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The valence band photoemission (VB PE) spectra of the [Ni(Salen)] molecular complex were measured by ultraviolet, soft X-ray and resonant photoemission (ResPE) using photons with energies ranging from 21.2 eV to 860 eV. It was found that the Ni 3d atomic orbitals’ (AOs) contributions are most significant for molecular orbitals (MOs), which are responsible for the low-energy PE band at a binding energy of 3.8 eV in the VB PE spectra. In turn, the PE bands in the binding energies range of 8–16 eV are due to the photoionization of the MOs of the [Ni(Salen)] complex with dominant contributions from C 2p AOs. A detailed consideration was made for the ResPE spectra obtained using photons with absorption resonance energies in the Ni 2p3/2, N 1s, and O 1s Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra. A strong increase in the intensity of the PE band ab was found when using photons with an energy 854.4 eV in the Ni 2p3/2 NEXAFS spectrum. This finding is due to the high probability of the participator-Auger decay of the Ni 2p3/2−13d9 excitation and confirms the relationship between the PE band ab with the Ni 3d-derived MOs.

The results of the research of a composite based on multi-walled carbon nanotubes (MWCNTs) decorated with CuO/Cu2O/Cu nanoparticles deposited by the cupric formate pyrolysis are discussed. The study used a complementary set of methods, including scanning and transmission electron microscopy, X-ray diffractometry, Raman, and ultrasoft X-ray spectroscopy. The investigation results show the good adhesion between the copper nanoparticles coating and the MWCNT surface through the oxygen atom bridge formation between the carbon atoms of the MWCNT outer graphene layer and the oxygen atoms of CuO and Cu2O oxides. The formation of the Cu–O–C bond between the coating layer and the outer nanotube surface is clearly confirmed by the results of the O 1s near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) of the Cu/MWCNTs nanocomposite. The XPS measurements were performed using a laboratory spectrometer with sample charge compensation, and the NEXAFS studies were carried out using the synchrotron radiation of the Russian–German dipole beamline at BESSY-II (Berlin, Germany) and the NanoPES station at the Kurchatov Center for Synchrotron Radiation and Nanotechnology (Moscow, Russia).

A great variety of two-dimensional (2D) boron allotropes (borophenes) were extensively studied in the past decade in the quest for graphene-like materials with potential for advanced technological applications. Among them, the 2D honeycomb boron is of specific interest as a structural analogue of graphene. Recently it has been synthesized on the Al(111) substrate; however it remains unknown to what extent does honeycomb boron behave like graphene. Here we elucidate the structural and electronic properties of this unusual 2D material with a combination of core-level X-ray spectroscopies, scanning tunneling microscopy, and DFT calculations. We demonstrate that in contrast to graphene on lattice-mismatched metal surfaces, honeycomb boron cannot wiggle like a blanket on Al(111), but rather induces reconstruction of the top metal layer, forming a stoichiometric AlB2 sheet on top of Al. Our conclusions from theoretical modeling are fully supported by X-ray absorption spectra showing strong similarity in the electronic structure of honeycomb boron on Al(111) and thick AlB2 films. On the other hand, a clear separation of the electronic states of the honeycomb boron into π- and σ-subsystems indicates an essentially 2D nature of the electronic system in both one-layer AlB2 and bulk AlB2.

Using a set of microscopic, spectroscopic, and electrochemical methods, a detailed study of the interrelation between the structural and electrochemical properties of the as-prepared nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) and their modified derivatives is carried out. It was found that after treatment of nanotubes with hydrochloric acid, their structure is improved by removing amorphous carbon from the outer layers of N-MWCNTs. On the contrary, ion bombardment leads to the formation of vacancy-type structural defects both on the surface and in the bulk of N-MWCNTs. It is shown that the treated nanotubes have an increased specific capacitance (up to 27 F·g−1) compared to the as-prepared nanotubes (13 F·g−1). This is due to an increase in the redox capacitance. It is associated with the reversible Faraday reactions with the participation of electrochemically active pyridinic and pyrrolic nitrogen inclusions and oxygen-containing functional groups (OCFG). Based on the comparison between cyclic voltammograms of N-MWCNTs treated in HCl and with an ion beam, the peaks on these curves were separated and assigned to specific nitrogen inclusions and OCFGs. It is shown that the rate of redox reactions with the participation of OCFGs is significantly higher than that of reactions with nitrogen inclusions in the pyridinic and pyrrolic forms. Moreover, it was established that treatment of N-MWCNTs in HCl is accompanied by a significant increase in the activity of nitrogen centers, which, in turn, leads to an increase in the rate of redox reactions involving OCFGs. Due to the significant contribution of redox capacitance, the obtained results can be used to develop supercapacitors with increased total specific capacitance.

