Length-dependent optical effects in single walled carbon nanotubes

Recently, Heller et al. reported length-dependent effects on the relative photoluminescence (PL) quantum yield of single walled carbon nanotubes (SWNTs) [Heller et al J. Am. Chem. Soc. 2004, 126, 14567-14573]. We propose a simple model involving thermal diffusion of excitons along the nanotube axis and quenching at the ends, to explain the observed trend in their data. By fitting to our model, we extract a diffusion coefficient of 6 cm(2)/s for excitons in SWNTs. Assuming a mono exponential decay of exciton PL, we also predict that effective length-dependent PL lifetimes for these excitons lie in the range of 1-27 ps. Experimental observations are shown to be consistent with stochastic rather than wavepacket-like exciton migration, which is in agreement with ultrafast excitonic dephasing. Edge effects seem to limit the use of short SWNTs in imaging and optical sensing applications.     

Purity assessment of single-wall carbon nanotubes, using optical absorption spectroscopy

A demand currently exists for a method of assessing the purity of single-wall carbon nanotubes (SWNTs), which will allow for meaningful material comparisons. An established metric and protocol will enable accurate and reproducible purity claims to be substantiated. In the present work, the ability to accurately quantify the mass fraction of SWNTs in the carbonaceous portion of a given sample is demonstrated, using optical absorption spectroscopy on both laser and arc discharge-generated SWNT-N,N-dimethylacetamide (DMA) dispersions. Verification of purity assessment protocols is based upon constructed sample sets comprising designed mass fractions of purified SWNTs and representative carbonaceous synthesis byproducts. Application of a previously reported method based on a ratio of the areal absorbance from linear subtractions of the second interband electronic transitions of semiconducting SWNTs ((S)E(22)) has shown a severe overestimation of SWNT purity (average error >24%). Instead, the development of a nonlinear pi-plasmon model, which considers overlap of electronic transitions and peak broadening, has dramatically improved the purity assessment accuracy (average error <7%), derived from a strong correlation to the constructed sample sets. This approach has enabled corroboration of rapid assessment procedures, such as absorbance peak maxima ratio and Beer's law analysis, directed at purification monitoring and synthesis sample screening. Specifically, a simple protocol for purity assessment of laser and arc-discharge SWNTs has been established that can be extended to other synthetic types (i.e. CVD, HiPco, etc.) and diameter distributions.     

Fundamental properties of single-wall carbon nanotubes

Single-wall carbon nanotubes (SWCNTs) represent an excellent example of materials by design with many of their outstanding properties predicted by theory prior to their synthesis. Both experimental and theoretical work on these novel nanowires continue to increase at a breathtaking pace. Herein we describe some of their fundamental properties on which much of this work is built. After discussing their structure and symmetries, we emphasize their exceptional electronic properties. The standard one-parameter graphene sheet model of SWCNTs, introduced in the earliest published paper on extended SWCNTs, is discussed in terms of both its successes and limitations. The strong interplay between theory and experiment that this area has enjoyed is also discussed. In addition, several opportunities for further study are touched upon.     

Control of hole opening in single-wall carbon nanotubes and single-wall carbon nanohorns using oxygen

Due to the simplicity of the process, holes in the graphene walls of single-wall carbon nanotubes (SWNTs) and single-wall carbon nanohorns (SWNHs) have often been opened using O2 gas at high temperatures, even though this contaminates the nanotubes with carbonaceous dust (C-dust). To open holes with less C-dust contamination, we found that a slow temperature increase of 1 degrees C/min or less, in air, was effective. We also found that SWNHs having little C-dust could store a large quantity of materials inside the tubes. We infer that the local temperature increase due to the exothermic reaction of combustion may have been suppressed in the slow combustion process, which was effective in reducing the C-dust.     

Charge transfer events in semiconducting single-wall carbon nanotubes

Electron-donating ferrocene units have been attached to SWNTs, with different degrees of functionalization. By means of a complementary series of novel spectroscopic techniques (i.e., steady-state and time-resolved), we have documented that mutual interactions between semiconducting SWNT and the covalently attached electron donor (i.e., ferrocene) lead, in the event of photoexcitation, to the formation of radical ion pairs. In the accordingly formed radical ion pairs, oxidation of ferrocene and reduction of SWNT were confirmed by spectroelectrochemistry. It is, however, shown that only a few semiconducting SWNTs [i.e., (9,4), (8,6), (8,7), and (9,7)] are susceptible to photoinduced electron transfer processes. These results are of relevant importance for the development of SWNT-based photovoltaics.     

