Electrochemical tailoring of lamellar-structured ZnO films by interfacial surfactant templating.

Zinc oxide films with ordered lamellar structures can be electrochemically produced by interfacial surfactant templating. This method utilizes amphiphile assemblies at the solid-liquid interface (i.e., the surface of a working electrode) as a template to electrodeposit inorganic nanostructures. To gain the ability to precisely tailor inorganic lamellar structures, the effect of various chemical and electrochemical parameters on the repeat distances, homogeneity, orientation, and quality of the interfacial amphiphilic bilayers were investigated. Surfactants with anionic headgroups (e.g., 1-hexadecanesulfonate sodium salt, dodecylbenzenesulfonate sodium salt, dioctyl sulfosuccinate sodium salt, mono-dodecyl phosphate, and sodium dodecyl sulfate) are critical because they incorporate Zn(2+) ions into their bilayer assemblies as counterions and guide the lamellar growth of ZnO films. Unlike surfactant structures in solution, the interfacial surfactant assemblies are insensitive to the surfactant concentration in solution. The use of organic cosolvents (e.g., ethylene glycol, dimethyl sulfoxide) can increase the homogeneity of bilayer assemblies when multiple repeat distances are possible in a pure aqueous medium. In addition, organic cosolvents can make the interfacial structure responsive to the change in bulk surfactant concentrations. The presence of quaternary alkylammonium salts (e.g., cetyltrimethylammonium bromide) as cationic cosurfactants improves the ordering of anionic bilayers significantly. Consequently, it also affects the orientation of lamellar structures relative to the substrate as well as the surface texture of the films. The quality of lamellar structures incorporated in ZnO films is also dependent on the deposition potentials that determine deposition rates. A higher degree of ordering is achieved when a slower deposition rate (I < 0.15 mA/cm(2)) is used. The results described here will provide a useful foundation to design and optimize synthetic conditions for the electrochemical construction of broader types of inorganic nanostructures.