Plasmon Local Field Research Articles

Plasmon-enhanced high-harmonic generation from silicon

High-harmonic emission from crystalline silicon can be made ten times brighter by exploiting local plasmonic fields in arrays of nano-antennas. Plasmonic antennas can enhance the intensity of a nanojoule laser pulse by localizing the electric field in their proximity1. It has been proposed that the field can become strong enough to convert the fundamental laser frequency into high-order harmonics through an extremely nonlinear interaction with gas atoms that occupy the nanoscopic volume surrounding the antennas2,3,4. However, the small number of gas atoms that can occupy this volume limits the generation of high harmonics5,6,7. Here we use an array of monopole nano-antennas to demonstrate plasmon-assisted high-harmonic generation directly from the supporting crystalline silicon substrate. The high density of the substrate compared with a gas allows macroscopic buildup of harmonic emission. Despite the sparse coverage of antennas on the surface, harmonic emission is ten times brighter than without antennas. Imaging the high-harmonic radiation will allow nanometre and attosecond measurement of the plasmonic field8 thereby enabling more sensitive plasmon sensors9 while opening a new path to extreme-ultraviolet-frequency combs10.

Superior LSPR substrates based on electromagnetic decoupling for on-a-chip high-throughput label-free biosensing

Localized surface plasmon resonance (LSPR) biosensing based on supported metal nanoparticles offers unparalleled possibilities for high-end miniaturization, multiplexing and high-throughput label-free molecular interaction analysis in real time when integrated within an opto-fluidic environment. However, such LSPR-sensing devices typically contain extremely large regions of dielectric materials that are open to molecular adsorption, which must be carefully blocked to avoid compromising the device readings. To address this issue, we made the support essentially invisible to the LSPR by carefully removing the dielectric material overlapping with the localized plasmonic fields through optimized wet-etching. The resulting LSPR substrate, which consists of gold nanodisks centered on narrow SiO2 pillars, exhibits markedly reduced vulnerability to nonspecific substrate adsorption, thus allowing, in an ideal case, the implementation of thicker and more efficient passivation layers. We demonstrate that this approach is effective and fully compatible with state-of-the-art multiplexed real-time biosensing technology and thus represents the ideal substrate design for high-throughput label-free biosensing systems with minimal sample consumption.

Direct observation of localized surface plasmon field enhancement by Kelvin probe force microscopy

A surface plasmon (SP) is a fundamental excitation state that exists in metal nanostructures. Over the past several years, the performance of optoelectronic devices has been improved greatly via the SP enhancement effect. In our previous work, the responsivity of GaN ultraviolet detectors was increased by over 30 times when using Ag nanoparticles. However, the physics of the SP enhancement effect has not been established definitely because of the lack of experimental evidence. To reveal the physical origin of this enhancement, Kelvin probe force microscopy (KPFM) was used to observe the SP-induced surface potential reduction in the vicinity of Ag nanoparticles on a GaN epilayer. Under ultraviolet illumination, the localized field enhancement induced by the SP forces the photogenerated electrons to drift close to the Ag nanoparticles, leading to a reduction of the surface potential around the Ag nanoparticles on the GaN epilayer. For an isolated Ag nanoparticle with a diameter of ~200 nm, the distribution of the SP localized field is located within 60 nm of the boundary of the Ag nanoparticle. For a dimer of Ag nanoparticles, the localized field enhancement between the nanoparticles was the strongest. The results presented here provide direct experimental proof of the localized field enhancement. These results not only explain the high performance of GaN detectors observed with the use of Ag nanoparticles but also reveal the physical mechanism of SP enhancement in optoelectronic devices, which will help us further understand and improve the performance of SP-based optoelectronic devices in the future.

Lighting up long-range charge-transfer states by a localized plasmonic field.

The long-range charge-transfer states in a donor-acceptor system exhibit well separated electron-hole pairs, but are often difficult to achieve by optical means owing to a very small overlap between the wave functions of the donor and acceptor. We have found that the introduction of a spatially confined plasmon can enhance the transition probability to the long-range charge-transfer states as it can effectively break the intrinsic symmetry selection rule imposed on the system. Meanwhile, the intensity borrowed from local excitations could also be selectively promoted, allowing the manipulation of the excited quantum states. In addition, our calculations reveal that the donor and acceptor moieties can be unambiguously visualized in real space by tip-enhanced resonance Raman images. These findings can benefit light-harvesting and also be readily extended to diverse optical processes.

Landau damping of surface plasmons in metal nanostructures

We develop a quantum-mechanical theory for Landau damping of surface plasmons in metal nanostructures larger that the characteristic length for nonlocal effects. We show that the electron surface scattering, which facilitates plasmon decay in small nanostructures, can be incorporated into the metal dielectric function on par with phonon and impurity scattering. The derived surface scattering rate is determined by the plasmon local field polarization relative to the metal-dielectric interface and is highly sensitive to the system geometry. We illustrate our model by providing analytical results for surface scattering rate in some common shape nanostructures.

