P. G. Etchegoin

An analytic model for the optical properties of gold

A simple analytic model for the optical properties of gold is proposed. The model includes a minimum set of parameters necessary to represent the complex dielectric function of gold in the visible and near-uv regions. Explicit values for the parameters to reproduce the Johnson and Christy data [Phys. Rev. B 6, 4370 (1972)] on the optical properties of gold are provided.

Single-Molecule Surface-Enhanced Raman Spectroscopy

A general overview of the field of single-molecule (SM) surface-enhanced Raman spectroscopy (SERS) as it stands today is provided. After years of debates on the basic aspects of SM-SERS, the technique is emerging as a well-established subfield of spectroscopy and SERS. SM-SERS is allowing the observation of subtle spectroscopic phenomena that were not hitherto accessible. Examples of the latter are natural isotopic substitutions in single molecules, observation of the true homogeneous broadening of Raman peaks, Raman excitation profiles of individual molecules, and SM electrochemistry. With background examples of the contributions produced by our group, properly interleaved with results by other practitioners in the field, we present some of the latest developments and promising new leads in this new field of spectroscopy.

Single-Molecule Surface-Enhanced Raman Spectroscopy of Nonresonant Molecules

Single-molecule surface-enhanced Raman scattering (SERS) detection of nonresonant molecules is demonstrated experimentally using the bianalyte SERS method. To this end, bianalyte SERS is performed at 633 nm excitation using the nonresonant molecule 1,2-di-(4-pyridyl)-ethylene (BPE) in combination with a benzotriazole derivative as a partner. The results are then extended to the even more challenging case of a small nonresonant molecule, adenine, using an isotopically substituted adenine as bianalyte SERS partners. In addition, SERS cross sections of single-molecule events are quantified, thus providing estimates of the enhancement factors needed to see them. It turns out that an enhancement factor on the order of approximately 5 x 10(9) was sufficient for single-molecule detection of BPE, while maximum enhancement factors of approximately 5 x 10(10) were observed in extreme cases. In the case of adenine, single-molecule detection was only possible in the rare cases with enhancement factors of approximately 10(11). This study constitutes a quantitative fundamental test into the lowest detection limits (in terms of differential cross sections) for single-molecule SERS.

A Scheme for Detecting Every Single Target Molecule with Surface-Enhanced Raman Spectroscopy

Surface-enhanced Raman spectroscopy (SERS) is now a well-established technique for the detection, under appropriate conditions, of single molecules (SM) adsorbed on metallic nanostructures. However, because of the large variations of the SERS enhancement factor on the surface, only molecules located at the positions of highest enhancement, so-called hot-spots, can be detected at the single-molecule level. As a result, in all SM-SERS studies so far only a small fraction, typically less than 1%, of molecules are actually observed. This complicates the analysis of such experiments and means that trace detection via SERS can in principle still be vastly improved. Here we propose a simple scheme, based on selective adsorption of the target analyte at the SERS hot-spots only, that allows in principle detection of every single target molecule in solution. We moreover provide a general experimental methodology, based on the comparison between average and maximum (single molecule) SERS enhancement factors, to verify the efficiency of our approach. The concepts and tools introduced in this work can readily be applied to other SERS systems aiming for detection of every single target molecule.

Combining Surface Plasmon Resonance (SPR) Spectroscopy with Surface-Enhanced Raman Scattering (SERS)

The simultaneous measurement of surface plasmon resonance (SPR) spectroscopy and surface-enhanced Raman scattering (SERS) on flat metallic surfaces is demonstrated on a relatively simple experimental setup based on the Kretschmann configuration. This setup requires only minor modifications to standard Raman microscopes, and we show that it can be applied successfully to the most common conditions of SPR spectroscopy, i.e., water-based solutions on gold films. Our results emphasize the peculiar properties of the Kretschmann configuration for spectroscopy in general and SERS measurements in particular, especially in terms of the asymmetry between excitation and collection requirements. The combination of simultaneous SPR-SERS spectroscopy opens up interesting prospects in analytical science to study, for example, reaction kinetics at surfaces under conditions which are already available in commercial SPR instruments.

