Probing electronic transitions in individual carbon nanotubes by Rayleigh scattering

Rayleigh scattering spectra were obtained from individual single-walled carbon nanotubes with the use of a laser-generated visible and near-infrared supercontinuum. This diagnostic method is noninvasive and general for nanoscale objects. The approach permits clear identification of excited states in arbitrary metallic and semiconducting nanotubes. We analyzed spectral lineshapes in relation to the role of excitonic effects and correlated the results with Raman scattering data on individual tubes. The nanotube structure remained the same over distances of tens of micrometers. Small nanotube bundles retained distinct Rayleigh spectroscopic signatures of their component nanotubes, thus allowing the probing of nanotube-nanotube interactions.     

Quantized phonon spectrum of single-wall carbon nanotubes

The electronic spectra of carbon nanotubes and other nanoscale systems are quantized because of their small radii. Similar quantization in the phonon spectra has been difficult to observe because of the far smaller energy scale. We probed this regime by measuring the temperature-dependent specific heat of purified single-wall nanotubes. The data show direct evidence of one-dimensional quantized phonon subbands. Above 4 kelvin, they are in excellent agreement with model calculations of individual nanotubes and differ markedly from the specific heat of two-dimensional graphene or three-dimensional graphite. Detailed modeling yields an energy of 4.3 millielectron volts for the lowest quantized phonon subband and a tube-tube (or "lattice") Debye energy of 1.1 millielectron volts, implying a small intertube coupling in bundles.     

Optical signatures of the Aharonov-Bohm phase in single-walled carbon nanotubes

We report interband magneto-optical spectra for single-walled carbon nanotubes in high magnetic fields up to 45 tesla, confirming theoretical predictions that the band structure of a single-walled carbon nanotube is dependent on the magnetic flux phi threading the tube. We have observed field-induced optical anisotropy as well as red shifts and splittings of absorption and photoluminescence peaks. The amounts of shifts and splittings depend on the value of phi/phi(0) and are quantitatively consistent with theories based on the Aharonov-Bohm effect. These results represent evidence of the influence of the Aharonov-Bohm phase on the band gap of a solid.     

Energy gaps in "metallic" single-walled carbon nanotubes

Metallic single-walled carbon nanotubes have been proposed to be good one-dimensional conductors. However, the finite curvature of the graphene sheet that forms the nanotubes and the broken symmetry due to the local environment may modify their electronic properties. We used low-temperature atomically resolved scanning tunneling microscopy to investigate zigzag and armchair nanotubes, both thought to be metallic. "Metallic" zigzag nanotubes were found to have energy gaps with magnitudes that depend inversely on the square of the tube radius, whereas isolated armchair tubes do not have energy gaps. Additionally, armchair nanotubes packed in bundles have pseudogaps, which exhibit an inverse dependence on tube radius. These observed energy gaps suggest that most "metallic" single-walled nanotubes are not true metals, and they have implications for our understanding of the electronic properties and potential applications of carbon nanotubes.     

Single-Electron Transport in Ropes of Carbon Nanotubes

The electrical properties of individual bundles, or "ropes," of single-walled carbon nanotubes have been measured. Below about 10 kelvin, the low-bias conductance was suppressed for voltages less than a few millivolts. In addition, dramatic peaks were observed in the conductance as a function of a gate voltage that modulated the number of electrons in the rope. These results are interpreted in terms of single-electron charging and resonant tunneling through the quantized energy levels of the nanotubes composing the rope.     

Simultaneous fluorescence and Raman scattering from single carbon nanotubes

Single-molecule fluorescence spectroscopy was used to determine the electronic properties of individual single-walled carbon nanotubes. Carbon nanotube structure was determined simultaneously from Raman spectroscopy. Fluorescence spectra from individual nanotubes with identical structures have different emission energies and linewidths that likely arise from defects or the local environment. Unlike most other molecules studied to date, the fluorescence intensity or spectrum from a single nanotube unexpectedly did not fluctuate.     

