Scanning tunneling microscopy of carbon nanotubes

This article reports on the application of scanning tunneling microscopy for the study of surface structures and electronic properties of carbon nanotubes. Geometric effects resulting from the cylindrical shape of the tubes as well as the particular band structure of the graphitic crystal lattice can lead to a variety of contrast patterns. On the atomic scale, it is sometimes possible to see the full honeycomb lattice structure but often different structures are observed. Besides distortions caused by tip–sample interactions, we find that a complex superstructure superimposed on the simple atomic contrast pattern arises from elastic scattering of the Fermi states at defects or impurities. From a careful analysis of high-resolution images it is possible to extract information about elastic strain of individual tubes. A new combination of scanning tunneling and scanning force microscopy enables near-atomic point resolution of the force signal the tubes can be identified without the need of a conducting substrate. This imaging mode is a crucial step for the characterization of electronic devices based on individual single-wall tubes. This mode can be further enhanced by the use of single-walled tubes as probe tips. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 4 August 1999     

Carbon nanotubes as nanoparticles collector

This communication reports on a new method for the collection of nanoparticles using carbon nanotubes (CNT) as collecting surfaces, by which the problem of agglomeration of nanoparticles can be circumvented. CNT (10–50 nm in diameter, 1–10 μm in length) were grown by thermal CVD at 923 K in a 7 v/v% C₂H₂ in N₂ mixture on electroless nickel-plated copper transmission electron microscopy (TEM) grids and Monel coupons. These samples were then placed downstream of an arc plasma reactor to collect individual copper nanoparticles (5–30 nm in diameter). It was observed that the Cu nanoparticles preferentially adhere onto CNT and that the macro-particles (diameter >1 μm), a usual co-product obtained with metal nanoparticles in the arc plasma synthesis, are not collected. Cu–Ni nanoparticles, a catalyst for CNT growth, were deposited on CNT to grow multibranched CNT. CNT-embedded thin films were produced by re-melting the deposited nanoparticles.     

Ferromagnetic resonance of cobalt nanoparticles used as a catalyst for the carbon nanotubes synthesis

Catalyst is considered to be the most crucial parameter for the growth of carbon nanotubes. In this work we study the ferromagnetic resonance (FMR) spectra of the catalyst nanoclusters. Moreover we report for the first time the angle FMR studies of catalyst particles with and without CNT layer. The dependencies of the FMR spectra, X-ray diffraction (XRD) patterns, Raman spectra and morphology of the CNT layers on the growth conditions are discussed.     

Solidification of gold nanoparticles in carbon nanotubes

The structure and the solidification of gold nanoparticles in a carbon nanotube are investigated using molecular dynamics simulations. The simulations indicate that the predicted solidification temperature of the enclosed particle is lower than its bulk counterpart, but higher than that observed for clusters placed in vacuum. A comparison with a phenomenological model indicates that, in the considered range of tube radii (R(CNT)) of 0.5 < R(CNT) < 1.6 nm, the solidification temperature depends mainly on the length of the particle with a minor dependence on R(CNT).     

Carbon nanotubes decorated by graphitic shells encapsulated Cu nanoparticles

Carbon nanotubes (CNTs) decorated by graphitic shells encapsulated Cu nanoparticles were fabricated by low-energy hydrocarbon ion deposition with using Cu as hold substrate at 900°C. Scanning electron microscopy shows that the surface of CNTs becomes very coarse by hydrocarbon ion treatment. The investigation of transmission electron microscope shows that the full surfaces of CNTs are coated by dense graphitic shells encapsulated Cu nanoparticles. The graphitic shells consist of 7–10 layers and the size of Cu core is 1–2 nm.     

Carbon ad-dimer defects in carbon nanotubes

The adsorption of carbon dimers on carbon nanotubes leads to a rich spectrum of structures and electronic structure modifications. Barriers for the formation of carbon dimer induced defects are calculated and found to be considerably lower than those for the Stone-Wales defect. The electronic states introduced by the ad-dimers depend on defect structure and tube type and size. Multiple carbon ad-dimers provide a route to structural engineering of patterned tubes that may be of interest for nanoelectronics.     

Carbon nanotubes filled with long continuous cobalt nanowires

In this paper, we report the catalytic synthesis of carbon nanotubes filled with long continuous cobalt nanowires by a simple chemical process. The average diameter of the multi-walled nanotubes is about 40 nm. The nanowires are a few micrometers long with a diameter of 20 nm. X-ray diffraction analysis reveals that the as-prepared material, following treatment with HCl, shows the cobalt nanowires, encapsulated in the carbon nanotubes, as having an fcc and not the table hexagonal structure. The filled nanotubes can be seperated by using a permanent magnet. TEM, XPS and Raman spectroscopy were also used to analyze the products.     

