Abstract
The use of electrolyte additives to affect nanocrystallite shape and film morphology in electroless and electrodeposited metal films is presented. Copper electrodeposited onto gold results in preferential square pyramidal copper nanostructure morphologies in the presence of the organic additive malachite green (MG). We have employed in-situ and ex situ methods to investigate the additive effects, including nonlinear optical spectroscopy, electrochemical scanning tunneling microscopy, linear sweep and cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). These shape-controlled additive effects are supported by additive adsorption energy calculations, which indicate preferential interactions, and differential growth kinetics on different facets of the film's growing nanostructures during electrodeposition. Facet-specific interactions have also been exploited in the epitaxial electroless deposition of noble metals onto single crystal Ag(100) substrates. Here, we examine the role of specific anions in determining the resulting film and nanostructure morphologies via SEM and high resolution transmission electron microscopy (HRTEM). These effects have been exploited to yield large area patterned, and shape-controlled nanoarrays of single crystal metal nanostructures for plasmonic and metamaterial applications. These approaches offer new and cost effective routes to achieve shape-controlled surface nanostructure.
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