Implementation of plasmonic band structure to understand polariton hybridization within metamaterials.

Gap surface plasmons (GSPs) serve a diverse range of plasmonic applications, including energy harvesting, communications, molecular sensing, and optical detection. GSPs may be realized where tightly spaced plasmonic structures exhibit strong spatial overlap between the evanescent fields. We demonstrate that within similar, nested geometries that the near-fields of the GSPs within the individual nanostructures are hybridized. This creates two or more distinct resonances exhibiting near-field distributions extended over adjacent spatial regions. In contrast, dissimilar, nested structures exhibit two distinct resonances with nominally uncoupled near-fields, resulting in two or more individual antenna resonance modes. We deploy plasmonic band structure calculations to provide insight into the type and degree of hybridization within these systems, comparing the individual components. This understanding can be used in the optimized design of polaritonic metamaterial structures for desired applications.

Imaging of Anomalous Internal Reflections of Hyperbolic Phonon-Polaritons in Hexagonal Boron Nitride.

We use scanning near-field optical microscopy to study the response of hexagonal boron nitride nanocones at infrared frequencies, where this material behaves as a hyperbolic medium. The obtained images are dominated by a series of "hot" rings that occur on the sloped sidewalls of the nanocones. The ring positions depend on the incident laser frequency and the nanocone shape. Both dependences are consistent with directional propagation of hyperbolic phonon-polariton rays that are launched at the edges and zigzag through the interior of the nanocones, sustaining multiple internal reflections off the sidewalls. Additionally, we observe a strong overall enhancement of the near-field signal at discrete resonance frequencies. These resonances attest to low dielectric losses that permit coherent standing waves of the subdiffractional polaritons to form. We comment on potential applications of such shape-dependent resonances and the field concentration at the hot rings.

Low-loss, extreme subdiffraction photon confinement via silicon carbide localized surface phonon polariton resonators.

Plasmonics provides great promise for nanophotonic applications. However, the high optical losses inherent in metal-based plasmonic systems have limited progress. Thus, it is critical to identify alternative low-loss materials. One alternative is polar dielectrics that support surface phonon polariton (SPhP) modes, where the confinement of infrared light is aided by optical phonons. Using fabricated 6H-silicon carbide nanopillar antenna arrays, we report on the observation of subdiffraction, localized SPhP resonances. They exhibit a dipolar resonance transverse to the nanopillar axis and a monopolar resonance associated with the longitudinal axis dependent upon the SiC substrate. Both exhibit exceptionally narrow linewidths (7-24 cm(-1)), with quality factors of 40-135, which exceed the theoretical limit of plasmonic systems, with extreme subwavelength confinement of (λ(res)3/V(eff))1/3 = 50-200. Under certain conditions, the modes are Raman-active, enabling their study in the visible spectral range. These observations promise to reinvigorate research in SPhP phenomena and their use for nanophotonic applications.

Mie resonance-enhanced light absorption in periodic silicon nanopillar arrays.

Mie-resonances in vertical, small aspect-ratio and subwavelength silicon nanopillars are investigated using visible bright-field µ-reflection measurements and Raman scattering. Pillar-to-pillar interactions were examined by comparing randomly to periodically arranged arrays with systematic variations in nanopillar diameter and array pitch. First- and second-order Mie resonances are observed in reflectance spectra as pronounced dips with minimum reflectances of several percent, suggesting an alternative approach to fabricating a perfect absorber. The resonant wavelengths shift approximately linearly with nanopillar diameter, which enables a simple empirical description of the resonance condition. In addition, resonances are also significantly affected by array density, with an overall oscillating blue shift as the pitch is reduced. Finite-element method and finite-difference time-domain simulations agree closely with experimental results and provide valuable insight into the nature of the dielectric resonance modes, including a surprisingly small influence of the substrate on resonance wavelength. To probe local fields within the Si nanopillars, µ-Raman scattering measurements were also conducted that confirm enhanced optical fields in the pillars when excited on-resonance.

Hyperbolic and plasmonic properties of silicon/Ag aligned nanowire arrays.

The hyperbolic and plasmonic properties of silicon nanowire/Ag arrays have been investigated. The aligned nanowire arrays were formed and coated by atomic layer deposition of Ag, which itself is a metamaterial due to its unique mosaic film structure. The theoretical and numerical studies suggest that the fabricated arrays have hyperbolic dispersion in the visible and IR ranges of the spectrum. The theoretical predictions have been indirectly confirmed by polarized reflection spectra, showing reduction of the reflection in p polarization in comparison to that in s polarization. Studies of dye emission on top of Si/Ag nanowire arrays show strong emission quenching and shortening of dye emission kinetics. This behavior is also consistent with the predictions for hyperbolic media. The measured SERS signals were enhanced by almost an order of magnitude for closely packed and aligned nanowires, compared to random nanowire composites. These results agree with electric field simulations of these array structures.

