Luminescence quantum yield of single gold nanorods

We study the luminescence quantum yield (QY) of single gold nanorods with different aspect ratios and volumes. Compared to gold nanospheres, we observe an increase of QY by about an order of magnitude for particles with a plasmon resonance >650 nm. The observed trend in QY is further confirmed by controlled reshaping of a single gold nanorod to a spherelike shape. Moreover, we identify two spectral components, one around 500 nm originating from a combination of interband transitions and the transverse plasmon and one coinciding with the longitudinal plasmon band. These components are analyzed by correlating scattering and luminescence spectra of single nanorods and performing polarization sensitive measurements. Our study contributes to the understanding of luminescence from gold nanorods. The enhanced QY we report can benefit applications in biological and soft matter studies.     

Probing dynamically tunable localized surface plasmon resonances of film-coupled nanoparticles by evanescent wave excitation

The localized surface plasmon resonance (LSPR) spectrum associated with a gold nanoparticle (NP) coupled to a gold film exhibits extreme sensitivity to the nanogap region where the fields are tightly localized. The LSPR of an ensemble of film-coupled NPs can be observed using an illumination scheme similar to that used to excite the surface plasmon resonance (SPR) of a thin metallic film; however, in the present system, the light is used to probe the highly sensitive distance-dependent LSPR of the gaps between NPs and film rather than the delocalized SPR of the film. We show that the SPR and LSPR spectral contributions can be readily distinguished, and we compare the sensitivities of both modes to displacements in the average gap between a collection of NPs and the gold film. The distance by which the NPs are suspended in solution above the gold film is fixed via a thin molecular spacer layer and can be further modulated by subjecting the NPs to a quasistatic electric field. The observed LSPR spectral shifts triggered by the applied voltage can be correlated with angstrom scale displacements of the NPs, suggesting the potential for chip-scale or flow-cell plasmonic nanoruler devices with extreme sensitivity.     

Spatial control of coherent anti-stokes emission with height-modulated gold zig-zag nanowires

Intrinsic coherent anti-Stokes emission is observed in lithographically patterned gold nanowires. Polarization dependent measurements reveal that the nanostructure's anti-Stokes response is polarized in the direction of the transverse surface plasmon resonance of the wire. We have used specially fabricated gold nanozigzag wires that are modulated in height between 20 and 80 nm to demonstrate tuning of the plasmon polarizability through control of wire height. Stronger anti-Stokes emission is shown to correlate with structures that support higher plasmon polarizability, underlining the primary role of the transverse plasmon resonance in the generation of anti-Stokes radiation from gold nanostructures. Our results also point out that a potential surface-enhanced coherent anti-Stokes Raman scattering (CARS) assay for detecting the vibrational response of surface-tethered molecules needs to include a mechanism for separating the molecular response from the strong intrinsic anti-Stokes emission of the metallic nanosubstrate.     

Calculations of light scattering from isolated and interacting metallic nanowires of arbitrary cross section by means of Green's theorem surface integral equations in parametric form

We study theoretically the light scattering from metal wires of arbitrary cross section, with emphasis on the occurrence of plasmon resonances. We make use of the rigorous formulation of the Green's theorem surface integral equations of the electromagnetic wave scattering, written for an arbitrary number of scatterers described in parametric form. We have investigated the scattering cross sections for nanowires of various shapes (circle, triangles, rectangles, and stars), either isolated or interacting. The relationship between the cross sectional shape and the spectral dependence of the plasmon resonances is studied, including the impact of nanoparticle coupling in the case of interacting scatterers. Near-field intensity maps are also shown that shed light on the plasmon resonance features and the occurrence of local field enhancements.     

