Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling

Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements.     

Uniform gold nanorod arrays from polyethylenimine-coated alumina templates

Monolithic Au nanorod arrays can be grown by electrodeposition in Au-backed nanoporous alumina templates using polyethylenimine (PEI) as an adhesion layer, with excellent height control between 300 nm and 1.4 microm. The local height distribution can be extremely narrow with relative standard deviations well below 2%. The uniform growth rate appears to be determined by the adsorbed PEI matrix, which controls the growth kinetics of the grains comprising the nanorods. The nanorods can be retained as free-standing 2D arrays after careful removal of the AAO template. Reflectance spectroscopy reveals a collective plasmon mode with a maximum near 1.2 microm, in accord with recent calculations for 2D arrays of closely spaced cylindrical nanoparticles.     

Grating-induced plasmon mode in gold nanoparticle arrays

We study the dipolar coupling of gold nanoparticles arranged in regular two-dimensional arrays by extinction micro-spectroscopy. When the interparticle spacing approaches the plasmon resonance wavelength of the individual particles, an additional band of very narrow width emerges in the extinction spectrum. By systematically changing the particles dielectric environment, the particles shape, the grating constant and angle of incidence, we show how this band associated to a grating induced-resonance can be influenced in strength and spectral position. The spectral position can be qualitatively understood by considering the conditions for grazing grating orders whereas the strength can be related to the strength of dipolar scattering from the individual particles.     

Design and Implementation of Noble Metal Nanoparticle Cluster Arrays for Plasmon Enhanced Biosensing

Nanoparticle Cluster Arrays (NCAs) are a class of electromagnetic materials that comprise chemically defined nanoparticles assembled into clusters of defined size in an extended deterministic arrangement. NCAs are fabricated through integration of chemically synthesized building blocks into predefined patterns using a hybrid top-down/bottom-up fabrication approach that overcomes some of the limitations of conventional top-down fabrication methods with regard to minimum available feature size and structural complexity. NCAs can sustain near-field interactions between nanoparticles within individual clusters as well as between entire neighboring clusters. The availability of near-field interactions on multiple length scales - together with the ability to further enhance the coupled plasmon modes through photonic modes in carefully designed array morphologies - leads to a multiscale cascade electromagnetic field enhancement throughout the array. This feature article introduces the design and fabrication fundamentals of NCAs and characterizes the electromagnetic coupling mechanisms in the arrays. Furthermore, it reviews how the optical properties of NCAs can be tuned through the size and shape of the nanoparticle building blocks and the geometry, size, and separation of the assembled clusters. NCAs have potential applications in many different areas; this feature article focuses on plasmon enhanced biosensing and surface enhanced Raman spectroscopy (SERS), in particular.     

A unified view of propagating and localized surface plasmon resonance biosensors

The intense colors of noble metal nanoparticles have inspired artists and fascinated scientists for hundreds of years. In this review, we describe refractive index sensing platforms based on the tunability of the localized surface plasmon resonance (LSPR) of arrays of silver nanoparticles and of single nanoparticles. Specifically, the color associated with single nanoparticles and surface-confined nanoparticle arrays will be shown to be tunable and useful as platforms for chemical and biological sensing. Finally, the LSPR nanosensor will be compared to traditional, flat surface, propagating surface plasmon resonance sensors.     

Two-dimensional self-organization of polystyrene-capped gold nanoparticles

Thiol end-functionalized polystyrene chains have been introduced onto the surface of gold nanoparticles via a two-step grafting-to method. This simple grafting procedure is demonstrated to be efficient for gold nanoparticles of different sizes and for particles initially dispersed in either aqueous or organic media. The method has been applied successfully for a relatively large range of polystyrene chain lengths. Grafting densities, as determined by thermogravimetric analysis, are found to decrease with increasing chain length. In all cases, the grafting density indicates a dense brush conformation for the tethered chains. The resulting functionalized nanoparticles self-organize into hexagonally ordered monolayers when cast onto solid substrates from chloroform solution. Furthermore, the distance between the gold cores in the dried monolayer is controlled by the molecular weight of the grafted polystyrene. Optical absorption spectra recorded for the organized monolayers show the characteristic plasmon absorption of the gold particles. Importantly, the plasmon resonance frequency exhibits a distinct dependence on interparticle separation that can be attributed to plasmon coupling between neighboring gold cores.     

