Electrochemical Approach To Structurally Well Defined Nano And Micro Materials

Author : Tatiana Dorofeeva
Publisher :
ISBN 13 : 9781369795356
Total Pages : pages
Book Rating : 4.7/5 (953 download)

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Download or read book Modification of Patterned Nanoporous Gold Thin Film Electrodes Via Electro-annealing and Electrochemical Etching written by Tatiana Dorofeeva and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Nanostructured materials have had a major impact on various fields, including medicine, catalysis, and energy storage, for the major part due to unique phenomena that arise at nanoscale. For this reason, there is a sustained need for new nanostructured materials, techniques to pattern them, and methods to precisely control their nanostructure. To that end, the primary focus of this dissertation is to demonstrate novel techniques to fabricate and tailor the morphology of a class of nanoporous metals, obtained by a process known as dealloying. In this process, while the less noble constituent of an alloy is chemically dissolved, surface-diffusion of the more noble constituent leads to self-assembly of a bicontinuous ligament network with characteristic porosity of ~70% and ligament diameter of 10s of nanometers. As a model material produced by dealloying, this work employ nanoporous gold (np-Au), which has attracted significant attention of desirable features, such as high effective surface area, electrical conductivity, well-defined thiol-based surface modification strategies, microfabrication-compatibility, and biocompatibility. The most commonly method used to modify the morphology of np-Au is thermal treatment, where the enhanced diffusivity of the surface atoms leads to ligament (and consequently pore) coarsening. This method, however, is not conducive to modifying the morphology of thin films at specific locations on the film, which is necessary for creating devices that may need to contain different morphologies on a single device. In addition, coarsening attained by thermal treatment also leads to an undesirable reduction in effective surface area. In response to these challenges, this work demonstrates two different techniques that enables in situ modification of np-Au thin film electrodes obtained by sputter-deposition of a precursors silver-rich gold-silver alloy. The first method, referred to as electro-annealing, is achieved by injecting electrical current to np-Au electrodes, which leads coarsening due to a combination of Joule heating and other mechanisms. This method offers the capability to anneal different electrodes to varying degrees of coarsening in one step, by employing electrodes patterns with different cross-sectional areas – easily attained since np-Au can be patterned into arbitrary shapes via photolithography – to control electrode resistivity, thus current density and the amount of electro-annealing of an electrode. A surprising finding was that electro-annealing lead to electrode coarsening at much lower temperatures than conventional thermal treatment, which was attributed to augmented electron-surface atom interactions at high current densities that may in turn enhance surface atom diffusivity. A major advantage of electro-annealing is the ability to monitor the resistance change of the electrode (surrogate for electrode morphology) in real-time and vary the electro-annealing current accordingly to establish a closed-loop electro-annealing configuration. In nanostructured materials, the electrical resistance is often a function of nanostructure, thus changes in resistance can be directly linked to morphological changes of the electrode. Examination of the underlying mechanisms of nanostructure-dependent resistance change revealed that both ligament diameter and grain size play a role in dictating the observed electrode resistance change. The second method relies on electrochemical etching of ligaments to modify electrode morphology in order to maintain both a high effective surface area and large pores for unhindered transport of molecules to/from the ligament surfaces – an important consideration for many physico-chemical processes, such fuel cells, electrochemical sensors, and drug delivery platforms. The advantage of this method over purely chemical approach is that while an entire sample in exposed to the chemical reagent, the etching process does not occur until the necessary electrochemical potential is applied. Similar to the electro-annealing methods, electrical addressability allows for differentially modifying the morphology individual electrodes on a single substrate. The results of this study also revealed that electrochemical etching is a combination of coarsening and etching processes, where the optimization of etching parameters makes it possible precisely control the etching by favoring one process over the other. In summary, the two techniques, taken together in combination with np-Au’s compatibility with microfabrication processes, can be extended to create multiple electrode arrays that display different morphologies for studying structure−property relationships and tuning catalysts/sensors for optimal performance.