Showing papers on "Plasmon published in 2008"

Noble Metals on the Nanoscale: Optical and Photothermal Properties and Some Applications in Imaging, Sensing, Biology, and Medicine

Abstract: Noble metal nanostructures attract much interest because of their unique properties, including large optical field enhancements resulting in the strong scattering and absorption of light. The enhancement in the optical and photothermal properties of noble metal nanoparticles arises from resonant oscillation of their free electrons in the presence of light, also known as localized surface plasmon resonance (LSPR). The plasmon resonance can either radiate light (Mie scattering), a process that finds great utility in optical and imaging fields, or be rapidly converted to heat (absorption); the latter mechanism of dissipation has opened up applications in several new areas. The ability to integrate metal nanoparticles into biological systems has had greatest impact in biology and biomedicine. In this Account, we discuss the plasmonic properties of gold and silver nanostructures and present examples of how they are being utilized for biodiagnostics, biophysical studies, and medical therapy. For instance, takin...

Plasmon-Induced Transparency in Metamaterials

Abstract: A plasmonic "molecule" consisting of a radiative element coupled with a subradiant (dark) element is theoretically investigated. The plasmonic molecule shows electromagnetic response that closely resembles the electromagnetically induced transparency in an atomic system. Because of its subwavelength dimension, this electromagnetically induced transparency-like molecule can be used as a building block to construct a "slow light" plasmonic metamaterial.

A hybrid plasmonic waveguide for subwavelength confinement and long-range propagation

Abstract: The emerging field of nanophotonics1 addresses the critical challenge of manipulating light on scales much smaller than the wavelength. However, very few feasible practical approaches exist at present. Surface plasmon polaritons2,3 are among the most promising candidates for subwavelength optical confinement3,4,5,6,7,8,9,10. However, studies of long-range surface plasmon polaritons have only demonstrated optical confinement comparable to that of conventional dielectric waveguides, because of practical issues including optical losses and stringent fabrication demands3,11,12,13. Here, we propose a new approach that integrates dielectric waveguiding with plasmonics. The hybrid optical waveguide consists of a dielectric nanowire separated from a metal surface by a nanoscale dielectric gap. The coupling between the plasmonic and waveguide modes across the gap enables ‘capacitor-like’ energy storage that allows effective subwavelength transmission in non-metallic regions. In this way, surface plasmon polaritons can travel over large distances (40–150 µm) with strong mode confinement (ranging from λ2/400 to λ2/40). This approach is fully compatible with semiconductor fabrication techniques and could lead to truly nanoscale semiconductor-based plasmonics and photonics. Xiang Zhang and colleagues from the University of California, Berkeley, propose a new approach for confining light on scales much smaller than the wavelength of light. Using hybrid waveguides that incorporate dielectric and plasmonic waveguiding techniques, they are able to confine surface plasmon polaritons very strongly over large distances. The advance could lead to truly nanoscale plasmonics and photonics.

A plasmonic photocatalyst consisting of silver nanoparticles embedded in titanium dioxide.

Abstract: Titanium dioxide (TiO2) displays photocatalytic behavior under near-ultraviolet (UV) illumination. In another scientific field, it is well understood that the excitation of localized plasmon polaritons on the surface of silver (Ag) nanoparticles (NPs) causes a tremendous increase of the near-field amplitude at well-defined wavelengths in the near UV. The exact resonance wavelength depends on the shape and the dielectric environment of the NPs. We expected that the photocatalytic behavior of TiO2 would be greatly boosted if it gets assisted by the enhanced near-field amplitudes of localized surface plasmon (LSP). Here we show that this is true indeed. We named this new phenomenon "plasmonic photocatalysis". The key to enable plasmonic photocatalysis is to deposit TiO2 on a NP comprising an Ag core covered with a silica (SiO2) shell to prevent oxidation of Ag by direct contact with TiO2. The most appropriate diameter for Ag NPs and thickness for the SiO2 shell giving rise to LSP in the near UV were estimated from Mie scattering theory. Upon implementing a device that took these design considerations into account, the measured photocatalytic activity under near UV illumination of such a plasmonic photocatalyst, monitored by decomposition of methylene blue, was enhanced by a factor of 7. The enhancement of the photocatalytic activity increases with a decreased thickness of the SiO2 shell. The plasmonic photocatalysis will be of use as a high performance photocatalyst in nearly all current applications but will be of particular importance for applications in locations of minimal light exposure.