Electromagnetic interactions in plasmonic nanoparticle arrays

Single two-dimensional planar silver arrays and one-dimensional linear gold chains of nanoparticles were investigated by dark-field surface plasmon spectroscopy and studied as a function of interparticle distance, particle size, and number of particles. In agreement with recent theoretical predictions, a red shift of the surface plasmon resonance occurring in two-dimensional arrays was found for lattice spacings below 200 nm. This red shift is associated with a significant broadening of the resonance and is attributed to the onset of near-field interactions. We found that the relative contributions of the long-range and short-range interactions in two-dimensional arrays of particles are fundamentally different to those occurring in individual linear chains.     

The optically detected coherent lattice oscillations in silver and gold monolayer periodic nanoprism arrays: the effect of interparticle coupling

Using femtosecond transient spectroscopy, we studied the optically detected laser-induced coherent phonon oscillation of monolayers of periodic arrays of prismatic-shaped silver and gold nanoparticles, assembled by using the technique of nanosphere lithography. In this method, the same size of polystyrene sphere and the same vacuum conditions are used. Under these circumstances, the gold nanoprisms formed are found to have sharper tips than the corresponding silver nanoprisms. For both gold and silver nanoparticles, the surface plasmon absorption maximum is found to depend linearly on size. The coherent lattice oscillation periods are also found to depend linearly on size. However, although the observed dependence for the silver nanoparticle is found to follow the calculated dependence of a single particle on size (based on a one-dimensional standing wave model), the gold nanoparticle deviates from this model, and the deviation is found to increase with the size of the nanoparticles. This deviation can be explained by considering interparticle coupling. A simple interparticle lattice oscillating dipolar coupling model of the dimer is found to qualitatively account for both the sign and the size dependence of the deviation. The absence of this deviation in the silver nanoparticle arrays is blamed on the weak interparticle coupling due to their rounded tips and the possibility of oxidation of their surfaces.     

Second harmonic excitation spectroscopy of silver nanoparticle arrays

Frequency-scanned excitation profiles of coherent second harmonic generation (SHG) were measured for silver nanoparticle arrays prepared by nanosphere lithography. The frequency of the fundamental beam did not coincide with the localized surface plasmon resonance (LSPR) of the nanoparticles and was tuned so that the coherent second harmonic (SH) emission was in the region of the LSPR at 720-750 nm. The SH emission from the arrays was compared with a smooth silver film to identify an enhancement of SH emission efficiency that peaks near approximately 650 nm for nanoparticles 50 nm in height. The polarization and orientation dependence of this enhancement suggests that it is related to a dipolar LSPR mode polarized normal to the plane of the substrate. Linear extinction spectra are dominated by in-plane dipoles and do not show this weak out-of-plane LSPR mode. The nanoparticle arrays are truncated tetrahedrons symmetrically oriented by nanosphere lithography to cancel SH from in-plane dipoles which allows observation of the weak out-of-plane component.     

Gold particle interaction in regular arrays probed by surface enhanced Raman scattering

Lithographically designed two-dimensional arrays consisting of gold nanoparticles deposited on a smooth gold film are used as substrate to examine the SERS effect of the trans-1,2-bis (4-pyridyl) ethylene molecule. These arrays display two plasmon bands instead of the single one observed for the same arrays of particles but deposited on indium tin oxide coated glass. Laser excitation within the short wavelength band does not bring about any SERS spectrum, while excitation within the long wavelength band yields SERS spectra with a gain per molecule rising up to 10(8). The simultaneous investigation of extinction and Raman spectra of arrays exhibiting various topography parameters enables us to suggest an interpretation for both the occurrence of the two plasmon resonances and for the high Raman enhancement. We suggest to assign the short wavelength band to a plasmon wave propagating at the gold glass interface and the long wavelength one to an air/gold surface plasmon mode modified by particle-particle interaction.     

