Optical detection and spectroscopy of single molecules and single nanoparticles have been achieved at room temperature with the use of surface-enhanced Raman scattering. Individual silver colloidal nanoparticles were screened from a large heterogeneous population for special size-dependent properties and were then used to amplify the spectroscopic signatures of adsorbed molecules. For single rhodamine 6G molecules adsorbed on the selected nanoparticles, the intrinsic Raman enhancement factors were on the order of 10 14 to 10 15 , much larger than the ensemble-averaged values derived from conventional measurements. This enormous enhancement leads to vibrational Raman signals that are more intense and more stable than single-molecule fluorescence.

http://science.sciencemag.org/content/sci/275/5303/1102.full.pdf

Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering

Localized surface plasmon resonance (LSPR) spectroscopy of metallic nanoparticles is a powerful technique for chemical and biological sensing experiments. Moreover, the LSPR is responsible for the electromagnetic-field enhancement that leads to surface-enhanced Raman scattering (SERS) and other surface-enhanced spectroscopic processes. This review describes recent fundamental spectroscopic studies that reveal key relationships governing the LSPR spectral location and its sensitivity to the local environment, including nanoparticle shape and size. We also describe studies on the distance dependence of the enhanced electromagnetic field and the relationship between the plasmon resonance and the Raman excitation energy. Lastly, we introduce a new form of LSPR spectroscopy, involving the coupling between nanoparticle plasmon resonances and adsorbate molecular resonances. The results from these fundamental studies guide the design of new sensing experiments, illustrated through applications in which researchers use both LSPR wavelength-shift sensing and SERS to detect molecules of chemical and biological relevance.

https://www.photonics.ethz.ch/fileadmin/user_upload/Courses/NanoOptics/willets.pdf

Localized Surface Plasmon Resonance Spectroscopy and Sensing

In the Raman effect, incident light is inelastically scattered from a sample and shifted in frequency by the energy of its characteristic molecular vibrations. Since its discovery in 1927, the effect has attracted attention from a basic research point of view as well as a powerful spectroscopic technique with many practical applications. The advent of laser light sources with monochromatic photons at high flux densities was a milestone in the history of Raman spectroscopy and resulted in dramatically improved scattering signals (for a general overview of modern Raman spectroscopy, see refs 1-5). In addition to this so-called spontaneous or incoherent Raman scattering, the development of lasers also opened the field of stimulated or coherent Raman spectroscopies, in which molecular vibrations are coherently excited. Whereas the intensity of spontaneous Raman scattering depends linearly on the number of probed molecules, the coherent Raman signal is proportional to the square of this number (for an overview, see refs 6 and 7). Coherent Raman techniques can provide interesting new opportunities such as vibrational imaging of biological samples,8 but they have not yet advanced the field of ultrasensitive trace detection. Therefore, in the following article, we shall focus on the spontaneous Raman effect, in the following simply called Raman scattering. Today, laser photons over a wide range of frequencies from the near-ultraviolet to the near-infrared region are used in Raman scattering studies, allowing selection of optimum excitation conditions for each sample. By choosing wavelengths which excite appropriate electronic transitions, resonance Raman studies of selected components of a sample or parts of a molecule can be performed.9 In the past few years, the range of excitation wavelengths has been extended to the near-infrared (NIR) region, in which background fluorescence is reduced and photoinduced degradation from the sample is diminished. High-intensity NIR diode lasers are easily available, making this region attractive for compact, low cost Raman instrumentation. Further, the development of low noise, high quantum efficiency multichannel detectors (chargecoupled device (CCD) arrays), combined with highthroughput single-stage spectrographs used in combination with holographic laser rejection filters, has led to high-sensitivity Raman spectrometers (for an overview on state-of-the-art NIR Raman systems, see ref 10). As we shall show in section 2, the nearinfrared region also has special importance for ultrasensitive Raman spectroscopy at the singlemolecule level. As with optical spectroscopy, the Raman effect can be applied noninvasively under ambient conditions in almost every environment. Measuring a Raman spectrum does not require special sample preparation techniques, in contrast with infrared absorption spectroscopy. Optical fiber probes for bringing excitation laser light to the sample and transporting scattered light to the spectrograph enable remote detection of Raman signals. Furthermore, the spatial and temporal resolution of Raman scattering are determined by the spot size and pulse length, respectively, of the excitation laser. By using a confocal microscope, Raman signals from femtoliter volumes (∼1 μm3) can by observed, enabling spatially resolved measurements in chromosomes and cells.11 Techniques such as multichannel Hadamard transform Raman microscopy12,13 or confocal scanning Fourier transform Raman microscopy14 allow generation of high-resolution Raman images of a sample. Recently, Raman spectroscopy was performed using near-field optical microscopy.15-17 Such techniques overcome the diffraction limit and allow volumes significantly smaller than the cube of the wavelength to be investigated. In the time domain, Raman spectra can be measured on the picosecond time scale, providing information on short-lived species such as excited 2957 Chem. Rev. 1999, 99, 2957−2975

