Light-controlled plasmon switching using hybrid metal-semiconductor nanostructures

We present a proof of concept for the dynamic control over the plasmon resonance frequencies in a hybrid metal-semiconductor nanoshell structure with Ag core and TiO(2) coating. Our method relies on the temporary change of the dielectric function ε of TiO(2) achieved through temporarily generated electron-hole pairs by means of a pump laser pulse. This change in ε leads to a blue shift of the Ag surface plasmon frequency. We choose TiO(2) as the environment of the Ag core because the band gap energy of TiO(2) is larger than the Ag surface plasmon energy of our nanoparticles, which allows the surface plasmon being excited without generating electron-hole pairs in the environment at the same time. We calculate the magnitude of the plasmon resonance shift as a function of electron-hole pair density and obtain shifts up to 126 nm at wavelengths around 460 nm. Using our results, we develop the model of a light-controlled surface plasmon polariton switch.     

GSH、L-Cys和6-MP诱导纳米金聚集行为的分析与应用

利用纳米金的表面等离子共振吸收光谱研究了谷胱甘肽(GSH)、L半胱氨酸(L-Cys)和6-巯基嘌呤(6-MP)3种巯基化合物与纳米金作用的机理.结果表明,3种巯基化合物均能诱导纳米金聚集导致其表面等离子共振吸收峰红移.聚集后的纳米金对介质环境(如溶液极性)的变化较敏感,其吸收峰随着加入分析物的极性变化有规律地红移,并且吸光度也线性下降.可根据波长的红移或吸光度变化确立定量关系,可望用于分析对象的定量检测.     

Surface-enhanced Raman scattering of carbon nanotubes by decoration of ZnS nanoparticles

ZnS nanoparticles anchored on the single-walled carbon nanotubes (SWNTs) were fabricated by a chemical vapor deposition (CVD) method. The CVD method shows no selectivity for growth of ZnS nanoparticles on types and defects of the SWNTs, and thus ensures the uniform decoration of all SWNTs on the substrate. ZnS nanoparticles with a diameter of 10 nm were decorated on the SWNTs surface with an interparticle distance of about 20 nm. This method provides the possibility to realize the optimal configurations of ZnS nanoparticles on SWNTs for obtaining surface-enhanced Raman spectroscopy (SERS) of SWNTs. Investigations of mechanism reveal that charge transfer (a small amount of excitation electrons) from ZnS nanoparticles to SWNTs weakly affects Raman intensity, and the coupled surface plasmon resonance (SPR) formed from plenty of excitation electrons on the surface of ZnS nanoparticles contributes to the strong surface enhancement. It would be an alternative approach for SERS after metal (normally gold or silver) nanoparticles' decoration on the SWNTs surface.     

Optical response of Ag-Au bimetallic nanoparticles to electron storage in aqueous medium

Composition and structure dependence of the shift in the position of the surface plasmon resonance band upon introduction of NaBH4 to aqueous solutions of gold and silver nanoparticles are presented. Silver and gold nanoalloys in different compositions were prepared by co-reduction of the corresponding salt mixtures using sodium citrate as the reducing agent. After addition of NaBH4 to the resultant nanoalloys, the maximum of their surface plasmon resonance band, ranging between that of pure silver (ca. 400 nm) and of pure gold (ca. 530 nm), is blue-shifted as a result of electron storage on the particles. The extent of this blue shift increases non-linearly with the mole fraction of silver in the nanoparticle, parallel to the trends reported previously for both the frequency and the extinction coefficient of the plasmon band shifts. Gold(core)@silver(shell) nanoparticles were prepared by sequential reduction of gold and silver, where addition of NaBH4 results in relatively large spectral shift in the plasmon resonance band when compared with the nanoalloys having a similar overall composition. The origin of the large plasmon band shift in the core-shell is related with a higher silver surface concentration on these particles. Hence, the chemical nature of the nanoparticle emerges as the dominating factor contributing to the extent of the spectral shift as a result of electron storage in bimetallic systems.     

