Influence of ion energy and substrate temperature on the optical and electronic properties of tetrahedral amorphous carbon (ta-C) films

The properties of amorphous carbon (a-C) deposited using a filtered cathodic vacuum arc as a function of the ion energy and substrate temperature are reported. The sp3 fraction was found to strongly depend on the ion energy, giving a highly sp3 bonded a-C denoted as tetrahedral amorphous carbon (ta-C) at ion energies around 100 eV. The optical band gap was found to follow similar trends to other diamondlike carbon films, varying almost linearly with sp2 fraction. The dependence of the electronic properties are discussed in terms of models of the electronic structure of a-C. The structure of ta-C was also strongly dependent on the deposition temperature, changing sharply to sp2 above a transition temperature, T1, of ≈200°C. Furthermore, T1 was found to decrease with increasing ion energy. Most film properties, such as compressive stress and plasmon energy, were correlated to the sp3 fraction. However, the optical and electrical properties were found to undergo a more gradual transition with the deposition temperature which we attribute to the medium range order of sp2 sites. We attribute the variation in film properties with the deposition temperature to diffusion of interstitials to the surface above T1 due to thermal activation, leading to the relaxation of density in context of a growth model. © 1997 American Institute of Physics.

Graphite intercalation compounds under pressure

Motivated by recent experimental work, we use first-principles density functional theory methods to conduct an extensive search for low enthalpy structures of C$_6$Ca under pressure. As well as a range of buckled structures, which are energetically competitive over an intermediate range of pressures, we show that the high pressure system ($\gtrsim 18$ GPa) is unstable towards the formation of a novel class of layered structures, with the most stable compound involving carbon sheets containing five- and eight-membered rings. As well as discussing the energetics of the different classes of low enthalpy structures, we comment on the electronic structure of the high pressure compound and its implications for superconductivity.

Nature of disorder and localization in amorphous carbon

The electronic structure of amorphous diamond-like carbon is studied. Analysis of the participation ratio shows that π states within the σ-σ* gap are localized. The localization arises from dihedral angle disorder. The localization of π states causes the mobility gap to exceed the optical gap, which accounts for the low carrier mobility and the flat photoluminesence excitation spectrum. © 1998 Elsevier Science B.V. All rights reserved.

High-resolution TEM characterization of ZnO core-shell nanowires for dye-sensitized solar cells

Recently ZnO nanowire films have been used in very promising and inexpensive dye-sensitized solar cells (DSSC). It was found that the performance of the devices can be enhanced by functionalising the nanowires with a thin metal oxide coating. This nm-scale shell is believed to tailor the electronic structure of the nanowire, and help the absorption of the dye. Core-shell ZnO nanowire structures are synthesised at low temperature (below 120°C) by consecutive hydrothermal growth steps. Different materials are investigated for the coating, including Mg, Al, Cs and Zr oxides. High resolution TEM is used to characterise the quality of both the nanowire core and the shell, and to monitor the thickness and the degree of crystallisation of the oxide coating. The interface between the nanowire core and the outer shell is investigated in order to understand the adhesion of the coating, and give valuable feedback for the synthesis process. Nanowire films are packaged into dye-sensitised solar cell prototypes; samples coated with ZrO2 and MgO show the largest enhancement in the photocurrent and open-circuit voltage and look very promising for further improvement. © 2010 IOP Publishing Ltd.

Tailoring the local interaction between graphene layers in graphite at the atomic scale and above using scanning tunneling microscopy.

With recent developments in carbon-based electronics, it is imperative to understand the interplay between the morphology and electronic structure in graphene and graphite. We demonstrate controlled and repeatable vertical displacement of the top graphene layer from the substrate mediated by the scanning tunneling microscopy (STM) tip-sample interaction, manifested at the atomic level as well as over superlattices spanning several tens of nanometers. Besides the full-displacement, we observed the first half-displacement of the surface graphene layer, confirming that a reduced coupling rather than a change in lateral layer stacking is responsible for the triangular/honeycomb atomic lattice transition phenomenon, clearing the controversy surrounding it. Furthermore, an atomic scale mechanical stress at a grain boundary in graphite, resulting in the localization of states near the Fermi energy, is revealed through voltage-dependent imaging. A method of producing graphene nanoribbons based on the manipulation capabilities of the STM is also implemented.

Machine learning for predictive condensed-phase simulation

We show how machine learning techniques based on Bayesian inference can be used to reach new levels of realism in the computer simulation of molecular materials, focusing here on water. We train our machine-learning algorithm using accurate, correlated quantum chemistry, and predict energies and forces in molecular aggregates ranging from clusters to solid and liquid phases. The widely used electronic-structure methods based on density-functional theory (DFT) give poor accuracy for molecular materials like water, and we show how our techniques can be used to generate systematically improvable corrections to DFT. The resulting corrected DFT scheme gives remarkably accurate predictions for the relative energies of small water clusters and of different ice structures, and greatly improves the description of the structure and dynamics of liquid water.

Accurate screened exchange band structures for the transition metal monoxides MnO, FeO, CoO and NiO.

We report calculations of the band structures and density of states of the four transition metal monoxides MnO, FeO, CoO and NiO using the hybrid density functional sX-LDA ('screened exchange local density approximation'). Late transition metal oxides are prototypical examples of strongly correlated materials, which pose challenges for electronic structure methods. We compare our results with available experimental data and show that our calculations generally yield accurate predictions for the fundamental band gaps and valence bands, in favourable agreement with previously reported theoretical studies. For MnO, the band gaps are still underestimated, suggesting additional many-body effects that are not captured by our screened hybrid functional approach.

Theory of defects in amorphous semiconductors

We review the electronic structure of defects in aSi:H, aGaAs and aSi3N4, emphasising in aSi:H the doping mechanism, the evidence that its dangling bond defect has a small electron-lattice coupling and a positive correlation energy, and possible atomic mechanisms for the Staebler-Wronski effect. © 1985.