Search

Recent studies of core-level x-ray photoelectron spectroscopy (XPS) spectra of silicene on ZrB_2(0001) were found to be inconsistent with the density of states (DOS) of a planar-like structure that has been proposed as the ground state by density functional theory (DFT). To resolve the discrepancy, a reexamination of the XPS spectra and direct theoretical access of accurate single-particle excitation energies are desired. By analyzing the XPS data using symmetric Voigt functions, different binding energies and their sequence of Si 2p orbitals can be assigned from previously reported ones where asymmetric pseudo-Voigt functions are adopted. Theoretically, we have adopted an approach developed very recently, which follows the sophisticated Δ self-consistent field (ΔSCF) methods, to study the single-particle excitation of core states. In the calculations, each single-particle energy and the renormalized core-hole charge density are calculated straightforwardly via two SCF calculations. By comparing the results, the theoretical core-level absolute binding energies including the splitting due to spin-orbit coupling are in good agreement with the observed high-resolution XPS spectra. The good agreement not only resolves the puzzling discrepancy between experiment and theory (DOS) but also advocates the success of DFT in describing many-body interactions of electrons at the surface.

In its freestanding, yet hypothetical form, the Si counterpart of graphene called silicene is predicted to possess massless Dirac fermions and to exhibit an experimentally accessible quantum spin Hall effect. Such interesting electronic properties are not realized in two-dimensional (2D) Si honeycomb lattices prepared recently on metallic substrates where the crystal and hybrid electronic structures of these 'epitaxial silicene' phases are strongly influenced by the substrate, and thus different from those predicted for isolated 2D structures. While the realization of such low-dimensional Si π materials has hardly been imagined previously, it is evident that the materials science behind silicene remains challenging. In this contribution, we will review our recent results that lead to an enhanced understanding of epitaxial silicene formed on diboride thin films, and discuss the remaining challenges that must be addressed in order to turn Si 2D nanostructures into technologically interesting nanoelectronic materials.

So far, it represents a challenging task to reproduce angle-resolved photoelectron (ARPES) spectra of epitaxial silicene by first-principles calculations. Here, we report on the resolution of the previously controversial issue related to the structural configuration of silicene on the ZrB_2(0001) surface and its band structure. In particular, by representing the band structure in a large Brillouin zone associated with a single Si atom, it is found that the imaginary part of the one-particle Green's function follows the spectral weight observed in ARPES spectra. By additionally varying the in-plane lattice constant, the results of density functional theory calculations and ARPES data obtained in a wide energy range converge into the “planarlike” phase and provide the orbital character of electronic states in the vicinity of the Fermi level. It is anticipated that the choice of a smaller commensurate unit cell for the representation of the electronic structure will be useful for the study of epitaxial two-dimensional materials on various substrates in general., identifier:https://dspace.jaist.ac.jp/dspace/handle/10119/12324

The interplay of sp^2- and sp^3-type bonding defines silicon allotropes in two- and three-dimensional forms. A two-dimensional phase bearing structural resemblance to a single MoS_2 layer is found to possess a lower total energy than low-buckled silicene and to be stable in terms of its phonon dispersion relations. A set of cigar-shaped nematic orbitals originating from the Si sp^2 orbitals realizes bonding with a sixfold coordination of the inner Si atoms of the layer. The identification of these nematic orbitals advocates diverse Si bonding configurations different from those of C atoms., identifier:https://dspace.jaist.ac.jp/dspace/handle/10119/12910

High-resolution X-ray photoelectron spectroscopy of two-dimensional films of adenine on a highly oriented pyrolitic graphite [0 0 0 1] surface reveal bonding changes induced by exposure to water. The hydrogen-bond interactions between adenine molecules were replaced by adenine-water hydrogen bonds in a stepwise pattern. This reaction destroyed the film network and changed the chemical state of the nitrogen sites. The reaction with water molecules affected both the donor and acceptor states of the oxygen atoms, as compared to those in water.

