Band Gap Opening Induced by the Structural Periodicity in Epitaxial Graphene Buffer Layer.

The epitaxial graphene buffer layer on the Si face of hexagonal SiC shows a promising band gap, of which the precise origin remains to be understood. In this work, we correlate the electronic to the atomic structure of the buffer layer by combining angle resolved photoemission spectroscopy (ARPES), scanning tunneling microscopy (STM), and high-resolution scanning transmission electron microscopy (HR-STEM). We show that the band structure in the buffer has an electronic periodicity related to the structural periodicity observed in STM images and published X-ray diffraction. Our HR-STEM measurements show the bonding of the buffer layer to the SiC at specific locations separated by 1.5 nm. This is consistent with the quasi 6 × 6 periodic corrugation observed in the STM images. The distance between buffer C and SiC is 1.9 Å in the bonded regions and up to 2.8 Å in the decoupled regions, corresponding to a 0.9 Å corrugation of the buffer layer. The decoupled regions are sp2 hybridized. Density functional tight binding (DFTB) calculations demonstrate the presence of a gap at the Dirac point everywhere in the buffer layer, even in the decoupled regions where the buffer layer has an atomic structure close to that of graphene. The surface periodicity also promotes band in the superperiodic Brillouin zone edges as seen by photoemission and confirmed by our calculations.

Wide Band Gap Semiconductor from a Hidden 2D Incommensurate Graphene Phase.

Producing a usable semiconducting form of graphene has plagued the development of graphene electronics for nearly two decades. Now that new preparation methods have become available, graphene's intrinsic properties can be measured and the search for semiconducting graphene has begun to produce results. This is the case of the first graphene "buffer" layer grown on SiC(0001) presented in this work. We show, contrary to assumptions of the last 40 years, that the buffer graphene layer is not commensurate with SiC. The new modulated structure we've found resolves a long-standing contradiction where ab initio calculations expect a metallic buffer, while experimentally it is found to be a semiconductor. Model calculations using the new incommensurate structure show that the semiconducting π-band character of the buffer comes from partially hybridized graphene incommensurate boundaries surrounding unperturbed graphene islands.

Charge transfer and electronic doping in nitrogen-doped graphene.

Understanding the modification of the graphene's electronic structure upon doping is crucial for enlarging its potential applications. We present a study of nitrogen-doped graphene samples on SiC(000) combining angle-resolved photoelectron spectroscopy, scanning tunneling microscopy and spectroscopy and X-ray photoelectron spectroscopy (XPS). The comparison between tunneling and angle-resolved photoelectron spectra reveals the spatial inhomogeneity of the Dirac energy shift and that a phonon correction has to be applied to the tunneling measurements. XPS data demonstrate the dependence of the N 1s binding energy of graphitic nitrogen on the nitrogen concentration. The measure of the Dirac energy for different nitrogen concentrations reveals that the ratio usually computed between the excess charge brought by the dopants and the dopants' concentration depends on the latter. This is supported by a tight-binding model considering different values for the potentials on the nitrogen site and on its first neighbors.

Atomic structure of epitaxial graphene sidewall nanoribbons: flat graphene, miniribbons, and the confinement gap.

Graphene nanoribbons grown on sidewall facets of SiC have demonstrated exceptional quantized ballistic transport up to 15 µm at room temperature. Angular-resolved photoemission spectroscopy (ARPES) has shown that the ribbons have the band structure of charge neutral graphene, while bent regions of the ribbon develop a bandgap. We present scanning tunneling microscopy and transmission electron microscopy of armchair nanoribbons grown on recrystallized sidewall trenches etched in SiC. We show that the nanoribbons consist of a single graphene layer essentially decoupled from the facet surface. The nanoribbons are bordered by 1-2 nm wide bent miniribbons at both the top and bottom edges of the nanoribbons. We establish that nanoscale confinement in the graphene miniribbons is the origin of the local large band gap observed in ARPES. The structural results presented here show how this gap is formed and provide a framework to help understand ballistic transport in sidewall graphene.

Exceptional ballistic transport in epitaxial graphene nanoribbons.

Graphene nanoribbons will be essential components in future graphene nanoelectronics. However, in typical nanoribbons produced from lithographically patterned exfoliated graphene, the charge carriers travel only about ten nanometres between scattering events, resulting in minimum sheet resistances of about one kilohm per square. Here we show that 40-nanometre-wide graphene nanoribbons epitaxially grown on silicon carbide are single-channel room-temperature ballistic conductors on a length scale greater than ten micrometres, which is similar to the performance of metallic carbon nanotubes. This is equivalent to sheet resistances below 1 ohm per square, surpassing theoretical predictions for perfect graphene by at least an order of magnitude. In neutral graphene ribbons, we show that transport is dominated by two modes. One is ballistic and temperature independent; the other is thermally activated. Transport is protected from back-scattering, possibly reflecting ground-state properties of neutral graphene. At room temperature, the resistance of both modes is found to increase abruptly at a particular length--the ballistic mode at 16 micrometres and the other at 160 nanometres. Our epitaxial graphene nanoribbons will be important not only in fundamental science, but also--because they can be readily produced in thousands--in advanced nanoelectronics, which can make use of their room-temperature ballistic transport properties.

