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The in-plane and c-axis structure of KHx—GIC's and KDy—GIC's is studied using transmission electron microscopy (TEM) and x-ray diffraction as a function of intercalation temperature and time. With the TEM, two commensurate in-plane phases are found to coexist in these compounds with relative concentrations depending on intercalation conditions. When the direct intercalation method is used, the first step of intercalation is the formation of a stage n potassium-GIC and the final compound is a stage n KHx—GIC (or KDy—GIC). Highresolution (00l) lattice images show direct evidence for intermediate phases in the intercalation process. These intermediate phases are hydrogen (deuterium) deficient and are found at the boundary between pure potassium regions and regions with high hydrogen (deuterium) content. A comparison of the structure for the two methods of intercalation of KH is also presented.
Because of their unusually large specific surface area (SSA), Activated Carbon Fibers (ACF's) have a huge density of micropores and defects. The Raman scattering technique and low-temperature dc electrical conductivity measurements were used as characterization tools to study the disorder in ACF's with SSA ranging from 1000 m2/g to 3000 m2/g. Two peaks were observed in every Raman spectrum for ACF's and they could be identified with the disorder-induced peak near ∼1360 cm−1 and the Breit–Wigner–Fano peak near ∼1610 cm−1 associated with the Raman-active E2g2 mode of graphite. The graphitic nature of the ACF's is shown by the presence of a well-defined graphitic structure with La values of 20–30 Å. We observed that the Raman scattering showed more sensitivity to the precursor materials than to the SSA of the ACF's. From 4 K to room temperature, the dc electrical resistivity in ACF's is observed to follow the exp [(T0/T)1/2] functional form and it can be accounted for by a charge-energy-limited tunneling conduction mechanism. Coulomb-gap conduction and n-dimensional (n ≤ 3) variable-range hopping conduction models were also considered but they were found to give unphysical values for their parameters.
A digitization of the TEM pictures of fluorine-intercalated graphite fibers has been used to carry out quantitative measurements of the defect structure of this material. Emphasis is given to both the computer analysis technique and to the characterization of the defects. The amount of intercalation-induced disorder increases with increasing fluorine concentration. The fast Fourier transform of the digitized TEM image exhibits two diffuse spots, corresponding to the c-axis repeat distance of the intercalation compound. The length and width of the spots are a measure of the out-of-plane and in-plane disorder present in the fibers. From the fast Fourier transform, the distribution of interlayer repeat distances and the fraction of unintercalated graphite regions throughout the material is obtained. By selecting a small range of repeat distances and carrying out an inverse fast Fourier transform, the spatial distribution of material with a given repeat distance is determined. Regions with the same repeat distance are found to form islands. This particular feature of fluorine graphite intercalation compounds, as well as the nature of the microscopic defects and the staging behavior of fluorine-intercalated graphite fibers, are discussed in connection with the dual covalent and ionic nature of the carbon-fluorine bond in fluorine-intercalated graphite.
The Raman line at 1430 cm−1 (M-line) in single crystal La2CuO4−y was studied as a function of doping, temperature, magnetic field, and excitation wavelength. Upon Li doping the line becomes broader, and it vanishes rapidly with Sr-doping. The line also broadens with increasing temperature and increasing applied magnetic field. Resonance enhancement was found for decreasing laser excitation energies but was not as pronounced as the enhancement of several alleged two-phonon lines. Many of these features are correlated with the 2D antiferromagnetic ordering measured in this system by neutron scattering. The possible identification of this line as a one-spin excitation is favored by the data though a two-phonon excitation is also considered.
Using a two-zone method, the possible formation of an intercalation compound of hexagonal boron nitride (BN) with Cs and Br2 was investigated. Only a few percent weight increase was observed by doping BN with Cs and Br2. The electron paramagnetic resonance (EPR) signal was significantly modified by Cs doping, which is attributed to the reaction between the Cs atoms and spin resonance centers (N vacancies) in BN; no change in the EPR spectra was observed with Br2 doping. However, the deep blue colored Cs-BN complex reported by Mugiya and co-workers was not obtained with the two-zone method. Though no evidence of systematic intercalation reaction in BN was observed in contrast to graphite host materials, intercalation islands induced by the introduction of Cs atoms were suggested by the transmission electron microscopy (TEM) observations.