Symmetry breaking in plasmonic nanocavities: subradiant LSPR sensing and a tunable Fano resonance.

Abstract: A metallic nanostructure consisting of a disk inside a thin ring supports superradiant and very narrow subradiant modes. Symmetry breaking in this structure enables a coupling between plasmon modes of differing multipolar order, resulting in a tunable Fano resonance. The LSPR sensitivities of the subradiant and Fano resonances are predicted to be among the largest yet for individual nanostructures.

Collective resonances in gold nanoparticle arrays.

Abstract: We present experimental evidence of sharp spectral features in the optical response of 2D arrays of gold nanorods. A simple coupled dipole model is used to describe the main features of the observed spectral line shape. The resonance involves an interplay between the excitation of plasmons localized on the particles and diffraction resulting from the scattering by the periodic arrangement of these particles. We investigate this interplay by varying the particle size, aspect ratio, and interparticle spacing, and observe the effect on the position, width, and intensity of the sharp spectral feature.

Design principles for particle plasmon enhanced solar cells

Abstract: We develop fundamental design principles for increasing the efficiency of solar cells using light trapping by scattering from metal nanoparticles. We show that cylindrical and hemispherical particles lead to much higher path length enhancements than spherical particles, due to enhanced near-field coupling, and that the path length enhancement for an electric point dipole is even higher than the Lambertian value. Silver particles give much higher path length enhancements than gold particles. The scattering cross section of the particles is very sensitive to the thickness of a spacer layer at the substrate, which provides additional tunability in the design of particle arrays.

Plasmonic nanoparticle enhanced light absorption in GaAs solar cells

Abstract: We demonstrate an improvement in efficiency of optically thin GaAs solar cells decorated with size-controlled Ag nanoparticles fabricated by masked deposition through anodic aluminum oxide templates. The strong scattering by the interacting surface plasmons in densely formed high aspect-ratio nanoparticles effectively increases the optical path of the incident light in the absorber layers resulting in an 8% increase in the short circuit current density of the cell. The nanoparticle array sheet conductivity also reduces the cell surface sheet resistance evidenced by an improved fill factor. This dual function of plasmonic nanoparticles has potential to enable thinner photovoltaic layers in solar cells.

Three-dimensional metamaterials at optical frequencies

Abstract: We experimentally demonstrate the implementation of three-dimensional optical metamaterials. We investigate the interaction between adjacent stacked layers using the method of plasmon hybridization and analyze the optical properties of stacked metamaterials with increasing layer numbers.

Metallic Nanoparticle Arrays: A Common Substrate for Both Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption

Abstract: Nanoshell arrays have recently been found to possess ideal properties as a substrate for combining surface enhanced raman scattering (SERS) and surface enhanced infrared absorption (SEIRA) spectroscopies, with large field enhancements at the same spatial locations on the structure. For small interparticle distances, the multipolar plasmon resonances of individual nanoshells hybridize and form red-shifted bands, a relatively narrow band in the near-infrared (NIR) originating from quadrupolar nanoshell resonances enhancing SERS, and a very broadband in the mid-infrared (MIR) arising from dipolar resonances enhancing SEIRA. The large field enhancements in the MIR and at longer wavelengths are due to the lightning-rod effect and are well described with an electrostatic model.

