Universal Fabrication of Highly Efficient Plasmonic Thin-Films for Label-Free SERS Detection.

The development of novel, highly efficient, reliable, and robust surface enhanced Raman scattering (SERS) substrates containing a large number of hot spots with programmed size, geometry, and density is extremely interesting since it allows the sensing of numerous (bio-)chemical species. Herein, an extremely reliable, easy to fabricate, and label-free SERS sensing platform based on metal nanoparticles (NPs) thin-film is developed by the layer-by-layer growth mediated by polyelectrolytes. A systematic study of the effect of NP composition and size, as well as the number of deposition steps on the substrate's performance, is accomplished by monitoring the SERS enhancement of 1-naphtalenethiol (532 nm excitation). Distinct evidence of the key role played by the interlayer (poly(diallyldimethylammonium chloride) (PDDA) or PDDA-functionalized graphene oxide (GO@PDDA)) on the overall SERS efficiency of the plasmonic platforms is provided, revealing in the latter the formation of more uniform hot spots by regulating the interparticle distances to 5 ± 1 nm. The SERS platform efficiency is demonstrated via its high analytical enhancement factor (≈106 ) and the detection of a prototypical substance(tamoxifen), both in Milli-Q water and in a real matrix, viz. tap water, opening perspectives towards the use of plasmonic platforms for future high-performance sensing applications.

Optimization of an optical wireless nanolink using directive nanoantennas.

Optical connects will become a key point in the next generation of integrated circuits, namely the upcoming nanoscale optical chips. In this context, nano-optical wireless links using nanoantennas have been presented as a promising alternative to regular plasmonic waveguide links, whose main limitation is the range propagation due to the metal absorption losses. In this paper we present the complete design of a high-capability wireless nanolink using matched directive nanoantennas. It will be shown how the use of directive nanoantennas clearly enhances the capability of the link, improving its behavior with respect to non-directive nanoantennas and largely outperforming regular plasmonic waveguide connects.

Chiral Seeded Growth of Gold Nanorods Into Fourfold Twisted Nanoparticles with Plasmonic Optical Activity.

A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology may hold the key to the practical utilization of these materials. An optimized chiral growth method to prepare fourfold twisted gold nanorods is described herein, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges are found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl4 , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent. From detailed electron microscopy analysis of the crystallographic structures, it is proposed that the dissymmetry results from the development of chiral facets in the form of protrusions (tilted ridges) on the initial nanorods, eventually leading to a twisted shape. The role of cysteine is attributed to assisting enantioselective facet evolution, which is supported by density functional theory simulations of the surface energies, modified upon adsorption of the chiral molecule. The development of R-type and S-type chiral structures (small facets, terraces, or kinks) would thus be non-equal, removing the mirror symmetry of the Au NR and in turn resulting in a markedly chiral morphology with high plasmonic optical activity.

Method-of-moments formulation for the analysis of plasmonic nano-optical antennas.

We present a surface integral equation (SIE) to model the electromagnetic behavior of metallic objects at optical frequencies. The electric and magnetic current combined field integral equation considering both tangential and normal equations is applied. The SIE is solved by using a method-of-moments (MoM) formulation. The SIE-MoM approach is applied only on the material boundary surfaces and interfaces, avoiding the cumbersome volumetric discretization of the objects and the surrounding space required in differential-equation formulations. Some canonical examples have been analyzed, and the results have been compared with analytical reference solutions in order to prove the accuracy of the proposed method. Finally, two plasmonic Yagi-Uda nanoantennas have been analyzed, illustrating the applicability of the method to the solution of real plasmonic problems.

Micelle-directed chiral seeded growth on anisotropic gold nanocrystals.