The role of nitrogen in the charge transfer and storage capacity of lithium-intercalated heterocyclic oligophenylenes was investigated using photoelectron spectroscopy. The development of new occupied states at low binding energies in the valence band region, as well as core level chemical shifts at both carbon and nitrogen sites, demonstrates partial charge transfer from lithium atoms to the organic component during formation of the intercalated compound. In small compounds, i.e., biphenyl and bipyridine derivatives, the position of the nitrogen heteroatom significantly affects the spacing between gap states in the Li-intercalated film; yet it has minimal effects on the charge storage capacity. In larger, branched systems, the presence of nitrogen in the aromatic system significantly enhances the charge storage capacity while the Li-N bond strength at high intercalation levels is significantly weakened relative to the nitrogen-free derivative. These observations have strong implications towards improved deintercalation processes in organic electrodes in lithium-ion batteries., identifier:https://dspace.jaist.ac.jp/dspace/handle/10119/7788

Highly ordered, multilayer films composed of alternating, oppositely charged, polyionic copper phthalocyanines were prepared on HOPG [0001] substrates via layer-by-layer deposition from aqueous solution and characterized by scanning force microscopy and photoelectron spectroscopies. In films of up to four layers, individual layers alternate. Angle-resolved ultraviolet photoelectron spectra are consistent with a molecular orientation parallel to the substrate surface and indicate that structural order is reduced with film thickness © 2007 American Chemical Society.

The role of nitrogen in the charge transfer and storage capacity of lithium-intercalated heterocyclic oligophenylenes was investigated using photoelectron spectroscopy. The development of new occupied states at low binding energies in the valence band region, as well as core level chemical shifts at both carbon and nitrogen sites, demonstrates partial charge transfer from lithium atoms to the organic component during formation of the intercalated compound. In small compounds, i.e., biphenyl and bipyridine derivatives, the position of the nitrogen heteroatom significantly affects the spacing between gap states in the Li-intercalated film, yet it has minimal effects on the charge storage capacity. In larger, branched systems, the presence of nitrogen in the aromatic system significantly enhances the charge storage capacity while the Li-N bond strength at high intercalation levels is significantly weakened relative to the nitrogen-free derivative. These observations have strong implications towards improved deintercalation processes in organic electrodes in lithium-ion batteries. © 2007 American Institute of Physics.

Struktura a elektronické vlastnosti výchozích a lithiem interkalovaných fenylem terminovaných dimerů anilinu byly studovány fotoelektronovou spektroskopií a kvantovými výpočty. Bylo zjištěno, že elektronová struktura redukované a oxidované formy je jen slabě ovlivněna izovmerií. Po interkalaci byl pozorován významný přenos náboje z Li, který byl lokalizován na N atomy, přičemž jsou energeticky favorizovány konfigurace, kdy jsou oba N atomky dimeru vázány s Li. Konverze N skupin je různá pro obě formy dimerů anilinu a není kompletní ani při vysokých hladinách interkalace, což naznačuje významnou roli solid-state efektů při vzniku takových látek., Structural and electronic properties of pristine and lithium-intercalated, phenyl-capped aniline dimers as a model for the lithium-polyaniline system have been studied by photoelectron spectroscopy and quantum chemical calculations. It was found that the electronic structure of reduced and oxidized forms of oligoanilines is only weakly affected by isomerism. Upon intercalation, charge transfer from the Li-atoms is remarkable and highly localized at N-atomic sites, where configurations are energetically favored in which both N atoms of the dimers are bound to Li atoms. Conversion of nitrogen sites is different for the two forms of aniline dimers and incomplete up to high intercalation levels, indicating a pronounced role of solid-state effects in the formation of such compounds.

