Atomic Layer Deposition on Carbon Nanotubes and their Assemblies.

摘要

Global issues related to energy and the environment have motivated development of advanced material solutions outside of traditional metals ceramics, and polymers. Taking inspiration from composites, where the combination of two or more materials often yields superior properties, the field of organic-inorganic hybrids has recently emerged. Carbon nanotube (CNT)-inorganic hybrids have drawn widespread and increasing interest in recent years due to their multifunctionality and potential impact across several technologically important application areas. Before the impacts of CNT-inorganic hybrids can be realized however, processing techniques must be developed for their scalable production.;Optimization in chemical vapor deposition (CVD) methods for synthesis of CNTs and vertically aligned CNT arrays has created production routes both high throughput and economically feasible. Additionally, control of CVD parameters has allowed for growth of CNT arrays that are able to be drawn into aligned sheets and further processed to form a variety of aligned 1, 2, and 3-dimensional bulk assemblies including ribbons, yarns, and foams. To date, there have only been a few studies on utilizing these bulk assemblies for the production of CNT-inorganic hybrids. Wet chemical methods traditionally used for fabricating CNT-inorganic hybrids are largely incompatible with CNT assemblies, since wetting and drying the delicate structures with solvents can destroy their structure. It is therefore necessary to investigate alternative processing strategies in order to advance the field of CNT-inorganic hybrids.;In this dissertation, atomic layer deposition (ALD) is evaluated as a synthetic route for the production of large-scale CNT-metal oxide hybrids as well as pure metal oxide architectures utilizing CNT arrays, ribbons, and ultralow density foams as deposition templates. Nucleation and growth behavior of alumina was evaluated as a function of CNT surface chemistry. While highly graphitic and defect-free CNTs were shown to produce alumina beads on their surfaces, plasma-treated CNTs with a high concentration of oxygen- containing functional groups on their surface promoted conformal film formation. Furthermore, it was determined that ultrahigh aspect ratio CNT assemblies could be uniformly coated throughout the cross-section by orienting the CNT axes parallel to the direction of precursor flow, as well as by removing any barriers to the pump/purge process such as growth substrates or non-porous sample holders.;Heat treatment of CNT-alumina hybrids in air not only led to the crystallization of alumina, but also oxidative removal of CNTs from the core-shell structure. In the case of CNT arrays, this resulted in a weak array of alumina nanotubes. When the same process was applied to alumina-coated CNT foams (CNTFs) however, a robust and resilient aerogel-like material remained post-calcination. Further inspection of this novel material revealed that the foam was made up of a three-dimensional network of interconnect alumina nanotubes resulting from the direct templating of alumina on the CNTF structure. With an average density of 1.2 mg cm-3, it is an order of magnitude lower than the lowest density alumina aerogel reported to date, and is among the lowest density for any inorganic aerogel reported to date as well.;The structure, and therefore, properties of these novel foams could be easily tuned by varying the thickness of the alumina coating. Evaluation of the compressive behavior of all foams revealed that their mechanical properties exceed those of various foams with similar densities. This was found to be a result of efficient load transfer through the structure due to good connectivity among nanotube ligaments. This connectivity also provided unprecedented elastic recoverability following compression, particularly for thin-walled samples with CNTFs still intact. Structural stability to liquid infiltration and drying increased with the number of ALD cycles, as well as thermal insulation ability.