Reduced Ensemble Plasmon Line Widths and Enhanced Two-Photon Luminescence in Anodically Formed High Surface Area Au-TiO2 3D Nanocomposites.

Localized surface plasmon resonances (LSPR) in TiO2 nanorod and nanotube arrays decorated by gold nanoparticles can be exploited to improve photocatalytic activity, enhance nonlinear optical coefficients, and increase light harvesting in solar cells. However, the LSPR typically has a low quality factor, and the resonance is often obscured by the Urbach tail of the TiO2 band gap absorption. Attempts to increase the LSPR extinction intensity by increasing the density of gold nanoparticles on the surface of the TiO2 nanostructures invariably produce peak broadening due to the effects of either agglomeration or polydispersity. We present a new class of hybrid nanostructures containing gold nanoparticles (NPs) partially embedded in nanoporous/nanotubular TiO2 by performing the anodization of cosputtered Ti-Au thin films containing a relatively high ratio of Au:Ti. Our method of anodizing thin film stacks containing alternate layers of Ti and TiAu results in very distinctive LSPR peaks with quality factors as high as 6.9 and ensemble line widths as small as 0.33 eV even in the presence of an Urbach tail. Unusual features in the anodization of such films are observed and explained, including oscillatory current transients and the observation of coherent heterointerfaces between the Au NPs and anatase TiO2. We further show that such a plasmonic NP-embedded nanotube structure dramatically outperforms a plasmonic NP-decorated anodic nanotube structure in terms of the extinction coefficient, and achieves a strongly enhanced two-photon fluorescence due to the high density of gold nanoparticles in the composite film and the plasmonic local field enhancement.

Polarization-Directed Surface Plasmon Polariton Launching.

The relative intensities of propagating surface plasmons (PSPs) simultaneously launched from opposing edges of a symmetric trench structure etched into a silver thin film may be controllably varied by tuning the linear polarization of the driving field. This is demonstrated through transient multiphoton photoemission electron microscopy measurements performed using a pair of spatially separated phase-locked femtosecond pulses. Our measurements are rationalized using finite-difference time domain simulations, which reveal that the coupling efficiency into the PSP modes is inversely proportional to the magnitude of the localized surface plasmon fields excited at the trench edges. Our combined experimental and computational results allude to the interplay between localized and propagating surface plasmon modes in the trench; strong coupling to the localized modes at the edges correlates to weak coupling to the PSP modes. Polarization-directed PSP launching measurements reveal an optimal PSP contrast ratio of 4.2 using a 500 nm wide trench.

Controlled Growth of Sulfide on Gold Nanotriangles with Tunable Local Field Distribution and Enhanced Photocatalytic Activity

Metal–semiconductor heteronanostructures have attracted increasing attention due to the strong interactions between the two nanoscale-spaced components. Herein, a steerable hydrothermal method is used to control the growth of Ag2S shells onto Au nanotriangles with tunable plasmon resonance and local field distribution. Through adjusting pH value and sulfur source, three types of Au/Ag2S heteronanostructures are obtained, including shells on the tips (Au/Ag2S (tips)), shells on the sides (Au/Ag2S (sides)), and complete shells (Au@Ag2S). The surface plasmon resonance and local field confinement are demonstrated to vary with the shell position. Furthermore, compact CdS nanoshells are coated onto the Au@Ag2S without any shape change of Au cores. By testing the photodegradation rate of Rhodamine B (RhB) under visible-light irradiation, the Au@Ag2S@CdS hybrids exhibit enhanced photocatalytic activity compared with Au@CdS and CdS. The strong local electric field, the enhanced visible-light absorption, and the op...

Surface plasmon lifetime in metal nanoshells

The lifetime of localized surface plasmon plays an important role in many aspects of plasmonics and its applications. In small metal nanostructures, the dominant mechanism restricting plasmon lifetime is size-dependent Landau damping. We performed quantum-mechanical calculations of Landau damping for the bright surface plasmon mode in a metal nanoshell. In contrast to the conventional model based on the electron surface scattering, we found that the damping rate decreases as the nanoshell thickness is reduced. The origin of this behavior is traced to the spatial distribution of plasmon local field inside the metal shell. We also found that, due to interference of electron scattering amplitudes from nanoshell's two metal surfaces, the damping rate exhibits pronounced quantum beats with changing shell thickness.

Theory for Modeling of High Resolution Resonant and Nonresonant Raman Images.

