Dynamics of nanoscale systems probed by time-resolved STM-induced luminescence

The efficiency and peculiarities of processes such as surface adsorption or electron-to-photon energy conversion in organic and inorganic structures are determined by the dynamics at the scale of individual molecules, atoms and charges. The timescales of such effects reach down to the ps regime, which can be routinely probed using ultrafast optics methods. However, these far-field techniques suffer from ensemble-averaging that obscures the information encoded at the atomic level. These limits can be overcome by combining scanning tunnelling microscopy (STM) with time-resolved light detection so that pm and ps scales can be reached simultaneously. STM-induced luminescence (STML) methodologies are employed in this thesis to explore the nanoscale dynamics of different systems: light emitting defects in C60 thin films, H2 molecules weakly physisorbed on Au(111), metal-metal tunnel junctions and single atom contacts.

First, we study the dynamics associated with the radiative decay of single excitons at defect-related emission centres localized in the C60 molecular film. Such emission centres serve as the smallest possible model of an organic light emitting diode where a single electron and hole recombine producing a photon. Using time-resolved STML (TR-STML) excited by voltage pulses, we follow the formation of an individual exciton and map this process in real space with ns resolution. Besides the excitonic emission, on C60 thin films we observe luminescence due to the radiative decay of plasmons. We study the interplay of these two processes and create a nanoscale bimodal source whose emission can be dynamically tuned by controlling the charge injection rate. A kinetic model is employed to thoroughly describe the charge and exciton dynamics in this system.

The developed kinetic model can be also used to analyse the motion of hydrogen molecules adsorbed on an Au(111) crystal. The weak interaction with the metal and the continuous charge injection by the tip leads to recurrent excursions of the molecule inside and outside from the tunnelling junction, which chop the plasmonic luminescence intensity. These dynamical changes in the light intensity can be followed by correlation spectroscopy and allow extraction of the molecule's residence and excursion times.

In the next step, we probe the dynamics of a generic metal-metal tunnel junction. Interestingly, when a high bias is applied, the emission from the junction exhibits photon bunching on a time scale below 50 ps as evidenced by Hanbury Brown-Twiss interferometry. Such a process is a result of a distribution of the energy of one electron between two photons, which may possibly be entangled. The opposite process may occur as well, under conditions where two electrons interact supplying energy to one photon. This overbias emission is a feature of single atom contacts and is used here to probe the fluctuations of plasmonic enhancement driven by the motion of single atoms in the vicinity of such a contact.