Synthesis of 1D regular arrays of gold nanoparticles and modeling of their optical properties

Self-organized formation of uniform coating of semiconductor substrate by metal nanoparticles offers a convenient and efficient access to large-scale arrays of uniform metal-semiconductor nanostructures. We used a cheap and facile method of photoinduced chemical gold deposition from an aqueous or alcohol gold salt solution onto semiconductor surface (GaAs, InP). By controlling of both the solution composition and the deposition conditions, gold particles of 10-50 nm in diameter were obtained and the gold covering degree of the semiconductor surface was varied in a wide range. Morphology of the nano/micro structures formed was characterized by atomic force microscopy and scanned electron microscopy with local element analysis. The investigations show that the semiconductor surface patterning can be used for the selective deposition of gold nanoparticles, because they are located predominantly at the tops of the microrelief. We have used specially textured by the anisotropic chemical etching microrelief surfaces of semiconductor single crystal as templates and have obtained nanoparticle arrays in the shape of 1D systems of near parallel quasiperiodical wires. For the periodic 1D array of metal nanowires built into the air-semiconductor interface the spectral and angular dependencies of the transmittance/reflectance of the polarized light have been obtained theoretically using differential formalism. These dependencies demonstrate non-monotonic behaviour at surface plasmon polariton excitation conditions and show possibility of designing functional subwavelength devices.     

Moving nanoparticles with Raman scattering

We show how to change optically the distance between two protein-linked gold nanoparticles by Raman-induced motion of the linker protein. Rayleigh scattering spectroscopy of the coupled-particle plasmon allows us to compare the inter-nanoparticle distance of individual protein-linked gold nanoparticle dimers before and after surface-enhanced Raman scattering (SERS). We find that low-intensity (50 microW/microm2) laser light in resonance with the nanoparticle-dimer plasmon provokes a change of the inter-nanoparticle distance on the order of 0.5 nm whenever SERS from the proteins connecting the nanoparticles can be observed.     

Optical and topological characterization of gold nanoparticle dimers linked by a single DNA double strand

We demonstrate that symmetric or asymmetric gold nanoparticle dimers with substantial scattering cross sections and plasmon coupling can be produced with a perfectly controlled chemical environment and a high purity using a single DNA linker as short as 7 nm. A statistical analysis of the optical properties and morphology of single dimers is performed using darkfield and cryo-electron microscopies. These results, correlated to Mie theory calculations, indicate that the particle dimers are stretched in water by electrostatic interactions.     

Optical properties of star-shaped gold nanoparticles

Here we report the synthesis, structure, and optical properties of ca. 100 nm star-shaped gold nanoparticles. Single particle spectroscopy measurements revealed that these nanoparticles have multiple plasmon resonances resulting in polarization-dependent scattering with multiple spectral peaks, which correspond to the different tips on the star-shaped structure. The plasmon resonances were also found to be extremely sensitive to the local dielectric environment.     

Polarization dependence of surface-enhanced Raman scattering in gold nanoparticle-nanowire systems

We study the polarization dependence of surface-enhanced Raman scattering (SERS) in coupled gold nanoparticle-nanowire systems. The coupling between the continuous nanowire plasmons and the localized nanoparticle plasmons results in significant field enhancements and SERS enhancements comparable to those found in nanoparticle dimer junctions. The SERS intensity is maximal when the incident light is polarized across the particle and the wire, and the enhancement is remarkably insensitive to the detailed geometrical structures of the nanoparticles.     

Dependence of fluorescence intensity on the spectral overlap between fluorophores and plasmon resonant single silver nanoparticles

We investigate the fluorescence from dyes coupled to individual DNA-functionalized metal nanoparticles. We use single-particle darkfield scattering and fluorescence microscopy to correlate the fluorescence intensity of the dyes with the localized surface plasmon resonance (LSPR) spectra of the individual metal nanoparticles to which they are attached. For each of three different dyes, we observe a strong correlation between the fluorescence intensity of the dye and the degree of spectral overlap with the plasmon resonance of the nanoparticle. On average, we observe the brightest fluorescence from dyes attached to metal nanoparticles that have a LSPR scattering peak approximately 40-120 meV higher in energy than the emission peak of the fluorophore. These results should prove useful for understanding and optimizing metal-enhanced fluorescence.     

