Carbon nanotube conditioning part 1-effect of interwall interaction on the electronic band gap of double-walled carbon nanotubes.

Ab initio density functional theory simulations were used to calculate the electronic structure and the total energy of double-walled carbon nanotubes (DWCNTs). The relaxed configurations studied were uncapped, infinitely-long zigzag@zigzag double-walled carbon nanotubes. The lowest energy configuration was found to correspond to an interwall distance of 0.35 nm, except for the configurations with inner tube chiral indices (5,0), (6,0) and (7,0). The largest binding energies were found to correspond to a 0.35 nm interwall distance for all the DWCNT configurations studied, and increasing with DWCNT average diameter. In terms of the effect of the interwall interaction on the electronic band gap of DWCNTs, four regions of band gap were obtained which were termed: zero band gap, narrow band gap, small band gap, and medium band gap regions. These regions offer the possibility to first tune the electronic band gap to a region with a desired range, and further tune that choice within the region itself by varying the interwall distance. It was also found that zigzag@zigzag DWCNTs with outer tube leading chiral index n = 3k + 1 or n = 3k + 2 (k being an integer) follow, as a general trend, an inversely proportional relation of the electronic band gap with respect to the average diameter.

On-chip integrated vertically aligned carbon nanotube based super- and pseudocapacitors.

On-chip energy storage and management will have transformative impacts in developing advanced electronic platforms with built-in energy needs for operation of integrated circuits driving a microprocessor. Though success in growing stand-alone energy storage elements such as electrochemical capacitors (super and pseusocapacitors) on a variety of substrates is a promising step towards this direction. In this work, on-chip energy storage is demonstrated using architectures of highly aligned vertical carbon nanotubes (CNTs) acting as supercapacitors, capable of providing large device capacitances. The efficiency of these structures is further increased by incorporating electrochemically active nanoparticles such as MnOx to form pseudocapacitive architectures thus enhancing device capacitance areal specific capacitance of 37 mF/cm2. The demonstrated on-chip integration is up and down-scalable, compatible with standard CMOS processes, and offers lightweight energy storage what is vital for portable and autonomous device operation with numerous advantages as compared to electronics built from discrete components.

Negative Differential Conductance & Hot-Carrier Avalanching in Monolayer WS2 FETs.

The high field phenomena of inter-valley transfer and avalanching breakdown have long been exploited in devices based on conventional semiconductors. In this Article, we demonstrate the manifestation of these effects in atomically-thin WS2 field-effect transistors. The negative differential conductance exhibits all of the features familiar from discussions of this phenomenon in bulk semiconductors, including hysteresis in the transistor characteristics and increased noise that is indicative of travelling high-field domains. It is also found to be sensitive to thermal annealing, a result that we attribute to the influence of strain on the energy separation of the different valleys involved in hot-electron transfer. This idea is supported by the results of ensemble Monte Carlo simulations, which highlight the sensitivity of the negative differential conductance to the equilibrium populations of the different valleys. At high drain currents (>10 µA/µm) avalanching breakdown is also observed, and is attributed to trap-assisted inverse Auger scattering. This mechanism is not normally relevant in conventional semiconductors, but is possible in WS2 due to the narrow width of its energy bands. The various results presented here suggest that WS2 exhibits strong potential for use in hot-electron devices, including compact high-frequency sources and photonic detectors.

Thermally Assisted Nonvolatile Memory in Monolayer MoS2 Transistors.

We demonstrate a novel form of thermally-assisted hysteresis in the transfer curves of monolayer MoS2 FETs, characterized by the appearance of a large gate-voltage window and distinct current levels that differ by a factor of ∼102. The hysteresis emerges for temperatures in excess of 400 K and, from studies in which the gate-voltage sweep parameters are varied, appears to be related to charge injection into the SiO2 gate dielectric. The thermally-assisted memory is strongly suppressed in equivalent measurements performed on bilayer transistors, suggesting that weak screening in the monolayer system plays a vital role in generating its strongly sensitive response to the charge-injection process. By exploiting the full features of the hysteretic transfer curves, programmable memory operation is demonstrated. The essential principles demonstrated here point the way to a new class of thermally assisted memories based on atomically thin two-dimensional semiconductors.

Conduction Mechanisms in CVD-Grown Monolayer MoS2 Transistors: From Variable-Range Hopping to Velocity Saturation.