Large area and structured epitaxial graphene produced by confinement controlled sublimation of silicon carbide.

After the pioneering investigations into graphene-based electronics at Georgia Tech, great strides have been made developing epitaxial graphene on silicon carbide (EG) as a new electronic material. EG has not only demonstrated its potential for large scale applications, it also has become an important material for fundamental two-dimensional electron gas physics. It was long known that graphene mono and multilayers grow on SiC crystals at high temperatures in ultrahigh vacuum. At these temperatures, silicon sublimes from the surface and the carbon rich surface layer transforms to graphene. However the quality of the graphene produced in ultrahigh vacuum is poor due to the high sublimation rates at relatively low temperatures. The Georgia Tech team developed growth methods involving encapsulating the SiC crystals in graphite enclosures, thereby sequestering the evaporated silicon and bringing growth process closer to equilibrium. In this confinement controlled sublimation (CCS) process, very high-quality graphene is grown on both polar faces of the SiC crystals. Since 2003, over 50 publications used CCS grown graphene, where it is known as the "furnace grown" graphene. Graphene multilayers grown on the carbon-terminated face of SiC, using the CCS method, were shown to consist of decoupled high mobility graphene layers. The CCS method is now applied on structured silicon carbide surfaces to produce high mobility nano-patterned graphene structures thereby demonstrating that EG is a viable contender for next-generation electronics. Here we present for the first time the CCS method that outperforms other epitaxial graphene production methods.

Spectroscopy of covalently functionalized graphene.

In order to engineer a band gap into graphene, covalent bond-forming reactions can be used to change the hybridization of the graphitic atoms from sp(2) to sp(3), thereby modifying the conjugation length of the delocalized carbon lattice; similar side-wall chemistry has been shown to introduce a band gap into metallic single-walled carbon nanotubes. Here we demonstrate that the application of such covalent bond-forming chemistry modifies the periodicity of the graphene network thereby introducing a band gap (∼0.4 eV), which is observable in the angle-resolved photoelectron spectroscopy of aryl-functionalized graphene. We further show that the chemically-induced changes can be detected by Raman spectroscopy; the in-plane vibrations of the conjugated π-bonds exhibit characteristic Raman spectra and we find that the changes in D, G, and 2D-bands as a result of chemical functionalization of the graphene basal plane are quite distinct from that due to localized, physical defects in sp(2)-conjugated carbon.

Topical application of green and white tea extracts provides protection from solar-simulated ultraviolet light in human skin.

BACKGROUND: Tea polyphenols have been found to exert beneficial effects on the skin via their antioxidant properties. AIMS: We sought to determine whether topical application of green tea or white tea extracts would prevent simulated solar radiation-induced oxidative damages to DNA and Langerhans cells that may lead to immune suppression and carcinogenesis. METHODS: Skin samples were analysed from volunteers or skin explants treated with white tea or green tea after UV irradiation. In another group of patients, the in vivo immune protective effects of green and white tea were evaluated using contact hypersensitivity to dinitrochlorobenzene. RESULTS: Topical application of green and white tea offered protection against detrimental effects of UV on cutaneous immunity. Such protection is not because of direct UV absorption or sunscreen effects as both products showed a sun protection factor of 1. There was no significant difference in the levels of protection afforded by the two agents. Hence, both green tea and white tea are potential photoprotective agents that may be used in conjunction with established methods of sun protection.

Electronic confinement and coherence in patterned epitaxial graphene.

Ultrathin epitaxial graphite was grown on single-crystal silicon carbide by vacuum graphitization. The material can be patterned using standard nanolithography methods. The transport properties, which are closely related to those of carbon nanotubes, are dominated by the single epitaxial graphene layer at the silicon carbide interface and reveal the Dirac nature of the charge carriers. Patterned structures show quantum confinement of electrons and phase coherence lengths beyond 1 micrometer at 4 kelvin, with mobilities exceeding 2.5 square meters per volt-second. All-graphene electronically coherent devices and device architectures are envisaged.

Protective effects of tea polyphenols and caffeine.

Compounds derived from botanical sources, such as polyphenols from tea, have been of interest as possible therapeutic agents. Their benefits in terms of cancer chemoprevention have also been investigated primarily through in vitro and animal in vivo studies. Ultraviolet light from solar radiation has been proven to initiate and promote skin cancer, which is the most common malignancy in light-skinned populations. This review discusses the effects of tea polyphenols in preventing cutaneous carcinogenesis. Although many of the mechanisms and pathways discussed may be applicable to other carcinogens, this review focuses mainly on those related to ultraviolet light-induced processes and potential action sites for tea polyphenols. Since caffeine is a component of tea, and has also been suggested as a possible chemoprotective agent, it is included in this review. Based on data from numerous studies published in the scientific literature, tea polyphenols are promising chemopreventive agents against ultraviolet-induced skin cancers. Their antioxidant properties, inhibitory effects on signal transduction pathways, cell proliferation, angiogenesis and capacity for apoptosis induction, as well as possible immune protective effects, are among the mechanisms that contribute to skin cancer prevention.