The prototypical organic-oxide interface: intra-molecular resolution of sexiphenyl on In$_2$O$_3$(111)

Abstract: The performance of an organic-semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. While an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material is essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In$_2$O$_3$(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide (ITO) is based on. The onset of nucleation and formation of the first monolayer are followed with atomically-resolved scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Annealing to 200$^\circ$C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests a twisted adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with poor long-range order. Eventually the molecules re-orient and form an ordered monolayer. This first monolayer has a densely packed, well-ordered (2$\times$1) structure with one 6P per In$_2$O$_3$(111) substrate unit cell, i.e., a molecular density of 5.64$\times$10$^{13}$ cm$^{-2}$.