Surfactant-assisted seeded growth of metal nanoparticles (NPs) can be engineered to produce anisotropic gold nanocrystals with high chiroptical activity through the templating effect of chiral micelles formed in the presence of dissymmetric cosurfactants. Mixed micelles adsorb on gold nanorods, forming quasihelical patterns that direct seeded growth into NPs with pronounced morphological and optical handedness. Sharp chiral wrinkles lead to chiral plasmon modes with high dissymmetry factors (~0.20). Through variation of the dimensions of chiral wrinkles, the chiroptical properties can be tuned within the visible and near-infrared electromagnetic spectrum. The micelle-directed mechanism allows extension to other systems, such as the seeded growth of chiral platinum shells on gold nanorods. This approach provides a reproducible, simple, and scalable method toward the fabrication of NPs with high chiral optical activity.

Optimization of Nanoparticle-Based SERS Substrates through Large-Scale Realistic Simulations.

Surface-enhanced Raman scattering (SERS) has become a widely used spectroscopic technique for chemical identification, providing unbeaten sensitivity down to the single-molecule level. The amplification of the optical near field produced by collective electron excitations -plasmons- in nanostructured metal surfaces gives rise to a dramatic increase by many orders of magnitude in the Raman scattering intensities from neighboring molecules. This effect strongly depends on the detailed geometry and composition of the plasmon-supporting metallic structures. However, the search for optimized SERS substrates has largely relied on empirical data, due in part to the complexity of the structures, whose simulation becomes prohibitively demanding. In this work, we use state-of-the-art electromagnetic computation techniques to produce predictive simulations for a wide range of nanoparticle-based SERS substrates, including realistic configurations consisting of random arrangements of hundreds of nanoparticles with various morphologies. This allows us to derive rules of thumb for the influence of particle anisotropy and substrate coverage on the obtained SERS enhancement and optimum spectral ranges of operation. Our results provide a solid background to understand and design optimized SERS substrates.

Pillar[5]arene-Based Supramolecular Plasmonic Thin Films for Label-Free, Quantitative and Multiplex SERS Detection.

Novel plasmonic thin films based on electrostatic layer-by-layer (LbL) deposition of citrate-stabilized Au nanoparticles (NPs) and ammonium pillar[5]arene (AP[5]A) have been developed. The supramolecular-induced LbL assembly of the plasmonic nanoparticles yields the formation of controlled hot spots with uniform interparticle distances. At the same time, this strategy allows modulating the density and dimensions of the Au aggregates, and therefore the optical response, on the thin film with the number of AuNP-AP[5]A deposition cycles. Characterization of the AuNP-AP[5]A hybrid platforms as a function of the deposition cycles was performed by means of visible-NIR absorption spectroscopy, and scanning electron and atomic force microscopies, showing larger aggregates with the number of cycles. Additionally, the surface enhanced Raman scattering efficiency of the resulting AuNP-AP[5]A thin films has been investigated for three different laser excitations (633, 785, and 830 nm) and using pyrene as Raman probe. The best performance was shown by the AuNP-AP[5]A film obtained with two deposition cycles ((AuNP-AP[5]A)2) when excited with a 785 laser line. The optical response and SERS efficiency of the thin films were also simulated using the M3 solver and employing computer aided design models built based on SEM images of the different films. The use of host molecules as building blocks to fabricate (AuNP-AP[5]A)2) films has enabled the ultradetection, in liquid and gas phase, of low molecular weight polyaromatic hydrocarbons, PAHs, with no affinity for gold but toward the hydrophobic AP[5]A cavity. Besides, these plasmonic platforms allowed achieving quantitative detection within certain concentration regimes. Finally, the multiplex sensing capabilities of the AuNP-AP[5]A)2 were evaluated for their ability to detect in liquid and gas phase three different PAHs.

Collective Plasmonic Properties in Few-Layer Gold Nanorod Supercrystals.

