Tip-Enhanced Raman Imaging and Nanospectroscopy: Sensitivity, Symmetry, and Selection Rules

The fundamental mechanisms of tip-enhanced Raman spectroscopy (TERS) have been investigated, including the role of the plasmonic excitation of the metallic tips, the nature of the optical tip–sample coupling, and the resulting local-field enhancement and confinement responsible for ultrahigh resolution imaging down to just several nanometers. Criteria for the distinction of near-field signature from far-field imaging artifacts are addressed. TERS results of molecules are presented. With enhancement factors as high as 10⁹, single-molecule spectroscopy is demonstrated. Spatially resolved vibrational mapping of crystalline nanostructures and determination of crystallographic orientation and domains is discussed making use of the symmetry properties of the tip scattering response and the intrinsic Raman selection rules.     

Nano-Raman Spectroscopy: Surface Plasmon Emission, Field Gradients, and Fundamentally Near Field Propagation Effects

Nano-Raman spectra differ from far-field Raman spectra. The differences result from a strong electric field gradient near the metal tip, propagation, and polarization, but the dependence upon probe-sample distance can only be explained by the inclusion of surface plasmons and the near-field, non-propagating terms of the dipole emission. A simple model based upon these components accurately describes distance-dependent data measured with a near-field scanning optical microscope. Our essentially near-field model will apply generally to Raman spectroscopy near a nanoscale conductor.     

Selective enhancement of Raman or fluorescence spectra of biomolecules using specifically annealed thick gold films

Annealing of "thick" metal films deposited onto a smooth dielectric substrate leads to high-order self-organization of metal clusters on the film surface. This work presents the first experimental evidence that the "thick" gold film (TGF) may be specifically annealed to serve as a substrate for surface-enhanced fluorescence or surface-enhanced Raman scattering (SERS) spectroscopy of the same molecule. High-resolved SERS spectra of mitoxantrone (mitox) were recorded on the TGF annealed at 340 degrees C whereas no Raman enhancement but an increase of mitox fluorescence signal were detected on the TGF annealed at 240 degrees C. The mitox fluorescence was further enhanced by deposition of monolayers of pentanethiol or poly-L-lysine on the surface of annealed TGF. The maximal fluorescence enhancement factor per mitox molecule of approximately 50 that was obtained on the annealed TGF covered with poly-L-lysine makes the system promising for applications in immunofluorescence assays and in microspectrofluorescence analysis.     

Optical Near-Field Enhancement with Graphene Bowtie Antennas

In this paper, the optical near-field enhancement of graphene bowtie antennas is numerically investigated at terahertz frequencies using boundary element method. The enhanced field intensity at the gap region is a result of the mutual coupling between two triangular elements upon the excitation of graphene plasmons. Firstly, wide plasmon frequency tunability is demonstrated by changing the chemical potential of graphene without the need to alter the antenna geometry. Secondly, by varying the tip angle and radius of curvature of the graphene antennas, the field intensity enhancement at the gap center of the two-element antennas is systematically studied. It is found that graphene bowtie antennas with two round-cornered equilateral triangles have superior performance to other two-element antennas, such as ribbon pair, sharp-cornered bowtie, and disk pair antennas. Last but not least, by applying a moderate chemical potential of 0.4 eV to graphene bowtie antennas, we found that the field intensity enhancement at gap center is about 220 times as much as using gold of comparable sizes. In short, graphene bowtie antennas of rounded corners give rise to considerable near-field enhancement and are promising for a wide range of applications such as molecular sensing at terahertz frequencies.

     

Plasmonic Enhancement of Fluorescence and Raman Scattering by Metal Nanotips

We report modifications to the optical properties of fluorophores in the vicinity of noble metal nanotips. The fluorescence from small clusters of quantum dots has been imaged using an apertureless scanning near-field optical microscope. When a sharp gold tip is brought close to the sample surface, a strong distance-dependent enhancement of the quantum dot fluorescence is observed, leading to a simultaneous increase in optical resolution. These results are consistent with simulations of the electric field and fluorescence enhancement near plasmonic nanostructures. Highly ordered periodic arrays of silver nanotips have been fabricated by nanosphere lithography. Using fluorescence lifetime imaging microscopy, we have created high-resolution spatial maps of the lifetime components of vicinal fluorophores; these show an order of magnitude increase in decay rate from a localized volume around the nanotips, resulting in a commensurate enhancement in the fluorescence emission intensity. Spatial maps of the Raman scattering signal from molecules on the nanotips shows an enhancement of more than five orders of magnitude.     

