In situ video-STM studies of the mechanisms and dynamics of electrochemical bismuth nanostructure formation on Au.

The microscopic mechanisms of Bi electrodeposition on Au(111) and Au(100) electrodes in the overpotential regime were studied by in situ scanning tunneling microscopy with high spatial and temporal resolution. Atomic resolution images of the needle-like Bi(110) deposits formed on Au(111) reveal the central influence of covalent Bi-Bi bonds on the deposit morphology. In the straight steps along the needle edges the Bi atoms are interlinked by these bonds, whereas at the needle tip and at kinks along the needle edges dangling bonds exist, explaining the rapid structural fluctuations at these sites. For ultrathin Bi deposits on Au(100) a more open atomic arrangement was found within the surface plane, which was tentatively assigned to an epitaxially stabilised Bi(111) film. Furthermore, well-defined nanowires, consisting of zigzag chains of Bi surface atoms, were observed on this surface.

Photoinduced Enhancement of the Charge Density Wave Amplitude.

Symmetry breaking and the emergence of order is one of the most fascinating phenomena in condensed matter physics. It leads to a plethora of intriguing ground states found in antiferromagnets, Mott insulators, superconductors, and density-wave systems. Exploiting states of matter far from equilibrium can provide even more striking routes to symmetry-lowered, ordered states. Here, we demonstrate for the case of elemental chromium that moderate ultrafast photoexcitation can transiently enhance the charge-density-wave (CDW) amplitude by up to 30% above its equilibrium value, while strong excitations lead to an oscillating, large-amplitude CDW state that persists above the equilibrium transition temperature. Both effects result from dynamic electron-phonon interactions, providing an efficient mechanism to selectively transform a broad excitation of the electronic order into a well-defined, long-lived coherent lattice vibration. This mechanism may be exploited to transiently enhance order parameters in other systems with coupled degrees of freedom.

The Atomic scale structure of liquid metal-electrolyte interfaces.

Electrochemical interfaces between immiscible liquids have lately received renewed interest, both for gaining fundamental insight as well as for applications in nanomaterial synthesis. In this feature article we demonstrate that the atomic scale structure of these previously inaccessible interfaces nowadays can be explored by in situ synchrotron based X-ray scattering techniques. Exemplary studies of a prototypical electrochemical system - a liquid mercury electrode in pure NaCl solution - reveal that the liquid metal is terminated by a well-defined atomic layer. This layering decays on length scales of 0.5 nm into the Hg bulk and displays a potential and temperature dependent behaviour that can be explained by electrocapillary effects and contributions of the electronic charge distribution on the electrode. In similar studies of nanomaterial growth, performed for the electrochemical deposition of PbFBr, a complex nucleation and growth behaviour is found, involving a crystalline precursor layer prior to the 3D crystal growth. Operando X-ray scattering measurements provide detailed data on the processes of nanoscale film formation.

UV/Vis Spectroscopy Studies of the Photoisomerization Kinetics in Self-Assembled Azobenzene-Containing Adlayers.

Direct comparative studies of the photoisomerization of azobenzene derivatives in self-assembled adlayers on Au and as free molecules in dichloromethane solution were performed using UV/vis spectroscopy. For all studied systems a highly reversible trans-cis isomerization in the adlayer is observed. Quantitative studies of the absorbance changes and photoisomerization kinetics reveal that in azobenzenes mounted as freestanding vertical groups on the surface via triazatriangulene-based molecular platforms photoswitching is nearly uninhibited by the local environment in the adlayer. The blue-shift of the π-π* transition in adlayers of these molecules is in good agreement with theoretical studies of the effect of excitonic coupling between the molecules. In contrast, in azobenzene-containing thiol self-assembled monolayers the fraction of photoswitching molecules and the photoisomerization kinetics are significantly reduced compared to free molecules in solution.

Surface layering at the mercury-electrolyte interface.

X-ray reflectometry reveals atomic layering at a liquid-liquid interface--mercury in a 0.01 M NaF solution. The interface width exceeds capillary wave theory predictions and displays an anomalous dependence on the voltage applied across it, displaying a minimum positive of the potential of zero charge. The latter is explained by electrocapillary effects and an additional intrinsic broadening of the interface profile, tentatively assigned to polarization of the conduction electrons due to the electric field of the electrochemical double layer at the interface.

Quantitative measurements of adsorbate-adsorbate interactions at solid-liquid interfaces.

The interactions between adsorbates at a solid-liquid interface were studied by video-rate STM for the case of sulfur on Cu(100) electrode surfaces in HCl solution. Quantitative data were obtained by analyzing the S(ad) dimer dynamics within the surrounding c(2 x 2)-Cl adlattice as well as the adsorbate configurations. The interactions are repulsive for S(ad) separated by one or two lattice spacings and attractive at a separation of square root of 2 with energies comparable to adsorbates at the solid-vacuum interface. The S(ad) diffusion barriers are significantly reduced in the vicinity of a neighboring adsorbate.