A Unified Approach to Surface-Enhanced Raman Spectroscopy

Abstract: We present a unified expression for surface-enhanced Raman spectroscopy (SERS). The expression contains a product of three resonance denominators, representing the surface plasmon resonance, the metal-molecule charge-transfer resonance at the Fermi energy, and an allowed molecular resonance. This latter resonance is that from which intensity is borrowed for charge transfer, and when the molecular resonance is active it is responsible for surface-enhanced resonance Raman spectroscopy. We examine this expression in various limits, to explore the relative contribution or each resonance. First, we look at the situation in which only the surface plasmon resonance is active and examine the various contributions to the Raman signal, including the surface selection rules. Then we examine additional contributions from charge-transfer or molecular resonances. We show that the three resonances are not totally independent, since they are linked by a product of four matrix elements in the numerator. These linked matrix elements provide comprehensive selection rules for SERS. One involves a harmonic oscillator in the observed normal mode. This is the same mode which appears in the vibronic coupling operator linking one of the states of the allowed molecular resonance to the charge-transfer state. The charge-transfer transition moment is linked to the surface plasmon resonance by the requirement that the transition dipole moment be polarized along the direction of maximum amplitude of the field produced by the plasmon (i.e., perpendicular to the metal surface). We show that these selection rules govern the observed SERS spectral intensities and apply these to the observed spectra of several molecules. We also suggest a quantitative measure of the degree to which charge transfer contributes to the overall SERS enhancement.

Extremely narrow plasmon resonances based on diffraction coupling of localized plasmons in arrays of metallic nanoparticles.

Abstract: We experimentally demonstrate extremely narrow plasmon resonances with half-width of just several nanometers in regular arrays of metallic nanoparticles. These resonances are observed at Rayleigh's cutoff wavelengths for Wood anomalies and based on diffraction coupling of localized plasmons. We show experimentally that reflection from an array of nanoparticles can be completely suppressed at certain wavelengths. As a result, our metal nanostructures exhibit pi-jump for the phase of the reflected light.

Resonant plasmonic and vibrational coupling in a tailored nanoantenna for infrared detection.

Abstract: A novel resonant mechanism involving the interference of a broadband plasmon with the narrowband vibration from molecules is presented. With the use of this concept, we demonstrate experimentally the enormous enhancement of the vibrational signals from less than one attomol of molecules on individual gold nanowires, tailored to act as plasmonic nanoantennas in the infrared. By detuning the resonance via a change in the antenna length, a Fano-type behavior of the spectral signal is observed, which is clearly supported by full electrodynamical calculations. This resonant mechanism can be a new paradigm for sensitive infrared identification of molecular groups.

Free-standing graphene at atomic resolution

Abstract: Research interest in graphene, a two-dimensional crystal consisting of a single atomic plane of carbon atoms, has been driven by its extraordinary properties, including charge carriers that mimic ultra-relativistic elementary particles. Moreover, graphene exhibits ballistic electron transport on the submicrometre scale, even at room temperature, which has allowed the demonstration of graphene-based field-effect transistors and the observation of a room-temperature quantum Hall effect. Here we confirm the presence of free-standing, single-layer graphene with directly interpretable atomic-resolution imaging combined with the spatially resolved study of both the pi --> pi* transition and the pi + sigma plasmon. We also present atomic-scale observations of the morphology of free-standing graphene and explore the role of microstructural peculiarities that affect the stability of the sheets. We also follow the evolution and interaction of point defects and suggest a mechanism by which they form ring defects.

Plasmon-controlled fluorescence: a new paradigm in fluorescence spectroscopy

Abstract: Fluorescence spectroscopy is widely used in biological research. Until recently, essentially all fluorescence experiments were performed using optical energy which has radiated to the far-field. By far-field we mean at least several wavelengths from the fluorophore, but propagating far-field radiation is usually detected at larger macroscopic distances from the sample. In recent years there has been a growing interest in the interactions of fluorophores with metallic surfaces or particles. Near-field interactions are those occurring within a wavelength distance of an excited fluorophore. The spectral properties of fluorophores can be dramatically altered by near-field interactions with the electron clouds present in metals. These interactions modify the emission in ways not seen in classical fluorescence experiments. In this review we provide an intuitive description of the complex physics of plasmons and near-field interactions. Additionally, we summarize the recent work on metal-fluorophore interactions and suggest how these effects will result in new classes of experimental procedures, novel probes, bioassays and devices.

