Multiwall nanotubes, multilayers, and hybrid nanostructures: new frontiers for technology and Raman spectroscopy.

Technological progress is determined, to a great extent, by developments in material science. Breakthroughs can happen when a new type of material or new combinations of known materials with different dimensionality and functionality are created. Multilayered structures, being planar or concentric, are now emerging as major players at the forefront of research. Raman spectroscopy is a well-established characterization technique for carbon nanomaterials and is being developed for layered materials. In this issue of ACS Nano, Hirschmann et al. investigate triple-wall carbon nanotubes via resonant Raman spectroscopy, showing how a wealth of information can be derived about these complex structures. The next challenge is to tackle hybrid heterostructures, consisting of different planar or concentric materials, arranged "on demand" to achieve targeted properties.

Fabrication, densification, and replica molding of 3D carbon nanotube microstructures

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, labon- a-chip devices, and their applications. In particular, capabilities for cost-effective fabrication of polymer microstructures were transformed by the advent of soft lithography and other micromolding techniques 1,2, and this led a revolution in applications of microfabrication to biomedical engineering and biology. Nevertheless, it remains challenging to fabricate microstructures with well-defined nanoscale surface textures, and to fabricate arbitrary 3D shapes at the micro-scale. Robustness of master molds and maintenance of shape integrity is especially important to achieve high fidelity replication of complex structures and preserving their nanoscale surface texture. The combination of hierarchical textures, and heterogeneous shapes, is a profound challenge to existing microfabrication methods that largely rely upon top-down etching using fixed mask templates. On the other hand, the bottom-up synthesis of nanostructures such as nanotubes and nanowires can offer new capabilities to microfabrication, in particular by taking advantage of the collective self-organization of nanostructures, and local control of their growth behavior with respect to microfabricated patterns. Our goal is to introduce vertically aligned carbon nanotubes (CNTs), which we refer to as CNT "forests", as a new microfabrication material. We present details of a suite of related methods recently developed by our group: fabrication of CNT forest microstructures by thermal CVD from lithographically patterned catalyst thin films; self-directed elastocapillary densification of CNT microstructures; and replica molding of polymer microstructures using CNT composite master molds. In particular, our work shows that self-directed capillary densification ("capillary forming"), which is performed by condensation of a solvent onto the substrate with CNT microstructures, significantly increases the packing density of CNTs. This process enables directed transformation of vertical CNT microstructures into straight, inclined, and twisted shapes, which have robust mechanical properties exceeding those of typical microfabrication polymers. This in turn enables formation of nanocomposite CNT master molds by capillary-driven infiltration of polymers. The replica structures exhibit the anisotropic nanoscale texture of the aligned CNTs, and can have walls with sub-micron thickness and aspect ratios exceeding 50:1. Integration of CNT microstructures in fabrication offers further opportunity to exploit the electrical and thermal properties of CNTs, and diverse capabilities for chemical and biochemical functionalization 3. © 2012 Journal of Visualized Experiments.

Hierarchical carbon nanowire microarchitectures made by plasma-assisted pyrolysis of photoresist

We present a new approach for the fabrication and integration of vertically aligned forests of amorphous carbon nanowires (CNWs), using only standard lithography, oxygen plasma treatment, and thermal processing. The simplicity and scalability of this process, as well as the hierarchical organization of CNWs, provides a potential alternative to the use of carbon nanotubes and graphene for applications in microsystems and high surface area materials. The CNWs are highly branched at the nanoscale, and novel hierarchical microstructures with CNWs connected to a solid amorphous core are made by controlling the plasma treatment time. By multilayer processing we demonstrate deterministic joining of CNW micropillars into 3D sensing networks. Finally we show that these networks can be chemically functionalized and used for measurement of DNA binding with increased sensitivity. © 2011 American Chemical Society.

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.

A temperature sensor from a self-assembled carbon nanotube microbridge

Recent studies show that carbon nanotubes (CNTs) can be used as temperature sensors, and offer great opportunities towards extreme miniaturization, high sensitivity, low power consumption, and rapid response. Previous CNT based temperature sensors are fabricated by either dielectrophoresis or piece-wise alignment of read-out electronics around randomly dispersed CNTs. We introduce a new deterministic and parallel microsensor fabrication method based on the self-assembly of CNTs into three-dimensional microbridges. We fabricated prototype microbridge sensors on patterned electrodes, and found their sensitivity to be better than -0.1 %/K at temperatures between 300K and 420K. This performance is comparable to previously published CNT based temperature sensors. Importantly, however, our research shows how unique sensor architectures can be made by self-assembly, which can be achieved using batch processing rather than piecewise assembly. ©2010 IEEE.

