Tip-enhanced Raman microscopy: practicalities and limitations

The feasibility of apertureless scanning near-field Raman microscopy, exploiting the local enhancement in Raman scattering in the vicinity of a silver or gold tip, was investigated. Using the finite difference time domain method we calculated the enhancement of electric field strength, and hence Raman scattering, achieved through the resonant excitation of local modes in the tip. By modelling the frequency-dependent dielectric response of the metal tip we were able to highlight the resonant nature of the tip-enhancement and determine the excitation wavelength required for the strongest electric field enhancement, and hence Raman scattering intensity, which occurs for the excitation of modes localized at the tip apex. It is demonstrated that a peak Raman enhancement of 10(7)-fold should be achievable with <5 nm spatial resolution. We show that surface-enhanced Raman scattering from carbon contamination on a silver or gold tip can be significant. However, we find for a tip of radius of curvature 20 nm that the Raman enhancement should decay totally within 20 nm from the tip. Hence withdrawal of the tip by this distance should lead to the disappearance of the tip-enhanced signal, leaving only that from carbon contamination on the tip itself and the intrinsic signal from the sample. Copyright (C) 2003 John Wiley Sons, Ltd.

Rapid, quantitative analysis of ppm/ppb nicotine using surface-enhanced Raman scattering from polymer-encapsulated Ag nanoparticles (gel-colls)

Rapid, quantitative SERS analysis of nicotine at ppm/ppb levels has been carried out using stable and inexpensive polymer-encapsulated Ag nanoparticles (gel-colls). The strongest nicotine band (1030 cm(-1)) was measured against d(5)-pyridine internal standard (974 cm(-1)) which was introduced during preparation of the stock gel-colls. Calibration plots of I-nic/I-pyr against the concentration of nicotine were non-linear but plotting I-nic/I-pyr against [nicotine](x) (x = 0.6-0.75, depending on the exact experimental conditions) gave linear calibrations over the range (0.1-10 ppm) with R-2 typically ca. 0.998. The RMS prediction error was found to be 0.10 ppm when the gel-colls were used for quantitative determination of unknown nicotine samples in 1-5 ppm level. The main advantages of the method are that the gel-colls constitute a highly stable and reproducible SERS medium that allows high throughput (50 sample h(-1)) measurements.

SURFACE-ENHANCED RAMAN-SCATTERING STUDIES OF METALLOPORPHYRINS ON SILVER SOLS, MELLFS, AND ELECTRODES - EVIDENCE FOR REVERSIBLE PHOTOINDUCED DEMETALATION OF A SILVER(II) PORPHYRIN

A series of metalloporphyrins of the type M(TMPyP) (where M = Ag(II), Zn(II), Cu(II) and TMPyP = meso-tetrakis(4-N-methylpyridyl)porphyrin) have been investigated in solution and on the surface of silver sols, electrodes, and MELLFs (metal liquidlike films). Similar spectra were recorded on all three surfaces but significant differences in detailed behavior were found. In particular, a novel, reversible, and rapid photoinduced demetalation reaction has been observed for the AgII(TMPyP)/MELLF system. An apparently similar demetalation reaction for the same metalloporphyrin was observed on Ag electrodes but this reversed at a very much slower rate. No demetalation of Ag(II)(TMPyP) was observed with Ag sols nor with any of the other metalloporphyrins at any of the surfaces investigated. The implications of the findings in relation to the nature of the MELLF environment are briefly considered.

Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO₂ films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO₂ film to UV light. All such films exhibit the optical characteristics (λ_max ≅ 390 nm) of small (<20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (>40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapordeposited films. The Ag/TiO₂ films exhibit a lower residual standard deviation (∼25%) compared with Ag vapor-deposited films (∼45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (<7%) by spinning the film during the SERS measurement. The Ag/TiO₂ films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO₂ films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO₂, is briefly discussed. 

