Quasicrystalline structure formation in a classical crystalline thin-film system.

The discovery of quasicrystals--crystalline structures that show order while lacking periodicity--forced a paradigm shift in crystallography. Initially limited to intermetallic systems, the observation of quasicrystalline structures has recently expanded to include 'soft' quasicrystals in the fields of colloidal and supermolecular chemistry. Here we report an aperiodic oxide that grows as a two-dimensional quasicrystal on a periodic single-element substrate. On a Pt(111) substrate with 3-fold symmetry, the perovskite barium titanate BaTiO3 forms a high-temperature interface-driven structure with 12-fold symmetry. The building blocks of this dodecagonal structure assemble with the theoretically predicted Stampfli-Gähler tiling having a fundamental length-scale of 0.69 nm. This example of interface-driven formation of ultrathin quasicrystals from a typical periodic perovskite oxide potentially extends the quasicrystal concept to a broader range of materials. In addition, it demonstrates that frustration at the interface between two periodic materials can drive a thin film into an aperiodic quasicrystalline phase, as proposed previously. Such structures might also find use as ultrathin buffer layers for the accommodation of large lattice mismatches in conventional epitaxy.

Band-Resolved Double Photoemission Spectroscopy on Correlated Valence Electron Pairs in Metals.

Correlated valence electrons in Ag and Cu are investigated using double photoemission spectroscopy driven by a high-order harmonic light source. Electron pairs consisting of two d electrons as well as pairs with one sp and one d electron are resolved in the two-dimensional energy spectrum. Surprisingly, the intensity ratio of sp-d to d-d pairs from Ag is 3 times higher than in the self-convoluted density of states. Our results directly show the band-resolved configurations of electron pairs in solids and emphasize a band-dependent picture for electron correlation even in these paradigmatic metals.

Structure of single polythiophene molecules on Au(001) prepared by in situ UHV electrospray deposition.

Poly(3-hexylthiophene) (P3HT) adsorption on the quasihexagonally reconstructed Au(001) surface via differentially pumped electrospray deposition is reported. In situ scanning tunneling microscopy reveals a complex adsorption behaviour of P3HT. Weakly adsorbed chains are found which exhibit a 2D random coil like chain configuration across the reconstructed surface. Other molecules are constraint into a fully stretched configuration along the [110] high-symmetry directions of the square Au(001) lattice indicating a strong molecule-substrate interaction. This adsorption is accompanied by local lifting of the reconstruction underneath the polymer chains.

Thermally and photoinduced polymerization of ultrathin sexithiophene films.

The thermally-induced polymerization of α-sexithiophene (6T) molecules on Ag(001) and Au(001) gives rise to long unbranched polymer chains or branched polymer networks depending on the annealing parameters. There, the onset temperature for polymerization depends on the strength of interaction with the underlying substrate. Similar polymerization processes are also induced by ultraviolet radiation with photon energies between 3.0 and 4.2 eV. Radical formation by an electronic excitation in the 6T molecule is proposed as the driving mechanism that necessitates the interplay with the metallic substrate.

Synthesis of Cu(core) Pt(shell) nanoparticles as model structures for core-shell electrocatalysts by direct platinum electrodeposition on copper.

The synthesis of Cu(core)Pt(shell) model catalysts by the direct electrochemical deposition of Pt on Cu particles is presented. Cu particles with an average diameter of 200 nm have been deposited on glassy-carbon electrodes by double pulse electrodeposition from a copper sulfate solution. Subsequent deposition from a platinum nitrate solution under potential control allows for a high selectivity of the Pt deposition towards Cu. Using a combination of cyclic voltammetry, XPS and sputtering, the structure of the generated particles has been analyzed and their core-shell configuration proven. It is shown that the electrocatalytic activity for the oxygen reduction is similar to that of other PtCu catalyst systems. The synthesized structures could allow for the analysis of structure-activity relations of core-shell catalysts on the way to the simple and controlled synthesis of supported Cu(core)Pt(shell) nanoparticles as oxygen reduction catalysts.

2D honeycomb transformation into dodecagonal quasicrystals driven by electrostatic forces.

