Redox-activity and self-organization of iron-porphyrin monolayers at a copper/electrolyte interface.

The electrochemical behaviour and molecular structure of a layer of water-soluble 5,10,15,20-Tetrakis-(N-methyl-4-pyridyl)-porphyrin-Fe(III) pentatosylate, abbreviated as FeTMPyP, on a chloride modified Cu(100) electrode surface were investigated by means of cyclic voltammetry (CV) and in-situ electrochemical scanning tunneling microscopy. Voltammetric results of HOPG in an electrolyte containing FeTMPyP molecules indicate three distinguishable redox steps involving both the central iron metal and the π-conjugated ring system. However, only the first two reduction steps are observable within the narrow potential window of CVs of Cu(100) measured in the same electrolyte. In the potential range below the first reduction peak, at which the [Fe(III)TMPyP](5+) molecules are reduced to the corresponding [Fe(II)TMPyP](4+) species, in-situ scanning tunneling microscopy (STM) images revealed, for the first time, a highly ordered adlayer of this reduced porphyrin species on the chloride terminated Cu(100) surface. The ordered adlayer exhibits a (quasi)square unit cell with the lattice vectors |a→2|=|b→2|=1.53±0.1 nm and an angle of 93° ± 2° between them. A model is proposed based on the STM observation illustrating the arrangement of the [Fe(II)TMPyP](4+) molecules at the electrolyte/copper interface.

Chloride-induced morphology transformations of the Cu(110) surface in dilute HCl.

Morphological changes of a bare Cu(110) substrate in 10 mM HCl aqueous solution have been studied using cyclic voltammetry (CV), electrochemical scanning tunneling microscopy (EC-STM), and reflectance anisotropy spectroscopy (RAS). At cathodic potentials more positive than the hydrogen evolution reaction, a bare copper surface (1 × 1) structure is found by EC-STM. At anodic potentials more negative than the copper(II) dissolution reaction, a furrowed structure is found. The governing factor that rules Cu(110)-Cl interface processes is discussed as an interplay among Cl(-) adsorption/desorption, the dynamic rearrangement of the surface atoms on the substrate, and strain in order to reduce the surface energy. The information provided by EC-STM and RAS complements that of CV, supplies detailed information on the surface morphology, and correlates peaking Faraday currents to structural modifications. Furthermore, RAS and EC-STM show changes in the surface appearance in a potential range where no specific charge transfer is observed. CV indicates that the Cu(110) surface chemistry compares much better to that of amorphous Cu than to that of the more stable (100) and (111) surfaces, respectively.

Molecular ordering at electrified interfaces: Template and potential effects.

A combination of cyclic voltammetry and in situ scanning tunneling microscopy was employed to examine the adsorption and phase transition of 1,1'-dibenzyl-4,4'-bipyridinium molecules (abbreviated as DBV(2+)) on a chloride-modified Cu(111) electrode surface. The cyclic voltammogram (CV) of the Cu(111) electrode exposed to a mixture of 10 mM HCl and 0.1 mM DBVCl2 shows three distinguishable pairs of current waves P1/P'1, P2/P'2, and P3/P'3 which are assigned to two reversible electron transfer steps, representing the reduction of the dicationic DBV(2+) to the corresponding radical monocationic DBV(+•) (P1/P'1) and then to the uncharged DBV(0) (P3/P'3) species, respectively, as well as the chloride desorption/readsorption processes (P2/P'2). At positive potentials (i.e., above P1) the DBV(2+) molecules spontaneously adsorb and form a highly ordered phase on the c(p × âˆš3)-precovered Cl/Cu(111) electrode surface. A key element of this DBV(2+) adlayer is an assembly of two individual DBV(2+) species which, lined up, forms a so-called "herring-bone" structure. Upon lowering the electrode potential the first electron transfer step (at P1) causes a phase transition from the DBV(2+)-related herring-bone phase to the so-called "alternating stripe" pattern built up by the DBV(+•) species following a nucleation and growth mechanism. Comparison of both observed structures with those found earlier at different electrode potentials on a c(2 × 2)Cl-precovered Cu(100) electrode surface enables a clear assessment of the relative importance of adsorbate-substrate and adsorbate-adsorbate interactions, i.e., template vs self-assembly effects, in the structure formation process of DBV cations on these modified Cu electrode surfaces.

Molecular self-assembly at metal-electrolyte interfaces.

