Plasma-enabled, catalyst-free growth of carbon nanotubes on mechanically-written Si features with arbitrary shape

Simple, rapid, catalyst-free synthesis of complex patterns of long, vertically aligned multiwalled carbon nanotubes, strictly confined within mechanically-written features on a Si(1 0 0) surface is reported. It is shown that dense arrays of the nanotubes can nucleate and fully fill the features when the low-temperature microwave plasma is in a direct contact with the surface. This eliminates additional nanofabrication steps and inevitable contact losses in applications associated with carbon nanotube patterns. Using metal catalyst has long been considered essential for the nucleation and growth of surface-supported carbon nanotubes (CNTs) [1] and [2]. Only very recently, the possibility of CNT growth using non-metallic (e.g., oxide [3] and SiC [4]) catalysts or artificially created carbon-enriched surface layers [5] has been demonstrated. However, successful integration of carbon nanostructures into Si-based nanodevice platforms requires catalyst-free growth, as the catalyst nanoparticles introduce contact losses, and their catalytic activity is very difficult to control during the growth [6]. Furthermore, in many applications in microfluidics, biological and molecular filters, electronic, sensor, and energy conversion nanodevices, the CNTs need to be arranged in specific complex patterns [7] and [8]. These patterns need to contain the basic features (e.g., lines and dots) written using simple procedures and fully filled with dense arrays of high-quality, straight, yet separated nanotubes. In this paper, we report on a completely metal or oxide catalyst-free plasma-based approach for the direct and rapid growth of dense arrays of long vertically-aligned multi-walled carbon nanotubes arranged into complex patterns made of various combinations of basic features on a Si(1 0 0) surface written using simple mechanical techniques. The process was conducted in a plasma environment [9] and [10] produced by a microwave discharge which typically generates the low-temperature plasmas at the discharge power below 1 kW [11]. Our process starts from mechanical writing (scribing) a pattern of arbitrary features on pre-treated Si(1 0 0) wafers. Before and after the mechanical feature writing, the Si(1 0 0) substrates were cleaned in an aqueous solution of hydrofluoric acid for 2 min to remove any possible contaminations (such as oil traces which could decompose to free carbon at elevated temperatures) from the substrate surface. A piece of another silicon wafer cleaned in the same way as the substrate, or a diamond scriber were used to produce the growth patterns by a simple arbitrary mechanical writing, i.e., by making linear scratches or dot punctures on the Si wafer surface. The results were the same in both cases, i.e., when scratching the surface by Si or a diamond scriber. The procedure for preparation of the substrates did not involve any possibility of external metallic contaminations on the substrate surface. After the preparation, the substrates were loaded into an ASTeX model 5200 chemical vapour deposition (CVD) reactor, which was very carefully conditioned to remove any residue contamination. The samples were heated to at least 800 °C to remove any oxide that could have formed during the sample loading [12]. After loading the substrates into the reactor chamber, N2 gas was supplied into the chamber at the pressure of 7 Torr to ignite and sustain the discharge at the total power of 200 W. Then, a mixture of CH4 and 60% of N2 gases were supplied at 20 Torr, and the discharge power was increased to 700 W (power density of approximately 1.49 W/cm3). During the process, the microwave plasma was in a direct contact with the substrate. During the plasma exposure, no external heating source was used, and the substrate temperature (∼850 °C) was maintained merely due to the plasma heating. The features were exposed to a microwave plasma for 3–5 min. A photograph of the reactor and the plasma discharge is shown in Fig. 1a and b.

Increasing the length of single-wall carbon nanotubes in a magnetically enhanced arc discharge

It is demonstrated that a magnetic field has a profound effect on the length of a single-wall carbon nanotube (SWCNT) synthesized in the arc discharge. The average length of SWCNT increases by a factor of 2 in discharge with magnetic field as compared with the discharge without magnetic field, and the yield of long nanotubes with lengths above 5 μm also increases. A model of SWCNT growth on metal catalyst in arc plasma was developed. Monte-Carlo simulations confirm that the increase of the plasma density in the magnetic field leads to an increase in the nanotube growth rate and thus leads to longer nanotubes.