Plasmon-enhanced resonance Raman scattering and fluorescence in Langmuir-Blodgett monolayers

Localized surface plasmon resonances in silver and gold nanostructures are engaged to enhance the inelastic Raman scattering and the fluorescence of a phopholipid containing a sulforhodamine 101 acid chloride dye known as Texas Red. The most efficient coupling and enhancement are attained when the excitation laser line is in resonance with both the chromophore and the plasmon absorption of the nanostructure, the case of surface-enhanced resonance Raman scattering, allowing single-molecule detection. The tagged phospholipid was incorporated into a single fatty acid Langmuir monolayer at varying concentrations and transferred onto an evaporated Ag nanoparticle film. Surface-enhanced fluorescence is achieved using shell-isolated silica-coated gold nanoparticles, an emission enhancement named SHINEF.     

Tuning gold nanorod-nanoparticle hybrids into plasmonic Fano resonance for dramatically enhanced light emission and transmission

We investigate the optical response of a gold nanorod array coupled with a semicontinuous nanoparticle film. We find that, as the gold nanoparticle film is adjusted to the percolating regime, the nanorod-film hybrids are tuned into plasmonic Fano resonance, characterized by the coherent coupling of discrete plasmonic modes of the nanorod array with the continuum band of the percolating film. Consequently, optical transmission of the percolating film is substantially enhanced. Even more strikingly, electromagnetic fields around the nanorod array become much stronger, as reflected by 2 orders of magnitude enhancement in the avalanche multiphoton luminescence. These findings may prove instrumental in the design of various plasmonic nanodevices.     

Reversible tuning of plasmon coupling in gold nanoparticle chains using ultrathin responsive polymer film

We demonstrate large and reversible tuning of plasmonic properties of gold nanoparticles mediated by the reversible breaking and making of linear and branched chains of gold nanoparticles adsorbed on an ultrathin (1 nm) responsive polymer film. Atomic force microscopy revealed that at pH below the isoelectric point of the polybase (extended state of the polymer chains), gold nanoparticles adsorbed on the polymer layer existed primarily as individual nanoparticles. On the other hand, at higher pH, the polymer chains transition from coil to globule (collapsed) state, resulting in the formation of linear and branched chains with strong interparticle plasmon coupling. Reversible aggregation of the nanoparticles resulted in large and reversible change in the optical properties of the metal nanostructure assemblies. In particular, we observed a large redistribution of the intensity between the individual and coupled plasmon bands and a large shift (nearly 95 nm) in the coupled plasmon band with change in pH. Large tunability of plasmonic properties of the metal nanostructure chains reported here is believed to be caused by the chain aggregates of nanoparticles and un-cross-linked state of the adsorbed polymer enabling large changes in polymer chain conformation.     

Distance dependent spectral tuning of two coupled metal nanoparticles

The spectral properties of two spherical metallic nanoparticles of 80 nm in diameter are examined with regard to the interparticle distance and relative polarization of the excitation light. One Au nanoparticle is attached to a scanning fiber probe and the second to a scanning substrate. This configuration allows three-dimensional and arbitrary manipulation of both distance and relative orientation with respect to the incident light polarization. As supported by numerical simulations, a periodic modulation of the coupled plasmon resonance is observed for separations smaller than 1.5 microm. This interparticle coupling affects the scattering cross section in terms of spectral position and spectral width as well as the integral intensity of the Mie-scattered light.     

Langmuir-Blodgett films of gold/silica core/shell nanorods

We report the preparation of Langmuir- and Langmuir-Blodgett films of mesoporous silica coated gold nanorods. The silica coating on the gold nanorods was found to prevent the aggregation of the plasmonic particles trapped at the air/water interface. Due to the small aspect ratio of the gold core and the presence of the silica shell, the orientational alignment of the nanorods in the Langmuir-Blodgett film is hindered. After particle deposition, no plasmon coupling was observed, which enables the design of the resulting film's optical property at the particle level. By using mesoporous silica as the shell material, the accessibility of the metal core's surface is preserved. Organic dye (Rhodamine 6G) was found to be able to penetrate into the mesoporous shell of the gold nanorods, resulting in a red shift of the longitudinal plasmon mode.     

