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.

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.

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.

Vertically aligned carbon nanotubes growth using self-assembled Ni nanoparticles produced by ion implantation

An alternative method for seeding catalyst nanoparticles for carbon nanotubes and nanowires growth is presented. Ni nanoparticles are formed inside a 450 nm SiO2 film on (100) Si wafers through the implantation of Ni ions at fluences of 7.5×1015 and 1.7×1016 ions.cm-2 and post-annealing treatments at 700, 900 and 1100°C. After exposed to the surface by HF dip etching, the Ni nanoparticles are used as catalyst for the growth of vertically aligned carbon nanotubes by direct current plasma enhanced chemical vapor deposition. © 2007 Materials Research Society.

Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Europium-directed self-assembly of a luminescent supramolecular gel from a tripodal terpyridine-based ligand.

Eu(III), the last piece in the puzzle: Europium-induced self-assembly of ligands having a C(3)-symmetrical benzene-1,3,5-tricarboxamide core results in the formation of luminescent gels. Supramolecular polymers are formed through hydrogen bonding between the ligands. The polymers are then brought together into the gel assembly through the coordination of terpyridine ends by Eu(III) ions (blue dashed arrow: distance between two ligands in the strand direction).

Growth of highly-quality single-wall carbon nanotubes without amorphous carbon formation

A simple way to deposit single-wall carbon nanotubes by CVD without the co-deposition of unwanted a-C was demonstrated. It was found that the catalytic deposition of SWCNTs occurs at a substantial rate compared to the self-pyrolysis of the hydrocarbon gas used.

Fabrication of large grain Nd-Ba-Cu-O by seeded melt growth

Large, single grain Nd-Ba-Cu-O (NdBCO) composite samples of NdBa2Cu3O7-δ (Nd-123) containing 15 and 20 mol. % non-superconducting Nd4Ba2Cu2O10 (Nd-422) phase inclusions have been fabricated successfully by a variety of techniques based on top-seeded melt growth under reduced oxygen partial pressure. Specifically, individual grains up to 2cm in diameter have been grown using (100) oriented MgO seeding, self (NdBCO) seeding at elevated temperature and self-seeding of Ag and Au doped precursor pellets. The latter exhibit a reduced peritectic decomposition temperature compared with the undoped compound. These techniques, which vary in degree of difficulty and hence reliability, yield grains with a range of microstructural homogeneity. This paper describes the general aspects of large NdBCO grain fabrication and presents the results of the different fabrication techniques.

Single domain YBCO/Ag bulk superconductors fabricated by seeded infiltration and growth

We have applied the seeded infiltration and growth (IG) technique to the processing of samples containing Ag in an attempt to fabricate Ag-doped Y-Ba-Cu-O (YBCO) bulk superconductors with enhanced mechanical properties. The IG technique has been used successfully to grow bulk Ag-doped YBCO superconductors of up to 25 mm in diameter in the form of single grains. The distribution of Ag in the parent Y-123 matrix fabricated by the IG technique is observed to be at least as uniform as that in samples grown by conventional top seeded melt growth (TSMG). Fine Y-211 particles were observed to be embedded within the Y-123 matrix for the IG processed samples, leading to a high critical current density, Jc, of over 70 kA/cm2 at 77.3 K in self-field. The distribution of Y-211 in the IG sample microstructure, however, is inhomogeneous, which leads to a variation in the spatial distribution of Jc throughout the bulk matrix. A maximum-trapped field of around 0.43 T at 1.2 mm above the sample surface (i.e. including 0.7 mm for the sensor mould thickness) is observed at liquid nitrogen temperature, despite the relatively small grain size of the sample (20 mm diameter × 7 mm thickness). © 2008 IOP Publishing Ltd.

Seeded infiltration and growth of bulk YBCO nano-composites

The seeded infiltration and growth (SIG) technique offers near-net shape processing of bulk superconductors with significant improvement in reduced Y2BaCuO5 (Y-211) inclusion size, reduced shrinkage, reduced porosity and improved current density compared to samples fabricated by top seeded melt growth (TSMG). Y2Ba4CuMOy phases where M=Nb, Mo, W, Ta, etc., have been shown to form nano-scale inclusions in the YBa2Cu3Oy (Y-123) phase matrix and to contribute to enhanced magnetic flux pinning in these materials. In this paper, we describe the introduction of Y2Ba 4CuWOy nano-scale inclusions into bulk superconductors processed by the seeded infiltration growth process. Critical current density, Jc, in excess of 105 A/cm2 at 77 K in self-field is observed for samples containing Y2Ba 4CuWOy. © 2011 IEEE.