Aligned carbon nanotube arrays formed by cutting a polymer resin--nanotube composite

A simple technique is described here that produces aligned arrays of carbon nanotubes. The alignment method is based on cutting thin slices (50 to 200 nanometers) of a nanotube-polymer composite. With this parallel and well-separated configuration of nanotubes it should be possible to measure individual tube properties and to demonstrate applications. The results demonstrate the nature of rheology, on nanometer scales, in composite media and flow-induced anisotropy produced by the cutting process. The fact that nanotubes do not break and are straightened after the cutting process also suggests that they have excellent mechanical properties.     

Molecular ordering of organic molten salts triggered by single-walled carbon nanotubes

When mixed with imidazolium ion-based room-temperature ionic liquid, pristine single-walled carbon nanotubes formed gels after being ground. The heavily entangled nanotube bundles were found to untangle within the gel to form much finer bundles. Phase transition and rheological properties suggest that the gels are formed by physical cross-linking of the nanotube bundles, mediated by local molecular ordering of the ionic liquids rather than by entanglement of the nanotubes. The gels were thermally stable and did not shrivel, even under reduced pressure resulting from the nonvolatility of the ionic liquids, but they would readily undergo a gel-to-solid transition on absorbent materials. The use of a polymerizable ionic liquid as the gelling medium allows for the fabrication of a highly electroconductive polymer/nanotube composite material, which showed a substantial enhancement in dynamic hardness.     

Structure-based carbon nanotube sorting by sequence-dependent DNA assembly

Wrapping of carbon nanotubes (CNTs) by single-stranded DNA (ssDNA) was found to be sequence-dependent. A systematic search of the ssDNA library selected a sequence d(GT)n, n = 10 to 45 that self-assembles into a helical structure around individual nanotubes in such a way that the electrostatics of the DNA-CNT hybrid depends on tube diameter and electronic properties, enabling nanotube separation by anion exchange chromatography. Optical absorption and Raman spectroscopy show that early fractions are enriched in the smaller diameter and metallic tubes, whereas late fractions are enriched in the larger diameter and semiconducting tubes.     

Self-assembly of subnanometer-diameter single-wall MoS2 nanotubes

We report on the synthesis, structure, and self-assembly of single-wall subnanometer-diameter molybdenum disulfide tubes. The nanotubes are up to hundreds of micrometers long and display diverse self-assembly properties on different length scales, ranging from twisted bundles to regularly shaped "furry" forms. The bundles, which contain interstitial iodine, can be readily disassembled into individual molybdenum disulfide nanotubes. The synthesis was performed using a novel type of catalyzed transport reaction including C(60) as a growth promoter.     

Optical spectroscopy of individual single-walled carbon nanotubes of defined chiral structure

We simultaneously determined the physical structure and optical transition energies of individual single-walled carbon nanotubes by combining electron diffraction with Rayleigh scattering spectroscopy. These results test fundamental features of the excited electronic states of carbon nanotubes. We directly verified the systematic changes in transition energies of semiconducting nanotubes as a function of their chirality and observed predicted energy splittings of optical transitions in metallic nanotubes.     

Engineering carbon nanotubes and nanotube circuits using electrical breakdown

Carbon nanotubes display either metallic or semiconducting properties. Both large, multiwalled nanotubes (MWNTs), with many concentric carbon shells, and bundles or "ropes" of aligned single-walled nanotubes (SWNTs), are complex composite conductors that incorporate many weakly coupled nanotubes that each have a different electronic structure. Here we demonstrate a simple and reliable method for selectively removing single carbon shells from MWNTs and SWNT ropes to tailor the properties of these composite nanotubes. We can remove shells of MWNTs stepwise and individually characterize the different shells. By choosing among the shells, we can convert a MWNT into either a metallic or a semiconducting conductor, as well as directly address the issue of multiple-shell transport. With SWNT ropes, similar selectivity allows us to generate entire arrays of nanoscale field-effect transistors based solely on the fraction of semiconducting SWNTs.     

Farm crop waste as a promising resource for forming carbon nanotubes

It has been found that mechanical activation of amorphous carbon obtained from Katerina SV corn waste encourages formation of carbon nanotubes. At the same time, carbon tube output after 7 and 42 hours of mechanical activation is 11 and 42% by weight, respectively.     

