Gate-Controlled Sum-Frequency Vibrational Spectroscopy for Probing Charged Oxide/Water Interfaces

The rich chemistry of oxide/aqueous interfaces originates from the interfacial layer formed by surface charges and adjoining water molecules. Yet not much is clear about such layers, because they are difficult to access, and measurements unavoidably collect signals from the diffuse layer nearby, which is perturbed by the surface potential extending into the bulk water. Here we show that gating of a semiconductor/oxide/water junction can effectively vary the surface charge density at the oxide/water interface but keep the surface potential low and barely varying, allowing effective removal of the diffuse layer contribution. With sum-frequency vibrational spectroscopy on a silicon/silica/deionized-water model junction, the variation of the bonded layer water structure in response to surface charging can be readily detected. This new scheme is generally applicable to all oxide/water interfaces, providing opportunities for future investigations at a deeper molecular level.