Electrochemical Deposition of a Single‐Crystalline Nanorod Polycyclic Aromatic Hydrocarbon Film with Efficient Charge and Exciton Transport

Electrochemical deposition has emerged as an efficient technique for preparing conjugated polymer films on electrodes. However, this method encounters difficulties in synthesizing crystalline products and controlling their orientation on electrodes. Here we report electrochemical film deposition of a large polycyclic aromatic hydrocarbon. The film is composed of single‐crystalline nanorods, in which the molecules adopt a cofacial stacking arrangement along the π–π direction. Film thickness and crystal size can be controlled by electrochemical conditions such as scan rate and electrolyte species, while the choice of anode material determines crystal orientation. The film supports exceptionally efficient migration of both free carriers and excitons: the free carrier mobility reaches over 30 cm(2) V(−1) s(−1), whereas the excitons are delocalized with a low binding energy of 118.5 meV and a remarkable exciton diffusion length of 45 nm.