We fabricate transistors from chemical vapor deposition-grown monolayer MoS2 crystals and demonstrate excellent current saturation at large drain voltages (Vd). The low-field characteristics of these devices indicate that the electron mobility is likely limited by scattering from charged impurities. The current-voltage characteristics exhibit variable range hopping at low Vd and evidence of velocity saturation at higher Vd. This work confirms the excellent potential of MoS2 as a possible channel-replacement material and highlights the role of multiple transport phenomena in governing its transistor action.

Effect of interwall interaction on the electronic structure of double-walled carbon nanotubes.

Through this study, the results of density functional theory calculations within the local density approximation of the electronic structure of zigzag-zigzag double-walled carbon nanotubes (DWCNTs), with chiral indices (n, 0)@(m, 0) for n = 7-15, and m = 15-26, has been presented and the effects of interwall interaction and orbital hybridization on the electronic structure of these systems has been discussed. It was observed that the electronic band gap of the aforementioned DWCNTs depends on the interwall distance only for metallic-semiconductor configurations and on the intrinsic properties of the constituent tubes in all other combinations. It was also observed that the calculated band gap for most of the metallic-metallic DWCNTs was smaller than semiconductor-metallic, metallic-semiconductor, and semiconductor-semiconductor configurations. Metallic-semiconductor DWCNTs were found to be desirable for band gap tuning applications because of their dependence on interwall distance, opening up the possibility of using such systems in electronic device applications, such as transistors. Other applications include the use of DWCNTs in macroscopic carbon nanotube conducting wires, for which metallic-metallic and semiconducting-metallic zigzag-zigzag DWCNTs were found to be the most desirable configurations due to their small band gaps.

Imaging molecular adsorption and desorption dynamics on graphene using terahertz emission spectroscopy.

Being an atomically thin material, graphene is known to be extremely susceptible to its environment, including defects and phonons in the substrate on which it is placed as well as gas molecules that surround it. Thus, any device design using graphene has to take into consideration all surrounding components, and device performance needs to be evaluated in terms of environmental influence. However, no methods have been established to date to readily measure the density and distribution of external perturbations in a quantitative and non-destructive manner. Here, we present a rapid and non-contact method for visualizing the distribution of molecular adsorbates on graphene semi-quantitatively using terahertz time-domain spectroscopy and imaging. We found that the waveform of terahertz bursts emitted from graphene-coated InP sensitively changes with the type of atmospheric gas, laser irradiation time, and ultraviolet light illumination. The terahertz waveform change is explained through band structure modifications in the InP surface depletion layer due to the presence of localized electric dipoles induced by adsorbed oxygen. These results demonstrate that terahertz emission serves as a local probe for monitoring adsorption and desorption processes on graphene films and devices, suggesting a novel two-dimensional sensor for detecting local chemical reactions.

Enhanced field emission properties from CNT arrays synthesized on Inconel superalloy.

One of the most promising materials for fabricating cold cathodes for next generation high-performance flat panel devices is carbon nanotubes (CNTs). For this purpose, CNTs grown on metallic substrates are used to minimize contact resistance. In this report, we compare properties and field emission performance of CNTs grown via water assisted chemical vapor deposition using Inconel vs silicon (Si) substrates. Carbon nanotube forests grown on Inconel substrates are superior to the ones grown on silicon; low turn-on fields (∼1.5 V/µm), high current operation (∼100 mA/cm(2)) and very high local field amplification factors (up to ∼7300) were demonstrated, and these parameters are most beneficial for use in vacuum microelectronic applications.

Magnetic quantum ratchet effect in graphene.

A periodically driven system with spatial asymmetry can exhibit a directed motion facilitated by thermal or quantum fluctuations. This so-called ratchet effect has fascinating ramifications in engineering and natural sciences. Graphene is nominally a symmetric system. Driven by a periodic electric field, no directed electric current should flow. However, if the graphene has lost its spatial symmetry due to its substrate or adatoms, an electronic ratchet motion can arise. We report an experimental demonstration of such an electronic ratchet in graphene layers, proving the underlying spatial asymmetry. The orbital asymmetry of the Dirac fermions is induced by an in-plane magnetic field, whereas the periodic driving comes from terahertz radiation. The resulting magnetic quantum ratchet transforms the a.c. power into a d.c. current, extracting work from the out-of-equilibrium electrons driven by undirected periodic forces. The observation of ratchet transport in this purest possible two-dimensional system indicates that the orbital effects may appear and be substantial in other two-dimensional crystals such as boron nitride, molybdenum dichalcogenides and related heterostructures. The measurable orbital effects in the presence of an in-plane magnetic field provide strong evidence for the existence of structure inversion asymmetry in graphene.