Ultrasensitive Chemical Analysis by Raman Spectroscopy

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

/pdf/present-and-future-of-surface-enhanced-raman-scattering-34aqgcm385.pdf

Present and Future of Surface-Enhanced Raman Scattering

To explore the relationship between local electromagnetic field enhancement and the large SERS (surface enhanced Raman scattering) enhancement that enables the observation of single molecule Raman spectra, we measure both resonant Rayleigh scattering spectra and rhodamine 6G Raman spectra from single Ag particles. Our apparatus combines the techniques of dark-field optical microscopy for resonant Rayleigh measurements, and grazing incidence Raman spectroscopy. The Rayleigh spectra show that the citrate-reduced Ag colloid is extremely heterogeneous. Only the larger particles, in part created by salt induced aggregation, show a large SERS effect. In agreement with the work of Nie and Emory, we find that a few nanocrystals show huge single molecule R6G SERS intensities. While all SERS active particles have some resonant Rayleigh scattering at the 514.5 nm laser wavelength, there is no correlation between the resonant Rayleigh spectra and the SERS intensity. We discuss a model in which huge SERS intensities r...

/pdf/surface-enhanced-raman-spectroscopy-of-individual-rhodamine-x75quuss1v.pdf

Surface Enhanced Raman Spectroscopy of Individual Rhodamine 6G Molecules on Large Ag Nanocrystals

This paper presents a combined experimental and theoretical study of the hyper‐Raman spectrum of pyridine adsorbed onto roughened silver electrodes. The surface enhanced hyper‐Raman spectra (SEHRS) were measured using a focused cw mode‐locked Nd:YAG laser with a peak power density of approximately 107 W/cm2 . Dominant bands in the pyridine spectra are the same (totally symmetric) bands as have been seen in the corresponding Raman (SERS) spectrum, although the relative intensities are different. To interpret these spectra, we present a semiempirical molecular orbital method for determining excitation energies, polarizability derivatives, and hyperpolarizability derivatives that is based on the π‐electron Pariser–Parr–Pople (PPP) method. An empirical molecular force field is used to derive vibrational information, and the accuracy of the spectra is assessed by comparison with normal Raman spectra for liquid pyridine and with SERS spectra. The resulting SEHRS spectra are in good agreement with the measured s...

A surface enhanced hyper‐Raman scattering study of pyridine adsorbed onto silver: Experiment and theory

We present a combined experimental/theoretical study of the coverage and frequency dependence of surface (enhanced) resonance Raman scattering [S(E)RRS] of cobalt phthalocyanine (CoPc) on CaF2 roughened silver films. The experimental spectra indicate a rather strong coverage dependence at very low coverage for excitation at or close to the molecular resonance frequency, with a peak at 0.07 monolayer (ML) followed by a rapid decrease above that. This coverage dependence differs strongly with observations on smooth films, where a much weaker dependence is observed. At very low coverage on the rough Ag films S(E)RRS enhancements comparable to SERS are observed. To model this coverage dependence, we consider the electromagnetic interactions between the adsorbate and substrate, with the substrate modeled as a metal spheroid and the adsorbate as a layer with variable coverage. Two models for this layer are considered, an effective medium model in which the layer is taken to have a coverage dependent dielectric constant, and a coupled dipole model in which both the molecules and metal are taken to be polarizable dipoles. The dependence of field enhancement and S(E)RRS intensity is studied for these two models as a function of frequency, coverage, and Stokes shift. It is found that although there are differences between the two models, the coverage dependence is similar in both, with peak intensities at about 0.1 ML for reasonably prolate spheroids. These models also demonstrate that the drop in intensity above 0.1 ML arises from damping of the plasmon resonance by the adsorbed layer. Interadsorbate interactions are found to play a role in determining the coverage dependence of the S(E)RRS intensity that is secondary to this damping. The large enhancements seen below 0.1 ML suggest that excited state quenching by the surface is not important for this nonfluorescent molecule.

K. T. Carron

Papers

A surface enhanced hyper‐Raman scattering study of pyridine adsorbed onto silver: Experiment and theory

A surface enhanced resonance Raman study of cobalt phthalocyanine on rough Ag films: Theory and experiment

A Surface Enhanced Hyper-Raman Scattering Study of Pyridine Adsorbed onto Silver: Experiment and Theory.