Plasmon‐Mediated Synthesis of Silver Cubes with Unusual Twinning Structures Using Short Wavelength Excitation

The plasmon‐mediated synthesis of silver nanoparticles is a versatile synthetic method which leverages the localized surface plasmon resonance (LSPR) of nanoscale silver to generate particles with non‐spherical shapes and control over dimensions. Herein, a method is reported for controlling the twinning structure of silver nanoparticles, and consequently their shape, via the plasmon‐mediated synthesis, solely by varying the excitation wavelength between 400, 450, and 500 nm, which modulates the rate of Ag⁺ reduction. Shorter, higher energy excitation wavelengths lead to faster rates of reaction, which in turn yield structures containing a greater number of twin boundaries. With this method, silver cubes can be synthesized using 450 nm excitation, which represents the first time this shape has been realized by a plasmon‐mediated synthetic approach. In addition, these cubes contain an unusual twinning structure composed of two intersecting twin boundaries or multiple parallel twin boundaries. With respect to their twinning structure, these cubes fall between planar‐twinned and multiply twinned nanoparticles, which are synthesized using 500 and 400 nm excitation, respectively.     

银纳米颗粒的化学还原法制备简介及其应用

银纳米颗粒的光学性能,如局域表面等离子体共振(Localized Surface Plasmon Resonance,LSPR)特性可通过其形貌、尺寸、外部介电环境的调控而实现变化。不同形貌的银纳米颗粒具有强弱不同的局域表面等离子体共振效应,从而表现出独特的光学性质。综述了利用化学还原法制备不同形貌的银纳米颗粒,主要包括柠檬酸钠还原法、多元醇法以及种子介导生长法,分析了这3种合成方法的机理和特点,将近年来不同形貌银纳米颗粒的研究进展进行了综述。最后介绍了不同形貌银纳米颗粒在表面增强拉曼散射(Surface-Enhanced Roman scattering,SERS)基底、催化、抗菌领域上的应用研究,并总结和展望了银纳米颗粒在合成和相关应用领域的发展前景。     

Probe for sensitive direct determination of sulphide ions based on gold nanoparticles

A highly selective and sensitive optical sensor based on localised surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) for the determination of a sulphide ion in aqueous solution is presented. The existence of sulphide is change the intensity of the LSPR band around 520 nm. In this sensor, sulphide ions were recognised and measured by UV–vis spectrophotometry. Three factors such as pH, time and concentration of AuNPs have been studied. The optimisation of effective parameters is done by one at a time method. This method was simple, rapid and cost efficient for the detection of sulphide. The linear range is 1.00–10.00 (4.16–41.63 µM) ppm with the correlation coefficient of 0.9874 and the detection limit of 0.54 ppm. The relative standard deviation of the reported method is 1.01%.Inspec keywords: surface plasmon resonance, chemical sensors, pH, nanoparticles, spectrophotometry, gold, optical sensors, nanosensors, nanofabrication, photodetectors, nanophotonics, optical fabrication, ultraviolet spectra, visible spectraOther keywords: gold nanoparticles, localised surface plasmon resonance, LSPR band, highly sensitive optical sensor, time method, sulphide ion determination, highly selective optical sensor, aqueous solution, UV–vis spectrophotometry, optical correlation coefficient, pH, Au     

Fabrication and optical characteristics of a novel optical fiber doped with the Au nanoparticles

Optical fibers containing gold metal nanoparticles were developed by modified chemical vapor deposition, in which Au(OH)3 and tetraethyl-orthosilicate (TEOS) was used via sol-gel process to incorporate gold metals by providing the reduction atmosphere. The absorption peak appeared near 490 nm was found to be due to the surface plasmon resonance of the gold nanoparticles incorporated in the fiber core.     

A facile and novel way for the synthesis of nearly monodisperse silver nanoparticles

A facile and novel way was reported for the preparation of nearly monodisperse silver nanoparticles with controlled hydrophilic or hydrophobic surface, using trioctylphosphine as the surfactant and stabilizer. The synthesized nanoparticles were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and UV-vis spectroscopy. The monodisperse silver nanoparticles showed a strong surface plasmon resonance band at 402 nm from the UV-vis spectrum.     

贵金属纳米颗粒的表面等离子共振研究

通过修正的Mie理论分别对单金属Ag、单金属Cu和Cu核Ag壳纳米颗粒/玻璃复合材料的吸收光谱进行了理论计算.计算结果表明,对单金属Ag纳米颗粒/玻璃复合材料,Ag的吸收峰位于425nm左右,不随颗粒尺寸变化而发生偏移;对单金属Cu纳米颗粒/玻璃复合材料,Cu的吸收峰也不随尺寸变化发生偏移但强度较弱;对Cu核Ag壳纳米...     

