Tip-enhanced Raman spectroscopy: near-fields acting on a few molecules.

Tip-enhanced Raman spectroscopy (TERS) is a very powerful variant of surface-enhanced Raman spectroscopy (SERS). In a sense, TERS overcomes most of the drawbacks of SERS but keeps its advantages, such as its high sensitivity. TERS offers the additional advantages of high spatial resolution, much beyond the Abbe limit, and the possibility to correlate TER and other scanning probe microscope images, i.e., to correlate topographic and chemical data. TERS finds application in a number of fields, such as surface science, material science, and biology. Single-molecule TERS has been observed even for TERS enhancements of "only" 10(6)-10(7). In this review, TERS enhancements are discussed in some detail, including a condensed overview of measured contrasts and estimated total enhancements. Finally, recent developments for TERS under ultrahigh vacuum conditions are presented, including TERS on a C(60) island with a diameter of a few tens of nanometers, deposited on a smooth Au(111) surface.

Studying surface chemistry beyond the diffraction limit: 10 years of TERS.

The use of an illuminated scanning probe tip to greatly enhance Raman scattering from the sample underneath the tip is one of the most intriguing developments in optical spectroscopy, and the steeply increasing number of publications per year shows that chemists, physicists and biologists alike recognize the importance and great potential of this technique. With tip-enhanced Raman spectroscopy (TERS), one of the main goals in surface science has been achieved, namely the combination of scanning probe microscopy and optical spectroscopy such as Raman spectroscopy. Important here is the use of the tip as an optical antenna to substantially increase the emitted radiation and to simultaneously improve the optical resolution much beyond the Abbe diffraction limit. This permits the correlation of topographic and chemical information of the same surface region. The synergy of detailed insight in morphology and the chemical nature of the target species facilitates data interpretation significantly and enables characterization of interfaces at the nanometer scale. A wide variety of substrates and sample molecules have been studied with TERS since the first publication of tip-enhanced Raman spectra, and the technique has reached a first level of maturity on its 10th birthday, with TERS applications extending into various research fields from surface chemistry over biology to nanoscale physics.

In situ discrimination between axially complexed and ligand-free co porphyrin on Au(111) with tip-enhanced Raman spectroscopy.

Simultaneous chemical and topographic information about cobalt tetraphenyl-porphyrin (CoTPP) adlayers formed on a Au(111) single crystal is obtained with tip-enhanced Raman (TER) spectroscopy. We distinguish in situ between sample areas covered with an ordered adlayer of CoTPP and areas covered with a spontaneously formed disordered phase. The Raman vibrational fingerprints collected from the nanometer-sized near-field region just below a scanning tunnelling microscope (STM) tip are correlated with the adsorbate structures seen in the STM images. We assign the TER spectral features of the disordered phase to CoTPP complexes with CO and/or NO axial ligands, whereas the TER spectrum obtained from the ordered phase does not show any indication of additional axial complexation of CoTPP.

AFM studies of solid-supported lipid bilayers formed at a Au(111) electrode surface using vesicle fusion and a combination of Langmuir-Blodgett and Langmuir-Schaefer techniques.

Atomic force microscopy (AFM) has been used to characterize the formation of a phospholipid bilayer composed of 1,2-dimyristyl-sn-glycero-3-phosphocholine (DMPC) at a Au(111) electrode surface. The bilayer was formed by one of two methods: fusion of lamellar vesicles or by the combination of Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) deposition. Results indicate that phospholipid vesicles rapidly adsorb and fuse to form a film at the electrode surface. The resulting film undergoes a very slow structural transformation until a characteristic corrugated phase is formed. Force-distance curve measurements reveal that the thickness of the corrugated phase is consistent with the thickness of a bilayer lipid membrane. The formation of the corrugated phase may be explained by considering the elastic properties of the film and taking into account spontaneous curvature induced by the asymmetric environment of the bilayer, in which one side faces the gold substrate and the other side faces the solution. The effect of temperature and electrode potential on the stability of the corrugated phase has also been described.

Tip-enhanced Raman spectroscopy and microscopy on single dye molecules with 15 nm resolution.

Our recently developed approach of UHV-tip-enhanced Raman spectroscopy permits us to acquire Raman spectra of a few single brilliant cresyl blue (BCB) molecules and even a single one adsorbed on a Au(111) surface. This is substantiated by simultaneously recorded STM images. Furthermore, because of the reduced photobleaching in UHV, the time frame for spectral acquisition is sufficiently extended to allow tip-enhanced Raman imaging of a single BCB molecule with a lateral resolution of 15 nm.

High-resolution microscope for tip-enhanced optical processes in ultrahigh vacuum.

An optical microscope based on tip-enhanced optical processes that can be used for studies on adsorbates as well as thin layers and nanostructures is presented. The microscope provides chemical and topographic informations with a resolution of a few nanometers and can be employed in ultrahigh vacuum as well as gas phase. The construction involves a number of improvements compared to conventional instruments. The central idea is to mount, within an UHV system, an optical platform with all necessary optical elements to a rigid frame that also carries the scanning tunneling microscope unit and to integrate a high numerical aperture parabolic mirror between the scanning probe microscope head and the sample. The parabolic mirror serves to focus the incident light and to collect a large fraction of the scattered light. The first experimental results of Raman measurements on silicon samples as well as brilliant cresyl blue layers on single crystalline gold and platinum surfaces in ultrahigh vacuum are presented. For dye adsorbates a Raman enhancement of approximately 10(6) and a net signal gain of up to 4000 was observed. The focus diameter ( approximately lambda2) was measured by Raman imaging the focal region on a Si surface. The requirements of the parabolic mirror in terms of alignment accuracy were experimentally determined as well.