The transport properties of isotropic pitch-based carbon fibers with surface area 1000 m2/g have been investigated. We report preliminary results on the electrical conductivity, the magnetoresistance, the thermal conductivity, and the thermopower of these fibers as a function of temperature. Comparisons are made to transport properties of other disordered carbons.
Photoconductivity was measured on a series of carbon aerogels to investigate their electronic properties. Carbon aerogels are a special class of low-density microcellular foams, consisting of interconnected carbon particles (∼120 Å diameter) and narrow graphitic ribbons (∼25 Å width) intertwined within each particle. Both the dark- and photoconductivities show drastic changes in the temperature range 5–300 K, which are similar to those in a-Si and chalcogenide photoconductors. At high temperatures, the photoconductivity is dominated by the carrier recombination within each particle. The photoconductivity at low temperatures is dominated by the same carrier transport mechanism as that for the dark conductivity, which is based on hopping and tunneling transport. The activation energy values for transport and recombination identify the electronic structure of the particles among samples of different bulk density. The long decay time of the photoconductivity suggests a relaxation mechanism associated with the dangling bonds.
The structure of pulsed laser irradiated graphite surfaces has been elucidated. The pulse fluences range up to 4 J cm−2 with durations no longer than 30 ns. The region exterior to the irradiated spot is littered with ∼0.1 μm diameter carbon spheroids. The boundary region is characterized by both spheroids and torn layers 1–5 μm. in lateral extent. The central region displays carbon spheroids and surface upheavals. The carbon spheroids are attributed to hydrodynamic sputtering of carbon. The surface upheavals and torn carbon layers are attributed to constrained thermal expansion and contraction of the irradiated region. It is estimated that a nearly instantaneous 1000°C temperature change is necessary to cause the observed surface deformation. Pulse fluences in excess of 0.8 J cm−2 cause a thin layer of carbon to melt. This is proven by the fact that the irradiated layer in the solid phase has a turbostratic structure. Electron diffraction experiments and dark-field imaging experiments show that the basal plane grain size of the resolidified material varies from ∼20 Å at the melt threshold to ∼100 Å for samples irradiated with 4.0 J cm−2.
The conductivity and photoconductivity are measured on a high-surface-area disordered carbon material, i.e., activated carbon fibers, to investigate their electronic properties. This material is a highly disordered carbon derived from a phenolic precursor, having a huge specific surface area of 1000–2000 m2/g. Our preliminary thermopower measurements show that the dominant carriers are holes at room temperature. The x-ray diffraction pattern reveals that the microstructure is amorphous-like with Lc ≃ 10 Å. The intrinsic electrical conductivity, on the order of 20 S/cm at room temperature, increases by a factor of several with increasing temperature in the range 30–290 K. In contrast, the photoconductivity in vacuum decreases with increasing temperature. The magnitude of the photoconductive signal was reduced by a factor of ten when the sample was exposed to air. The recombination kinetics changes from a monomolecular process at room temperature to a bimolecular process at low temperatures, indicative of an increase in the photocarrier density at low temperatures. The high density of localized states, which limits the motion of carriers and results in a slow recombination process, is responsible for the observed photoconductivity.
Group theoretical methods are used to obtain the form of the elastic moduli matrices and the number of independent parameters for various symmetries. Particular attention is given to symmetry groups for which 3D and 2D isotropy is found for the stress-strain tensor relation. The number of independent parameters is given by the number of times the fully symmetric representation is contained in the direct product of the irreducible representations for two symmetrical second rank tensors. The basis functions for the lower symmetry groups are found from the compatibility relations and are explicitly related to the elastic moduli. These types of symmetry arguments should be generally useful in treating the elastic properties of solids and composites.
