132 research outputs found
Enhancement of the Electron Spin Resonance of Single-Walled Carbon Nanotubes by Oxygen Removal
We have observed a nearly fourfold increase in the electron spin resonance
(ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to
oxygen desorption. By performing temperature-dependent ESR spectroscopy both
before and after thermal annealing, we found that the ESR in SWCNTs can be
reversibly altered via the molecular oxygen content in the samples. Independent
of the presence of adsorbed oxygen, a Curie-law (spin susceptibility ) is seen from 4 K to 300 K, indicating that the probed spins are
finite-level species. For both the pre-annealed and post-annealed sample
conditions, the ESR linewidth decreased as the temperature was increased, a
phenomenon we identify as motional narrowing. From the temperature dependence
of the linewidth, we extracted an estimate of the intertube hopping frequency;
for both sample conditions, we found this hopping frequency to be 100
GHz. Since the spin hopping frequency changes only slightly when oxygen is
desorbed, we conclude that only the spin susceptibility, not spin transport, is
affected by the presence of physisorbed molecular oxygen in SWCNT ensembles.
Surprisingly, no linewidth change is observed when the amount of oxygen in the
SWCNT sample is altered, contrary to other carbonaceous systems and certain 1D
conducting polymers. We hypothesize that physisorbed molecular oxygen acts as
an acceptor (-type), compensating the donor-like (-type) defects that are
responsible for the ESR signal in bulk SWCNTs.Comment: 14 pages, 7 figure
Transfer-free electrical insulation of epitaxial graphene from its metal substrate
High-quality, large-area epitaxial graphene can be grown on metal surfaces
but its transport properties cannot be exploited because the electrical
conduction is dominated by the substrate. Here we insulate epitaxial graphene
on Ru(0001) by a step-wise intercalation of silicon and oxygen, and the
eventual formation of a SiO layer between the graphene and the metal. We
follow the reaction steps by x-ray photoemission spectroscopy and demonstrate
the electrical insulation using a nano-scale multipoint probe technique.Comment: Accepted for publication in Nano Letter
Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study
Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements
Probing the Thermal Deoxygenation of Graphene Oxide using High Resolution In Situ X-Ray based Spectroscopies
Despite the recent developments in Graphene Oxide due to its importance as a
host precursor of Graphene, the detailed electronic structure and its evolution
during the thermal reduction remain largely unknown, hindering its potential
applications. We show that a combination of high resolution in situ X-ray
photoemission and X-ray absorption spectroscopies offer a powerful approach to
monitor the deoxygenation process and comprehensively evaluate the electronic
structure of Graphene Oxide thin films at different stages of the thermal
reduction process. It is established that the edge plane carboxyl groups are
highly unstable, whereas carbonyl groups are more difficult to remove. The
results consistently support the formation of phenol groups through reaction of
basal plane epoxide groups with adjacent hydroxyl groups at moderate degrees of
thermal activation (~400 {\deg}C). The phenol groups are predominant over
carbonyl groups and survive even at a temperature of 1000 {\deg}C. For the
first time a drastic increase in the density of states (DOS) near the Fermi
level at 600 {\deg}C is observed, suggesting a progressive restoration of
aromatic structure in the thermally reduced graphene oxideComment: Pagona Papakonstantinou as Corresponding author, E-mail:
[email protected]
Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy
[[abstract]]This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced
graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve
defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the
GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily
reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature.
Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure
spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are
bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat
and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and
the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further
support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based
on experimental results and first-principles calculations, the variation in magnetic behavior from GO
to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-
derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with
oxygen-containing and hydroxyl groups on GO sheets.[[notice]]補正完
In Situ Observations during Chemical Vapor Deposition of Hexagonal Boron Nitride on Polycrystalline Copper.