Intercalant-induced superbundle formation of single-wall carbon nanotubes

The formation of a massive quantity of single-wall carbon nanotube (SWCNT) superbundles has been introduced through sonicating SWCNTs in tetramethylene sulfone/chloroform solution in which nitronium hexafluoroantimonate (NHFA) is dissolved. Most SWCNT bundles with the NHFA treatment are enlarged by about 10 times compared with those of the pristine sample. It is proposed that the formation of SWCNTs can occur in solution by formation of an SWCNT-intercalant charge complex. The specific surface area of the superbundle is almost doubled, while its micropore surface area is amplified by about 7 times. This development of microporosity results from the enhanced interstitial sites in the SWCNT superbundles.     

Hydrogen confined in single-wall carbon nanotubes: Anisotropy effects on ro-vibrational quantum levels

The energy levels of a hydrogen molecule embedded in the cavity of single-walled carbon nanotubes with different morphologies are studied using quantum dynamics simulations. All degrees of freedom of the confined molecule are explicitly included in our model, revealing that the vibrational motion is notably affected by the presence of a confining potential. The most relevant effects are nevertheless found in the rotational motion of the molecule and the appearance of a quantized translational motion. We further analyze the dependence of the confinement effects on the interaction potential, considering different parameters for the carbon-hydrogen interaction.     

Determination of moisture content of single-wall carbon nanotubes

Several techniques were evaluated for the establishment of reliable water/moisture content of single-wall carbon nanotubes. Karl Fischer titration (KF) provides a direct measure of the water content and was used for benchmarking against results obtained by conventional oven drying, desiccation over anhydrous magnesium perchlorate as well as by thermogravimetry and prompt gamma-ray activation analysis. Agreement amongst results was satisfactory with the exception of thermogravimetry, although care must be taken with oven drying as it is possible to register mass gain after an initial moisture loss if prolonged drying time or elevated temperatures (120 °C) are used. Thermogravimetric data were precise but a bias was evident that could be accounted for by considering the non-selective loss of mass as volatile carbonaceous components. Simple drying over anhydrous magnesium perchlorate for a minimum period of 8-10 days is recommended if KF is not available for this measurement.     

Water-soluble, exfoliated, nonroping single-wall carbon nanotubes

The scalable superacid solvent, radical-initiated aryldiazonium functionalization process produces individual SWNTs without the need for surfactant wrapping, centrifugation, or sonication. This work provides a facile pathway to aryl sulfonic acid-functionalized SWNTs that are not roped or bundled, and the functionalized nanotubes are water soluble.     

Rectifying diodes from asymmetrically functionalized single-wall carbon nanotubes

Asymmetrically functionalized single-wall carbon nanotubes (SWNTs) have been prepared by a covalent reaction of an 11-mercaptoundecanol-modified Au surface with oxidized SWNT cylinders. While one end of the tubes is attached to gold substrate via ester groups, the free carboxylic substituents on the other end can be either ionized (CO2-) or esterified (CO2Et), creating a donor-acceptor asymmetric and acceptor-acceptor symmetric SWNT, respectively. Study of the SWNT monolayer conductance in Hg drop junction experiments reveals a pronounced diode-like behavior for donor-SWNT-acceptor junctions, while acceptor-SWNT-acceptor junctions are electrically symmetric.     

Ni adsorption on Stone-Wales defect sites in single-wall carbon nanotubes

Ni adsorption on Stone-Wales defect sites in (10,0) zigzag and (5,5) armchair single-wall carbon nanotubes was studied using the density functional theory. The stable adsorption sites and their binding energies on different Stone-Wales defect types were analyzed and compared to those on perfect side walls. It was determined that the sites formed via fusions of 7-7 and 6-7 rings are the most exothermic in the cases of (10,0) and (5,5) defective tubes. In addition C-C bonds associated with Stone-Wales defects are more reactive than the case for a perfect hexagon, thus enhancing the stability of the Ni adsorption. Moreover, the Ni adsorption was found to show a noticeable relationship to the orientation of the Stone-Wales defects with respect to the tube axis. The nature of the Ni adsorption on Stone-Wales defects that have the similar orientation is identical, in spite of the different chiralities.     