In situ surface x-ray diffraction studies of homoepitaxial electrochemical growth on Au(100).

Direct in situ x-ray surface scattering studies of growth at a solid-liquid interface are demonstrated using the homoepitaxial electrodeposition on Au(100) as an example. With decreasing potential transitions from step-flow to layer-by-layer growth, manifested by layering oscillations in the x-ray intensity, then to multilayer growth, and finally back to layer-by-layer growth were observed. This complex growth behavior can be explained by the effect of anion coadsorbates and the potential-dependent Au surface reconstruction on the Au surface mobility.

Video STM studies of adsorbate diffusion at electrochemical interfaces.

Direct in situ studies of the surface diffusion of isolated adsorbates at an electrochemical interface by high-speed scanning tunneling microscopy (video STM) are presented for sulfide adsorbates on Cu(100) in HCl solution. As revealed by a quantitative statistical analysis, the adsorbate motion can be described by thermally activated hopping between neighboring adsorption sites with an activation energy that increases linearly with electrode potential by 0.50 eV per V. This can be explained by changes in the adsorbate dipole moment during the hopping process and contributions from coadsorbates.

Electrocompression of the Au(111) surface layer during Au electrodeposition.

In situ grazing-incidence x-ray diffraction studies of reconstructed Au(111) electrodes in aqueous electrolyte solutions are presented, which reveal a significantly increased compression of the Au surface layer during Au electrodeposition as compared to Au(111) surfaces under ultrahigh vacuum conditions or in the Au-free electrolyte. The compression increases towards more negative potentials, reaching 5.3% at the most negative potentials studied. It may be explained within a simple thermodynamic model by a release of potential-induced surface stress.

Quasi-collective motion of nanoscale metal strings in metal surfaces.

Mass transport processes on metal surfaces play a key role in epitaxial growth and coarsening processes. They are usually described in terms of independent, statistical diffusion and attachment/detachment of individual metal adatoms or vacancies. Here we present high-speed scanning tunnelling microscopy (video-STM) observations of the dynamic behaviour of five-atom-wide, hexagonally ordered strings of Au atoms embedded in the square lattice of the Au(100)-(1x1) surface that reveal quasi-collective lateral motion of these strings perpendicular to as well as along the string direction. The perpendicular motion can be ascribed to small atomic displacements in the strings induced by propagating kinks, which also provides a mechanism for the exchange of Au atoms between the two string ends, required for motion in string direction. In addition, quasi-one-dimensional transport of Au adatoms along the string boundaries may contribute to the latter phenomenon according to density functional calculations.

Potential-induced strain relaxation in au mono- and bilayer films on Pt(111) electrode surfaces.

In situ scanning tunneling microscopy observations of 1-2 monolayer thick Au films on Pt(111) electrodes are presented, which show a complex, potential-dependent structural phase behavior of the Au film. Starting from a pseudomorphic structure at <0.35 V(Ag/AgCl), a sequence of transitions into dislocation network structures occurs with increasing potential: (1x1)--> "striped phase" --> "hex phase" in the Au bilayer, (1x1)--> striped phase in the Au monolayer. This is explained by a reduction of the in-plane stress in the Au surface layer(s) due to anion adsorption and a strain energy minimization as described by the Frenkel-Kontorova model.

In situ video-STM studies of dynamic processes at electrochemical interfaces.

Atomic-scale dynamic processes during Cu(100) dissolution/deposition in pure and Cu-containing 0.01 M HCl solution were studied in situ by high-speed electrochemical STM (video-STM). Direct observations of the equilibrium fluctuations at atomic kinks in the steps on the crystal surface due to the local removal/addition of atoms reveal the same anisotropic behavior found previously in Cu-free electrolytes, caused by the influence of the ordered (2 x 2) Cl adlayer on the kink structure. A first quantitative analysis of these fluctuations and interpretation in terms of a local current exchange density was attempted. In addition, observations on the nucleation of vacancy- or ad-rows at terrace corners and within the Cu steps are presented and the relevance of these processes for the macroscopic current density is discussed.

The role of atomic ensembles in the reactivity of bimetallic electrocatalysts.

Bimetallic electrodes are used in a number of electrochemical processes, but the role of particular arrangements of surface metal atoms (ensembles) has not been studied directly. We have evaluated the electrochemical/catalytic properties of defined atomic ensembles in atomically flat PdAu(111) electrodes with variable surface stoichiometry that were prepared by controlled electrodeposition on Au(111). These properties are derived from infrared spectroscopic and voltammetric data obtained for electrode surfaces for which the concentration and distribution of the respective metal atoms are determined in situ by atomic resolution scanning tunneling microscopy with chemical contrast. Palladium monomers are identified as the smallest ensemble ("critical ensemble") for carbon monoxide adsorption and oxidation, whereas hydrogen adsorption requires at least palladium dimers.