In this work, NiO films were deposited by reactive radio frequency sputtering, varying either the oxygen flow or the power during deposition. The morphology was studied by atomic force microscopy. The Ni/O and Ni/H ratios were determined by Rutherford backscattering spectroscopy and forward recoil spectroscopy. The microstructure of pristine and colored or bleached films were investigated by means of X-ray diffraction. The electrochromic and mechanical behavior in aqueous alkaline electrolyte were investigated in situ. Samples deposited at low oxygen flow (or high power) are transparent, and have the highest Ni/O ratio and the lowest Ni/H ratio. The effective area is also greater for these samples. Samples deposited at high oxygen flow (or low power) are dark brown and present the lowest Ni/O ratio and the highest Ni/H ratio. For all samples, the Ni/O ratio is lower than 1. All films were cubic NiO, with preferred orientation in the (111) direction. Lattice parameters and crystalline grain size increase with the increase of oxygen flow (or decrease of power) during deposition. The highest optical contrast and lowest stress changes upon intercalation were obtained for samples deposited at low oxygen flow. Nonintentional, low-size dopants, like H, favor the mechanical stability of the films.
The electrochromic properties of transition metal oxides are a consequence of an ion/electron intercalation process. In nickel oxide electrodes, the electrochemical/electrochromic reaction has been pointed out to be a proton/electron intercalation process. However, recent works showed that the mechanism of the reaction could be much more complex. In this work, we studied the electrochemical reactions of r.f. sputtered thin nickel oxide films in aqueous electrolytes containing different cations.An electrochemical quartz crystal microbalance has been used in order to follow the mass changes during the experiments. Also, the mechanical stress changes has been measured in situ by an optical technique. The results showed that the incorporation of the cations in the film has to be considered; possible reaction mechanisms are discussed in this work.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.