Tunable Broadband Optical Responses of Substrate-Supported Metal/Dielectric/Metal Nanospheres

Using the image charge theory and finite element methods, we present the first comprehensive study on the optical properties of substrate-supported, three-layer, metal/dielectric/metal nanospheres. By adopting dipolar and quadrupolar approximations of the quasistatic image charge theory, we derive analytical expressions for the polarization-dependent polarizabilities of a three-layer nanosphere near a substrate and use them to find the nanosphere’s plasmon resonance wavelengths as functions of the geometric and material parameters of the nanosphere–substrate system. By calculating the resonance wavelength of substrate-supported gold/silica/gold nanosphere over a sufficiently large domain of the nanosphere’s dimensions, we show that this wavelength can be tuned from visible to infrared regions by altering only the size of the nanosphere’s core. We also show that the resonance position as well as the enhancement and confinement of the near-field can be dynamically tuned over broad ranges by changing the polarization of the excitation light. Of significance for the applicability of our results in practice is that we employ size-dependent permittivity of gold, which allows experimentalists to readily produce these substrate-supported nanospheres with desired optical responses. Upon comparing our analytical results with the results of numerical simulations, we reveal the range of the nanospheres’ outer radii within which the dipolar and quadrupolar approximations adequately describe the nanosphere–substrate interaction. Since majority of the optical functions are realized with light polarized parallel to the substrate, our results allow one to readily engineer the broadband optical responses of substrate-supported metal/dielectric/metal nanospheres for applications in resonance-enhanced sensing, in light harvesting, and in biomedicine.     

Antenna-Attached Parabolic Probe for Excitation and Collection Modes in SNOM

A novel optical fiber probe with a parabola-like shape and a nano-antenna mounted on the center of its endface is proposed for simultaneous excitation and collection modes in scanning near-field optical microscopy. The working principles of the probe are demonstrated, and its optical properties are theoretically investigated and compared with the conventional tip-on-aperture probe. It shows that the probe can greatly boost both the enhancement factor for the excitation mode and the collection efficiency for the collection mode. The proposed probe is a promising tool to realize low-cost and high resolution for a wide variety of near-field measurements in biology, physics, and chemistry.     

A Facile Strategy for All-Optical Controlling Platform by Using Plasmonic Perfect Absorbers

Dual-band light absorption with the maximal absorptivity up to 99.7% and the minimal spectral bandwidth down to 3 nm is obtained in the plasmonic absorbers consisting of triple-layer plasmonic crystal-nonlinear medium cavity-metal substrate structure, where the intercalated dielectric material is chosen to be a Kerr medium cavity. Efficient all-optical controlling with high spectral intensity change ratios and detecting signal-to-noise is achieved for the system after a slight increase of pumping intensity. These impressive results mainly result from the strong plasmonic resonant field confinement in the middle nonlinear Kerr medium cavity and the near-perfect relative intensity change response by the ultra-sharp anti-reflection spectrum. This work can lay a foundation for advanced all-optical devices by exploiting light perfect absorption behavior and resonant optical field enhancement.     

Visualization of Near-Field Enhancements of Gold Triangles by Nonlinear Photopolymerization

We report in this paper the near-field distribution in the case of gold triangle arrays by means of two-photon polymerization for a dipole and a quadrupole plasmon mode. In order to link the finite difference in the time domain (FDTD) simulations of the triangle array and the experimental results, extinction spectra for both cases in air and SU-8 environments are shown. In case of the 40-nm thick gold triangles with 85-nm side-length, we show that the calculated and experimentally obtained near-field for the excited dipole mode has the same distribution along the polarization of the exciting laser beam. In case of bigger triangles of 540-nm side-length a quadrupole mode is excited, which leads to a rotation of the near-field distribution by 90° referred to the polarization of the beam. This effect is also shown in the FDTD simulations.     