Surface-Enhanced Raman Scattering from Metallic Nanostructures: Bridging the Gap between the Near-Field and Far-Field Responses

We present here a detailed study of the complex relationship between the electromagnetic near-field and far-field responses of "real" nanostructured metallic surfaces. The near-field and far-field responses are specified in terms of (spectra of) the surface-enhanced Raman-scattering enhancement factor (SERS EF) and optical extinction, respectively. First, it is shown that gold nanorod- and nanotube-array substrates exhibit three distinct localized surface plasmon resonances (LSPRs): a longitudinal, a transverse, and a cavity mode. The cavity mode simultaneously has the largest impact on the near-field behavior (as observed through the SERS EF) and the weakest optical interaction: It has a "near-field-type" character. The transverse and longitudinal modes have a significant impact on the far-field behavior but very little impact on SERS: They have a "far-field-type" character. We confirm the presence of the cavity mode using a combination of SERS EF spectra, electron microscopy, and electromagnetic modeling and thus clearly illustrate and explain the (lack of) correlation between the SERS EF spectra and the optical response in terms of the contrasting character of the three LSPRs. In doing so, we experimentally demonstrate that, for a surface that supports multiple LSPRs, the near-field and far-field properties can in fact be tuned almost independently. It is further demonstrated that small changes in geometrical parameters that tune the spectral location of the LPSRs can also drastically influence the character of these modes, resulting in certain unusual behavior, such as the far-field resonance redshift as the near-field resonance blueshifts. DOI: 10.1103/PhysRevX.3.011001

Metal Oxide Nanoparticle Mediated Enhanced Raman Scattering and Its Use in Direct Monitoring of Interfacial Chemical Reactions

Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (X10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

INFLUENCE OF METAL GRAIN-SIZE ON SURFACE-ENHANCED RAMAN-SCATTERING

The surface roughness of nominally smooth and of randomly roughened thin silver films is characterized using scanning tunneling microscopy and the metal grain size is assessed using transmission electron microscopy. On each type of substrate used, glass or CaF2-roughened glass, the silver films are deposited either very slowly (approximately 0.15 nm s-1) or quite quickly (approximately 2.0 nm s-1). Only silver films deposited on CaF2-roughened glass yield measurable surface-enhanced Raman signals for benzoic acid; the enhancement is brought about by surface field amplification due to the excitation of delocalized surface-plasmon polaritons. However, the surface-enhanced Raman signals obtained from the slow-deposited silver films are significantly better (by about a factor of 3) than those obtained from the fast-deposited silver films on a given CaF2-roughened substrate. The explanation of this observation does not lie with different surface roughness; both types of film yield closely similar data on the scanning tunneling microscope. Rather, it is suggested that the relatively small grain size of the fast-deposited silver films leads to increased elastic scattering of surface-plasmon polaritons at the grain boundaries, with a consequent increase of internal damping. This results in a reduction of the scattered Raman signal.

SURFACE ENHANCED RAMAN-SCATTERING FROM MILDLY ROUGHENED SURFACES - VARIATION OF SIGNAL WITH METAL GRAIN-SIZE

The intensity of surface enhanced Raman scattering from benzoic acid derivatives on mildly roughened, thermally evaporated Ag films shows a remarkably strong dependence on metal grain size. Large grained (slowly deposited) films give a superior response, by up to a factor of 10, to small grained (quickly deposited) films, with films of intermediate grain size yielding intermediate results. The optical field amplification underlying the enhancement mechanism is due to the excitation of surface plasmon polaritons (SPPs). Since surface roughness characteristics, as determined by STM, remain relatively constant as a function of deposition rate, it is argued that the contrast in Raman scattering is due to differences in elastic grain boundary scattering of SPPs (leading to different degrees of internal SPP damping), rather than differences in the interaction of SPPs with surface inhomogeneities.

Manipulating plasmon modes in tip-enhanced Raman microscopy

The influence of polarization on the plasmon modes excited in tip-enhanced near-field optical microscopy have been investigated using the Finite Difference Time Domain Method. Analysis of the calculated results have laid particular emphasis on the ability to align local field enhancements with the orientation of molecules in order to optimize Raman signals, with particular relevance to recent experimental work on carbon nanotubes.

Application of AAO Matrix in Aligned Gold Nanorod Array Substrates for Surface-Enhanced Fluorescence and Raman Scattering

In this paper, we probed surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from probe molecule Rhodamine 6G (R6G) on self-standing Au nanorod array substrates made using a combination of anodization and potentiostatic electrodeposition. The initial substrates were embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix, SEF and SERS were observed exhibiting an inverse relationship. SERS and SEF showed a non-linear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod which was supported by FDTD calculations. We showed that by optimizing the level of AAO thickness, we could obtain either maximized SERS, SEF or simultaneously observe both SERS and SEF together.