Currently, X-ray photoelectron spectroscopy (XPS) is widely used to characterize the nanostructured material surface. The ability to determine the atom distribution and chemical state with depth without the sample destruction is important for studying the internal structure of the coating layer several nanometers thick, and makes XPS the preferable tool for the non-destructive testing of nanostructured systems. In this work, ultra-soft X-ray spectroscopy methods are used to study hidden layers and interfaces of pyrolytic tungsten carbide nanoscale coatings on the multi-walled carbon nanotube (MWCNT) surfaces. XPS measurements were performed using laboratory spectrometers with sample charge compensation, and Near Edge X-ray Absorption Fine Structure (NEXAFS) studies using the Russian&ndash, German dipole beamline (RGBL) synchrotron radiation at BESSY-II. The studied samples were tested by scanning and transmission electron microscopy, X-ray diffractometry, Raman scattering and NEXAFS spectroscopy. It was shown that the interface between MWCNT and the pyrolytic coating of tungsten carbide has a three-layer structure: (i) an interface layer consisting of the outer graphene layer carbon atoms, forming bonds with oxygen atoms from the oxides adsorbed on the MWCNT surface, and tungsten atoms from the coating layer, (ii) a non-stoichiometric tungsten carbide WC1-x nanoscale particles layer, (iii) a 3.3 nm thick non-stoichiometric tungsten oxide WO3-x layer on the WC1-x/MWCNT nanocomposite outer surface, formed in air. The tungsten carbide nanosized particle&rsquo, s adhesion to the nanotube outer surface is ensured by the formation of a chemical bond between the carbon atoms from the MWCNT upper layer and the tungsten atoms from the coating layer.

For practical electronic device applications of graphene nanoribbons (GNRs), it is essential to have abrupt and well-defined contacts between the ribbon and the adjacent metal lead. By analogy with graphene, these contacts can induce electron or hole doping, which may significantly affect the I/V characteristics of the device. Cu is among the most popular metals of choice for contact materials. In this study, we investigate the effect of in situ intercalation of Cu on the electronic structure of atomically precise, spatially aligned armchair GNRs of width N = 7 (7-AGNRs) fabricated via a bottom-up method on the Au(788) surface. Scanning tunneling microscopy data reveal that the complete intercalation of about one monolayer of Cu under 7-AGNRs can be facilitated by gentle annealing of the sample at 80 °C. Angle-resolved photoemission spectroscopy (ARPES) data clearly reflect the one-dimensional character of the 7-AGNR band dispersion before and after intercalation. Moreover, ARPES and core-level photoemission results show that intercalation of Cu leads to significant electron injection into the nanoribbons, which causes a pronounced downshift of the valence and conduction bands of the GNR with respect to the Fermi energy (ΔE ~ 0.5 eV). As demonstrated by ARPES and X-ray absorption spectroscopy measurements, the effect of Cu intercalation is restricted to n-doping only, without considerable modification of the band structure of the GNRs. Post-annealing of the 7-AGNRs/Cu/Au(788) system at 200 °C activates the diffusion of Cu into Au and the formation of a Cu-rich surface Au layer. Alloying of intercalated Cu leads to the recovery of the initial position of GNR-related bands with respect to the Fermi energy (EF), thus, proving the tunability of the induced n-doping. [Figure not available: see fulltext.] (Less)

The energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Quasimolecular analysis of the experimental absorption spectra measured in the region of the 2p and 1s ionization thresholds of complexing metal atoms, as well as the 1s thresholds of ligand atoms (nitrogen and carbon), is based on the comparison of the corresponding spectra with each other and with the spectra of the simplest nickel porphyrin NiP. It has been established that, despite a general similarity of the spectra of nitrogen and carbon in CoTPP and NiTPP, the fine structure of the 2p and 1s absorption spectra of cobalt and nickel atoms are radically different. The observed differences in the spectra of cobalt and nickel are associated with the features of the energy distribution of vacant 3d electron states. The presence in CoTPP of the partially filled valence 3db2g molecular orbital (MO) results in the appearance in the cobalt spectra of a low-energy band, which is absent in the spectrum of nickel in NiTPP and leads to a doublet structure of transitions to b1g and eg MOs due to the exchange interaction between 3d electrons in partially filled 3db2g and 3db1g or 3deg MOs. The spectrum of vacant states in CoTPP differs from that in NiTPP also due to the smaller energy distance between 3db1g and eg MOs and the different positions of nonbonding MOs with the C2p character of the porphine ligand.

