Studying the onset of galvanic steel corrosionin situusing thin films: film preparation, characterization and application to pitting.

This work reports about a novel approach for investigating surface processes during the early stages of galvanic corrosion of stainless steelin situby employing ultra-thin films and synchrotron x-radiation. Characterized by x-ray techniques and voltammetry, such films, sputter deposited from austenitic steel, were found representing useful replicas of the target material. Typical for stainless steel, the surface consists of a passivation layer of Fe- and Cr-oxides, a couple of nm thick, that is depleted of Ni. Films of ≈4 nm thickness were studiedin situin an electrochemical cell under potential control (-0.6 to +0.8 V vs Ag/AgCl) during exposure to 0.1 M KCl. Material transport was recorded with better than 1/10 monolayer sensitivity by x-ray spectroscopy. Leaching of Fe was observed in the cathodic range and the therefor necessary reduction of Fe-oxide appears to be accelerated by atomic hydrogen. Except for minor leaching, reduction of Ni, while expected from Pourbaix diagram, was not observed until at a potential of about +0.8 V Cr-oxide was removed from the steel film. After couple of minutes exposure at +0.8 V, the current in the electrochemical cell revealed a rapid pitting event that was simultaneously monitored by x-ray spectroscopy. Continuous loss of Cr and Ni was observed during the induction time leading to the pitting, suggesting a causal connection with the event. Finally, a spectroscopic image of a pit was recordedex situwith 50 nm lateral and 1 nm depth resolution by soft x-ray scanning absorption microscopy at the Fe L2,3-edges by using a 80 nm film on a SiN membrane, which is further demonstrating the usefulness of thin films for corrosion studies.

Energy-level alignment at strongly coupled organic-metal interfaces.

Energy-level alignment at organic-metal interfaces plays a crucial role for the performance of organic electronic devices. However, reliable models to predict energetics at strongly coupled interfaces are still lacking. We elucidate contact formation of 1,2,5,6,9,10-coronenehexone (COHON) to the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy, x-ray photoelectron spectroscopy, the x-ray standing wave technique, and density functional theory calculations. While for low COHON thicknesses, the work-functions of the systems vary considerably, for thicker organic films Fermi-level pinning leads to identical work functions of 5.2 eV for all COHON-covered metals irrespective of the pristine substrate work function and the interfacial interaction strength.

Water Dissociates at the Aqueous Interface with Reduced Anatase TiO2 (101).

Elucidating the structure of the interface between natural (reduced) anatase TiO2 (101) and water is an essential step toward understanding the associated photoassisted water splitting mechanism. Here we present surface X-ray diffraction results for the room temperature interface with ultrathin and bulk water, which we explain by reference to density functional theory calculations. We find that both interfaces contain a 25:75 mixture of molecular H2O and terminal OH bound to titanium atoms along with bridging OH species in the contact layer. This is in complete contrast to the inert character of room temperature anatase TiO2 (101) in ultrahigh vacuum. A key difference between the ultrathin and bulk water interfaces is that in the latter water in the second layer is also ordered. These molecules are hydrogen bonded to the contact layer, modifying the bond angles.

Bridging Hydroxyls on Anatase TiO2(101) by Water Dissociation in Oxygen Vacancies.

Titanium dioxide is a promising candidate for photocatalytic H2 fuel production, and understanding water splitting on TiO2 surfaces is vital toward explaining and improving the generation of H2. In this work, we electron irradiate anatase TiO2(101) at room temperature to create metastable surface oxygen vacancies in order to investigate their ability to dissociate H2O. Our scanning tunneling microscopy investigations suggest that the surface oxygen vacancies can dissociate H2O by forming bridging OH species. This claim is supported by theoretical calculations from the literature and our previously published spectroscopic measurements.

Underpotential deposition of Cu on Au(111) from neutral chloride containing electrolyte.