The self-assembly of molecular layers has become an important strategy in modern design of functional materials. However, in particular, large organic molecules may no longer be sufficiently volatile to be deposited by vapor deposition. In this case, deposition from solution may be a promising route; in ionic form, these molecules may even be soluble in water. In this contribution, we present and discuss results on the electrochemical deposition of viologen- and porphyrin molecules as well as their co-adsorption on chloride modified Cu(100) and Cu(111) single crystal electrode surfaces from aqueous acidic solutions. Using in situ techniques like cyclic voltametry and high resolution scanning tunneling microscopy, as well as ex-situ photoelectron spectroscopy data the highly ordered self-assembled organic layers are characterized with respect to their electrochemical behavior, lateral order and inner conformation as well as phase transitions thereof as a function of their redox-state and the symmetry of the substrate. As a result, detailed structure models are derived and are discussed in terms of the prevailing interactions.

Electrochemical scanning tunneling microscopy.

The electrochemical scanning tunneling microscope was the first tool for the investigation of solid-liquid interfaces that allowed in situ real space imaging of electrode surfaces at the atomic level. Therefore it quickly became an important addition to the repertoire of methods for the determination of the local surface structure as well as the dynamics of reactions and processes taking place at surfaces in an electrolytic environment. In this short overview we present several examples to illustrate the powerful capabilities of the EC-STM, including the observation of clean metal surfaces as well as the adsorption of thin metal layers, specifically adsorbed anions and non-specifically adsorbed organic cations. In several cases the electrode potential has a significant influence on structure and reactivity of the surface that can be explained by the observations made with the EC-STM.

Redox activity and structural transition of heptyl viologen adlayers on Cu(100).

The redox behaviour and potential-dependent adsorption structure of heptyl viologen (1,1'-diheptyl-4,4'-bipyridinium dichloride, DHV(2+)) on a Cu(100) electrode was investigated in a chloride-containing electrolyte solution by cyclic voltammetry (CV) and in situ electrochemical scanning tunneling microscopy (EC-STM). The dicationic DHV molecules generate a few pairs of current waves in CV measurements which are ascribed to two typical one-electron transfer steps. STM images obtained in a KCl-containing electrolyte solution disclose a well-ordered c(2x2) chloride adlayer on a Cu(100) electrode surface. After injecting DHV(2+) molecules into the KCl electrolyte solution, a highly ordered 2D "dot-array" structure in STM images emerges on the c(2x2)-Cl modified Cu(100) electrode surface. DHV(2+) molecules spontaneously arrange themselves with their molecular planes facing the electrode surface and their long molecular axis parallel to the step edge. Such adsorption structure can be described by mirror domains and rotational domains which stably exist between 200 mV and -100 mV. One-electron reduction of the dications DHV(2+) around -150 mV causes a phase transition from a 'dot-array' assembly to a stripe pattern formed by DHV(*+) radical monocations in STM images which has a bilayer structure. With a further decrease of the applied electrode potential, the structure of the DHV(*+) adlayer undergoes a change from a loose stripe phase to a more compact stripe phase, a subsequent decay of the compact structure, and finally the formation of a new dimer phase. A further electron transfer reaction at -400 mV causes the formation of an amorphous phase on the chloride free electrode surface. In a reverse anodic sweep, the reproduction of the ordered DHV(*+) stacking phase occurs again on top of the chloride lattice.

Molecular structures of dicarboxylated viologens on a Cu(100) surface during an ongoing charge transfer reaction.

Molecular structures of dicarboxylated viologens (1,1'-bis (7-carboxyheptyl)-4,4'-bipyridinium dibromide molecules, V-(C(7)-COOH)(2)) on a Cu(100) surface are studied by means of in situ scanning tunneling microscopy (STM) in combination with cyclic voltammetry (CV). Self-assembled monolayers of adsorbed dicarboxylated viologens form during an ongoing charge transfer reaction. Mainly six structures of the organic molecules are observed, including a dot array, metastable phases, stripe patterns, a closed stacking stripe pattern, chloride desorption, and a dimer phase. The molecular structural models for all the structures have been successfully established. The carboxylated viologen molecules in the dicationic state prefer the face-on configuration on the surface and form the dot array phase. The other phases are shown by the radical state of the viologens. The metastable phases show two forms: cluster-like and stripe pattern-like structures. Main features of the metastable phases are face-to-face configurations of the radical viologens in π-stacking form between neighboring parallel bipyridiniums. Hydrogen bonding is considered to be the major factor in constructing the network of the stripe pattern. At a more negative potential, the bilayers of the stripe pattern transform to be a monolayer of the closed stacking stripe pattern because of the enhanced electrostatic force. The closed stacking stripe pattern is stable on the surface until chloride desorption. As the chloride anions desorb from the Cu(100) surface, the disordered dimers transform to an ordered dimer phase on a Cu(100)-1×1 surface due to the hydrogen bonding between neighboring dimer rows.

