Non-destructive characterization of structural hierarchy within aligned carbon nanotube assemblies

Understanding and controlling the hierarchical self-assembly of carbon nanotubes (CNTs) is vital for designing materials such as transparent conductors, chemical sensors, high-performance composites, and microelectronic interconnects. In particular, many applications require high-density CNT assemblies that cannot currently be made directly by low-density CNT growth, and therefore require post-processing by methods such as elastocapillary densification. We characterize the hierarchical structure of pristine and densified vertically aligned multi-wall CNT forests, by combining small-angle and ultra-small-angle x-ray scattering (USAXS) techniques. This enables the nondestructive measurement of both the individual CNT diameter and CNT bundle diameter within CNT forests, which are otherwise quantified only by delicate and often destructive microscopy techniques. Our measurements show that multi-wall CNT forests grown by chemical vapor deposition consist of isolated and bundled CNTs, with an average bundle diameter of 16 nm. After capillary densification of the CNT forest, USAXS reveals bundles with a diameter 4 m, in addition to the small bundles observed in the as-grown forests. Combining these characterization methods with new CNT processing methods could enable the engineering of macro-scale CNT assemblies that exhibit significantly improved bulk properties. © 2011 American Institute of Physics.

Fabrication and electrical integration of robust carbon nanotube micropillars by self-directed elastocapillary densification

Vertically aligned carbon nanotube (CNT) 'forest' microstructures fabricated by chemical vapor deposition (CVD) using patterned catalyst films typically have a low CNT density per unit area. As a result, CNT forests have poor bulk properties and are too fragile for integration with microfabrication processing. We introduce a new self-directed capillary densification method where a liquid is controllably condensed onto and evaporated from the CNT forests. Compared to prior approaches, where the substrate with CNTs is immersed in a liquid, our condensation approach gives significantly more uniform structures and enables precise control of the CNT packing density. We present a set of design rules and parametric studies of CNT micropillar densification by self-directed capillary action, and show that self-directed capillary densification enhances Young's modulus and electrical conductivity of CNT micropillars by more than three orders of magnitude. Owing to the outstanding properties of CNTs, this scalable process will be useful for the integration of CNTs as a functional material in microfabricated devices for mechanical, electrical, thermal and biomedical applications. © 2011 IOP Publishing Ltd.

Controlled growth orientation of carbon nanotube pillars by catalyst patterning in microtrenches

We present a novel method for controlling the growth orientation of individual carbon nanotube (CNT) microstructures on a silicon wafer substrate. Our method controls the CNT forest orientation by patterning the catalyst layer used in the CNTs growth on slanted KOH edges. The overlap of catalyst area on the horizontal bottom and sloped sidewall surfaces of the KOH-etched substrate enables precise variation of the growth direction. These inclined structures can profit from the outstanding mechanical, electrical, thermal, and optical properties of CNTs and can therefore improve the performance of several MEMS devices. Inclined CNT microstructures could for instance be used as cantilever springs in probe card arrays, as tips in dip-pen lithography, and as sensing element in advanced transducers. ©2009 IEEE.

Advanced carbon nanotubes and carbon nanotube fibers for biosensing applications

Since the discovery of Carbon Nanotubes (CNTs) by Iijima in 1991[1, 2], there has been an explosion of research into the physical and chemical properties of this novel material. CNT based biosensors can play an important role in amperometric, immunosensor and nucleic-acid sensing devices, e.g. for detection of life threatening biological agents in time of war or in terrorist attacks, saving life and money for the NHS. CNTs offer unique advantages in several areas, like high surfacevolume ratio, high electrical conductivity, chemical stability and strong mechanical strength, and CNT based sensors generally have higher sensitivities and lower detection limit than conventional ones. In this review, recent advances in biosensors utilising carbon nanotubes and carbon nanotube fibres will be discussed. The synthesis methods, nanostructure approaches and current developments in biosensors using CNTs will be introduced in the first part. In the second part, the synthesis methods and up-to-date progress in CNT fibre biosensors will be reviewed. Finally, we briefly outline some exciting applications for CNT and CNT fibres which are being targeted. By harnessing the continual advancements in micro and nano- technology, the functionality and capability of CNT-based biosensors will be enhanced, thus expanding and enriching the possible applications that can be delivered by these devices. © 2012 Bentham Science Publishers. All rights reserved.

Bouncing Water Droplet on a Superhydrophobic Carbon Nanotube Array

Over the past few decades, superhydrophobic materials have attaracted a lot of interests, due to their numerous practical applications. Among various superhydrophobic materials, carbon nanotube arrays have gained enormous attentions simply because of their outstanding properties. The impact dynamic of water droplet on a superhydrophobic carbon nanotube array is shown in this fluid dynamics video.

Reversible tuning of the wettability of carbon nanotube arrays: the effect of ultraviolet/ozone and vacuum pyrolysis treatments.

Among diverse types of synthetic materials, arrays of vertically aligned carbon nanotubes have attracted the most attention, mainly because of their exceptional mechanical, electrical, optical, and thermal properties. However, their wetting properties are yet to be understood. In this present study, oxygenated surface functional groups have been identified as a vital factor in controlling the wetting properties of carbon nanotube arrays. The results presented herein indeed show that a combination of ultraviolet/ozone and vacuum pyrolysis treatments can be used to vary the surface concentration of these functional groups such that the carbon nanotube array can be repeatedly switched between hydrophilic and hydrophobic.

Nanoengineering coaxial carbon nanotube-dual-polymer heterostructures.

