Plasma-assisted self-sharpening of platelet-structured single-crystalline carbon nanocones

A mechanism and model for the vertical growth of platelet-structured vertically aligned single-crystalline carbon nanostructures by the formation of graphene layers on a flat top surface are proposed and verified experimentally. It is demonstrated that plasma-related effects lead to self-sharpening of tapered nanocones to form needlelike nanostructures, in a good agreement with the predicted dependence of the radius of a nanocone's flat top on the incoming ion flux and surface temperature. The growth mechanism is relevant to a broad class of nanostructures including nanotips, nanoneedles, and nanowires and can be used to improve the predictability of nanofabrication processes. © 2007 American Institute of Physics.

Effect of plasma environment on synthesis of vertically aligned carbon nanofibers in plasma-enhanced chemical vapor deposition

We present a theoretical model describing a plasma-assisted growth of carbon nanofibers (CNFs), which involves two competing channels of carbon incorporation into stacked graphene sheets: via surface diffusion and through the bulk of the catalyst particle (on the top of the nanofiber), accounting for a range of ion- and radical-assisted processes on the catalyst surface. Using this model, it is found that at low surface temperatures, Ts, the CNF growth is indeed controlled by surface diffusion, thus quantifying the semiempirical conclusions of earlier experiments. On the other hand, both the surface and bulk diffusion channels provide a comparable supply of carbon atoms to the stacked graphene sheets at elevated synthesis temperatures. It is also shown that at low Ts, insufficient for effective catalytic precursor decomposition, the plasma ions play a key role in the production of carbon atoms on the catalyst surface. The model is used to compute the growth rates for the two extreme cases of thermal and plasma-enhanced chemical vapor deposition of CNFs. More importantly, these results quantify and explain a number of observations and semiempirical conclusions of earlier experiments.

Defect healing and enhanced nucleation of carbon nanotubes by low-energy ion bombardment

Structural defects inevitably appear during the nucleation event that determines the structure and properties of single-walled carbon nanotubes. By combining ion bombardment experiments with atomistic simulations we reveal that ion bombardment in a suitable energy range allows these defects to be healed resulting in an enhanced nucleation of the carbon nanotube cap. The enhanced growth of the nanotube cap is explained by a nonthermal ion-induced graphene network restructuring mechanism.

SWCNT networks on nanoporous silica catalyst support : morphological and connectivity control for nanoelectronic, gas-sensing, and biosensing devices

Effective control of morphology and electrical connectivity of networks of single-walled carbon nanotubes (SWCNTs) by using rough, nanoporous silica supports of Fe catalyst nanoparticles in catalytic chemical vapor deposition is demonstrated experimentally. The very high quality of the nanotubes is evidenced by the G-to-D Raman peak ratios (>50) within the range of the highest known ratios. Transitions from separated nanotubes on smooth SiO2 surface to densely interconnected networks on the nanoporous SiO2 are accompanied by an almost two-order of magnitude increase of the nanotube density. These transitions herald the hardly detectable onset of the nanoscale connectivity and are confirmed by the microanalysis and electrical measurements. The achieved effective nanotube interconnection leads to the dramatic, almost three-orders of magnitude decrease of the SWCNT network resistivity compared to networks of similar density produced by wet chemistry-based assembly of preformed nanotubes. The growth model, supported by multiscale, multiphase modeling of SWCNT nucleation reveals multiple constructive roles of the porous catalyst support in facilitating the catalyst saturation and SWCNT nucleation, consistent with the observed higher density of longer nanotubes. The associated mechanisms are related to the unique surface conditions (roughness, wettability, and reduced catalyst coalescence) on the porous SiO2 and the increased carbon supply through the supporting porous structure. This approach is promising for the direct integration of SWCNT networks into Si-based nanodevice platforms and multiple applications ranging from nanoelectronics and energy conversion to bio- and environmental sensing.

