We investigate photocurrents driven by femtosecond laser excitation of a (sub)-nanometer tunnel junction in an ultrahigh vacuum low-temperature scanning tunneling microscope (STM). The optically driven charge transfer is revealed by tip retraction curves showing a current contribution for exceptionally large tip-sample distances, evidencing a strongly reduced effective barrier height for photoexcited electrons at higher energies. Our measurements demonstrate that the magnitude of the photo-induced electron transport can be controlled by the laser power as well as the applied bias voltage. In contrast, the decay constant of the photocurrent is only weakly affected by these parameters. Stable STM operation with photoelectrons is demonstrated by acquiring constant current topographies. An effective non-equilibrium electron distribution as a consequence of multiphoton absorption is deduced by the analysis of the photocurrent using a one-dimensional potential barrier model.

We present a combination of pulsed optical excitation and scanning tunneling microscopy with a highly flexible pulse generation method. A high frequency arbitrary wave generator drives a gigahertz electro-optical modulator, which processes a continuous-wave laser beam of a low-noise laser diode into the desired wave shape. For pump-probe excitation we generate optical pulse series in an all-electronic way. Thereby we can easily adapt parameters like pulse amplitude, width, or repetition cycle to the demands of the experiment. This setup is used to study different dynamic processes at the GaAs(110) surface. Separating thermally induced effects from electrically induced effects allows us to quantify the thermal contribution of the optical excitation in STM experiments. Time-resolved decay spectra of the photo-generated electron-hole pairs demonstrate the nanoscale spatial resolution.

Atomic scale studies of the anchoring of catalytically active complexes to surfaces may provide valuable insights for the design of new catalytically active hybrid systems. In this work, the self-assembly of 1D, 2D and 3D structures of the complex fac-Re(bpy)(CO)3Cl (bpy = 2,2′-bipyridine), a CO2 reduction catalyst, on the Ag(001) surface are studied by a combination of low-temperature scanning tunneling microscopy and density functional theory calculations. Infrared and sum frequency generation spectroscopy confirm that the complex remains chemically intact under sublimation. Deposition of the complexes onto the silver surface at 300 K leads to strong local variations in the resulting surface coverage on the nanometer scale, indicating that in the initial phase of deposition a large fraction of the molecules is desorbing from the surface. Low coverage regions show a decoration of step edges aligned along the crystal’s symmetry axes <110>. These crystallographic directions are found to be of major importance to the binding of the complexes to the surface. Moreover, the interaction between the molecules and the substrate promotes the restructuring of surface steps along these directions. Well-aligned and decorated steps are found to act as nucleation point for monolayer growth (2D) before 3D growth starts.

The structure of a physisorbed sub-monolayer of 1,2-bis(4-pyridyl)ethylene (bpe) on epitaxial graphene is investigated by Low-Energy Electron Diffraction and Scanning Tunneling Microscopy. Additionally, non-equilibrium heat-transfer between bpe and the surface is studied by Ultrafast Low-Energy Electron Diffraction. Bpe arranges in an oblique unit cell which is not commensurate with the substrate. Six different rotational and/or mirror domains, in which the molecular unit cell is rotated by 28±0.1 with respect to the graphene surface, are identified. The molecules are weakly physisorbed, as evidenced by the fact that they readily desorb at room temperature. At liquid nitrogen temperature, however, the layers are stable and time-resolved experiments can be performed. The temperature changes of the molecules and the surface can be measured independently through the Debye-Waller factor of their individual diffraction features. Thus, the heat flow between bpe and the surface can be monitored on a picosecond timescale. The time-resolved measurements, in combination with model simulations, show the existence of three relevant thermal barriers between the different layers. The thermal boundary resistance between the molecular layer and graphene was found to be 2±1•10-8 K m 2 W-1. Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff))

Nanoconfinement of catalytically active molecules is a powerful strategy to control their chemical activity; however, the atomic-scale mechanisms are challenging to identify. In the present study, the site-specific reactivity of a model rhenium catalyst is studied on the subnanometer scale for complexes confined within quasi–one-dimensional molecular chains on the Ag(001) surface by scanning tunneling microscopy. Injection of tunneling electrons causes ligand dissociation in single molecules. Unexpectedly, while half of the complexes show only the dissociation, the confined molecules show also the reverse reaction. On the basis of density functional theory calculations, this drastic difference can be attributed to the limited space in confinement. That is, the split-off ligand adsorbs closer to the molecule and the dissociation causes less structural disruption. Both of these facilitate the reverse reaction. We demonstrate formation and disruption of single chemical bonds of nanoconfined molecules with potential application in molecular data storage.