Controllable electrode activities of nano-carbon films while maintaining surface flatness by electrochemical pretreatment

A carbon film consisting nanocrystallites with mixed sp² and sp³ bonds formed by using the electron cyclotron resonance (ECR) sputtering method was studied with respect to the changes in characteristics caused by electrochemical pretreatment (ECP). Unlike glassy carbon, our sputtered nanocrystalline carbon film deposited at an acceleration voltage of 75 V (ECR-75 nano-carbon film) largely retained its surface flatness after the ECP. This robust surface could be caused by an increase of 42% in the sp³ carbon realized by increasing the acceleration voltage during sputtering. The electrode activity of ECR-75 nano-carbon film was improved for surface sensitive species including Fe^3+/2+ unlike the boron doped diamond (BDD) electrode. This is because a sufficient quantity of surface sp² bonds remained and because the introduction of surface oxygen-containing groups is more efficient than with the BDD electrode. With pretreated ECR-75 nano-carbon film, the peak potential of glutathione was reduced solely due to the increase in the surface hydrophilicity with a sufficient quantity of surface sp² bonds, thus achieving the lowest detection limit (0.4 μM) ever obtained with carbon electrodes. We also achieved the stable measurement of 30 μM of serotonin (20 times) without the electrode surface fouling found with other electrodes.