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.

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.

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.

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.

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.

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.

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.

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.

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.

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.