Dodecagonal oxide quasicrystals are well established as examples of long-range aperiodic order in two dimensions. However, despite investigations by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), low-energy electron microscopy (LEEM), photoemission spectroscopy as well as density functional theory (DFT), their structure is still controversial. Furthermore, the principles that guide the formation of quasicrystals (QCs) in oxides are elusive since the principles that are known to drive metallic QCs are expected to fail for oxides. Here we demonstrate the solution of the oxide QC structure by synchrotron-radiation based surface x-ray diffraction (SXRD) refinement of its largest-known approximant. The oxide QC formation is forced by large alkaline earth metal atoms and the reduction of their mutual electrostatic repulsion. It drives the n = 6 structure of the 2D Ti2O3 honeycomb arrangement via Stone-Wales transformations into an ordered structure with empty n = 4, singly occupied n = 7 and doubly occupied n = 10 rings, as supported by DFT.

Epitaxial BaTiO3(100) films on Pt(100): a low-energy electron diffraction, scanning tunneling microscopy, and x-ray photoelectron spectroscopy study.

The growth of epitaxial ultrathin BaTiO(3) films on a Pt(100) substrate has been studied by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and x-ray photoelectron spectroscopy (XPS). The films have been prepared by radio-frequency-assisted magnetron sputter deposition at room temperature and develop a long-range order upon annealing at 900 K in O(2). By adjusting the Ar and O(2) partial pressures of the sputter gas, the stoichiometry was tuned to match that of a BaTiO(3)(100) single crystal as determined by XPS. STM reveals the growth of continuous BaTiO(3) films with unit cell high islands on top. With LEED already for monolayer thicknesses, the formation of a BaTiO(3)(100)-(1 × 1) structure has been observed. Films of 2-3 unit cell thickness show a brilliant (1 × 1) LEED pattern for which an extended set of LEED I-V data has been acquired. At temperatures above 1050 K the BaTiO(3) thin film starts to decay by formation of vacancy islands. In addition (4 × 4) and (3 × 3) surface reconstructions develop upon prolonged heating.

Vibrational characterization of ethylene adsorption and its thermal evolution on Si(001)-(2 x 1): identification of majority and minority species.

The vibrational and structural properties of a single-domain Si(001)-(2 x 1) surface upon ethylene adsorption have been studied by density functional cluster calculations and high-resolution electron energy loss spectroscopy. The detailed analysis of the theoretically and the experimentally determined vibrational frequencies reveals two coexisting adsorbate configurations. The majority species consist of ethylene molecules which are di-sigma bonded to the two Si atoms of a single Si-Si dimer. The local symmetry of this adsorption complex is reduced to C(2) for ethylene saturation coverage as determined by surface selection rules for the vibrational excitation process. The symmetry reduction includes the rotation of the C-C bond around the surface normal and the twist of the methylene groups around the C-C axis. Experimentally, 17 ethylene-derived modes are found and assigned for the majority and the minority species based on a comparison with calculated vibrational frequencies. The minority species which can account up to 14% of the total ethylene coverage is spectroscopically identified for the first time. It is assigned to ethylene molecules di-sigma bonded to two adjacent Si-Si dimers (in an end-bridge configuration). One part of the minority species desorbs molecularly at 665 K, about 50 K higher than the majority species, whereas the remaining part dissociates to adsorbed acetylene at temperatures around 630 K. For the latter, a di-sigma end-bridge like bonding configuration is proposed based on a comparison with vibrational data for adsorbed acetylene on Si(100)-(2 x 1).

From flat to tilted: gradual interfaces in organic thin film growth.

We investigate domain formation and local morphology of thin films of α-sexithiophene (α-6T) on Au(100) beyond monolayer coverage by combining high resolution scanning tunneling microscopy (STM) experiments with electronic structure theory calculations and computational structure search. We report a layerwise growth of highly-ordered enantiopure domains. For the second and third layer, we show that the molecular orbitals of individual α-6T molecules can be well resolved by STM, providing access to detailed information on the molecular orientation. We find that already in the second layer the molecules abandon the flat adsorption structure of the monolayer and adopt a tilted conformation. Although the observed tilted arrangement resembles the orientation of α-6T in the bulk, the observed morphology does not yet correspond to a well-defined surface of the α-6T bulk structure. A similar behavior is found for the third layer indicating a growth mechanism where the bulk structure is gradually adopted over several layers.

Ultrafast coupled charge and spin dynamics in strongly correlated NiO.

