Cross-impact of surface and interaction anisotropy in the self-assembly of organic adsorption monolayers: a Monte Carlo and transfer-matrix study

Abstract

Using a simple lattice gas model we study the features of self-assembly in adsorption layers where both “molecule–surface” and “molecule–molecule” interactions are anisotropic. Based on the example of adsorption layers of mono-functional organic molecules on the heterogeneous surface with strip-like topography, we have revealed plenty of possible self-assembled structures in this simple system, such as discrete, linear, zigzag, chess board-like, two-dimensional porous and close-packed patterns. However, the phase behavior of the adsorption layer is much richer, if the interactions between functional and non-functional parts of adjacent adsorbed molecules have comparable strength and opposite signs. It is demonstrated that filling of the strips composed of relatively “strong” adsorption sites with the increase of chemical potential can be non-monotonic. This effect is associated with surface anisotropy and results from the changing of the driving force of the self-assembly process – interactions between the adsorbed molecule and the surface dominate at low surface coverages, but intermolecular forces prevail at higher ones. Additionally, when the width of the strip composed of “strong” adsorption sites is two or more times greater than that of the adsorbed molecule, a local assembly of the ordered phases on the “strong” adsorption sites is observed. Our results suggest strategies for controlling the self-assembly in experiments involving mono-functional organic molecules on a strip-like heterogeneous surface.