Comparative studies of pentacene and perfluoropentacene grown on a Bi(0001) surface.

We report two distinct growth modes of pentacene (PEN) and perfluoropentacene (PFP) films on a Bi(0001) substrate investigated by scanning tunneling microscopy (STM). PEN grows epitaxially on Bi(0001) at room temperature (RT), resulting in the formation of bulk-like crystalline films. In contrast, submonolayer PFP forms a two-dimensional (2D) liquid-like phase with PFP molecules loosely bound on Bi(0001). Beyond one monolayer, the PFP molecules diffuse over very long distances to aggregate into three-dimensional (3D) islands, leading to a rough film morphology. Utilizing the stacking interaction at the PFP/PEN interface, we deposited PFP on the template of an ordered PEN monolayer formed on Bi. It is found that PFP molecules nucleate into ordered crystalline islands with PFP molecules standing-up. The different morphologies of PEN and PFP overlayers can be understood in terms of perfluorination induced decoupling of PFP molecules from the Bi substrate below.