Role of surface electronic structure in thin film molecular ordering

We show that the orientation of pentacene molecules is controlled by the electronic structure of the surface on which they are deposited. We suggest that the near-Fermi level density of states above the surface controls the interaction of the substrate with the pentacene π orbitals. A reduction of this density as compared to noble metals, realized in semimetallic Bi(001) and Si(111)(5×2)Au surfaces, results in pentacene standing up. Interestingly, pentacene grown on Bi(001) is highly ordered, yielding the first vertically oriented epitaxial pentacene thin films observed to date. © 2005 The American Physical Society.