Surfaces: two-dimensional templates.

Producing nanoscale structures on solid surfaces in a controlled way is a technologicalchallenge that has an important impact on a variety of fields such as microelectronics, magnetic storagetechnology, and heterogeneous catalysis. Currently most processes are based on a top-down approach,which relies on an active patterning of a surface by, for example, lithography or imprinting. As thedesired structures become smaller these top-down processes will reach the physical limit of their resolution.A bottom-up approach, which is based on a template-controlled growth of nanostructures on a prestructuredsubstrate, can provide access to structural dimensions of only a few nanometers. The challenge forthe growth of such nanostructures on surfaces is to identify and design suitable surfaces, which act astemplates due to their intrinsic physical and chemical properties. These 2-dimensional (2D) templates canthen be utilized to produce nanostructures of metals, semiconductors, or organic compounds.

Kinetics of solvent supported tubule formation of Lotus (Nelumbo nucifera) wax on highly oriented pyrolytic graphite (HOPG) investigated by atomic force microscopy.

The time dependence of the formation of lotus wax tubules after recrystallization from various chloroform-based solutions on an HOPG surface at room temperature was studied by atomic force microscopy (magnetic AC mode) taking series of consecutive images of the formation process. The growth of the tubules oriented in an upright fashion follows a sequential rodlet→ring→tubule behavior. The influence of a number of factors, e.g., different wax concentration in chloroform, the additional presence of water, or salts [(NH4)2SO4, NH4NO3] or a mixture of salt/water in the solution on the growth rate and orientation of the tubules is also investigated. Different wax concentrations were found to have no effect on the growth rate or the orientation of tubules in none of the solutions. The presence of water, however, considerably increased the growth rate of tubule formation, while the presence of salt was again found to have no effect on growth rate or orientation of tubules.

X-ray diffraction and STM study of reactive surfaces under electrochemical control: Cl and I on Cu(100).

The surface structure of Cu(100) modified by chloride and iodide has been studied in an electrochemical environment by means of in-situ scanning tunneling microscopy in combination with in-situ surface X-ray diffraction with a particular focus on adsorbate and potential dependent surface relaxation phenomena. For positive potentials close to the on-set of the copper dissolution reaction, the X-ray data disclose an extraordinarily large Cu-Cl bond length of 2.61 A for the c(2 x 2)-Cl phase. This finding points to a largely ionic character of the Cu-Cl interaction at the Cu(100) surface, with chloride particles likely to retain their full charge upon adsorption. Together with the positive surface charging at these high potentials, this ionic Cu-Cl bond drives the observed 2.2% outward relaxation between the first two copper layers. These results indicate that the bond between the first and the second copper layer is significantly weakened which appears as the crucial prerequisite for the high surface mobility of copper-chloride species under electrochemical annealing conditions at these high potentials. With 2.51 A the Cu-I bond is 4% shorter than the Cu-Cl bond implying that the nature of the Cu-I bond is mainly covalent. Accordingly, we observe a significant inward relaxation of the top Cu layers upon substituting chloride by iodide at the same electrode potential, which suggests that the iodide adsorption involves charge transfer from the halide to the copper substrate.

Phthalocyanine adsorption on Au(1 1 0): 1D ordering and adaptive reconstruction.

The adsorption of metal-free phthalocyanine molecules on an anisotropic Au(1 1 0)(1 × 2) surface has been studied with ultraviolet (UV) photoemission, low-energy electron diffraction and low-temperature scanning tunneling microscopy. In all cases, the molecules form rows in the [1 [Formula: see text] 0] direction, i.e. along the troughs of the reconstructed substrates. However, depending on the exposure and adsorption temperature, the substrate maintains (1 × 2)- or transforms into a (1 × 3)-reconstruction, and the molecular separation along the rows shrink from six to five times the Au-Au interatomic distance. The results are in agreement with previous density functional theory (DFT) calculations.

