Jake Fontana

Large surface-enhanced Raman scattering from self-assembled gold nanosphere monolayers

We demonstrate an average surface-enhanced Raman scattering enhancement on the order of 108 from benzenethiol molecules using self-assembled, macroscopic, and tunable gold nanosphere monolayers on non-templated substrates. The self-assembly of the nanosphere monolayers uses a simple and efficient technique that allows for the creation of a high-density, chemically functionalized gold nanosphere monolayers with enhancement factors comparable to those produced using top-down fabrication techniques. These films may provide an approach for the future development of portable chemical/biological sensors.

Virus-Templated Plasmonic Nanoclusters with Icosahedral Symmetry via Directed Self-Assembly

The assembly of plasmonic nanoparticles with precise spatial and orientational order may lead to structures with new electromagnetic properties at optical frequencies. The directed self-assembly method presented controls the interparticle-spacing and symmetry of the resulting nanometer-sized elements in solution. The self-assembly of three-dimensional (3D), icosahedral plasmonic nanosclusters (NCs) with resonances at visible wavelengths is demonstrated experimentally. The ideal NCs consist of twelve gold (Au) nanospheres (NSs) attached to thiol groups at predefined locations on the surface of a genetically engineered cowpea mosaic virus with icosahedral symmetry. In situ dynamic light scattering (DLS) measurements confirm the NSs assembly on the virus. Transmission electron micrographs (TEM) demonstrate the ability of the self-assembly method to control the nanoscopic symmetry of the bound NSs, which reflects the icosahedral symmetry of the virus. Both, TEM and DLS show that the NCs comprise of a distribution of capsids mostly covered (i.e., 6–12 NS/capsid) with NSs. 3D finite-element simulations of aqueous suspensions of NCs reproduce the experimental bulk absorbance measurements and major features of the spectra. Simulations results show that the fully assembled NCs give rise to a 10-fold surface-averaged enhancement of the local electromagnetic field.

Highly tunable gold nanorod dimer resonances mediated through conductive junctions

We study the optical properties of gold nanorod (Au NR) dimers connected end-to-end by a thin metallic junction. The plasmonic oscillations along the long axis of the dimer gives rise to two dominant modes: a bonding dimer plasmon emerging from the dipolar mode of each individual nanorod and a charge transfer plasmon involving the entire dimer structure. We find the charge transfer plasmon absorbance peak shift from the dimer structure is proportional to the NR aspect ratio (AR) behaving as it was a single NR with an AR nearly an order of magnitude larger. The charge transfer plasmon absorbance peak sensitively depends on the material and geometry of the connecting junction, theoretically tuning the absorbance peak from 1 μm to 10 μm. A straightforward “Drude-like” model to describe the charge transfer plasmon response is presented. The development of charge transfer plasmon nanostructures may open up new classes of plasmonic nanostructures leading to disruptive metamaterial technologies.

The effects of nanoparticle shape and orientation on the low frequency dielectric properties of nanocomposites

In this paper, we examine the effects of aspect ratio and orientational order of nanoparticles on the dielectric properties of nanocomposites. The motivation is to clearly establish the effects of orientational order, since ambiguities exist in the literature. We focus on metallic nanoparticles, and show that, in the dilute concentration limit, theory, experiments and numerical simulations all unequivocally indicate that the effective dielectric constant increases with increasing aspect ratio and increasing degree of alignment of rod-like nanoparticles when they orient in direction of the electric field.

Generation of fluorescent silver nanoscale particles in reverse micelles using gamma irradiation

Reverse micelles (RMs) containing aqueous solutions of Ag(+) ions in their core produce fluorescent Ag species, upon exposure to gamma irradiation. A two-phase liquid system is used for RM formation. The RMs can be employed in novel gamma radiation detectors with appearance of fluorescence indicating that radiation was once present.

Electric field induced orientational order of gold nanorods in dilute organic suspensions

The electric field controlled alignment of gold nanorods offers a paradigm for anisotropic molecules with the potential for a wide variety of phases and structures. We experimentally study the optical absorption from gold nanorod suspensions aligned using external electric fields. We show that the absorption from these suspensions depends linearly on the orientational order parameter. We provide evidence that the critical electric field needed to orient the gold nanorods is proportional to the nanorod volume and depolarization anisotropy. Utilizing this critical field dependence, we demonstrate for suspensions with two different nanorod sizes that the alignment of each population can be controlled. We also develop a technique to determine the imaginary parts of the longitudinal and transverse electric susceptibilities of the nanorods. The ability to selectively address specific parts of the nanorod populations in a mixture using external fields may have significant potential for future display and optical...