Localized Surface Plasmon Resonances in Aluminum Nanodisks

Abstract: The plasmonic properties of arrays of supported Al nanodisks, fabricated by hole-mask colloidal lithography (HCL), are analyzed for the disk diameter range 61-492 nm at a constant disk height of 20 nm. Strong and well-defined (UV-vis-NIR) localized surface plasmon resonances are found and experimentally characterized with respect to spectral peak positions, peak widths, total cross sections, and radiative and nonradiative decay channels. Theoretically, the plasmon excitations are described by electrostatic spheroid theory. Very good qualitative and quantitative agreement between model and experiment is found for all these observables by assuming a nanoparticle embedded in a few nanometer thick homogeneous (native) aluminum oxide shell. Other addressed aspects are: (i) the role of the strong interband transition in Al metal, located at 1.5 eV, for the plasmonic excitations of Al nanoparticles, (ii) the role of the native oxide layer, and (iii) the possibility of using the plasmon excitation as an ultrasensitive, remote, real-time probe for studies of oxidation/corrosion kinetics in metal nanoparticle systems.

Plexcitonic nanoparticles: plasmon-exciton coupling in nanoshell-J-aggregate complexes.

Abstract: Stable Au nanoshell-J-aggregate complexes are formed that exhibit coherent coupling between the localized plasmons of a nanoshell and the excitons of molecular J-aggregates adsorbed on its surface. By tuning the nanoshell plasmon energies across the exciton line of the J-aggregate, plasmon-exciton coupling energies for these complexes are obtained. The strength of this interaction is dependent on the specific plasmon mode of the nanoparticle coupled to the J-aggregate exciton. From a model based on Gans theory, we obtain an expression for the plasmon-exciton hybridized states of the complex.

Plasmon enhanced performance of organic solar cells using electrodeposited Ag nanoparticles

Abstract: To enhance solar harvesting in organic solar cells, uniform-sized metal nanoparticles of ∼13 nm were incorporated to the device via pulse-current electrodeposition, which is a kind of simple and quick solution process that can control the density and size of metal nanoparticles. By incorporating plasmonic Ag nanoparticles on surface modified transparent electrodes, overall power conversion efficiency was increased from 3.05% to 3.69%, mainly resulting from the improved photocurrent density as a result of enhanced absorption of the photoactive conjugate polymer due to the high electromagnetic field strength in the vicinity of the excited surface plasmons.

Tailoring plasmonic substrates for surface enhanced spectroscopies

Abstract: Our understanding of how the geometry of metallic nanostructures controls the properties of their surface plasmons, based on plasmon hybridization, is useful for developing high-performance substrates for surface enhanced spectroscopies. In this tutorial review, we outline the design of metallic nanostructures tailored specifically for providing electromagnetic enhancements for surface enhanced Raman scattering (SERS). The concepts developed for nanoshell-based substrates can be generalized to other nanoparticle geometries and scaled to other spectroscopies, such as surface enhanced infrared absorption spectroscopy (SEIRA).

Graphene Terahertz Plasmon Oscillators

Abstract: In this paper we propose and discuss coherent terahertz sources based on charge density wave (plasmon) amplification in two-dimensional graphene. The coupling of the plasmons to interband electron-hole transitions in population inverted graphene layers can lead to plasmon amplification through stimulated emission. Plasmon gain values in graphene can be very large due to the small group velocity of the plasmons and the strong confinement of the plasmon field in the vicinity of the graphene layer. We present a transmission line model for plasmon propagation in graphene that includes plasmon dissipation and plasmon interband gain due to stimulated emission. Using this model, we discuss design for terahertz plasmon oscillators and derive the threshold condition for oscillation taking into account internal losses and also losses due to external coupling. The threshold condition is shown to depend on the ratio of the external impedance and the characteristic impedance of the plasmon transmission line. The large gain values available at terahertz frequencies in graphene can lead to integrated oscillators that have dimensions in the 1-10 mum range.

Noble metal nanocrystals: plasmon electron transfer photochemistry and single-molecule Raman spectroscopy.