Controlling the surface roughness of epitaxial SiC on silicon

The surface of cubic silicon carbide (3C-SiC) hetero-epitaxial films grown on the (111) surface of silicon is a promising template for the subsequent epitaxial growth of III-V semiconductor layers and graphene. We investigate growth and post-growth approaches for controlling the surface roughness of epitaxial SiC to produce an optimal template. We first explore 3C-SiC growth on various degrees of offcut Si(111) substrates, although we observe that the SiC roughness tends to worsen as the degree of offcut increases. Hence we focus on post-growth approaches available on full wafers, comparing chemical mechanical polishing (CMP) and a novel plasma smoothening process. The CMP leads to a dramatic improvement, bringing the SiC surface roughness down to sub-nanometer level, though removing about 200 nm of the SiC layer. On the other hand, our proposed HCl plasma process appears very effective in smoothening selectively the sharpest surface topography, leading up to 30% improvement in SiC roughness with only about 50 nm thickness loss. We propose a simple physical model explaining the action of the plasma smoothening.

Interface of graphane with copper : a van der Waals density-functional study

Various forms of hydrogenated graphene have been produced to date by several groups, while the synthesis of pure graphane has not been achieved yet. The study of the interface between graphane, in all its possible hydrogenation configurations, and catalyst metal surfaces can be pivotal to assess the feasibility of direct CVD growth methods for this material. We investigated the adhesion of graphane to a Cu(111) surface by adopting the vdW-DF2-C09 exchange-correlation functional, which is able to describe dispersion forces. The results are further compared with the PBE and the LDA exchange-correlation functionals. We calculated the most stable geometrical configurations of the slab/graphane interface and evaluated how graphane's geometrical parameters are modified. We show that dispersion forces play an important role in the slab/graphane adhesion. Band structure calculations demonstrated that in the presence of the interaction with copper, the band gap of graphane is not only preserved, but also enlarged, and this increase can be attributed to the electronic charge accumulated at the interface. We calculated a substantial energy barrier at the interface, suggesting that CVD graphane films might act as reliable and stable insulating thin coatings, or also be used to form compound layers in conjunction with metals and semiconductors.

Temperature and strain-rate dependent fracture strength of graphynes

Graphyne is an allotrope of graphene. The mechanical properties of graphynes (α-, β-, γ- and 6,6,12-graphynes) under uniaxial tension deformation at different temperatures and strain rates are studied using molecular dynamics simulations. It is found that graphynes are more sensitive to temperature changes than graphene in terms of fracture strength and Young's modulus. The temperature sensitivity of the different graphynes is proportionally related to the percentage of acetylenic linkages in their structures, with the α-graphyne (having 100% of acetylenic linkages) being most sensitive to temperature. For the same graphyne, temperature exerts a more pronounced effect on the Young's modulus than fracture strength, which is different from that of graphene. The mechanical properties of graphynes are also sensitive to strain rate, in particular at higher temperatures.

High performance all-carbon thin film supercapacitors

We fabricated high performance supercapacitors by using all carbon electrodes, with volume energy in the order of 10−3 Whcm−3, comparable to Li-ion batteries, and power densities in the range of 10 Wcm−3, better than laser-scribed-graphene supercapacitors. All-carbon supercapacitor electrodes are made by solution processing and filtering electrochemically-exfoliated graphene sheets mixed with clusters of spontaneously entangled multiwall carbon nanotubes. We maximize the capacitance by using a 1:1 weight ratio of graphene to multi-wall carbon nanotubes and by controlling their packing in the electrode film so as to maximize accessible surface and further enhance the charge collection. This electrode is transferred onto a plastic-paper-supported double-wall carbon nanotube film used as current collector. These all-carbon thin films are combined with plastic paper and gelled electrolyte to produce solid-state bendable thin film supercapacitors. We assembled supercapacitor cells in series in a planar configuration to increase the operating voltage and find that the shape of our supercapacitor film strongly affects its capacitance. An in-line superposition of rectangular sheets is superior to a cross superposition in maintaining high capacitance when subject to fast charge/discharge cycles. The effect is explained by addressing the mechanism of ion diffusion into stacked graphene sheets.

Enhanced interfacial thermal transport across graphene–polymer interfaces by grafting polymer chains

Thermal transport in graphene-polymer nanocomposite is complicated and has not been well understood. The interfacial thermal transport between graphene nanofiller and polymer matrix is expected to play a key role in controlling the overall thermal performance of graphene-polymer nanocomposite. In this work, we investigated the thermal transport across graphene-polymer interfaces functionalized with end-grafted polymer chains using molecular dynamics simulations. The effects of grafting density, chain length and initial morphology on the interfacial thermal transport were systematically investigated. It was found that end-grafted polymer chains could significantly enhance interfacial thermal transport and the underlying mechanism was considered to be the enhanced vibration coupling between graphene and polymer. In addition, a theoretical model based on effective medium theory was established to predict the thermal conductivity in graphene-polymer nanocomposites.