Collective Phonon-Polaritonic Modes in Silicon Carbide Subarrays.

Localized surface phonon polaritons (LSPhPs) can be implemented to engineer light-matter interactions through nanoscale patterning for a range of midinfrared application spaces. However, the polar material systems studied to date have mainly focused on simple designs featuring a single element in the periodic unit cell. Increasing the complexity of the unit cell can serve to modify the resonant near-fields and intra- and inter-unit-cell coupling as well as to dictate spectral tuning in the far-field. In this work, we exploit more complicated unit-cell structures to realize LSPhP modes with additional degrees of design freedom, which are largely unexplored. Collectively excited LSPhP modes with distinctly symmetric and antisymmetric near-fields are supported in these subarray designs, which are based on nanopillars that are scaled by the number of subarray elements to ensure a constant unit-cell size. Moreover, we observe an anomalous mode-matching of the collective symmetric mode in our fabricated subarrays that is robust to changing numbers of pillars within the subarrays as well as to defects intentionally introduced in the form of missing pillars. This work therefore illustrates the hierarchical design of tailored LSPhP resonances and modal near-field profiles simultaneously for a variety of IR applications such as surface-enhanced spectroscopies and biochemical sensing.

Large-area plasmonic hot-spot arrays: sub-2 nm interparticle separations with plasma-enhanced atomic layer deposition of Ag on periodic arrays of Si nanopillars.

Initial reports of plasmonic 'hot-spots' enabled the detection of single molecules via surface-enhanced Raman scattering (SERS) from random distributions of plasmonic nanoparticles. Investigations of systems with near-field plasmonically coupled nanoparticles began, however, the ability to fabricate reproducible arrays of such particles has been lacking. We report on the fabrication of large-area, periodic arrays of plasmonic 'hot-spots' using Ag atomic layer deposition to overcoat Si nanopillar templates leading to reproducible interpillar gaps down to <2 nm. These plasmonic 'hot-spots' arrays exhibited over an order of magnitude increase in the SERS response in comparison to similar arrays with larger interpillar separations.

The effect of size and size distribution on the oxidation kinetics and plasmonics of nanoscale Ag particles.

We employed a simple and effective electroless (EL) plating approach to produce silver nanoparticles (NPs) on bare silicon, on dielectric ZnO nanowires (NWs) and on Si NWs, respectively. The surface stability of the homogeneous Ag NPs formed on the ZnO NW surfaces was investigated by surface enhanced Raman spectroscopy (SERS), which show that the attachment of thiol to the Ag surface can slow down the oxidation process, and the SERS signal remains strong for more than ten days. To further examine the Ag NP oxidation process in air, the oxygen content in the silicon nanowire core/Ag sheath composites was monitored by the energy dispersive x-ray (EDX) method. The amount of oxygen in the system increases with time, indicating the silver NPs were continuously oxidized, and it is not clear if saturation is reached in this time period. To investigate the influence of the Ag NPs size distribution on the oxidation process, the oxygen amount in the NPs formed by EL deposition and e-beam (EB) evaporation on a bare silicon surface was compared. Results indicate a faster oxidation process in the EL formed Ag NPs than those produced by EB evaporation. We attribute this observation to the small diameter of the EL produced silver particles, which results in a higher surface energy.

Plasmonic coupling on dielectric nanowire core-metal sheath composites.

We have developed dielectric core/metal sheath nanowire (NW) composites for surface-enhanced Raman scattering (SERS), in which an electroless (EL) Ag plating approach was employed. The NW surface was uniformly covered with a high density of 3D silver islands, having a diameter in the 20-30 nm range and spaced less than approximately 10 nm apart. In comparison with the silver deposition via e-beam evaporation, the EL coating approach has the advantage of full metal coverage of the NWs. This approach also provides a fast and simple way to completely cover any nanostructures with Ag, including nanowires, regardless of the orientation or shape. SERS measurements were performed using benzene thiol and the SERS signal strength of the EL-coated NW composites was significantly greater than expected, since the surface plasmon resonance (SPR) of 20 nm Ag nanospheres is weak and in the UV, while our measurements were performed using a 514.5 nm laser line. However, we have modeled this system using our electric field calculations and the results indicate that the strong SERS signal is due to plasmonic coupling of neighboring closely spaced islands, as well as an enhanced substrate effect. In addition, the nanowire core serves as a template for the formation of these small, closely spaced Ag islands, resulting in the strong SERS signal.

Atomic-scale photonic hybrids for mid-infrared and terahertz nanophotonics.

