Chen-Jen Hung

POTENTIAL OSCILLATIONS DURING THE ELECTROCHEMICAL SELF-ASSEMBLY OF COPPER/CUPROUS OXIDE LAYERED NANOSTRUCTURES

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.

Electrodeposited defect chemistry superlattices

Nanometer-scale layered structures based on thallium(III) oxide were electrodeposited in a beaker at room temperature by pulsing the applied potential during deposition. The conducting metal oxide samples were superlattices, with layers as thin as 6.7 nanometers. The defect chemistry was a function of the applied overpotential: High overpotentials favored oxygen vacancies, whereas low overpotentials favored cation interstitials. The transition from one defect chemistry to another in this nonequilibrium process occurred in the same potential range (100 to 120 millivolts) in which the rate of the back electron transfer reaction became significant. The epitaxial structures have the high carrier density and low electronic dimensionality of high transition temperature superconductors.

An Electrochemical Method for CuO Thin Film Deposition from Aqueous Solution

An electrochemical procedure is described for the anodic deposition of CuO thin films from solution precursors at 25-30°C in an alkaline medium (pH > 13). The deposition bath was similar to Fehlings solution using tartrate ions as a complexing agent for Cu(II). Cupric oxide deposited onto a platinum substrate at an anodic current density of 5 mA cm - 2 has a preferred orientation of [010]. Rietveld refinement of the powder diffraction pattern reveals pure Cu(II) oxide with no trace of other copper oxides. The suggested mechanism involves the irreversible electrochemical oxidation of the tartrate ligand of the Cu(II) complex leading to the CuO precipitation. The same bath can also be used to deposit Cu 2 O films using a cathodic electrodeposition process. In this case, cuprous oxide deposited onto a platinum electrode has a [111] preferred orientation.

Scanning tunneling microscopy of electrodeposited ceramic superlattices

Cleaved cross sections of nanometer-scale ceramic superlattices fabricated from materials of the lead-thallium-oxygen system were imaged in the scanning tunneling microscope (STM). The apparent height differences between the layers were attributed to composition-dependent variations in local electrical properties. For a typical superlattice, the measured modulation wavelength was 10.6 nanometers by STM and 10.8 nanometers by x-ray diffraction. The apparent height profile for potentiostatically deposited superlattices was more square than that for galvanostatically deposited samples. These results suggest that the composition follows the applied potential more closely than it follows the applied current. The x-ray diffraction pattern of a superlattice produced under potential control had satellites out to the fourth order around the (420) Bragg reflection.

Scanning probe nanolithography of conducting metal oxides

The scanning tunneling microscope (STM) was used to form nanometer-size holes in thin conducting films of thallium (III) oxide. Hole formation was only observed when the process was performed in humid ambient conditions. The hole formation was attributed to localized electrochemical etching reactions beneath the STM tip. Etching reactions consistent with the observed hole formation are a direct electrochemical reduction of thallium (III) oxide to soluble Tl (I) at negative sample bias, and local reduction of pH at positive sample bias. The fastest etching was observed at negative sample bias. Holes as small as 10 nm or as large as 1 μm in diameter could be etched in the films.