Single cell analysis using surface enhanced Raman scattering (SERS) tags

Fluorescence is a mainstay of bioanalytical methods, offering sensitive and quantitative reporting, often in multiplexed or multiparameter assays. Perhaps the best example of the latter is flow cytometry, where instruments equipped with multiple lasers and detectors allow measurement of 15 or more different fluorophores simultaneously, but increases beyond this number are limited by the relatively broad emission spectra. Surface enhanced Raman scattering (SERS) from metal nanoparticles can produce signal intensities that rival fluorescence, but with narrower spectral features that allow a greater degree of multiplexing. We are developing nanoparticle SERS tags as well as Raman flow cytometers for multiparameter single cell analysis of suspension or adherent cells. SERS tags are based on plasmonically active nanoparticles (gold nanorods) whose plasmon resonance can be tuned to give optimal SERS signals at a desired excitation wavelength. Raman resonant compounds are adsorbed on the nanoparticles to confer a unique spectral fingerprint on each SERS tag, which are then encapsulated in a polymer coating for conjugation to antibodies or other targeting molecules. Raman flow cytometry employs a high resolution spectral flow cytometer capable of measuring the complete SERS spectra, as well as conventional flow cytometry measurements, from thousands of individual cells per minute. Automated spectral unmixing algorithms extract the contributions of each SERS tag from each cell to generate high content, multiparameter single cell population data. SERS-based cytometry is a powerful complement to conventional fluorescence-based cytometry. The narrow spectral features of the SERS signal enables more distinct probes to be measured in a smaller region of the optical spectrum with a single laser and detector, allowing for higher levels of multiplexing and multiparameter analysis.     

Electromagnetic Enhancement Effect Caused by Aggregation on SERS-Active Gold Nanoparticles

We report a morphology-correlated surface-enhanced Raman scattering (SERS) from molecules on the surface of individual clusters of gold nanoparticles of two types and compare the signal from clusters of two, three, four, and five nanoparticles with the signal from single particles. Cluster geometry and particle morphology are determined from transmission electron microscopy for both clusters of 78- to 133-nm nanospheres and clusters of ~250-nm-etched cylindrical particles with crevices and sharp edges, formed in templates. Scattering from molecules on etched cylinders, but not spheres, is sufficiently strong to allow spectra to be collected from single particles illuminated at 632.8 nm. SERS intensities from clusters of cylinders are found to scale linearly with particle number, whereas, for nanospheres, the scaling is non-linear. The linear scaling of SERS from cylinders is a reflection of the high enhancement provided by the sharp features of the individual particles; whereas, the non-linear scaling of SERS from clusters of spheres is found to be consistent with the near-field enhancement from inter-particle coupling simulated for clusters of spheres arranged in representative-observed geometries.     

Characterization of multilayer-enhanced surface-enhanced raman scattering (SERS) substrates and their potential for SERS nanoimaging

Multilayer gold surface-enhanced Raman scattering (SERS) substrates, which consist of continuous gold films that are separated by self-assembled monolayers (SAMs) and cast over 430-nm diameter silica nanospheres on a glass slide, have been evaluated as a means of further enhancing the SERS signals produced from conventional metal film over nanostructure substrates. Evaluation of the effect of various SAMs, with different terminal functional groups, on the SERS enhancement factor were measured and compared to conventional single-layer gold film over nanostructure substrates, revealing relative enhancements as great as 22.4-fold in the case of 2-mercapto-ethanol spacer layers. In addition to evaluation of the effect of different terminal functionalities, the effect of spacer length was also investigated, revealing that the shorter chain length alcohols provided the greatest signals. Employing the optimal SERS multilayer geometry, SERS nanoimaging probes were fabricated and the SERS enhancement factor and variability in enhancement factor were measured over the SERS active imaging area, providing absolute enhancements similar to previous silver-based SERS nanoimaging probes (i.e., 1.2 × 10⁸). Varying the size of the multilayer gold islands that were deposited on the tip of the SERS active nanoimaging probe, it is possible to tune the optimal SERS excitation wavelength accurately and predictably over the range of approximately 450 to 600 nm, without coating the entire surface of the probe and significantly reducing the transmission and resulting signal-to-noise ratio of the images obtained.     