Gold nanorod supercrystals have been widely employed for the detection of relevant bioanalytes with detection limits ranging from nano- to picomolar levels, confirming the promising nature of these structures for biosensing. Even though a relationship between the height of the supercrystal (i.e., the number of stacked nanorod layers) and the enhancement factor has been proposed, no systematic study has been reported. In order to tackle this problem, we prepared gold nanorod supercrystals with varying numbers of stacked layers and analyzed them extensively by atomic force microscopy, electron microscopy and surface enhanced Raman scattering. The experimental results were compared to numerical simulations performed on real-size supercrystals composed of thousands of nanorod building blocks. Analysis of the hot spot distribution in the simulated supercrystals showed the presence of standing waves that were distributed at different depths, depending on the number of layers in each supercrystal. On the basis of these theoretical results, we interpreted the experimental data in terms of analyte penetration into the topmost layer only, which indicates that diffusion to the interior of the supercrystals would be crucial if the complete field enhancement produced by the stacked nanorods is to be exploited. We propose that our conclusions will be of high relevance in the design of next generation plasmonic devices.

Gold Nanorod-pNIPAM Hybrids with Reversible Plasmon Coupling: Synthesis, Modeling, and SERS Properties.

The thermoresponsive optical properties of Au nanorod-doped poly(N-isopropylacrylamide) (Au NR-pNIPAM) microgels with different Au NR payloads and aspect ratios are presented. Since the volume phase transition of pure pNIPAM microgels is reversible, the optical response reversibility of Au NR-pNIPAM hybrids is systematically analyzed. Besides, extinction cross-section and near-field enhancement simulations for Au NR-microgel hybrids are performed using a new numerical method based on the surface integral equation method of moments formulation (M3 solver). Additionally, the Au NR-microgel hybrid systems are expected to serve as excellent broadband surface-enhanced Raman scattering (SERS) substrates due to the temperature-controlled formation of hot spots and the tunable optical properties. The optical enhancing properties related to SERS are tested with three laser lines, evidencing excitation wavelength-dependent efficiency that can be easily controlled by either the aspect ratio (length/width) of the assembled Au NR or by the Au NR payload per microgel. Finally, the SERS efficiency of the prepared Au NR-pNIPAM hybrids is found to be stable for months.

Radial growth of plasmon coupled gold nanowires on colloidal templates.

The library of plasmonic nanosystems keeps expanding with novel structures with the potential to provide new solutions to old problems in science and technology. We report the synthesis of a novel plasmonic system based on the growth of gold nanowires radially branching from the surface of silica particles. The nanowires length could be controlled by tuning the molar ratio between metal salt and surface-grafted seeds. Electron microscopy characterization revealed that the obtained one-dimensional nanoparticles are polycrystalline but uniformly distributed on the spherical template. The length of the nanowires in turn determines the optical response of the metallodielectric particles, so that longer wires display red-shifted longitudinal plasmon bands. Accurate theoretical modeling of these complex objects revealed that the densely organized nanowires display intrinsically coupled plasmon modes that can be selectively decoupled upon detachment of the nanowires from the surface of the colloidal silica template.

Toward ultimate nanoplasmonics modeling.

Advances in the field of nanoplasmonics are hindered by the limited capabilities of simulation tools in dealing with realistic systems comprising regions that extend over many light wavelengths. We show that the optical response of unprecedentedly large systems can be accurately calculated by using a combination of surface integral equation (SIE) method of moments (MoM) formulation and an expansion of the electromagnetic fields in a suitable set of spatial wave functions via fast multipole methods. We start with a critical review of volume versus surface integral methods, followed by a short tutorial on the key features that render plasmons useful for sensing (field enhancement and confinement). We then use the SIE-MoM to examine the plasmonic and sensing capabilities of various systems with increasing degrees of complexity, including both individual and interacting gold nanorods and nanostars, as well as large random and periodic arrangements of ∼1000 gold nanorods. We believe that the present results and methodology raise the standard of numerical electromagnetic simulations in the field of nanoplasmonics to a new level, which can be beneficial for the design of advanced nanophotonic devices and optical sensing structures.