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Self-organised ferromagnetic nanowires encapsulated by multiwalled carbon nanotubes produced by CVD methods based on the thermal decomposition of ferrocene commonly contain the elemental phases: α-Fe, γ-Fe, and the carbide Fe 3 C. A continuous α-Fe nanowire and control of nanowire and nanotube length and diameter are desirable. High α-Fe nanowire content has been achieved through synthesis temperature modification, vapour flow-rate, and post-synthesis heat treatment. Length and diameter are intimately related to the self-organisational growth processes; reported approaches include regulation of the vapour supply to minimise dispersion in the nucleation process and introduction of other growth-modifying precursor elements. High vapour flow-rate produces downstream fluctuation resulting in discontinuous nanowires and diameter dispersion, or external decoration with spherical particles, results from rapid evaporation of the ferrocene precursor. We report a low vapour flow-rate and constant evaporation temperature method which achieves continuous α-Fe nanowires on the same scale as the nanotube for lengths >10 μm without the necessity of post-synthesis heat-treatment or introduction of other precursor elements. The low vapour flow-rate regime has the advantage of sustaining the intrinsic temperature gradient at the tip of the forming structure which drives the vapour feedstock to the growth front to guarantee continuous nanowire formation.

The use of thermoelectric technology is attractive in many potential applications, such as energy scavenging from waste heat. The basic principles for harvesting electricity from a temperature gradient were first discovered around 180 years ago, but the contemporary technology utilizing inorganic semiconductors was only developed since the early 1950s. The widespread use of this platform has so far been limited by a combination of relatively low efficiency in energy conversion or by issues related to the utilization of rare, expensive and/or toxic elements that can be difficult to process. Much interest has been focused on the use of organic materials in thermoelectric devices, prompted by the possibility of developing large-area, low-cost devices. Research over the last 20 years has been focused on understanding and improving organic thermoelectric properties, but only recently remarkable progress published for compounds such as poly(3,4-ethylenedioxythiophene) have attracted considerable attention. This has opened the door to developing a number of organic–inorganic composites for thermoelectric applications which combine the inherently low thermal conductivity and solution processing of organic materials with the high electrical conductivity of many inorganics.

The chapter details the underlying phenomena that underpin electronic applications that have followed from the discoveries of C60 and carbon nanotubes. The reduced dimensionality of these self-organised structures, high electron mobility, weak electromigration, and the plethora of quantum electronic effects exhibited by these structures suggest they are serious candidates for molecular electronics. The detail of the surface chemistry and conditions of synthesis assume greater importance than for conventional electronic materials since all atoms are on the exterior of these structures, as is outlined with references to the wider literature. Essential electronic structure information is given with reference to the transport measurements that have contributed greatly to the evolution of the field with emphasis on the Coulomb blockade and ballistic transport phenomena. The major electronic applications are then outlined, giving the state-of-the-art figures of merit for performance and comments on prospects for realisation.

Boundary layer chemical vapour synthesis is a new technique that exploits random fluctuations in the viscous boundary layer between a laminar flow of pyrolysed metallocene vapour and a rough substrate to yield ferromagnetically filled radial-carbon-nanotube structures departing from a core agglomeration of spherical nanocrystals individually encapsulated by graphitic shells. The fluctuations create the thermodynamic conditions for the formation of the central agglomeration in the vapour which subsequently defines the spherically symmetric diffusion gradient that initiates the radial growth. The radial growth is driven by the supply of vapour feedstock by local diffusion gradients created by endothermic graphitic-carbon formation at the vapour-facing tips of the individual nanotubes and is halted by contact with the isothermal substrate. The radial structures are the dominant product and the reaction conditions are self-sustaining. Ferrocene pyrolysis yields three common components in the nanowire encapsulated by multiwall carbon nanotubes, Fe3C, α-Fe, and γ-Fe. Magnetic tuning in this system can be achieved through the magnetocrystalline and shape anisotropies of the encapsulated nanowire. Here we demonstrate proof that alloying of the encapsulated nanowire is an additional approach to tuning of the magnetic properties of these structures by synthesis of radial-carbon-nanotube structures with γ-FeNi encapsulated nanowires.

Carbon nanotubes filled with continuous crystalline nanowires of nanometre-scale diameter and micrometre-scale length of the ferromagnetic phase α-Fe were produced with a new chemical vapour deposition method. We report a new two-stage approach, a perturbed-vapour method of synthesis followed by a post-synthesis heat treatment that produces multiwall carbon nanotubes filled with at least 19 micrometre-length nanowires of α-Fe. Previously reported synthesis routes use steady-state conditions to guarantee nanowire continuity but result only in small (less than one-micrometre length) nanowires comprising isolated or mixed phases of either α-Fe, Fe 3 C, or γ-Fe. Here flower-like clusters of carbon nanotubes continuously filled with α-Fe were produced by perturbation of a laminar ferrocene (Fe(C 5 H 5 ) 2 ) vapour flow in a conventional horizontal chemical vapour deposition reactor. Single-phase filling was achieved by a post-synthesis annealing at 500 °C for 15 h in Ar flow. Electron microscopy studies revealed the high quality of the structural integrity of both nanotubes and encapsulated nanowires. These nanostructures possess a high coercivity of 580 Oe and a very high saturation magnetization of 189.5 emu/g comparable with bulk α-Fe.

