Tunable plasmonic lattices of silver nanocrystals

Silver nanocrystals are ideal building blocks for plasmonic materials that exhibit a wide range of unique and potentially useful optical phenomena. Individual nanocrystals display distinct optical scattering spectra and can be assembled into hierarchical structures that couple strongly to external electromagnetic fields. This coupling, which is mediated by surface plasmons, depends on the shape and arrangement of the nanocrystals. Here we demonstrate the bottom-up assembly of polyhedral silver nanocrystals into macroscopic two-dimensional superlattices using the Langmuir-Blodgett technique. Our ability to control interparticle spacing, density and packing symmetry allows for tunability of the optical response over the entire visible range. This assembly strategy offers a new, practical approach to making novel plasmonic materials for application in spectroscopic sensors, subwavelength optics and integrated devices that utilize field-enhancement effects.     

Tunable plasmonic coupling between silver nano-cubes and silver nano-hole arrays

A quasi-three-dimensional (quasi-3D) system composed of Ag nano-cubes and Ag nano-hole arrays was fabricated through a low cost chemical process. The coupling of localized surface plasmons (LSPs) in the cube-hole array system has been investigated through surface-enhanced Raman scattering (SERS) from Rhodamine 6G (R6G) molecules. A SERS enhancement factor as large as 1.1 × 10(8) can be achieved due to this plasmonic coupling effect, and is highly sensitive to geometrical parameters, such as cube-hole array distance, hole diameter, inter-hole spacing and Ag film thickness.     

Synthesis of silver nanorods by low energy excitation of spherical plasmonic seeds

Plasmon excitation of Ag seed particles with 600-750 nm light in the presence of Ag(+) and trisodium citrate was used to synthesize penta-twinned nanorods. Importantly, the excitation wavelength can be used to control the reaction rate and, consequently, the aspect ratio of the nanorods. When the excitation wavelength is red-shifted from the surface plasmon resonance of the spherical seed particles, the rate of Ag(+) reduction becomes slower and more kinetically controlled. Such conditions favor the deposition of silver onto the tips of the growing nanorods as compared to their sides, resulting in the generation of higher aspect ratio rods. However, control experiments reveal that there is only a range of low energy excitation wavelengths (between 600 and 750 nm) that yields monodisperse nanorods. This study further highlights the utility of using wavelength to control the size and shape of growing nanoparticles using plasmon-mediated methods.     

Tunable near-infrared epsilon-near-zero and plasmonic properties of Ag-ITO co-sputtered composite films

Series of co-sputtered silver-indium tin oxide (Ag-ITO) films are systematically fabricated. By tuning the atomic ratio of silver, composite films are manifested to have different microstructures with limited silver amount (<3 at.%). Two stages for film morphology changing are proposed to describe different status and growth mechanisms. The introduction of silver improves the preferred orientations of In₂O₃ component significantly. Remarkably, dielectric permittivity of Ag-ITO films is highly adjustable, allowing the cross-over wavelengths λ_c to be changed by more than 300 nm through rapid post-annealing, and thus resulting in tunable epsilon-near-zero and plasmonic properties in the near-infrared region. Lower imaginary permittivity compared with pure metal films, as well as larger tunability in λ_c than pure ITO films suggest the potentiality of Ag-ITO films as substituted near-infrared plasmonic materials. Extended Maxwell-Garnett model is applied for effective medium approximation and the red-shifting of epsilon-near-zero region with the increase of silver content is well-fitted. Angle-variable prism coupling is carried out to reveal the surface plasmon polariton features of our films at optical communication wavelength. Broad dips in reflectance curves around 52–56° correspond to the SPP in Ag-ITO films.     

