Developments in and practical guidelines for tip-enhanced Raman spectroscopy

This feature review provides an overview of the state-of the art and recent developments in tip-enhanced Raman spectroscopy (TERS), in-depth information about the different available types of instruments including their (dis-)advantages and capabilities as well as a short glance at a number of samples that have recently been investigated using TERS. Issues concerning the progression of TERS from point spectroscopy to an imaging technique are discussed, as well as problems arising from background and contamination signals. This review is concluded with a short TERS 'user guideline', trying to aid researchers new in the field to properly align and test their own TERS setups. Finally, a short outlook is given and some critical issues are raised that need to be solved by the community sooner or later, in order to promote TERS towards a 'push-button' operation.     

Enhanced Terbium Emission Due to Plasmonic Silver Nanoparticles in Bismuth Silicate

A simple way to select a suitable host material, when doped with any rare‐earth (RE) ion and incorporated with silver nanoparticles (NPs), to cause overlap between an excitation band of the RE ions and the localized surface plasmon resonance (LSPR) of the metallic NPs to study possible plasmonic enhancement is presented using Mie theory calculations. Unlike in previous studies, plasmonic enhancement was studied in a crystalline host instead of amorphous hosts. Bismuth silicate was synthesized using the sol–gel method and successfully doped with only terbium or silver, or co‐doped with terbium and silver. The formation of silver NPs was investigated using diffuse reflectance spectroscopy, transmission electron microscopy, and Auger electron spectroscopy (AES). Luminescence properties of the terbium‐doped bismuth silicate containing silver NPs were explored in detail and an enhancement of the emission from terbium ions at 545 nm when excited at 485 nm of about 2.5 times is attributed to amplification of the electric field associated with the LSPR of the silver NPs.     

Comparative study of a Surface Plasmon Resonance Biosensor based on Metamaterial and Graphene

In this study, a surface plasmon resonance biosensor at near infrared frequency based on a metamaterial is proposed. The proposed biosensor utilizes the properties of plasmons and metamaterial for enhancement of its performance parameters i.e. sensitivity, detection accuracy and quality factor. The thickness of the metamaterial and gold film has been optimized for optimal performance of the proposed biosensor at near infrared wavelengths. Results obtained from the proposed biosensor were compared with existing two-dimensional nanomaterials such as a graphene based biosensor and a conventional surface plasmon resonance biosensor. Finally, it is observed that the performance parameters of the proposed biosensor are very high when compared to existing surface plasmon resonance biosensors.     

Plasmonic molecular nanohybrids-spectral dependence of fluorescence quenching

We demonstrate strong spectral dependence of the efficiency of fluorescence quenching in molecular systems composed of organic dyes and gold nanoparticles. In order to probe the coupling with metallic nanoparticles we use dyes with varied spectral overlap between the plasmon resonance and their absorption. Hybrid molecular structures were obtained via conjugation of metallic nanoparticles with the dyes using biotin-streptavidin linkage. For dyes featuring absorption above the plasmon excitation in gold nanoparticles, laser excitation induces minute changes in the fluorescence intensity and its lifetime for both conjugated and non-conjugated mixtures, which are the reference. In contrast, when the absorption of the dye overlaps with the plasmon resonance, the effect is quite dramatic, reaching 85% and 95% fluorescence quenching for non-conjugated and conjugated mixtures, respectively. The degree of fluorescence quenching strongly depends upon the concentration of metallic nanoparticles. Importantly, the origin of the fluorescence quenching is different in the case of the conjugated mixture, as evidenced by time-resolved fluorescence. For conjugated mixtures of dyes resonant with plasmon, excitation features two-exponential decay. This is in contrast to the single exponential decay measured for the off-resonant configuration. The results provide valuable insight into spectral dependence of the fluorescence quenching in molecular assemblies involving organic dyes and metallic nanoparticles.     

