Irradiation-mediated tailoring of carbon nanotubes

The ever-increasing demand for faster computers in various areas, ranging from entertaining electronics to computational science, is pushing the semiconductor industry towards its limits on decreasing the sizes of electronic devices based on conventional materials. According to the famous law by Gordon E. Moore, a co-founder of the world s largest semiconductor company Intel, the transistor sizes should decrease to the atomic level during the next few decades to maintain the present rate of increase in the computational power. As leakage currents become a problem for traditional silicon-based devices already at sizes in the nanometer scale, an approach other than further miniaturization is needed to accomplish the needs of the future electronics. A relatively recently proposed possibility for further progress in electronics is to replace silicon with carbon, another element from the same group in the periodic table. Carbon is an especially interesting material for nanometer-sized devices because it forms naturally different nanostructures. Furthermore, some of these structures have unique properties. The most widely suggested allotrope of carbon to be used for electronics is a tubular molecule having an atomic structure resembling that of graphite. These carbon nanotubes are popular both among scientists and in industry because of a wide list of exciting properties. For example, carbon nanotubes are electronically unique and have uncommonly high strength versus mass ratio, which have resulted in a multitude of proposed applications in several fields. In fact, due to some remaining difficulties regarding large-scale production of nanotube-based electronic devices, fields other than electronics have been faster to develop profitable nanotube applications. In this thesis, the possibility of using low-energy ion irradiation to ease the route towards nanotube applications is studied through atomistic simulations on different levels of theory. Specifically, molecular dynamic simulations with analytical interaction models are used to follow the irradiation process of nanotubes to introduce different impurity atoms into these structures, in order to gain control on their electronic character. Ion irradiation is shown to be a very efficient method to replace carbon atoms with boron or nitrogen impurities in single-walled nanotubes. Furthermore, potassium irradiation of multi-walled and fullerene-filled nanotubes is demonstrated to result in small potassium clusters in the hollow parts of these structures. Molecular dynamic simulations are further used to give an example on using irradiation to improve contacts between a nanotube and a silicon substrate. Methods based on the density-functional theory are used to gain insight on the defect structures inevitably created during the irradiation. Finally, a new simulation code utilizing the kinetic Monte Carlo method is introduced to follow the time evolution of irradiation-induced defects on carbon nanotubes on macroscopic time scales. Overall, the molecular dynamic simulations presented in this thesis show that ion irradiation is a promisingmethod for tailoring the nanotube properties in a controlled manner. The calculations made with density-functional-theory based methods indicate that it is energetically favorable for even relatively large defects to transform to keep the atomic configuration as close to the pristine nanotube as possible. The kinetic Monte Carlo studies reveal that elevated temperatures during the processing enhance the self-healing of nanotubes significantly, ensuring low defect concentrations after the treatment with energetic ions. Thereby, nanotubes can retain their desired properties also after the irradiation. Throughout the thesis, atomistic simulations combining different levels of theory are demonstrated to be an important tool for determining the optimal conditions for irradiation experiments, because the atomic-scale processes at short time scales are extremely difficult to study by any other means.