Tip-enhanced Raman imaging is capable of resolving the inner structure of a single molecule owing to the generation of highly localized nanocavity plasmon. Here we present a general theory and detailed computational methodology to fully describe resonant and nonresonant Raman scattering under the localized plasmonic field. We use an allylcarbinol molecule adsorbed on the gold surface as a model system to illustrate different effects on the Raman images. It is found that the ability of distinguishing an individual vibration mode is highly limited under the resonant condition due to the dominant contribution from the Franck-Condon term and the mode-independent component of the Herzberg-Teller term. The nonresonant Raman images of the single molecule are vibrationally distinguishable and present the vibrational motion of the corresponding vibrational modes in real space. Furthermore, the calculated results confirm that nonlinear optical effects can further improve the resolution of the images. The theoretical and computational methods presented here provide the basic tools to model high resolution Raman images at the single molecular level.

Strong electric field enhancements in asymmetric metallic nanostructures and high-order harmonic generation.

Numerical investigation of high-order harmonic generation (HHG) is carried out in noble gases near metal nano-dimers. The effect of geometry, shape, and gap of the dimers in plasmon resonance and local electric field enhancement has been investigated numerically by using finite-difference time-domain methods. It is shown that a lack of symmetry in dimer shapes plays an important role in the HHG process, producing appreciable modifications to the energy-resolved photoelectron spectra.

Far-Field Super-resolution Detection of Plasmonic Near-Fields.

We demonstrate a far-field single molecule super-resolution method that maps plasmonic near-fields. The method is largely invariant to fluorescence quenching (arising from probe proximity to a metal), has reduced point-spread-function distortion compared to fluorescent dyes (arising from strong coupling to nanoscopic metallic features), and has a large dynamic range (of 2 orders of magnitude) allowing mapping of plasmonic field-enhancements regions. The method takes advantage of the sensitivity of quantum dot (QD) stochastic blinking to plasmonic near-fields. The modulation of the blinking characteristics thus provides an indirect measure of the local field strength. Since QD blinking can be monitored in the far-field, the method can measure localized plasmonic near-fields at high throughput using a simple far-field optical setup. Using this method, propagation lengths and penetration depths were mapped-out for silver nanowires of different diameters and for different dielectric environments, with a spatial accuracy of ∼15 nm. We initially use sparse sampling to ensure single molecule localization for accurate characterization of the plasmonic near-field with plans to increase density of emitters in further studies. The measured propagation lengths and penetration depths values agree well with Maxwell finite-difference time-domain calculations and with published literature values. This method offers advantages such as low cost, high throughput, and superresolved mapping of localized plasmonic fields at high sensitivity and fidelity.

Far-Field and Near-Field Investigation of Longitudinal Plasmons of AgAuAg Nanorods

We studied the localized surface plasmons of AgAuAg-nanorods (NRs) using far-field dark-field spectro-microscopy and scattering-type scanning near-field optical microscopy (sSNOM) techniques. We observe that the far-field scattering spectra of individual AgAuAg-NRs exhibit longitudinal dipolar and octupolar resonances that are mainly determined by the overall lengths of the NRs and are fairly insensitive to the relative compositions of Ag and Au. Corresponding near-field distributions measured by sSNOM further reveal plasmonic local field patterns that closely resemble those of monolithic Au-NRs. These show that the longitudinal plasmons of AgAuAg-NRs oscillate along the entire length of the NRs, although resonance widths indicate appreciable damping by the Ag–Au interfaces. The result constitutes an interesting counter-example of tunability of plasmons by composition variation and, thus, provides an important design rule for composition-tunable bimetallic plasmonic structures.

Tip-Enhanced Raman Spectroscopic Imaging of Individual Carbon Nanotubes with Subnanometer Resolution.

Individual carbon nanotubes (CNTs) have been investigated by tip-enhanced Raman spectroscopy (TERS) using silver tips on the Ag(111) substrate with a low-temperature ultrahigh-vacuum scanning tunneling microscope. Thanks to the strong and highly localized plasmonic field offered by the silver nanogap, the spatial resolution of TERS on CNTs is driven down to about 0.7 nm. Such a high spatial resolution allows to visualize in real space the spatial extent of the defect-induced D-band scattering, to track the strain-induced spectral evolution, and to resolve the spectral differences between the inner and the outer sides of a bent CNT, all at the nanometer scale.

금속물질에 따른 나노구조를 이용한 국소 표면 플라즈몬 공명 센서 특성 분석

We explored localized plasmonic field enhancements using nanowire patterns to improve the sensitivity of a surface plasmon resonance (SPR) sensor. Two different materials, gold and silver, were considered for sample materials. Gold and silver nanowire patterns were fabricated by electron beam lithography for experimental measurements. The wavelength SPR sensor was also designed for these experiments. The material-dependent field enhancements on nanowire patterns were first calculated based on Maxwell’s equations. Resonance wavelength shifts were indicated as changes in the refractive index from 1.33 to 1.36. The SPR sensor with silver nanowire patterns showed a much larger resonance wavelength shift than the sensor with gold nanowire patterns, in good agreement with simulation results. These results suggest that silver nanowire patterns are more efficient than gold nanowire patterns, and could be used for sensitivity enhancements in situations where biocompatibility is not a consideration.