Time and temperature dependence of multi-walled carbon nanotube growth on Inconel 600.

The growth kinetics of vertically aligned multi-walled carbon nanotubes (MWNTs) on conductive substrates is investigated by synthesizing MWNTs at different growth temperatures and measuring ex situ the length of the nanotubes as a function of growth duration. A typical 'root growth' mechanism (saturation of MWNT lengths with increasing growth duration) was observed. The value of the activation energy (E(a)≈136 ± 5 kJ mol(-1)) of the MWNT growth reaction is suggestive of carbon diffusion through the bulk of the iron catalyst particle versus diffusion on its surface. These findings will help in optimizing MWNT growth on conductive substrates for various applications.

First-principles study of defect-induced magnetism in carbon.

We have studied the role of defects on the magnetic properties of carbon materials using first-principles density functional methods. We show that, while the total magnetization decreases both for diamond and graphite with increase in vacancy density, the magnetization decreases more rapidly for graphitic structures. The presence of nitrogen nearby a vacancy is shown to produce larger macroscopic magnetic signals as compared to a standalone carbon vacancy. The results indicate the possibility of tuning magnetization in carbon by controlled defect generation and doping.

Direct growth of aligned carbon nanotubes on bulk metals.

There are several advantages of growing carbon nanotubes (CNTs) directly on bulk metals, for example in the formation of robust CNT-metal contacts during growth. Usually, aligned CNTs are grown either by using thin catalyst layers predeposited on substrates or through vapour-phase catalyst delivery. The latter method, although flexible, is unsuitable for growing CNTs directly on metallic substrates. Here we report on the growth of aligned multiwalled CNTs on a metallic alloy, Inconel 600 (Inconel), using vapour-phase catalyst delivery. The CNTs are well anchored to the substrate and show excellent electrical contact with it. These CNT-metal structures were then used to fabricate double-layer capacitors and field-emitter devices, which demonstrated improved performance over previously designed CNT structures. Inconel coatings can also be used to grow CNTs on other metallic substrates. This finding overcomes the substrate limitation for nanotube growth which should assist the development of future CNT-related technologies.

Irradiation-induced magnetism in carbon nanostructures.

Nitrogen (15N) and carbon (12C) ion implantations with implant energy of 100 keV for different doses were performed on nanosized diamond (ND) particles. Magnetic measurements on the doped ND show ferromagnetic hysteresis behavior at room temperature. The saturation magnetization (M(s)) in the case of 15N implanted samples was found to be higher compared to the 12C implanted samples for dose sizes greater than 10(14) cm(-2). The role of structural modification or defects along with the carbon-nitrogen (C-N) bonding states for the observed enhanced ferromagnetic ordering in 15N doped samples is explained on the basis of x-ray photoelectron spectroscopy measurements.

Flow-induced planar assembly of parallel carbon nanotubes and crossed nanotube junctions.

We report the in-situ assembly of carbon nanotubes by chemical vapor deposition of hydrocarbon precursor (a solution of ferrocene dissolved in isopropyl alcohol). We utilized the vapor stream inside the reaction chamber to comb carbon nanotubes along the same direction and obtained two-dimensional (planar) assembly of nanotubes with tunable distributions. When the carbon source was flowing at a relatively higher rate of approximately 0.2 ml/min, most of nanotubes were driven along the vapor flow direction during their growth process and formed a thin freestanding mat featured with a parallel arrangement, whereas a lower flowing rate (approximately 0.05 ml/min) only resulted in random spider-web structures consisting of crossed nanotube junctions with a variety of configurations (e.g., "+", "Y", "T" shapes and twists). The measured direction-dependent electrical resistance of these two assemblies was in agreement with respective structures, which was anisotropic for parallel nanotubes and nearly isotropic for random networks. Such large-area planar carbon nanotube arrays with controlled orientation and various junction configurations will facilitate the design and fabrication of electronic and mechanical devices.

Controlled growth of carbon nanotubes.