Distribution of Pd clusters on ultrathin, epitaxial TiO x films on Pt3Ti(111).

Scanning tunnelling microscopy (STM) was used to investigate the nucleation and growth of palladium clusters on two different, ultrathin, epitaxial, titania films grown on a Pt3Ti(111) surface. The first oxide phase, z'-TiO x , is anisotropic and consists of parallel stripes separated by trenches. Defects (i.e., oxygen vacancies) in this structure are confined to these trenches and act as nucleation sites. Therefore, the Pd clusters are mostly arranged in unidirectional rows along the trenches, creating a template effect. The second phase, w'-TiO x , exhibits a hexagonal, long range, (7 × 7)R21.8°, Moiré-type superstructure with fewer and shallower defects, making the template effect less discernible.

In situ scanning tunneling microscopy study of Ca-modified rutile TiO2(110) in bulk water.

Despite the rising technological interest in the use of calcium-modified TiO2 surfaces in biomedical implants, the Ca/TiO2 interface has not been studied in an aqueous environment. This investigation is the first report on the use of in situ scanning tunneling microscopy (STM) to study calcium-modified rutile TiO2(110) surfaces immersed in high purity water. The TiO2 surface was prepared under ultrahigh vacuum (UHV) with repeated sputtering/annealing cycles. Low energy electron diffraction (LEED) analysis shows a pattern typical for the surface segregation of calcium, which is present as an impurity on the TiO2 bulk. In situ STM images of the surface in bulk water exhibit one-dimensional rows of segregated calcium regularly aligned with the [001] crystal direction. The in situ-characterized morphology and structure of this Ca-modified TiO2 surface are discussed and compared with UHV-STM results from the literature. Prolonged immersion (two days) in the liquid leads to degradation of the overlayer, resulting in a disordered surface. X-ray photoelectron spectroscopy, performed after immersion in water, confirms the presence of calcium.

Structural and compositional characterization of ultrathin titanium oxide films grown on Pt3Ti(111).

We have investigated the growth of ultrathin titanium oxide (TiO(x)) films on a Pt(3)Ti(111) single crystal surface as a function of oxidation temperature (300-1000 K) and oxygen exposure (up to 4500 l) by means of Auger electron spectroscopy, low-energy electron diffraction, ultraviolet photoelectron spectroscopy and high-resolution electron energy loss spectroscopy (HREELS). Both the surface composition and the surface structure of the resulting TiO(x) films exhibit a strong dependence on the preparation conditions. Loss of the chemical order and Ti segregation are observed at the Pt(3)Ti(111) surface upon oxygen exposures of more than 135 l at 1000 K. Increasing oxygen exposure enhances Ti segregation and oxide growth. At a threshold of ≈220 l (at 1000 K) a transition in the oxide structure occurs, namely from a (6 × 3√3) rectangular structure (a = 16.6 Å, b = 14.4 Å) below 220 l to a (7 × 7)R21.8° hexagonal structure (a = b = 19.3 Å) above 220 l. Two additional incommensurate rectangular metastable structures are observed for the highest oxygen exposures (above 900 l) at intermediate oxidation temperatures (800-900 K). In all cases the changes in the valence band spectra and the work function with respect to the clean Pt(3)Ti(111) surface are independent of the chosen oxidation parameters. Based on their HREELS spectra we identify the (6 × 3√3) and (7 × 7)R21.8° structures grown at 1000 K with a stoichiometric TiO phase, while the other and less stable oxide phases grown at 800-900 K exhibit more complex phonon structures that could not simply be associated with any of the stoichiometric phases TiO, Ti(2)O(3) or TiO(2). Our results are rather similar to those found by Granozzi et al for the deposition of Ti onto a Pt(111) surface in an oxygen atmosphere, except a few interesting deviations as a consequence of the different preparation conditions.

Recrystallization of tubules from natural lotus (Nelumbo nucifera) wax on a Au(111) surface.

We present here the first results on the self-assembly of tubules of natural wax from lotus leaves on a single crystal Au(111) surface. A comparison of the tubule growth on Au(111) to that on HOPG is discussed. Although the tubule formation on both Au(111) and HOPG takes place on an intermediate wax film which should mask the substrate properties, the tubule orientations differ. In contrast to a vertical tubule orientation on HOPG, the tubules lie flat on Au(111). Taking into account the physical properties of HOPG and Au(111), we put forward a hypothesis which can explain the different tubule orientations on both substrates.

