Pockels effect of water in the electric double layer at the interface between water and transparent electrode

We have obtained the first experimental evidence for the Pockels effect of water, which is induced by a high electric field in the electric double layer (EDL) on the water–transparent electrode interface. The electric-field induced energy shift of the visible interference fringes of a 300 nm indium–tin–oxide (ITO) electrode layer is observed, indicating a negative refractive index change at the interface. Numerical calculation reproduces well the experimental observation, showing that the signal mainly originates from water in the EDL. The Pockels constants of water are estimated to be r33 = 5.1 × 100 pm/V and r13 = 1.7 × 100 pm/V. The large anisotropy of the Pockels effect of water is deduced from the incidence angle dependence of the p-polarization signal. At the same time, the ITO shows a blue shift of the band gap in the UV due to the band population effect in the space charge layer. The plasma frequency in the near IR is also expected to increase due to the band population effect, since the ITO has a high doped carrier population close to metal. A negative refractive index change in the ITO space charge layer is induced from both effects, but its effect on the signal is estimated to be much smaller than that of the negative refractive index change of water in the EDL.