p-Si type electrodes modified with different organic monolayers were investigated by reaction with radical anion and
cation electrogenerated at a microelectrode operating in
the configuration of a scanning electrochemical microscope. The method proves to be a convenient tool for
investigating both the quality and the redox properties of
the layer as previously demonstrated on metallic electrodes especially when the sample cannot be electrically
connected. Approach curves recorded with the different
mediators were used to investigate the electron-transfer
rates across alkyl monolayers bound to p-type silicon
substrates. Preliminary results indicate that the interfacial
electron transfer occurs via electron tunneling through the
organic layer as generally described for SAMs grafted on
gold electrodes