In this research, a model for electrodeposition of zinc oxide (ZnO) nanostructures over indium-doped tin-oxide (ITO) glass using pulsed current and zinc chloride as source of zinc was proposed. For the model, reactions kinetics rate constants were evaluated by obtaining the reaction product solid mass of the various species through time using an electrochemical quartz crystal microbalance (EQCM). To obtain a mathematical model of the electrodeposition using Ansys CFX 2D simulation software, the reaction kinetics rates were used to calculate mass transfer in the volume closest to the surface. The model was applied to the experimental electrodeposition conditions to validate its accuracy. Dense wurtzite nanostructures with controlled morphology were obtained on a indium-doped tin-oxide (ITO) glass. Sample characterization was performed using high-resolution field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) on focused ion beam milled (FIBed) sheets from wurtzite mono-crystals. Average crystallite size was evaluated by X-ray diffraction (XRD) using the Scherrer equation, and superficial areas were evaluated by Brunauer, Emmett, and Teller (BET) method. Through the experimental results, a chemical model was developed for the competing reactions based on the speciation of zinc considering pH evolution, and kinetic constants, on the oxygen rich aqueous environment. Owing to the model, an accurate prediction of thickness and type of electrodeposited layers, under given conditions, is achieved. This allows an excellent control of the optical properties of Wurtzite as a photon absorber, for an efficient separation of the electron-hole pair for conduction of the electric charges formed. The large surface area, and small wurtzite crystallites evenly distributed on the thin film electrodeposited over the ITO conductive layer are promising features for later dye-sensitized photovoltaic cell production.
Keywords: ZnO; electrochemical modelling; morphology control; nanorods.