Enhancement of electron field emission of vertically aligned carbon nanotubes by nitrogen plasma treatment

The electron field emission (EFE) characteristics from vertically aligned carbon nanotubes (VACNTs) without and with treatment by the nitrogen plasma are investigated. The VACNTs with the plasma treatment showed a significant improvement in the EFE property compared to the untreated VACNTs. The morphological, structural, and compositional properties of the VACNTs are extensively examined by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and energy dispersive X-ray spectroscopy. It is shown that the significant EFE improvement of the VACNTs after the nitrogen plasma treatment is closely related to the variation of the morphological and structural properties of the VACNTs. The high current density (299.6 μA/cm2) achieved at a low applied field (3.50 V/μm) suggests that the VACNTs after nitrogen plasma treatment can serve as effective electron field emission sources for numerous applications.

Graphene and carbon nanotubes from arc plasmas : experiment and plasma modeling

Graphene and carbon nanotubes are the most promising nanomaterials for application in various modern nanodevices. The successful production of the nanotubes and graphene in a single process was achieved by using a magnetically enhanced arc discharge in helium atmosphere between carbon and metal electrodes. A 3-D fluid model has been used to investigate the discharge parameters.

3-Orders-of-magnitude density control of single-walled carbon nanotube networks by maximizing catalyst activation and dosing carbon supply

Tailoring the density of random single-walled carbon nanotube (SWCNT) networks is of paramount importance for various applications, yet it remains a major challenge due to the insufficient catalyst activation in most growth processes. Here we report on a simple and effective method to maximise the number of active catalyst nanoparticles using catalytic chemical vapor deposition (CCVD). By modulating short pulses of acetylene into a methane-based CCVD growth process, the density of SWCNTs is dramatically increased by up to three orders of magnitude without increasing the catalyst density and degrading the nanotube quality. In the framework of a vapor-liquid-solid model, we attribute the enhanced growth to the high dissociation rate of acetylene at high temperatures at the nucleation stage, which can be effective in both supersaturating the larger catalyst nanoparticles and overcoming the nanotube nucleation energy barrier of the smaller catalyst nanoparticles. These results are highly relevant to numerous applications of random SWCNT networks in next-generation energy, sensing and biomedical devices. © 2011 The Royal Society of Chemistry.

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.

Single-step synthesis and magnetic separation of graphene and carbon nanotubes in arc discharge plasmas

The unique properties of graphene and carbon nanotubes made them the most promising nanomaterials attracting enormous attention, due to the prospects for applications in various nanodevices, from nanoelectronics to sensors and energy conversion devices. Here we report on a novel deterministic, single-step approach to simultaneous production and magnetic separation of graphene flakes and carbon nanotubes in an arc discharge by splitting the high-temperature growth and low-temperature separation zones using a non-uniform magnetic field and tailor-designed catalyst alloy, and depositing nanotubes and graphene in different areas. Our results are very relevant to the development of commercially-viable, single-step production of bulk amounts of high-quality graphene.

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.

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.

Plasma-assembled carbon nanotubes : electric field–related effects

The paper presents results of comparative investigation of carbon nanotubes growth processes in dense low-temperature plasma and on substrate surface. Hybrid/Monte-Carlo numerical simulations were used to demonstrate the differences in the ion fluxes, growth rates and kinetics of adsorbed atoms re-distribution on substrate and nanotubes surfaces. We show that the plasma parameters significantly affect the nanotubes growth kinetics. We demonstrate that the growth rates of the nanotubes in plasma and on surface can differ by three orders, and the specific fluxes to the nanotube in the plasma can exceed the flux to surface-grown nanotube by six orders. We also show that the metal catalyst used for the nanotubes production on surface and in arc is a subject to very different conditions and this may be a key factor for the nanotube growth mode. The obtained dependencies for the ion fluxes to the nanotubes and nanotubes growth rates on the plasma parameters may be useful for selection of the production methods.