Atomic scale engineering of carbon nanotubes

Carbon nanotubes, seamless cylinders made from carbon atoms, have outstanding characteristics: inherent nano-size, record-high Young’s modulus, high thermal stability and chemical inertness. They also have extraordinary electronic properties: in addition to extremely high conductance, they can be both metals and semiconductors without any external doping, just due to minute changes in the arrangements of atoms. As traditional silicon-based devices are reaching the level of miniaturisation where leakage currents become a problem, these properties make nanotubes a promising material for applications in nanoelectronics. However, several obstacles must be overcome for the development of nanotube-based nanoelectronics. One of them is the ability to modify locally the electronic structure of carbon nanotubes and create reliable interconnects between nanotubes and metal contacts which likely can be used for integration of the nanotubes in macroscopic electronic devices. In this thesis, the possibility of using ion and electron irradiation as a tool to introduce defects in nanotubes in a controllable manner and to achieve these goals is explored. Defects are known to modify the electronic properties of carbon nanotubes. Some defects are always present in pristine nanotubes, and naturally are introduced during irradiation. Obviously, their density can be controlled by irradiation dose. Since different types of defects have very different effects on the conductivity, knowledge of their abundance as induced by ion irradiation is central for controlling the conductivity. In this thesis, the response of single walled carbon nanotubes to ion irradiation is studied. It is shown that, indeed, by energy selective irradiation the conductance can be controlled. Not only the conductivity, but the local electronic structure of single walled carbon nanotubes can be changed by the defects. The presented studies show a variety of changes in the electronic structures of semiconducting single walled nanotubes, varying from individual new states in the band gap to changes in the band gap width. The extensive simulation results for various types of defect make it possible to unequivocally identify defects in single walled carbon nanotubes by combining electronic structure calculations and scanning tunneling spectroscopy, offering a reference data for a wide scientific community of researchers studying nanotubes with surface probe microscopy methods. In electronics applications, carbon nanotubes have to be interconnected to the macroscopic world via metal contacts. Interactions between the nanotubes and metal particles are also essential for nanotube synthesis, as single walled nanotubes are always grown from metal catalyst particles. In this thesis, both growth and creation of nanotube-metal nanoparticle interconnects driven by electron irradiation is studied. Surface curvature and the size of metal nanoparticles is demonstrated to determine the local carbon solubility in these particles. As for nanotube-metal contacts, previous experiments have proved the possibility to create junctions between carbon nanotubes and metal nanoparticles under irradiation in a transmission electron microscope. In this thesis, the microscopic mechanism of junction formation is studied by atomistic simulations carried out at various levels of sophistication. It is shown that structural defects created by the electron beam and efficient reconstruction of the nanotube atomic network, inherently related to the nanometer size and quasi-one dimensional structure of nanotubes, are the driving force for junction formation. Thus, the results of this thesis not only address practical aspects of irradiation-mediated engineering of nanosystems, but also contribute to our understanding of the behaviour of point defects in low-dimensional nanoscale materials.

New Strategies for the Enrichment of Metallic Single-Walled Carbon Nanotubes

Enrichment of metallic single-walled carbon nanotubes (SWNTs) has been accomplished by several means, including new extraction and synthetic procedures and by interaction with metal nanoparticles as well as electron donor molecules. In the presence of Fe(CO)(5) the arc discharge method yields nearly pure metallic nanotubes. Fluorous chemistry involving the preferential diazotization of metallic SWNTs offers a good procedure of obtaining the pure metallic species. Interaction of gold or platinum nanoparticles as well as of electron-donor molecules such as aniline and tetrathiafulvalene (TTF) transform semiconducting SWNTs into metallic ones. Raman and electroni spectroscopies provide ideal means to monitor enrichment of metallic SWNTs.

Excitation energy transfer from a fluorophore to single-walled carbon nanotubes

We study the process of electronic excitation energy transfer from a fluorophore to the electronic energy levels of a single-walled carbon nanotube. The matrix element for the energy transfer involves the Coulombic interaction between the transition densities on the donor and the acceptor. In the Foumlrster approach, this is approximated as the interaction between the corresponding transition dipoles. For energy transfer from a dye to a nanotube, one can use the dipole approximation for the dye, but not for the nanotube. We have therefore calculated the rate using an approach that avoids the dipole approximation for the nanotube. We find that for the metallic nanotubes, the rate has an exponential dependence if the energy that is to be transferred, h is less than a threshold and a d(-5) dependence otherwise. The threshold is the minimum energy required for a transition other than the k(i,perpendicular to)=0 and l=0 transition. Our numerical evaluation of the rate of energy transfer from the dye pyrene to a (5,5) carbon nanotube, which is metallic leads to a distance of similar to 165 A degrees up to which energy transfer is appreciable. For the case of transfer to semiconducting carbon nanotubes, apart from the process of transfer to the electronic energy levels within the one electron picture, we also consider the possibility of energy transfer to the lowest possible excitonic state. Transfer to semiconducting carbon nanotubes is possible only if>=epsilon(g)-epsilon(b). The long range behavior of the rate of transfer has been found to have a d(-5) dependence if h >=epsilon(g). But, when the emission energy of the fluorophore is in the range epsilon(g)>h >=epsilon(g)-epsilon(b), the rate has an exponential dependence on the distance. For the case of transfer from pyrene to the semiconducting (6,4) carbon nanotube, energy transfer is found to be appreciable up to a distance of similar to 175 A degrees.