Metallic nano-particles for trapping light

We study metallic nano-particles for light trapping by investigating the optical absorption efficiency of the hydrogenated amorphous silicon thin film with and without metallic nano-particles on its top. The size and shape of these nano-particles are investigated as to their roles of light trapping: scattering light to the absorption medium and converting light to surface plasmons. The optical absorption enhancement in the red light region (e.g., 650nm) due to the light trapping of the metallic nano-particles is observed when a layer of metallic nano-particle array has certain structures. The investigation of the light with incident angles shows the importance of the coupling efficiency of light to surface plasmons in the metallic nano-particle light trapping.

PACS

73.20.Mf, 42.25.s, 88.40.hj     

Plasmon features in electron energy loss spectra from carbon materials

A phenomenological approach is proposed to derive plasmon energies for C materials as a function of mass density ρ and sp² fraction f. It is shown that the energy of the graphite in-plane (π and π + σ) and out-of-plane plasmons, as well as the energy of the diamond bulk (σ) plasmon are correctly reproduced by the model. Crucial factors in this respect - and responsible for the deviation from a free electron picture - are the energy of interband transitions associated with plasmon excitation and the screening of π electrons due to σ electron polarization. Plasmon energies, derived as a function of ρ and f, are discussed.     

Dark-field microscopy studies of polarization-dependent plasmonic resonance of single gold nanorods: rainbow nanoparticles

Orientation sensors require the monitoring of polarization-dependent surface plasmons of single nanoparticles. Herein, we present both the longitudinal and transverse surface plasmonic resonance from a single gold nanorod (AuNR) using conventional dark-field microscopy. The relative peak intensities of the transverse and longitudinal surface plasmons of a single AuNR can be successfully tuned by polarized excitation, which is an important step towards the use of transverse plasmon resonance of single AuNRs without photo-induced reshaping of nanoparticles. More interestingly, compared with AuNRs with small diameters, unique optical properties from AuNRs with diameters greater than 30 nm are revealed. As a result, optical images with different colors, rainbow nanoparticles (sea green, brown, red, yellow and green), depending on the polarization angle, can be revealed by a single AuNR. This result holds great promise for polarization-controlled colorimetric nanomaterials and single particle tracers in living cells and microfluidic flows.     

Photoluminescence decay rate of silicon nanoparticles modified with gold nanoislands

We investigated plasmon-assisted enhancement of emission from silicon nanoparticles (ncs-Si) embedded into porous SiO _x matrix in the 500- to 820-nm wavelength range. In the presence in the near-surface region of gold nanoisland film, ncs-Si exhibited up to twofold luminescence enhancement at emission frequencies that correspond to the plasmon resonance frequency of Au nanoparticles. Enhancement of the photoluminescence (PL) intensity was attributed to coupling with the localized surface plasmons (LSPs) excited in Au nanoparticles and to increase in the radiative decay rate of ncs-Si. It has been shown that spontaneous emission decay rate of ncs-Si modified by thin Au film over the wide emission spectral range was accelerated. The emission decay rate distribution was determined by fitting the experimental decay curves to the stretched exponential model. The observed increase of the PL decay rate distribution width for the Au-coated nc-Si-SiO _x sample in comparison with the uncoated one was explained by fluctuations in the surface-plasmon excitation rate.

PACS

78. 67. Bf; 78.55.-m     

Tip-enhanced Raman spectroscopy reveals rich nanoscale adsorption chemistry of 2-mercaptopyridine on Ag

Adsorption of 2-mercatopyridine (2MPy) on Ag surfaces was studied by tip-enhanced Raman spectroscopy (TERS), which allows the measurement of Raman spectra with nanometer scale spatial resolution on flat surfaces that themselves do not show any surface-enhancement Raman scattering (SERS) activity. We found that the adsorption behavior of 2MPy was affected by the parameters of the preparation for the adsorbate layers, i.e., solution concentration, solution volume, and the exposure time. Besides that, variation of the TERS spectra at randomly chosen sample positions was observed. Only some of the bands appearing in SERS experiments showed up in each TERS measurement. We propose that this is caused by different local adsorption behavior of 2MPy on the Ag surfaces. This observation perfectly demonstrates the advantage of TERS over SERS, i.e., TERS can give localized chemical information on the nanometer scale, whereas SERS can only afford average spectra with micrometer scale resolution. Finally, TERS mapping with a spatial resolution of 24 nm was demonstrated.     