Control over the charge transfer in dye-nanoparticle decorated graphene

Charge transfer interaction between silver decorated graphene and three differently charged dyes, cationic (rhodamine 6G), neutral (rhodamine B) and anionic (fluorescein 27) has been studied. The ground state association constants have been evaluated and changes in the fluorescence intensity and lifetimes have been obtained in two solvents. Strength of complex-formation has been found to be higher with the cationic molecule in water. In a higher viscosity solvent, the ground state complex formation is restricted. Local field of localized surface plasmons of nanoparticles adsorbed on the graphene sheets leads to enhanced absorption and fluorescence of fluorescein 27.

Improved biomolecular detection based on a plasmonic nanoporous gold film fabricated by oblique angle deposition.

We demonstrated an enhanced surface plasmon resonance (SPR) detection by incorporating a nanoporous gold film on a thin gold substrate. Nanoscale control of thickness and roughness of the nanoporous layer was successfully accomplished by oblique angle deposition. In biosensing experiments, the results obtained by biotin-streptavidin interaction showed that SPR samples with a nanoporous gold layer provided a notable sensitivity improvement compared to a conventional bare gold film, which is attributed to an excitation of local plasmon field and an increased surface reaction area. Imaging sensitivity enhancement factor was employed to estimate an overall sensor performance of the fabricated samples and an optimal SPR structure was determined. Our approach is intended to show the feasibility and extend the applicability of the nanoporous gold film-mediated SPR biosensor to diverse biomolecular binding events.

Light-induced heating of dense 2D ensemble of gold nanoparticles: dependence on detuning from surface plasmon resonance

The extinction of white light by dense 2D ensemble of gold nanoparticles with size of 22 nm and interparticle distance of 40 nm has been studied at the simultaneous illumination of nanoparticles by the continuous-wave laser beam in dependence of the detuning of laser frequency from the surface plasmon resonance (SPR). The appreciable red shift, broadening, and increase of intensity of the plasmonic extinction band have been observed at approaching of the laser frequency to SPR. The plasmon band shift and broadening reveal the heating of gold nanoparticles that has an evident resonant character. The strong increase of nanoparticle temperature of 590 K has been observed at moderate laser intensity of 5 × 103 W/cm2 and detuning of 24.6 nm. Such strong heating is probably due to the accumulative effect and the light extinction enhancement by intense local plasmonic field of coupled Au nanoparticles in dense 2D ensemble.

Bipyramid-templated synthesis of monodisperse anisotropic gold nanocrystals.

Much of the interest in noble metal nanoparticles is due to their plasmonic resonance responses and local field enhancement, both of which can be tuned through the size and shape of the particles. However, both properties suffer from the loss of monodispersity that is frequently associated with various morphologies of nanoparticles. Here we show a method to generate diverse and monodisperse anisotropic gold nanoparticle shapes with various tip geometries as well as highly tunable size augmentations through either oxidative etching or seed-mediated growth of purified, monodisperse gold bipyramids. The conditions employed in the etching and growth processes also offer valuable insights into the growth mechanism difficult to realize with other gold nanostructures. The high-index facets and more complicated structure of the bipyramid lead to a wider variety of intriguing regrowth structures than in previously studied nanoparticles. Our results introduce a class of gold bipyramid-based nanoparticles with interesting and potentially useful features to the toolbox of gold nanoparticles.

Tunable multiple plasmon resonances and local field enhancement of nanocrescent/nanoring structure**Project supported by the National Natural Science Foundation of China (Grant Nos. 61275153 and 61320106014), the Natural Science Foundation of Zhejiang Province, China (Grant No. LY12A04002), the Natural Science Foundation of Ningbo City, China (Grant Nos. 2010D10018 and 2012A610107), and the K. C. Wong Magna Foundation of Ningbo University, China.

According to the plasmon hybridization theory, the plasmon resonance characteristics of the gold nanocrescent/nanoring (NCNR) structure are systematically investigated by the finite element method. It is found that the extinction spectra of NCNR structure exhibit multiple plasmon resonance peaks, which could be attributed to the result of the plasmon couplings between the multipolar plasmon modes of nanocrescent and the dipolar, quadrupolar, hexapolar, octupolar, decapolar plasmon modes of nanoring. By changing the geometric parameters, the intense and separate multiple plasmon resonance peaks are obtained and can be tuned in a wide wavelength range. It is further found that the plasmon coupling induces giant multipole electric field enhancements around the tips of the nanocrescent. The tunable and intense multiple plasmon resonances of NCNR structure may provide effective applications in multiplex biological sensing.