We investigate the bottom-up growth of N = 7 armchair graphene nanoribbons (7-AGNRs) from the 10,10′-dibromo-9,9′-bianthracene (DBBA) molecules on Ag(111) with the focus on the role of the organometallic (OM) intermediates. It is demonstrated that DBBA molecules on Ag(111) are partially debrominated at room temperature and lose all bromine atoms at elevated temperatures. Similar to DBBA on Cu(111), debrominated molecules form OM chains on Ag(111). Nevertheless, in contrast with the Cu(111) substrate, formation of polyanthracene chains from OM intermediates via an Ullmann-type reaction is feasible on Ag(111). Cleavage of C–Ag bonds occurs before the thermal threshold for the surface-catalyzed activation of C–H bonds on Ag(111) is reached, while on Cu(111) activation of C–H bonds occurs in parallel with the cleavage of the stronger C–Cu bonds. Consequently, while OM intermediates obstruct the Ullmann reaction between DBBA molecules on the Cu(111) substrate, they are required for the formation of polyanthracene chains on Ag(111). If the Ullmann-type reaction on Ag(111) is inhibited, heating of the OM chains produces nanographenes instead. Heating of the polyanthracene chains produces 7-AGNRs, while heating of nanographenes causes the formation of the disordered structures with the possible admixture of short GNRs.

Thermal dependence of mineralized bone structure is examined both experimentally by measuring the near edge x-ray absorption fine structure (NEXAFS) and theoretically by applying the 3DSL model to clarify relationship between the local electronic and atomic structure and hierarchical organization of skeleton. The high energy resolution NEXAFS spectra are acquired near the Ca 2p edges in native bone heated from RT up to 450 °C and hydroxyapatite (Ca10(PO4)6(OH)2, OH-Ap) to understand the interplay of short-, long- and super-range order parameters of bone matter. Our focus is on the thermal changes of spectral distribution of oscillator strength for Ca 2p1/2,3/2 → 3d transition in bone and OH-Ap. The investigations have confirmed the assignment of the OH-Ap-to-bone spectral changes to the predicted hierarchy effect on electronic and atomic structure of mineralized bone. At RT the OH-Ap-to-bone red shift δE3dof the transition energy is found equal ≈ 0.2 eV and ≈ 0.1 eV for mature and young bone respectively. We stated that the shift behaves irregular and its magnitude varies from 0.1 eV up to 0.3 eV when the heating temperature grows. Two mechanisms associated with the thermal-induced dehydration of the inter-nanocrystallite spaces and with the subsequent atomic restructuring of the nanocrystallite interface in mineralized phase are revealed. We have detected that the OH-Ap-to-bone red shifts of the Ca 2p → 3d transition in young bone are smaller than those of in mature bone. The origin of the age differences is discussed.

A very rich Fe-C phase diagram makes the formation of graphene on iron surfaces a challenging task. Here we demonstrate that the growth of graphene on epitaxial iron films can be realized by chemical vapor deposition at relatively low temperatures, and that the formation of carbides can be avoided in excess of the carbon-containing precursors. The resulting graphene monolayer creates a novel periodically corrugated pattern on Fe(110). Using low-energy electron microscopy and scanning tunneling microscopy, we show that it is modulated in one dimension forming long waves with a period of similar to 4 nm parallel to the [001] direction of the substrate, with an additional height modulation along the wave crests. The observed topography of the graphene/Fe superstructure is well reproduced by density functional theory calculations, and found to result from a unique combination of the lattice mismatch and strong interfacial interaction, as probed by core-level photoemission and x-ray absorption spectroscopy.

