Electrochemical reduction of O-2 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid containing Zn2+ cations: deposition of non-polar oriented ZnO nanocrystalline films

The influence of the Zn2+ concentration and temperature on the electrochemical reduction of O-2 in a solution of zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)(2)) salt in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) ionic liquid is presented. ZnO nanocrystalline films were then electrodeposited, under enhanced O-2 reduction, at temperatures in the 75-150 degrees C range. Their morphology, chemical composition, structural and optical properties were analyzed. In contrast to the polar-oriented ZnO usually obtained from aqueous and conventional solvent based electrolytes, nanocrystalline films oriented along non-polar directions, (11 (1) over bar0) and (11 (2) over bar0), were obtained from this ionic liquid electrolyte. A significant content of carbon was detected in the films, pointing to the active participation and crucial effect of pyrrolidinium cation (and/or byproducts) during the electrodeposition. The films showed semiconducting behavior with an optical gap between 3.43 and 3.53 eV as measured by optical transmittance. Their room temperature photoluminescence spectra exhibited two different bands centered at similar to 3.4 and similar to 2.2 eV. The intensity ratio between both bands was found to depend on the deposition temperature. This work demonstrates the great potential of ionic liquids based electrolytes for the electrodeposition of ZnO nanocrystalline thin films with innovative microstructural and optoelectronic properties.