Distribution of ion-current density on substrate between carbon nanotubes grown from low-temperature plasma

Using Monte Carlo simulation technique, we have calculated the distribution of ion current extracted from low-temperature plasmas and deposited onto the substrate covered with a nanotube array. We have shown that a free-standing carbon nanotube is enclosed in a circular bead of the ion current, whereas in square and hexagonal nanotube patterns, the ion current is mainly concentrated along the lines connecting the nearest nanotubes. In a very dense array (with the distance between nanotubes/nanotube-height ratio less than 0.05), the ions do not penetrate to the substrate surface and deposit on side surfaces of the nanotubes.

Magnetic-field-enhanced synthesis of single-wall carbon nanotubes in arc discharge

The ability to control the properties of single-wall nanotubes (SWNTs) produced in the arc discharge is important for many practical applications. Our experiments suggest that the length of SWNTs significantly increases (up to 4000 nm), along with the purity of the carbon deposit, when the magnetic field is applied to arc discharge. Scanning electron microscopy and transmission electron microscopy analyses have demonstrated that the carbon deposit produced in the magnetic-field-enhanced arc mainly consists of the isolated and bunched SWNTs. A model of a carbon nanotube interaction and growth in the thermal plasma was developed, which considers several important effects such as anode ablation that supplies the carbon plasma in an anodic arc discharge technique, and the momentum, charge, and energy transfer processes between nanotube and plasma. It is shown that the nanotube charge with respect to the plasma as well as nanotube length depend on plasma density and electric field in the interelectrode gap. For instance, nanotube charge changes from negative to positive value with an electron density decrease. The numerical simulations based on the Monte Carlo technique were performed, which explain an increase in the nanotubes produced in the magnetic-field-enhanced arc discharge. © 2008 American Institute of Physics.

Plasma-controlled metal catalyst saturation and the initial stage of carbon nanostructure array growth

The kinetics of the nucleation and growth of carbon nanotube and nanocone arrays on Ni catalyst nanoparticles on a silicon surface exposed to a low-temperature plasma are investigated numerically, using a complex model that includes surface diffusion and ion motion equations. It is found that the degree of ionization of the carbon flux strongly affects the kinetics of nanotube and nanocone nucleation on partially saturated catalyst patterns. The use of highly ionized carbon flux allows formation of a nanotube array with a very narrow height distribution of half-width 7 nm. Similar results are obtained for carbon nanocone arrays, with an even narrower height distribution, using a highly ionized carbon flux. As the deposition time increases, nanostructure arrays develop without widening the height distribution when the flux ionization degree is high, in contrast to the fairly broad nanostructure height distributions obtained when the degree of ionization is low.

Modes of nanotube growth in plasmas and reasons for single-walled structure

The conditions for carbon nanotube synthesis in the bulk of arc discharges and on plasma-exposed solid surfaces are compared to reveal the main distinguishing features of the growth kinetics and explain the striking difference between the growth of the nanotubes in both cases. It is shown that this difference is due to very different exposure of the discharge-synthesized and surface-bound nanotubes to ion fluxes, with the ratio of the ion fluxes collected per nanotube in the two cases reaching up to six orders of magnitude. Depending on the plasma parameters and the sizes of the nanotubes and metal catalyst particles, four distinct growth modes of the nanotubes in the plasma bulk have been identified. These results shed light on why single-walled carbon nanotube growth is more favourable in the bulk of arc plasmas rather than on plasma-exposed surfaces.