Novel nanostructured carbon nanotube electron sources

In this chapter, we present a review of our continuing efforts toward the development of discrete, low-dimensional nanostructured carbon-based electron emitters. Carbon nanotubes and nanofibers, herein referred to simply as CNTs, are one-dimensional carbon allotropes formed from cylindrically rolled and nested graphene sheets, have diameters between 1 and 500 nm and lengths of up to several millimeters, and are perfect candidates for field emission (FE) applications. By virtue of their extremely strong sp2 C-C bonding, intrinsic to the graphene hexagonal lattice, CNTs have demonstrated impressive chemical inertness, unprecedented thermal stabilities, significant resistance to electromigration, and exceptionally high axial current carrying capacities, even at elevated temperatures. These near ideal cold cathode electron emitters have incredibly high electric field enhancing aspect ratios combined with virtual point sources of the order of a few nanometers in size. The correct integration and judicious development of suitable FE platforms based on these extraordinary molecules is critical and will ultimately enable enhanced technologies. This chapter will review some of the more recent platforms, devices and structures developed by our group, as well as our contributions towards the development of industry-scalable technologies for ultra-high-resolution electron microscopy, portable x-ray sources, and flexible environmental lighting technologies. © 2012 by Pan Stanford Publishing Pte. Ltd. All rights reserved.

Nanotubes complexed with DNA and proteins for resistive-pulse sensing

We use a resistive-pulse technique to analyze molecular hybrids of single-wall carbon nanotubes (SWNTs) wrapped in either single-stranded DNA or protein. Electric fields confined in a glass capillary nanopore allow us to probe the physical size and surface properties of molecular hybrids at the single-molecule level. We find that the translocation duration of a macromolecular hybrid is determined by its hydrodynamic size and solution mobility. The event current reveals the effects of ion exclusion by the rod-shaped hybrids and possible effects due to temporary polarization of the SWNT core. Our results pave the way to direct sensing of small DNA or protein molecules in a large unmodified solid-state nanopore by using nanofilaments as carriers. © 2013 American Chemical Society.

Superhydrophobic carbon nanotube electrode produces a near-symmetrical alternating current from photosynthetic protein-based photoelectrochemical cells

The construction of protein-based photoelectrochemical cells that produce a variety of alternating currents in response to discontinuous illumination is reported. The photovoltaic component is a protein complex from the purple photosynthetic bacterium Rhodobacter sphaeroides which catalyses photochemical charge separation with a high quantum yield. Photoelectrochemical cells formed from this protein, a mobile redox mediator and a counter electrode formed from cobalt disilicide, titanium nitride, platinum, or multi-walled carbon nanotubes (MWCNT) generate a direct current during continuous illumination and an alternating current with different characteristics during discontinuous illumination. In particular, the use of superhydrophobic MWCNT as the back electrode results in a near symmetrical forward and reverse current upon light on and light off, respectively. The symmetry of the AC output of these cells is correlated with the wettability of the counter electrode. Potential applications of a hybrid biological/synthetic solar cell capable of generating an approximately symmetrical alternating current are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bio-inspired hierarchical polymer fiber-carbon nanotube adhesives.

Hierarchical pillar arrays consisting of micrometer-sized polymer setae covered by carbon nanotubes are engineered to deliver the role of spatulae, mimicking the fibrillar adhesive surfaces of geckos. These biomimetic structures conform well and achieve better attachment to rough surfaces, providing a new platform for a variety of applications.

Evaluation of bimetallic catalysts for the growth of carbon nanotube forests

We systematically study the growth of carbon nanotube forests by chemical vapor deposition using evaporated monometallic or bimetallic Ni, Co, or Fe films supported on alumina. Our results show two regimes of catalytic activity. When the total thickness of catalyst is larger than nominally 1nm, bimetallic catalysts tend to outperform the equivalent layers of a single metal, yielding taller forests of multi-walled carbon nanotubes (CNTs). In contrast, for layers thinner than ~1nm, bimetallic catalysts are notably less active than individually. However, the amount of small diameter and single-walled CNTs is significantly increased. This possible transition at ~1nm might be related to different catalyst composition after annealing, depending whether or not the films overlap during evaporation and alloy during catalyst formation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mode-locking by nanotubes of a raman laser based on a highly doped GeO2 fiber

A mode-locked Raman laser, using 25 m of a GeO2 doped fiber as the gain medium, is reported employing carbon nanotubes. The oscillator generates 850 ps chirped pulses, which are externally compressed to 185 ps. © OSA 2012.

Dry oxidation and vacuum annealing treatments for tuning the wetting properties of carbon nanotube arrays.

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.(1,2) These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.(2) Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.(3-5) The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

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.

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.