J. David Carey

Beyond graphene: stable elemental monolayers of silicene and germanene.

Two-dimensional materials are one of the most active areas of nanomaterials research. Here we report the structural stability, electronic and vibrational properties of different monolayer configurations of the group IV elemental materials silicene and germanene. The structure of the stable configuration is calculated and for planar and low (<1 Å) atomic buckling configurations, analysis of the electronic band structure reveals linear band dispersion giving rise to massless Dirac Fermions with a Fermi velocity about two-thirds that of graphene. Monolayer stability is shown to be directly attributed to the phonons present with the instability being driven by the out-of-plane ZA and ZO phonon modes. Long momentum relaxation lengths and high carrier mobilities are predicted for silicene and germanene based devices as carrier relaxation via phonon scattering is found to be inhibited as the electron-optical phonon coupling matrix elements are calculated to be small, being about a factor of 25 times smaller than in graphene. The consequences for phonon scattering, high energy electrical transport and integration of elemental monolayers into electronic devices are further discussed.

The importance of oxygen-containing defects on carbon nanotubes for the detection of polar and non-polar vapours through hydrogen bond formation

We report the electrical responses of water vapour and O2 adsorption onto macroscopic multi-walled carbon nanotube (MWCNT) ropes, and compare the results with mats of acid-treated MWCNTs on SiO2 substrates in order to investigate the importance of oxygen-containing defects on CNTs. In the outgassed state both carbon nanotube (CNT) materials exhibit rapid changes in electrical resistance when exposed to dry air, humid air or water vapour at standard temperature and pressure (STP). The measured electrical responses are highly reversible at STP when cycled between humid air, vacuum and dry air. We report a decrease in resistance for the CNT materials in dry air, attributed to O2 p-type doping of the CNTs, whereas there is an increase in resistance when exposed to a humid environment. This latter effect is attributed to the formation of hydrogen bonding from the polar water molecules with the oxygen-containing defects on the CNTs. Our observations indicate that the increase in electrical resistance upon water absorption affects a reduction of the electron-withdrawing power of the oxygen-containing defect groups, thus leading to a reduced hole carrier concentration in the p-type nanotubes.

Carbon-nanotube-polymer nanocomposites for field-emission cathodes.

The electron field-emission (FE) characteristics of functionalized single-walled carbon-nanotube (CNT)-polymer composites produced by solution processing are reported. It is shown that excellent electron emission can be obtained by using as little as 0.7% volume fraction of nanotubes in the composite. Furthermore by tailoring the nanotube concentration and type of polymer, improvements in the charge transfer through the composite can be obtained. The synthesis of well-dispersed randomly oriented nanotube-polymer composites by solution processing allows the development of CNT-based large area cathodes produced using a scalable technology. The relative insensitivity of the cathodes FE characteristics to the electrical conductivity of the composite is also discussed.

Enhanced electrical conductivity of silver nanoparticles for high frequency electronic applications.

An enhancement in the electrical performance of low temperature screen-printed silver nanoparticles (nAg) has been measured at frequencies up to 220 GHz. We show that for frequencies above 80 GHz the electrical losses in coplanar waveguide structures fabricated using nAg at 350 °C are lower than those found in conventional thick film Ag conductors consisting of micrometer-sized grains and fabricated at 850 °C. The improved electrical performance is attributed to the better packing of the silver nanoparticles resulting in lower surface roughness by a factor of 3. We discuss how the use of silver nanoparticles offers new routes to high frequency applications on temperature sensitive conformal substrates and in sub-THz metamaterials.

Control of ZnO nanorod array density by Zn supersaturation variation and effects on field emission

We demonstrate control of ZnO nanorod density for self-organized growth on ZnO buffer layers on Si by varying Zn supersaturation during the initial growth phase, thereby altering the competition between 2D and 1D growth modes. Higher initial supersaturation favours nanorods of diameter 1000, attributed to sharp facet edges, and indicate that lower density arrays have more uniform emission due to a reduction in screening effects.

Influence of silver incorporation on the structural and electrical properties of diamond-like carbon thin films.

A simple approach is proposed for obtaining low threshold field electron emission from large area diamond-like carbon (DLC) thin films by sandwiching either Ag dots or a thin Ag layer between DLC and nitrogen-containing DLC films. The introduction of silver and nitrogen is found to reduce the threshold field for emission to under 6 V/μm representing a near 46% reduction when compared with unmodified films. The reduction in the threshold field is correlated with the morphology, microstructure, interface, and bonding environment of the films. We find modifications to the structure of the DLC films through promotion of metal-induced sp2 bonding and the introduction of surface asperities, which significantly reduce the value of the threshold field. This can lead to the next-generation, large-area simple and inexpensive field emission devices.