Charge excitations across an electronic band gap play an important role in opto-electronics and light harvesting. In contrast to conventional semiconductors, studies of above-band-gap photoexcitations in strongly correlated materials are still in their infancy. Here we reveal the ultrafast dynamics controlled by Hund's physics in strongly correlated photoexcited NiO. By combining time-resolved two-photon photoemission experiments with state-of-the-art numerical calculations, an ultrafast (≲10 fs) relaxation due to Hund excitations and related photo-induced in-gap states are identified. Remarkably, the weight of these in-gap states displays long-lived coherent THz oscillations up to 2 ps at low temperature. The frequency of these oscillations corresponds to the strength of the antiferromagnetic superexchange interaction in NiO and their lifetime vanishes slightly above the Néel temperature. Numerical simulations of a two-band t-J model reveal that the THz oscillations originate from the interplay between local many-body excitations and antiferromagnetic spin correlations.

Full real-space analysis of a dodecagonal quasicrystal.

The atomically resolved real-space structure of a long-range-ordered dodecagonal quasicrystal is determined based on scanning tunnelling microscopy. For the BaTiO3-derived oxide quasicrystal which spontaneously forms on a Pt(111) surface, 8100 atomic positions have been determined and are compared with an ideal Niizeki-Gähler tiling. Although the Niizeki-Gähler tiling has a complex three-element structure, the abundance of the triangle, square and rhomb tiling elements in the experimental data closely resembles the ideal frequencies. Similarly, the frequencies of all possible next-neighbour tiling combinations are, within the experimental uncertainty, identical to the ideal tiling. The angular and orientational distributions of all individual tiling elements show the characteristics of the dodecagonal quasicrystal. In contrast, the analysis of the orientation of characteristic and more complex tiling combinations indicates the partial decomposition of the quasicrystal into small patches with locally reduced symmetry. These, however, preserve the long-range quasicrystal coherence. The symmetry reduction from dodecagonal to sixfold is assigned to local interaction with the threefold substrate. It leads to atomic flips which preserve the number of quasicrystal tiling elements.

Growth and lattice dynamics of ultrathin BaO films on Pt(0 0 1).

We report on the surface phonons of long-range ordered BaO thin films grown on Pt(0 0 1). In the thickness range between 4 and 28 ML, we find unstrained BaO(0 0 1)-([Formula: see text]) bulk-like terminated films which coincide with a Pt(0 0 1)-c([Formula: see text]) lattice periodicity. The dipole-active lattice vibrations were determined using high-resolution electron energy loss spectroscopy. For all BaO film thicknesses, a single Fuchs-Kliewer phonon-polariton is observed. Its intensity increases and its frequency softens with increasing film thickness. These thickness-dependent properties and the spectral shape are quantitatively discussed on the basis of dielectric theory, where a proper modeling requires three components: the dielectric response of the BaO film itself, the plasmonic response of the metallic substrate, and a weak damping due to a defect-induced doping within the oxide film. For a full description, also the quantization of the phonon wavevector due to the confinement within the film of finite thickness has to be taken into account.

Observation of a dodecagonal oxide quasicrystal and its complex approximant in the SrTiO3-Pt(1 1 1) system.

We report on the formation of a SrTiO3-derived dodecagonal oxide quasicrystal (OQC) at the interface to Pt(1 1 1). This is the second observation of a two-dimensional quasicrystal in the class of oxides. The SrTiO3-derived OQC exhibits strong similarities to the BaTiO3-derived OQC with respect to the local tiling geometry. However, the characteristic length scale of the SrTiO3-derived OQC is 1.8% smaller. Coexisting with the OQC a large scale approximant structure with a monoclinic unit cell is identified. It demonstrates the extraordinary level of complexity that oxide approximant structures can reach.

Vibrational characterization of different benzene phases on flat and vicinal Si(100) surfaces.

Based on high-resolution electron energy loss spectroscopy and temperature-programmable desorption, benzene chemisorption on vicinal and nominally flat Si(100) surfaces has been studied for various adsorption, annealing, and site blocking treatments. Three different chemisorbed benzene (C6H6 and C6D6) phases with distinct thermal desorption characteristics and different vibrational spectra have been separated and characterized on both substrates. All three phases are identified as 1,4-cyclohexadiene-like structures with butterfly geometry. Whereas the dominant phase is di-sigma bonded to the two Si atoms of a single Si-Si dimer, the benzene orientation (double bond orientation) in the other phases is rotated. Di-sigma bonding to Si atoms of adjacent Si-Si dimer for the latter cases is most likely. Coverage and temperature dependent conversions between the different phases have been addressed by vibrational spectroscopy.