The controlled synthesis of materials by methods that permit their assembly into functional nanoscale structures lies at the crux of the emerging field of nanotechnology. Although only one of several materials families is of interest, carbon-based nanostructured materials continue to attract a disproportionate share of research effort, in part because of their wide-ranging properties. Additionally, developments of the past decade in the controlled synthesis of carbon nanotubes and nanofibers have opened additional possibilities for their use as functional elements in numerous applications. Vertically aligned carbon nanofibers (VACNFs) are a subclass of carbon nanostructured materials that can be produced with a high degree of control using catalytic plasma-enhanced chemical-vapor deposition (C-PECVD). Using C-PECVD the location, diameter, length, shape, chemical composition, and orientation can be controlled during VACNF synthesis. Here we review the CVD and PECVD systems, growth control mechanisms, catalyst preparation, resultant carbon nanostructures, and VACNF properties. This is followed by a review of many of the application areas for carbon nanotubes and nanofibers including electron field-emission sources, electrochemical probes, functionalized sensor elements, scanning probe microscopy tips, nanoelectromechanical systems (NEMS), hydrogen and charge storage, and catalyst support. We end by noting gaps in the understanding of VACNF growth mechanisms and the challenges remaining in the development of methods for an even more comprehensive control of the carbon nanofiber synthesis process.

In this paper we present the fabrication and initial testing results of high aspect ratio vertically aligned carbon nanofiber (VACNF)-based electrochemical probes. Electron beam lithography was used to define the catalytic growth sites of the VACNFs. Following catalyst deposition, VACNF were grown using a plasma enhanced chemical vapor deposition process. Photolithography was performed to realize interconnect structures. These probes were passivated with a thin layer of SiO2, which was then removed from the tips of the VACNF, rendering them electrochemically active. We have investigated the functionality of completed devices using cyclic voltammetry (CV) of ruthenium hexammine trichloride, a highly reversible, outer sphere redox system. The faradaic current obtained during CV potential sweeps shows clear oxidation and reduction peaks at magnitudes that correspond well with the geometry of these nanoscale electrochemical probes. Due to the size and the site-specific directed synthesis of the VACNFs, these probes are ideally suited for characterizing electrochemical phenomena with an unprecedented degree of spatial resolution.

Carbon nanofibers are high-aspect ratio graphitic materials that have been investigated for numerous applications due to their unique physical properties such as high strength, low density, metallic conductivity, tunable morphology, chemical and environmental stabilities, as well as compatibility with organochemical modification. Surface studies are extremely important for nanomaterials because not only is the surface structurally and chemically quite different from the bulk, but its properties tend to dominate at the nanoscale due to the drastically increased surface-to-volume ratio. This review surveys recent developments in surface analysis techniques used to characterize the surface structure and chemistry of carbon nanofibers and related carbon materials. These techniques include scanning probe microscopy, infrared and electron spectroscopies, electron microscopy, ion spectrometry, temperature-programed desorption, and atom probe analysis. In addition, this article evaluates the methods used to modify the surface of carbon nanofibers in order to enhance their functionality to perform across an exceedingly diverse application space.

We report on techniques for catalytic synthesis of rigid, high-aspect-ratio, vertically aligned carbon nanofibres by dc plasma enhanced chemical vapour deposition that are tailored for applications that require arrays of individual fibres that feature long fibre lengths (up to 20 µm) such as scanning probe microscopy, penetrant cell and tissue probing arrays and mechanical insertion approaches for gene delivery to cell cultures. We demonstrate that the definition of catalyst nanoparticles is the critical step that enables growth of individual, long-length fibres and discuss methods for catalyst particle preparation that allow the growth of individual isolated nanofibres from catalyst dots with diameters as large as 500 nm. This development enables photolithographic definition of catalyst and therefore the inexpensive, large-scale production of such arrays.