Electron Tunneling and Electrochemical Currents through Interfacial Water Inside an STM Junction

The apparent barrier height for charge transfer through an interfacial water layer between a Pt/Ir tip and a gold surface has been measured using STM technique. The average thickness of the interfacial water layer inside an STM junction was controlled by the amount of moisture. A thin water layer on the surface was formed when relative humidity was in the range of 10 to 80%. In such a case, electron tunneling through the thin water layer became the majority of charge transfers. The value of the barrier height for the electron tunneling was determined to be 0.95 eV from the current vs. distance curve, which was independent of the tip-sample distance. On the other hand, the apparent barrier height for charge transfer showed a dependence on tip-sample distance in the bias range of 0.1-0.5 V at a relative humidity of approximately 96%. The non-exponentiality for current decay under these conditions has been explained in terms of electron tunneling and electrochemical processes. In addition, the plateau current was observed at a large tip-sample distance, which was caused by electrochemical processes and was dependent on the applied voltage.