We report a new chemical vapor synthesis method that exploits random fluctuations in the viscous boundary layer between a laminar vapor flow and a surface to yield a not previously observed product: radial ferromagnetically filled-carbon-nanotube structures departing from a central particle. The filling of the nanotube capillary is continuous over a scale much greater than that which can be achieved by conventional CVD. This is a simple method which does not require ultra-fine control of process parameters or highly-engineered reactor components in which a single, self-organized, ordered product is formed in randomly fluctuating vapor in the boundary layer by vapor-, liquid-, solid-phase self-organization. These fluctuations create the thermodynamic conditions for formation of the central particle in the vapor which in turn defines the spherically symmetric diffusion gradient that initiates the radial growth. The subsequent radial growth is driven by the supply of vapor feedstock by local diffusion gradients created by endothermic graphitic carbon formation at the vapor-facing tips of the individual nanotubes and is halted by contact with the surface. The radial structures are the dominant product and the reaction conditions are self-sustaining. We argue that the method has potential for scalable production of metal-carbon nanostructures with other unusual morphologies.

Self supporting nickel substrates coated with nickel nanorods having diameters distributed between 110 nm and 170 nm were electrochemically synthesised using a two-step anodisation process, using as freshly anodised nanoporous alumina membrane as template. Field emission from the nanorods was observed at a relatively low bias potential Vbias (Vbias ≤ 1 V) using scanning tunnelling microscopy; the emission current was found to be larger than that from the nickel substrate at least by a factor of 4 at Vbias = 1.0 V. Experimental results were interpreted in the modified Millikan–Lauritsen plot and values of the emission parameters were estimated using the value of the work function measured by the Kelvin probe technique.

It is shown that the dominant conduction mechanism in single-wall carbon nanotube networks at room temperature is variable range hopping. Thin networks follow a variable range hopping law throughout the temperature range 4 K < T < 300 K, thick networks display variable range hopping characteristics in the range 50 K < T < 300 K, with deviation to Bloch–Gruneisen behaviour at lower temperatures. The adsorption state of these materials is shown to determine the sign of change in conductance upon subsequent exposure to oxygen. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The development of new flexible and stretchable sensors addresses the demands of upcoming application fields like internet-of-things, soft robotics, and health/structure monitoring. However, finding a reliable and robust power source to operate these devices, particularly in off-the-grid, maintenance-free applications, still poses a great challenge. The exploitation of ubiquitous temperature gradients, as the source of energy, can become a practical solution, since the recent discovery of the outstanding thermoelectric properties of a conductive polymer, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS). Unfortunately the use of PEDOT:PSS is currently constrained by its brittleness and limited processability. Herein, PEDOT:PSS is blended with a commercial elastomeric polyurethane (Lycra), to obtain tough and processable self-standing films. A remarkable strain-at-break of ≈700% is achieved for blends with 90 wt% Lycra, after ethylene glycol treatment, without affecting the Seebeck voltage. For the first time the viability of these novel blends as stretchable self-powered sensors is demonstrated.

A facile chemical vapor deposition-based method for the texturing of substrate-supported iron-filled multiwalled carbon nanotube arrays is reported. The method is based on the interplay of temperature gradients and modulated vapor flow that produces annular height variation and a vertical-array-to-spherulitic morphological transformation in experimental conditions, which result in uniform, close-packed arrays of constant height in an unmodulated vapor flow. These observations are proposed to result from creation of stationary cells of feedstock vapor above the growth front.

Thermoelectric power was used to elucidate the electrical transport properties of aligned and randomly oriented carbon nanotube systems in the temperature range 77--450 K. A weakly negative thermoelectric power, comparable with that of a graphite flake, was observed for a macroscopic bundle of multiwall carbon nanotubes with individual axes aligned parallel to the main axis. However, mats of randomly oriented multiwall carbon nanotubes gave a strongly positive thermoelectric power, as did mats of single-wall nanotubes. This is evidence of the importance of intertube contacts in the interpretation of the thermoelectric power data for carbon nanotube systems. Models for thermoelectric power behavior incorporating contact effects are described.

The electronic and optical properties of nitrogen doped tetrahedral amorphous carbon (ta-C:N) are compared with those of a new form of carbon ta-C film in which nanotube regions are included (ta-C:(NT)). It is found that nanotubes in ta-C inhibit the N doping effect in ta-C and leads to a reduction in conductivity. The results point to the nanotube regions acting as electronically isolated graphitic regions in ta-C. The refractive index in ta-C:(NT) is found to have the opposite dependency on wavelength to that of ta-C. It is proposed that the refractive index can be used as a signature for the presence of nanotubes and other large graphitic regions in ta-C.

