Atomic Scale Insights into Reversible Oxygen Storage in Vanadium Oxide Thin Films.

Monolayer vanadium oxide films grown on Pt(111) can be reversibly switched between an oxygen-poor and an oxygen-rich composition, equivalent to V2O3 and V2O5, respectively. While the overall oxygen storage capacity of the film is quantified by X-ray photoelectron spectroscopy, the atomic binding sites of the extra O species are determined by low-temperature scanning tunneling microscopy and electron diffraction. In the O-poor phase, the oxide takes the form of a honeycomb lattice that gets partially covered with vanadyl (V=O) groups at higher O exposure. Upon transition to the O-rich phase, isolated V6O12 rings emerge in the film first, which then evolves towards a disordered O-V-O trilayer on the Pt(111) surface. Our works thus unravels the microscopic nature of reversible oxygen storage in a model system for heterogeneous catalysis.

Interaction of water and carbon monoxide with MnO(001) thin films on Au(111).

Atomically defined MnO(001) thin films were grown on an Au(111) substrate, and their interaction with water (D2O) was investigated by infrared reflection absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). Carbon monoxide adsorption experiments were performed to probe surface atoms and defects on oxide films. Next, water interaction was investigated from which an associative binding pathway and a dissociative binding pathway were revealed, where the water molecules adsorb at terraces and water dissociation takes place at oxygen vacancies mediated by nearby Mn2+ sites. The IRAS data are supported by TDS experiments, which also manifest the importance of defects in the adsorption characteristics of MnO.

Light Emission from Single Oxygen Vacancies in Cu2O Films Probed with Scanning Tunneling Microscopy.

Global photoluminescence (PL) and spatially resolved scanning tunneling microscopy (STM) luminescence are compared for thick Cu2O films grown on Au(111). While the PL data reveal two peaks at 750 and 850 nm, assigned to radiative electron decays via localized gap states induced by O vacancies, a wide-band emission between 700 and 950 nm is observed in STM luminescence. The latter is compatible with cavity plasmons stimulated by inelastic electron tunneling and contains no spectral signature of the Cu2O defects. The STM luminescence is nonetheless controlled by O vacancies that provide inelastic excitation channels for the cavity plasmons. In fact, the emission yield sharply peaks at 2.2 V sample bias, when tip electrons are resonantly injected into O defect states and recombine with holes at the valence-band top via plasmon stimulation. The spatially confined emission centers detected in photon maps of the Cu2O films are therefore assigned to excitation channels mediated by single or few O vacancies in the oxide matrix.

Termination-dependent electronic structure and atomic-scale screening behavior of the Cu2O(111) surface.

By combining differential conductance (dI/dV) spectroscopy with a scanning tunneling microscope and hybrid density functional theory simulations we explore the electronic characteristics of the (1 × 1) and (√3 × âˆš3)R30° terminations of the Cu2O(111) surface close to thermodynamic equilibrium. Although frequently observed experimentally, the composition and atomic structure of these two terminations remain controversial. Our results show that their measured electronic signatures, such as the conduction band onset deduced from dI/dVmeasurements, the bias-dependent appearance of surface topographic features, as well as the work function retrieved from field emission resonances unambiguously confirm their recent assignment to a (1 × 1) Cu-deficient (CuD) and a (√3 × âˆš3)R30° nano-pyramidal reconstruction. Moreover, we demonstrate that due to a different localization of the screening charges at these Cu-deficient terminations, their electronic characteristics qualitatively differ from those of the stoichiometric (1 × 1) and O-deficient (√3 × âˆš3) terminations often assumed in the literature. As a consequence, aside from the topographic differences recently pointed out, also their electronic characteristics may contribute to a radical change in the common perception of the Cu2O(111) surface reactivity.

Electron stimulated desorption of vanadyl-groups from vanadium oxide thin films on Ru(0001) probed with STM.