Abstract: The excited electronic states of noble metal Au and Ag nanocrystals are very different than those of molecules. Ag and Au nanocrystal optical transitions (plasmons) in the visible can be so intense that they significantly modify the local electromagnetic field. Also, coherent elastic Rayleigh light scattering is stronger than normal electronic absorption of photons for larger nanocrystals. These two facts make Au and Ag nanocrystals ideal nanoantennas, in that they focus incident light into the local neighborhood of subwavelength size. Surface-enhanced Raman scattering (SERS), in which the Raman scattering rate of nearby molecules increases by many orders of magnitude, is a consequence of this nanoantenna effect. Metallic nanocrystals also have no band gap; this makes them extraordinarily polarizable. Their electronic transitions sense the local environment. An extreme case is the interaction of two 30 nm Ag nanocrystals separated by a 1 nm gap. Their mutual polarization completely transforms the nature o...

Tunable plasmonic lattices of silver nanocrystals

Abstract: Silver nanocrystals are ideal building blocks for plasmonicmaterials that exhibit a wide range of unique and potentially usefuloptical phenomena. Individual nanocrystals display distinct opticalscattering spectra and can be assembled into hierarchical structures thatcouple strongly to external electromagnetic fields. This coupling, whichis mediated by surface plasmons, depends on their shape and arrangement.Here we demonstrate the bottom-up assembly of polyhedral silvernanocrystals into macroscopic two-dimensional superlattices using theLangmuir-Blodgett technique. Our ability to control interparticlespacing, density, and packing symmetry allows for tunability of theoptical response over the entire visible range. This assembly strategyoffers a new, practical approach to making novel plasmonic materials forapplication in spectroscopic sensors, sub-wavelength optics, andintegrated devices that utilize field enhancement effects.

Distance-Dependent Plasmon Resonant Coupling between a Gold Nanoparticle and Gold Film

Abstract: We present an experimental analysis of the plasmonic scattering properties of gold nanoparticles controllably placed nanometers away from a gold metal film. We show that the spectral response of this system results from the interplay between the localized plasmon resonance of the nanoparticle and the surface plasmon polaritons of the gold film, as previously predicted by theoretical studies. In addition, we report that the metal film induces a polarization to the single nanoparticle light scattering, resulting in a doughnut-shaped point spread function when imaged in the far-field. Both the spectral response and the polarization effects are highly sensitive to the nanoparticle−film separation distance. Such a system shows promise in potential biometrology and diagnostic devices.

Nonlocal Effects in the Plasmons of Strongly Interacting Nanoparticles, Dimers, and Waveguides

Abstract: Spatial nonlocality in the optical response of noble metals is shown to produce significant blue shift and near-field quenching of plasmons in nanoparticle dimers, nanoshells, and thin metal waveguides. Compared with a local description relying on the use of frequency-dependent dielectric functions, we predict resonance shifts as large as 10% and field-intensity reduction of an order of magnitude at interparticle distances or metal thicknesses below 2 A, although sizable effects are already observed for dimers separated by 2 nm. The calculation method (a combination of the specular-reflection model and a suitable nonlocal extension of measured local dielectric functions) is simple to implement and can be easily generalized to arbitrarily complex nanostructures.

Close Encounters between Two Nanoshells

Abstract: Plasmonic nanoparticle pairs known as “dimers” embody a simple system for generating intense nanoscale fields for surface enhanced spectroscopies and for developing an understanding of coupled plasmons. Individual nanoshell dimers in directly adjacent pairs and touching geometries show dramatically different plasmonic properties. At close distances, hybridized plasmon modes appear whose energies depend extremely sensitively on the presence of a small number of molecules in the interparticle junction. When touching, a new plasmon mode arising from charge transfer oscillations emerges. The extreme modification of the overall optical response due to minute changes in very reduced volumes opens up new approaches for ultrasensitive molecular sensing and spectroscopy.

