Raman spectroscopy study of isolated double-walled carbon nanotubes with different metallic and semiconducting configurations

A double-walled carbon nanotube (DWNT) provides the simplest system to study the interaction between concentric layers in carbon nanotubes. The inner and outer walls of a DWNT can be metallic (M) or semiconducting (S), and each of the four possible configurations (M@M, M@S, S@S, S@M) has different electronic properties. Here we report, for the first time, detailed Raman spectroscopy experiments carried out on individual DWNTs, where both concentric tubes are measured under resonance conditions, in order to understand the dependence of their electronic and optical properties according to their configuration. Interestingly, for the three DWNTs that were studied, the inner-outer tube distance (e.g., 0.31-0.33 nm) was less than the interlayer spacing in graphite. We believe these results have important implications in the fabrication of electronic devices using different types of S and M tubular interconnects.     

Selective tuning of the electronic properties of coaxial nanocables through exohedral doping

The electronic properties of exohedrally doped double-walled carbon nanotubes (DWNTs) have been investigated using density functional theory and resonance Raman spectroscopy (RRS) measurements. First-principles calculations elucidate the effects of exohedral doping on the M@S and S@M systems, where a metallic (M) tube is either inside or outside a semiconducting (S) one. The results demonstrate that metallic nanotubes are extremely sensitive to doping even when they are inner tubes, in sharp contrast to semiconducting nanotubes, which are not affected by doping when the outer shell is a metallic nanotube (screening effects). The theoretical predictions are in agreement with RRS data on Br2- and H2SO4-doped DWNTs. These results pave the way to novel nanoscale electronics via exohedral doping.     

Synthesis and electronic properties of ferrocene-filled double-walled carbon nanotubes

Double-walled carbon nanotubes (DWNTs) are filled with ferrocene molecules by a vapour diffusion method for the first time. The as-synthesized ferrocene-filled DWNTs are characterized by transmission electron microscopy (TEM), energy-dispersive x-ray spectrometry (EDX) and Raman spectroscopy. Electronic properties of double-walled carbon nanotubes (DWNTs) filled with ferrocene molecules are studied by fabricating them as the channels of field-effect transistor (FET) devices. Our results reveal that electronic properties of ferrocene-filled DWNTs are greatly modified due to the charge transfer between ferrocene molecules and DWNTs. In addition, after ferrocene molecules are decomposed inside DWNTs, electronic properties of DWNTs exhibit a further change due to Fe encapsulation, and unipolar n-type semiconducting DWNTs are consequently obtained.     

Fast mass transport through carbon nanotube membranes

The May 19, 2006 issue of Science included a paper by Holt et al. on "Fast Mass Transport Through Sub-2-Nanometer Carbon Nanotubes". The paper was also featured on the cover, showing methane molecules translating inside a carbon nanotube (CNT). The authors explained how they prepared 2-6-mum thin membranes consisting of double-walled carbon nanotubes (DWNTs) all aligned perpendicular to the apparent membrane surface. These tubes are open at both ends and the space between the tubes is filled with dense Si(3)N(4). Pure gas and water fluxes were measured at room temperature with the application of a small pressure difference. Interpretation of the results led to the conclusion that the membranes showed much higher fluxes than what was estimated from Knudsen gas diffusion and Poiseuille viscous flow models. The membranes have a straight-channel morphology with a narrow pore-size distribution and exceptionally smooth pore walls. The unusual geometry and surface properties make it difficult to compare the membrane's properties with common membranes but there is no question that the mass transport in the aligned DWNTs is fast indeed. To appreciate how fast, we will consider their transport properties starting from the perspective of "conventional" porous membrane technology. Recent molecular dynamics simulations suggest that none of the classic models for gas (Knudsen) and water (Poiseuille) permeation work in a meaningful way for these nanotube membranes, and new models are needed.     

Electron beam induced structural transformations of SWNTs and DWNTs grown on Si3N4/Si substrates

Electron beam induced structural transformations are investigated in single-wall carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs) and crossed nanotube junctions. The nanotubes studied here are synthesized by the chemical vapor deposition method. The response of the nanotubes to an electron beam is found to be influenced by the presence of coatings of amorphous carbon, graphene fragments and structural defects on the tube surface. The dependence of structural modifications on electron beam irradiation dose is measured. While nanotubes with amorphous carbon, graphene fragment coverage and/or defects undergo rapid transformation leading to structure disintegration, those without such coverage or defects are more resistant to beam damage. In addition, it is shown that the amorphous carbon coverage on the double-wall nanotubes can be transformed into graphene layers during electron beam irradiation of coated nanotubes. Finally, the relative stability of nanotube side-wall and end-walls are investigated through sub-threshold energy and above threshold energy irradiation of a model system, C60-filled nanotubes (Peapods). The data indicates that electron beams could be used to join nanotubes end-to-end without damaging the side-walls.     

