Electro-oxidation of p-silicon in fluoride-containing electrolyte: a physical model for the regime of negative differential resistance

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.