Characterisation of gold nanoparticles on substrate

This thesis investigated the interaction between light and gold nanoparticles, for gold nanoparticles sitting on a variety of surfaces. The work was both experimental and theoretical in nature. Using a custom designed experimental set-up we were able to probe the interaction of light with individual nanoparticles. We were also able to predict the interaction of light with gold nanoparticles sitting on graphene substrates. The work presented lays the groundwork for more extensive investigation of surfaces enhanced by the addition of gold nanoparticles.

Structural and electronic properties of layered arsenic and antimony arsenide

Layered materials exhibit intriguing electronic characteristics and the search for new types of two-dimensional (2D) structures is of importance for future device fabrication. Using state-of-art first principle calculations, we identify and characterize the structural and electronic properties of two 2D layered arsenic materials, namely, arsenic and its alloy AsSb. The stable 2D structural configuration of arsenic is confirmed to be the low-buckled two-dimensional hexagonal structure by phonon and binding energy calculations. The monolayer exhibits indirect semiconducting properties with gap around 1.5 eV (corrected to 2.2 eV by hybrid function), which can be modulated into a direct semiconductor within a small amount of tensile strain. These semiconducting properties are preserved when cutting into 1D nanoribbons, but the band gap is edge dependent. It is interesting to find that an indirect to direct gap transition can be achieved under strain modulation of the armchair ribbon. Essentially the same phenomena can be found in layered AsSb, except a weak Rashba induced band splitting is present in AsSb due to the nonsymmetric structure and spin orbit coupling. When an additional layer is added on the top, a semiconductor–metal transition will occur. The findings here broaden the family of 2D materials beyond graphene and transition metal dichalcogenides and provide useful information for experimental fabrication of new layered materials with possible application in optoelectronics.

First-principle engineering magnetism in low-dimensional boron nitride materials

Nanotubes and nanosheets are low-dimensional nanomaterials with unique properties that can be exploited for numerous applications. This book offers a complete overview of their structure, properties, development, modeling approaches, and practical use. It focuses attention on boron nitride (BN) nanotubes, which have had major interest given their special high-temperature properties, as well as graphene nanosheets, BN nanosheets, and metal oxide nanosheets. Key topics include surface functionalization of nanotubes for composite applications, wetting property changes for biocompatible environments, and graphene for energy storage applications

Transition metal layered double hydroxides for energy storage

Various types of layered double hydroxides, a type of clay, were synthesised. They were then electrochemically tested to determine whether the samples would be suitable to store energy as supercapacitors. A manganese aluminium layered double hydroxide was electrochemically tested for the first time and found to have a large capacitance.

Synthesis and applications of carbon nanomaterials for energy generation and storage

The world is facing an energy crisis due to exponential population growth and limited availability of fossil fuels. Carbon, one of the most abundant materials found on earth, and its allotrope forms have been proposed in this project for novel energy generation and storage devices. This studied investigated the synthesis and properties of these carbon nanomaterials for applications in organic solar cells and supercapacitors.

Single layer lead iodide: Computational exploration of structural, electronic and optical properties, strain induced band modulation and the role of spin-orbital-coupling

Graphitic like layered materials exhibit intriguing electronic structures and thus the search for new types of two-dimensional (2D) monolayer materials is of great interest for developing novel nano-devices. By using density functional theory (DFT) method, here we for the first time investigate the structure, stability, electronic and optical properties of monolayer lead iodide (PbI2). The stability of PbI2 monolayer is first confirmed by phonon dispersion calculation. Compared to the calculation using generalized gradient approximation, screened hybrid functional and spin–orbit coupling effects can not only predicts an accurate bandgap (2.63 eV), but also the correct position of valence and conduction band edges. The biaxial strain can tune its bandgap size in a wide range from 1 eV to 3 eV, which can be understood by the strain induced uniformly change of electric field between Pb and I atomic layer. The calculated imaginary part of the dielectric function of 2D graphene/PbI2 van der Waals type hetero-structure shows significant red shift of absorption edge compared to that of a pure monolayer PbI2. Our findings highlight a new interesting 2D material with potential applications in nanoelectronics and optoelectronics.