Plasmonic nanoparticle chains via a morphological, sphere-to-string transition

Au nanoparticles encapsulated within polystyrene-block-poly(acrylic acid) (PS-b-PAA) micelles assemble into regular, one-dimensional arrays when they are exposed to solvent conditions that relax interfacial curvature in the micellar shell. Nanoparticle chaining was induced by adding salt, acid, or cationic carbodiimide to the suspension of purified encapsulated Au nanoparticles (Au@PS-b-PAA). The resulting assemblies were characterized by scanning and transmission electron microscopies, by dark-field optical microscopy, and by visible absorption spectroscopy. The length of the chains was modulated by varying the concentration of additive. More importantly, the spacing between Au nanoparticles was dictated entirely by the shell thickness of the Au@PS-b-PAA starting material. Far-field polarization microspectroscopy demonstrated directional surface plasmon coupling in a straightened nanoparticle chain, which is a basic requirement for the use of these assemblies as plasmon waveguides.     

Plasmon coupling in nanorod assemblies: optical absorption, discrete dipole approximation simulation, and exciton-coupling model

The shape anisotropy of nanorods gives rise to two distinct orientational modes by which nanorods can be assembled, i.e., end-to-end and side-by-side, analogous to the well-known H and J aggregation in organic chromophores. Optical absorption spectra of gold nanorods have earlier been observed to show a red-shift of the longitudinal plasmon band for the end-to-end linkage of nanorods, resulting from the plasmon coupling between neighboring nanoparticles, similar to the assembly of gold nanospheres. We observe, however, that side-by-side linkage of nanorods in solution shows a blue-shift of the longitudinal plasmon band and a red-shift of the transverse plasmon band. Optical spectra calculated using the discrete dipole approximation method were used to simulate plasmon coupling in assembled nanorod dimers. The longitudinal plasmon band is found to shift to lower energies for end-to-end assembly, but a shift to higher energies is found for the side-by-side orientation, in agreement with the optical absorption experiments. The strength of plasmon coupling was seen to increase with decreasing internanorod distance and an increase in the number of interacting nanorods. For both side-by-side and end-to-end assemblies, the strength of the longitudinal plasmon coupling increases with increasing nanorod aspect ratio as a result of the increasing dipole moment of the longitudinal plasmon. For both the side-by-side and end-to-end orientation, the simulation of a dimer of nanorods having dissimilar aspect ratios showed a longitudinal plasmon resonance with both a blue-shifted and a red-shifted component, as a result of symmetry breaking. A similar result is observed for a pair of similar aspect ratio nanorods assembled in a nonparallel orientation. The internanorod plasmon coupling scheme concluded from the experimental results and simulations is found to be qualitatively consistent with the molecular exciton coupling theory, which has been used to describe the optical spectra of H and J aggregates of organic molecules. The coupled nanorod plasmons are also suggested to be electromagnetic analogues of molecular orbitals. Investigation of the plasmon coupling in assembled nanorods is important for the characterization of optical excitations and plasmon propagation in these nanostructures. The surface plasmon resonance shift resulting from nanorod assembly also offers a promising alternative for analyte-sensing assays.     

