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http://dx.doi.org/10.3740/MRSK.2013.23.12.695

Influence of Reactivity of Reinforcing Nanoparticles with Aqueous Solution on Electroplating Copper Films  

Park, Jieun (Department of Cogno-mechatronics Engineering, Pusan National University)
Oh, Minju (Department of Cogno-mechatronics Engineering, Pusan National University)
Kim, Yiseul (Department of Advanced Circuit Interconnection, Pusan National University)
Lee, Dongyun (Department of Cogno-mechatronics Engineering, Pusan National University)
Publication Information
Korean Journal of Materials Research / v.23, no.12, 2013 , pp. 695-701 More about this Journal
Abstract
To understand how reactivity between reinforcing nanoparticles and aqueous solution affects electrodeposited Cu thin films, two types of commercialized cerium oxide (ceria, $CeO_2$) nanoparticles were used with copper sulfate electrolyte to form in-situ nanocomposite films. During this process, we observed variation in colors and pH of the electrolyte depending on the manufacturer. Ceria aqueous solution and nickel sulfate ($NiSO_4$) aqueous solutions were also used for comparison. We checked several parameters which could be key factors contributing to the changes, such as the oxidation number of Cu, chemical impurities of ceria nanoparticles, and so on. Oxidation number was checked by salt formation by chemical reaction between $CuSO_4$ solution and sodium hydroxide (NaOH) solution. We observed that the color changed when $H_2SO_4$ was added to the $CuSO_4$ solution. The same effect was obtained when $H_2SO_4$ was mixed with ceria solution; the color of ceria solution changed from white to yellow. However, the color of $NiSO_4$ solution did not show any significant changes. We did observe slight changes in the pH of the solutions in this study. We did not obtain firm evidence to explain the changes observed in this study, but changes in the color of the electrolyte might be caused by interaction of Cu ion and the by-product of ceria. The mechanical properties of the films were examined by nanoindentation, and reaction between ceria and electrolyte presumably affect the mechanical properties of electrodeposited copper films. We also examined their crystal structures and optical properties by X-ray diffraction (XRD) and UV-Vis spectroscopy.
Keywords
cerium oxide(ceria); oxidation number; salt formation; XRD; nanoindentation;
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