Journal of Electroanalytical Chemistry, Vol.486, No.2, 190-203, 2000
A model for electrochemical oscillations at the Si vertical bar electrolyte contact Part II. Simulations and experimental results
Specifications of the theoretical model (article I) on electrochemical oscillations at silicon electrodes are made. The specifications concern: (i) the first synchronization state p(I)(t) which is derived using the experimental observation that oxide growth on the initially bare silicon surface occurs by nucleation of islands with finite size; (ii) the development of the probability distribution q(i,s)((t) over bar) for the periods of the thickness oscillators involves oxide growth and an etching mechanism based on crack and pore formation due to lattice mismatch; (iii) the shape of the elementary current peak E-i((t) over bar) is determined by simultaneous passivation and etching during the growth phase of a thickness oscillator. The model describes damped as well as sustained oscillations. Damped oscillations are obtained for an almost constant shape of q(i,s)((t) over bar). This corresponds to an almost constant morphological defect density during a cycle. For sustained oscillations, a feedback mechanism is introduced modeled by the contraction of q(i,s)((t) over bar) during a cycle. This reflects the increasing defect density towards the end of a cycle where oxides formed later are etched faster. Hence synchronization is due to the local etching behavior. It is shown that the model is able to reproduce various experimental data. Besides the simulation of damped and sustained current oscillations, rather complicated cases such as the setting behavior and results on semi-immersed electrodes can also be reproduced very well.