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.     

h/e magnetic flux modulation of the energy gap in nanotube quantum dots

We report experiments on quantum dot single-electron-tunneling (SET) transistors made from short multiwall nanotubes and threaded by magnetic flux. Such systems allow us to probe the electronic energy spectrum of the nanotube and its dependence on the magnetic field. Evidence is provided for the interconversion between gapped (semiconducting) and ungapped (metallic) states. Our tubes exhibit h/e-period magnetic flux dependence, in agreement with simple tight-binding calculations.     

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.     

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.     

Band gap fluorescence from individual single-walled carbon nanotubes

Fluorescence has been observed directly across the band gap of semiconducting carbon nanotubes. We obtained individual nanotubes, each encased in a cylindrical micelle, by ultrasonically agitating an aqueous dispersion of raw single-walled carbon nanotubes in sodium dodecyl sulfate and then centrifuging to remove tube bundles, ropes, and residual catalyst. Aggregation of nanotubes into bundles otherwise quenches the fluorescence through interactions with metallic tubes and substantially broadens the absorption spectra. At pH less than 5, the absorption and emission spectra of individual nanotubes show evidence of band gap-selective protonation of the side walls of the tube. This protonation is readily reversed by treatment with base or ultraviolet light.     

Selective etching of metallic carbon nanotubes by gas-phase reaction

Metallic and semiconducting carbon nanotubes generally coexist in as-grown materials. We present a gas-phase plasma hydrocarbonation reaction to selectively etch and gasify metallic nanotubes, retaining the semiconducting nanotubes in near-pristine form. With this process, 100% of purely semiconducting nanotubes were obtained and connected in parallel for high-current transistors. The diameter- and metallicity-dependent "dry" chemical etching approach is scalable and compatible with existing semiconductor processing for future integrated circuits.     

Crossed nanotube junctions

Junctions consisting of two crossed single-walled carbon nanotubes were fabricated with electrical contacts at each end of each nanotube. The individual nanotubes were identified as metallic (M) or semiconducting (S), based on their two-terminal conductances; MM, MS, and SS four-terminal devices were studied. The MM and SS junctions had high conductances, on the order of 0.1 e(2)/h (where e is the electron charge and h is Planck's constant). For an MS junction, the semiconducting nanotube was depleted at the junction by the metallic nanotube, forming a rectifying Schottky barrier. We used two- and three-terminal experiments to fully characterize this junction.     

Tunable quasi-two-dimensional electron gases in oxide heterostructures

We report on a large electric-field response of quasi-two-dimensional electron gases generated at interfaces in epitaxial heterostructures grown from insulating oxides. These device structures are characterized by doping layers that are spatially separated from high-mobility quasi-two-dimensional electron gases and therefore present an oxide analog to semiconducting high-electron mobility transistors. By applying a gate voltage, the conductivity of the electron gases can be modulated through a quantum phase transition from an insulating to a metallic state.     

Crystal Structures at High Pressures of Metallic Modifications of Silicon and Germanium

Studies of germanium and silicon by x-ray diffraction reveal that their crystal structure changes at high pressures from the semiconducting diamond-type structure to the metallic white tin structure, in analogy to the known "gray" to "white" transition in tin itself.     

Porous semiconductor chalcogenide aerogels

Chalcogenide aerogels based entirely on semiconducting II-VI or IV-VI frameworks have been prepared from a general strategy that involves oxidative aggregation of metal chalcogenide nanoparticle building blocks followed by supercritical solvent removal. The resultant materials are mesoporous, exhibit high surface areas, can be prepared as monoliths, and demonstrate the characteristic quantum-confined optical properties of their nanoparticle components. These materials can be synthesized from a variety of building blocks by chemical or photochemical oxidation, and the properties can be further tuned by heat treatment. Aerogel formation represents a powerful yet facile method for metal chalcogenide nanoparticle assembly and the creation of mesoporous semiconductors.     