Imaging surface plasmon of gold nanoparticle arrays by far-field Raman scattering

We present Raman spectra and Raman images of the methylene blue molecule adsorbed as a single layer on gold nanoparticles regularly arranged in periodic arrays. Spectra and images are recorded in the same spatial and spectral regions using an excitation under total internal reflection. Images of the Raman scattering appear as spots of circular shape located at the particle positions with size defined by the diffraction limit. It appears that all excited particles contribute equally to the Raman signal if the Gaussian intensity distribution of the laser beam is taken into account. These results demonstrate that Raman scattering can be a useful technique to study plasmon properties.     

Voltage-induced adsorbate damping of single gold nanorod plasmons in aqueous solution

Unbiased gold nanoparticles are negatively charged in aqueous solution but not hydrated. Optical spectroscopy of voltage-clamped single gold nanoparticles reveals evidence that anion adsorption starts at positive potentials above the point of zero charge, causing severe but reversible plasmon damping in combination with a spectral red shift exceeding the linear double layer charging effect. Plasmon damping by adsorbate is relevant for the use of nanoparticles in catalysis, in biodiagnostics, and in surface enhanced Raman scattering.     

Hybridized surface-plasmon resonances of platinum colloid-adsorbed gold nanospheres

The surface-plasmon resonances of gold nanospheres dispersed in water split into two bands and shift to the red with the adsorption of colloidal platinum. These spectral changes are quite different from both the calculated and the experimental spectral variations of gold nanospheres with the thickness of coating platinum. Thus, these spectral changes have been attributed to the elementary plasmon interactions of the core gold and the adsorbed colloidal platinum as well as to the modification of the medium refraction index of the gold nanospheres. A simple and intuitive picture has been drawn to describe the hybridization plasmon interactions of a platinum colloid-adsorbed gold nanosphere.     

Optical organophosphate sensor based upon gold nanoparticle functionalized fumed silica gel

We report on the creation of a high surface area, chemically selective material for the efficient adsorption of organophosphate and organophosphonate species. Using silica microparticles in conjunction with gold nanoparticles and surface modification chemistry, we have demonstrated a material with a binding constant for organophosphonates and organophosphates (OPPs) of K=2x10(6) M-1. The binding of OPPs to the modified gold nanoparticles appears as a spectral shift in the gold nanoparticle resonance. The sensitivity of this technique is limited by scattering losses of suspensions of the particles, and we report on how this sensitivity can be recovered to a significant extent by the use of solvents with a refractive index close to that of the silica particles.     

Controlling the aggregation behavior of gold nanoparticles

The aggregation of Au nanoparticles (NPs) in solution is influenced by cationic and oligocationic species. The polarization of the conduction electron oscillations in adjacent gold nanoparticles causes a new red-shifted plasmon absorbance attributed to the coupling of the plasmon absorbance of the particles. This appearance of an additional plasmon band is of particular interest to the field of SERS and has led to research works directed at the stabilization of small colloid aggregates in solution. The surface plasmon coupling can be tuned by controlling the aggregation of gold nanoparticles by the addition of some “cross-linking” agent. Here we develop a simple method to fabricate linear-chainlike aggregates of gold nanoparticles (so-called nanochains), tuning the linear optical properties in a wide wavelength range from visible to the near-infrared. The aggregation behavior and linear self-assembly mechanism of citrate-stabilized gold colloids as provoked by the addition of cetyltrimethylammonium bromide (CTAB) and 11-mercaptoundecanoic acid (MUA) are also analyzed. The line-assembly mechanism of gold nanochain is attributed to the preferential binding of CTAB molecules on a certain facet of gold NPs and the Au NP electrostatic interactions. We also found that the 11-mercaptoundecanoic acid was effective to prevent the further aggregation of CTAB-modified gold colloids.