High-field electron emission of carbon nanotubes grown on carbon fibers

Carbon nanotubes with uniform density were synthesized on carbon fiber substrate by the floating catalyst method. The morphology and microstructure were characterized by scanning electron microscopy and Raman spectroscopy. The results of field emission showed that the emission current density of carbon nanotubes/carbon fibers was 10 μA/cm² and 1 mA/cm² at the field of 1.25 and 2.25 V/μm, respectively, and the emission current density could be 10 and 81.2 mA/cm² with the field of 4.5 and 7 V/μm, respectively. Using uniform and sparse density distribution of carbon nanotubes on carbon fiber substrate, the tip predominance of carbon nanotubes can be exerted, and simultaneously the effect of screening between adjacent carbon nanotubes on field emission performance can also be effectively decreased. Therefore, the carbon nanotubes/carbon fibers composite should be a good candidate for a cold cathode material.     

Carbon nanocrystals produced by pulsed laser ablation of carbon

Plasma laser ablation experiments were performed irradiating glassy-carbon targets placed in vacuum through a pulsed Nd:YAG laser operating at the second harmonic (532 nm), 9 ns pulse width and 10⁹ W/cm² density power.

Thin films of ablated carbon were deposited on silicon oxide substrates placed at different distances and angles with respect to the target.

The analysis of the deposited material was carried out by using surface profiler, scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) and Raman spectroscopy.

Results show the evidence of carbon nanocrystals and nanostructures with dimension of the order of 100 nm deposited on the substrates together with a large amount of amorphous phase. The spectroscopic investigations and the SEM images indicate the formation of nanodiamond seeds as a nucleation process induced on the substrate surface. Nanostructures were investigated as a function of the laser intensity and angle distribution. Experimental results were compared with the literature data coming from nanodiamonds growth with different techniques.

Experiments performed at Instituto Nazionale di Fisica Nucleare-Laboratori Nazionali del Sud (INFN-LNS) of Catania (Italy) and data analysis conducted at Dipartimento di Fisica and DFMTA of the Università of Messina (Italy), CNR-ITIS of Messina and ST-Microelectronics of Catania will be presented and discussed.     

Synthesis of a composite consisting of carbon nanotubes and graphite shell-encapsulated cobalt nanoparticles using plasma-enhanced chemical vapor deposition

We report a simple and effective one-step synthesis route for synthesizing a composite consisted of carbon nanotubes (CNTs) and graphite shell-encapsulated cobalt nanoparticles using plasma-enhanced chemical vapor deposition on Si (1 0 0) substrate covered with catalyst Co particles, discharging a mixture of H₂ and CH₄ gas, and characterize the obtained composite by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscope, and X-ray photoelectron spectroscopy. The results show that CNTs align perpendicularly to the substrate and graphite shell-encapsulated Co nanoparticles clung to the external surfaces of aligned CNTs. The diameter of the graphite shell-encapsulated Co nanoparticles increases with increasing the H₂ content in H₂ and CH₄ carbonaceous gas. A possible growth mechanism of the CNTs and graphite shell-encapsulated cobalt nanoparticles composite has been explored.     

Synthesis and crystallinity of carbon nanotubes produced by a vapor-phase growth method

We have studied the effect of temperature on the growth and crystallinity of carbon nanotubes (CNTs), synthesized by a vapor-phase growth method using a catalytic reaction of iron pentacarbonyl (Fe(CO)₅) and acetylene (C₂H₂) gas. By increasing the growth temperature from 750 °C to 950 °C, both the growth rate and the diameter of the CNTs increase. Moreover, the crystallinity of the graphite sheets improves progressively with increasing growth temperature. Adjustment of the growth temperature gives potential for controlled growth of CNTs in a large-scale synthesis of CNTs. PACS 61.46.+w; 68.37.-d; 81.07.De     

Electronic structure of Pd nanoparticles on carbon nanotubes

The effect of the oxygen plasma treatment on the electronic states of multi-wall carbon nanotubes (MWCNTs) is analyzed by X-ray photoemission measurements (XPS) and UPS, both using synchrotron radiation. It is found that the plasma treatment effectively grafts oxygen at the CNT-surface. Thereafter, the interaction between evaporated Pd and pristine or oxygen plasma-treated MWCNTs is investigated. Pd is found to nucleate at defective sites, whether initially present or introduced by oxygen plasma treatment. The plasma treatment induced a uniform dispersion of Pd clusters at the CNT-surface. The absence of additional features in the Pd 3d and C 1s core levels spectra testifies that no Pd-C bond is formed. The shift of the Pd 3d core level towards high-binding energy for the smallest clusters is attributed to the Coulomb energy of the charged final state.     

Third-order nonlinear optical properties of multiwalled carbon nanotubes modified by CdS nanoparticles

CdS nanoparticles were coated on the side wall of multiwalled carbon nanotubes (MWCNTs) by a wet chemical synthesis approach via noncovalent functionalization of MWCNTs with poly(diallyldimethylammonium chloride) (PDDA). The as-prepared material was characterized by X-ray diffraction (XRD), UV–vis absorption, fluorescence and transmission electron microscopy (TEM). The results indicated that CdS nanoparticles were uniformly coated on the surface of MWCNTs. Third-order optical nonlinearity of the as-prepared material was studied with the Z-scan technique with picosecond laser pulses at 532 nm. The Z-scan curve revealed that CdS nanoparticle-modified MWCNTs exhibited negative nonlinear refraction index and positive absorption coefficient. The real part and imaginary part of the third-order nonlinear susceptibility χ⁽³⁾ were calculated to be −4.9 × 10⁻¹² and 6.8 × 10⁻¹³ esu, respectively.     

