Surface Self-Assembly, Film Morphology, and Charge Transport Properties of Semiconducting Triazoloarenes.

Surface-assisted molecular self-assembly is a powerful strategy for forming molecular-scale architectures on surfaces. These molecular self-assemblies have potential applications in organic electronics, catalysis, photovoltaics, and many other technologies. Understanding the intermolecular interactions on a surface can help predict packing, stacking, and charge transport properties of films and allow for new molecular designs to be tailored for a required function. We have previously studied a molecular platform, tris( N-phenyltriazole) (TPT), that exhibits planar stacking through >20 molecular layers through donor-acceptor-type intermolecular π-π contacts between the electron-deficient tris(triazole) core and electron-rich peripheral phenyl units. Here, we investigate an expanded family of TPT-based molecules with variations made on the peripheral aryl groups to modulate the molecular electron distribution and examine the impact on molecular packing and charge transport properties. Molecular-resolution scanning tunneling microscopy was used to compare the molecular packing in the monolayer and to investigate the effects that the structural and electronic modifications have on the stacking in subsequent layers. Conductivity measurements were made using the four-point probe van der Pauw technique to demonstrate charge transport properties comparable to pentacene. Although molecular packing is clearly impacted by the chemical structure, we find that the charge transport efficiency is quite tolerant to small structural variations.