Double-walled carbon nanotubes (DWNTs), synthesized by the catalytic decomposition of methane, were explored by resonance Raman spectroscopy using different energies for laser excitation. Based on the radial breathing mode frequencies, the indices of the two layers of a DWNT were approximately assigned, depending on the interlayer separation of the two coaxial layers of the DWNT, which ranged from 0.34 to 0.40 nm. From the tentatively assigned results, it was found that the two walls of the DWNT are not strongly selected by chirality and diameter. The results, however, suggest that, for the tubes that are resonant with the available laser excitation energies, most of the outer layers of the observed DWNTs in our samples are semiconducting, while the inner layers of the observed DWNTs are either semiconducting or metallic based on the assembled DWNTs. The characteristics of the G, D, and G′ band of the DWNTs are discussed, and a double peak feature in the D and G′ band, originating from the inner and outer layers of the DWNTs, is reported.
Structural evolution of undoped and boron-doped submicron vapor-grown carbon fibers (S-VGCFs) was monitored as a function of heat-treatment temperature (HTT). Based on x-ray and Raman data, over the range of HTT from 1800 to 2600 °C, it was found that boron atoms act as catalysts to promote graphitization due to boron's higher diffusivity. For the range of HTT from 2600 to 2800 °C, the process of boron out-diffusion from the host material induces defects, such as tilt boundaries; this process would be related with the improved capacity and Coulombic efficiency of boron-doped S-VGCFs. When 10 wt% S-VGCFs was used as an additive to synthetic graphite, the cyclic efficiency of the capacities was improved to almost 100%.
We calculate the optimized geometry and the corresponding electronic structure of Li ions doped in a small graphite cluster with dangling bonds or hydrogen terminations at the edge surrounding the cluster. The calculations imply both covalent and ionic bonds of Li ions to carbon atoms, which may be relevant to explaining the broad signal of the 7Li NMR Knight shift spectra. Li intercalation, in particular, is possible even at the hydrogen-terminated edges. Because of the finite size effect of the cluster, the ionicity of intercalated Li ions has a large distribution of values, ranging from positive values close to that in graphite intercalation compounds to even slightly negative values, depending on the bonding geometry. We propose that the cluster edge surface plays a special role in accommodating excess Li ions in the disordered graphite system.
New structural features observed in heat-treated vapor-grown carbon fibers (VGCF's), produced by the thermal decomposition of hydrocarbon vapor, are reported using image analysis of the lattice plane structure observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The TEM lattice image of well-ordered graphite fibers (heat-treated VGCF's at 2800 °C) was treated by a two-dimensional fast Fourier transform, showing sharp bright spots associated with the 002 and 100 lattice planes. The heat-treated VGCF's consist of a polygonally shaped shell, and the long and short fringe structures in the TEM lattice image reflect the 002 and 100 lattice planes, respectively. From this analysis, new facts about the lattice structure are obtained visually and quantitatively. The 002 lattice planes remain and are highly parallel to each other along the fiber axis, maintaining a uniform interlayer spacing of 3.36 Å. The 100 lattice planes are observed to make several inclined angles with the 002 lattice planes relative to the plane normals, caused by the gliding of adjacent graphene layers. This work visually demonstrates coexistence of the graphitic stacking, as well as the gliding of the adjacent graphene layers, with a gliding angle of about 3–20°. These glide planes are one of the dominant stacking defects in heat-treated VGCF's. On the other hand, turbostratic structural evidence was suggested by AFM observations. The structural model of coexisting graphitic, glide, and turbostratic structures is proposed as a transitional stage to perfect three-dimensional stacking in the graphitization process. These structural features could also occur in common carbons and in carbon nanotubes.