The degree of crystallinity, the structure and orientation of crystallites, and the morphology of thin pentacene films grown by vapor deposition in an ultrahigh vacuum environment on polycrystalline copper substrates have been investigated by x-ray diffraction and tapping-mode scanning force microscopy (TM-SFM). Depending on the substrate temperature during deposition, very different results are obtained: While at 77 K a long-range order is missing, the films become crystalline at elevated temperatures. From a high-resolution x-ray-diffraction profile analysis, the volume-weighted size of the crystallites perpendicular to the film surface could be determined. This size of the crystallites increases strongly upon changing temperature between room temperature and 333 K, at which point the size of individual crystallites typically exceeds 100 nm. In this temperature region, three different polymorphs are identified. The vast majority of crystallites have a fiber texture with the (001) net planes parallel to the substrate. In this geometry, the molecules are oriented standing up on the substrate (end-on arrangement). This alignment is remarkably different from that on single-crystalline metal surfaces, indicating that the growth is not epitaxial. Additionally, TM-SFM images show needlelike structures which suggest the presence of at least one additional orientation of crystallites (flat-on or edge-on). These results indicate that properties of thin crystalline pentacene films prepared on technologically relevant polycrystalline metal substrates for fast electronic applications may be compromised by the simultaneous presence of different local molecular aggregation states at all temperatures. © 2006 American Institute of Physics.

Structural and electronic properties of pristine and lithium-intercalated, phenyl-capped aniline dimers as a model for the lithium-polyaniline system have been studied by photoelectron spectroscopy and quantum chemical calculations. It was found that the electronic structure of reduced and oxidized forms of oligoanilines is only weakly affected by isomerism. Upon intercalation, charge transfer from the Li-atoms is remarkable and highly localized at N-atomic sites, where configurations are energetically favored in which both N atoms of the dimers are bound to Li atoms. Conversion of nitrogen sites is different for the two forms of aniline dimers and incomplete up to high intercalation levels, indicating a pronounced role of solid-state effects in the formation of such compounds. © 2006 American Chemical Society.

We used ultraviolet photoelectron spectroscopy (UPS) to investigate the energy level alignment at contacts between pentacene and Ag(1 1 1) in the presence of interfacial 6,13-pentacenequinone (PQ). Depending on the metal pre-coverage with PQ, we found evidence for three distinctly different interface morphologies and molecular orientations, accompanied by significant changes of the energy level alignment. Consequently, the hole injection barrier between pentacene and Ag(1 1 1) varied between 1.1 eV (pristine Ag) and 0.45 eV (5.4 nm PQ pre-coverage on Ag). In addition, our UPS results suggest that PQ can act as deep trap for electrons in a pentacene matrix. Depending on the exact mutual orientation of PQ and pentacene, the depth of these traps can be in the range of 0.2-0.75 eV. © 2006 Elsevier B.V. All rights reserved.

Nonferromagnetic Mn2+ ions can be readily formed at the surface of half metallic La0.7 Sr0.3 MnO3 manganite as demonstrated by deoxygenating surface treatments. The 3 d5 contribution of these Mn2+ ions to the valence-band electronic structure has been characterized using Mn(2p) to 3d resonant photoemission measurements. The Mn2+ related 3d electrons were found to be stabilized by about 2 eV with respect to the mixed-valence 3d states, indicating their strong localization. Active participation of Mn2+ states in both spin and charge conductivity processes is therefore excluded. A two-channel picture, including independent Mn3+ Mn4+ and Mn2+ channels, emerges from detailed data analysis. Reversible Mn2+ formation and straightforward oxygen annealing effects point to a direct bonding between Mn2+ and oxygen vacancies that are most probably created at preexisting structural defects. The t2g and eg states of the mixed valence Mn3+ Mn4+ ions remain unaffected as the Mn2+ content increases, indicating a robust Mn3+ Mn4+ channel independent of structural defects. © 2006 The American Physical Society.

The vibrational coupling in the ground and excited states of positively charged naphthalene, anthracene, tetracene, and pentacene molecules is studied on the basis of a joint experimental and theoretical study of ionization spectra using high-resolution gas-phase photoelectron spectroscopy and first-principles correlated quantum-mechanical calculations. Our theoretical and experimental results reveal that, while the main contribution to relaxation energy in the ground state of oligoacene systems comes from high-energy vibrations, the excited-state relaxation energies show a significant redistribution toward lower-frequency vibrations. A direct correlation is found between the nature of the vibronic interaction and the pattern of the electronic state structure. © 2006 American Chemical Society.

