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.     

碳纳米管的振动研究进展

综述了近年来碳纳米管的振动特性的理论数值方法研究进展,着重介绍了基于经典连续体理论、分子结构力学/原子有限元以及基于原子研究的分子动力学等方法研究单、多壁碳纳米管振动特性的现状。     

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.     

碳纳米管改性的蜡基复合粘结剂

通过熔融共混将功能化的碳纳米管引入到蜡基粘结剂中,得到碳纳米管改性的复合粘结剂.扫描电镜（SEM）显微照片显示,功能化的碳纳米管能均匀分散在粘结剂基体中.偏光显微照片和热性能分析结果表明,碳纳米管的加入能有效地提高粘结剂的结晶度和热稳定性,进而改善生坯在脱脂时的保形性.碳纳米管与粘结剂的非共价键结合有助于碳纳米管的均匀分散,更可能有利于复合材料成型后的脱脂.     

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.     

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.     

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.     

Carbon nanotubes with temperature-invariant viscoelasticity from -196 degrees to 1000 degrees C

Viscoelasticity describes the ability of a material to possess both elasticity and viscosity. Viscoelastic materials, such as rubbers, possess a limited operational temperature range (for example, for silicone rubber it is -55° to 300°C), above which the material breaks down and below which the material undergoes a glass transition and hardens. We created a viscoelastic material composed from a random network of long interconnected carbon nanotubes that exhibited an operational temperature range from -196° to 1000°C. The storage and loss moduli, frequency stability, reversible deformation level, and fatigue resistance were invariant from -140° to 600°C. We interpret that the thermal stability stems from energy dissipation through the zipping and unzipping of carbon nanotubes at contacts.     

Transparent, conductive carbon nanotube films

We describe a simple process for the fabrication of ultrathin, transparent, optically homogeneous, electrically conducting films of pure single-walled carbon nanotubes and the transfer of those films to various substrates. For equivalent sheet resistance, the films exhibit optical transmittance comparable to that of commercial indium tin oxide in the visible spectrum, but far superior transmittance in the technologically relevant 2- to 5-micrometer infrared spectral band. These characteristics indicate broad applicability of the films for electrical coupling in photonic devices. In an example application, the films are used to construct an electric field-activated optical modulator, which constitutes an optical analog to the nanotube-based field effect transistor.     

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.     

Microscopic Growth Mechanisms for Carbon Nanotubes

The uncatalyzed edge growth of carbon nanotubes was investigated by first-principles molecular dynamics simulations. At experimental temperatures the open end of single-walled nanotubes closed spontaneously into a graphitic dome, which may explain why these nanotubes do not grow in the absence of transition metal catalysts. On the other hand, chemical bonding between the edges of adjacent coaxial tubes ("lip-lip" interactions) trapped the end of a double-walled nanotube in a metastable energy minimum, thus preventing dome closure. These calculations show that this end geometry exhibits a high degree of chemical activity and easily accommodates incoming carbon fragments, supporting a model of growth by chemisorption from the vapor phase.     

Magnetic susceptibility of molecular carbon: nanotubes and fullerite

Elemental carbon can be synthesized in a variety of geometrical forms, from three-dimensional extended structures (diamond) to finite molecules (C(60) fullerite). Results are presented here on the magnetic susceptibility of the least well-understood members of this family, nanotubes and C(60) fullerite. (i) Nanotubes represent the cylindrical form of carbon, intermediate between graphite and fullerite. They are found to have significantly larger orientation-averaged susceptibility, on a per carbon basis, than any other form of elemental carbon. This susceptibility implies an average band structure among nanotubes similar to that of graphite. (ii) High-resolution magnetic susceptibility data on C(60) fullerite near the molecular orientational-ordering transition at 259 K show a sharp jump corresponding to 2.5 centimeter-gram-second parts per million per mole of C(60). This jump directly demonstrates the effect of an intermolecular cooperative transition on an intramolecular electronic property, where the susceptibility jump may be ascribed to a change in the shape of the molecule due to lattice forces.     

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.     

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.     

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.     

Temperature-induced hydrophobic-hydrophilic transition observed by water adsorption

The properties of nanoconfined and interfacial water in the proximity of hydrophobic surfaces play a pivotal role in a variety of important phenomena such as protein folding. Water inside single-walled carbon nanotubes (SWNTs) can provide an ideal system for investigating such nanoconfined interfacial water on hydrophobic surfaces, provided that the nanotubes can be opened without introducing excess defects. Here, we report a hydrophobic-hydrophilic transition upon cooling from 22 degrees C to 8 degrees C via the observation of water adsorption isotherms in SWNTs measured by nuclear magnetic resonance. A considerable slowdown in molecular reorientation of such adsorbed water was also detected. The observed transition demonstrates that the structure of interfacial water could depend sensitively on temperature, which could lead to intriguing temperature dependences involving interfacial water on hydrophobic surfaces.     

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.     

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.     

应用纳米碳管固相萃取环境中有机污染物研究进展

随着对纳米碳管研究的不断深入,对碳纳米管的应用研究越来越受到人们的重视。本文主要对应用碳纳米管萃取环境中有机污染物的研究进展作一综述,并对其在此领域的应用前景进行了展望。     

混酸预处理多壁碳纳米管吸附Cr~(3+)性能的影响

采用混酸对多壁碳纳米管(MWCNTs)进行处理,并考察了溶液浓度、pH值、时间、共存离子、不同洗脱剂等因素对混酸处理前后多壁碳纳米管吸附Cr3+离子性能的影响。实验结果显示:吸附量随时间和pH值增加而增大,且混酸处理后增加效果更加明显;吸附过程符合Freundlich等温吸附模型;0.5 mol/L HCl和0.1mol/L EDTA对吸附后MWCNTs解吸率均>80%。对混酸处理前后的多壁碳纳米管进行TEM、Zeta电位I、R、分散性测试表征。结果显示:混酸处理MWCNTs后,使其孔容、比表面积、表面基团数量及水溶性均有所增加,这可能是处理后MWCNTs吸附能力提高的主要原因。