硅烯量子点二聚物的等离激元激发

基于含时密度泛函理论,研究了随着间距改变时硅烯量子点二聚物的等离激元激发特性。沿垂直于硅烯所在平面方向激发时,在一定间距范围内,硅烯量子点二聚物中形成了长程电荷转移激发模式。参与长程电荷转移激发的π电子主要在两个量子点之间运动。该等离激元模式随着间隙的减小发生蓝移。此外,在不同间距时,体系中还有两个等离激元共振带,分别位于7和15 eV附近。沿平行于硅烯所在平面方向激发时,由于两个量子点之间的耦合,在低能     

Fluorescence Emission Mediated by Metal-Dielectric-Metal Fishnet Metasurface: Spatially Selective Excitation and Double Enhancement

Enhancement of fluorescent radiation is of great importance for applications including biological imaging, high-sensitivity detectors, and integrated light sources. Strong electromagnetic fields can be created around metallic nanoparticles or in gap of nanostructures, where the local state density of radiating mode is then dramatically enhanced. While enhanced fluorescent emission has been demonstrated in many metallic nanoparticles and nanoparticle pairs, simultaneous mediation of absorption and emission processes of fluorescent emitters remains challenging in metallic nanostructures. Here, we investigate fluorescent emission mediated by metal-dielectric-metal fishnet metasurface, in which localized surface plasmon (LSP) and magnetic plasmon polaritons (MPPs) modes are coupled with absorption and emission processes, respectively. For absorption process, coupling of the LSP mode enables spatially-selective excitation of the fluorescent emitters by rotating the polarization of the pump laser beam. In addition, the polarization-dependent MPP mode enables manipulation of both polarization and wavelength of the fluorescent emission by introducing a rectangular fishnet structure. All the experimental observations are further corroborated by finite-difference time-domain simulations. The structure reported here has great potentialfor application to color light-emitting devices and nanoscale integrated light sources.     

Au纳米粒子表面附近偶氮苯分子的吸收光谱

我们将时空间含时密度泛函理论与经典的电动力学时空间有限差分技术相结合,对吸附在Au纳米粒子表面附近的偶氮苯分子顺式和反式两种同分异构体的光学性质进行了研究。计算结果显示,一方面表面等离子激元共振会增大其周围激光外场的强度,从而使得偶氮苯分子的吸收光谱得到增强,另一方面,吸附分子与金属纳米粒子之间的相互耦合作用也会对一些低能特殊谱峰的强度及位置产生影响,从而使得谱线的形状与单独的偶氮苯分子或Au纳米粒子并不相同。此外,等离子激元的增强效应会随着分子与金属纳米粒子之间的距离以及纳米粒子尺寸的变化而发生变化。     

Nanofluidic system for the studies of single DNA molecules

Here, we describe a simple and low-cost lithographic technique to fabricate size-controllable nanopillar arrays inside the microfluidic channels for the studies of single DNA molecules. In this approach, nanosphere lithography has been employed to grow a single layer of well-ordered close-packed colloidal crystals inside the microfluidic channels. The size of the polymeric colloidal nanoparticles could be trimmed by oxygen plasma treatment. These size-trimmed colloidal nanoparticles were then used as the etching mask in a deep etching process. As a result, well-ordered size-controllable nanopillar arrays could be fabricated inside the microfluidic channels. The gap distance between the nanopillars could be tuned between 20 and 80 nm allowing the formation of nanofluidic system where the behavior of a single lambda-phage DNA molecule has been investigated. It was found that the lambda-phage DNA molecule could be fully stretched in the nanofluidic system formed by nanopillars with 50 nm gap distance at a field of 50 V/cm.     

Spontaneous formation of cluster array of gold particles by convective self-assembly