Carbon nanotubes have extraordinary mechanical and electronic properties and hold great promise for future applications. The most important aspects of this structure are its low density, high aspect ratio, one dimensionality, high mechanical strength and high electrical and thermal conductivity. We present a short, state-of-the-art account of tailored nanotube growth. To provide these properties in real devices there exists a need for producing nanotubes on substrates. The challenge in the creation of mesoscale nanotube-based architectures and tailored nanotube networks consisting of thousands of tubes in a predefined order is obviously great. Currently, chemical vapour deposition (CVD) appears to be the most powerful method for achieving such required structures. We describe our work on a new synthesis method, based on catalytic CVD using mainly gas-phase catalyst delivery. Gas-phase catalyst delivery allows us to assemble single-walled and multi-walled carbon nanotubes in predetermined multiple orientations on substrates to build one- to three-dimensional architectures. We are able to control, to a large extent, the types of nanotubes produced, their lengths, locations and their orientations. The ability to make mesoscale architectures with nanotubes should lead us to develop applications in areas such as nano-electromechanical systems.

Carbon nanotube filters.

Over the past decade of nanotube research, a variety of organized nanotube architectures have been fabricated using chemical vapour deposition. The idea of using nanotube structures in separation technology has been proposed, but building macroscopic structures that have controlled geometric shapes, density and dimensions for specific applications still remains a challenge. Here we report the fabrication of freestanding monolithic uniform macroscopic hollow cylinders having radially aligned carbon nanotube walls, with diameters and lengths up to several centimetres. These cylindrical membranes are used as filters to demonstrate their utility in two important settings: the elimination of multiple components of heavy hydrocarbons from petroleum-a crucial step in post-distillation of crude oil-with a single-step filtering process, and the filtration of bacterial contaminants such as Escherichia coli or the nanometre-sized poliovirus ( approximately 25 nm) from water. These macro filters can be cleaned for repeated filtration through ultrasonication and autoclaving. The exceptional thermal and mechanical stability of nanotubes, and the high surface area, ease and cost-effective fabrication of the nanotube membranes may allow them to compete with ceramic- and polymer-based separation membranes used commercially.

Mobility of carbon nanotubes in high electric fields.

The influence of electric fields on carbon nanotubes is experimentally demonstrated. Alignment of nanotubes along field lines, directed motion of nanotubes between electrodes separated by several thousand micrometers, and impressive solid-state actuation behavior of nanotube-embedded structures are demonstrated, taking into account the polarization and charging of the nanotubes. These effects are reported for long strands of nanotubes, nanotubes dispersed on substrates, and nanotube-embedded polymer strips. The relative magnitude of the field responsible for polarization and directed motion was found to be dependent on the morphology of the nanotubes used. These observations may foreshadow novel electromechanical applications for nanotube elements.

Direct synthesis of long single-walled carbon nanotube strands.

In the processes that are used to produce single-walled nanotubes (electric arc, laser ablation, and chemical vapor deposition), the typical lengths of tangled nanotube bundles reach several tens of micrometers. We report that long nanotube strands, up to several centimeters in length, consisting of aligned single-walled nanotubes can be synthesized by the catalytic pyrolysis of n-hexane with an enhanced vertical floating technique. The long strands of nanotubes assemble continuously from arrays of nanotubes, which are intrinsically long.

Microfabrication technology: organized assembly of carbon nanotubes.

Nanoscale structures need to be arranged into well-defined configurations in order to build integrated systems. Here we use a chemical-vapour deposition method with gas-phase catalyst delivery to direct the assembly of carbon nanotubes in a variety of predetermined orientations onto silicon/silica substrates, building them into one-, two- and three-dimensional arrangements. The preference of nanotubes to grow selectively on and normal to silica surfaces forces them to inherit the lithographically machined template topography of their substrates, allowing the sites of nucleation and the direction of growth to be controlled.

Carbon nanotube-magnesium oxide cube networks.

For future applications based on carbon nanotubes, two- and three-dimensional architectures of nanotubes need to be assembled. In many cases this will involve the creation of nanotube units and nodes from which these nanotubes can be distributed in a network. We demonstrate that this idea is plausible by using a template of the correct dimensions and shape, and that has facets that provide the right growth conditions: submicrometer-sized MgO cubes are used to grow nanotubes by chemical vapor deposition. The resulting networks often show that the MgO cubes function as distribution sites for arrays of aligned nanotubes.