The structure of a chloride terminated copper monolayer electrodeposited onto Au(111) from a CuSO4/KCl electrolyte was investigated ex situ by three complementary experimental techniques (scanning tunneling microscopy (STM), photoelectron spectroscopy (PES), X-ray standing wave (XSW) excitation) and density functional theory (DFT) calculations. STM at atomic resolution reveals a stable, highly ordered layer which exhibits a Moiré structure and is described by a (5 × 5) unit cell. The XSW/PES data yield a well-defined position of the Cu layer and the value of 2.16 Å above the topmost Au layer suggests that the atoms are adsorbed in threefold hollow sites. The chloride exhibits some distribution around a distance of 3.77 Å in agreement with the observed Moiré pattern due to a higher order commensurate lattice. This structure, a high order commensurate Cl overlayer on top of a commensurate (1 × 1) Cu layer with Cu at threefold hollow sites, is corroborated by the DFT calculations.

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO2-Acetic Acid Interface.

The positions of atoms in and around acetate molecules at the rutile TiO2(110) interface with 0.1 M acetic acid have been determined with a precision of ±0.05 Å. Acetate is used as a surrogate for the carboxylate groups typically employed to anchor monocarboxylate dye molecules to TiO2 in dye-sensitized solar cells (DSSC). Structural analysis reveals small domains of ordered (2 × 1) acetate molecules, with substrate atoms closer to their bulk terminated positions compared to the clean UHV surface. Acetate is found in a bidentate bridge position, binding through both oxygen atoms to two 5-fold titanium atoms such that the molecular plane is along the [001] azimuth. Density functional theory calculations provide adsorption geometries in excellent agreement with experiment. The availability of these structural data will improve the accuracy of charge transport models for DSSC.

In operando GISAXS studies of mound coarsening in electrochemical homoepitaxy.

Kinetic roughening during electrodeposition was studied by grazing incidence small angle x-ray scattering for the case of Au(001) homoepitaxial growth in Cl- containing electrolytes. The formation and coarsening of an isotropic mound distribution on unreconstructed Au(001) and of [110]-oriented anisotropic mounds on the "hex" reconstructed surface was observed. The lateral mound coarsening is described by a well-defined scaling law. On unreconstructed Au a transition in the coarsening exponent from ≈1/4 to ≈1/3 with increasing potential is found, which can be explained by the pronounced potential dependence of surface transport processes in an electrochemical environment.

Chemically resolved interface structure of epitaxial graphene on SiC(0001).

Atomic-layer 2D crystals have unique properties that can be significantly modified through interaction with an underlying support. For epitaxial graphene on SiC(0001), the interface strongly influences the electronic properties of the overlaying graphene. We demonstrate a novel combination of x-ray scattering and spectroscopy for studying the complexities of such a buried interface structure. This approach employs x-ray standing wave-excited photoelectron spectroscopy in conjunction with x-ray reflectivity to produce a highly resolved chemically sensitive atomic profile for the terminal substrate bilayers, interface, and graphene layers along the SiC[0001] direction.

Anomalous potential dependence in homoepitaxial Cu(001) electrodeposition: an in situ surface x-ray diffraction study.

Homoepitaxial Cu electrodeposition on Cu(001) in chloride-containing electrolyte was studied by time-resolved in situ surface x-ray diffraction at growth rates up to 38 ML/ min. With increasing Cu electrode potential, transitions from step-flow to layer-by-layer and then to multilayer growth are observed. This potential dependence is opposite to that expected theoretically and found experimentally for the Au(001) homoepitaxial electrodeposition [K. Krug et al., Phys. Rev. Lett. 96, 246101 (2006)]. The anomalous behavior is rationalized by a decisive influence of the ordered c(2 × 2)-Cl adlayer on the surface energy landscape, specifically on the effective change in dipole moment during adatom diffusion.

Graphene on Ir(111): physisorption with chemical modulation.