Preparation and layer-by-layer solution deposition of Cu(In,Ga)O2 nanoparticles with conversion to Cu(In,Ga)S2 films.

We present a method of Cu(In,Ga)S2 (CIGS) thin film formation via conversion of layer-by-layer (LbL) assembled Cu-In-Ga oxide (CIGO) nanoparticles and polyelectrolytes. CIGO nanoparticles were created via a novel flame-spray pyrolysis method using metal nitrate precursors, subsequently coated with polyallylamine (PAH), and dispersed in aqueous solution. Multilayer films were assembled by alternately dipping quartz, Si, and/or Mo substrates into a solution of either polydopamine (PDA) or polystyrenesulfonate (PSS) and then in the CIGO-PAH dispersion to fabricate films as thick as 1–2 microns. PSS/CIGO-PAH films were found to be inadequate due to weak adhesion to the Si and Mo substrates, excessive particle diffusion during sulfurization, and mechanical softness ill-suited to further processing. PDA/CIGO-PAH films, in contrast, were more mechanically robust and more tolerant of high temperature processing. After LbL deposition, films were oxidized to remove polymer and sulfurized at high temperature under flowing hydrogen sulfide to convert CIGO to CIGS. Complete film conversion from the oxide to the sulfide is confirmed by X-ray diffraction characterization.

Nanoparticle doping for improved Er-doped fiber lasers

A nanoparticle (NP) doping technique was used for making erbium-doped fibers (EDFs) for high energy lasers. The nanoparticles were doped into the silica soot of preforms, which were drawn into fibers. The Er luminescence lifetimes of the NP-doped cores are longer than those of corresponding solution-doped silica, and substantially less Al is incorporated into the NP-doped cores. Optical-to-optical slope efficiencies of greater than 71% have been measured. Initial investigations of stimulated Brillouin scattering (SBS) have indicated that SBS suppression is achieved by NP doping, where we observed a low intrinsic Brillouin gain coefficient, of ~1× 10-11 m/W and the Brillouin bandwidth was increased by 2.5x compared to fused silica.

Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps

We created centimeter-scale area metasurfaces consisting of a quasi-hexagonally close packed monolayer of gold nanospheres capped with alkanethiol ligands on glass substrates using a directed self-assembly approach. We experimentally characterized the morphology and the linear and nonlinear optical properties of metasurfaces. We show these metasurfaces, with interparticle gaps of 0.6 nm, are modeled well using a classical (without charge transfer) description. We find a large dispersion of linear refractive index, ranging from values less than vacuum, 0.87 at 600 nm, to Germanium-like values of 4.1 at 880 nm, determined using spectroscopic ellipsometry. Nonlinear optical characterization was carried out using femtosecond Z-scan and we observe saturation behavior of the nonlinear absorption (NLA) and nonlinear refraction (NLR). We find a negative NLR from these metasurfaces two orders of magnitude larger (n2,sat = -7.94x10-9 cm2/W at Isat,n2 = 0.43 GW/cm2) than previous reports on gold nanostructures at similar femtosecond time scales. We also find the magnitude of the NLA comparable to the largest values reported (β2,sat = -0.90x105 cm/GW at Isat,β2 = 0.34 GW/cm2). Precise knowledge of the index of refraction is of crucial importance for emerging dispersion engineering technologies. Furthermore, utilizing this directed self-assembly approach enables the nanometer scale resolution required to develop the unique optical response and simultaneously provides high-throughput for potential device realization.

Toward high throughput optical metamaterial assemblies.

Optical metamaterials have unique engineered optical properties. These properties arise from the careful organization of plasmonic elements. Transitioning these properties from laboratory experiments to functional materials may lead to disruptive technologies for controlling light. A significant issue impeding the realization of optical metamaterial devices is the need for robust and efficient assembly strategies to govern the order of the nanometer-sized elements while enabling macroscopic throughput. This mini-review critically highlights recent approaches and challenges in creating these artificial materials. As the ability to assemble optical metamaterials improves, new unforeseen opportunities may arise for revolutionary optical devices.