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.     

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.     

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.     

Separation of metallic from semiconducting single-walled carbon nanotubes

We have developed a method to separate metallic from semiconducting single-walled carbon nanotubes from suspension using alternating current dielectrophoresis. Our method takes advantage of the difference of the relative dielectric constants of the two species with respect to the solvent, resulting in an opposite movement of metallic and semiconducting tubes along the electric field gradient. Metallic tubes are attracted toward a microelectrode array, leaving semiconducting tubes in the solvent. Proof of the effectiveness of separation is given by a comparative Raman spectroscopy study on the dielectrophoretically deposited tubes and on a reference sample.     

Extreme oxygen sensitivity of electronic properties of carbon nanotubes

The electronic properties of single-walled carbon nanotubes are shown here to be extremely sensitive to the chemical environment. Exposure to air or oxygen dramatically influences the nanotubes' electrical resistance, thermoelectric power, and local density of states, as determined by transport measurements and scanning tunneling spectroscopy. These electronic parameters can be reversibly "tuned" by surprisingly small concentrations of adsorbed gases, and an apparently semiconducting nanotube can be converted into an apparent metal through such exposure. These results, although demonstrating that nanotubes could find use as sensitive chemical gas sensors, likewise indicate that many supposedly intrinsic properties measured on as-prepared nanotubes may be severely compromised by extrinsic air exposure effects.     

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.     

Magnetic clusters on single-walled carbon nanotubes: the Kondo effect in a one-dimensional host

Single-walled carbon nanotubes are ideal systems for investigating fundamental properties and applications of one-dimensional electronic systems. The interaction of magnetic impurities with electrons confined in one dimension has been studied by spatially resolving the local electronic density of states of small cobalt clusters on metallic single-walled nanotubes with a low-temperature scanning tunneling microscope. Spectroscopic measurements performed on and near these clusters exhibit a narrow peak near the Fermi level that has been identified as a Kondo resonance. Using the scanning tunneling microscope to fabricate ultrasmall magnetic nanostructures consisting of small cobalt clusters on short nanotube pieces, spectroscopic studies of this quantum box structure exhibited features characteristic of the bulk Kondo resonance, but also new features due to finite size.     

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.     

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.     

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.     

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.     

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.     

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.     

Self-sorted, aligned nanotube networks for thin-film transistors

To find use in electronics, single-walled carbon nanotubes need to be efficiently separated by electronic type and aligned to ensure optimal and reproducible electronic properties. We report the fabrication of single-walled carbon nanotube (SWNT) network field-effect transistors, deposited from solution, possessing controllable topology and an on/off ratio as high as 900,000. The spin-assisted alignment and density of the SWNTs are tuned by different surfaces that effectively vary the degree of interaction with surface functionalities in the device channel. This leads to a self-sorted SWNT network in which nanotube chirality separation and simultaneous control of density and alignment occur in one step during device fabrication. Micro-Raman experiments corroborate device results as a function of surface chemistry, indicating enrichment of the specific SWNT electronic type absorbed onto the modified dielectric.     

Structure-assigned optical spectra of single-walled carbon nanotubes

Spectrofluorimetric measurements on single-walled carbon nanotubes (SWNTs) isolated in aqueous surfactant suspensions have revealed distinct electronic absorption and emission transitions for more than 30 different semiconducting nanotube species. By combining these fluorimetric results with resonance Raman data, each optical transition has been mapped to a specific (n,m) nanotube structure. Optical spectroscopy can thereby be used to rapidly determine the detailed composition of bulk SWNT samples, providing distributions in both tube diameter and chiral angle. The measured transition frequencies differ substantially from simple theoretical predictions. These deviations may reflect combinations of trigonal warping and excitonic effects.     

Atom collision-induced resistivity of carbon nanotubes

We report the observation of unusually strong and systematic changes in the electron transport in metallic single-walled carbon nanotubes that are undergoing collisions with inert gas atoms or small molecules. At fixed gas temperature and pressure, changes in the resistance and thermopower of thin films are observed that scale as roughly M(1/3), where M is the mass of the colliding gas species (He, Ar, Ne, Kr, Xe, CH4, and N2). Results of molecular dynamics simulations are also presented that show that the maximum deformation of the tube wall upon collision and the total energy transfer between the colliding atom and the nanotube also exhibit a roughly M(1/3) dependence. It appears that the transient deformation (or dent) in the tube wall may provide a previously unknown scattering mechanism needed to explain the atom collision-induced changes in the electrical transport.     

双空位缺陷对金属性碳纳米管量子电子学特性的影响研究

采用第一性原理的密度泛函理论计算方法,研究了2种不同分布的双原子空位缺陷(平行于管轴和斜交于管轴)对金属型(12,0)碳纳米管量子电子特性的影响。研究结果表明,平行于管轴的五边形-八边形-五边形(5-8-5)缺陷的转变能是最小的,是最稳定的缺陷结构分布;平行于管轴的5-8-5缺陷和斜交于管轴5-8-5缺陷都在价带部分引入了出现2个电子背散射中心,这对电子输运非常不利;斜交于管轴5-8-5缺陷比平行于管轴5-8-5缺陷对电导的抑制作用更大,这是由于斜交于管轴5-8-5缺陷破环了碳纳米管的轴向对称性。     

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.     

Atomically resolved single-walled carbon nanotube intramolecular junctions

Intramolecular junctions in single-walled carbon nanotubes are potentially ideal structures for building robust, molecular-scale electronics but have only been studied theoretically at the atomic level. Scanning tunneling microscopy was used to determine the atomic structure and electronic properties of such junctions in single-walled nanotube samples. Metal-semiconductor junctions are found to exhibit an electronically sharp interface without localized junction states, whereas a more diffuse interface and low-energy states are found in metal-metal junctions. Tight-binding calculations for models based on observed atomic structures show good agreement with spectroscopy and provide insight into the topological defects forming intramolecular junctions. These studies have important implications for applications of present materials and provide a means for assessing efforts designed to tailor intramolecular junctions for nanoelectronics.     

Oxygen doping modifies near-infrared band gaps in fluorescent single-walled carbon nanotubes

Controlled chemical modifications of single-walled carbon nanotubes (SWCNTs) that tune their useful properties have been sought for multiple applications. We found that beneficial optical changes in SWCNTs resulted from introducing low concentrations of oxygen atoms. Stable covalently oxygen-doped nanotubes were prepared by exposure to ozone and then light. Treated samples showed distinct, structure-specific near-infrared fluorescence at wavelengths 10 to 15% longer than displayed by pristine semiconducting SWCNTs. Dopant sites harvest light energy absorbed in undoped nanotube regions by trapping mobile excitons. The oxygen-doped SWCNTs are much easier to detect and image than pristine SWCNTs because they give stronger near-infrared emission and do not absorb at the shifted emission wavelength.