Near-IR photorefractive composites based on oxidized single-wall carbon nanotubes

The photoelectric, nonlinear optical, and photorefractive characteristics of polymer composites made from unplasticized polyvinylcarbazole (PVK) and single-wall carbon nanotubes containing surface oxygen groups (at C:O ratio of 77.8:22.2%) were analyzed. The dependences of the quantum efficiency of charge-carrier generation on the applied electric field E measured at 1064 and 1550 nm coincide and are approximated by the Onsager equation expanded to the E ⁴ term, at π₀ = 0.012 and r ₀ = 9.8 Å. The third-order optical nonlinearity determined by the EFISH technique at a nanotube content of 0.26 wt % is 2 × 10⁵ pm²/V² or 2.3 × 10^?29 C⁴ m/J³ in SI units. The pattern of photorefractive kinetic curves indicates that the mean free path of holes is longer than the mean range of electrons. The photorefractive net gain coefficient of the signal beam measured at 1064 nm in a field of E = 170 V/μm is Γ ? α = 55 cm^?1 (α = 10 cm^?1 is the optical absorption coefficient at 1064 nm). At 1550 nm, the net gain coefficient measured in a field of E = 265 V/μm is Γ ? α = 55.7 cm^?1 (α = 3.3 cm^?1 at 1550 nm). In the presence of oxygen groups, there is no transfer of electrons photogenerated in carbon nanotubes to the external acceptor C⁶⁰. This effect can be associated with an increase in the ionization potential of nanotubes by almost 0.8 eV as a result of oxidation.     

Raman spectroscopy of free-standing individual semiconducting single-wall carbon nanotubes

The radial breathing modes and tangential modes have been systematically measured on a large number of individual semiconducting single-wall carbon nanotubes (thin bundles) suspended between plots (free-standing single-wall carbon nanotubes). The strong intensity of the Raman spectra ensures the precision of the experimentally determined line shapes and frequencies of these modes. The diameter dependence of the frequencies of the tangential modes was measured. This dependence is discussed in relation with recent calculations. The present data confirm/contradict some previous interpretations.     

IR-extended photoluminescence mapping of single-wall and double-wall carbon nanotubes

A simple and efficient technique is described for measuring photoluminescence (PL) maps of carbon nanotubes (NTs) in the extended IR range (1-2.3 mum). It consists of preparing an NT/surfactant/gelatin film and measuring PL spectra using a combination of a tunable Ti-sapphire laser excitation and FTIR detection. This procedure has been applied to a wide range of single- and double-wall NTs unveiling chirality and diameter distributions that have so far been very difficult to measure. The problems associated with deducing these distributions are discussed by comparing absorption and PL mapping data for NT samples prepared under different conditions.     

Ultrathin "bed-of-nails" membranes of single-wall carbon nanotubes

Single-wall carbon nanotubes (SWNTs) were arranged in a membrane similar to a "bed-of-nails", in which a single layer of parallel SWNTs was densely packed and aligned along the normal to the membrane. The planar, free-standing, ultrathin SWNT membranes were prepared by milling a neat SWNT fiber with a gallium focused ion beam. The approach is readily applicable to cutting nanotubes to a desirable and precise length and enables further fabrication of devices using the "bed-of-nails" membranes to test the transport properties of SWNTs.     

Adsorption of spillover hydrogen atoms on single-wall carbon nanotubes

Spillover of hydrogen on nanostructured carbons is a phenomenon that is critical to understand in order to produce efficient hydrogen storage adsorbents for fuel cell applications. The spillover and interaction of atomic hydrogen with single-walled carbon nanotubes (SWNTs) is the focus of this combined theoretical and experimental work. To understand the spillover mechanism, very low occupancies (i.e., 1 and 2 H atoms adsorbed) on (5,0), (7,0), (9,0) zigzag (semiconducting) SWNTs and a (5,5) armchair (metallic) SWNT, with corresponding diameters of 3.9, 5.5, 7.0, and 6.8 A, were investigated. The adsorption binding energy of H atoms depends on H occupancy, tube diameter, and helicity (or chirality), as well as endohedral (interior) vs exohedral (exterior) binding. Exohedral binding energies are substantially higher than endohedral binding energies due to easier sp(2)-sp(3) transition in hybridization of carbon on exterior walls upon binding. A binding energy as low as -8.9 kcal/mol is obtained for 2H atoms on the exterior wall of a (5, 0) SWNT. The binding energies of H atoms on the metallic SWNT are significantly weaker (about 23 kcal/mol weaker) than that on the semiconductor SWNT, for both endohedral and exohedral adsorption. The binding energy is generally higher on SWNTs of larger diameters, while its dependence on H occupancy is relatively weak except at very low occupancies. Experimental results at 298 K and for pressures up to 10 MPa with a carbon-bridged composite material containing SWNTs demonstrate the presence of multiple adsorption sites based on desorption hysteresis for the spiltover H on SWNTs, and the experimental results were in qualitative agreement with the molecular orbital calculation results.