The field of nanophotonics focuses on the ability to confine light to nanoscale dimensions, typically much smaller than the wavelength of light. The goal is to develop light-based technologies that are impossible with traditional optics. Subdiffractional confinement can be achieved using either surface plasmon polaritons (SPPs) or surface phonon polaritons (SPhPs). SPPs can provide a gate-tunable, broad-bandwidth response, but suffer from high optical losses; whereas SPhPs offer a relatively low-loss, crystal-dependent optical response, but only over a narrow spectral range, with limited opportunities for active tunability. Here, motivated by the recent results from monolayer graphene and multilayer hexagonal boron nitride heterostructures, we discuss the potential of electromagnetic hybrids--materials incorporating mixtures of SPPs and SPhPs--for overcoming the limitations of the individual polaritons. Furthermore, we also propose a new type of atomic-scale hybrid--the crystalline hybrid--where mixtures of two or more atomic-scale (∼3 nm or less) polar dielectric materials lead to the creation of a new material resulting from hybridized optic phonon behaviour of the constituents, potentially allowing direct control over the dielectric function. These atomic-scale hybrids expand the toolkit of materials for mid-infrared to terahertz nanophotonics and could enable the creation of novel actively tunable, yet low-loss optics at the nanoscale.

Aspect-ratio driven evolution of high-order resonant modes and near-field distributions in localized surface phonon polariton nanostructures.

Polar dielectrics have garnered much attention as an alternative to plasmonic metals in the mid- to long-wave infrared spectral regime due to their low optical losses. As such, nanoscale resonators composed of these materials demonstrate figures of merit beyond those achievable in plasmonic equivalents. However, until now, only low-order, phonon-mediated, localized polariton resonances, known as surface phonon polaritons (SPhPs), have been observed in polar dielectric optical resonators. In the present work, we investigate the excitation of 16 distinct high-order, multipolar, localized surface phonon polariton resonances that are optically excited in rectangular pillars etched into a semi-insulating silicon carbide substrate. By elongating a single pillar axis we are able to significantly modify the far- and near-field properties of localized SPhP resonances, opening the door to realizing narrow-band infrared sources with tailored radiation patterns. Such control of the near-field behavior of resonances can also impact surface enhanced infrared optical sensing, which is mediated by polarization selection rules, as well as the morphology and strength of resonator hot spots. Furthermore, through the careful choice of polar dielectric material, these results can also serve as the guiding principles for the generalized design of optical devices that operate from the mid- to far-infrared.

A surface-enhanced Raman study of N-methylquinolinium tricyanoquinodimethanide adsorbed on Ag nanospheres: Determination of molecular orientation and order.

Quinolinium tricyanoquinodimethanides are among the most promising molecules for electronic applications. Disorder can be detrimental to the desired electronic properties of a monolayer, and as such, a reliable method to characterize a monolayer without destroying or creating defects is paramount to determining potential applications. Here, the normal and surface-enhanced Raman scattering spectra of N-methylquinolinium tricyanoquinodimethanide (CH3Q-3CNQ) on silver coated nanosurfaces have been obtained and analyzed. Theoretical treatment of CH3Q-3CNQ was performed. Optimization and frequency search was conducted using the B3LYP functional with the 6-31G(d) basis set. A complete list of frequencies and assignments for the molecules are presented. The spectroscopic evidence points to the fact that a monolayer of CH3Q-3CNQ can be formed through the self-assembly process, and the SERS data indicate that the monolayer attaches to the silver surface through the nitrile groups.

Determination of molecular orientation and order of N-(6-mercaptoacetylhexyl)quinolinium tricyanoquinodimethanide adsorbed on Ag nanoparticles.

The surface-enhanced and tip-enhanced Raman scattering spectra of N-(6-Mercaptoacetylhexyl)quinolinium tricyanoquinodimethanides on silver coated nanosurfaces have been obtained, analyzed using Density Functional Theory Calculations, and a complete list of frequencies and assignments for the molecules are presented. The spectroscopic evidence points to the fact that monolayers of the molecule can be formed through the self-assembly process and the SERS data indicate that the monolayer attach to the silver surface through the nitrile groups. SERS spectroscopy was useful in determining the orientation of the monolayer as well as estimating its order. Deprotection the thiol group thereby terminating the tail of the molecule with a sulfur atom allowed for a selectively oriented monolayer to be formed which permanently bound the molecules to the surface preventing rearrangements. This orientation of AcSC6H12Q-3CNQ on silver a surface allowed the electron pairs of the nitrogen to be available for interaction with a second contact. Based on trigonometric tangent function calculations the tilt angle was calculated to be 38° for the protected molecule and 70° for the deprotected alkane thiol monolayer.

