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The use of an electrolyte as a gate electrode and the reference electrode to establish the gate potential is called electrochemical gating. The operating principle of this technique is that the Fermi energy of the source and drain electrodes can be raised or lowered by controlling their potentials with respect to the reference electrode. For example, driving the source electrode to more positive potentials (with respect to the reference) lowers the Fermi energy and hence the energy of the electrons within the electrode. The positive charge on the source electrode is balanced by anions in the electrolyte. The presence of excess electrolyte anions, in turn, raises the orbital energy of the surface-bound redox species. Oxidation of the redox species ensues when the potential of the source electrode reaches a level positive enough to accept an electron from the redox species.
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A referee has asked how we excluded interpenetration of the monolayers. Although we cannot rule out the possibility that the two opposing SAMs interpenetrate, the fact that negligible electron transfer occurs between an electrode and the redox centers on the neighboring electrode is consistent with the mechanism proposed in Figure 3.
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