The nonlocal van der Waals density functional approach is applied to calculate the binding of graphene to Ir(111). The precise agreement of the calculated mean height h = 3.41 Å of the C atoms with their mean height h = (3.38±0.04) Å as measured by the x-ray standing wave technique provides a benchmark for the applicability of the nonlocal functional. We find bonding of graphene to Ir(111) to be due to the van der Waals interaction with an antibonding average contribution from chemical interaction. Despite its globally repulsive character, in certain areas of the large graphene moiré unit cell charge accumulation between Ir substrate and graphene C atoms is observed, signaling a weak covalent bond formation.

High-speed in situ surface X-ray diffraction studies of the electrochemical dissolution of Au(001).

We present in situ X-ray surface diffraction studies of interface processes with data acquisition rates in the millisecond regime, using the electrochemical dissolution of Au(001) in Cl-containing solution as an example. This progress in time resolution permits monitoring of atomic-scale growth and etching processes at solid-liquid interfaces at technologically relevant rates. Au etching was found to proceed via a layer-by-layer mechanism in the entire active dissolution regime up to rates of ∼20 ML/s. Furthermore, we demonstrate that information on the lateral surface morphology and in-plane lattice strain during the electrochemical process can be obtained.

Aggregation and contingent metal/surface reactivity of 1,3,8,10-tetraazaperopyrene (TAPP) on Cu(111).

The structural chemistry and reactivity of 1,3,8,10-tetraazaperopyrene (TAPP) on Cu(111) under ultra-high-vacuum (UHV) conditions has been studied by a combination of experimental techniques (scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy, XPS) and DFT calculations. Depending on the deposition conditions, TAPP forms three main assemblies, which result from initial submonolayer coverages based on different intermolecular interactions: a close-packed assembly similar to a projection of the bulk structure of TAPP, in which the molecules interact mainly through van der Waals (vDW) forces and weak hydrogen bonds; a porous copper surface coordination network; and covalently linked molecular chains. The Cu substrate is of crucial importance in determining the structures of the aggregates and available reaction channels on the surface, both in the formation of the porous network for which it provides the Cu atoms for surface metal coordination and in the covalent coupling of the TAPP molecules at elevated temperature. Apart from their role in the kinetics of surface transformations, the available metal adatoms may also profoundly influence the thermodynamics of transformations by coordination to the reaction product, as shown in this work for the case of the Cu-decorated covalent poly(TAPP-Cu) chains.

Determining the aluminium occupancy on the active T-sites in zeolites using X-ray standing waves.

Zeolites are microporous crystalline materials that find wide application in industry, for example, as catalysts and gas separators, and in our daily life, for example, as adsorbents or as ion exchangers in laundry detergents. The tetrahedrally coordinated silicon and aluminium atoms in the zeolite unit cell occupy the so-called crystallographic T-sites. Besides their pore size, the occupation of specific T-sites by the aluminium atoms determines the performance of the zeolites. Despite its importance, the distribution of aluminium over the crystallographic T-sites remains one of the most challenging, unresolved issues in zeolite science. Here, we report how to determine unambiguously and directly the distribution of aluminium in zeolites by means of the X-ray standing wave technique using brilliant, focused X-rays from a third-generation synchrotron source. We report in detail the analysis of the aluminium distribution in scolecite, which demonstrates how the aluminium occupancy in zeolites can systematically be determined.

Adsorption-induced intramolecular dipole: correlating molecular conformation and interface electronic structure.

The interfaces formed between pentacene (PEN) and perfluoropentacene (PFP) molecules and Cu(111) were studied using photoelectron spectroscopy, X-ray standing wave (XSW), and scanning tunneling microscopy measurements, in conjunction with theoretical modeling. The average carbon bonding distances for PEN and PFP differ strongly, that is, 2.34 A for PEN versus 2.98 A for PFP. An adsorption-induced nonplanar conformation of PFP is suggested by XSW (F atoms 0.1 A above the carbon plane), which causes an intramolecular dipole of approximately 0.5 D. These observations explain why the hole injection barriers at both molecule/metal interfaces are comparable (1.10 eV for PEN and 1.35 eV for PFP) whereas the molecular ionization energies differ significantly (5.00 eV for PEN and 5.85 eV for PFP). Our results show that the hypothesis of charge injection barrier tuning at organic/metal interfaces by adjusting the ionization energy of molecules is not always readily applicable.