Photoluminescence from inner walls in double-walled carbon nanotubes: some do, some do not

Double-walled carbon nanotubes (DWNTs) have recently been recognized as important members in the carbon nanotube family because they are expected to have certain unique properties. For example, DWNTs are expected to replace single-walled carbon nanotubes (SWNTs) in biomarker applications and optoelectronics if the observed luminescence from DWNTs can be verified. However, due to unavoidable byproducts, such as SWNTs, optical properties of DWNTs still remain controversial. There is an ongoing debate concerning the ability of DWNTs to exhibit photoluminescence (PL). In this report, we aim to clearly resolve this debate through the study of carefully separated DWNTs. DWNTs were successfully separated from SWNTs using density gradient ultracentrifugation. Here we clearly show that light is emitted from the inner wall of DWNTs; however, the intensity of the emission is significantly quenched. Interestingly, it was found that a very narrow range of diameters of the inner walls of DWNTs is required for PL to be observable. All other diameters led to complete PL quenching in DWNTs. In short, we have shown that both sides of the debate are correct under certain situations. The real answer to the question is that some DWNTs do emit light but most DWNTs do not.     

Covalent Surface Chemistry of Single‐Walled Carbon Nanotubes

In this review article, we explore covalent chemical strategies for the functionalization of carbon‐nanotube surfaces. In recent years, nanotubes have been treated as chemical reagents (be it inorganic or organic) in their own right. Indeed, from their inherent structure, one can view nanotubes as sterically bulky, π‐conjugated ligands, or conversely as electron‐deficient alkenes. Hence, herein we seek to understand, from a structural perspective, the breadth and types of reactions single‐walled nanotubes (SWNTs) can undergo in solution phase, not only at the ends and defect sites but also along the sidewalls. Controllable chemical functionalization suggests that the unique electronic and mechanical properties of SWNTs can be tailored in a determinable manner. Moreover, prevailing themes in nanotube functionalization have been involved with dissolution of tubes.     

Structure determinations of double-wall carbon nanotubes grown by catalytic chemical vapor deposition

We report an application of nanoarea electron diffraction for structure determination of double-wall carbon nanotubes (DWNT) grown by catalytic chemical vapor deposition. The structures of 30 tubes were determined from experimental diffraction patterns. Among these tubes, the inner and outer wall structure of 18 tubes was precisely determined by comparison with kinematic electron diffraction simulations. For the structure of the DWNTs, our experiment revealed a mixture of semiconducting-metallic (S-M), S-S and M-M tubes. The spacing between the two walls ranges from 0.335 nm to 0.384 nm. Most DWNTs are incommensurate and chiral.     

Electronic properties of a single-walled carbon nanotube/150mer-porphyrin system measured by point-contact current imaging atomic force microscopy

The electronic properties of a single-walled carbon nanotube/150mer of porphyrin polymer wire system were investigated. Current-voltage (I-V) curves were measured simultaneously along with topographic observations using point-contact current imaging atomic force microscopy. Symmetric I-V curves were obtained at bare single-walled carbon nanotubes but characteristic asymmetrical rectifying behavior was found at the single-walled carbon nanotube/150mer-porphyrin junctions. This finding is of key importance for the development of new nanoscale molecular electronic devices.     

Synthesis of uniform double-walled carbon nanotubes using iron disilicide as catalyst

The preparation of carbon nanotube (CNT) materials with high purity is critical for many potential applications. These materials not only need to be free of carbonaceous impurities but also have uniform diameters. Within the CNT family, double-walled carbon nanotubes (DWNTs), as the simplest member of multiwalled carbon nanotubes, have demonstrated good potential in many bulk applications. However, the synthesis of DWNTs with uniform diameter and high purity is still a challenge. Here, a method to prepare high-purity DWNTs using iron disilicide (FeSi2) as catalyst is demonstrated. Over 90% of CNTs in the sample were DWNTs with a narrow diameter distribution in the range of 4-5 nm. An additional advantage of using FeSi2 as catalyst is to simplify the process to prepare suitable catalyst because commercially available FeSi2 can be used directly without any further treatment.     

