Electronic Structure of Nitrogen- and Phosphorus-Doped Graphenes Grown by Chemical Vapor Deposition Method

Heteroatom doping is a widely used method for the modification of the electronic and chemical properties of graphene. A low-pressure chemical vapor deposition technique (CVD) is used here to grow pure, nitrogen-doped and phosphorous-doped few-layer graphene films from methane, acetonitrile and methane-phosphine mixture, respectively. The electronic structure of the films transferred onto SiO2/Si wafers by wet etching of copper substrates is studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy using a synchrotron radiation source. Annealing in an ultra-high vacuum at ca. 773 K allows for the removal of impurities formed on the surface of films during the synthesis and transfer procedure and changes the chemical state of nitrogen in nitrogen-doped graphene. Core level XPS spectra detect a low n-type doping of graphene film when nitrogen or phosphorous atoms are incorporated in the lattice. The electrical sheet resistance increases in the order: graphene < P-graphene < N-graphene. This tendency is related to the density of defects evaluated from the ratio of intensities of Raman peaks, valence band XPS and NEXAFS spectroscopy data. View Full-Tex

Light-induced sulfur transport inside single-walled carbon nanotubes

Filling of single-walled carbon nanotubes (SWCNTs) and extraction of the encapsulated species from their cavities are perspective treatments for tuning the functional properties of SWCNT-based materials. Here, we have investigated sulfur-modified SWCNTs synthesized by the ampoule method. The morphology and chemical states of carbon and sulfur were analyzed by transmission electron microscopy, Raman scattering, thermogravimetric analysis, X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopies. Successful encapsulation of sulfur inside SWCNTs cavities was demonstrated. The peculiarities of interactions of SWCNTs with encapsulated and external sulfur species were analyzed in details. In particular, the donor-acceptor interaction between encapsulated sulfur and host SWCNT is experimentally demonstrated. The sulfur-filled SWCNTs were continuously irradiated in situ with polychromatic photon beam of high intensity. Comparison of X-ray spectra of the samples before and after the treatment revealed sulfur transport from the interior to the surface of SWCNTs bundles, in particular extraction of sulfur from the SWCNT cavity. These results show that the moderate heating of filled nanotubes could be used to de-encapsulate the guest species tuning the local composition, and hence, the functional properties of SWCNT-based materials

On the stability of Li intercalated fine grained graphitic material

In order to study the performance, cycling stability and safety of electrochemical storage devices, various characterisation methods are applied. Magic angle spinning MAS NMR enables ex situ studies of electrochemical reactions with high resolution. In the present work, we follow the changes that occur in the MAS NMR spectra of lithiated graphitic materials after storage. The measuring time has been significantly shortened by using fine grained graphitic material with 65 13C isotope enrichment. Our results show that for 13C graphitic electrode material with a low lithiation degree, visible changes in the 13C NMR spectra are observed already in few hours, whereas the samples with a higher lithiation degree demonstrated greater stability even after several days. We analyzed the deintercalation behavior in these materials using 7Li MAS NMR and oxidation processes using in situ X ray photoelectron spectroscopy. During storage Li ions migrate to the other interlayers redistribution , large pores and to the surface, where interaction with air takes place. Effects of charge transfer from Li to graphite across four graphitic layers guarantees that 13C NMR spectra are less affected by these effects. The key finding is that special care has to be paid to the ex situ characterisation of electrochemically prepared graphitized material

Graphene nanochains and nanoislands in the layers of room-temperature fluorinated graphite

International audienceIntercalated compound of graphite fluoride with n-heptane has been synthesized at room temperature using a multi-stage process including fluorination by a gaseous BrF3 and a set of intercalant exchange reactions. It was found that composition of the compound is CF0.40(C7H16)0.04 and the guest molecules interact with the graphite fluoride layers through the van der Waals forces. Since the distance between the filled layers is 1.04 nm and the unfilled layers are separated by ∼0.60 nm, the obtained compound can be considered as a stack of the fluorinated graphenes. These fluorinated graphenes are large in area making it possible to study local destruction of the π conjugated system on the basal plane. It was shown that fluorine atoms form short chains, while non-fluorinated sp2 carbon atoms are organized in very narrow ribbons and aromatic areas with a size smaller than 3 nm. These π electron nanochains and nanoislands preserved after the fluorination process are likely responsible for the value of the energy gap of the compound of ∼2.5 eV. Variation in the size and the shape of π electron regions within the fluorinated graphene layers could be a way for tuning the electronic and optical characteristics of the graphene-based materials