Investigation of chemically modified barium titanate beads as surface-enhanced Raman scattering (SERS) active substrates for the detection of benzene thiol, 1,2-benzene dithiol, and rhodamine 6G.

SERS active surfaces were prepared by depositing silver films using Tollen's reaction on to barium titanate beads. The SERS activity of the resulting surfaces was probed using two thiols (benzene thiol and 1,2-benzene dithiol) and rhodamine 6G. The intensity of the SERS signal for the three analytes was investigated as a function of silver deposition time. The results indicate that the SERS intensity increased with increasing thickness of the silver film until a maximum signal intensity was achieved; additional silver deposition resulted in a decrease in the SERS intensity for all of the studied molecules. SEM measurement of the Ag coated barium titanate beads, as a function of silver deposition time, indicate that maximum SERS intensity corresponded with the formation of atomic scale islands of silver nanoparticles. Complete silver coverage of the beads resulted in a decreased SERS signal and the most intense SERS signals were observed at deposition times of 30 min for the thiols and 20 min for rhodamine 6G.

Surface-enhanced Raman scattering of a Ag/oligo(phenyleneethynylene)/Ag sandwich.

α,ω-Dithiols are a useful class of compounds in molecular electronics because of their ability to easily adsorb to two metal surfaces, producing a molecular junction. We have prepared Ag nanosphere/oligo(phenyleneethynylene)/Ag sol (AgNS/OPE/Ag sol) and Ag nanowire/oligo(phenyleneethynylene)/Ag sol (AgNW/OPE/Ag sol) sandwiches to simulate the architecture of a molecular electronic device. This was achieved by self-assembly of OPE on the silver nanosurface, deprotection of the terminal sulfur, and deposition of Ag sol atop the monolayer. These sandwiches were then characterized by surface-enhanced Raman scattering (SERS) spectroscopy. The resulting spectra were compared to the bulk spectrum of the dimer and to the Ag nanosurface/OPE SERS spectra. The intensities of the SERS spectra in both systems exhibit a strong dependence on Ag deposition time and the results are also suggestive of intense interparticle coupling of the electromagnetic fields in both the AgNW/OPE/Ag and the AgNS/OPE/Ag systems. Three previously unobserved bands (1219, 1234, 2037 cm(-1)) arose in the SER spectra of the sandwiches and their presence is attributed to the strong enhancement of the electromagnetic field which is predicted from the COSMOL computational package. The 544 cm(-1) disulfide bond which is observed in the spectrum of solid OPE but is absent in the AgNS/OPE/Ag and AgNW/OPE/Ag spectra is indicative of chemisorption of OPE to the nanoparticles through oxidative dissociation of the disulfide bond.

Plasmonic nanopillar arrays for large-area, high-enhancement surface-enhanced Raman scattering sensors.

Efforts to create reproducible surface-enhanced Raman scattering (SERS)-based chemical and biological sensors has been hindered by difficulties in fabricating large-area SERS-active substrates with a uniform, reproducible SERS response that still provides sufficient enhancement for easy detection. Here we report on periodic arrays of Au-capped, vertically aligned silicon nanopillars that are embedded in a Au plane upon a Si substrate. We illustrate that these arrays are ideal for use as SERS sensor templates, in that they provide large, uniform and reproducible average enhancement factors up to ∼1.2 × 10(8) over the structure surface area. We discuss the impact of the overall geometry of the structures upon the SERS response at 532, 633, and 785 nm incident laser wavelengths. Calculations of the electromagnetic field distributions and intensities within such structures were performed and both the wavelength dependence of the predicted SERS response and the field distribution within the nanopillar structure are discussed and support the experimental results we report.

Toward surface-enhanced Raman imaging of latent fingerprints.

Exposure to light or heat, or simply a dearth of fingerprint material, renders some latent fingerprints undetectable using conventional methods. We begin to address such elusive fingerprints using detection targeting photo- and thermally stable fingerprint constituents: surface-enhanced Raman spectroscopy (SERS). SERS can give descriptive vibrational spectra of amino acids, among other robust fingerprint constituents, and good sensitivity can be attained by improving metal-dielectric nanoparticle substrates. With SERS chemical imaging, vibrational bands' intensities recreate a visual of fingerprint topography. The impact of nanoparticle synthesis route, dispersal methodology-deposition solvent, and laser wavelength are discussed, as are data from enhanced vibrational spectra of fingerprint components. SERS and Raman chemical images of fingerprints and realistic contaminants are shown. To our knowledge, this represents the first SERS imaging of fingerprints. In conclusion, this work progresses toward the ultimate goal of vibrationally detecting latent prints that would otherwise remain undetected using traditional development methods.