Polarization-dependent effects in surface-enhanced Raman scattering (SERS)

A few key examples of polarization effects in surface-enhanced Raman scattering (SERS) are highlighted and discussed. It is argued that the polarization of the local field, which is felt by an analyte molecule in a location of high electromagnetic field enhancement (hot-spot), can be very different from that of the incident exciting beam. The polarization dependence of the SERS signal is, therefore, mostly dictated by the coupling of the laser to the plasmons rather than by the symmetry of the Raman tensor of the analyte. This sets serious restrictions for the interpretation of both single-molecule SERS polarization studies and for the use of circularly polarized light in techniques like surface-enhanced Raman optical activity.

Experimental demonstration of surface selection rules for SERS on flat metallic surfaces

We have measured the polarization and incident angle dependence of the Surface-Enhanced Raman Scattering (SERS) signal of a nile blue monolayer adsorbed on a flat gold surface. Comparisons with predictions of electromagnetic (EM) theory indicate that the molecules are predominantly adsorbed flat on the surface. These results provide the most direct demonstration of the concept of surface selection rules in SERS, and further confirm the validity of the SERS-EM model beyond the |E|(4)-approximation.

Resolving Single Molecules in Surface-Enhanced Raman Scattering within the Inhomogeneous Broadening of Raman Peaks

We demonstrate both the observation of either a single or a few molecules resolved within the inhomogeneous broadening of a peak in surface-enhanced raman scattering (SERS). Our results demonstrate a fundamental aspect of spectroscopy and also a possible technique to learn more about the varying interactions that single molecules can have with a given SERS substrate. Resolving more than one molecule within the inhomogeneous broadening is only possible thanks to the combination of (i) high-resolution measurements, and (ii) low temperatures (to narrow down the intrinsic homogeneous broadening as much as possible). Besides being a textbook-like example of laser spectroscopy, this result provides yet another confirmation of single molecule sensitivity in SERS. We show specific experimental examples for these effects in single molecule SERS spectra of the molecules nile blue (NB) and rhodamine 800 (RH800). The possible physical origins of the fluctuations in terms of (i) interactions with the substrate, (ii) isotopic effects, or (iii) instrumental contributions, are explained and discussed.

Quantifying Resonant Raman Cross Sections with SERS

We propose a method based on surface-enhanced Raman scattering (SERS) to estimate the resonance Raman cross sections of dyes. The latter are notoriously difficult (or impossible) to obtain by normal (spontaneous) constant wave Raman spectroscopy when the fluorescence quantum yield of the molecules is good and the overwhelming effect of fluorescence masks the Raman spectrum. We propose here to use the fluorescence quenching occurring in SERS conditions to overcome simply this problem. The principles of the method are described and its limitations discussed in detail. The method is demonstrated by estimating the resonance Raman differential cross sections for Rhodamine 6G for seven different excitation wavelengths across the visible range.

Influence of Photostability on Single-Molecule Surface Enhanced Raman Scattering Enhancement Factors

Experimental determinations of enhancement factors in Surface Enhanced Raman Scattering (SERS) are intimately intertwined with the photostability of the probes. We study the effect of the limited photostability in single-molecule SERS (SM-SERS) events and show explicitly how this may result in a large under-estimation of the SERS enhancement factors (EFs) obtained experimentally. To this end, we use the bianalyte technique with isotopically edited probes to provide the best-case scenario for the isolation of single molecule events, and study the statistics of EFs at different incident laser powers. When photobleaching stops playing an important role within the integration time used to capture the spectra, SM-SERS EFs approach an upper bound, which is in agreement with estimations of the EFs within the electromagnetic theory of SERS enhancements. Our results reinforce, in addition, the fact that the highest SM-SERS EFs observed experimentally are typically of the order of approximately 10(10).