Kate L Klein

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...

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

We report four-probe I–V measurements on individual vertically aligned carbon nanofibers (VACNFs). These measurements were enabled by the fabrication of multiple Ti/Au ohmic contacts on individual fibers that exhibited resistance of only a few kilohms. These measurements demonstrate that VACNFs exhibit linear I–V behavior at room temperature, with a resistivity of approximately 4.2×10−3 Ω cm. Our measurements are consistent with a dominant transport mechanism of electrons traveling through intergraphitic planes in the VACNFs.

Surface characterization and functionalization of carbon nanofibers

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 modif...

Controlling thin film structure for the dewetting of catalyst nanoparticle arrays for subsequent carbon nanofiber growth

Vertically aligned carbon nanofiber (CNF) growth is a catalytic chemical vapor deposition process in which structure and functionality is controlled by the plasma conditions and the properties of the catalyst nanoparticles that template the fiber growth. We have found that the resultant catalyst nanoparticle network that forms by the dewetting of a continuous catalyst thin film is dependent on the initial properties of the thin film. Here we report the ability to tailor the crystallographic texture and composition of the nickel catalyst film and subsequently the nanoparticle template by varying the rf magnetron sputter deposition conditions. After sputtering the Ni catalyst thin films, the films are heated and exposed to an ammonia dc plasma, to chemically reduce the native oxide on the films and induce dewetting of the film to form nanoparticles. Subsequent nanoparticle treatment in an acetylene plasma at high substrate temperature results in CNF growth. Evidence is presented that the texture and composition of the nickel thin film has a significant impact on the structure and composition of the formed nanoparticle, as well as the resultant CNF morphology. Nickel films with a preferred (111) or (100) texture were produced and conditions favoring interfacial silicidation reactions were identified and investigated. Both compositional and structural analysis of the films and nanoparticles indicate that the properties of the as-deposited Ni catalyst film influences the subsequent nanoparticle formation and ultimately the catalytic growth of the carbon nanofibers.

Synthesis of vertically aligned carbon nanofibres for interfacing with live systems

The ability to synthesize carbon nanofibres (CNFs) with a high degree of control over their geometry, location and structure via catalytic plasma-enhanced chemical vapour deposition has expanded the possibility of new applications. The nanoscale dimensions and high aspect ratio of vertically aligned carbon nanofibres (VACNFs), along with favourable physical and chemical characteristics, has provided a nanostructured material with properties that are well-suited for interfacing with live cells and tissues. This review surveys the aspects of synthesis, integration and functionalization of VACNFs, followed by examples of how VACNFs have been used to interface with live systems for a variety of advanced nanoscale biological applications.

Single-crystal nanowires grown via electron-beam-induced deposition

Electron-beam-induced deposition (EBID) is a useful technique for direct-writing of 3-dimensional dielectric, semiconductor, and metallic materials with nanoscale precision and resolution. The EBID process, however, has been limited in many cases because precursor byproducts (typically from organic precursors like W(CO)6) are incorporated into the deposited material resulting in contaminated and amorphous structures. In this manuscript, we have investigated the structure and composition of EBID tungsten nanostructures as-deposited from a tungsten hexafluoride (WF6) precursor. High-resolution transmission electron microscopy, electron diffraction and electron spectroscopy were employed to determine the effects that the electron beam scanning conditions have on the deposit characteristics. The results show that slow, one-dimensional lateral scanning produces textured -tungsten nanowire cores surrounded by an oxide secondary layer, while stationary vertical growth leads to single-crystal [100]-oriented W3O nanowires. Furthermore we correlate how the growth kinetics affect the resultant nanowire structure and composition.

Control of carbon nanostructure: From nanofiber toward nanotube and back

The unique properties of carbon nanofibers (CNFs) make them attractive for numerous applications ranging from field emitters to biological probes. In particular, it is the deterministic synthesis of CNFs, which requires precise control over geometrical characteristics such as location, length, diameter, and alignment, that enables the diverse applications. Catalytic plasma enhanced chemical vapor deposition of vertically aligned CNFs is a growth method that offers substantial control over the nanofiber geometry. However, deterministic synthesis also implies control over the nanofiber’s physical and chemical properties that are defined by internal structure. Until now, true deterministic synthesis has remained elusive due to the lack of control over internal graphitic structure. Here we demonstrate that the internal structure of CNFs can be influenced by catalyst preparation and ultimately defined by growth conditions. We have found that when the growth rate is increased by 100-fold, obtained through maxim...

Focused helium and neon ion beam induced etching for advanced extreme ultraviolet lithography mask repair

The gas field ion microscope was used to investigate helium and neon ion beam induced etching of nickel as a candidate technique for extreme ultraviolet (EUV) lithography mask editing. No discernable nickel etching was observed for room temperature helium exposures at 16 and 30 keV in the dose range of 1 × 1015–1 × 1018 He+/cm2; however, transmission electron microscopy (TEM) revealed subsurface damage to the underlying Mo-Si multilayer EUV mirror. Subsequently, neon beam induced etching at 30 keV was investigated over a similar dose range and successfully removed the entire 50 nm nickel top absorber film at a dose of ∼3 × 1017 Ne+/cm2. Similarly, TEM revealed subsurface damage in the underlying Mo-Si multilayer. To further understand the helium and neon damage, the authors simulated the ion–solid interactions with our EnvizION Monte-Carlo model, which reasonably correlated the observed damage and bubble formation to the nuclear energy loss and the implanted inert gas concentration, respectively. A critical nuclear energy density loss of ∼80 eV/nm3 and critical implant concentration of ∼2.5 × 1020 atoms/cm3 have been estimated for damage generation in the multilayer structure.

Tailored transport through vertically aligned carbon nanofibre membranes; controlled synthesis, modelling, and passive diffusion experiments

The ability to control the permeability of a synthetic membrane structure formed by a spatially stochastic forest of vertically aligned carbon nanofibres is demonstrated. Control of membrane pore size and morphology was achieved by varying the thickness of a uniform, conformal coating of SiO2 on the nanofibre surfaces. Characterization of passive diffusion using fluorescence microscopy and labelled latex beads confirms the ability to alter membrane permeability. Further, statistically reproducible transport regimes are predicted for the spatially stochastic membrane as a function of the nanofibre diameter by a Monte Carlo simulation technique. Realizing predictable nanoscale behaviour in a microscopically random, statistical structure is essential for applications requiring controlled, species specific transport.

A synergetic description of carbon nanofiber growth

A self-consistent mathematical model of the growth of carbon nanofiber in a catalytic chemical vapor deposition process has been developed. This model includes the balance equation for carbon transport through the catalyst and the equation for mechanical and chemical balance in the catalyst-nanofiber system. It is demonstrated that the most important parameter that governs the nanofiber growth behavior is the difference in the carbon chemical potentials in the catalyst and nanofiber. This parameter determines the carbon transport to the nanofiber. It is also responsible for the catalyst shape and topology of the interface between the catalyst and nanofiber. The solutions of the model are in qualitative agreement with numerous experimental results. The model can be used in designing experiments and explaining existing results. It leaves the opportunity for more a precise and complex mathematical calculation of different aspects of the growth process.