The electrodissolution of p-type silicon in a fluoride-containing electrolyte is a prominent electrochemical oscillator with a still unknown oscillation mechanism. In this article, we present a study of its dynamical states occurring in a wide range of the applied voltage–external resistance parameter plane. We provide evidence that the system possesses inherent birhythmicity, and thus at least two distinct feedback loops promoting oscillatory behavior. The two parameter regions in which the different limit cycles exist are separated by a band in which the dynamics exhibit bistability between two branches with different multimode oscillations. Following the states along one path through this bistable region, one observes that each branch undergoes a different transition to chaos, namely, a period doubling cascade and a quasiperiodic route with a torus-breakdown, respectively, making Si electrodissolution one of the few experimental systems exhibiting bichaoticity.
Using dynamic multifrequency analysis (DMFA), we investigated the oscillatory reaction dynamics that govern the anodic electrodissolution of p‐type silicon in fluoride‐containing electrolytes, in which the anodization of silicon is followed by the chemical etching of the oxide layer. By applying a constant voltage to the silicon electrode, stable oscillations are found in the presence of an external resistance. The dynamic impedance spectra acquired through DMFA were fitted to a suitable electrical equivalent circuit. In doing so, it was possible to investigate the temporal evolution of the kinetic parameters throughout the formation and dissolution of the silicon oxide.
When Si is anodically oxidized in a fluoride containing electrolyte, an oxide layer is grown. Simultaneously, the layer is etched by the fluoride containing electrolyte. The resulting stationary state exhibits a negative slope of the current-voltage characteristics in a certain range of applied voltage. We propose a physical model that reproduces this negative slope. In particular, our model assumes that the oxide layer consists of both partially and fully oxidized Si and that the etch rate depends on the effective degree of oxidation. Finally, we show that our simulations are in good agreement with measurements of the current-voltage characteristics, the oxide layer thickness, the dissolution valence, and the impedance spectra of the electrochemical system.
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