Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Channel selective tunnelling through a nanographene assembly.

We report selective tunnelling through a nanographene intermolecular tunnel junction achieved via scanning tunnelling microscope tip functionalization with hexa-peri-hexabenzocoronene (HBC) molecules. This leads to an offset in the alignment between the energy levels of the tip and the molecular assembly, resulting in the imaging of a variety of distinct charge density patterns in the HBC assembly, not attainable using a bare metallic tip. Different tunnelling channels can be selected by the application of an electric field in the tunnelling junction, which changes the condition of the HBC on the tip. Density functional theory-based calculations relate the imaged HBC patterns to the calculated molecular orbitals at certain energy levels. These patterns bear a close resemblance to the π-orbital states of the HBC molecule calculated at the relevant energy levels, mainly below the Fermi energy of HBC. This correlation demonstrates the ability of an HBC functionalized tip as regards accessing an energy range that is restricted to the usual operating bias range around the Fermi energy with a normal metallic tip at room temperature. Apart from relating to molecular orbitals, some patterns could also be described in association with the Clar aromatic sextet formula. Our observations may help pave the way towards the possibility of controlling charge transport between organic interfaces.

Electronic and magnetic properties of Ti(2)O(3), Cr(2)O(3), and Fe(2)O(3) calculated by the screened exchange hybrid density functional.

The electronic and magnetic properties of the transition metal sesqui-oxides Cr(2)O(3), Ti(2)O(3), and Fe(2)O(3) have been calculated using the screened exchange (sX) hybrid density functional. This functional is found to give a band structure, bandgap, and magnetic moment in better agreement with experiment than the local density approximation (LDA) or the LDA+U methods. Ti(2)O(3) is found to be a spin-paired insulator with a bandgap of 0.22 eV in the Ti d orbitals. Cr(2)O(3) in its anti-ferromagnetic phase is an intermediate charge transfer Mott-Hubbard insulator with an indirect bandgap of 3.31 eV. Fe(2)O(3), with anti-ferromagnetic order, is found to be a wide bandgap charge transfer semiconductor with a 2.41 eV gap. Interestingly sX outperforms the HSE functional for the bandgaps of these oxides.

Calculation of point defects in rutile TiO 2 by the screened-exchange hybrid functional

The formation energies of the oxygen vacancy and titanium interstitial in rutile TiO 2 were calculated by the screened-exchange (sX) hybrid density functional method, which gives a band gap of 3.1 eV, close to the experimental value. The oxygen vacancy gives rise to a gap state lying 0.7 eV below the conduction band edge, whose charge density is localized around the two of three Ti atoms next to the vacancy. The Ti interstitial (Ti int) generates four defect states in the gap, whose unpaired electrons lie on the interstitial and the adjacent Ti 3d orbitals. The formation energy for the neutral oxygen vacancy is 1.9 eV for the O-poor chemical potential. The neutral Ti interstitial has a lower formation energy than the O vacancy under O-poor conditions. This indicates that both the O vacancy and Ti int are relevant for oxygen deficiency in rutile TiO 2 but the O vacancy will dominate under O-rich conditions. This resolves questions about defect localization and defect predominance in the literature. © 2012 American Physical Society.

Does the orbital degeneracy play any role in the high thermopower of lamellar cobaltites?

This article investigates the role of the CoO6 octahedron distortion on the electronic properties and more particularly on the high value of the Seebeck coefficient in the BiCaCoO lamellar cobaltites. Our measurements provide clues indicating that the t2g orbital degeneracy lifting has to be considered to account for the observed high temperature limit of the thermopower. They also provide experimental arguments for locating the a1g and eg′ orbitals levels on the energy scale, through the compression of the octahedron. These results are in agreement with recent ab initio calculation including the electronic correlations and concluding for the inversion of these levels as compared to the expectation from the crystal field theory. © 2007 American Institute of Physics.