Atomic force microscopy investigation of electrochemically produced carbon nanotubes

Carbon nanostructures have been synthesized in NaCl-MgCl₂ and in NaCl-CaCl₂ salt melts and the extracted material was investigated by tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy. Some interesting new nanostructures were found and investigated as torus-shaped carbon structures with a ring diameter of 300-400 nm and 10-15 nm height. These tori are closely related to the wrapped SWNT rings described recently. They are probably formed during the electrolysis. A chain-like structure was also revealed.     

A mechanism for cutting carbon nanotubes with a scanning tunneling microscope

We discuss the local cutting of single-walled carbon nanotubes by a voltage pulse to the tip of a scanning tunneling microscope. The tip voltage ( V) is the key physical quantity in the cutting process. After reviewing several possible physical mechanisms we conclude that the cutting process relies on the weakening of the carbon-carbon bonds through a combination of localized particle-hole excitations induced by inelastically tunneling electrons and elastic deformation due to the electric field between tip and sample. The carbon network releases part of the induced mechanical stress by forming topological defects that act as nucleation centers for the formation of dislocations that dynamically propagate towards bond-breaking. Received 6 April 2000     

Magnetic properties of carbon nanotubes produced by the arc-discharge method under different conditions

Physics of the Solid State - The diamagnetic susceptibility and EPR signals of multi-walled carbon nanotubes produced at different helium pressures and rates of feed of the graphite anode are...     

Aligned carbon nanotubes catalytically grown on iron-based nanoparticles obtained by laser-induced CVD

Iron-based nanoparticles are prepared by a laser-induced chemical vapor deposition (CVD) process. They are characterized as body-centered Fe and Fe₂O₃ (maghemite/magnetite) particles with sizes ≤5 and 10 nm, respectively. The Fe particles are embedded in a protective carbon matrix. Both kind of particles are dispersed by spin-coating on SiO₂/Si(1 0 0) flat substrates. They are used as catalyst to grow carbon nanotubes by a plasma- and filaments-assisted catalytic CVD process (PE-HF-CCVD). Vertically oriented and thin carbon nanotubes (CNTs) were grown with few differences between the two samples, except the diameter in relation to the initial size of the iron particles, and the density. The electron field emission of these samples exhibit quite interesting behavior with a low turn-on voltage at around 1 V/μm.     

Catalytic oxidation of carbon nanotubes with noble metal nanoparticles

Catalytic oxidation of multi-walled carbon nanotubes (MWNCTs) with some noble metal nanoparticles was observed by environmental transmission electron microscopy (E-TEM). Amoeba-like movement of the nanoparticles was observed even at a temperature of ∼400 °C, which is much lower than the melting points of any of the metals. In particular, rhodium particles reacted intensely with MWCNTs, and assumed a droplet-like shape. On the other hand, gold particles caused very little erosion of the MWCNTs under the conditions of this study.     

Surface growth of single-walled carbon nanotubes from ruthenium nanoparticles

In this paper, we report that ruthenium is an active and efficient catalyst for growth of single-walled carbon nanotubes (SWNTs) by a chemical vapor deposition (CVD) process for the first time. High density random and horizontally superlong well-oriented SWNTs on substrate can be fabricated via CH₄ or EtOH as carbon source under suitable conditions. Scanning and transition electron microscopy investigations, Raman spectroscopy and atomic force microscopy measurements show the tubular structure, the high crystallinity, and the properties of the grown nanotubes. The results show that the SWNTs from ruthenium have better structural uniformity with less defects and provides an alternative catalyst for SWNTs growth. The successful growth of SWNTs by Ru catalyst provides new experimental information for understanding the growth mechanism of SWNTs, which may be helpful for their controllable synthesis.     

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional (2D) surface-enhanced Raman scattering (SERS) substrate is fabricated by decorating carbon nanotube (CNT) films with Ag nanoparticles (AgNPs) in different sizes, via simple and low-cost chemical reduction method and self-assembling method. The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles (CNTs/AgNPs) composites with varying size of AgNPs are investigated by using rhodamine 6G (R6G) as a probe molecule. Meanwhile, the scattering cross section of AgNPs and the distribution of electric field of CNTs/AgNPs composite are simulated through finite difference time domain (FDTD) method. Surface plasmon resonance (SPR) wavelength is redshifted as the size of AgNPs increases, and the intensity of SERS and electric field increase with AgNPs size increasing. The experiment and simulation results show a Raman scattering enhancement factor (EF) of 10⁸ for the hybrid substrate.