Matryoshka-caged gold nanorods: Synthesis,plasmonic properties,and catalytic activity

Matryoshka-caged gold nanorods (mCGNRs) were successfully synthesized by alternating between a seed-mediated silver-coating method and galvanic replacement reactions (GRRs). As the number of matryoshka layers of the mCGNRs increased, the plasmon resonance peak broadened and was red-shifted, and the catalytic activity towards the reduction of 4-nitrophenol (4-NTP) increased. When mCGNRs with 6 layers were used as nanocatalysts in the reduction of 4-nitrophenol, the reaction rate coefficient was 5.2- and 3.7-times higher than that of the gold-nanorod- and caged-gold-nanorod-catalyzed reductions of 4-nitrophenol, respectively. In addition, the surface-plasmon-resonance-based absorption of light enhanced the catalytic performance of the mCGNRs. With the support of a polyurethane foam, the mCGNRs synthesized in this study can be applied as recyclable heterogeneous catalysts for the reduction of 4-nitrophenol.

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Self-organized silver nanoparticles for three-dimensional plasmonic crystals

Metal nanostructures that support surface plasmons are compelling as plasmonic circuit elements and as the building blocks for metamaterials. We demonstrate here the spontaneous self-assembly of shaped silver nanoparticles into three-dimensional plasmonic crystals that display a frequency-selective response in the visible wavelengths. Extensive long-range order mediated by exceptional colloid monodispersity gives rise to optical passbands that can be tuned by particle volume fraction. These metallic supercrystals present a new paradigm for the fabrication of plasmonic materials, delivering a functional, tunable, completely bottom-up optical element that can be constructed on a massively parallel scale without lithography.     

A simple template method for hierarchical dendrites of silver nanorods and their applications in catalysis

A novel strategy has been put forward to prepare hierarchical dendrites of silver nanorods via a simple integration method using “Devarda's template” as a reducing agent and architecture template with the assistance of ultrasonic waves, in which the template was firstly fabricated and employed. The individual silver dendrite is composed of a long central trunk with secondary branches, which preferentially grew in a parallel direction with a definite angle to the trunk. The results reveal that the dendrites are single crystalline in nature and interestingly prove that the silver single crystal has the preferential orientation in 〈1 1 1〉 direction in normal conditions. The contrast experiments demonstrated that both “Devarda's template” and the ultrasonic irradiation are necessary for building hierarchically silver dendrites in a water system. Moreover, the experimental results show that the dendrites of silver nanorods are the superior electrode materials for the electrochemical sensors to detect directly NO₂⁻ in aqueous solution.     

铬酸银纳米棒组装体的简易合成及其光学性能

在简单温和的条件下利用模板法,首次合成出了铬酸银纳米棒组装体,构成该组装体的纳米棒长度约为150～250nm,直径约70nm.当激发波长为383nm时,发射出432nm的蓝光;产物在紫外-可见光谱356nm处有明显的宽化吸收.     

Dimensional and compositional dependent analysis of plasmonic bimetallic nanorods

The individual noble metal nanoparticles (NPs) are combined to form alloys with improved optical response, cost effectiveness and better stability. The selection of noble metal alloy NPs for their better use in plasmonic applications is being made on the bases of surface plasmon resonance peak position, its intensity and full width at half maxima (FWHM). Presently, the effect of metal composition (x), aspect ratio (R), size and metal type on the longitudinal plasmon resonance (LPR) of noble metal Ag–Au alloy nanorods (NRs) has been studied by applying modified Gans theory including finite wavelength effects and found that the LPR shifts towards the longer wavelength region with increase in aspect ratio and size of the NR. Moreover, a linear relationship which is in good agreement to the experimental results between the plasmon resonance and aspect ratio has been obtained. The aspect ratio and NR width-dependent absorption efficiency and FWHM have also been calculated. Further, a negligible effect of metal composition and its type is found on the LPR.     