The structural and electronic properties of fluorine- and bromine-intercalated graphite fibers and HOPG are summarized. In contrast to the bromine intercalate, which is purely ionic for any experimentally attainable intercalate concentration, fluorine has a dual ionic and covalent behavior in graphite. Furthermore, whereas bromine-intercalated graphite is ordered, fluorine-intercalated graphite is disordered. The stiff graphene planes are buckled and islands of various fluorine concentrations are formed. A thermodynamic model is proposed that accounts for the differences between fluorine- and bromine-intercalated graphite materials. The model describes the competition between ionically bonded and covalently bonded intercalate phases of fluorine in graphite. Covalent bonding is more favorable energetically, but an important nucleation barrier exists due to strain and to the destruction of the conjugation of the double bonds.
We report on the magnetic-field dependent surface resistance of polycrystalline YBa2Cu3O7 (Tc ≃ 92 K), measured using a brass cylindrical cavity resonator, operating at 16.5 GHz in the TE011 mode. A de magnetic field Happ is applied parallel to the superconducting sample surface, and the temperature dependence of the surface resistance is measured for four different values of Happ (0 T, 0.22 T, 1 T, 5 T). An effective medium theory and the two-fluid model are used to fit the surface resistance versus temperature measurements both in zero field and for various applied fields. These results are applied to characterize the microwave properties of a polycrystalline ceramic superconductor.
Raman scattering, x-ray diffraction, and BET measurements are used to study the effect of heat treatment on the microstructure of activated carbon fibers (ACFs) and to correlate the structural changes with the metal-insulator transition observed in the electronic transport properties of heat-treated ACFs. A sequence of events is identified, starting with desorption, followed by micropore collapse plus the stacking of basic structural units in the c-direction, and ending up with in-plane crystallization. The graphitization process closely resembles that depicted by Oberlin's model, except that the final material at high-temperature heat treatment remains turbostratic. Because the metal-insulator transition was observed to occur at heat-treatment temperature THT ≃ 1200 °C, which is well below the THT value (2000 °C) for in-plane crystallization, we conclude that this electronic transition is not due to in-plane ordering but rather to the collapse of the micropore structure in the ACFs. Raman scattering also provides strong evidence for the presence of local two-dimensional graphene structures, which is the basis for the transport phenomena observed in heat-treated ACFs.
A review of the structure and properties of fullerenes is presented. Emphasis is given to their behavior as molecular solids. The structure and property modifications produced by alkali-metal doping are summarized, including modification to the electronic structure, lattice modes, transport, and optical properties. Particular emphasis is given to the alkali-metal-doped fullerenes because of their importance as superconductors. A review of the structure and properties of fullerene-based graphene tubules is also given, including a model for their one-dimensional electronic band structure. Potential applications for fullerene-based materials are suggested.
A resonant Raman study of single-wall carbon nanotubes (SWNT) using several laser lines between 0.94 and 3.05 eV is presented. A detailed lineshape analysis shows that the bands associated with the nanotube radial breathing mode are composed of a sum of individual peaks whose relative intensities depend strongly on the laser energy, in agreement with prior work. On the other hand, the shape of the Raman bands associated with the tangential C–C stretching motions in the 1500–1600 cm−1 range does not depend significantly on the laser energy for laser excitation energies in the ranges 0.94–1.59 eV and 2.41–3.05 eV. However, new C–C stretching modes are observed in the spectra collected using laser excitations with energies close to 1.9 eV. The new results are discussed in terms of the difference between the 1D electronic density of states for the semiconducting and metallic carbon nanotubes.
The optical properties of inorganic fullerene-like and nanotube MS2 (M = Mo, W) material are studied through absorption and resonance Raman, and compared to those of the corresponding bulk material. The absorption measurements show that the semiconductivity is preserved. Nevertheless, the positions of the excitons are altered in comparison to the bulk. The Raman spectra of the nanoparticles show a close correspondence to that of the bulk. However, the first-order peaks are broadened and, under resonance conditions, new peaks are observed. The new peaks are assigned to disorder-induced zone edge phonons.