Carbon nanotube flow sensors

We report that the flow of a liquid on single-walled carbon nanotube bundles induces a voltage in the sample along the direction of the flow. The voltage that was produced fit a logarithmic velocity dependence over nearly six decades of velocity. The magnitude of the voltage depended sensitively on the ionic conductivity and on the polar nature of the liquid. Our measurements suggest that the dominant mechanism responsible for this highly nonlinear response involves a direct forcing of the free charge carriers in the nanotubes by the fluctuating Coulombic field of the liquid flowing past the nanotubes. We propose an explanation based on pulsating asymmetric ratchets. Our work highlights the device potential for nanotubes as sensitive flow sensors and for energy conversion.     

Imaging electron wave functions of quantized energy levels in carbon nanotubes

Carbon nanotubes provide a unique system for studying one-dimensional quantization phenomena. Scanning tunneling microscopy was used to observe the electronic wave functions that correspond to quantized energy levels in short metallic carbon nanotubes. Discrete electron waves were apparent from periodic oscillations in the differential conductance as a function of the position along the tube axis, with a period that differed from that of the atomic lattice. Wave functions could be observed for several electron states at adjacent discrete energies. The measured wavelengths are in good agreement with the calculated Fermi wavelength for armchair nanotubes.     

Solution properties of single-walled carbon nanotubes

Naked metallic and semiconducting single-walled carbon nanotubes (SWNTs) were dissolved in organic solutions by derivatization with thionychloride and octadecylamine. Both ionic (charge transfer) and covalent solution-phase chemistry with concomitant modulation of the SWNT band structure were demonstrated. Solution-phase near-infrared spectroscopy was used to study the effects of chemical modifications on the band gaps of the SWNTs. Reaction of soluble SWNTs with dichlorocarbene led to functionalization of the nanotube walls.     

The optical resonances in carbon nanotubes arise from excitons

Optical transitions in carbon nanotubes are of central importance for nanotube characterization. They also provide insight into the nature of excited states in these one-dimensional systems. Recent work suggests that light absorption produces strongly correlated electron-hole states in the form of excitons. However, it has been difficult to rule out a simpler model in which resonances arise from the van Hove singularities associated with the one-dimensional band [corrected] structure of the nanotubes. Here, two-photon excitation spectroscopy bolsters the exciton picture. We found binding energies of approximately 400 millielectron volts for semiconducting single-walled nanotubes with 0.8-nanometer diameters. The results demonstrate the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.     

Carbon nanotubes as high-pressure cylinders and nanoextruders

Closed-shell carbon nanostructures, such as carbon onions, have been shown to act as self-contracting high-pressure cells under electron irradiation. We report that controlled irradiation of multiwalled carbon nanotubes can cause large pressure buildup within the nanotube cores that can plastically deform, extrude, and break solid materials that are encapsulated inside the core. We further showed by atomistic simulations that the internal pressure inside nanotubes can reach values higher than 40 gigapascals. Nanotubes can thus be used as robust nanoscale jigs for extruding and deforming hard nanomaterials and for modifying their properties, as well as templates for the study of individual nanometer-sized crystals under high pressure.     

Defects in carbon nanostructures

Previous high-resolution electron microscopy (HREM) observations of the carbon nanotubes have led to a "Russian doll" structural model that is based on hollow concentric cylinders capped at both ends. The structures of the carbon nanotubes and particles were characterized here by bulk physical and chemical property measurements. The individual nanostructure is as compressible as graphite in the c axis, and such nanostructures can be intercalated with potassium and rubidium, leading to a saturation composition of "MC(8)." These results are counter to expectations that are based on a Russian doll structure. HREM after intercalation with potassium and deintercalation indicates that individual nanoparticles are a "paper-mache" of smaller graphite layers. Direct current magnetization and electron spin resonance measurements indicate that the electronic properties of the nanostructures are distinctly different from those of graphite. Although the nanostructures have distinct morphologies and electronic properties, they are highly defective and have a local structure similar to turbostratic graphite.     

Direct synthesis of long single-walled carbon nanotube strands

In the processes that are used to produce single-walled nanotubes (electric arc, laser ablation, and chemical vapor deposition), the typical lengths of tangled nanotube bundles reach several tens of micrometers. We report that long nanotube strands, up to several centimeters in length, consisting of aligned single-walled nanotubes can be synthesized by the catalytic pyrolysis of n-hexane with an enhanced vertical floating technique. The long strands of nanotubes assemble continuously from arrays of nanotubes, which are intrinsically long.