Two-dimensional ultrathin gold film composed of steadily linked dense nanoparticle with surface plasmon resonance

Background

Noble metallic nanoparticles have prominent optical local-field enhancement and light trapping properties in the visible light region resulting from surface plasmon resonances.

Results

We investigate the optical spectral properties and the surface-enhanced Raman spectroscopy of two-dimensional distinctive continuous ultrathin gold nanofilms. Experimental results show that the one- or two-layer nanofilm obviously increases absorbance in PEDOT:PSS and P3HT:PCBM layers and the gold nanofilm acquires high Raman-enhancing capability.

Conclusions

The fabricated novel structure of the continuous ultrathin gold nanofilms possesses high surface plasmon resonance properties and boasts a high surface-enhanced Raman scattering (SERS) enhancement factor, which can be a robust and cost-efficient SERS substrate. Interestingly, owing to the distinctive morphology and high light transmittance, the peculiar nanofilm can be used in multilayer photovoltaic devices to trap light without affecting the physical thickness of solar photovoltaic absorber layers and yielding new options for solar cell design.     

Surface-Enhanced Raman Scattering on Silver Nanoparticles in Different Aggregation Stages

Enhancement factors of surface-enhanced Raman scattering (SERS) are compared for crystal violet attached to 15–60-nm-sized colloidal silver particles in various aggregation stages using 830 nm and 407 nm laser excitation. Enhancement factors on the order of 10⁶–10⁷ have been measured at 407 nm excitation for molecules adsorbed on spatially-isolated silver spheres exhibiting strong, sharp, single-sphere plasmon resonance at 395 nm. Extremely large SERS enhancement factors on the order of 10¹⁴ are obtained at near infrared excitation for molecules on clusters built from colloidal particles. The SERS enhancement factor is demonstrated to be independent of the size of the clusters. The increase of SERS enhancement factors by 7–8 orders of magnitude by the formation of aggregates, as well as the extremely small density of “hot sites” exhibiting this high level of enhancement, provide further strong arguments for the electromagnetic origin of the hot spots and for strongly enhanced local optical fields as a key effect in SERS at an extremely high enhancement level.     

Studying the local character of Raman features of single-walled carbon nanotubes along a bundle using TERS

Here, we show that the Raman intensity of the G-mode in tip-enhanced Raman spectroscopy (TERS) is strongly dependent on the height of the bundle. Moreover, using TERS we are able to position different single-walled carbon nanotubes along a bundle, by correlating the observed radial breathing mode (RBM) with the AFM topography at the measuring point. The frequency of the G^- mode behaves differently in TERS as compared to far-field Raman. Using the RBM frequency, the diameters of the tubes were calculated and a very good agreement with the G^- -mode frequency was observed.     

Noble metal nanocrystals: plasmon electron transfer photochemistry and single-molecule Raman spectroscopy