Using a combination of complementary in situ X-ray photoelectron spectroscopy and X-ray diffraction, we study the fundamental mechanisms underlying the chemical vapor deposition (CVD) of hexagonal boron nitride (h-BN) on polycrystalline Cu. The nucleation and growth of h-BN layers is found to occur isothermally, i.e., at constant elevated temperature, on the Cu surface during exposure to borazine. A Cu lattice expansion during borazine exposure and B precipitation from Cu upon cooling highlight that B is incorporated into the Cu bulk, i.e., that growth is not just surface-mediated. On this basis we suggest that B is taken up in the Cu catalyst while N is not (by relative amounts), indicating element-specific feeding mechanisms including the bulk of the catalyst. We further show that oxygen intercalation readily occurs under as-grown h-BN during ambient air exposure, as is common in further processing, and that this negatively affects the stability of h-BN on the catalyst. For extended air exposure Cu oxidation is observed, and upon re-heating in vacuum an oxygen-mediated disintegration of the h-BN film via volatile boron oxides occurs. Importantly, this disintegration is catalyst mediated, i.e., occurs at the catalyst/h-BN interface and depends on the level of oxygen fed to this interface. In turn, however, deliberate feeding of oxygen during h-BN deposition can positively affect control over film morphology. We discuss the implications of these observations in the context of corrosion protection and relate them to challenges in process integration and heterostructure CVD.P.R.K. acknowledges funding from the Cambridge Commonwealth Trust and the Lindemann
Trust Fellowship. R.S.W. acknowledges a research fellowship from St. John’s College,
Cambridge. S.H. acknowledges funding from ERC grant InsituNANO (no. 279342), EPSRC
under grant GRAPHTED (project reference EP/K016636/1), Grant EP/H047565/1 and EU FP7
Work Programme under grant GRAFOL (project reference 285275). The European Synchrotron
Radiation Facility (ESRF) is acknowledged for provision of synchrotron radiation and assistance
in using beamline BM20/ROBL. We acknowledge Helmholtz-Zentrum-Berlin Electron storage
ring BESSY II for synchrotron radiation at the ISISS beamline and continuous support of our
experiments.This is the final version. It was first published by ACS at http://pubs.acs.org/doi/abs/10.1021/cm502603
Interdependency of subsurface carbon distribution and graphene-catalyst interaction.
The dynamics of the graphene-catalyst interaction during chemical vapor deposition are investigated using in situ, time- and depth-resolved X-ray photoelectron spectroscopy, and complementary grand canonical Monte Carlo simulations coupled to a tight-binding model. We thereby reveal the interdependency of the distribution of carbon close to the catalyst surface and the strength of the graphene-catalyst interaction. The strong interaction of epitaxial graphene with Ni(111) causes a depletion of dissolved carbon close to the catalyst surface, which prevents additional layer formation leading to a self-limiting graphene growth behavior for low exposure pressures (10(-6)-10(-3) mbar). A further hydrocarbon pressure increase (to ∼10(-1) mbar) leads to weakening of the graphene-Ni(111) interaction accompanied by additional graphene layer formation, mediated by an increased concentration of near-surface dissolved carbon. We show that growth of more weakly adhered, rotated graphene on Ni(111) is linked to an initially higher level of near-surface carbon compared to the case of epitaxial graphene growth. The key implications of these results for graphene growth control and their relevance to carbon nanotube growth are highlighted in the context of existing literature.R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge. S.H.
acknowledges funding from ERC grant InsituNANO (No. 279342) and EPSRC under grant
GRAPHTED (Ref. EP/K016636/1). We acknowledge the Helmholtz-Zentrum-Berlin Electron
storage ring BESSY II for provision of synchrotron radiation at the ISISS beamline and we thank
the BESSY staff for continuous support of our experiments. This research was partially
supported by the EU FP7 Work Programme under grant Graphene Flagship (No. 604391). PRK
acknowledges funding the Cambridge Commonwealth Trust. H.A. and C.B. acknowledge J.-Y.
Raty and B. Legrand for fruitful discussions.This is the final published version. It's also available from ACS at http://pubs.acs.org/doi/abs/10.1021/ja505454v
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