Direct observation of the double-layering quantized growth of mica-confined ionic liquids

Since the interface between ionic liquids (ILs) and solids always plays a critical role in important applications such as coating, lubrication, energy storage and catalysis, it is essential to unravel the molecular structure and dynamics of ILs confined to solid surfaces. Here we report direct observation of a unique double-layering quantized growth of three IL (i.e. [Emim][FAP], [Bmim][FAP] and [Hmim][FAP]) nanofilms on mica. AFM results show that the IL nanofilms initially grow only by covering more surface areas at the constant film thickness of 2 monolayers (ML) until a quantized increase in the film thickness by another 2 ML occurs. Based on the AFM results, we propose a double-layering model describing the molecular structure of IL cations and anions on the mica surface. The interesting double-layering structure can be explained as the result of several competing interactions at the IL-mica interface. Meanwhile, the time-dependent AFM results indicate that the topography of IL nanofilms could change with time and mobility of the nanofilm is lower for ILs with longer alkyl chains, which can be attributed to the stronger solvophobic interaction. The findings here have important implications on the molecular structure and dynamics of ILs confined to solid surfaces.