No abstract

The authors review the use of core-level resonant photoemission and resonant Auger spectroscopy to study femtosecond charge-transfer dynamics. Starting from simple models of the relevant processes, they examine the rationale for this approach and illustrate the approximations and known subtleties for the inexperienced experimentalist. Detailed analysis of case studies of increasing complexity are taken up, as well as the connection to related approaches using both valence excitation and the core-level fluorescent channel.

The ultrafast timescale of electron transfer processes is crucial to their role in many biological systems and technological devices. In dye-sensitized solar cells, the electron transfer from photo-excited dye molecules to nanostructured semiconductor substrates needs to be sufficiently fast to compete effectively against loss processes and thus achieve high solar energy conversion efficiencies. Time-resolved laser techniques indicate an upper limit of 20 to 100 femtoseconds for the time needed to inject an electron from a dye into a semiconductor, which corresponds to the timescale on which competing processes such as charge redistribution and intramolecular thermalization of excited states occur. Here we use resonant photoemission spectroscopy, which has previously been used to monitor electron transfer in simple systems with an order-of-magnitude improvement in time resolution, to show that electron transfer from an aromatic adsorbate to a TiO(2) semiconductor surface can occur in less than 3 fs. These results directly confirm that electronic coupling of the aromatic molecule to its substrate is sufficiently strong to suppress competing processes.

Atomically precise graphene nanoribbons (GNRs) can be fabricated via thermally induced polymerization of halogen containing molecular precursors on metal surfaces. In this paper the effect of substrate reactivity on the growth and structure of armchair GNRs (AGNRs) grown on inert Au(111) and active Cu(111) surfaces has been systematically studied by a combination of corelevel X-ray spectroscopies and scanning tunneling microscopy. It is demonstrated that the activation threshold for the dehalogenation process decreases with increasing catalytic activity of the substrate. At room temperature the 10,10′-dibromo-9,9′-bianthracene (DBBA) precursor molecules on Au(111) remain intact, while on Cu(111) a complete surface-assisted dehalogenation takes place. Dehalogenation of precursor molecules on Au(111) only starts at around 80 °C and completes at 200 °C, leading to the formation of linear polymer chains. On Cu(111) tilted polymer chains appear readily at room temperature or slightly elevated temperatures. Annealing of the DBBA/Cu(111) above 100 °C leads to intramolecular cyclodehydrogenation and formation of flat AGNRs at 200 °C, while on the Au(111) surface the formation of GNRs takes place only at around 400 °C. In STM, nanoribbons have significantly reduced apparent height on Cu(111) as compared to Au(111), 70 ± 11 pm versus 172 ± 14 pm, independently of the bias voltage. Moreover, an alignment of GNRs along low-index crystallographic directions of the substrate is evident for Cu(111), while on Au(111) it is more random. Elevating the Cu(111) substrate temperature above 400 °C results in a dehydrogenation and subsequent decomposition of GNRs; at 750 °C the dehydrogenated carbon species self-organize in graphene islands. In general, our data provide evidence for a significant influence of substrate reactivity on the growth dynamics of GNRs.