Controlled synthesis and optical properties of Au and Au@PS nanoparticles

In this study, uniform gold (Au) nanoparticles (NPs) were prepared using seed-mediated growth method. The particle size was controlled by tuning the dosage of seed solution. Au@PS core–shell NPs were then synthesized by introducing a polystyrene (PS) shell (2–3 nm thick) around the core of Au NPs (115 nm). Evaluation of the surface plasmon (SP) optical properties indicated that wavelength of SP resonance of Au NPs increased gradually with increase in the particle size. This red shift was about 0.92 nm per 1 nm increase in particle size. The results also indicated that the zeta potential and optical properties of Au NPs could be adjusted by coating PS on the outside. Therefore, surface modifications and surface coating were effective ways to control the optical properties of Au NPs.     

超支化聚(胺-酯)为模板Ag纳米粒子的制备

以超支化聚(胺-酯)为模板,采用NaBH4直接还原和紫外灯光照射合成了Ag纳米粒子。超支化聚(胺-酯)对Ag纳米粒子形成起着重要的作用。TEM分析表明,Ag纳米粒子形貌为球形结构,分布均匀,粒径约为45 nm(NaBH4还原)和20 nm(紫外灯光照射)。发现在UV-Vis谱图中420 nm左右有Ag纳米粒子特征表面等离子共振吸收峰。FT-IR分析发现Ag纳米粒子和超支化聚(胺-酯)之间有较强的相互作用,超支化聚(胺-酯)对Ag纳米粒子的稳定性起保护作用。     

Optical changes and writing on hydrotalcite supported gold nanoparticles

Gold nanoparticles (AuNP) incorporated into hydrotalcite (HT), provide an interesting type of pigment in which temperature can modulate the plasmon resonance and the aggregation phenomenon. As inferred from microscopy techniques, the preferential binding sites are located at the border of the HT external basal surface, leading to aggregates of gold nanoparticles displaying characteristic plasmon resonance and interference bands around 520 and 700 nm, respectively. The thermally induced color changes in the HT-supported gold material arise from the competition between of nanoparticles aggregation and fusion processes, as characterized by TEM and STM. A laser beam can also induce such changes, allowing the writing of optical information on this type of material.     

Synthesis of hybrid Au–ZnO nanoparticles using a one pot polyol process

In this work, we report on the synthesis of hybrid Au–ZnO nanoparticles using a one-pot chemical method that makes use of 1,3-propanediol as a solvent, a reducing agent and a stabilizing layer. The produced nanoparticles consisted of Au cores decorated with ZnO nanoparticles. The structure and morphology of the nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDX) and Raman spectroscopy. Optical extinction measurements, combined with numerical simulations, showed that the Au–ZnO nanoparticles exhibit a localized surface plasmon resonance (SPR) clearly red-shifted with respect to that of bare Au nanoparticles (AuNPs). This work contributes to the emergence of multi-functional nanomaterials with possible applications in surface plasmon resonance based biosensors, energy-conversion devices, and in water-splitting hydrogen production.     

Influence of the interaction between two Ag nanoparticles on optical properties of Ag/PGMEA nanocomposite materials

We report local electric field calculations in Ag/PGMEA nanocomposite materials using the dipole discrete approximation. We employ calculation and simulation to show that the nanoparticle radius and the interparticle distance could control and tune the surface plasmon resonances, which influence the extinction spectra and the near-field enhancement of Ag/PGMEA nanostructures. With decreasing interparticle distance, the near-field coupling between particles will induce the shift of surface plasmon resonance peak and improve the near-field intensity. With increasing radius (r), the resonance wavelength peak is red-shifted because of the interaction between two Ag nanoparticles. At 449 nm, the highest near-field enhancement factor obtained in the center of the gap was 30.5 for two interacting Ag nanoparticles of r = 11 nm with a gap of 5 nm.     