Influence of acoustic cavitation on the controlled ultrasonic dispersion of carbon nanotubes.

Ultrasonication is the most widely used technique for the dispersion of a range of nanomaterials, but the intrinsic mechanism which leads to stable solutions is poorly understood with procedures quoted in the literature typically specifying only extrinsic parameters such as nominal electrical input power and exposure time. Here we present new insights into the dispersion mechanism of a representative nanomaterial, single-walled carbon nanotubes (SW-CNTs), using a novel up-scalable sonoreactor and an in situ technique for the measurement of acoustic cavitation activity during ultrasonication. We distinguish between stable cavitation, which leads to chemical modification of the surface of the CNTs, and inertial cavitation, which favors CNT exfoliation and length reduction. Efficient dispersion of CNTs in aqueous solution is found to be dominated by mechanical forces generated via inertial cavitation, which in turn depends critically on surfactant concentration. This study highlights that careful measurement and control of cavitation rather than blind application of input power is essential in the large volume production of nanomaterial dispersions with tailored properties.

Electrical performance of carbon nanotube-polymer composites at frequencies up to 220 GHz

We have measured the sub-THz electrical response of screen printed carbon nanotube-poly(methyl methacrylate) polymer composites up to 220 GHz. The measured electrical losses using mm long coplanar waveguide geometries averaged as low as 0.15 dB/mm in the frequency range 40 GHz–110 GHz and showed a reduction in signal loss with increasing frequency; a behaviour opposite to that found in conventional metallic conductors. Between 140 and 220 GHz, the electrical losses averaged 0.28 dB/mm. We show that the low electrical losses are associated with the capacitive coupling between the nanotubes and discuss potential high frequency applications.

Efficient coupling of optical energy for rapid catalyzed nanomaterial growth: high-quality carbon nanotube synthesis at low substrate temperatures.

The synthesis of high-quality nanomaterials depends on the efficiency of the catalyst and the growth temperature. To produce high-quality material, high-growth temperatures (often up to 1000 °C) are regularly required and this can limit possible applications, especially where temperature sensitive substrates or tight thermal budgets are present. In this study, we show that high-quality catalyzed nanomaterial growth at low substrate temperatures is possible by efficient coupling of energy directly into the catalyst particles by an optical method. We demonstrate that using this photothermal-based chemical vapor deposition method that rapid growth (under 4 min, which includes catalyst pretreatment time) of high-density carbon nanotubes can be grown at substrate temperatures as low as 415 °C with proper catalyst heat treatment. The growth process results in nanotubes that are high quality, as judged by a range of structural, Raman, and electrical characterization techniques, and are compatible with the requirements for interconnect technology.

Engineering Graphene Conductivity for Flexible and High-Frequency Applications

Advances in lightweight, flexible, and conformal electronic devices depend on materials that exhibit high electrical conductivity coupled with high mechanical strength. Defect-free graphene is one such material that satisfies both these requirements and which offers a range of attractive and tunable electrical, optoelectronic, and plasmonic characteristics for devices that operate at microwave, terahertz, infrared, or optical frequencies. Essential to the future success of such devices is therefore the ability to control the frequency-dependent conductivity of graphene. Looking to accelerate the development of high-frequency applications of graphene, here we demonstrate how readily accessible and processable organic and organometallic molecules can efficiently dope graphene to carrier densities in excess of 10(13) cm(-2) with conductivities at gigahertz frequencies in excess of 60 mS. In using the molecule 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane (F2-HCNQ), a high charge transfer (CT) of 0.5 electrons per adsorbed molecule is calculated, resulting in p-type doping of graphene. n-Type doping is achieved using cobaltocene and the sulfur-containing molecule tetrathiafulvalene (TTF) with a CT of 0.41 and 0.24 electrons donated per adsorbed molecule, respectively. Efficient CT is associated with the interaction between the π electrons present in the molecule and in graphene. Calculation of the high-frequency conductivity shows dispersion-less behavior of the real component of the conductivity over a wide range of gigahertz frequencies. Potential high-frequency applications in graphene antennas and communications that can exploit these properties and the broader impacts of using molecular doping to modify functional materials that possess a low-energy Dirac cone are also discussed.