Plasmonic band gaps and waveguide effects in carbon nanotube arrays based metamaterials

Highly dense periodic arrays of multiwalled carbon nanotubes behave like low-density plasma of very heavy charged particles, acting as metamaterials. These arrays with nanoscale lattice constants can be designed to display extended plasmonic band gaps within the optical regime, encompassing the crucial optical windows (850 and 1550 nm) simultaneously. We demonstrate an interesting metamaterial waveguide effect displayed by these nanotube arrays containing line defects. The nanotube arrays with lattice constants of 400 nm and radius of 50 nm were studied. Reflection experiments conducted on the nanoscale structures were in agreement with numerical calculations.

Mechanical response of carbon fiber composite sandwich panels with pyramidal truss cores

The combination of light carbon fiber reinforced polymer (CFRP) composite materials with structurally efficient sandwich panel designs offers novel opportunities for ultralight structures. Here, pyramidal truss sandwich cores with relative densities ρ̄ in the range 1-10% have been manufactured from carbon fiber reinforced polymer laminates by employing a snap-fitting method. The measured quasi-static shear strength varied between 0.8 and 7.5 MPa. Two failure modes were observed: (i) Euler buckling of the struts and (ii) delamination failure of the laminates. Micro-buckling failure of the struts was not observed in the experiments reported here while Euler buckling and delamination failures occurred for the low (ρ̄≤1%) and high (ρ̄>1%) relative density cores, respectively. Analytical models for the collapse of the composite cores by these failure modes are presented. Good agreement between the measurements and predictions based on the Euler buckling and delamination failure of the struts is observed while the micro-buckling analysis over-predicts the measurements. The CFRP pyramidal cores investigated here have a similar mechanical performance to CFRP honeycombs. Thus, for a range of multi-functional applications that require an "open-celled" architecture (e.g. so that cooling fluid can pass through a sandwich core), the CFRP pyramidal cores offer an attractive alternative to honeycombs. © 2012 Elsevier Ltd. All rights reserved.

Brillouin scattering of cluster-assembled carbon films

The low frequency vibrational spectrum of cluster beam deposited carbon films was studied by Brillouin light scattering. In thin films the values of both bulk modulus and shear modulus has been estimated from the shifts of surface phonon peaks. The values found indicate a mainly sp2 coordinated random network with low density. In thick films a bulk longitudinal phonon peak was detected in a spectral range compatible with the value of the index of refraction and of the elastic constants of thin films. High surface roughness, combined with a rather strong bulk central peak, prevented the observation of surface phonon features. © 1998 Elsevier Science Ltd. All rights reserved.

Mechanics of capillary forming of aligned carbon nanotube assemblies.

Elastocapillary self-assembly is emerging as a versatile technique to manufacture three-dimensional (3D) microstructures and complex surface textures from arrangements of micro- and nanoscale filaments. Understanding the mechanics of capillary self-assembly is essential to engineering of properties such as shape-directed actuation, anisotropic wetting and adhesion, and mechanical energy transfer and dissipation. We study elastocapillary self-assembly (herein called "capillary forming") of carbon nanotube (CNT) microstructures, combining in situ optical imaging, micromechanical testing, and finite element modeling. By imaging, we identify sequential stages of liquid infiltration, evaporation, and solid shrinkage, whose kinetics relate to the size and shape of the CNT microstructure. We couple these observations with measurements of the orthotropic elastic moduli of CNT forests to understand how the dynamic of shrinkage of the vapor-liquid interface is coupled to the compression of the forest. We compare the kinetics of shrinkage to the rate of evporation from liquid droplets having the same size and geometry. Moreover, we show that the amount of shrinkage during evaporation is governed by the ability of the CNTs to slip against one another, which can be manipulated by the deposition of thin conformal coatings on the CNTs by atomic layer deposition (ALD). This insight is confirmed by finite element modeling of pairs of CNTs as corrugated beams in contact and highlights the coupled role of elasticity and friction in shrinkage and stability of nanoporous solids. Overall, this study shows that nanoscale porosity can be tailored via the filament density and adhesion at contact points, which is important to the development of lightweight multifunctional materials.

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.

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.

Spectroscopic characterization of protein-wrapped single-wall carbon nanotubes and quantification of their cellular uptake in multiple cell generations

We study the spectral characteristics of bovine serum albumin (BSA) protein conjugated single-wall carbon nanotubes (SWNTs), and quantify their uptake by macrophages. The binding of BSA onto the SWNT surface is found to change the protein structure and to increase the doping of the nanotubes. The G-band Raman intensity follows a well-defined power law for SWNT concentrations of up to 33 μg ml-1 in aqueous solutions. Subsequently, in vitro experiments demonstrate that incubation of BSA-SWNT complexes with macrophages affects neither the cellular growth nor the cellular viability over multiple cell generations. Using wide spot Raman spectroscopy as a fast, non-destructive method for statistical quantification, we observe that macrophages effectively uptake BSA-SWNT complexes, with the average number of nanotubes internalized per cell remaining relatively constant over consecutive cell generations. The number of internalized SWNTs is found to be ∼30 × 106 SWNTs/cell for a 60 mm-2 seeding density and ∼100 × 10 6 SWNTs/cell for a 200 mm-2 seeding density. Our results show that BSA-functionalized SWNTs are an efficient molecular transport system with low cytotoxicity maintained over multiple cell generations. © 2013 IOP Publishing Ltd.

