Application of a constant cathodic current to an electrode in an alkaline Cu(II) lactate solution results in oscillation of the electrode potential during the electrodeposition of copper/cuprous oxide layered nanostructures. The electrochemical quartz crystal microbalance (EQCM) is used for in situ phase analysis measurements of the nanoscale layers and the results are compared with bulk XRD measurements. The EQCM is also used to estimate the layer thicknesses and overall modulation wavelength of the nanostructures. We propose that Cu2O is deposited during the positive spikes in electrode potential, while a composite of Cu and Cu2O is deposited during the more negative plateau region of the oscillation. The modulation wavelength calculated from the EQCM is in good agreement with that observed with scanning electron microscopy. The EQCM is shown to be a useful tool for estimating layer thicknesses and phase compositions for layers that are too thin to be examined by other instrumental techniques.

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Layered nanostructures of copper metal and cuprous oxide are electrodeposited from alkaline solutions of Cu(II) lactate at room temperature. No subsequent heat treatment is necessary to effect crystallization. The electrode potential spontaneously oscillates during constant-current deposition. At a fixed current density the oscillation period decreases as either the pH or temperature is increased. The oscillations are periodic in stirred solution, but show period doubling and evidence of quasi-periodic or chaotic behavior in unstirred solution. The phase composition and resistivity of the films can be controlled by varying the applied current density. The resistivity of the films can be varied over ten orders of magnitude. Scanning electron microscopy shows that the films are layered.

Nanocomposite films of copper metal and cuprous oxide, Cu.O, are electrodeposited at room temperature from alkaline solutions of copper(Il) lactate. The electrode potential oscillates spontaneously if the films are deposited galvanostatically. The oscillation period is a function of pH, varying from 69 seconds at pH 8.7 to 11 seconds at pH 9.7. No oscillations are observed if the pH is below 8.5 or above 10. The phase composition of films deposited at 0.5 mNcm z is a function of pH. The composition varies from nearly pure copper (93 mole%) at pH 8, to 42 mole% copper at pH 9.5, to pure cuprous oxide when the pH exceeds 10. The observation of quasi-periodic potential oscillations suggests that the nanocomposites are layered. The calculated faradaic thickness of cuprous oxide is 5-8 nm, and the thickness of the copper layer is 1-11 nm. The thickness of each of the layers increases as the pH is lowered.

Nanocomposite films of copper metal and cuprous oxide were electrodeposited at room temperature from an alkaline copper(11) lactate solution. The electrode potential oscillated spontaneously during constant-current deposition of the composites. The oscillations were periodic in a stirred solution, but became chaotic in unstirred solution. For a given current density the phase composition was a strong function of solution pH. As the pH was increased, the cuprous oxide content increased. At pH 12, no oscillations were observed, and pure cuprous oxide was deposited. At pH 9, the phase composition varied from pure cuprous oxide at current densities below 0.1 mA/cm2 to 96 mole percent copper at 2.5 mA/cm2.