Ways to increase the length of single wall carbon nanotubes in a magnetically enhanced arc discharge

Ability to control the properties of single-wall nanotubes produced in the arc discharge is important for many practical applications. Our experiments suggest that the length and purity of single-wall nanotubes significantly increase when the magnetic field is applied to the arc discharge. A model of a single wall carbon nanotube interaction and growth in the thermal plasma was developed which considers several important effects such as anode ablation that supplies the carbon plasma in an anodic arc discharge technique, and the momentum, charge and energy transfer processes between nanotube and plasma. The numerical simulations based on Monte-Carlo technique were performed, which explain an increase of the nanotubes produced in the magnetic field - enhanced arc discharge.

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.

Prediction of thermal expansion properties of carbon nanotubes using molecular dynamics simulations

The axial coefficients of thermal expansion (CTE) of various carbon nanotubes (CNTs), i.e., single-wall carbon nanotubes (SWCNTs), and some multi-wall carbon nanotubes (MWCNTs), were predicted using molecular dynamics (MDs) simulations. The effects of two parameters, i.e., temperature and the CNT diameter, on CTE were investigated extensively. For all SWCNTs and MWCNTs, the obtained results clearly revealed that within a wide low temperature range, their axial CTEs are negative. As the diameter of CNTs decreases, this temperature range for negative axial CTEs becomes narrow, and positive axial CTEs appear in high temperature range. It was found that the axial CTEs vary nonlinearly with the temperature, however, they decrease linearly as the CNT diameter increases. Moreover, within a wide temperature range, a set of empirical formulations was proposed for evaluating the axial CTEs of armchair and zigzag SWCNTs using the above two parameters. Finally, it was found that the absolute value of the negative axial CTE of any MWCNT is much smaller than those of its constituent SWCNTs, and the average value of the CTEs of its constituent SWCNTs. The present fundamental study is very important for understanding the thermal behaviors of CNTs in such as nanocomposite temperature sensors, or nanoelectronics devices using CNTs.

Engineering the mechanical properties of graphene nanotube hybrid structures through structural modulation

The excellent multi-functional properties of carbon nanotube (CNT) and graphene have enabled them as appealing building blocks to construct 3D carbon-based nanomaterials or nanostructures. The recently reported graphene nanotube hybrid structure (GNHS) is one of the representatives of such nanostructures. This work investigated the relationships between the mechanical properties of the GNHS and its structure basing on large-scale molecular dynamics simulations. It is found that increasing the length of the constituent CNTs, the GNHS will have a higher Young’s modulus and yield strength. Whereas, no strong correlation is found between the number of graphene layers and Young’s modulus and yield strength, though more graphene layers intends to lead to a higher yield strain. In the meanwhile, the presences of multi-wall CNTs are found to greatly strengthen the hybrid structure. Generally, the hybrid structures exhibit a brittle behavior and the failure initiates from the connecting regions between CNT and graphene. More interestingly, affluent formations of monoatomic chains and rings are found at the fracture region. This study provides an in-depth understanding of the mechanical performance of the GNHSs while varying their structures, which will shed lights on the design and also the applications of the carbon-based nanostructures.

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.

Formation of carbon nanoscrolls from graphene nanoribbons : a molecular dynamics study

Carbon nanoscrolls (CNSs) are one of the carbon-based nanomaterials similar to carbon nanotubes (CNTs) but are not widely studied in spite of their great potential applications. Their practical applications are hindered by the challenging fabrication of the CNSs. A physical approach has been proposed recently to fabricate the CNS by rolling up a monolayer graphene nanoribbon (GNR) around a CNT driven by the interaction energy between them. In this study, we perform extensive molecular dynamics (MD) simulations to investigate the various factors that impact the formation of the CNS from GNR. Our simulation results show that the formation of the CNS is sensitive to the length of the CNT and temperature. When the GNR is functionalized with hydrogen, the formation of the CNS is determined by the density and distribution of the hydrogen atoms. Graphyne, the allotrope of graphene, is inferior to graphene in the formation of the CNS due to the weaker bonds and the associated smaller atom density. The mechanism behind the rolling of GNR into CNS lies in the balance between the GNR–CNT van der Waals (vdW) interactions and the strain energy of GNR. The present work reveals new important insights and provides useful guidelines for the fabrication of the CNS.