Optical Properties and Growth Aspects of Silver Nanoprisms Produced by a Highly Reproducible and Rapid Synthesis at Room Temperature

Abstract: A rapid and readily reproducible seed-based method for the production of high quality silver nanoprisms in high yield is presented. The edge-length and the position of the main plasmon resonance of the nanoprisms can be readily controlled through adjustment of reaction conditions. From UV-vis spectra of solutions of the nanoprisms, the inhomogeneously broadened line width of the in-plane dipole plasmon resonance is measured and trends in the extent of plasmon damping as a function of plasmon resonance energy and nanoprism size have been elucidated. In addition, an in-depth analysis of the lamellar defect structure of silver nanoprisms is provided that confirms that the defects can lead to a transformation of the crystal structure in the vicinity of the defects. These defects can combine give rise to lamellar regions, thicker than 1 nm, that extend across the crystal, where the silver atoms are arranged in a continuous hexagonal-close-packed (hcp) structure. This hcp structure has a periodicity of 2.50 A, thus explaining the 2.50 A lattice fringes that are commonly observed in 〈111〉 oriented flat-lying nanoprisms. A new understanding of the mechanisms behind anisotropic growth in silver nanoprisms is presented.

Non-local effects in the plasmons of strongly interacting nanoparticles, dimers, and waveguides

Abstract: Non-local effects in the optical response of noble metals are shown to produce significant blueshift and near-field quenching of plasmons in nanoparticle dimers, nanoshells, and thin metal waveguides. Compared with a local description relying on the use of frequency-dependent dielectric functions, we predict resonance shifts as large as 10% and field-intensity reduction of an order of magnitude at inter-particle distances or metal thicknesses below 2 \AA. Our results are based upon the specular-reflection model combined with a suitable non-local extension of measured local dielectric functions. We present a roadmap to design plasmon resonances in nanometer metallic elements with application to optical antennas and improved photovoltaic, light-emitting, and sensing devices.

Tooth-shaped plasmonic waveguide filters with nanometeric sizes

Abstract: A novel nanometeric plasmonic filter in a tooth-shaped metal-insulator-metal waveguide is proposed and demonstrated numerically. An analytic model based on the scattering matrix method is given. The result reveals that the single tooth-shaped filter has a wavelength-filtering characteristic and an ultracompact size in the length of a few hundred nanometers, compared to gratinglike surface plasmon polariton (SPP) filters. Both analytic and simulation results show that the wavelength of the trough of the transmission has linear and nonlinear relationships with the tooth depth and the tooth width, respectively. The waveguide filter could be utilized to develop ultracompact photonic filters for high integration.

Dark-field microscopy studies of single metal nanoparticles: understanding the factors that influence the linewidth of the localized surface plasmon resonance

Abstract: This article provides a review of our recent Rayleigh scattering measurements on single metal nanoparticles. Two different systems will be discussed in detail: gold nanorods with lengths between 30 and 80 nm, and widths between 8 and 30 nm; and hollow gold-silver nanocubes (termed nanoboxes or nanocages depending on their exact morphology) with edge lengths between 100 and 160 nm, and wall thicknesses of the order of 10 nm. The goal of this work is to understand how the linewidth of the localized surface plasmon resonance depends on the size, shape, and environment of the nanoparticles. Specifically, the relative contributions from bulk dephasing, electron-surface scattering, and radiation damping (energy loss via coupling to the radiation field) have been determined by examining particles with different dimensions. This separation is possible because the magnitude of the radiation damping effect is proportional to the particle volume, whereas, the electron-surface scattering contribution is inversely proportional to the dimensions. For the nanorods, radiation damping is the dominant effect for thick rods (widths greater than 20 nm), while electron-surface scattering is dominant for thin rods (widths less than 10 nm). Rods with widths in between these limits have narrow resonances-approaching the value determined by the bulk contribution. For nanoboxes and nanocages, both radiation damping and electron-surface scattering are significant at all sizes. This is because these materials have thin walls, but large edge lengths and, therefore, relatively large volumes. The effect of the environment on the localized surface plasmon resonance has also been studied for nanoboxes. Increasing the dielectric constant of the surroundings causes a red-shift and an increase in the linewidth of the plasmon band. The increase in linewidth is attributed to enhanced radiation damping.