The excited electronic states of noble metal Au and Ag nanocrystals are very different than those of molecules. Ag and Au nanocrystal optical transitions (plasmons) in the visible can be so intense that they significantly modify the local electromagnetic field. Also, coherent elastic Rayleigh light scattering is stronger than normal electronic absorption of photons for larger nanocrystals. These two facts make Au and Ag nanocrystals ideal nanoantennas, in that they focus incident light into the local neighborhood of subwavelength size. Surface-enhanced Raman scattering (SERS), in which the Raman scattering rate of nearby molecules increases by many orders of magnitude, is a consequence of this nanoantenna effect. Metallic nanocrystals also have no band gap; this makes them extraordinarily polarizable. Their electronic transitions sense the local environment. An extreme case is the interaction of two 30 nm Ag nanocrystals separated by a 1 nm gap. Their mutual polarization completely transforms the nature of the metallic excited electronic state. Single particles have an excited state uniformly distributed throughout the interior, while the nanocrystal dimer has its excited state localized on the metal surface in the junction. This creates an electromagnetic "hot spot" in the junction, enabling the observation of single-molecule SERS. The fact that surface molecules are typically chemisorbed and exchange electrons with the metal has interesting chemical consequences. First, the enhanced Raman intensities are controlled by quantum mechanical coupling of the molecular lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) with the optically excited electrons in the metal. Second, charge-transfer photochemistry can result from metal plasmon excitation. In crystalline Ag nanocrystals the photochemistry quantum yield can be high because the nanocrystal surface dominates plasmon nonradiative relaxation. Colloidal Ag nanocrystals stabilized by sodium citrate build up a photovoltage under visible excitation, caused by irreversible "hot hole" photo-oxidation of adsorbed citrate anion. This creates a driving force for photochemical transformation of round 8 nm Ag seeds into 70 nm single-crystal disk prisms under room lights, in a novel type of light-driven Ostwald ripening.     

Nanoplasmonic sensing of metal-halide complex formation and the electric double layer capacitor

Many nanotechnological devices are based on implementing electrochemistry with plasmonic nanostructures, but these systems are challenging to understand. We present a detailed study of the influence of electrochemical potentials on plasmon resonances, in the absence of surface coatings and redox active molecules, by synchronized voltammetry and spectroscopy. The experiments are performed on gold nanodisks and nanohole arrays in thin gold films, which are fabricated by improved methods. New insights are provided by high resolution spectroscopy and variable scan rates. Furthermore, we introduce new analytical models in order to understand the spectral changes quantitatively. In contrast to most previous literature, we find that the plasmonic signal is caused almost entirely by the formation of ionic complexes on the metal surface, most likely gold chloride in this study. The refractometric sensing effect from the ions in the electric double layer can be fully neglected, and the charging of the metal gives a surprisingly small effect for these systems. Our conclusions are consistent for both localized nanoparticle plasmons and propagating surface plasmons. We consider the results in this work especially important in the context of combined electrochemical and optical sensors.     

Ab initio Modelling of Plasmons in Metal-semiconductor Bilayer Transition-metal Dichalcogenide Heterostructures

Two-dimensional transition-metal dichalcogenides (TMDs) have attracted enormous interest, due to the richness of their optical and electronic properties. Here, we consider two prototypical two-dimensional TMD metal-semiconductor bilayer heterostructures, VSe₂-MoSe₂ and VSe₂-WSe₂, and investigate the effect of the semiconducting layer on the plasmons supported by the metallic layer using first principles time-dependent density functional theory (TDDFT) calculations. We focus on the flat region of the plasmon dispersion, where momentum transfer is larger than 0.05 Å⁻¹ and the interband transitions gain importance. With the addition of the semiconducting layer, we show that the electronic band structure undergoes significant changes close to the Fermi level, and hybridization occurs, which leads to strengthening of the interband transitions and a significant redshift in the plasmon energy.     

Multiple metallic-shell nanocylinders for surface-enhanced spectroscopes

The optical properties of multiple dielectric-core-gold-shell nanocylinder pairs are investigated by two-dimensional finite difference time domain method. The core-shell cylinders are assumed to be of the same dimension and composition. For normal incidence, the diffraction spectra of multiple cylinder pairs contain the lightning-rod plasmon mode, and the electric field intensity is concentrated in the gap between the nanocylinder pairs in the infrared region. The resonance wavelength and local field enhancement of this plasmon mode can be tuned by varying the pair-distance between the pairs, the gap-distance between the pairs, and the optical constants of the dielectric-core and the surrounding medium. The results show that the multiple core-shell nanocylinder pair contains the plasmon mode same as that of the solid metallic cylinder pairs at the long wavelength part of the spectrum. The large electric field intensity in the infrared region at long wavelength makes multiple core-shell cylinders as ideal candidates for surface-enhanced spectroscopes.     