We describe studies of new nanostructured materials consisting of carbon nanotubes wrapped in sequential coatings of two different semiconducting polymers, namely, poly(3-hexylthiophene) (P3HT) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT). Using absorption spectroscopy and steady-state and ultrafast photoluminescence measurements, we demonstrate the role of the different layer structures in controlling energy levels and charge transfer in both solution and film samples. By varying the simple solution processing steps, we can control the ordering and proportions of the wrapping polymers in the solid state. The resulting novel coaxial structures open up a variety of new applications for nanotube blends and are particularly promising for implementation into organic photovoltaic devices. The carbon nanotube template can also be used to optimize both the electronic properties and morphology of polymer composites in a much more controlled fashion than achieved previously, offering a route to producing a new generation of polymer nanostructures.

Effect of dry oxidation on the performance of carbon nanotube arrays electrochemical capacitors

In this study, the effect of dry oxidation on the electrochemical properties of carbon nanotube arrays is investigated. Oxygenated surface functional groups were introduced to the arrays by oxygen plasma treatment, where their surface concentrations were varied by controlling the exposure time. The finding presented herein shows an augmentation of nearly thirty times in term of specific capacitance when the arrays are oxidized. Similar behavior is also observed in the non-aqueous electrolytes where the specific capacitance of the oxidized carbon nanotube arrays is measured more than three times higher than that of the pristine ones. However, overexposure to oxygen plasma treatment reverses this effect. At such high oxidation level, the damage to the graphitic structure becomes more pronounced such that the capacitive behavior of the arrays is overshadowed by their resistive behavior. These findings are important for further development of carbon nanotube based electrochemical capacitors. © 2012 Materials Research Society.

Fabrication and integration of horizontally aligned carbon nanotube C60 films for UV sensors

Carbon nanotubes (CNTs) are promising for microsystems applications, yet few techniques effectively enable integration of CNTs with precise control of placement and alignment of the CNTs at sufficiently high densities necessary for compelling mechanical or electrical performance. This paper explores new methods for scalable integration of dense, horizontally aligned (HA) CNTs with patterned electrodes. Our technique involves the synthesis of vertically aligned (VA) CNTs directly on a conductive underlayer and subsequent mechanical transformation into HA-CNTs, thus making electrical contact between two electrodes. We compare elasto-capillary folding and mechanical rolling as methods for transforming VA-CNTs, which lead to distinctly different HA-CNT morphologies and potentially impact material and device properties. As an example application of this novel CNT morphology, we investigate fabrication of electrically addressable CNT-C60 hybrid thin films that we previously demonstrated as photodetectors. We synthesize these assemblies by crystallizing C60 from dispersion on HA-CNT thin-film scaffoldings. HA-CNTs fabricated by rolling result in relatively low packing density, so C 60 crystals embed inside the HA-CNT matrix during synthesis. On the other hand, C60 crystallization is restricted to near the surface of HA-CNT films made by the elasto-capillary process. © 2013 IEEE.

The effect of carbon nanotube orientation on erosive wear resistance of CNT-epoxy based composites

Aligned carbon nanotube (CNT) polymer composites are envisioned as the next-generation composite materials for a wide range of applications. In this work, we investigate the erosive wear behavior of epoxy matrix composites reinforced with both randomly dispersed and aligned carbon nanotube (CNT) arrays. The aligned CNT composites are prepared in two different configurations, where the sidewalls and ends of nanotubes are exposed to the composite surface. Results have shown that the composite with vertically aligned CNT-arrays exhibits superior erosive wear resistance compared to any of the other types of composites, and the erosion rate reaches a similar performance level to that of carbon steel at 20° impingement angle. The erosive wear mechanism of this type of composite, at various impingement angles, is studied by Scanning Electron Microscopy (SEM). We report that the erosive wear performance shows strong dependence on the alignment geometries of CNTs within the epoxy matrix under identical nanotube loading fractions. Correlations between the eroded surface roughness and the erosion rates of the CNT composites are studied by surface profilometry. This work demonstrates methods to fabricate CNT based polymer composites with high loading fractions of the filler, alignment control of nanotubes and optimized erosive wear properties. © 2014 Elsevier Ltd. All rights reserved.

Hybrids of carbon nanotube forests and gold nanoparticles for improved surface plasmon manipulation.

We report the fabrication and characterization of hybrids of vertically-aligned carbon nanotube forests and gold nanoparticles for improved manipulation of their plasmonic properties. Raman spectroscopy of nanotube forests performed at the separation area of nanotube-nanoparticles shows a scattering enhancement factor of the order of 1 × 10(6). The enhancement is related to the plasmonic coupling of the nanoparticles and is potentially applicable in high-resolution scanning near-field optical microscopy, plasmonics, and photovoltaics.

Physicochemical characteristics and droplet impact dynamics of superhydrophobic carbon nanotube arrays.

The physicochemical and droplet impact dynamics of superhydrophobic carbon nanotube arrays are investigated. These superhydrophobic arrays are fabricated simply by exposing the as-grown carbon nanotube arrays to a vacuum annealing treatment at a moderate temperature. This treatment, which allows a significant removal of oxygen adsorbates, leads to a dramatic change in wettability of the arrays, from mildly hydrophobic to superhydrophobic. Such change in wettability is also accompanied by a substantial change in surface charge and electrochemical properties. Here, the droplet impact dynamics are characterized in terms of critical Weber number, coefficient of restitution, spreading factor, and contact time. Based on these characteristics, it is found that superhydrophobic carbon nanotube arrays are among the best water-repellent surfaces ever reported. The results presented herein may pave a way for the utilization of superhydrophobic carbon nanotube arrays in numerous industrial and practical applications, including inkjet printing, direct injection engines, steam turbines, and microelectronic fabrication.