Study on Young's modulus and microhardness of carbon nanotubes reinforced copper nanocomposite

Carbon nanotubes (CNTs) were discovered by Iijima in 1991 as the fourth form of carbon. Carbon nanotubes are the ultimate form of the carbon fibre because of its high Young's modulus in the order of 1 TPa, which is very useful for load transfer in nanocomposites. In the present work, CNT/Cu nanocomposites were fabricated by the powder metallurgy technique, and after extrusion of the nanocomposites, bright field transmission electron microscopic studies were carried out. From the transmission electron microscopic images obtained, a novel method of ascertaining the Young's modulus of multiwalled CNTs is worked out in the present paper, which turns out to be 0.94 TPa, which is consistent with experimental results. Furthermore, an attempt is made to investigate the microhardness of copper by reinforcing it with multiwalled CNTs. There is an increase in hardness by twofold in CNT/Cu nanocomposites as compared to pure Cu matrix. This is due to high relative density, even distribution of CNTs and proper bonding at CNT/Cu interfaces.

Simplified theory of carrier back-scattering in semiconducting carbon nanotubes: A Kane's model approach

We present a simplified yet analytical formulation of the carrier backscattering coefficient for zig-zag semiconducting single walled carbon nanotubes under diffusive regime. The electron-phonon scattering rate for longitudinal acoustic, optical, and zone-boundary phonon emissions for both inter- and intrasubband transition rates have been derived using Kane's nonparabolic energy subband model.The expressions for the mean free path and diffusive resistance have been formulated incorporating the aforementioned phonon scattering. Appropriate overlap function in Fermi's golden rule has been incorporated for a more general approach. The effect of energy subbands on low and high bias zones for the onset of longitudinal acoustic, optical, and zone-boundary phonon emissions and absorption have been analytically addressed. 90% transmission of the carriers from the source to the drain at 400 K for a 5 mu m long nanotube at 105 V m(-1) has been exhibited. The analytical results are in good agreement with the available experimental data. (c) 2010 American Institute of Physics.

Rapid growth of nanotubes and nanorods of wurtzite ZnO through microwave-irradiation of a metalorganic complex of zinc and a surfactant in solution

Large quantities of single-crystalline ZnO nanorods and nanotubes have been prepared by the microwave, irradiation of a metalorganic complex of zinc, in the presence of a surfactant. The method is simple, fast, and inexpensive (as it uses a domestic microwave oven), and yields pure nanostructures of the hexagonal wurtzite phase of ZnO in min, and requires no conventional templating. The ZnO nanotubes formed have a hollow core with inner diameter varying from 140-160 nm and a wall of thickness, 40-50 nm. The length of nanorods and nanotubes varies in the narrow range of 500-600 nm. These nanostructures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The ZnO nanorods and nanotubes are found by SAED to be single-crystalline. The growth process of ZnO nanorods and nanotubes has been investigated by varying the surfactant concentration and microwave irradiation time. Based on the various results obtained, a tentative and plausible mechanism for the formation of ZnO nanostructures is proposed.