Nanoarray-based biomolecular detection using individual Au nanoparticles with minimized localized surface plasmon resonance variations

Here, we present a mean to expand the use of individual metallic nanoparticles to two-dimensional plasmonic nanoarrays. An optical detection platform to track down localized surface plasmon resonance (LSPR) signals of individual nanoparticles on substrates was built for the application of plasmonic nanoarrays. A pseudoimage of nanoparticles on a substrate was reconstructed from their scattering spectra obtained by scanning a user-defined area. The spectral and spatial resolutions of the system were also discussed in detail. Most importantly, we present a method to normalize the localized surface plasmon resonance from geometrically different nanoparticles. After normalization, plasmonic responses from different particles become highly consistent, creating well-fitted dose-response curves of both surrounding refractive index changes and receptor-analyte binding to the surface of individual nanoparticles. Finally, the proof-of-concept system for plasmonic nanoarray detection is demonstrated by the measurement of the aptamer-thrombin binding event.     

Luminescence of CdSe quantum dots near a layer of silver nanoparticles ion-synthesized in sapphire

We study the characteristics of the luminescence of composite films based on polymethyl methacrylate with CdSe quantum dots deposited from solution onto the surface of a sapphire substrate containing a preliminarily formed layer with ion-synthesized silver nanoparticles. The sapphire layer with silver nanoparticles exhibits selective plasmon absorption in the visible spectral range with a peak at 463 nm. Enhancement in the exciton luminescence intensity of quantum dots with a peak at 590 nm is observed upon excitation at wavelengths lying in the region of plasmon resonance of metal nanoparticles, as well as luminescence quenching for quantum dots located in the vicinity of silver nanoparticles.     

Gold nanoparticles reduced in situ and dispersed in polymer thin films: optical and thermal properties

Optical and thermal activity of plasmon-active nanoparticles in transparent dielectric media is of growing interest in thermal therapies, photovoltaics and optoelectronic components in which localized surface plasmon resonance (LSPR) could play a significant role. This work compares a new method to embed gold nanoparticles (AuNPs) in dense, composite films with an extension of a previously introduced method. Microscopic and spectroscopic properties of the two films are related to thermal behavior induced via laser excitation of LSPR at 532?nm in the optically transparent dielectric. Gold nanoparticles were incorporated into effectively nonporous 680?μm thick polydimethylsiloxane (PDMS) films by (1) direct addition of organic-coated 16?nm nanoparticles; and (2) reduction of hydrogen tetrachloroaurate (TCA) into AuNPs. Power loss at LSPR excitation frequency and steady-state temperature maxima at 100?mW continuous laser irradiation showed corresponding increases with respect to the mass of gold introduced into the PDMS films by either method. Measured rates of temperature increase were higher for organic-coated NP, but higher gold content was achieved by reducing TCA, which resulted in larger overall temperature changes in reduced AuNP films.     

Magneto-Plasmonic Effect in Cobalt Thin Film Incorporating Core–Shell Ag@Au Nanoparticles

We report enhanced magneto-optical Kerr rotation in the magneto-plasmonic structure of a cobalt thin film incorporating silver/gold core–shell nanoparticles. Metallic nanoparticles with core–shell structure of silver/gold were fabricated by laser ablation in liquid method and the magneto-optical medium was prepared by electron beam deposition technique. Excitation of localized surface plasmon resonance was demonstrated for various incidence angles. The experimental results show direct evidence for localized surface plasmon resonance enhancement effect on the polar magneto-optical Kerr effect of the cobalt thin film.     

Complementary surface-enhanced resonance Raman spectroscopic biodetection of mixed protein solutions by chitosan- and silica-coated plasmon-tuned silver nanoparticles

Silver nanoparticles with identical plasmonic properties but different surface functionalities are synthesized and tested as chemically selective surface-enhanced resonance Raman (SERR) amplifiers in a two-component protein solution. The surface plasmon resonances of the particles are tuned to 413 nm to match the molecular resonance of protein heme cofactors. Biocompatible functionalization of the nanoparticles with a thin film of chitosan yields selective SERR enhancement of the anionic protein cytochrome b(5), whereas functionalization with SiO(2) amplifies only the spectra of the cationic protein cytochrome c. As a result, subsequent addition of the two differently functionalized particles yields complementary information on the same mixed protein sample solution. Finally, the applicability of chitosan-coated Ag nanoparticles for protein separation was tested by in situ resonance Raman spectroscopy.