Mechanistic study of the electrodeposition of nanoporous self-assembled ZnO/eosin Y hybrid thin films:: Effect of eosin concentration

ZnO films prepared by one-step electrodeposition in the presence of dissolved eosin molecules present an internal nanoporous hybrid structure resulting from self-assembling processes occurring in solution between ZnO and eosin components. This study aims to better understand the underlying growth mechanism, which is still unexplained. The films were deposited by cathodic electrodeposition from an oxygen-saturated aqueous zinc chloride solution. The effects of the addition of 10 to 100 mu mol center dot L-1 eosin Y, as a sodium salt, on the growth rate and film properties, were systematically studied while all other parameters remained constant (concentrations of zinc salt and supporting electrolyte, applied potential of-1.4V versus the mercurous sulfate electrode (MSE), temperature of 70 degrees C, rotating disk electrode at 300 rotations per min, and a glass-coated tin oxide electrode). It is shown that the addition of eosin provokes the formation of a nanoporous "cauliflower" structure whose nodule size and composition depend on the eosin concentration in the bath. The growth rate of the hybrid films increases markedly with the eosin concentration. The ZnO and eosin contents of the films are determined for each concentration by chemical analysis. Comparing with thickness determinations, it is shown that the total porosity increases up to 60-65% in volume fraction toward an eosin concentration of 100 mu mol center dot L-1. The empty pore volume fraction increases up to about 30% at an eosin concentration of about 20 mu mol center dot L-1 and then decreases. These correlations have been precisely established for the first time. It is shown that the global composition is fixed by the relative rate of deposition for zinc oxide, which is constant, and for the relative rate of eosin inclusion, which is proportional to the concentration in solution. This is explained on the basis of different steps in the growth mechanism, in particular, a diffusion effect limitation for both oxygen and eosin. This variation explains part of the increase in the growth rate. Another contribution is related by the structural effect on the nanoscale leading to the formation of the interpenetrated porous network. Competition between empty and eosin-filled parts of the pore network is evidenced. The formation of the porous network structure could be governed by a diffusion-limited aggregation mechanism. The system may represent a reference case of competing reactions in the electrochemical self-assembly of hybrid nanostructures.