Determination of substrate pinning in epitaxial and supported graphene layers via Raman scattering

The temperature-induced shift of the Raman G line in epitaxial graphene on SiC and Ni surfaces, as well as in graphene supported on SiO2, is investigated with Raman spectroscopy. The thermal shift rate of epitaxial graphene on 6H-SiC(0001) is found to be about three times that of freestanding graphene. This result is explained quantitatively as a consequence of pinning by the substrate. In contrast, graphene grown on polycrystalline Ni films is shown to be unpinned, i.e., to behave elastically as freestanding, despite the relatively strong interaction with the metal substrate. Moreover, it is shown that the transfer of exfoliated graphene layers onto a supporting substrate can result in pinned or unpinned layers, depending on the transfer protocol.Comment: 4 pages, 5 figures. To appear in Physical Review B, Brief Communicatio

Genome-inspired molecular identification in organic matter via Raman spectroscopy

Rapid, non-destructive characterization of molecular level chemistry for organic matter (OM) is experimentally challenging. Raman spectroscopy is one of the most widely used techniques for non-destructive chemical characterization, although it currently does not provide detailed identification of molecular components in OM, due to the combination of diffraction-limited spatial resolution and poor applicability of peak-fitting algorithms. Here, we develop a genome-inspired collective molecular structure fingerprinting approach, which utilizes ab initio calculations and data mining techniques to extract molecular level chemistry from the Raman spectra of OM. We illustrate the power of such an approach by identifying representative molecular fingerprints in OM, for which the molecular chemistry is to date inaccessible using non-destructive characterization techniques. Chemical properties such as aromatic cluster size distribution and H/C ratio can now be quantified directly using the identified molecular fingerprints. Our approach will enable non-destructive identification of chemical signatures with their correlation to the preservation of biosignatures in OM, accurate detection and quantification of environmental contamination, as well as objective assessment of OM with respect to their chemical contents

Diffraction of transmission light through triangular apertures in array of retro-reflective micro-prisms

The array of micro-prisms was described by model of multi-period blazed gratings consisting of triangular apertures. The origins of hexagram-shaped diffraction patterns were interpreted based on multiple-beam interference and diffraction array theorem. The relation between zonal /line ghost fringes and imperfectly fabricated array structures was analyzed. Geometrical performances (e.g., the dihedral angle of micro-prism) were tested by measuring the features of diffraction patterns of samples from three retro-reflective sheeting manufacturers.Comment: Applied Optics(in press), 17 pages, 9 figure

Evolution in Surface Morphology of Epitaxial Graphene Layers on SiC Induced by Controlled Structural Strain

The evolution in the surface morphology of epitaxial graphene films and 6H-SiC(0001) substrates is studied by electron channeling contrast imaging. Whereas film thickness is determined by growth temperature only, increasing growth times at constant temperature affect both internal stress and film morphology. Annealing times in excess of 8-10 minutes lead to an increase in the mean square roughness of SiC step edges to which graphene films are pinned, resulting in compressively stressed films at room temperature. Shorter annealing times produce minimal changes in the morphology of the terrace edges and result in nearly stress-free films upon cooling to room temperature.Comment: 3 pages, 2 figures. Applied Physics Letters 93 (2008), 19191

Low-energy electron diffraction study of potassium adsorbed on single-crystal graphite and highly oriented pyrolytic graphite

Potassium adsorption on graphite has been a model system for the understanding of the interaction of alkali metals with surfaces. The geometries of the s232d structure of potassium on both single-crystal graphite (SCG) and highly oriented pyrolytic graphite (HOPG) were investigated for various preparation conditions for graphite temperatures between 55 and 140 K. In all cases, the geometry was found to consist of K atoms in the hollow sites on top of the surface. The K-graphite average perpendicular spacing is 2.79±0.03 Å, corresponding to an average C-K distance of 3.13±0.03 Å, and the spacing between graphite planes is consistent with the bulk spacing of 3.35 Å. No evidence was observed for a sublayer of potassium. The results of dynamical LEED studies for the clean SCG and HOPG surfaces indicate that the surface structures of both are consistent with the truncated bulk structure of graphite