Low-temperature scanning tunnelling microscopy (STM) is employed to study electron-stimulated desorption of vanadyl groups from an ultrathin vanadium oxide film. The vanadia patches are prepared by reactive vapour deposition of V onto a Ru(0001) surface and comprise a highly ordered network of six and twelve membered V-O rings, some of them terminated by upright V[double bond, length as m-dash]O groups. The vanadyl units can be desorbed via electron injection from the STM tip in a reliable fashion. From hundreds of individual experiments, desorption rates are determined as a function of bias voltage and tunnelling current. Data analysis reveals a distinct threshold behaviour with bias onsets at +3.3 V and -2.6 V for positive and negative polarity, respectively. The desorption rate varies quadratically (cubically) with the tunnelling current at positive (negative) sample bias, indicating that V[double bond, length as m-dash]O desorption is a many-electron process. Based on our findings, a mechanism for desorption is proposed that includes resonant tunnelling into anti-bonding or out of bonding orbitals, followed by vibrational ladder climbing in the binding potential of the V[double bond, length as m-dash]O ad-system. The underlying electronic states can be identified directly in the STM conductance spectra taken on the oxide surface.

A fiber scanning tunneling microscope for optical analysis at the nanoscale.

A hybrid scanning tunneling/optical near-field microscope is presented, in which an optical fiber tip coated with 100 nm thick Ag/Cr films scans the surface. The tip metallization enables operating the instrument via a current-based distance control and guarantees sub-nanometer spatial resolution in the topographic channel. The fiber tip simultaneously serves as nanoscale light source, given the optical transparency of the metal coating. The emission response of the tip-sample junction is collected with two parabolic mirrors and probed with a far-field detector. To test the capabilities of the new setup, the evolution of the optical signal is monitored when the tip approaches a gold surface. The intensity rise and frequency shift of the emission provide evidence for the development of coupled plasmon modes in the tip-sample cavity. Photon mapping is employed to probe the optical inhomogeneity of Ru(0001) and TiO2(110) surfaces covered with silver deposits. While the 2D Ag flakes on Ru give rise to a near-field enhancement, the 3D particles on titania locally damp the gap plasmons and lower the emitted intensity. The lateral resolution in the optical channel has been estimated to be ∼1 nm, and optical and topographic signals are well correlated. Our fiber microscope thus appears to be suitable for probing optical surface properties at the nanoscale.

Growth and characterization of Ca-Mo mixed oxide films on Mo(001).

Calcium-molybdate ultrathin films were prepared on a Mo(001) crystal and characterized by means of scanning tunneling microscopy (STM), electron diffraction, photoelectron spectroscopy, and density functional theory (DFT). The films were grown via reactive Ca deposition, followed by a vacuum annealing step to trigger Mo diffusion from the support into the Ca-O ad-layer. A series of crystalline oxide configurations was revealed that evolves from a (3 × 3) to a (4 × 4) and (6 × 6) superstructure with increasing annealing temperature and finally decays to a binary MoOx phase. The stoichiometry of the initial (3 × 3) phase was estimated to CaMo3O6, yet with decreasing Ca concentration at higher temperature. In the search for a suitable structure model for DFT calculations, we have started with a bulk CaMo5O8 configuration that was iteratively modified to match the experimental data. The optimized structure is made of regular sequences of flat-lying and upright standing Mo octahedrons, being separated from each other by Ca2+ ion rows. With decreasing Ca content, the central Mo units grow in size, which explains the observed transition from (3 × 3) to (6 × 6) superstructures upon annealing. The proposed structure model rationalizes the periodicity and corrugation of the regular oxide surface as well as the characteristic domain patterns in the film. Its electronic properties, as deduced from STM conductance spectroscopy, can be correlated with an increasing metallicity of the ad-layer upon annealing. Our work presents a facile pathway to produce high-quality ternary oxide films via interdiffusion of atoms from a suitable metal support into a binary oxide layer.

Tungsten deposits facilitate oxidation of the NiAl(110) surface.

