1D nanowires of non-centrosymmetric molecular semiconductors grown by physical vapor deposition

Abstract

Understanding how dipolar, non-centrosymmetric organic semiconductors self-assemble, nucleate, and crystallize is integral for designing new molecular solids with unique physical properties and light-matter interactions. However, dipole–dipole and van der Waals interactions compete to direct the assembly of these compounds, making it difficult to predict how solids are formed from individual molecules. Here, we investigate four small molecules (TpCPD, TpDCF, AcCPD, and AcDCF) possessing anisotropic, non-planar structures and large dipole moments, and establish robust algorithms to control their molecular self-assembly via simple physical vapor deposition. Each molecule contains a central polar moiety, consisting of either a cyclopentadienone (CPD, ca. 3.5 D dipole moment) or dicyanofulvene (DCF, ca. 7.0 D dipole moment) core, that is surrounded by either four twisted phenyl (Tp) groups or a fused aromatic (acenaphthene, Ac) ring system. We find that only molecules containing the fused ring system form 1D nanowires due to the stronger van der Waals associations of the long, planar acenaphthene moieties. We examine the kinetics of self-assembly for AcDCF and create diverse 1D morphologies, including both curved and linear nanostructures. Finally, using conductive AFM (c-AFM) measurements, we show that 1D AcDCF wires support higher current densities relative to randomly-oriented clusters lacking long-range order.