Photo-Induced Charge Transfer in Single-Molecule p-n Junctions.

We measured photoinduced charge separation in isolated individual C69 tethered 2,5-dithienylpyrrole triad (C-60 triad) molecules with submolecular resolution using a custom-built laser-assisted scanning tunneling microscope. Laser illumination was introduced evanescently into the tunneling junction through total internal reflection, and the changes in tunneling current and electronic spectra caused by photoexcitation were measured and spatially resolved. Photoinduced charge separation was not detected for all C-60 triad molecules, indicating that the conformations of the molecules may affect the excitation probability, lifetime, and/or charge distribution. A photoinduced signal was not observed for dodecanethiol molecules in the surrounding matrix or for control molecules without C-60 moieties, as neither absorbs incident photons at this energy. This spectroscopic imaging technique has the potential to elucidate detailed photoinduced carrier dynamics, which are inaccessible via ensemble-scale (i.e., averaging) measurements, which can be used to direct the rational design and optimization of molecular p n junctions and assemblies for energy harvesting.