n-type and p-type silicon of various dopant concentrations (10 14 to 10 19 cm −3 ) are electrochemically characterized in a 1% hydrogen fluoride (HF) electrolyte with voltammetry, electrochemical impedance spectroscopy (EIS), and Mott−Schottky analysis. Voltammograms in conjunction with Mott−Schottky analysis are used to assign the EIS features to the underlying physical processes. The high-frequency (hf) semiconductor features (depletion for n-type Si and accumulation for p-type Si) are strongly influenced by the cathodic overpotentials (−0.4 to −1.5 V) and dopant concentration and are not apparent in the Nyquist plots. With an increase in dopant concentration, Si shows features similar to that of metals, with an hf reminiscence of the spacecharge capacitance. Nevertheless, the mid-frequency (mf) semicircle corresponding to the double layer dominates the EIS features. Moreover, at further lower potentials, various low-frequency (lf) features corresponding to the hydride formation and hydrogen evolution reaction are observed.
The rate of electron-transfer reactions, irrespective of electrochemical or electrocatalytic, is universally explained on the basis of the Butler-Volmer (B-V) theory. The charge-transfer coefficient (α) obtained is typically in the...
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