Vladimir I. Merkulov

Vertically aligned carbon nanofibers and related structures: Controlled synthesis and directed assembly

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.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, catal...

Patterned growth of individual and multiple vertically aligned carbon nanofibers

The results of studies of patterned growth of vertically aligned carbon nanofibers (VACNFs) prepared by plasma-enhanced chemical vapor deposition are reported. Nickel (Ni) dots of various diameters and Ni lines with variable widths and shapes were fabricated using electron beam lithography and evaporation, and served for catalytic growth of VACNFs whose structure was determined by high resolution transmission electron microscopy. It is found that upon plasma pre-etching and heating up to 600–700 °C, thin films of Ni break into droplets which initiate the growth of VACNFs. Above a critical dot size multiple droplets are formed, and consequently multiple VACNFs grow from a single evaporated dot. For dot sizes smaller than the critical size only one droplet is formed, resulting in a single VACNF. In the case of a patterned line, the growth mechanism is similar to that from a dot. VACNFs grow along the line, and above a critical linewidth multiple VACNFs are produced across the line. The mechanism of the form...

Effect of catalyst film thickness on carbon nanotube growth by selective area chemical vapor deposition

The correlation between prepatterned catalyst film thickness and carbon nanotube (CNT) growth by selective area chemical vapor deposition (CVD) was studied using Fe and Ni as catalyst. To eliminate sample-to-sample variations and create a growth environment in which the film thickness is the sole variable, samples with continuously changing catalyst film thickness from 0 to 60 nm were fabricated by electron-gun evaporation. Using thermal CVD CNTs preferentially grow as a dense mat on the thin regions of the catalyst film. Moreover, beyond a certain critical film thickness no tubes were observed. The critical film thickness for CNT growth was found to increase with substrate temperature. There appears to be no strong correlation between the film thickness and the diameter of the tubes. In contrast, using plasma enhanced CVD with Ni as catalyst, vertically oriented CNTs grow in the entire range of catalyst film thickness. The diameter of these CNTs shows a strong correlation with the catalyst film thickness...

Alignment mechanism of carbon nanofibers produced by plasma-enhanced chemical-vapor deposition

We report experimental evidence showing a direct correlation between the alignment of carbon nanofibers (CNFs) prepared by plasma-enhanced chemical-vapor deposition and the location of the catalyst particle during CNF growth. In particular, we find that CNFs that have a catalyst particle at the tip (i.e., growth proceeds from the tip) align along the electric-field lines, whereas CNFs with the particle at the base (i.e., growth proceeds from the base) grow in random orientations. We propose a model that explains the alignment process as a result of a feedback mechanism associated with a nonuniform stress (part tensile, part compressive) that is created across the interface of the catalyst particle with the CNF due to electrostatic forces. Furthermore, we propose that the alignment seen recently in some dense CNF films is due to a crowding effect and is not directly the result of electrostatic forces.

Shaping carbon nanostructures by controlling the synthesis process

The ability to control the nanoscale shape of nanostructures in a large-scale synthesis process is an essential and elusive goal of nanotechnology research. Here, we report significant progress toward that goal. We have developed a technique that enables controlled synthesis of nanoscale carbon structures with conical and cylinder-on-cone shapes and provides the capability to dynamically change the nanostructure shape during the synthesis process. In addition, we present a phenomenological model that explains the formation of these nanostructures and provides insight into methods for precisely engineering their shape. Since the growth process we report is highly deterministic in allowing large-scale synthesis of precisely engineered nanoscale components at defined locations, our approach provides an important tool for a practical nanotechnology.

Intracellular integration of synthetic nanostructures with viable cells for controlled biochemical manipulation

We demonstrate the integration of vertically aligned carbon nanofibre (VACNF) elements with the intracellular domains of viable cells for controlled biochemical manipulation. Deterministically synthesized VACNFs were modified with either adsorbed or covalently-linked plasmid DNA and were subsequently inserted into cells. Post insertion viability of the cells was demonstrated by continued proliferation of the interfaced cells and long-term (}22

Individually addressable vertically aligned carbon nanofiber-based electrochemical probes

>> 22 day) expression of the introduced plasmid. Adsorbed plasmids were typically desorbed in the intracellular domain and segregated to progeny cells. Covalently bound plasmids remained tethered to nanofibres and were expressed in interfaced cells but were not partitioned into progeny, and gene expression ceased when the nanofibre was no longer retained. This provides a method for achieving a genetic modification that is non-inheritable and whose extent in time can be directly and precisely controlled. These results demonstrate the potential of VACNF arrays as an intracellular interface for monitoring and controlling subcellular and molecular phenomena within viable cells for applications including biosensors, in vivo diagnostics, and in vivo logic devices.

Characterization of thin-film amorphous semiconductors using spectroscopic ellipsometry

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 ...

Operation of a gated field emitter using an individual carbon nanofiber cathode

Spectroscopic ellipsometry (SE) has been used to routinely characterize amorphous silicon nitride and diamond thin films. Since SE measurements do not yield quantities of interest directly, the SE data must first be fit to a model to obtain useful parameters such as film thickness and optical functions. Recently, we have developed the Tauc-Lorentz (TL) model for the optical functions of amorphous materials [Appl. Phys. Lett. 69, 371373, 2137 (1996).], which has been very useful in interpreting these SE results. A 4parameter model is usually sufficient to describe the optical functions of the thin film to the accuracy of the ellipsometer. One of these parameters, the band gap Eg, correlates with other mechanical and chemical properties of the film, such as the silicon-to-nitrogen ratio in silicon nitride films, and to the sp 3 -bonded carbon fraction and the hardness of

Four-probe charge transport measurements on individual vertically aligned carbon nanofibers

We report on the operation of an integrated gated cathode device using a single vertically aligned carbon nanofiber as the field emission element. This device is capable of operation in a moderate vacuum for extended periods of time without experiencing a degradation of performance. Less than 1% of the total emitted current is collected by the gate electrode, indicating that the emitted electron beam is highly collimated. As a consequence, this device is ideal for applications that require well-focused electron emission from a microscale structure.