Lattice Expansion in Seamless Bi layer Graphene Constrictions at High Bias

Our understanding of sp2 carbon nanostructures is still emerging and is important for the development of high performance all carbon devices. For example, in terms of the structural behavior of graphene or bi-layer graphene at high bias, little to nothing is known. To this end we investigated bi-layer graphene constrictions with closed edges (seamless) at high bias using in situ atomic resolution transmission electron microscopy. We directly observe a highly localized anomalously large lattice expansion inside the constriction. Both the current density and lattice expansion increase as the bi-layer graphene constriction narrows. As the constriction width decreases below 10 nm, shortly before failure, the current density rises to 4 \cdot 109 A cm-2 and the constriction exhibits a lattice expansion with a uniaxial component showing an expansion approaching 5 % and an isotropic component showing an expansion exceeding 1 %. The origin of the lattice expansion is hard to fully ascribe to thermal expansion. Impact ionization is a process in which charge carriers transfer from bonding states to antibonding states thus weakening bonds. The altered character of C-C bonds by impact ionization could explain the anomalously large lattice expansion we observe in seamless bi-layer graphene constrictions. Moreover, impact ionization might also contribute to the observed anisotropy in the lattice expansion, although strain is probably the predominant factor.Comment: to appear in NanoLetter

CVD growth of large area smooth-edged graphene nanomesh by nanosphere lithography

Current etching routes to process large graphene sheets into nanoscale graphene so as to open up a bandgap tend to produce structures with rough and disordered edges. This leads to detrimental electron scattering and reduces carrier mobility. In this work, we present a novel yet simple direct-growth strategy to yield graphene nanomesh (GNM) on a patterned Cu foil via nanosphere lithography. Raman spectroscopy and TEM characterizations show that the as-grown GNM has significantly smoother edges than post-growth etched GNM. More importantly, the transistors based on as-grown GNM with neck widths of 65-75 nm have a near 3-fold higher mobility than those derived from etched GNM with the similar neck widths

Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density

Silicon is receiving discernable attention as an active material for next generation lithium-ion battery anodes because of its unparalleled gravimetric capacity. However, the large volume change of silicon over charge-discharge cycles weakens its competitiveness in the volumetric energy density and cycle life. Here we report direct graphene growth over silicon nanoparticles without silicon carbide formation. The graphene layers anchored onto the silicon surface accommodate the volume expansion of silicon via a sliding process between adjacent graphene layers. When paired with a commercial lithium cobalt oxide cathode, the silicon carbide-free graphene coating allows the full cell to reach volumetric energy densities of 972 and 700 Whl(-1) at first and 200th cycle, respectively, 1.8 and 1.5 times higher than those of current commercial lithium-ion batteries. This observation suggests that two-dimensional layered structure of graphene and its silicon carbide-free integration with silicon can serve as a prototype in advancing silicon anodes to commercially viable technology.

Large-Diameter Single-Wall Carbon Nanotubes Formed Alongside Small-Diameter Double-Walled Carbon Nanotubes

Samples containing a majority of either single-wall carbon nanotubes (SWCNTs) or double-walled carbon nanotubes (DWCNTs) are prepared in the same catalytic chemical vapor deposition conditions but using slightly different catalytic materials, based on alumina impregnated with iron and molybdenum salts. There is a sharp SWCNTs-to-DWCNTs transition. By contrast to the usual findings, the selectivity is not correlated to the size of the iron-based catalyst nanoparticles, nor does the transition occur upon a decreasing carbon/catalyst ratio. The result is attributed to the increasing MoO3 concentration inducing modifications of the gas atmosphere, such as the formation of more reactive C2 species through C2H4 dissociation, which thus favors the nucleation and growth of a DWCNT. In the DWCNT sample, the average diameter of the SWCNTs is higher than the average outer diameter of the DWCNTs, which is uncommon, as many authors stress that SWCNTs show a lower diameter than DWCNTs. The study could provide guidelines for the synthesis of very small diameter DWCNTs

Porous graphitic materials obtained from carbonization of organic xerogels doped with transition metal salts

Porous carbons with a well developed graphitic phase were obtained via the pyrolysis of FeCl3-, NiCl2-, and CoCl2-doped organic xerogels. Doping was realized through salt solubilization in a water/methanol solution of resorcinol and furfural. Carbon xerogels with tailored particles, porous morphology and various degrees of graphitization were obtained depending of the water/methanol ratio and the salt content and type in the starting solution of substrates.When obtained via pyrolysis, carbon xerogels retain the overall open-celled structure exhibiting depleted microporosity and a well-developed mesoporic region that expands into macropores. The removal of metal leads to carbon xerogels with specific surface areas between 170 and 585 m2/g and pore volume up to 0·76 cm3/g. The possibility of enhancing the porosity of xerogels via templating with colloidal silica was also investigated. It was assumed that from the three investigated salts, FeCl3 makes the best choice for graphitization catalyst precursor to obtain uniformly graphitized mesoporous carbon xerogels. The obtained carbon samples were characterized by means of SEM, TEM, X-ray diffraction, Raman spectroscopy, N2 physisorption and thermogravimetric analysis. © Indian Academy of Sciences.113141sciescopu