Improvement of Transparent Metal Top Electrodes for Organic Solar Cells by Introducing a High Surface Energy Seed Layer

We present highly transparent and conductive silver thin films in a thermally evaporated dielectric/metal/dielectric (DMD) multilayer architecture as top electrode for efficient small molecule organic solar cells. DMD electrodes are frequently used for optoelectronic devices and exhibit excellent optical and electrical properties. Here, we show that ultrathin seed layers such as calcium, aluminum, and gold of only 1 nm thickness strongly influence the morphology of the subsequently deposited silver layer used as electrode. The wetting of silver on the substrate is significantly improved with increasing surface energy of the seed material resulting in enhanced optical and electrical properties. Typically thermally evaporated silver on a dielectric material forms rough and granular layers which are not closed and not conductive below thicknesses of 10 nm. With gold acting as seed layer, the silver electrode forms a continuous, smooth, conductive layer down to a silver thickness of 3 nm. At 7 nm silver thickness such an electrode exhibits a sheet resistance of 19 Ω/□ and a peak transmittance of 83% at 580 nm wavelength, both superior compared to silver electrodes without seed layer and even to indium tin oxide (ITO). Top‐illuminated solar cells using gold/silver double layer electrodes achieve power conversion efficiencies of 4.7%, which is equal to 4.6% observed in bottom‐illuminated reference devices employing conventional ITO. The top electrodes investigated here exhibit promising properties for semitransparent solar cells or devices fabricated on opaque substrates.     

Plasmonics Effects of Nanometal Embedded in a Dielectric Substrate

We numerically report on first realization of near-field interaction and localized surface Plasmon resonance of a pair of silver-shell nanospheres with different dielectric holes embedded in a dielectric substrate using finite element method. An electromagnetic mode different from the solid case of the same volume is excited inside and outside the shell surface, resulting in an intensity enhancement in a gap of particle pair surrounding the particle–substrate interface. We find that the embedded depth of the nanoparticles pair in a substrate will influence the position of the localized fields which is confined in the gap. Besides, the near-field intensity becomes less intense and the spectrum of peak resonances red-shifted as the index difference of interface and embedded depth decreases. The proposed models have been prepared to cover the ultraviolet-visible, visible, and near-infrared (NIR) regions with application to sensors and spectroscopy purposes by varying the embedded depth and pertinent to the functionality of sensors, spectroscopy, and other optical devices.     

Near- and Far-Field Plasmonic Properties of Different Types of Eccentric Core-Shell Nanodimers

Finite element method (FEM) simulations have been carried out on free-standing and finite dielectric substrate-supported eccentric (i) silica core-gold nanoshell dimers and (ii) gold core-silica nanoshell dimers for understanding their near- and far-field plasmonic properties. In the case of eccentric silica core-gold nanoshell dimers, multiple peaks are observed in the near- and far-field spectra due to the plasmon hybridization. The number of peaks is found to be sensitive to the core offset parameters of the nanoshells forming nanodimer. The wavelength locations of the peaks due to the constructive coupling of the lower order modes found relatively more sensitive to the dielectric substrate. The number of peaks in the near- and far-field spectra found the same presence and absence of the dielectric substrate. The values of full width at half maximum (FWHM) of the peaks observed in the near-field spectra are found larger as compared to those observed in the far-field spectra. In contrast, in the case of eccentric gold core-silica nanoshell dimers, multiple peaks have not been observed. The FWHM of the observed peak is found sensitive to the core offset parameters of the nanoshells, and the number of peaks in the near field- and far-field spectra found not same in the presence and absence of the dielectric substrate. Moreover, the differences in near- and far-field spectra of plasmonically coupled (i) concentric nanoshells, (ii) eccentric nanoshells, and (iii) concentric and eccentric nanoshells also investigated numerically.

     

Surface-Enhanced Resonance Raman Scattering (SERRS) Using Au Nanohole Arrays on Optical Fiber Tips

Circular and bow tie-shaped Au nanoholes arrays were fabricated on gold films deposited on the tips of single-mode optical fibers. The nanostructures were milled using focused ion beam with a high quality control of their shapes and sizes. The optical fiber devices were used for surface-enhanced resonance Raman scattering (SERRS) measurements in both back- and forward-scattering geometries, yielding promising performance in both detection arrangements. The effect of the hole shape on the SERRS performance was explored with the bow tie nanostructures presenting a better SERRS performance than the circular holes arrays. The results present here are another step towards the development of optical fiber tips modified with plasmonic nanostructures for SERRS applications.