Raman spectroscopic evidence for interfacial interactions in poly(bithiophene)/single-walled carbon nanotube composites

Electrochemical polymerization of 2,2′-bithiophene (BTh) on single-walled carbon nanotube (SWCNT) films has been studied by Raman scattering and infrared absorption spectroscopy. Covalent functionalization of SWCNTs with poly(bithiophene) (PBTh) in its un-doped and doped states is demonstrated. The occurrence of a charge transfer process at the interface of PBTh and SWCNTs, is shown by: (i) an up-shift of the Raman lines associated with the radial breathing modes of SWCNTs that reveals both a doping process and an additional twisting together as a rope with the conducting polymer as binding agent; (ii) a new Raman band in the range 1430-1450 cm⁻¹ indicating the functionalization of SWCNTs with PBTh in doped and un-doped states; (iii) strong absorption bands situated in the interval 600-800 cm⁻¹ resulting from steric hindrance produced by the nanotube binding to the polymeric chain. Treatment of the PBTh/SWCNT composite with aqueous NH₄OH solution forms un-doped PBTh covalently functionalized SWCNTs. At the resonant excitation of the metallic tubes, an additionally enhanced Raman process is generated by plasmon excitation in the metallic nanotubes. It is evidenced by a particular behavior in the Stokes and anti-Stokes branch of the PBTh Raman line at 1450 cm⁻¹.     

Dichroic Optical Diode Transmission in Two Dislocated Parallel Metallic Gratings

An optical diode structure with two dislocated parallel metallic gratings is proposed and investigated numerically. Dichroic optical diode transmission is realized in this structure, i.e., optical diode effect is observed in two wavebands corresponding to inverse transmission directions. In the structure, two parallel metallic gratings with different grating constants are separated by a dielectric slab in between. The first illuminated grating acts as a selector for exciting surface plasmons at a proper wavelength. The other grating acts as an emitter to realize optical transmission. When the incident direction is reversed, the roles of two gratings exchange and surface plasmons are excited at another wavelength. In dichroic transmission wavebands, the optical diode structure exhibits extraordinary transmission and possesses high optical isolation up to 1. Furthermore, the operating wavebands can be modulated by changing structure parameters.     

Scanning Near-Field Ellipsometry Microscopy: imaging nanomaterials with resolution below the diffraction limit

We introduce a simple Scanning Near-Field Ellipsometer Microscopy (SNEM) setup to address the rapidly increasing need for simple, routine optical imaging techniques with resolution well below the diffraction limit. Our setup is based on the combination of commercially available atomic force microscope (AFM) and ellipsometry equipment with gold-coated AFM tips to obtain near-field optical images with a demonstrated resolution below λ/10. AFM topographical data, obtained in contact mode, and near-field optical data were acquired simultaneously using a combined AFM-ellipsometer. The highly enhanced field due to lightning-rod effects and localized surface plasmons excited at the end of the gold-coated tip allowed us to resolve and identify metallic nanoparticles embedded in poly(methyl methacrylate) as well as microphases in microphase-separated block copolymer films.     

Photoluminescence enhancement of quantum dots on Ag nanoneedles

ABSTRACT: Noble-metal nanostructure allows us to tune optical and electrical properties, which has high utility for real-world application. We studied surface plasmon induced emission of semiconductor quantum dots (QDs) on engineered metallic nanostructures. Highly passive organic ZnS capped CdSe QDs were spin coated on poly-(methyl methacrylate) (PMMA) covered Ag films which brought QDs near to metallic surface. We obtained the enhanced electromagnetic field and reduced fluorescence lifetimes from CdSe/ZnS quantum dots (QDs) due to the strong coupling of emitters wave function with the Ag plasmon resonance. Observed changes include a six-fold increase in the fluorescence intensity and striking reduction in fluorescence lifetimes of CdSe/ZnS QDs on rough Ag nanoneedle compared to the case of smooth surfaces. The advantages of using those nanocomposites are expected for high efficiency light-emitting diodes, platform fabrication of biological and environmental monitoring, and high contrast imaging.