Synthesis and electrical properties of uniform silver nanoparticles for electronic applications

Silver nanoparticles are considered to apply a silver paste for electrode because of their high conductivity. However, the dispersion of silver nanoparticles in electronically conductive adhesives (ECAs) restricts them used as conductive fillers. A simple method had enabled the synthesis of silver nanoparticles by reducing silver nitrate with ethanol in the presence of poly(N-vinylpyrrolidone) (PVP). Reaction conditions, such as silver nitrate concentration, PVP concentration, reaction time, and reaction temperature, had been studied. Fine dispersion and narrow size distribution of silver nanoparticles were obtained. They were added to ECAs by re-dispersing them in ethanol while it was used as the diluent to adjust the volatility of ECAs, preventing them from the aggregation and increasing the chance to fill the gaps between silver flakes. This proposed process offers the possibility to effectively use these synthesized silver nanoparticles for improving the conductivity of ECAs.     

Isolation of discrete nanoparticle-DNA conjugates for plasmonic applications

Discrete DNA-gold nanoparticle conjugates with DNA lengths as short as 15 bases for both 5 and 20 nm gold particles have been purified by anion-exchange HPLC. Conjugates comprising short DNA (<40 bases) and large gold particles (> or =20 nm) are difficult to purify by other means and are potential substrates for plasmon coupling experiments. Conjugate purity is demonstrated by hybridizing complementary conjugates to form discrete structures, which are visualized by TEM.     

Fabrication and characterization of plasmonic nanorods with high aspect ratios

Metallic nanostructures with high aspect ratios are important for developing devices in photonics and integrated optics. However, fabricating well-aligned plasmonic arrays is challenging due to the difficulties of etching metals. In this work, we investigate the feasibility of constructing high aspect ratio nanorods with desired shapes and controllable geometric parameters using direct focused ion beam etching. The whole fabrication process only involves a metal-deposition step and a single milling of designed patterns. Detailed characterizations of the fabricated devices are also experimentally demonstrated.     

Tunable infrared plasmonic devices using graphene/insulator stacks

The collective oscillation of carriers--the plasmon--in graphene has many desirable properties, including tunability and low loss. However, in single-layer graphene, the dependence on carrier concentration of both the plasmonic resonance frequency and magnitude is relatively weak, limiting its applications in photonics. Here, we demonstrate transparent photonic devices based on graphene/insulator stacks, which are formed by depositing alternating wafer-scale graphene sheets and thin insulating layers, then patterning them together into photonic-crystal-like structures. We show experimentally that the plasmon in such stacks is unambiguously non-classical. Compared with doping in single-layer graphene, distributing carriers into multiple graphene layers effectively enhances the plasmonic resonance frequency and magnitude, which is different from the effect in a conventional semiconductor superlattice and is a direct consequence of the unique carrier density scaling law of the plasmonic resonance of Dirac fermions. Using patterned graphene/insulator stacks, we demonstrate widely tunable far-infrared notch filters with 8.2 dB rejection ratios and terahertz linear polarizers with 9.5 dB extinction ratios. An unpatterned stack consisting of five graphene layers shields 97.5% of electromagnetic radiation at frequencies below 1.2 THz. This work could lead to the development of transparent mid- and far-infrared photonic devices such as detectors, modulators and three-dimensional metamaterial systems.     

Tunable optical filter for colorimetric applications

A temperature-controlled tunable optical filter for use in the visible range and based on the Christiansen effect, in which the solid particles have been substituted with glass fibers, has been fabricated and tested. The construction of the filter and transmission properties are reported. For an operating temperature of 95°C, the peak wavelength was 509.5 nm, with a peak transmission of 50.8% and a FWHM of 71 nm.     

Integration of photonic and silver nanowire plasmonic waveguides

Future optical data transmission modules will require the integration of more than 10,000 x 10,000 input and output channels to increase data transmission rates and capacity. This level of integration, which greatly exceeds that of a conventional diffraction-limited photonic integrated circuit, will require the use of waveguides with a mode confinement below the diffraction limit, and also the integration of these waveguides with diffraction-limited components. We propose to integrate multiple silver nanowire plasmonic waveguides with polymer optical waveguides for the nanoscale confinement and guiding of light on a chip. In our device, the nanowires lay perpendicular to the polymer waveguide with one end inside the polymer. We theoretically predict and experimentally demonstrate coupling of light into multiple nanowires from the same waveguide, and also demonstrate control over the degree of coupling by changing the light polarization.     