Spectroscopy of single- and double-wall carbon nanotubes in different environments

Individual single-wall carbon nanotubes (SWNTs) and double-wall carbon nanotubes (DWNTs) were suspended in water for optical studies using sodium-cholate and other surfactants. We used time-resolved photoluminescence (PL) spectroscopy to study the influence of tube chirality and diameter as well as of the environment on nonradiative decay in small diameter tubes. The studies provide evidence for PL from small diameter core tubes in DWNTs and for a correlation of nonradiative decay with tube diameter and exciton red shift as induced by interaction with the environment.     

Growth of double-walled carbon nanotubes using a conditioning catalyst

Here we describe the effect of different synthetic conditions on the quality and purity of double-walled carbon nanotubes (DWNTs) with the aid of a conditioning catalyst. By lowering the reaction temperature down to 875 degrees C and utilizing a conditioning catalyst, increased purity and a decreased inner diameter of the DWNTs was achieved, while adverse results were observed with increasing reaction temperature. Based on detailed high-resolution transmission electron microscopy studies on the diameter distribution of the tubes, preferential growth conditions for DWNTs over single-wall carbon nanotubes are identified solely from increased carbon solubility considerations (caused by an increased portion of active carbon species by use of Mo) for the same distribution of metal particles.     

Carbon nanotube T junctions: formation and properties

The formation of carbon nanotube T junctions (CNTJs) and their transport properties are reviewed. The CNTJs were formed by coupling chemically functionalized nanotubes with linker molecules. Both end-to-side and end-to-end intermolecular junctions can be assembled by reacting chloride terminated nanotubes with aliphatic diamines. The functionalized nanotube mats were characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The incorporation of functional groups into nanotubes is indicated by the pronounced shift of tangential vibration modes in Raman spectra and of carbon is binding energy in X-ray photoelectron spectra. For transport measurements the functionalized nanotubes were adsorbed on Si substrates, and subsequent electrodes were painted on top of the selected T junctions by lithography and lift-off techniques. The bar of the "T" is used as the transistor channel and the stem of the "T" is used as the gate. In this configuration, the active area is confined to a few nanometers in all three dimensions.     

A structure model and growth mechanism for novel carbon nanotubes

The growth of carbon nanotubes from catalytic thermal decomposition of acetylene on fine iron particles has been studied. Electron microscopic images of the carbon nanotubes as formed and after annealing treatment are presented. Besides the ordinary carbon nanotubes which have been reported (S. Iijima, Nature, 354 (1991) 56), we have found, at first time, two other new kinds of carbon nanotubes: one is straight or curved nanotube with many irregular multi-layered diaphragms in the hollow core, in particular, the fringes of the wall of the tubes are not parallel to the axis of the tube; another one has many regular diaphragms (bamboo-like) which keep almost constant distance with each other. A model that postulates two steps growth of nanotubes from catalyst particles is proposed to explain the microstructure of the novel carbon nanotubes.     

Charge transfer in single-walled carbon nanotubes filled with cadmium halogenides

In this work the internal channels of the single-walled carbon nanotubes (SWCNTs) were filled with cadmium chloride, cadmium bromide, and cadmium iodide by a capillary method using melts of these salts. The influence of incorporated chemical compounds on the electronic properties of the carbon nanotubes was investigated by optical absorption spectroscopy, Raman spectroscopy, near edge X-ray absorption fine structure spectroscopy, and X-ray photoelectron spectroscopy. It was found that there is the chemical bonding between carbon atoms of nanotube walls and metal atoms of encapsulated CdX₂ nanocrystals. The obtained data testify acceptor doping effect of cadmium halogenides incorporated into the SWCNT channels, which is accompanied by the charge transfer from nanotube walls to introduced substances.     

In situ Raman study on single- and double-walled carbon nanotubes as a function of lithium insertion

We investigated the electrochemical lithium ion (Li(+)) insertion/desertion behavior on highly pure and bundled single- and double-walled carbon nanotubes (SWNTs and DWNTs) using an in situ Raman technique. In general, two storage sites could host Li(+) in SWNT and DWNT bundles when varying an external potential: a) the outer surface sites, and b) the interstitial spaces within the bundles. The most sensitive changes in the tangential mode (TM) of the Raman spectra upon doping with Li(+) can be divided into two regions. The first region was found from 2.8 to 1.0 V (the coverage of Li(+) on the outer surface of a bundled nanotube) and was characterized by the loss of resonant conditions via partial charge transfer, where the G(+) line of the SWNT and the TM of the outer tube of DWNTs experienced a highly depressed intensity, but remained almost constant in frequency. The appearance of a Breit-Wigner-Fano (BWF) profile provided strong evidence of metallic inner tubes within DWNTs. The second region was observed when the applied potentials ranged from 0.9 to 0 V and was characterized by Li(+) diffusion into the interstitial sites of the bundled nanotube material. This phenomenon invoked a large downshift of the G(-) band in SWNTs, and a small downshift of the TM of the inner tube of DWNTs caused by expansion of the C--C bonds due to the charge transferred to the nanotubes, and the disappearance of the BWF profile through the screening effect of the interstitial Li(+) layers.     

