Electrochemical investigations of ion-implanted oxide films

Oxide films (passive films) of 40-50 nm thickness were prepared by anodic polarization of hafnium and titanium electrodes up to 20 V. Multiple-energy ion implantation of palladium, iron and xenon was used in order to obtain modified films with constant concentration profiles of the implanted ions. Rutherford backscattering, X-ray photoelectron spectroscopy measurements and electrochemical charging curves prove the presence of implanted ions, but electrochemical and photoelectrochemical measurements indicate that the dominating effect of ion implantation is the disordering of the oxide film. The capacity of hafnium electrodes increases as a result of an increase in the dielectric constant D. For titanium the Schottky-Mott analysis shows that ion implantation causes an increase in D and the donor concentration N. Additional electronic states in the band gap which are created by the implantation improve the conductivity of the semiconducting or insulating films. This is seen in the enhancement of electron transfer reactions and its disappearance during repassivation and annealing. Energy changes in the band gap are derived from photoelectrochemical measurements; the absorption edge of hafnium oxide films decreases by approximately 2 e V because of ion implantation, but it stays almost constant for titanium oxide films. All changes in electrochemical behavior caused by ion implantation show little variation with the nature of the implanted ion. Hence the dominating effect seems to be a disordering of the oxide.