Enhanced infra-red emission from sub-millimeter microelectromechanical systems micro hotplates via inkjet deposited carbon nanoparticles and fullerenes

In this paper, we demonstrate a micro-inkjet printing technique as a reproducible post-process for the deposition of carbon nanoparticles and fullerene adlayers onto fully CMOS compatible micro-electro-mechanical silicon-on-insulator infrared (IR) light sources to enhance their infrared emission. We show experimentally a significant increase in the infrared emission efficiency of the coated emitters. We numerically validate these findings with models suggesting a dominant performance increase for wavelengths <5.5 μm. Here, the bimodal size distribution in the diameter of the carbon nanoparticles, relative to the fullerenes, is an effective mediator towards topologically enhanced emittance of our miniaturised emitters. A 90% improvement in IR emission power density has been shown which we have rationalised with an increase in the mean thickness of the deposited carbon nanoparticle adlayer. © 2013 AIP Publishing LLC.

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.

Use of vertically-aligned carbon nanotube array to enhance the performance of electrochemical capacitors

In the domain of energy storage, electrochemical capacitors have numerous applications ranging from hybrid vehicles to consumer electronics, with very high power density at the cost of relatively low energy storage. Here, we report an approach that uses vertically aligned carbon nanotube arrays as electrodes in electrochemical capacitors. Different electrolytes were used and multiple parameters of carbon nanotube array were compared: carbon nanotube arrays were shown to be two to three times better than graphite in term of specific capacitance, while the surface functionalization was demonstrated to be a critical factor in both aqueous and nonaqueous solutions to increase the specific capacitance. We found that a maximum energy density of 21 Wh/kg at a power density of 1.1 kW/kg for a hydrophilic electrode, could be easily achieved by using tetraethylammonium tetrafluoroborate in propylene carbonate. These are encouraging results in the path of energy-storage devices with both high energy density and power density, using only carbon-based materials for the electrodes with a very long lifetime, of tens of thousands of cycles. © 2011 IEEE.

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.

Hybrid core carbon fiber composite sandwich panels: Fabrication and mechanical response

Carbon fiber reinforced polymer (CFRP) composite sandwich panels with hybrid foam filled CFRP pyramidal lattice cores have been assembled from a carbon fiber braided net, 3D woven face sheets and various polymeric foams, and infused with an epoxy resin using a vacuum assisted resin transfer process. Sandwich panels with a fixed CFRP truss mass have been fabricated using a variety of closed cell polymer and syntactic foams, resulting in core densities ranging from 44-482kgm-3. The through thickness and in-plane shear modulus and strength of the cores increased with increasing foam density. The use of low compressive strength foams within the core was found to result in a significant reduction in the compressive strength contributed by the CFRP trusses. X-ray tomography led to the discovery that the trusses develop an elliptical cross-section shape during pressure assisted resin transfer. The ellipticity of the truss cross-sections increased, and the lattice contribution to the core strength decreased as the foam density was reduced. Micromechanical modeling was used to investigate the relationships between the mechanical properties and volume fractions of the core materials and truss topology of the hybrid core. The specific strength and moduli of the hybrid cores lay between those of the CFRP lattices and foams used to fabricate them. However, their volumetric and gravimetric energy absorptions significantly exceeded those of the materials from which they were fabricated. They compare favorably with other lightweight energy absorbing materials and structures. © 2013.

Multi-walled carbon nanotube conductivity enhancement and band gap widening via rapid pulsed thermal annealing

Herein we report on the transport characteristics of rapid pulsed vacuum-arc thermally annealed, individual and network multi-walled carbon nanotubes. Substantially reduced defect densities (by at least an order of magnitude), measured by micro-Raman spectroscopy, and were achieved by partial reconstruction of the bamboo-type defects during thermal pulsing compared with more traditional single-pulse thermal annealing. Rapid pulsed annealed processed networks and individual multi-walled nanotubes showed a consistent increase in conductivity (of over a factor of five at room temperature), attributed to the reduced number density of resistive axial interfaces and, in the case of network samples, the possible formation of structural bonds between crossed nanotubes. Compared to the highly defective as-grown nanotubes, the pulsed annealed samples exhibited reduced temperature sensitivity in their transport characteristics signifying the dominance of scattering events from structural defects. Transport measurements in the annealed multi-walled nanotubes deviated from linear Ohmic, typically metallic, behavior to an increasingly semiconducting-like behavior attributed to thermally induced axial strains. Rapid pulsed annealed networks had an estimated band gap of 11.26 meV (as-grown; 6.17 meV), and this observed band gap enhancement was inherently more pronounced for individual nanotubes compared with the networks most likely attributed to mechanical pinning effect of the probing electrodes which possibly amplifies the strain induced band gap. In all instances the estimated room temperature band gaps increased by a factor of two. The gating performance of back-gated thin-film transistor structures verified that the observed weak semiconductivity (p-type) inferred from the transport characteristic at room temperature. © 2014 Copyright Taylor & Francis Group, LLC.

Raman evidence for atomic correlation between the two constituent tubes in double-walled carbon nanotubes

Four well-resolved peaks with very narrow linewidths were found in the D-band and G'-band features of double-walled carbon nanotubes (DWNTs). This fact implies the occurrence of additional van Hove singularities (vHSs) in the joint density of states (JDOS) of DWNTs, which is consistent with theoretical calculations. According to their peak frequencies and theoretical analysis, the two outer peaks can be deduced to originate from a strong coupling between the two constituent tubes of commensurate DWNTs and the two inner peaks were curvature-related and assigned to originate from the two tubes with a weak coupling. This observation and elucidation constitute the first Raman evidence for atomic correlation and the resulting electronic structure change of the two constituent tubes in DWNTs. This result opens the possibility of predicting and modifying the electronic properties of DWNTs for their electronic applications.