Rethinking Coal: Thin Films of Solution Processed Natural Carbon Nanoparticles for Electronic Devices

Disordered carbon materials, both amorphous and with long-range order, have been used in a variety of applications, from conductive additives and contact materials to transistors and photovoltaics. Here we show a flexible solution-based method of preparing thin films with tunable electrical properties from suspensions of ball-milled coals following centrifugation. The as-prepared films retain the rich carbon chemistry of the starting coals with conductivities ranging over orders of magnitude, and thermal treatment of the resulting films further tunes the electrical conductivity in excess of 7 orders of magnitude. Optical absorption measurements demonstrate tunable optical gaps from 0 to 1.8 eV. Through low-temperature conductivity measurements and Raman spectroscopy, we demonstrate that variable range hopping controls the electrical properties in as-prepared and thermally treated films and that annealing increases the sp 2 content, localization length, and disorder. The measured hopping energies demonstrate electronic properties similar to amorphous carbon materials and reduced graphene oxide. Finally, Joule heating devices were fabricated from coal-based films, and temperatures as high as 285 °C with excellent stability were achieved

Evolution of topological order in Xe films on a quasicrystal surface

We report results of the first computer simulation studies of a physically adsorbed gas on a quasicrystalline surface, Xe on decagonal Al-Ni-Co. The grand canonical Monte Carlo method is employed, using a semi-empirical gas-surface interaction, based on conventional combining rules, and the usual Lennard-Jones Xe-Xe interaction. The resulting adsorption isotherms and calculated structures are consistent with the results of LEED experimental data. The evolution of the bulk film begins in the second layer, while the low coverage behavior is epitaxial. This transition from 5-fold to 6-fold ordering is temperature dependent, occurring earlier (at lower coverage) for the higher temperatures

Unintended consequences: Why carbonation can dominate in microscale hydration of calcium silicates

The initial microscale mechanisms and materials interfacial process responsible for hydration of calcium silicates are poorly understood even in model systems. The lack of a measured microscale chemical signature has confounded understanding of growth mechanisms and kinetics for microreaction volumes. Here, we use Raman and optical spectroscopies to quantify hydration and environmental carbonation of tricalcium silicates across length and time scales. We show via spatially resolved chemical analysis that carbonate formation during the initial byproduct in microscale reaction volumes is significant, even for subambient CO2 levels. We propose that the competition between carbonation and hydration is enhanced strongly in microscale reaction volumes by increased surface-to-volume ratio relative to macroscale volumes, and by increased concentration of dissolved Ca2+ ions under poor hydration conditions that promote evaporation. This in situ analysis provides the first direct correlation between microscale interfacial hydration and carbonation environments and chemically defined reaction products in cementitious materials.United States. Department of Homeland Security. Science and Technology DirectorateMIT Concrete Sustainability HubPortland Cement AssociationReady Mixed Concrete (RMC) Research & Education Foundatio

Adsorption of Xe and Ar on Quasicrystalline Al-Ni-Co

An interaction potential energy between and adsorbate (Xe and Ar) and the 10-fold Al-Ni-Co quasicrystal is computed by summing over all adsorbate-substrate interatomic interactions. The quasicrystal atoms' coordinates are obtained from LEED experiments and the Lennard-Jones parameters of Xe-Al, Xe-Ni and Xe-Co are found using semiempirical combining rules. The resulting potential energy function of position is highly corrugated. Monolayer adsorption of Xe and Ar on the quasicrystal surface is investigated in two cases: 1) in the limit of low coverage (Henry's law regime), and 2) at somewhat larger coverage, when interactions between adatoms are considered through the second virial coefficient, C_{AAS}. A comparison with adsorption on a flat surface indicates that the corrugation enhances the effect on Xe-Xe (Ar-Ar) interactions. The theoretical results for the low coverage adsorption regime are compared to experimental (LEED isobar) data.Comment: 12 pages, 8figure