Direct observation of adsorption geometry for the van der Waals adsorption of a single π-conjugated hydrocarbon molecule on Au(111)

Weak van der Waals adsorption of pi-conjugated hydrocarbon molecules onto the gold surface, Au(111), is one of the essential processes in constructing organic-metal interfaces in organic electronics. Here we provide a first direct observation of adsorption geometry of a single p-conjugated hydrocarbon molecule on Au(111) using an atomically resolved scanning tunneling microscopy study combined with van der Waals density functional methodology. For the purpose, we utilized a highly symmetric pi-conjugated hydrocarbon molecule, dehydrobenzo[12] annulene (DBA), which has a definite three-fold symmetry, the same as the Au(111) surface. Interestingly, our observations on an atomically resolved scale clearly indicate that the DBA molecule has only one adsorption configuration on Au(111) in spite of the weak van der Waals adsorption system. Based on the precisely determined adsorption geometry of DBA/Au(111), our calculation results imply that even a very small contribution of the interfacial orbital interaction at the organic-metal interface can play a decisive role in constraining the adsorption geometry even in the van der Waals adsorption system of a pi-conjugated hydrocarbon molecule on the noblest Au(111) surface. Our observations provide not only deeper insight into the weak adsorption process, but also new perspectives to organic electronics using pi-conjugated hydrocarbon molecules on the Au surface. (C) 2014 AIP Publishing LLC.