A. S. Vinogradov

From Graphene Nanoribbons on Cu(111) to Nanographene on Cu(110): Critical Role of Substrate Structure in the Bottom-Up Fabrication Strategy.

Bottom-up strategies can be effectively implemented for the fabrication of atomically precise graphene nanoribbons. Recently, using 10,10-dibromo-9,9-bianthracene (DBBA) as a molecular precursor to grow armchair nanoribbons on Au(111) and Cu(111), we have shown that substrate activity considerably affects the dynamics of ribbon formation, nonetheless without significant modifications in the growth mechanism. In this paper we compare the on-surface reaction pathways for DBBA molecules on Cu(111) and Cu(110). Evolution of both systems has been studied via a combination of core-level X-ray spectroscopies, scanning tunneling microscopy, and theoretical calculations. Experimental and theoretical results reveal a significant increase in reactivity for the open and anisotropic Cu(110) surface in comparison with the close-packed Cu(111). This increased reactivity results in a predominance of the molecular-substrate interaction over the intermolecular one, which has a critical impact on the transformations of DBBA on Cu(110). Unlike DBBA on Cu(111), the Ullmann coupling cannot be realized for DBBA/Cu(110) and the growth of nanoribbons via this mechanism is blocked. Instead, annealing of DBBA on Cu(110) at 250 °C results in the formation of a new structure: quasi-zero-dimensional flat nanographenes. Each nanographene unit has dehydrogenated zigzag edges bonded to the underlying Cu rows and oriented with the hydrogen-terminated armchair edge parallel to the [1-10] direction. Strong bonding of nanographene to the substrate manifests itself in a high adsorption energy of -12.7 eV and significant charge transfer of 3.46e from the copper surface. Nanographene units coordinated with bromine adatoms are able to arrange in highly regular arrays potentially suitable for nanotemplating.

An X-ray absorption and photoemission study of the electronic structure of Ni porphyrins and Ni N-confused porphyrin

Investigations of chemical bonding and electronic structure features for polycrystalline (porphyrinato)nickel (II) (NiP, the simplest Ni porphyrin), (5,10,15,20-tetraphenylporphyrinato)nickel (II) (NiTPP) and (2-aza-21-carba-5,10,15,20-tetraphenylporphyrinato)nickel (II) (N-confused NiTPP, NiNCTPP) have been performed by means of high-resolution soft x-ray absorption and x-ray photoemission spectroscopy. The Ni 2p(3/2) x-ray absorption spectra show strong π-back-bonding in these compounds leading to a high-energy shift (1.2xa0eV for the NiP and NiTPP) of the entire absorption structure compared to Ni metal. It has been found that the main absorption line of the Ni 2p(3/2) spectrum of the NiNCTPP is shifted by an additional 0.5xa0eV to higher energies in comparison with those for other nickel porphyrins. This shift is evidence of stronger back-donation (metal-to-ligand charge transfer) and a smaller effective number of 3d electrons on the central Ni atom in the NiNCTPP as compared to other Ni porphyrins. The confused N atom in the NiNCTPP is of pyrrolic type (protonated nitrogen), which was confirmed by the N 1s absorption and core-level photoemission spectra.

Controllable p-doping of graphene on Ir(111) by chlorination with FeCl3

The in situ chlorination of graphene on Ir(111) has been achieved by depositing FeCl(3) followed by its thermal decomposition on the surface into FeCl(2) and Cl. This process is accompanied by an intercalation of Cl under graphene and formation of an epitaxial FeCl(2) film on top, which can be removed upon further annealing. A pronounced hole doping of graphene has been observed as a consequence of the annealing-assisted intercalation of Cl. This effect has been studied by a combination of core-level and angle-resolved photoelectron spectroscopies (CL PES and ARPES, respectively), near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and low-energy electron diffraction (LEED). The ease of preparation, the remarkable reproducibility of the doping level and the reversibility of the doping upon annealing are the key factors making chlorination with FeCl(3) a promising route for tuning the electronic properties in graphene.

Impact of Oxygen Coadsorption on Intercalation of Cobalt under the h-BN Nanomesh.

