The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Dual-wavelength, carbon nanotube mode-locked fiber laser

We demonstrate a dual-wavelength, carbon nanotube mode-locked Er fiber laser. The laser outputs two wavelengths at 1549nm and 1562nm, and each wavelength corresponds to pulse duration of ∼1.3ps and repetition rate of ∼11.27MHz. © 2012 IEEE.

Ballasted & electrically steerable carbon nanotube field emitters

Here we present our on-going efforts toward the development of stable ballasted carbon nanotube-based field emitters employing hydrothermally synthesized zinc oxide nanowires and thin film silicon-on-insulator substrates. The semiconducting channel in each controllably limits the emission current thereby preventing detrimental burn-out of individual emitters that occurs due to unavoidable statistical variability in emitter characteristics, particularly in their length. Fabrication details and emitter characterization are discussed in addition to their field emission performance. The development of a beam steerable triode electron emitter formed from hexagonal carbon nanotube arrays with central focusing nanotube electrodes, is also described. Numerical ab-initio simulations are presented to account for the empirical emission characteristics. Our engineered ballasted emitters have shown some of the lowest reported lifetime variations (< 0.7%) with on-times of < 1 ms, making them ideally-suited for next-generation displays, environmental lighting and portable x-rays sources. © 2012 SPIE.

Carbon nanotube growth for through silicon via application.

Through silicon via (TSV) technology is key for next generation three-dimensional integrated circuits, and carbon nanotubes (CNT) provide a promising alternative to metal for filling the TSV. Three catalyst preparation methods for achieving CNT growth from the bottom of the TSV are investigated. Compared with sputtering and evaporation, catalyst deposition using dip-coating in a FeCl2 solution is found to be a more efficient method for realizing a bottom-up filling of the TSV (aspect ratio 5 or 10) with CNT. The CNT bundles grown in 5 min exceed the 50 μm length of the TSV and are multi-wall CNT with three to eight walls. The CNT bundles inside the TSV were electrically characterized by creating a direct contact using a four-point nanoprober setup. A low resistance of the CNT bundle of 69.7 Ω (297 Ω) was measured when the CNT bundle was contacted midway along (over the full length of) the 25 μm deep TSV. The electrical characterization in combination with the good filling of the TSV demonstrates the potential use of CNT in fully integrated TSV applications.

Computer generated holograms for carbon nanotube arrays.

Multiwalled carbon nanotubes are highly diffractive structures in the optical regime. Their metallic character and large scattering cross-section allow their usage as diffractive elements in Fraunhofer holograms. This work elaborates some important features of the far field diffraction patterns produced from periodic arrays of nanotubes. A theoretical approach for the interaction of arrays of nanotubes with light is presented and a computer generated hologram is calculated by means of periodical patterns. Based on the results, fabrication of carbon nanotube arrays (in holographic patterns) was performed. Experimentally measured diffraction patterns were in good agreement with the calculations.

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.

Capillary bending of Janus carbon nanotube micropillars.

We present a scalable process for the fabrication of slanted carbon nanotube micropillar arrays by inclined metal deposition and capillary self-assembly. Local control of the micropillar angle from vertical to nearly horizontal is achieved, and is explained using a finite element model. These structures may be useful for microscale contacts and anisotropic smart surfaces.

Structurally programmed capillary folding of carbon nanotube assemblies.

We demonstrate the fabrication of horizontally aligned carbon nanotube (HA-CNT) networks by spatially programmable folding, which is induced by self-directed liquid infiltration of vertical CNTs. Folding is caused by a capillary buckling instability and is predicted by the elastocapillary buckling height, which scales with the wall thickness as t(3/2). The folding direction is controlled by incorporating folding initiators at the ends of the CNT walls, and the initiators cause a tilt during densification which precedes buckling. By patterning these initiators and specifying the wall geometry, we control the dimensions of HA-CNT patches over 2 orders of magnitude and realize multilayered and multidirectional assemblies. Multidirectional HA-CNT patterns are building blocks for custom design of nanotextured surfaces and flexible circuits.