Effect of elliptical deformation on molecular polarizabilities of model carbon nanotubes from atomic increments

The interacting induced dipole polarization model implemented in our program POLAR is used for the calculation of the dipole-dipole polarizability alpha. The method is tested with single-wall carbon nanotube models as a function of nanotube radius and elliptical deformation. The results for polarizability follow the same trend as reference calculations performed with our version of the program PAPID. For the zigzag tubes, the polarizability is found to follow a remarkably simple law, that is, it varies as the inverse of the radius. A dramatic effect is also found with elliptical deformation. It is found that the polarizability and related properties can be modified continuously and reversibly by the external radial deformation. These results suggest an interesting technology in which mechanical deformation can control chemical properties of the carbon nanotubes. POLAR calculations differentiate more effectively than PAPID computations among single-wall nanotube models with increasing radial deformation. Different effective polarizabilities are calculated for the atoms at the highest and lowest curvature sites. POLAR calculations discriminate more efficiently than PAPID computations between the effective polarizabilities of the highest and lowest curvature sites. This remarkable and significant tunable polarizability can have important implications for metal coverage of metals on nanotubes and selective adsorption and desorption of foreign atoms and molecules on nanotubes and can lead to a wide variety of technological applications, such as catalysts, hydrogen storage, magnetic tubes, etc.     

Molecular dynamics study of hypothetical silicon nanotubes using the Tersoff potential

We have performed classical molecular dynamics simulations for hypothetical silicon nanotubes using the Tersoff potential. Our investigation presented a systematic study about the thermal behavior of hypothetical silicon nanotubes and showed the difficulty in producing silicon nanotubes or graphitelike sheets. However, since the elastic energy per atom to curve the sheet into cylinders for silicon atoms is as low as that for carbon atoms, if graphitelike sheets of silicon are formed, the extra cost to produce the tubes is of a similar order to that in carbon. Through the investigations on the structure and properties of a double-wall silicon nanotube, we concluded that quasi-one-dimensional structures consisting of silicon atoms become nanowires rather than nanotubes in order to minimize the number of sp2 bonds.     

Catalytic action of gold and copper crystals in the growth of carbon nanotubes

Multi-wall carbon nanotubes are grown in a chemical vapor deposition process by using bulk gold and copper substrates as catalysts. Nanotube growth starts from a nanometer-sized roughness on the metal surfaces and occurs in a mechanism where the catalyst particle is either at the tip (Au) or root (Cu) of the growing nanotube. Whereas Au leads to nanotubes with good structural perfection, nanotubes grown from Cu show a higher density of defects. High-resolution transmission electron microscopy shows the bonding between Au and carbon at the metal-nanotube interface whereas no bonds between Cu and carbon occur. Highly mobile Au or Cu atoms adsorb at the growing edge of a carbon nanotube from where diffusion along the nanotube wall can lead to the formation of Au or Cu nanowires inside the central hollow of carbon nanotubes.     

Effect of constructive rehybridization on transverse conductivity of aligned single-walled carbon nanotube films

Alignment of densely packed single-walled carbon nanotubes (SWNTs) largely preserves the extraordinary electronic properties of individual SWNTs in the alignment direction, while in transverse direction the films are very resistive due to large energy barriers for tunneling between adjacent SWNTs. We demonstrate that chromium atoms inserted between the sidewalls of parallel SWNTs effectively coordinate to the benzene rings of the nanotubes via hexahapto bonds that preserve the nanotube-conjugated electronic structure and serve as a conduit for electron transfer. The atomically interconnected aligned SWNTs exhibit enhanced transverse conductivity, which increases by ～2100% as a result of the photoactivated organometallic functionalization with Cr. The hexahapto mode of bonding the graphitic surfaces of carbon nanotubes with transition metal atoms offers an attractive route to the reversible chemical engineering of the transport properties of aligned carbon nanotube thin films. We demonstrate that a device fabricated with aligned SWNTs can be reversibly switched between a state of high electrical conductivity (ON) by light and low electrical conductivity (OFF) by applied potential. This study provides a route to the design of novel nanomaterials for applications in electrical atomic switches, optoelectronic and spintronic devices.