SERS signals with good homogeneity. Finally, the Au‐capped elliptical SiNW arrays can be hierarchically patterned by combining prism HL and conventional photolithography, and the highly enhanced fluorescence intensity associated with both the structural effects and the plasmon resonances is investigated.     

Self‐Assembled SERS Substrates with Tunable Surface Plasmon Resonances

The fabrication of surface‐enhanced Raman spectroscopy (SERS) substrates that are optimized for use with specific laser wavelength–analyte combinations is addressed. In order to achieve large signal enhancement, temporal stability, and reproducibility over large substrate areas at low cost, only self‐assembly and templating processes are employed. The resulting substrates consist of arrays of gold nanospheres with controlled diameter and spacing, properties that dictate the optical response of the structure. Tunability of the extended surface plasmon resonance is observed in the range of 520–1000 nm. It is demonstrated that the enhancement factor is maximized when the surface plasmon resonance is red‐shifted with respect to the SERS instrument laser line. Despite relying on self‐organization, site‐to‐site enhancement factor variations smaller than 10% are obtained.     

Formation of silicon nanocrystals with preferred (100) orientation in amorphous Si:H films grown on glass substrates and exposed to nanosecond pulses of ultraviolet radiation

Using Raman scattering, it was ascertained that silicon nanocrystals with sizes exceeding 2 nm are formed in amorphous silicon films exposed to nanosecond ultraviolet laser radiation with energy densities ranging from 75 to 150 mJ/cm²; it is shown that these nanocrystals have sizes no smaller than 2 nm and have preferred (100) orientation along the normal to the film surface. In a system of mutually oriented Si nanocrystals, anisotropic behavior of the Raman scattering intensity was experimentally detected in various polarization configurations, which made it possible to determine the volume fraction of oriented nanocrystals. The orientational effect is presumably caused by both the macroscopic fields of elastic stresses in the film and the local fields of elastic stresses around the nanocrystals.     

Polydisperse Aggregates of ZnO Nanocrystallites: A Method for Energy‐Conversion‐Efficiency Enhancement in Dye‐Sensitized Solar Cells

ZnO films consisting of either polydisperse or monodisperse aggregates of nanocrystallites were fabricated and studied as dye‐sensitized solar‐cell electrodes. The results revealed that the overall energy‐conversion efficiency of the cells could be significantly affected by either the average size or the size distribution of the ZnO aggregates. The highest overall energy‐conversion efficiency of ～4.4% was achieved with the film formed by polydisperse ZnO aggregates with a broad size distribution from 120 to 360 nm in diameter. Light scattering by the submicrometer‐sized ZnO aggregates was employed to explain the improved solar‐cell performance through extending the distance travelled by light so as to increase the light‐harvesting efficiency of photoelectrode film. The broad distribution of aggregate size provides the ZnO films with both better packing and an enhanced ability to scatter the incident light, and thus promotes the solar‐cell performance.     

Gold‐ and Silver‐Coated Barium Titanate Nanocomposites as Probes for Two‐Photon Multimodal Microspectroscopy

Improved multiphoton‐excited imaging and microspectroscopy require nanoprobes that can give different nonlinear optical signals. Here, composite nanostructures with a barium titanate core and a plasmonic moiety at their surface are synthesized and characterized. It is found that the core provides a high second‐order nonlinear susceptibility for sensitive second harmonic generation (SHG) imaging in living cells. As a second function in the two‐photon regime, the plasmonic part yields high local fields for resonant and nonresonant surface enhanced hyper Raman scattering (SEHRS). SEHRS complements the one‐photon surface enhanced Raman scattering (SERS) spectra that are also enhanced by the plasmonic shells. Barium titanate silver core–shell (Ag@BaTiO₃) composites are specifically suited for SEHRS and SHG excited at 1064 nm, while gold at barium titanate (Au@BaTiO₃) nanoparticles can be useful in a combination of SHG and SERS at lower wavelengths, here at 785 nm and 850 nm. The theoretical models show that the optical properties of the BaTiO₃ dielectric core depend on probing frequency, shape, size, and plasmonic properties of the surrounding gold nanoparticles so that they can be optimized for a particular type of experiment. These versatile, tunable probes give new opportunities for combined multiphoton probing of morphological structure and chemical properties of biosystems.     

MOCVD生长AlGaInN外延层的光学性质研究

对AlInGaN四元合金进行了微区发光和拉曼散射研究．根据V-形缺陷周围扫描电镜图像和阴极荧光光谱的分析，确定AlInGaN外延层中V-形缺陷的形成与铟的分凝之间的关系．同时，用波长为325纳米的短波长激光研究了AlInGaN外延薄层的拉曼散射，测量了合金铝组分改变引起的A1(LO)声子的频率移动，观测到了出射共振引起的LO声子拉曼散射谱的共振加强，此共振过程的机制是一种类级联的电子-多声子互作用机制．     

Novel Au–SiO2–WO3 Core–Shell Composite Nanoparticles for Surface‐Enhanced Raman Spectroscopy with Potential Application in Cancer Cell Imaging

With the rapid development of nanotechnology during the last decades, the ability to detect and control individual objects at the nanoscale has enabled us to deal with complex biomedical challenges. In cancer imaging, novel nanoparticles (NPs) offer promising potential to identify single cancer cells and precisely label larger areas of cancer tissues. Herein, a new class of size tunable core–shell composite (Au–SiO₂–WO₃) nanoparticles is reported. These nanoparticles display an easily improvable ≈10³ surface‐enhanced Raman scattering (SERS) enhancement factor with a double Au shell for dried samples over Si wafers and several orders of magnitude for liquid samples. WO₃ core nanoparticles measuring 20–50 nm in diameter are sheathed by an intermediate 10–60 nm silica layer, produced by following the Stöber‐based process and Turkevich method, followed by a 5–20 nm thick Au outer shell. By attaching 4‐mercaptobenzoic acid (4‐MBA) molecules as Raman reporters to the Au, high‐resolution Raman maps that pinpoint the nanoparticles' location are obtained. The preliminary results confirm their advantageous SERS properties for single‐molecule detection, significant cell viability after 24 h and in vitro cell imaging using coherent anti‐stokes Raman scattering. The long‐term objective is to measure SERS nanoparticles in vivo using near‐infrared light.