The process of penetration of cobalt atoms through the h-BN nanomesh on Rh(111) is investigated with both spectroscopic and microscopic techniques. It is discovered that oxygen coadsorption can drastically modify the physical properties and behavior of the deposited Co clusters upon postannealing. In the absence of oxygen, Co forms small nanoparticles in the pores (bonding parts) of the h-BN nanomesh, which start to agglomerate at elevated temperatures without any considerable intercalation. However, even a tiny amount of coadsorbed oxygen reduces cobalt agglomeration and greatly promotes its intercalation and trapping under h-BN. The oxygen exposure necessary for a complete intercalation of 1-2 monolayers of Co is very low, and the formation of oxidic species can be easily avoided. The nanomesh structure remains intact upon intercalating submonolayer amounts of Co, while further intercalation gradually distorts and finally destroys the periodic corrugation. Fortunately, this process is not accompanied by damaging the h-BN sheet itself, and the original structure can be restored by removing Co upon annealing at higher temperatures.

Observation of back-donation in 3d metal cyanide complexes through N K absorption spectra

d ¨¨ ¨ Abstract N K and 3d atom L absorption spectra of hexacyano complexes in solid K Fe(CN) , Na Fe(CN) , K Cr(CN) ,

X-ray absorption evidence for the back-donation in iron cyanide complexes

High-resolution, uniformly calibrated Fe 2p3/2 absorption spectra of various Fe(II) and Fe(III) compounds with the metal atom octahedrally coordinated to atomic and molecular ligands are analyzed expecting changes in the absorption spectra due to differences in the formal valence state and in the character of the chemical bond. Particular attention is given to revealing spectral characteristics of the 3dπ–2π(π*) charge transfer (π-back-donation effect) between the iron atom and cyanide ligands.

Comment on "Bottom-Up Graphene-Nanoribbon Fabrication Reveals Chiral Edges and Enantioselectivity"

Comment on Bottom-Up Graphene-Nanoribbon Fabrication Reveals Chiral Edges and Enantioselectivity

Hole doping of graphene supported on Ir(111) by AlBr3

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.

Nitrogen and oxygen core excitations in solid NaNO2 studied by X-ray absorption and resonant photoemission

Abstract The origin and properties of the nitrogen and oxygen K excitations in solid NaNO 2 were investigated combining high-resolution X-ray absorption and resonant photoemission spectroscopy. The absorption spectra obtained were treated on the basis of comparison between the spectra of solid NaNO 2 and gas-phase NO 2 and CH 3 NO 2 molecules, as a result of which main absorption bands were assumed to be associated with the core electron transitions to unoccupied π and σ molecular orbitals of the planar NO 2 Na quasimolecule – the structural unit of the crystal. Examining series of the photoemission spectra taken at the Nxa0K and Oxa0K edges, it was found that the π and σ excitations decay in different ways: three decay channels (spectator, participator and normal Auger processes) were observed for the π excitations whereas only the normal and spectator Auger decay channels were seen for the σ excitations. This fact was qualitatively explained in terms of differences in the spatial localization and lifetime of the corresponding core excitations. The results of the resonant photoemission study give a direct evidence for the quasimolecular NO 2 − origin of the lowest unoccupied electronic states of the π type in solid NaNO 2 .

Electronic structure of copper halides CuI and CuCl: A comparative X-Ray photoelectron and absorption spectroscopy study

The energy distributions of the occupied and unoccupied electronic states for copper halides CuCl and CuI have been investigated using X-ray photoemission and absorption spectroscopy with a highenergy resolution on the equipment of the Russian-German beamline for outlet and monochromatization of synchrotron radiation from the electron storage ring BESSY II. A quasi-molecular analysis of the obtained experimental spectra has revealed that there is a fundamental similarity of the energy structures of the valence band and the conduction band of copper halides CuX (X = Cl, I) due to the identical atomic structure of the studied compounds. The differences in the positions of individual energy subbands in the valence band and the conduction band of CuX and in their intensities in the spectra are associated with different degrees of hybridization of the Cu 3d, 4s and X(n + 1)s, np valence states, as well as with different sizes of structural units (CuCl4 and CuI4 quasi-molecules) of the studied crystals.