Structures comprising single-crystal, iron-carbon-based nanowires encapsulated by multiwall carbon nanotubes self-organize on inert substrates exposed to the products of ferrocene pyrolysis at high temperature. The most commonly observed encapsulated phases are Fe3C, α-Fe, and γ-Fe. The observation of anomalously long-period lattice spacings in these nanowires has caused confusion since reflections from lattice spacings of ≥0.4 nm are kinematically forbidden for Fe3C, most of the rarely observed, less stable carbides, α-Fe, and γ-Fe. Through high-resolution electron microscopy, selective area electron diffraction, and electron energy loss spectroscopy we demonstrate that the observed long-period lattice spacings of 0.49, 0.66, and 0.44 nm correspond to reflections from the (100), (010), and (001) planes of orthorhombic Fe3C (space group Pnma). Observation of these forbidden reflections results from dynamic scattering of the incident beam as first observed in bulk Fe3C crystals. With small amounts of beam tilt these reflections can have significant intensities for crystals containing glide planes such as Fe3C with space groups Pnma or Pbmn.

The discovery of carbon nanotubes in 1991 spurred an enormous worldwide research effort spanning the physical, chemical, and life sciences. This review will attempt to convey to the reader the unique physical attributes of carbon nanotubes and the range of possible applications.

The growth control of α-Fe inside multiwall carbon nanotubes has challenged researchers for more than a decade owing to the coexistence of this phase with Fe3C and γ-Fe. Previously, long heating treatments of 20 h have been used to decompose the encapsulated Fe-phases in C and Fe; however, these methods were limited by an unusual oxidation process leading to nanotube decomposition. In this letter, we report an alternative chemical vapour deposition approach that through an accurate control of the ferrocene-vapour flow-rate allows to achieve the direct encapsulation of 95% of α-Fe without additional heating treatments.

The importance of the intercalation reaction for the chemistry of carbon cannot be underestimated. More than 200 graphite intercalation compounds (GIC) discovered to date demonstrate how one can alter electronic properties of a host lattice by introducing a certain amount (often a very small amount) of intercalating agent into the spaces between graphene sheets. Intercalation and intercalation-related processes lie at the basis of such recently developed technologies as lithium-ion batteries and expanded graphite materials.

We report high electrical conductance enhancement in sparse single-walled carbon nanotube networks by decoration with Au nanoparticles. The optimized hybrid network exhibited a sheet resistance of 650 Ω sq(-1), 1/1500 of the resistance of the host undecorated network, with a negligible optical transmission penalty (90% transmittance at 550 nm wavelength). The electrical transport at room temperature in the host and decorated networks was dominated by two-dimensional variable range hopping. The high conductance enhancement was due to positive charge transfer from the decorating Au nanoparticles in intimate contact with the host network causing a Fermi energy shift into the high density of states at a van Hove singularity and enhanced electron delocalization relative to the host network which beneficially modifies the hopping parameters in such a way that the network behaves as an integral whole. The effect is most pronounced when the nanoparticle diameter is comparable to the electron mean free path in the bulk material at room temperature and there is minimum nanoparticle agglomeration. For higher than optimal values of nanoparticle coverage or nanoparticle diameter, the conductance enhancement is countered by metallic inclusions in the current pathways that are of higher resistance than the variable range hopping-controlled elements.

DC magnetoresistive effects were observed in above-percolation-threshold loaded Fe-filled carbon nanotube/polyurethane-urea composite samples. A phenomenological model is derived from interpretation of resistance relaxation for a range of axial strains. The large instantaneous magnetoresistance of + 90% observed at low axial strain was a result of conduction pathway breaking caused by preferential orientation of the conducting nanotubes perpendicular to the axial current flow: a result of the magnetic torque experienced by the ferromagnetic nanotube core. At large strain the observed large instantaneous change in resistance of - 90% resulted from voltage-driven relaxation in the conducting nanotube network. At high axial strain the competition between voltage-driven relaxation and a magnetic torque gave rise to an oscillatory component of resistance relaxation.

The electrical conductance of single- and double-wall carbon nanotube systems was measured by a mechanically controllable break-junction technique using freestanding nanotubes not subject to any chemical modification. For metallic single-wall carbon nanotubes, two channels with transmission coefficient of 0.88 contribute to ballistic electronic transport at room temperature. In double-wall carbon nanotubes, one metallic channel contributes to ballistic electronic transport and additional field- and temperature-dependent two-channel contributions were observed.

Carbon nanotubes are a significant addition to the emerging field of nanotube biotechnology. The biocompatibility, high structural integrity, and unique electronic and mechanical properties of carbon nanotubes complement or surpass those of self-assembled lipid nanotubes, peptide nanotubes, and template-synthesised nanotubes (metals, polymers, semiconductors, and carbons). Carbon nanotubes are candidates for a range of biomolecular applications that is likely to widen considerably in the future.