The hole-vibration coupling of the highest occupied state in pentacene thin films on graphite was studied by high-resolution ultraviolet photoemission spectroscopy. It was found that vibration satellites in the film are more intense than that in the gas phase and the vibrational energy in the film is slightly lower than that in the gas phase. This demonstrates that the reorganization energy (hole mobility) in the pentacene thin film is slightly larger (smaller) than that expected from the photoemission spectrum of free pentacene molecules.

During the past three decades, ultraviolet photoelectron spectroscopy of polymer films has evolved from a sort of appearance-potential ( valence band edge) measurement, into a tool for studying the full valence band region of thin polymer films, including insulating polymers, semiconducting polymers and electrically conducting polymers. Progress may be loosely divided into several categories: (A) the melding of thin polymer film technology with ultra high vacuum technology and the widespread use of helium resonance lamps for studies of solid surfaces, (B) the combined approach of measurements and appropriate theoretical-computational methods, and (C) the advent of synchrotron radiation resulting in multi-photon spectroscopies, nominally in the area of the near UV. A coincident discovery of electrically conducting polymers, and especially the evolution of applications of semiconducting polymers, added technologically driven emphasis to this development of UPS for polymer materials. This contribution traces a limited number of highlights in the evolution of UPS of polymers, from the '70' s through to 2005.

Thin films of aligned supramolecular architectures built from newly synthesized thiophene-substituted porphyrins have been processed from solution on surfaces. © The Royal Society of Chemistry 2005.

A combination of conventional and resonant photoemission spectroscopy, x-ray absorption spectroscopy and ground-state quantum-chemical calculations has been used to study the valence electronic structure of a phenyl-capped 3,4-ethylenedioxythiophene oligomer, in polycrystalline thin films. The photon energy-dependent intensities of specific resonant decay channels are interpreted in terms of the spatial overlap of the excitation site and the ground-state molecular orbital involved in the decay. By making use of chemical shifts, excitations on different atomic sites are distinguished. It is demonstrated that site-specific information on the electronic structure of relatively large and complex organic systems may be obtained experimentally from non-radiative resonant decay spectra. In addition, these spectra provide relevant insight into the interpretation of near-edge x-ray absorption fine structure spectra. © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.

Orbital-specific femtosecond charge transfer dynamics between Fe(II)-tetraphenylporphyrin molecules and semimetallic molybdenum disulfide substrates is investigated using core-level resonant photoemission spectroscopy. The electronic coupling to the substrate and the efficiency of charge transport across the interface is found to be different for the individual molecular electronic subsystems. In particular, electrons excited at the phenyl substituents are transferred within 3–6 fs, while hopping from the porphyrin ring is slower than 30 fs.

High-resolution C(1s) near-edge X-ray absorption and X-ray photoionization spectra of the free biphenyl molecule are presented and theoretically analyzed in order to allow an assignment of the observed spectral features. Finite lifetime broadening, a high density of vibrational states, and a strong overlap of contributions from chemically different carbon atom sites only partially allow resolving the vibrational fine structure. However, the shape and width of the spectral profiles are strongly determined by both chemical shifts and vibronic effects. In particular, different from photoionization of valence levels, both types of core level spectra do not contain contributions from dihedral modes which are related to the twisting motion of the two phenyl rings. Contrary to naphthalene, C-H stretching modes are significantly enhanced in the core excitation spectra of biphenyl while the contributions from C-C stretching modes are reduced. © 2005 American Chemical Society.