Electrochemical reactions at a porphyrin-copper interface.

The structure and reactivity of a Cu(100) single crystal electrode surface covered with free base meso-tetra (N-methyl-4-pyridinium) porphyrin (abbreviated as H(2)TMPyP) as a function of electrode potential have been investigated with cyclic voltammetry (CV), electrochemical scanning tunneling microscopy (ECSTM), and UV-Vis and Raman spectroscopy. The well-ordered self-assembled layer of the porphyrin is consistent with the adsorption of the reduced porphyrin species after the first two-electron reduction step. The copper dissolution reaction in the presence of the stable self-assembled porphyrin layer starts at step edges on both upper and lower terraces and coincides with the preferential oxidation of reduced porphyrin species at step sites. The dissolved copper cations are incorporated into the free base porphyrin molecules leading to the formation of CuTMPyP. As a consequence this new species accumulates in the solution with time and a copper redeposition in the cathodic potential scan is lacking.

Copper sulfide nanostripe patterns at the Au(111)/electrolyte interface studied by in situ STM.

One monolayer of Cu was prepared on Au(111) by underpotential deposition from CuSO4/H2SO4 solution and, by two electrolyte exchanges for (i) Cu-free H2SO4 and (ii) NaOH/Na2S solution, exposed to bisulfide. This procedure leads to several incommensurate phases with characteristic stripe patterns. These are irreversibly displaced upon cathodic potential sweeps by different structures, which, after returning to the initial potential, transform into the rectangular CuxS phase already known for the sulfidation of a Cu submonolayer on Au(111).

Disorder or complexity? Understanding a nanoscale template structure on alumina.

One strategy in creating functional nanostructures is templating where active nanoparticles are arranged on a regular nanoscale array of anchor sites on an inert substrate. An extraordinarily well ordered substrate with a 4.2 nm template periodicity is an alumina (aluminum oxide) film grown on a Ni3Al(111) metallic alloy support. Templating on the alumina film is facilitated by a dot and a network superstructure that can readily be prepared but has not yet been understood at the atomic scale. By imaging the alumina surface with dynamic scanning force microscopy (SFM) operated in the noncontact mode (NC-AFM), we reveal that the main structural element of the oxide film is a lattice of hexagons with a 0.29 nm side length that is pinned to the 0.51 nm periodicity of the substrate. The surface unit cell is defined by distinguished sites forming the dot structure. Pinning the oxide film to the substrate furthermore results in a honeycomb-like topographic modulation referred to as the network structure. These findings demonstrate how long range order is generated by the superposition of complex structures that locally exhibit apparent atomic disorder.

Surface structure of an ultrathin alumina film on Ni3Al(111): a dynamic scanning force microscopy study.

The surface structure of an ultrathin alumina film on a Ni3Al(111) substrate has been studied by dynamic scanning force microscopy. The alumina film exhibits a hexagonal superstructure with a lattice parameter of 4.14 nm and a (1/sqrt[3] x 1/sqrt[3])R30 degrees substructure. Two domains rotated by 24 degrees are present. The film is terminated by a hexagonal lattice of oxygen ions with a lattice parameter of 0.293 nm, which is rotated by 30 degrees with respect to the substrate lattice. The nodes of the 4.14 nm superstructure and the 2.39 nm substructure are pinned on points of the substrate lattice, where the surface atomic lattice is almost commensurable. The oxygen lattice is perfectly hexagonal close to these nodes and disordered in the surrounding regions.

Thin alumina films on Ni3Al(111): a template for nanostructured Pd cluster growth.

The growth of vapor deposited palladium on a well-ordered thin alumina film grown on a Ni3Al(111) surface was studied as a function of the sample temperature during deposition and the palladium flux. The superstructure of the oxide film turns out to be an excellent template for the growth of nanostructured palladium cluster arrays. By taking advantage of the growth steering properties of the alumina film we were able to prepare nearly perfectly ordered hexagonal arrays of palladium clusters with a uniform distance of 4.5 nm between the particles. Furthermore the dependence of the cluster height and diameter on the sample voltage as measured by STM has been investigated. In the range between 0.7 V and 2.0 V the measured cluster heights are nearly independent of the sample voltage whereas at voltages higher than 2 V they are continuously decreasing.