Time- and Temperature-Dependent Growth Behavior of Ionic Liquids on Au(111) Studied by Atomic Force Microscopy in Ultrahigh Vacuum

[Image: see text] We deposited defined amounts of [C(1)C(1)Im][Tf(2)N] on Au(111) at different temperatures and investigated the morphology and wetting behavior of the deposited films by atomic force microscopy. For multilayer coverages, we observe a drastically different growth behavior when comparing deposition at room temperature (RT) and deposition below 170 K followed by slow annealing to RT. Upon deposition at RT, we find the formation of 2–30 nm high and 50–500 nm wide metastable 3D droplets on top of a checkerboard-type wetting layer. These droplets spread out into stable 2D bilayers, on the time scale of hours and days. The same 2D bilayer structure is obtained after deposition below 170 K and slow annealing to RT. We present a statistical analysis on the time-dependent changes of the shape and volume of the 3D droplets and the 2D bilayers. We attribute the stabilization of the 2D bilayers on the wetting layer and on already formed bilayers to the high degree of order in these layers. Notably, the transformation process from the 3D droplets to 2D bilayer islands is accelerated by tip effects and also X-ray radiation.