Shape Control of Electrodeposited Copper Films and Nanostructures through Additive Effects

Abstract

The use of electrolyte additives to affect nanocrystallite shape and film morphology in electrodeposited copper films is presented. Linear sweep and cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) methods are employed to investigate the effects of alcohol additives and the organic additive malachite green (MG), on copper electrodeposited onto polycrystalline gold electrodes. The use of additives affects the deposition process by increasing cathodic peak potentials and decreasing corresponding peak currents. Copper films deposited from electrolyte solutions with additives show additive-specific nanostructure and crystallite morphology. Film analysis reveals a greater than five times reduction in both film roughness and grain size in the presence of even small concentrations of the additive MG. Use of MG results in the preferential electrodeposition of oriented, square pyramidal crystallites, while alcohol additives result in tetrahedral crystallite textures. 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. This approach offers a new and cost-effective route to achieve shape-controlled surface nanostructure.

Effect of glyphosate on X-ray diffraction of copper films prepared by electrochemical deposition

“…25 The inuence of the electrolyte additives on the shape and the morphology of nanocrystals in the electrodeposited copper lms has been investigated. 26 These organic additives were adsorbed on the active sites on the surface of the electrode and combined with the metal ions to form complexes that changed the nucleation and growth of the crystals. [27][28][29] The microstructure and the morphology of the deposited metal change, and the X-ray diffraction pattern changes accordingly.…”

Electrochemical deposition of layered copper thin films based on the diffusion limited aggregation

“…This growth is consistent with the observations of Yunyu Joseph Han et al , who used organic additive malachite green (MG) in Cu ECD on Au substrate to form square pyramidal crystallites with Cu (200) direction. They thought the reason was the interactions of MG with Cu (111) surface were stronger than those with Cu (200) surface, and this stronger interaction partly blocked epitaxial growth on Cu (111) surface and prompted further growth on Cu (200) surface 7 .…”

“…Among these methods, ECD as a green approach has gained extensive attention in recent years, it’s widely accepted that ECD is one of the most extensively used ways due to the cost-effective, time saving and facile technique. During the process of ECD, there are lots of alterable parameters can affect the nucleation and growth process of crystals, such as potential, current, additive, temperature and pH 6 7 8 .…”

“…Gu, C. D. et al deposited Cu films with absence and presence of additive of ethylene diamine (EDA), the thickness of films decreased from 11.5 μm to 7.7 μm own to the presence of EDA 1 . Han, Y. J. et al used organic additive malachite green to deposite copper films with square pyramidal crystallites on surface 7 . Based on the superb complexing ability of additive of sodium citrate to chelate copper ions, adsorb phase on Cu surface and transport hindering role for upcoming Cu ions, Whang, T. J. et al prepared homogeneous densely-packed grains and CuInSe 2 thin films with higher crystallinity 6 .…”

Patterning Cu nanostructures tailored for CO2 reduction to electrooxidizable fuels and oxygen reduction in alkaline media

“…This can be achieved by laser ablation of copper surfaces, 13,41 plasma etching, 19 dealloying, 30,31 electrochemical polishing, 53 thermal annealing, 54 or electrodeposition. 10,18,20,22,43,55,56 Gowthaman and John demonstrated that the applied substrate potential during Cu electrodeposition affects the geometry of the obtained deposit. They obtained cubic, spherical, dendritic and prickly CuNSs from the same solution.…”