Self-Assembly of Porphyrins on a Single Crystalline Organic Substrate

Layers of a free base porphyrin have been deposited from n-heptane solution onto single crystalline potassium acid phthalate substrates and the self-assembled structures have been characterized by atomic force microscopy and X-ray diffraction. Depending on the concentration of the porphyrin solution, different anisotropic structures are found that are epitaxially related to the substrate, with the length axis parallel to the [001] direction of the (010) substrate surface. For undersaturated solutions, islands, cellular structures, and a hole pattern of monolayers of approximately 2.5 nm height are formed, which correspond to porphyrin molecules stacking approximately perpendicular to the substrate surface. From supersaturated solutions, multilayers are formed. At the highest concentrations, nanosized needles develop, which cover the whole substrate, creating a “monocrystalline” film with a length scale of several millimeters.