Effects of ion energy and arrival rate on the composition of zirconium oxide films prepared by ion-beam assisted deposition

Thin zirconium oxide films were grown using the ion-beam assisted deposition method. Zirconium metal was evaporated by an electron beam and condensed on a Si substrate, while oxygen ions were directed simultaneously onto the substrate, allowing the fundamental deposition parameters of ion energy and arrival rate ratio ARR(O/Zr) to be measured and controlled easily. X-ray photoelectron spectroscopy (XPS) was used to study the oxidation and the composition of the films. XPS analyses indicated the presence of four oxidation states of zirconium (Zr4+−Zr1+) in Zr 3d spectra and two peaks in O 1s spectra; Zr4+ is a predominant ion in all the films and the two peaks in O 1s spectra are related to the oxide and to hydroxyl groups and/or carbonates, respectively. Composition analyses of the films suggested that these oxygen-associated species may be bound to zirconium. The variation of composition as a function of ion energy (from 2 to 20 keV) and ARR(O/Zr) (at 0.54 and 1.09) could be explained with the preferential sputtering of zirconium from the growing film by incoming oxygen ions and the incorporation of oxygen ions into the film.