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.

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).