In situ study of hydrogenation of graphene and new phases of localization between metal-insulator transitions.

Monolayer graphene synthesized by chemical vapor deposition was subjected to controlled and sequential hydrogenation using RF plasma while monitoring its electrical properties in situ. Low-temperature transport properties, namely, electrical resistance (R), thermopower (S), Hall mobility (µ), and magnetoresistance (MR), were measured for each sample and correlated with ex situ Raman scattering and X-ray photoemission (XPS) characteristics. For weak hydrogenation, the transport is seen to be governed by electron diffusion, and low-temperature transport properties show metallic behavior (conductance G remains nonzero as T → 0). For strong hydrogenation, the transport is found to be describable by variable range hopping (VRH) and the low T conductance shows insulating behavior (G → 0 as T → 0). Weak localization (WL) behavior is seen with a negative MR for weakly hydrogenated graphene, and these WL effects are seen to diminish as the hydrogenation progresses. A clear transition to strong localization (SL) is evident with the emergence of pronounced negative MR for strongly hydrogenated graphene.

Charge transfer and weak chemisorption of oxygen molecules in nanoporous carbon consisting of a disordered network of nanographene sheets.

The adsorption/desorption processes of oxygen are investigated in nanoporous carbon (activated carbon fiber (ACF)) consisting of a disordered network of nanographene sheets. The heat-induced desorption at 200 °C shows the decomposition of oxygen-including functional groups weakly bonded to nanographene edges. The removal of these oxygen-including negatively charged functional groups brings about a change in the type of majority carriers, from holes to electrons, through charge transfer from the functional groups to the interior of nanographene sheets. The oxygen adsorption brings ACF back to the electronic state with holes being majority carriers. In this process, a large concentration of negatively charged O(2)(δ-) molecules with δ ∼ 0.1 are created through charge transfer from nanographene sheets to the adsorbed oxygen molecules. The changes in the thermoelectric power and the electrical resistance in the oxygen desorption process is steeper than that in the oxygen adsorption process. This suggests the irreversibility between the two processes.

Composition controlled synthesis and Raman analysis of Ge-rich Si(x)Ge(1-x) nanowires.

Here, we report the synthesis of Si(x)Ge(1-x) nanowires with x values ranging from 0 to 0.5 using bulk nucleation and growth from larger Ga droplets. Room temperature Raman spectroscopy is shown to determine the composition of the as-synthesized Si(x)Ge(1-x) nanowires. Analysis of peak intensities observed for Ge (near 300 cm(-1)) and the Si-Ge alloy (near 400 cm(-1)) allowed accurate estimation of composition compared to that based on the absolute peak positions. The results showed that the fraction of Ge in the resulting Si(x)Ge(1-x) alloy nanowires is controlled by the vapor phase composition of Ge.

Desorption kinetics of oxygen in plasma treated SWNTs by in situ thermoelectric power measurements.

The functionalization and defect formation of SWNTs caused by isotropic plasma treatments were studied using oxygen desorption/adsorption kinetics by measuring the time dependence of the in situ thermoelectric power (TEP). It is shown that the plasma treatments result in the formation of low binding energy sites for oxygen adsorption. Raman and x-ray photoelectron spectroscopy (XPS) data are in good agreement with the results.

Side-by-side comparison of Raman spectra of anchored and suspended carbon nanomaterials.

Raman spectra of ordered carbon nanomaterials are quite sensitive to surface perturbations, including trace residues, structural defects and residual stress. This is demonstrated by a series of experiments with carbon nanotubes and graphene. Their spectra change due to subtle changes in preparation and attachment to the substrate and to each other. Differences are most clearly seen by forming a material into an air bridge and probing it in the air gap and at the anchor points. A monolayer graphene sheet, shows a larger disorder band at the anchor points than in the air gap. However, a bundle or rope of parallel-aligned single-wall nanotubes shows a larger disorder band in the gap than at the anchor points. For the graphene sheet the substrate surface deforms the graphene, leading to increases in the disorder band. For the rope, the close proximity of the nanotubes to each other appears to produce a larger stress than the rope resting on the substrate.

Electrostatic deposition of graphene.

Loose graphene sheets, one to a few atomic layers thick, are often observed on freshly cleaved HOPG surfaces. A straightforward technique using electrostatic attraction is demonstrated to transfer these graphene sheets to a selected substrate. Sheets from one to 22 layers thick have been transferred by this method. One sheet after initial deposition is measured by atomic force microscopy to be only an atomic layer thick (∼0.35 nm). A few weeks later, this height is seen to increase to ∼0.8 nm. Raman spectroscopy of a single layer sheet shows the emergence of an intense D band which dramatically decreases as the number of layers in the sheet increase. The intense D band in monolayer graphene is attributed to the graphene conforming to the roughness of the substrate. The disruption of the C-C bonds within the single graphene layer could also contribute to this intense D band as evidenced by the emergence of a new band at 1620 cm(-1).

Confined phonons in Si nanowires.

Raman microprobe studies of long crystalline Si nanowires reveal for the first time the evolution of phonon confinement with wire diameter. The Raman band at approximately 520 cm-1 in bulk Si is found to downshift and asymmetrically broaden to lower frequency with decreasing wire diameter D, in good agreement with a phenomenological model first proposed by Richter et al. An adjustable parameter (alpha) is added to the theory that defines the width of the Gaussian phonon confinement function. We find that this parameter is not sensitive to diameter over the range 4-25 nm.

Chemically doped double-walled carbon nanotubes: cylindrical molecular capacitors.

A double-walled carbon nanotube is used to study the radial charge distribution on the positive inner electrode of a cylindrical molecular capacitor. The outer electrode is a shell of bromine anions. Resonant Raman scattering from phonons on each carbon shell reveals the radial charge distribution. A self-consistent tight-binding model confirms the observed molecular Faraday cage effect, i.e., most of the charge resides on the outer wall, even when this wall was originally semiconducting and the inner wall was metallic.

Giant thermopower effects from molecular physisorption on carbon nanotubes.

Results are presented of in situ studies of the thermoelectric power and four-probe resistance of single-walled carbon nanotube films during the adsorption of cyclic hydrocarbons C(6)H(2n) (n=3-6). The size of the change in these transport parameters is found to be related to the pi electron population of the molecule, suggesting the coupling between these pi electrons and those in the nanotube wall may be responsible for the observed effects. A transport model for the SWNT film behavior is presented, incorporating the effects of a new scattering channel associated with the adsorbed molecules.

Raman-active modes of single-walled carbon nanotubes derived from the gas-phase decomposition of CO (HiPco process).

Here we report Raman scattering studies of ropes of Single-walled carbon nanotubes (SWNTs) grown by a high CO pressure process. Five samples from five different batches were studied as a function of excitation wavelength. Three of these samples exhibited Raman spectra similar to that found for SWNTs made by pulsed laser vaporization of arc-discharge methods. The other two samples were found by Raman scattering to contain a significant fraction of tubes with diameter < 1.0 nm. These samples exhibited unusual spectra that, however, can be well understood within the existing models for the electronic and phononic states in SWNTs. Spectra recorded with 1064 nm for the sample having a significant fraction of smaller diameter tubes shows strong modes present between 500 and 1200 cm-1. We suggest these modes arise due to the enhancement of Raman cross-section for small diameter tubes.