Angle-resolved reflectance of obliquely aligned silver nanorods

Arrays of silver nanorods (AgNRs) formed by oblique-angle deposition (OAD) are strongly anisotropic, with either metallic or dielectric characteristics depending on the polarization of incident light, and may be used to enhance Raman scattering and surface plasmon polaritons. This work investigates the polarization-dependent reflectance of inclined AgNR arrays at the wavelengths of 635 and 977 nm. The specular reflectance at various incidence angles and the bidirectional reflectance distribution function were measured with a laser scatterometer, while the directional-hemispherical reflectance was measured with an integrating sphere. The AgNR layer is modeled as an effectively homogenous, optically uniaxial material using the effective medium theory to elucidate the dielectric or metallic response for differently polarized incidence. The thin-film optics formulation is modified considering optical anisotropy and surface scattering. This study helps gain a better understanding of optical properties of nanostructured materials.     

Light propagation in curved silver nanowire plasmonic waveguides

Plasmonic waveguides made of metal nanowires (NWs) possess significant potential for applications in integrated photonic and electronic devices. Energy loss induced by bending of a NW during light propagation is critical in affecting its performance as a plasmonic waveguide. We report the characterization of the pure bending loss in curved crystalline silver NW plasmonic waveguides by decoupling the energy loss caused by bending and propagation. The energy attenuation coefficiency due purely to bending was also determined, which exhibited an exponential relationship with the bending radius. Finite-difference-time-domain (FDTD) methods were utilized for theoretical simulations, which matched the experimental results well.     

Fabrication of chiral plasmonic oligomers using cysteine-modified gold nanorods as monomers

Generation of circular dichroism （CD） beyond the UV region is of great interest in developing chiral sensors and chiroptical devices. Herein, we demonstrate a simple and versatile method for fabrication of plasmonic oligomers with strong CD response in the visible and near IR spectral range. The oligomers were fabricated by triggering the side-by-side assembly of cysteine-modified gold nanorods. The modified nanorods themselves did not exhibit obvious plasmonic CD signals; however, the oligomers show strong CD bands around the plasmon resonance wavelength. The sign of the CD band was dictated by the chirality of the absorbed cysteine molecules. By adjusting the size of the oligomers, the concentration of chiral molecules, and/or the aspect ratio of the nanorods, the CD intensity and spectral range were readily tunable. Theoretical calculations suggested that CD of the oligomers originated from a slight twist of adjacent nanorods within the oligomer. Therefore, we propose that the adsorbed chiral molecules are able to manipulate the twist angles between the nanorods and thus modulate the CD response of the oligomers.     

Tunable vancomycin releasing surfaces for biomedical applications

Local drug delivery methods allow for the opportunity to supply potent multispectrum antibiotics such as vancomycin hydrochloride to sites of infection, while avoiding systemic toxicity. In this work, layer-by-layer assembly of polymer multilayer films is applied to create vancomycin delivery coatings. By taking advantage of the versatile layer-by-layer spray and dip coating techniques, thin films were generated based on electrostatic and other secondary interactions discovered to exist between the film components. The importance of film interdiffusion during growth in promoting interactions between film components is found to be critical in the direct incorporation of the weakly charged vancomycin drug in these multilayer films. The resulting coatings are engineered with unprecedented drug densities ranging from 17-220 μg mm(-3) (approximately 20 wt%) for films that are micron to submicron scale in thickness, delivering vancomycin over timescales of 4 h to 2.5 days. The released drug is highly effective in inhibiting Staphylococcus aureus growth in vitro. Taking advantage of the difference in release characteristics between dip and spray assembled films, a composite film architecture was engineered to have both a bolus vancomycin release followed by a period of linear sustained drug release. The control over drug densities and release profiles displayed in this work is necessary to address the requirements of varying medical conditions, including those where immediate infection elimination is needed or long term infection prevention is required.