Low-temperature growth of large area, vertically aligned carbon nanotubes for field emission applications

Large area, highly uniform vertically aligned carbon nanotips (VACNTP) and other nanostructures have been grown on silicon (100) substrates with Ni catalyst in the low-temperature, low-frequency, high-density inductively coupled plasmas (ICP) of methane-hydrogen-argon gas mixtures. The control strategies for the morphology, crystalline structure and chemical states of the resulting nanostructures by varying the growth conditions are proposed. XRD and Roman analyses confirm that the nanotips are well graphitized, which is favorable for the field emission applications.

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.

Planar silver nanowire, carbon nanotube and PEDOT:PSS nanocomposite transparent electrodes

Highly conductive, transparent and flexible planar electrodes were fabricated using interwoven silver nanowires and single-walled carbon nanotubes (AgNW:SWCNT) in a PEDOT:PSS matrix via an epoxy transfer method from a silicon template. The planar electrodes achieved a sheet resistance of 6.6 ± 0.0 Ω/squ and an average transmission of 86% between 400 and 800 nm. A high figure of merit of 367 Ω−1 is reported for the electrodes, which is much higher than that measured for indium tin oxide and reported for other AgNW composites. The AgNW:SWCNT:PEDOT:PSS electrode was used to fabricate low temperature (annealing free) devices demonstrating their potential to function with a range of organic semiconducting polymer:fullerene bulk heterojunction blend systems.

An efficient hole transport material composite based on poly(3-hexylthiophene) and bamboo-structured carbon nanotubes for high performance perovskite solar cells

In this work, we have developed a new efficient hole transport material (HTM) composite based on poly(3- hexylthiophene) (P3HT) and bamboo-structured carbon nanotubes (BCNs) for CH3NH3PbI3 (MAPbI3) based perovskite solar cells. Compared to pristine P3HT, it is found that the crystallinity of P3HT was significantly improved by addition of BCNs, which led to over one order of magnitude higher conductivity for the composite containing 1–2 wt% BCNs in P3HT. In the meantime, the interfacial charge transfer between the MAPbI3 light absorbing layer and the HTM composite layer based on P3HT/BCNs was two-fold faster than pristine P3HT. More importantly, the HTM film with a superior morphological structure consisting of closely compact large grains was achieved with the composite containing 1 wt% BCNs in P3HT. The study by electrochemical impedance spectroscopy has confirmed that the electron recombination in the solar cells was reduced nearly ten-fold with the addition of 1 wt% carbon nanotubes in the HTM composite. Owing to the superior HTM film morphology and the significantly reduced charge recombination, the energy conversion efficiency of the perovskite solar cells increased from 3.6% for pristine P3HT to 8.3% for P3HT/(1 wt% BCNs) with a significantly enhanced open circuit voltage (Voc) and fill factor (FF). The findings of this work are important for development of new HTM for high performance perovskite solar cells.

Synergistic fusion of vertical graphene nanosheets and carbon nanotubes for high-performance supercapacitor electrodes

Graphene and carbon nanotubes (CNTs) are attractive electrode materials for supercapacitors. However, challenges such as the substrate-limited growth of CNTs, nanotube bundling in liquid electrolytes, under-utilized basal planes, and stacking of graphene sheets have so far impeded their widespread application. Here we present a hybrid structure formed by the direct growth of CNTs onto vertical graphene nanosheets (VGNS). VGNS are fabricated by a green plasma-assisted method to break down and reconstruct a natural precursor into an ordered graphitic structure. The synergistic combination of CNTs and VGNS overcomes the challenges intrinsic to both materials. The resulting VGNS/CNTs hybrids show a high specific capacitance with good cycling stability. The charge storage is based mainly on the non-Faradaic mechanism. In addition, a series of optimization experiments were conducted to reveal the critical factors that are required to achieve the demonstrated high supercapacitor performance.