Ordering of Small Molecules on Hydrophobic Self-Assembled n‑Alkanethiols: Delicate Balance of Interfacial and Intermolecular Interactions

Growth of molecular thin films with desired orders and orientations has become technologically relevant as the electronic industries seek new opportunities and applications. However, the delicate balance of interfacial and intermolecular forces and their complex influence on thin-film growths still require more understanding. Here, the effects of a hydrophobic self-assembled monolayer (SAM) surface on the crystallization of four common solventsacetonitrile, ethanol, methanol, and waterare investigated. Despite the absence of significant substrate–molecule forces, unexpected oriented growth is observed for these molecules except water. Acetonitrile and ethanol form a sustaining vertical assembly order with long-range crystalline structures. Coincident epitaxy with small lattice mismatches is found to be essential to these orderings, which are energetically favored but without a dominant azimuthal orientation. In contrast, a preferred in-plane registry of methanol overlayers is observed for an ultrathin nominal thickness and becomes lost in slightly thicker films. Such thickness-dependent ordering of methanol assemblies can be explained with semi-commensurate epitaxy with a tensile strain of ∼6.6% along hydrogen-bonded chains, whose quick relief results in the loss of order and even the phase. These rich observations suggest that SAM surfaces offer good opportunities for selective crystallization of molecular films worthy of further investigations.