- The physical properties of interfaces between organic semiconductors and metal surfaces crucially influence the performance of organic electronic devices. In order to enable the tailoring of such metal–organic hybrid interfaces we study the adsorption of heteromolecular thin films containing the prototypical molecules copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) on the Ag(111) surface. Here, we demonstrate how the lateral order can be tuned by changing the relative coverage of both adsorbates on the surface. The layer growth has been studied in real time with low energy electron microscopy, and—for different stoichiometries—the geometric properties of three heteromolecular submonolayer phases have been investigated using high resolution low energy electron diffraction and low temperature scanning tunneling microscopy. Furthermore, we have used a theoretical approach based on van der Waals and electrostatic potentials in order to reveal theThe physical properties of interfaces between organic semiconductors and metal surfaces crucially influence the performance of organic electronic devices. In order to enable the tailoring of such metal–organic hybrid interfaces we study the adsorption of heteromolecular thin films containing the prototypical molecules copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) on the Ag(111) surface. Here, we demonstrate how the lateral order can be tuned by changing the relative coverage of both adsorbates on the surface. The layer growth has been studied in real time with low energy electron microscopy, and—for different stoichiometries—the geometric properties of three heteromolecular submonolayer phases have been investigated using high resolution low energy electron diffraction and low temperature scanning tunneling microscopy. Furthermore, we have used a theoretical approach based on van der Waals and electrostatic potentials in order to reveal the influence of the intermolecular and the molecule–substrate interactions on the lateral order of heteromolecular films.…