Electrowetting in carbon nanotubes

We demonstrate reversible wetting and filling of open single-wall carbon nanotubes with mercury by means of electrocapillary pressure originating from the application of a potential across an individual nanotube in contact with a mercury drop. Wetting improves the conductance in both metallic and semiconducting nanotube probes by decreasing contact resistance and forming a mercury nanowire inside the nanotube. Molecular dynamics simulations corroborate the electrocapillarity-driven filling process and provide estimates for the imbibition speed and electrocapillary pressure.     

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.     

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.     

DNA-templated carbon nanotube field-effect transistor

The combination of their electronic properties and dimensions makes carbon nanotubes ideal building blocks for molecular electronics. However, the advancement of carbon nanotube-based electronics requires assembly strategies that allow their precise localization and interconnection. Using a scheme based on recognition between molecular building blocks, we report the realization of a self-assembled carbon nanotube field-effect transistor operating at room temperature. A DNA scaffold molecule provides the address for precise localization of a semiconducting single-wall carbon nanotube as well as the template for the extended metallic wires contacting it.     

Electronic structure control of single-walled carbon nanotube functionalization

Diazonium reagents functionalize single-walled carbon nanotubes suspended in aqueous solution with high selectivity and enable manipulation according to electronic structure. For example, metallic species are shown to react to the near exclusion of semiconducting nanotubes under controlled conditions. Selectivity is dictated by the availability of electrons near the Fermi level to stabilize a charge-transfer transition state preceding bond formation. The chemistry can be reversed by using a thermal treatment that restores the pristine electronic structure of the nanotube.     

Electronic structures of single-walled carbon nanotubes determined by NMR

Single-walled carbon nanotubes were studied by (13)C nuclear magnetic resonance (NMR). Two types of (13)C nuclear spins were identified with different spin-lattice relaxation rates. The fast-relaxing component, assigned to metallic tubes, followed the relaxation behavior expected in metals, and the density-of-states at the Fermi level increased with decreasing tube diameter. The slow-relaxing component has a significantly lower density-of-states at the Fermi level. Exposure to oxygen has a substantial effect on relaxation rates of both components.     

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.     

Extraction and STM Imaging of Spherical Giant Fullerenes

High-temperature, high-pressure extracts of soot produced by the Kr?tschmer-Huffman technique (KH carbon) were characterized by mass spectrometry and imaging with scanning tunneling microscopes (STMs). The mass spectra of these samples are similar to those of ambient-pressure, high-boiling-point solvent extractions, supporting the idea that solvent temperature and possibly pressure are key parameters in extraction of the giant fuilerenes. The STM images show that the giant fullerenes in these samples are roughly spherical in shape and range in diameter from approximately 1 to 2 nanometers, corresponding to fullerenes containing 60 to 330 atoms. No evidence of bucky tubes was found.     

Observational evidence for a possible new diffusion path

Transmission electron microscopy of experimentally deformed amphibolite suggests that submicroscopic intracrystalline tubes formed around linear defects may be a previously unrecognized kind of diffusion pathway. Deformed and compositionally altered plagioclase and amphibole crystals include moderate densities of linear defects that morphologically resemble unit dislocations but display unusual contrast. During prolonged electron irradiation, the core regions of the defects expand to well-defined tubes that are approximately 20 nanometers in diameter. Both observations suggest that the regions about the defect cores are glassy and were filled with silicate-water fluid during the experiments. Intracrystalline transport along these tubes would likely be several orders of magnitude faster than traditionally conceived processes of solid-state volume diffusion, grain-boundary solvent transfer, and ordinary pipe diffusion along dislocation cores.     

改进型过氧钼酸法制备无定形MoO3薄膜

通过金属钼粉与H2O2反应制得过氧钼酸溶胶液后，减压蒸馏除去过氧钼酸溶液中的溶剂水和过量的H2O2，再加入无水乙醇作为溶剂，采用浸泽一提拉法成功地在玻璃表面制备了平整均匀的无定形MoO3薄膜．并通过热分析和X射线衍射分析等对MoO3薄膜的制备机理进行了探讨．