Combined antenna and localized plasmon resonance in Raman scattering from Random arrays of silver-coated, vertically aligned multiwalled carbon nanotubes

The electric field enhancement associated with detailed structure within novel optical antenna nanostructures is modeled using the surface integral equation technique in the context of surface-enhanced Raman scattering (SERS). The antennae comprise random arrays of vertically aligned, multi-walled carbon nanotubes dressed with highly granular Ag. Different types of "hot-spot" underpinning the SERS are identified, but contrasting characteristics are revealed. Those at the outer edges of the Ag grains are antenna driven with field enhancement amplified in antenna antinodes while intergrain hotspots are largely independent of antenna activity. Hot-spots between the tops of antennae leaning towards each other also appear to benefit from antenna amplification.

Pterin detection using surface-enhanced Raman spectroscopy incorporating a straightforward silver colloid-based synthesis technique

Optical techniques toward the realization of sensitive and selective biosensing platforms have received considerable attention in recent times. Techniques based on interferometry, surface plasmon resonance, and waveguides have all proved popular, while spectroscopy in particular offers much potential. Raman spectroscopy is an information-rich technique in which the vibrational frequencies reveal much about the structure of a compound, but it is a weak process and offers poor sensitivity. In response to this problem, surface-enhanced Raman scattering (SERS) has received much attention, due to significant increases in sensitivity instigated by bringing the sample into contact with an enhancing substrate. Here we discuss a facile and rapid technique for the detection of pterins using SERS-active colloidal silver suspensions. Pterins are a family of biological compounds that are employed in nature in color pigmentation and as facilitators in metabolic pathways. In this work, small volumes of xanthopterin, isoxanthopterin, and 7,8-dihydrobiopterin have been examined while adsorbed to silver colloids. Limits of detection have been examined for both xanthopterin and isoxanthopterin using a 10-s exposure to a 12 mW 532 nm laser, which, while showing a trade-off between scan time and signal intensity, still provides the opportunity for the investigation of simultaneous detection of both pterins in solution. (C) 2011 Society of Photo-Optical Instrumentation Engineers (SPIE). [DOI: 10.1117/1.3600658]

RAMAN-SCATTERING AND SCANNING ELECTRON-TUNNELING STUDIES OF METAL LIQUID-LIKE FILMS PRODUCED FROM SILVER AND GOLD SOLS

Surface-enhanced Raman scattering (SERS) excited at several visible wavelengths and recorded using a cooled charged-coupled device detector is reported from the mobile, interfacial, liquid-like metal films (MELLFs) formed when solutions of metal complexes or pyridine in chlorocarbon solvents are mixed with aqueous sols of silver or gold. MELLF formation has not previously been reported for gold sols or for pyridine as stabilizer. Comparison of the spectra for the MELLFs formed from individual metal complexes and from 50:50 mixtures show that the spectral patterns observed for the latter are distinctive and are not generally equivalent to the sum of the spectra associated with the individual complexes, in contrast to the situation observed for sols where the individual spectra do appear to be additive. Raman scattering from both gold and silver MELLFs is readily observed at excitation wavelengths in the red, around 750 nm, but at 514 nm only that from silver films is detectable. These findings are considered in terms of particle size and absorption band intensities. A preliminary study of the film surface topography and particle size was carried out by scanning tunnelling electron microscopy (STM) of Ag MELLFs deposited on gold-coated mica substrates. Computer-processed images of the STM data show the presence on the film surface of finger-like bars, 200-400 nm long with approximately square cross-section, 40-60 nm side, together with other smaller cuboid features. The implications of these findings in relation to SERS are briefly considered.

Light emission from scanning tunnelling microscope on polycrystalline Au films - what is happening at the single-grain level?

When operated with a metallic tip and sample the scanning tunnelling microscope constitutes a nanoscale, plasmonic light source yielding broadband emission up to a photon energy determined by the applied bias. The emission is due to tunnelling electron excitation and subsequent radiative decay of localized plasmon modes, which can be on the lateral scale of a single metal grain (similar to 25 nm) or less. For a Au-tip/Au-polycrystalline sample under ambient conditions it is found that the intensity and spectral content of the emitted light are not dependent on the lateral grain dimension, but are predominantly determined by the tip geometry. However, the intensity increases strongly with increasing film thickness (grain depth) up to 20-25 nm or approximately the skin depth of the Au film. Photon maps can show less emissive grains and two classes of this occurrence are distinguished. The first is geometrical in origin - a double-tip structure in this case - while the second is due to a contamination-induced lowering of the local work function that causes the tunnel gap to increase. It is suggested that differences in work-function lowering between grains presenting different crystalline facets, combined with an exponential decay in emitted light intensity with tip - sample distance, leads to grain contrast. These results are relevant to tip-enhanced Raman scattering and the fabrication of micro/nano-scale planar, light-emitting tunnel devices.