Dependence of Apertureless Scanning Near-Field Spectroscopy on Nanoscale Refractive Index Changes

We numerically investigate the spectral dependence of the electric field enhancement on a gold tip above PbTiO₃ on platinum systems by means of a finite element approach. The localized surface plasmon resonance (LSPR) is verified to change with the incident angle, the tip radius, and the tip-sample distance as well as with the refractive index of the sample underneath the tip. The refractive index sensitivity reveals detectable variations of the LSPR peak’s wavelength and maximum field enhancement, respectively, large enough to discriminate, e.g., between ferroelectric and paraelectric PbTiO₃ in tip-enhanced Raman spectroscopy (TERS) configuration.     

Optical Absorption in Overcoats of Nanoparticle Arrays on a Metallic Substrate

Surface plasma oscillations in metallic particles as well as in thin metallic films have been studied extensively in the past decades. New features regarding surface plasma excitations are, however, constantly discovered, leading, for example, to surface-enhanced Raman scattering studies and enhanced optical transmission though metal films with nanohole arrays. In the present work, the role of a metallic substrate is examined in two cases, one involving an overcoat of dielectric nanoparticles and the other an overcoat of metallic nanoparticles. Theoretical results are obtained by modeling the nanoparticles as forming a two-dimensional, hexagonal lattice of spheres. The scattered electromagnetic field is then calculated using a variant of the Green function method. Comparison with experimental results is made for nanoparticles of tungsten oxide and tin oxide deposited on either gold or silver substrates, giving qualitative agreement on the extra absorption observed when the dielectric nanoparticles are added to the metallic surfaces. Such absorption would be attributed to the mirror image effects between the particles and the substrate. On the other hand, calculations of the optical properties of silver or gold nanoparticle arrays on a gold or a silver substrate demonstrate very interesting features in the spectral region from 400 to 1,000 nm. Interactions between the nanoparticle arrays surface plasmons and their images in the metallic substrate would be responsible for the red shift observed in the absorption resonance. Moreover, effects of particle size and ambient index of refraction are studied, showing a great potential for applications in biosensing with structures consisting of metallic nanoparticle arrays on metallic substrates.     

Gold Nanowire and Nanorod Plasmonic Mechanisms for Increasing Ultra-Thin Organic Photovoltaic Active Layer Absorption

We theoretically investigate the effect of incorporating gold cylindrical- and ellipsoidal-shaped nanowires and gold nanorods situated centrally within the active layer of organic bulk-heterojunction photovoltaic devices, on the optical absorption performance using finite element electromagnetic simulations. Gold cylindrical nanowire-embedded devices show increased active layer absorption enhancement with increasing radius; however, this effect decreases with the introduction of a polystyrene dielectric capping layer around the nanowires. Active layer absorption, with respect to changes in the orientation, aspect ratio, periodicity, and spacing between ellipsoidal nanowires were optimized. A maximum absorption enhancement weighted by AM 1.5 solar spectrum of 17 % is predicted for gold ellipsoidal nanowires of aspect ratio of 1.167 with in-plane horizontal orientation and arranged with periodicity of 35 nm within a 30-nm thin active layer. We attribute this enhancement primarily to interparticle electromagnetic coupling between adjacent nanowires, where, a maximum spatial and spectral overlap of the electromagnetic field with the absorption band of the active layer material is achieved. This effect increases with decreasing aspect ratio as well as decreasing periodicity with a trade-off observed between nanowire packing density and the active layer absorption enhancement. For gold nanorod-embedded organic photovoltaic devices, the inter-particle electromagnetic coupling effects are weaker and longitudinal surface–plasmon resonances supported by the nanorods are more pronounced. However, since the longitudinal surface–plasmon resonances occur at wavelengths greater than the absorption edge of the photovoltaic active layer, a mere 3.4 % increase in absorption enhancement is achieved for the photovoltaic device incorporating gold nanorods with aspect ratio of 1.167 and periodicity of 35 nm.