Multiwall carbon nanotubes from pyrolysis of tetrahydrofuran

Multiwalled carbon nanotubes have been prepared by pyrolysing tetrahydrofuran (THF) in the presence of nickelocene. Pyrolysis of the precursor mixture has been achieved at temperature as low as 600 degrees C. In this simple approach no carrier gas has been used. The yield of purified carbon nanotubes is found to be more than 65%. Characterization of the as-prepared and purified nanotubes are done by Xray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy and Raman spectra.

Hydrogel-assisted synthesis of nanotubes and nanorods of US, ZnS and CuS, showing some evidence for oriented attachment

By carrying out the reaction of appropriate metal compounds with Na2S in the presence of a tripodal cholamide-based hydrogel, nanotubes and nanorods of CdS, ZnS and CuS have been obtained. The nanostructures have been characterized by transmission electron microscopy and spectroscopic techniques. Evidence is presented for the assembly of short nanorods to form one-dimensional chains.

Novel Nanocomposites Made of Boron Nitride Nanotubes and a Physical Gel

This article describes successful incorporation of multiwalled boron nitride nanotubes (BNNTs) and various functionalized BNNTs by Lewis bases such as trioctylamine (TOA), tributylamine (TBA), and triphenylphosphine (TPP), etc., in organogels formed by triphenylenevinylene (TPV)-based low molecular weight gelator (LMWG) in toluene and consequent characterization of the resulting gel nanocomposites. Functionalized BNNTs were synthesized first,and the presence of tubular structures with high aspect ratio and increased diameter compared to the starting BNNTs was confirmed by SEM. TEM, and Raman spectroscopy. The micrographs of composites of I and BNNTs showed evidence of wrapping of the gelator molecules on to the BNNT surface presumably brought about by pi-pi stacking and van der Waals interactions, This leads to the formation of densely packed and directionally aligned fibrous networks. Such ``reinforced'' aggregation of the gelator molecules in presence of doped BNNTs led to an increase in the sot-to-gel transition temperature and the solidification temperature of the gel nanocomposites as revealed from differential scanning calorimetry. Rheological investigations of the gel nanocomposites indicate that the flow properties of the resulting materials become resistant to applied stress upon incorporation of even a very low wt % of BNNTs. Finally, the increase in thermal conductivity of the nanocomposite compared to the gelator alone was observed for the temperature range of 0-60 degrees C which may make these composites potentially useful in various applications depending on the choice and the amount of BNNT loading in the composite.

Synthesis of metal oxide nanorods using carbon nanotubes as templates

Nanorods of several oxides, with diameters in the range of 10-200 nm and lengths upto a few microns, have been prepared by templating against carbon nanotubes. The oxides include V2O5, WO3, MoO3 and Sb2O5 as well as metallic MoO2, RuO2 and IrO2. The nanorods tend to be single-crystalline structures. Nanotube structures have also been obtained in MoO3 and RuO2.

Terahertz Spectroscopy of Single-Walled Carbon Nanotubes in a Polymer Film: Observation of Low-Frequency Phonons

We investigate the dielectric response of single-walled carbon nanotubes dispersed in poly(vinyl alcohol) matrix by using terahertz time domain spectroscopy. Frequency-dependent real and imaginary parts of the complex dielectric function are measured experimentally in the terahertz regime. The low-frequency phonons of carbon nanotubes, though predicted theoretically, are directly observed for the first time at frequencies 0.26, 0.60, and 0.85 THz. Further, a broad resonance is observed at 1.15 THz associated with the longitudinal acoustic mode of vibration of straight-chain segments of the long polymeric molecules in the film. The latter is observed at 1.24 THz for a pristine polymer film and has been used to derive the size of crystalline lamellae in the film.

Electrochemical investigation of single-walled carbon nanotubes for hydrogen storage

Electrodes made of purified and open single walled carbon nanotubes behave like metal hydride electrodes in Ni-MH batteries, showing high electrochemical reversible charging capacity up to 800 mAh g(-1) corresponding to a hydrogen storage capacity of 2.9 wt% compared to known AB(5), AB(2) metal hydride electrodes. (C) 2000 Elsevier Science Ltd. All rights reserved.