Cluster arrays composed of metal nanoparticles are promising for application in sensing devices because of their interesting surface plasmon characteristics. Herein, we report the spontaneous formation of cluster arrays of gold colloids on flat substrates by vertical-deposition convective self-assembly. In this technique, under controlled temperature, a hydrophilic substrate is vertically immersed in a colloid suspension. Cluster arrays form when the particle concentration is extremely low (in the order of 10(-6)-10(-8) v/v). These arrays are arranged in a hierarchically ordered structure, where the particles form clusters that are deposited at a certain separation distance from each other, to form "dotted" lines that are in turn aligned with a constant spacing. The size of the cluster can be controlled by varying the particle concentration and temperature while an equal separation distance is maintained between the lines formed by the clusters. Our technique thus demonstrates a one-step, template-free fabrication method for cluster arrays. In addition, through the direct observation of the assembly process, the spacing between the dotted lines is found to result from the "stick-and-slip" behavior of the meniscus tip, which is entirely different from the formation processes observed for the striped patterns, which we reported previously at higher particle concentrations. The difference in the meniscus behavior possibly comes from the difference in colloidal morphology at the meniscus tip. These results demonstrate the self-regulating characteristics of the convective self-assembly process to produce colloidal patterns, whose structure depends on particle concentration and temperature.     

Plasmonic Nanobiosensor with Chain Reaction Amplification Mechanism

Herein we demonstrate a plasmonic nanobiosensor that explores chain reaction amplification mechanisms to transduce chemical signals released in biocatalytic reactions, turning optical signals into a visual spectral range. The sensor has a very simple design: gold nanoparticles resting in the surface of a grafted P2VP film. Changes in the gold nanoparticles’ position causes changes in the plasmon coupling mode. This is detected by means of a maximum absorbance shift.     

Tunable plasmonic response from alkanethiolate-stabilized gold nanoparticle superlattices: evidence of near-field coupling

We report on the self-assembly of large-area, highly ordered 2D superlattices of alkanethiolate-stabilized gold nanoparticles ( approximately 10.5 nm in core diameter) onto quartz substrates with varying lattice constants, which can be controlled by the alkyl chain lengths, ranging from C12 (1-dodecanethiolate), C14 (1-tetradecanethiolate), C16 (1-hexadecanethiolate), to C18 (1-octadecanethiolate). These 2D nanoparticle superlattices exhibit strong collective surface plasmon resonance that is tunable via the near-field coupling of adjacent nanoparticles. The approach presented here provides a unique and viable means of building artificial "plasmonic crystals" with precisely designed optical properties, which can be useful for the emerging fields of plasmonics, such as subwavelength integrated optics.     

High-density assembly of gold nanoparticles on multiwalled carbon nanotubes using 1-pyrenemethylamine as interlinker

In this article, we describe the formation of carbon nanotube (CNT)-gold nanoparticle composites in aqueous solution using 1-pyrenemethylamine (Py-CH2NH2) as the interlinker. The alkylamine substituent of 1-pyrenemethylamine binds to a gold nanoparticle, while the pyrene chromophore is noncovalently attached to the sidewall of a carbon nanotube via pi-pi stacking interaction. Using this strategy, gold nanoparticles with diameters of 2-4 nm can be densely assembled on the sidewalls of multiwalled carbon nanotubes. The formation of functionalized gold nanoparticles and CNT-Au nanoparticle composites was followed by UV-vis absorption and luminescence spectroscopy. After functionalization of gold nanoparticles with 1-pyrenemethylamine, the distinct absorption vibronic structure of the pyrene chromophore was greatly perturbed and its absorbance value was decreased. There was also a corresponding red shift of the surface plasmon resonance (SPR) absorption band of the gold nanoparticles after surface modification from 508 to 556 nm due to interparticle plasmon coupling. Further reduction of the pyrene chromophore absorbance was observed upon formation of the CNT-Au nanoparticle composites. The photoluminescence of 1-pyrenemethylamine was largely quenched after attaching to gold nanoparticles; formation of the CNT-Au nanoparticle composites further lowered its emission intensity. The pyrene fluoroprobe also sensed a relatively nonpolar environment after its attachment to the nanotube surface. The present approach to forming high-density deposition of gold nanoparticles on the surface of multiwalled carbon nanotubes can be extended to other molecules with similar structures such as N-(1-naphthyl)ethylenediamine and phenethylamine, demonstrating the generality of this strategy for making CNT-Au nanostructure composites.