The alumina film formed by oxidation of NiAl(110) has gained enormous attention as a surface-science compatible model system for a crystalline and atomically flat oxide surface. A main disadvantage is its small thickness of only 0.5 nm that limits possible uses in catalytic studies at elevated temperature and pressure. This work demonstrates how small amounts of tungsten pre-deposited onto the NiAl surface modify the oxidation characteristic. Oxidizing the surface at 850 K in the presence of W particles increases the film thickness to 2.5 nm, a value that rises to more than 5 nm at 1050 K oxidation temperature. Thickness, stoichiometry, and morphology of the thickened alumina films are analyzed in detail by means of X-ray photoelectron spectroscopy, electron-diffraction, and scanning tunneling microscopy. The promoted oxide formation is ascribed to the unique redox properties of tungsten that stabilizes O2 molecules from the gas phase and produces active oxygen species for further reaction.

Adsorption of squaraine molecules to Au(111) and Ag(001) surfaces.

The adsorption of anilino squaraines, an important chromophore for the use in organic solar cells, to Ag(001) and Au(111) has been studied with scanning tunneling microscopy. Self-assembly into square building blocks with eight molecules per unit cell is revealed on the Ag surface, while no ordering effects occur on gold. The squaraine-silver interaction is mediated by the carbonyl and hydroxyl oxygens located in the center of the molecule. The intermolecular coupling, on the other hand, is governed by hydrogen bonds formed between the terminal isobutyl groups and oxygen species of adjacent molecules. The latter gets maximized by rotating the molecules by a few degrees against a perfect square alignment. A similar molecular pattern does not form on Au(111) due to symmetry mismatch. Moreover, the high electronegativity of gold reduces the directing effect of oxygen-metal bonds that trigger the ordering process on silver. As a consequence, only frustrated three-fold symmetric units that do not expand into an ordered molecular network are present on the gold surface.

Temperature-dependent phase evolution of copper-oxide thin-films on Au(111).

The formation of ultrathin copper oxide layers on an Au(111) surface is explored with scanning tunneling microscopy and density functional theory. Depending on the thermal treatment of as-grown Cu-O samples, a variety of thin-film morphologies is observed. Whereas 1D oxide stripes with Au[112[combining macron]] and Au[11[combining macron]0] orientation emerge at 450 and 550 K annealing, respectively, a planar (2 × 2) Cu-O network with specific domain structure develops at higher temperature. The latter is ascribed to a Cu3O2 honeycomb lattice with oxygen ions alternatingly located in surface and interface positions. Strain minimization and a thermodynamic preference for Cu-rich edges lead to the formation of structurally well-defined boundaries, delimiting either triangular, elongated or stripe-like Cu3O2 domains. The low-temperature phases compirse complex arrangements of hexagonal and square Cu-O units, similar to those found in Cu2O(111) and (100) surfaces, respectively. The transitions between different thin-film phases are driven by Cu dissolution in the gold crystal and O2 evaporation and therefore accompanied by a thinning of the oxide layer with increasing temperature.

Incorrect DFT-GGA predictions of the stability of non-stoichiometric/polar dielectric surfaces: the case of Cu2O(111).

Scanning tunneling microscopy (STM) and hybrid density functional theory (DFT) have been used to study the stability and electronic characteristics of the Cu2O(111) surface. We challenge previous interpretations of its structure and composition and show that only appropriate (hybrid) calculations can correctly account for the relative thermodynamic stability of stoichiometric versus Cu-deficient terminations. Our theoretical finding of the stoichiometric surface to be most stable at oxygen-lean conditions is confirmed by an excellent matching between STM spectroscopy data and the calculated surface electronic structure. Beyond the specific case of the Cu2O(111) surface, and beyond the known deficiencies of GGA-based approaches in the description of oxide electronic structures, our work highlights the risk of an erroneous evaluation of the surface stability, in cases where the energetics and electronic characteristics are strongly coupled, as in a wide class of polar and/or non-stoichiometric oxide surfaces.

Formation of Water Chains on CaO(001): What Drives the 1D Growth?