Toward Raman fingerprints of single dye molecules at atomically smooth Au(111).

The creation of a highly enhanced electromagnetic (EM) field underneath a scanning tunneling microscope (STM) tip enables Raman spectroscopic studies of organic submonolayer adsorbates at atomically smooth single crystalline surfaces. To study the sensitivity of this technique, tip-enhanced resonance Raman (TERR) spectra of the dye malachite green isothiocyanate on Au(111) in combination with the corresponding STM images of the probed surface region were analyzed. The detection limit for unambiguous identification of the dye and semiquantitative determination of the surface coverage reaches < or =0.7 pmol/cm(2), or approximately five molecules present in the enhanced-field region, which is confirmed by STM images. Because of well-defined adsorption sites at atomically smooth Au(111) surfaces, no variation in band positions or relative band intensities was observed at the single- or few-molecule detection level when employing TERR spectroscopy.

A comparative study of hydroxide adsorption on the (111), (110), and (100) faces of silver with cyclic voltammetry, ex situ electron diffraction, and in situ second harmonic generation.

Hydroxide adsorption on the (111), (110), and (100) faces of silver electrodes from mixed NaOH/NaF solution is studied using cyclic voltammetry and in situ second harmonic generation (SHG). Cyclic voltammograms for the three low index silver planes in alkaline electrolytes are for the first time compared. They show two pairs of anodic and cathodic peaks in the potential interval below the equilibrium Ag/Ag(2)O potential. These are attributed to the specific adsorption of hydroxide ions followed by submonolayer oxide formation. The differences in the cyclic voltammograms for the (111), (110), and (100) planes are attributed to different (i) work functions, (ii) surface atomic densities, and (iii) corrugation potentials for these surfaces. Ex situ low energy electron diffraction (LEED) and reflection high energy electron diffraction (RHEED) show that disordered adlayers are formed on Ag(111) and Ag(100), in contrast to Ag(110), where ordered structures are produced in the region of the first pair of current peaks. In the region of the second pair of peaks, LEED indicates disordered oxide phases on each crystal plane and RHEED shows the presence of small islands of c(2 x 2) structure at some potentials on (110) and (100). SHG measurements were performed (i) in the potential scan mode at constant rotational angle and (ii) at constant potential as a function of the rotational angle. The isotropic (for the (111), (110), and (100) planes) and anisotropic (for the (110) and (111) planes) contributions to the SHG intensity were calculated by fitting the experimental data and are discussed in terms of their dependence on the charge density at the interface, on hydroxide adsorption, and on submonolayer oxide formation.

Nanoscale probing of adsorbed species by tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) is based on the optical excitation of localized surface plasmons in the tip-substrate cavity, which provides a large but local field enhancement near the tip apex. We report on TERS with smooth single crystalline surfaces as substrates. The adsorbates were CN- ions at Au(111) and malachite green isothiocyanate (MGITC) molecules at Au(111) and Pt(110) using either Au or Ir tips. The data analysis yields Raman enhancements of about 4 x 10(5) for CN- and up to 10(6) for MGITC at Au(111) with a Au tip, probing an area of less than 100 nm radius.

Organic compound adsorption on Au(111): simultaneous SHG/electrochemical studies.

Camphor has attracted considerable attention in electrochemical research because it adsorbs strongly on metal surfaces. Due to its surface activity it is able to inhibit surface reactions. Recently, camphor has been used in investigations of nonlinear surface dynamics and pattern formation. Details regarding its influence on the morphology of the metal surface, the significance of surface reconstruction, structural changes in the camphor adlayer and oxide formation remain unclear. We employ second harmonic generation (SHG) to elucidate the structural and electronic behaviour of Au(111) surfaces during camphor adsorption and desorption processes. Our technique allows measurement of the anisotropy of the SHG intensity while simultaneously performing cyclic voltammetry (CV) using the hanging meniscus configuration. The anisotropy data can be refined, yielding the symmetry components of the second order susceptibility tensor chi2 which are analysed as a function of external potential and related to the system's electrochemical behaviour. Results of SHG measurements are presented together with corresponding CV data and discussed with respect to the open questions mentioned above.

Structure and dynamics of the interface between a Ag single crystal electrode and an aqueous electrolyte.

The aim of this work is to elucidate the initial steps of the electrochemical oxidation of Ag(111) in alkaline electrolytes. We use electrochemical as well as ex situ (XPS) and in situ (SHG) spectroscopic techniques to reconstruct the Ag(111)/electrolyte interface as a complex dynamic entity. Moving in the direction from negative to positive potentials we first observe specific adsorption of hydroxide ions, which starts at ca. -1.1 V vs. Ag/Ag2O in 0.1 M NaOH. SHG data prove that hydroxide retains its negative charge. At -0.3 V oxidation of the surface sets in with the formation of negatively charged adsorbed oxygen species and Ag+ ions, which give rise to peaks at 528.2 +/- 0.2 eV and at 367.7 eV in the O 1s and the Ag 3d(5/2) XP spectra, respectively. Around -0.1 V the adlayer is transformed into an ordered surface oxide phase which grows via a nucleation and growth mechanism. Above the reversible Ag/Ag2O potential the 2D Ag(I) oxide transforms into a 3D Ag(I) oxide. The electrochemical oxidation is compared with the previously studied gas-phase process, demonstrating both remarkable similarities as well as some differences.