Portable chamber for the study of UHV prepared electrochemical interfaces by hard x-ray diffraction.

We report on a new electrochemical cell setup, combined with a portable UHV chamber, for in situ x-ray diffraction using synchrotron radiation. In contrast to more traditional electrochemical sample preparation schemes, atomically clean and well-ordered surfaces are routinely prepared by UHV methods, even in the case of reactive elements or alloys. Samples can be transferred from larger UHV systems into the portable chamber without exposure to ambient air. They can then be studied successively in UHV, in controlled gas atmospheres, and in contact with electrolyte solutions under applied electrochemical potential. The electrochemical setup employs a droplet geometry, which guarantees good electrochemical conditions during in situ x-ray measurements combined with voltammetry. We present first experimental results of Cu deposition on GaAs(001) and on freshly produced nanometric Pd(001) islands on Cu(0.83)Pd(0.17)(001), respectively.

Impact of bidirectional charge transfer and molecular distortions on the electronic structure of a metal-organic interface.

Interface energetics are of fundamental importance in organic and molecular electronics. By combining complementary experimental techniques and first-principles calculations, we resolve the complex interplay among several interfacial phenomena that collectively determine the electronic structure of the strong electron acceptor tetrafluoro-tetracyanoquinodimethane chemisorbed on copper. The combination of adsorption-induced geometric distortion of the molecules, metal-to-molecule charge transfer, and molecule-to-metal back transfer leads to a net increase of the metal work function.

Two-site adsorption model for the (square root 3 x square root 3)-R30 degrees dodecanethiolate lattice on Au(111) surfaces.

The surface structure of dodecanethiolate self-assembled monolayers (SAMs) on Au(111) surfaces, formed from the liquid phase, have been studied by grazing incidence X-ray diffraction (GIXRD), scanning tunneling microscopy (STM), and electrochemical techniques. STM images show that the surface structure consists of (square root 3 x square root 3)-R30 degrees domains with only a few domains of the c(4 x 2) lattice. The best fitting of GIXRD data for the (square root 3 x square root 3)-R30 degrees lattice is obtained with alkanethiolate adsorption at the top sites, although good fittings are also obtained for the fcc and hcp hollow sites. On the basis of this observation, STM data, electrochemical measurements, and previously reported data, we propose a two-site model that implies the formation of incoherent domains of alkanethiolate molecules at top and fcc hollow sites. This model largely improves the fitting of the GIXRD data with respect to those observed for single adsorption sites and, also, for the other possible two-site combinations. The presence of alkanethiolate molecules adsorbed at the less favorable top sites could result from the adsorption pathway that involves an initial physisorption step which, for steric reasons, takes place at on top sites. Once the molecules are chemisorbed, the presence of energy barriers for alkanethiolate surface diffusion, arising mostly from chain-chain interactions, "freezes" some of them at the on top sites, hindering their movement toward fcc hollow sites. By considering the length of the hydrocarbon chain and the adsorption time, the two-site model could be a tool to explain most of the controversial results on this matter reported in the literature.

Chemically resolved structure of the surface.

The structure and chemical states of the Sn/Ge(111) surface are characterized by x-ray standing waves combined with photoemission. For the room temperature square root 3xsquare root 3 phase two chemical components, approximately 0.4 eV apart, are observed for both Sn 3d and 4d core levels. Our model-independent, x-ray standing wave analysis shows unambiguously that the two components originate from Sn adatoms located at two different heights separated vertically by 0.23 A, in favor of a model composed of a fluctuating Sn layer. Contrary to the most accepted scenario, the stronger Sn 3d and 4d components, which appear at the lower binding-energy sides and account for 2/3 of the Sn adatoms, are identified to be associated with the higher Sn position, manifesting their filled valence state character.