Formation of partly dissociated water chains is observed on CaO(001) films upon water exposure at 300 K. While morphology and orientation of the 1D assemblies are revealed from scanning tunneling microscopy, their atomic structure is identified with infrared absorption spectroscopy combined with density functional theory calculations. The latter exploit an ab initio genetic algorithm linked to atomistic thermodynamics to determine low-energy H2O configurations on the oxide surface. The development of 1D structures on the C4v symmetric CaO(001) is triggered by symmetry-broken water tetramers and a favorable balance between adsorbate-adsorbate versus adsorbate-surface interactions at the constraint of the CaO lattice parameter.

Molecular Adsorption Changes the Quantum Structure of Oxide-Supported Gold Nanoparticles: Chemisorption versus Physisorption.

STM conductance spectroscopy and mapping has been used to analyze the impact of molecular adsorption on the quantized electronic structure of individual metal nanoparticles. For this purpose, isophorone and CO2, as prototype molecules for physisorptive and chemisorptive binding, were dosed onto monolayer Au islands grown on MgO thin films. The molecules attach exclusively to the metal-oxide boundary, while the interior of the islands remains pristine. The Au quantum well states are perturbed due to the adsorption process and increase their mutual energy spacing in the CO2 case but move together in isophorone-covered islands. The shifts disclose the nature of the molecule-Au interaction, which relies on electron exchange for the CO2 ligands but on dispersive forces for the organic species. Our experiments reveal how molecular adsorption affects individual quantum systems, a topic of utmost relevance for heterogeneous catalysis.

Exploring routes to tailor the physical and chemical properties of oxides via doping: an STM study.

Doping opens fascinating possibilities for tailoring the electronic, optical, magnetic, and chemical properties of oxides. The dopants perturb the intrinsic behavior of the material by generating charge centers for electron transfer into adsorbates, by inducing new energy levels for electronic and optical excitations, and by altering the surface morphology and hence the adsorption and reactivity pattern. Despite a vivid scientific interest, knowledge on doped oxides is limited when compared to semiconductors, which reflects the higher complexity and the insulating nature of many oxides. In fact, atomic-scale studies, aiming at a mechanistic understanding of dopant-related processes, are still scarce.In this article, we review our scanning tunneling microscopy (STM) experiments on thin, crystalline oxide films with a defined doping level. We demonstrate how the impurities alter the surface morphology and produce cationic/anionic vacancies in order to keep the system charge neutral. We discuss how individual dopants can be visualized in the lattice, even if they reside in subsurface layers. By means of STM-conductance and x-ray photoelectron spectroscopy, we determine the electronic impact of dopants, including the energies of their eigen states and local band-bending effects in the host oxide. Electronic transitions between dopant-induced gap states give rise to new optical modes, as detected with STM luminescence spectroscopy. From a chemical perspective, dopants are introduced to improve the redox potential of oxide materials. Electron transfer from Mo-donors, for example, alters the growth behavior of gold and activates O2 molecules on a wide-gap CaO surface. Such results demonstrate the enormous potential of doped oxides in heterogeneous catalysis. Our experiments address the issue of doping from a fundamental viewpoint, posing questions on the lattice position, charge state, and electron-transfer potential of the impurity ions. Whether doped oxides are suitable to catalyze surface reactions needs to be explored in more applied studies in the future.

Carbon dioxide activation and reaction induced by electron transfer at an oxide-metal interface.

A model system has been created to shuttle electrons through a metal-insulator-metal (MIM) structure to induce the formation of a CO2 anion radical from adsorbed gas-phase carbon dioxide that subsequently reacts to form an oxalate species. The process is completely reversible, and thus allows the elementary steps involved to be studied at the atomic level. The oxalate species at the MIM interface have been identified locally by scanning tunneling microscopy, chemically by IR spectroscopy, and their formation verified by density functional calculations.

Activating Nonreducible Oxides via Doping.