We report a Kelvin-probe force microscopy (KPFM) investigation on the structural and electronic properties of different submicronscale supramolecular architectures of a synthetic nanographene, including extended layers, percolated networks and broken patterm grown from solutions at surfaces. This study made it possible to determine the local work function (WF) of the different p-conjugated nanostructures adsorbed on mica with a resolution below 10 nm and 0.05 eV. It revealed that the WF strongly depends on the local molecular order at the surface, in particular on the delocalization of electrons in the p-states, on the molecular orientation at surfaces, on the molecular packing density, on the presence of defects in the film and on the different conformations of the aliphatic peripheral chains that might cover the conjugated core. These results were confirmed by comparing the KPFM-estimated local WF of layers supported on mica, where the molecules are preferentially packed edge-on on the substrate, with the ultraviolet photoelectron spectroscopy microscopically measured WF of layers adsorbed on graphite, where the molecules should tend to assemble face-on at the surface. It appears that local WF studies are of paramount importance for understanding the electronic properties of active organic nanostructures, being therefore fundamental for the building of high-performance organic electronic devices, including field-effect transistors, light-emitting diodes and solar cells. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

The hole-vibration coupling of the highest occupied state in pentacene thin films on graphite is studied by high-resolution ultraviolet photoelectron spectroscopy. Vibration satellites in the film show a take-off-angle dependence, indicating that the Franck-Condon principle is not strictly satisfied in this system. They are more intense than in the gas phase and the vibrational energy in the film is slightly lower than that in the gas phase. This demonstrates that the reorganization energy in pentacene thin films is slightly larger than that estimated from the photoelectron spectrum of free pentacene molecules. Furthermore, it is pointed out that the electron hopping in the low-temperature film may occur in the femtosecond scale before the electronic polarization of the surrounding medium is completed. © 2005 The American Physical Society.

Solid-state pyrolysis of organometallic precursors has emerged as an alternative method for preparing carbon nanostructures such as carbon nanotubes (CNT) and carbon anions. The morphology of the tubes can be controlled by the nature of the precursors and the pyrolysis procedures, and micrometer long nanotubes, composed of metal carbide wires encased in a graphitic sheath. Cobalt phthalocyanine (CoPc) as well as iron phthalocyanine were pyrolyzed at different temperatures to obtain CNTs. HRTEM and energy-dispersion X-Ray analysis disclosed that the core consisted of long, iron-containing single crystals and that the core was fully surrounded by crystallized graphic carbon. Iron-filled carbon nanotubes were also obtained from the pyrolysis of ferrocene by CVD method. Encapsulated iron carbide were also observed inside the carbon nanotubes formed after pyrolysis of FePc. These nanotubes and nanocables were considered useful for assembling miniaturized electronic device and sensors.

The initial state chemical shifts and vibrational fine structure of core excitations of naphthalene were analyzed using high-resolution x-ray photoelectron emission (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectra. The carbon atoms at peripheral sites were found to experience a small chemical shift and exhibit similar charge-vibrational coupling. The C-H stretching modes provide significant contributions to overall shape of spectra in the XPS spectra. The results show that vibrational fine structure dominates by particular C-C stretching modes, and in XPS of C2 and C3 sites also by high-energy C-H stretching modes.

The charge transfer in Li-intercalation compounds of the polyaromatic hydrocarbon perylene was examined. It was found that the valence and core-level photoelectron spectroscopies characterized the bonding configuration of the alkali metal atoms. The effect of intermolecular polarization on the ionization potential of Li atoms was compensated by a screening of the Madelung energy. The data collected illustrated that the large charge transfer in the a-perylene was due to the lower ionization potential of lithium atoms.

Ordered films of polycyclic aromatic hydrocarbons (PAHs) and porphyrins with functional (e.g. thiophene) side-groups are good candidates for (opto-)electronic applications where fast charge separation and transport are required. Such highly ordered thin films of PAHs, including discotic hexa-peri-hexabenzocoronene (HBC) and C-132-C-16,C-4, as well as brominated functionalized porphyrin molecules have been grown from solutions on semi-metallic molybdenum disulfide substrates and characterized by angle-resolved valence band photoelectron spectroscopy. A vertical growth of self-assembled supramolecular columns perpendicular to the basal plane of the substrate along with their lateral ordering on the surface has been achieved. Annealing made it possible to increase the structural order in the HBC columns, with molecules positioned at a regular offset from the columnar axis. This permitted the formation of extended pi-electronic states with a bandwidth of at least 0.1-0.2 eV at room temperature. (C) 2004 Elsevier B.V. All rights reserved.