Voltage-induced modulation of interfacial ionic liquids measured using surface plasmon resonant grating nanostructures

• Published in: The Journal of chemical physics 2024-07, Vol.161 (3)
• Main Authors: Aravind, Indu, Wang, Yu, Cai, Zhi, Li, Ruoxi, Shahriar, Rifat, Gibson, George N., Guignon, Ernest, Cady, Nathaniel C., Page, William D., Pilar, Arturo, Cronin, Stephen B.
• Format: Article
• Language: English
• Subjects: Benzene; Electric double layer; Electric fields; Electrodes; Electrolytes; Finite difference time domain method; Gratings (spectra); Ionic liquids; Modulation; Reflection; Refraction; Refractivity; Surface plasmon resonance; Thickness
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0202642

We have used surface plasmon resonant metal gratings to induce and probe the dielectric response (i.e., electro-optic modulation) of ionic liquids (ILs) at electrode interfaces. Here, the cross-plane electric field at the electrode surface modulates the refractive index of the IL due to the Pockels effect. This is observed as a shift in the resonant angle of the grating (i.e., Δϕ), which can be related to the change in the local index of refraction of the electrolyte (i.e., Δnlocal). The reflection modulation of the IL is compared against a polar (D2O) and a non-polar solvent (benzene) to confirm the electro-optic origin of resonance shift. The electrostatic accumulation of ions from the IL induces local index changes to the gratings over the extent of electrical double layer (EDL) thickness. Finite difference time domain simulations are used to relate the observed shifts in the plasmon resonance and change in reflection to the change in the local index of refraction of the electrolyte and the thickness of the EDL. Simultaneously using the wavelength and intensity shift of the resonance enables us to determine both the effective thickness and Δn of the double layer. We believe that this technique can be used more broadly, allowing the dynamics associated with the potential-induced ordering and rearrangement of ionic species in electrode–solution interfaces.