Nonreducible oxides are characterized by large band gaps and are therefore unable to exchange electrons or to form bonds with surface species, explaining their chemical inertness. The insertion of aliovalent dopants alters this situation, as new electronic states become available in the gap that may be involved in charge-transfer processes. Consequently, the adsorption and reactivity pattern of doped oxides changes with respect to their nondoped counterparts. This Account describes scanning tunneling microscopy (STM) and photoelectron spectroscopy (XPS) experiments that demonstrate the impact of dopants on the physical and chemical properties of well-defined crystalline oxide films. For this purpose, MgO and CaO as archetypical rocksalt oxides have been loaded either with high-valence (Mo, Cr) or low-valence dopants (Li). While the former generate filled states in the oxide band gap and serve as electron donors, the latter produce valence-band holes and give rise to an acceptor response. The dopant-related electronic states and their polarization effect on the surrounding host material are explored with XPS and STM spectroscopy on nonlocal and local scales. Moreover, charge-compensating defects were found to develop in the oxide lattice, such as Ca and O vacancies in Mo- and Li-doped CaO films, respectively. These native defects are able to trap the excess charges of the impurities and therefore diminish the desired doping effect. If noncompensated dopants reside in the host lattice, electron exchange with surface species is observed. Mo ions in CaO, for example, were found to donate electrons to surface Au atoms. The anionic Au strongly binds to the CaO surface and nucleates in the form of monolayer islands, in contrast to the 3D growth prevailing on pristine oxides. Charge transfer is also revealed for surface O2 that traps one Mo electron by forming a superoxo-species. The activated oxygen is characterized by a reinforced binding to the surface, an elongated O-O bond length, and a reduced barrier for dissociation, and represents an important intermediate for oxidation reactions. The charge-transfer processes described here are quenched if Li is inserted into the oxide lattice, neutralizing the effect of the extra electrons. The specific behavior of doped oxides has been explored on a mechanistic level, i.e. on thin-film model systems at ultrahigh vacuum and low temperature. We believe, however, that our results are transferrable to realistic conditions and doping might thus develop into a powerful method to improve the performance of nonreducible oxides in surface-catalyzed reactions.

Phonon-mediated electron transport through CaO thin films.

Scanning tunneling microscopy has developed into a powerful tool for the characterization of conductive surfaces, for which the overlap of tip and sample wave functions determines the image contrast. On insulating layers, as the CaO thin film grown on Mo(001) investigated here, direct overlap between initial and final states is not enabled anymore and electrons are transported via hopping through the conduction-band states of the oxide. Carrier transport is accompanied by strong phonon excitations in this case, imprinting an oscillatory signature on the differential conductance spectra of the system. The phonons show a characteristic spatial dependence and become softer around lattice irregularities in the oxide film, such as dislocation lines.

Erratum: Titration of Ce

This corrects the article DOI: 10.1103/PhysRevLett.111.206101.

Autocatalytic growth of ZnO nanorods from flat Au(111)-supported ZnO films.

Physical vapour deposition of ZnO on an Au(111) support has been investigated as a function of the oxygen chemical potential by means of scanning tunnelling microscopy and luminescence spectroscopy. Whereas a layer-by-layer growth of ZnO is revealed in oxygen excess, formation of oxide nanorods with large height-to-diameter ratio prevails at lower oxygen chemical potentials. We ascribe the formation of 3D nanostructures in the latter case to traces of Au atoms on the surface that promote trapping and dissociation of the incoming oxygen molecules. The Au residuals, acting as catalyst for the oxide formation, are indeed found on top of the ZnO nanorods.

Surface defects and their impact on the electronic structure of Mo-doped CaO films: an STM and DFT study.

The functionality of doped oxides sensitively depends on the spatial distribution of the impurity ions and their interplay with compensating defects in the lattice. In our combined scanning tunneling microscopy (STM) and density functional theory (DFT) study, we analyze defects occurring in Mo-doped CaO(001) films at the atomic scale. By means of topographic imaging, we identify common point and line defect in the doped oxide, in particular Mo donors and compensating Ca vacancies. The influence of charged defects on the oxide electronic structure is analyzed by STM conductance spectroscopy. The experimentally observed defect features are connected to typical point defects in the CaO lattice by means of DFT calculations. Apart from the identification of individual defects, our study reveals a pronounced inhomogeneity of the oxide electronic structure, reflecting the uneven spatial distribution of dopants in the lattice. Our results provide the basis for a better understanding of adsorption and reaction patterns on doped oxides, as widely used in heterogeneous catalysis.