Controlling the Dynamics of Ionic Liquid Thin Films via Multilayer Surface Functionalization.

The structural dynamics of planar thin films of an ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimNTf2) as a function of surface charge density and thickness were investigated using two-dimensional infrared (2D IR) spectroscopy. The films were made by spin coating a methanol solution of the IL on silica substrates that were functionalized with alkyl chains containing head groups that mimic the IL cation. The thicknesses of the ionic liquid films ranged from ∼50 to ∼250 nm. The dynamics of the films are slower than those in the bulk IL, becoming increasingly slow as the films become thinner. Control of the dynamics of the IL films can be achieved by adjusting the charge density on substrates through multilayer network surface functionalization. The charge density of the surface (number of positively charged groups in the network bound to the surface per unit area) is controlled by the duration of the functionalization reaction. As the charge density is increased, the IL dynamics become slower. For comparison, the surface was functionalized with three different neutral groups. Dynamics of the IL films on the functionalized neutral surfaces are faster than on any of the ionic surfaces but still slower than the bulk IL, even for the thickest films. These results can have implications in applications that employ ILs that have electrodes, such as batteries, as the electrode surface charge density will influence properties like diffusion close to the surface.