Abstract
Electron transfer processes at n‐type 
electrodes of moderate to low doping density were investigated by monitoring the cyclic voltammetric dark currents of a series of metallocenes in acetonitrile solutions. The formal reduction potentials of the metallocenes span the bandgap of 
, allowing a comparison of the cyclic voltammetric response as a function of the formal reduction potential and the energetic condition of the electrode surface. The energetic condition of the electrode surface during the cyclic voltammetry experiments was monitored by measurements of the capacitance of the space charge region. A simple chemical etching and electrochemical cycling procedure yielded reproducible surface energetics. The 
interface in the depletion condition responded ideally to changes in electrode potential, as evidenced by linear Mott‐Schottky plots, over a range of about 0.9V. It was possible to achieve an accumulation condition at negative potentials, but the interface could not be inverted at positive potentials. The 
interface is less susceptible to surface oxidation than is the 
interface. For each metallocene 
couple, the reversibility of cyclic voltammetric (CV) waves at 
was dependent on the doping density of the electrode
and the proximity of the formal reduction potential 
to the conduction bandedge 
. Couples with 
located negative of 
displayed nearly reversible CV waves. Couples with 
located in the bandgap were reduced irreversibly at overvoltages of 400–500 mV. A couple with 
located slightly positive of 
yielded a partially reversible CV wave at moderate 
, but the wave became irreversible at low 
. Oxidation of couples with 
positive of −0.5V vs. 
for ferricenium/ferrocene was not observed.