Multi-scale numerical simulations of thermal expansion properties of CNT-reinforced nanocomposites

In this work, the thermal expansion properties of carbon nanotube (CNT)-reinforced nanocomposites with CNT content ranging from 1 to 15 wt% were evaluated using a multi-scale numerical approach, in which the effects of two parameters, i.e., temperature and CNT content, were investigated extensively. For all CNT contents, the obtained results clearly revealed that within a wide low-temperature range (30°C ~ 62°C), thermal contraction is observed, while thermal expansion occurs in a high-temperature range (62°C ~ 120°C). It was found that at any specified CNT content, the thermal expansion properties vary with temperature - as temperature increases, the thermal expansion rate increases linearly. However, at a specified temperature, the absolute value of the thermal expansion rate decreases nonlinearly as the CNT content increases. Moreover, the results provided by the present multi-scale numerical model were in good agreement with those obtained from the corresponding theoretical analyses and experimental measurements in this work, which indicates that this multi-scale numerical approach provides a powerful tool to evaluate the thermal expansion properties of any type of CNT/polymer nanocomposites and therefore promotes the understanding on the thermal behaviors of CNT/polymer nanocomposites for their applications in temperature sensors, nanoelectronics devices, etc.

Graphene nanocomposites

Graphene, one of the allotropes (diamond, carbon nanotube, and fullerene) of carbon, is a monolayer of honeycomb lattice of carbon atoms discovered in 2004. The Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin Novoselov for their ground breaking experiments on the twodimensional graphene [1]. Since its discovery, the research communities have shown a lot of interest in this novel material owing to its unique properties. As shown in Figure 1, the number of publications on graphene has dramatically increased in recent years. It has been confirmed that graphene possesses very peculiar electrical properties such as anomalous quantum hall effect, and high electron mobility at room temperature (250000 cm2/Vs). Graphene is also one of the stiffest (modulus ~1 TPa) and strongest (strength ~100 GPa) materials. In addition, it has exceptional thermal conductivity (5000 Wm-1K-1). Based on these exceptional properties, graphene has found its applications in various fields such as field effect devices, sensors, electrodes, solar cells, energy storage devices and nanocomposites. Only adding 1 volume per cent graphene into polymer (e.g. polystyrene), the nanocomposite has a conductivity of ~0.1 Sm-1 [2], sufficient for many electrical applications. Significant improvement in strength, fracture toughness and fatigue strength has also been achieved in these nanocomposites [3-5]. Therefore, graphene-polymer nanocomposites have demonstrated a great potential to serve as next generation functional or structural materials.

Numerical Modelling of Mechanical Behaviour of Graphene

Graphene, one of the allotropes (diamond, carbon nanotube, and fullerene) of element carbon, is a monolayer of honeycomb lattice of carbon atoms, which was discovered in 2004. The Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin Novoselov for their ground breaking work on the two-dimensional (2D) graphene [1]. Since its discovery, the research communities have shown a lot of interest in this novel material owing to its intriguing electrical, mechanical and thermal properties. It has been confirmed that grapheme possesses very peculiar electrical properties such as anomalous quantum hall effect, and high electron mobility at room temperature (250000 cm2/Vs). Graphene also has exceptional mechanical properties. It is one of the stiffest (modulus ~1 TPa) and strongest (strength ~100 GPa) materials. In addition, it has exceptional thermal conductivity (5000 Wm-1K-1). Due to these exceptional properties, graphene has demonstrated its potential for broad applications in micro and nano devices, various sensors, electrodes, solar cells and energy storage devices and nanocomposites. In particular, the excellent mechanical properties of graphene make it more attractive for development next generation nanocomposites and hybrid materials...