Chemical functionalization of carbon nanotubes (CNTs), i.e., attachment of individual atoms/molecules or their aggregates to CNTs, can extend the field of application of these nanosystems in nanoelectronics, sensorics, hydrogen power engineering, bioengineering, medicine, etc. (Dresselhaus & Dresselhaus, 2001; Burghard, 2005). In this respect, the fluorination of CNTs is of special interest because the fluorination results in a considerable decrease in the chemical inertness of the initial systems. Therefore, the fluorination is considered as a promising technological process for the first stage of the CNT chemical functionalization (Mickelson et al., 1998; Mickelson et al., 1999; Khabashesku et al., 2002; Lee, 2007). However, carbon materials react with fluorine over a wide range of external conditions. Consequently, the chemical composition, as well as the atomic and electronic structures of fluorinated carbon nanotubes (F-CNTs), depends substantially on the structure and properties of the initial materials and fluorination conditions, such as the reaction temperature and duration, the presence of catalysts, pressure, and concentration of fluorinating reactants (Touhara & Okino, 2000). All these factors need comprehensive investigations of fluorination products by different experimental methods. Fitting of fluorination conditions that are necessary to perform the preset controllable restructuring of the CNT electronic structure remains at present the most topical problem of the carbon nanomaterial chemistry. Therefore, their atomic and electronic structures have been studied by using a limited number of experimental techniques. First and foremost, these are different microscopic techniques ensuring their visualization (Mickelson et al., 1998; Mickelson et al., 1999; Khabashesku et al., 2002; Lee, 2007; Touhara & Okino, 2000), Hamwi et al., 1997; Yudanov et. al., 2002; Hayashi et al., 2002; Lee et al., 2003), x-ray diffraction methods characterizing the degree of F-CNT crystallinity (Hamwi et al., 1997; Yudanov et. al., 2002) UV spectroscopy (Mickelson et al., 1999), Raman spectroscopy (Mickelson et al., 1998; Mickelson et al., 1999; Khabashesku et al., 2002; Lee, 2007; Touhara & Okino, 2000; Hamwi et al., 1997; Lee et al., 2003) and C 1s and F 1s core-level x-ray photoelectron spectroscopy (XPS) (Touhara & Okino, 2000; Hamwi et al., 1997; Lee et al., 2003; An et al, 2002) which provide information on the nature of chemical bonding between 4

The effect of modulating the structure of thin pentacene (C22H14) films by a nanopatterned inert substrate, known as hexagonal boron nitride nanomesh, is reported. Films of different thickness are grown and characterized by x-ray absorption, core-level photoemission, low-energy electron microscopy, microbeam low-energy electron diffraction, and scanning tunneling microscopy. Initially the pentacene molecules adsorb with the molecular plane lying flat on the substrate but they tend to flip up with increasing coverage, forming well-ordered monolayer-thick islands of upright molecules with low nucleation density. The herringbone packing of the upright molecules is observed with scanning tunneling microscopy. The electronic structure of the adsorbed molecules is very similar to that of the gas-phase pentacene, implying weak interaction with the substrate and between the molecules. The periodic corrugation of the substrate surface causes the monolayer of upright pentacene molecules to form two different coincidence superstructures. The lattice parameters of the pentacene unit cell for each of these two substrate-induced domains are determined from the microdiffraction patterns. Both domains can occur in several equivalent configurations, thus resulting in a number of twins with a typical size of a few micrometers. The first monolayer grows in a layer-by-layer mode until it is completed while the second monolayer forms diffusion-limited fractal islands. Upon annealing, the pentacene films are thermally stable up to approximately 80 degrees C and thereafter the onset of desorption is observed.

The atomic and electronic structure of the lattice-mismatched h-BN/Pt(111) and h-BN/Rh(111) interfaces formed by pyrolitic reactions with vaporized borazine has been studied by low-energy electron diffraction, scanning tunneling microscopy, x-ray-absorption spectroscopy, and core-level and valence-band photoemission. It has been found that on Pt(111), h-BN forms a nearly flat monolayer, insignificantly corrugated across the supercell. On Rh(111), h-BN grows in form of a nanomesh, as originally observed by Corso [Science 303, 217 (2004)]. The structural difference between the h-BN/Pt(111) and h-BN/Rh(111) interfaces is associated with the strength of chemical interaction between h-BN and the substrate surface. A stronger orbital hybridization on Rh(111) results in a stronger attraction of the monolayer to the metal surface at favorable adsorption sites resulting in a highly corrugated structure (nanomesh). It has been shown that the electronic structure of the outer (elevated) and inner (attracted to the surface) nanomesh sites is very different as a result of different chemical bonding to the substrate (weak and strong, respectively).

In this letter, we report an easy and tenable way to tune the type of charge carriers in graphene, using a buried layer of AlBr3 and its derivatives on the graphene/Ir(111) interface. Upon the deposition of AlBr3 on graphene/Ir(111) and subsequent temperature-assisted intercalation of graphene/Ir(111) with atomic Br and AlBr3, pronounced hole doping of graphene is observed. The evolution of the graphene/Br-AlBr3/Ir(111) system at different stages of intercalation has been investigated by means of microbeam low-energy electron microscopy/electron diffraction, core-level photoelectron spectroscopy, and angle-resolved photoelectron spectroscopy.

The paper presents the results of investigation of the chemical bond formation in fluorinated single-walled carbon nanotubes using X-ray absorption spectroscopy. All measurements were performed with the use of synchrotron radiation at the BESSY II. The C1s and F1s absorption spectra point to formation of covalent chemical bonding between the fluorine and carbon atoms in F-SWCNTs. The investigation of the local structure of the F-SWCNTs has been done on the basis of calculations by the Density Function Theory and Finite Difference methods.