Sergei Lebedkin

Single-wall carbon nanotubes with diameters approaching 6 nm obtained by laser vaporization

Abstract Single-wall carbon nanotubes (SWNTs) with large diameters from 2 to 5.6 nm were prepared by pulsed laser vaporization of carbon rods doped with Co, Ni and FeS in an atmosphere of Ar:H2. The SWNT material was characterized by SEM, HRTEM, Raman, IR, UV–VIS–NIR absorption spectroscopy and thermogravimetric analysis.

Selective Dispersion of Single-Walled Carbon Nanotubes with Specific Chiral Indices by Poly(N-decyl-2,7-carbazole)

Physico-chemical methods to sort single-walled carbon nanotubes (SWNTs) by chiral index are presently lacking but are required for in-depth experimental analysis and also for potential future applications of specific species. Here we report the unexpected selectivity of poly(N-decyl-2,7-carbazole) to almost exclusively disperse semiconducting SWNTs with differences of their chiral indices (n - m) ≥ 2 in toluene. The observed selectivity complements perfectly the dispersing features of the fluorene analogue poly(9,9-dialkyl-2,7-fluorene), which disperses semiconducting SWNTs with (n - m) ≤ 2 in toluene. The dispersed samples are further purified by density gradient centrifugation and analyzed by photoluminescence excitation spectroscopy. All-atom molecular modeling with decamer model compounds of the polymers and (10,2) and (7,6) SWNTs suggests differences in the π-π stacking interaction as origin of the selectivity. We observe energetically favored complexes between the (10,2) SWNT and the carbazole decamer and between the (7,6) SWNT and the fluorene decamer, respectively. These findings demonstrate that subtle structural changes of polymers lead to selective solvation of different families of carbon nanotubes. Furthermore, chemical screening of closely related polymers may pave the way toward simple, low-cost, and index-specific isolation of SWNTs.

Preparation and characterisation of C119

Abstract Thermolysis of C 120 O at 550–600°C yielded a soluble product fraction containing C 60 , C 119 and higher-mass species. Using a two-step HPLC procedure two species, both with molecular weight corresponding to C 119 , were isolated in 3.5% and 2% yield. The 125.76 MHz 13 C-NMR spectrum of the latter more stable product obtained from 13 C enriched samples proved that this species consists of two C 58 cages bridged by three sp 3 carbons, two of which are equivalent. NMR-consistent C 119 structures have been investigated by molecular modeling and turned out to exhibit C 2 symmetry.

Supramolecular discrimination of carbon nanotubes according to their helicity.

Adsorption of specifically designed and geometrically constrained polyaromatic amphiphiles on single-walled carbon nanotubes (SWNTs) was found to be selective of the nanotube helicity angle. Starting from the same SWNT mixture, photoluminescence and resonant Raman spectroscopies show that a pentacenic-based amphiphile leads to the solubilization of armchair SWNTs and that a quaterrylene-based amphiphile leads to the solubilization of zigzag SWNTs. The results were predicted by the design of the two amphiphiles and are consistent with a supramolecular recognition of the nanotube graphene-type atomic structure by the aromatic part of the molecules through optimized pi-pi-stacking interactions.

Preparation, characterization and applications of free-standing single walled carbon nanotube thin films

A method for the reliable fabrication of less than 200 nm thick, free-standing purified-SWNT films having large surface areas exceeding several cm2 is described. Films were characterized using a variety of optical, microscopic and spectroscopic methods. The procedure was also used to prepare thin films of as-prepared, acid-cut and octadecylamine (ODA) functionalized SWNTs. Such samples allow facile transmission measurements of SWNT derived solids.

Toward single-chirality carbon nanotube device arrays.

The large-scale integration of devices consisting of individual single-walled carbon nanotubes (SWCNT), all of the same chirality, is a critical step toward their electronic, optoelectronic, and electromechanical application. Here, the authors realize two related goals, the first of which is the fabrication of high-density, single-chirality SWCNT device arrays by dielectrophoretic assembly from monodisperse SWCNT solution obtained by polymer-mediated sorting. Such arrays are ideal for correlating measurements using various techniques across multiple identical devices, which is the second goal. The arrays are characterized by voltage-contrast scanning electron microscopy, electron transport, photoluminescence (PL), and Raman spectroscopy and show identical signatures as expected for single-chirality SWCNTs. In the assembled nanotubes, a large D peak in Raman spectra, a large dark-exciton peak in PL spectra as well as lowered conductance and slow switching in electron transport are all shown to be correlated to each other. By comparison to control samples, we conclude that these are the result of scattering from electronic and not structural defects resulting from the polymer wrapping, similar to what has been predicted for DNA wrapping.

Reversible modification of the absorption properties of single-walled carbon nanotube thin films via nitric acid exposure

Exposure of thin films of as-prepared single-walled carbon nanotubes (SWNT) to nitric acid induces dramatic bleaching of the first and second interband transitions of semiconducting tubes (S1 and S2). These near-IR absorption features can be restored by annealing of treated SWNT films to elevated temperatures. Annealing may also be accomplished by visible laser irradiation thus allowing for spatially resolved modifications to SWNT thin film optical absorption.

FTIR-luminescence mapping of dispersed single-walled carbon nanotubes

We have applied the FTIR-luminescence/FT-Raman technique to map the near-infrared photoluminescence?(PL) of water?surfactant dispersions of single-walled carbon nanotubes (SWNTs) in broad excitation (250?1500?nm) and emission (800?1700?nm) ranges. The excitation wavelength was scanned by using the monochromatized light of standard xenon and tungsten halogen lamps. The PL maps are presented for SWNTs with a mean diameter of ~1.3?nm prepared by the pulsed laser vaporization method. When dispersed by powerful ultrasonic agitation and separated by ultracentrifugation, these nanotubes show structured absorption bands and a PL quantum yield as high as ~10-3. This indicates a large fraction of individual nanotubes in the dispersion. Electronic interband transition energies of nanotubes derived from the PL data correspond reasonably to the energies calculated in the modified tight-binding model of Ding et al.

Tuning the spin-transition properties of pyrene-decorated 2,6-bispyrazolylpyridine based Fe(II) complexes.

Two 2,6-bispyrazolylpyridine ligands (bpp) were functionalized with pyrene moieties through linkers of different lengths. In the ligand 2,6-di(1H-pyrazol-1-yl)-4-(pyren-1-yl)pyridine (L1) the pyrene group is directly connected to the bpp moiety via a C-C single bond, while in the ligand 4-(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzyl-4-(pyren-1-yl)butanoate (L2) it is separated by a benzyl ester group involving a flexible butanoic chain. Subsequent complexation of Fe(II) salts revealed dramatic the influence of the nature of the pyrene substitution on the spin-transition behaviour of the resulting complexes. Thus, compound [Fe(L1)(2)](ClO(4))(2) (1) is blocked in its high spin state due to constraints caused by a strong intermolecular π-π stacking in its structure. On the other hand, the flexible chain of ligand L2 in compounds [Fe(L2)(2)](ClO(4))(2) (2) and [Fe(L2)(2)](BF(4))(2)·CH(3)CN·H(2)O (3) prevents structural constraints allowing for reversible spin transitions. Temperature-dependent studies of the photophysical properties of compound 3 do not reveal any obvious correlation between the fluorescence of the pyrene group and the spin state of the spin transition core.

Raman scattering study of C120, a C60 dimer

Abstract A modified preparation method and results of a Raman scattering study for C 120 , a dimer of C 60 , are reported. The Raman features of C 120 are compared with those of the dimer-like oxides C 120 O and C 120 O 2 , phototransformed C 60 and with calculations.