Relaxation Dynamics of Photoexcited Charge Carriers at the Bi(111) Surface

Bi possesses intriguing properties due to its large spin-orbit coupling, e.g. as a constituent of topological insulators. While its electronic structure and the dynamics of electron-phonon coupling have been studied in the past, photo-induced charge carriers have not been observed in the early phases of their respective relaxation pathways. Using two-photon photoemission (2PPE) we follow the de-excitation pathway of electrons along the unoccupied band structure and into a bulk hole pocket. Two decay channels are found, one of which involves an Auger process. In the hole pocket, the electrons undergo an energetic stabilization and recombine with the corresponding holes with an inverse rate of 2.5~ps. Our results contribute to the understanding of the charge carrier relaxation processes immediately upon photo-excitation, particularly along the $\Gamma T$-line where the electron dynamics have not been probed with time-resolved 2PPE so far.Comment: 8 pages, 5 figure

Unoccupied electronic band structure of the semi-metallic Bi(111) surface probed with two-photon photoemission

While many photoemission studies have dealt with both the bulk band structure and various surface states and resonances, the unoccupied electronic structure above the Fermi level of the Bi(111) surface has not yet been measured directly although understanding of this model semi-metal is of great interest for topological insulators, spintronics and related fields. We use angle-resolved two-photon photoemission to directly investigate the occupied and unoccupied p bands of Bi, including the bulk hole pocket at the T point, as well as the image potential states and surface states of Bi(111).Comment: 9 pages, 7 figure

Photo-induced and thermal reactions in thin films of an azobenzene derivative on Bi(111)

Azobenzene is a prototypical molecular switch which can be interconverted with UV and visible light between a trans and a cis isomer in solution. While the ability to control their conformation with light is lost for many molecular photoswitches in the adsorbed state, there are some examples for successful photoisomerization in direct contact with a surface. However, there the process is often driven by a different mechanism than in solution. For instance, photoisomerization of a cyano-substituted azobenzene directly adsorbed on Bi(111) occurs via electronic excitations in the substrate and subsequent charge transfer. In the present study we observe two substrate- mediated trans–cis photoisomerization reactions of the same azobenzene derivative in two different environments within a multilayer thin film on Bi(111). Both processes are associated with photoisomerization and one is around two orders of magnitude more efficient than the other. Furthermore, the cis isomers perform a thermally induced reaction which may be ascribed to a back-isomerization in the electronic ground state or to a phenyl ring rotation of the cis isomer

Image potential states at chevron-shaped graphene nanoribbons /Au(111) interfaces

Image potential states (IPSs) have been observed for various adsorbed carbon structures, such as graphene or carbon nanotubes. Graphene nanoribbons (GNRs) are intriguing nanostructures with a significant band gap which promise applications in nanotechnology. In the present paper we employ two-photon photoemission (2PPE) to investigate the unoccupied electronic structure and particularly the IPS of chevron-shaped GNR which are synthesized in a thermally activated on-surface synthesis on Au(111). Angle- and time-resolved 2PPE are utilized to gain further insights into the properties of the IPS. Compared to the pristine surface, reduced effective masses between 0.6 and 0.8 electron masses are observed and the lifetimes of the IPS are below the experimental detection limit, which is in the femtosecond regime. Independent of the concentration of N dopant atoms introduced in the GNR we observe a constant binding energy with respect to the vacuum level of the system

Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): Characterizing the role of spacer groups

We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface chemical bond. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N=N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.Comment: 9 pages including 6 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

The influence of the electronic structure of adsorbate–substrate complexes on photoisomerization ability

We use time-resolved two-photon photoemission to study two molecular photoswitches at the Au(111) surface, namely azobenzene and its derivative tetra-tert-butyl-azobenzene (TBA). Electronic states located at the substrate–adsorbate interface are found to be a sensitive probe for the photoisomerization of TBA. In contrast to TBA, azobenzene loses its switching ability at the Au(111) surface. Besides the different adsorption geometries of both molecules, we partly attribute the quenching in the case of azobenzene to a shift of the highest occupied molecular orbital (HOMO) with respect to the gold d-bands, which renders the hole transfer involved in the photoisomerization mechanism of TBA inefficient

Ultrafast Exciton Population, Relaxation, and Decay Dynamics in Thin Oligothiophene Films

Femtosecond time-resolved two-photon photoemission spectroscopy is utilized to determine the electronically excited states dynamics at the α-sexithiophene (6T)/Au(111) interface and within the 6T film. We found that a photoinduced transition between the highest occupied molecular orbital and lowest unoccupied molecular orbital is essential in order to observe exciton population, which occurs within 100 fs. In thin 6T films, the exciton exhibits a lifetime of 650 fs. On a time scale of 400 fs, an energetic stabilization is observed leading to the formation of a polaron or electron trapping at defect states. The lifetime of this state is 6.3 ps. Coverage-dependent measurements show that apart from the excited state decay within the film, a substrate- mediated relaxation channel is operative. The present study demonstrates that two-photon photoemission spectroscopy is a powerful tool to investigate the whole life cycle from creation to decay of excitons in an organic semiconductor

Electronic structure changes during the surface-assisted formation of a graphene nanoribbon

High conductivity and a tunability of the band gap make quasi-one-dimensional graphene nanoribbons (GNRs) highly interesting materials for the use in field effect transistors. Especially bottom-up fabricated GNRs possess well-defined edges which is important for the electronic structure and accordingly the band gap. In this study we investigate the formation of a sub-nanometer wide armchair GNR generated on a Au(111) surface. The on-surface synthesis is thermally activated and involves an intermediate non-aromatic polymer in which the molecular precursor forms polyanthrylene chains. Employing angle-resolved two-photon photoemission in combination with density functional theory calculations we find that the polymer exhibits two dispersing states which we attribute to the valence and the conduction band, respectively. While the band gap of the non-aromatic polymer obtained in this way is relatively large, namely 5.25 ± 0.06 eV, the gap of the corresponding aromatic GNR is strongly reduced which we attribute to the different degree of electron delocalization in the two systems

End states, band gap, and dispersion

Angle-resolved two-photon photoemission and high-resolution electron energy loss spectroscopy are employed to derive the electronic structure of a subnanometer atomically precise quasi-one-dimensional graphene nanoribbon (GNR) on Au(111). We resolved occupied and unoccupied electronic bands including their dispersion and determined the band gap, which possesses an unexpectedly large value of 5.1 eV. Supported by density functional theory calculations for the idealized infinite polymer and finite size oligomers, an unoccupied nondispersive electronic state with an energetic position in the middle of the band gap of the GNR could be identified. This state resides at both ends of the ribbon (end state) and is only found in the finite sized systems, i.e., the oligomers