Christopher Bronner - Academia.edu (original) (raw)

Papers by Christopher Bronner

The Journal of Physical Chemistry C, 2015

ABSTRACT The fabrication of graphene nanoribbons (GNR) requires a high degree of precision due to... more ABSTRACT The fabrication of graphene nanoribbons (GNR) requires a high degree of precision due to the sensitivity of the electronic structure on the edge shape. Using Br-substituted molecular precursors, this atomic precision can be achieved in a thermally induced two-step reaction following Br dissociation on a Au(111) surface. Using DFT we find evidence that the Br atoms are bound to the intermediate polyanthrylene chains. We employ temperature programmed desorption to demonstrate the associative desorption of HBr and molecular hydrogen during the final cyclodehydrogenation step of the reaction. Both processes are found to have similar activation barriers. Furthermore, we are able to remove Br atoms from the polyanthrylene chains by providing molecular hydrogen. The subsequent formation of GNR via a cyclodehydrogenation demonstrates that Br does not influence this part of the overall reaction.

New Journal of Physics, 2014

Azobenzene is a prototypical molecular switch which can be interconverted with UV and visible lig... more 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.

Physical Review B, 2015

ABSTRACT Image potential states (IPSs) have been observed for various adsorbed carbon structures,... more ABSTRACT 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.

Chem. Commun., 2015

We investigate the surface-catalyzed dissociation of the archetypal molecular switch azobenzene o... more We investigate the surface-catalyzed dissociation of the archetypal molecular switch azobenzene on the Cu(111) surface. Based on X-ray photoelectron spectroscopy, normal incidence X-ray standing waves and density functional theory calculations a detailed picture of the coverage-induced formation of phenyl nitrene from azobenzene is presented. Furthermore, a comparison to the azobenzene/Ag(111) interface provides insight into the driving force behind the dissociation on Cu(111). The quantitative decay of azobenzene paves the way for the creation of a defect free, covalently bonded monolayer. Our work suggests a route of surface functionalization via suitable azobenzene derivatives and the on surface synthesis concept, allowing for the creation of complex immobilized molecular systems.

Journal of the American Chemical Society, 2015

A fundamental requirement for the development of advanced electronic device architectures based o... more A fundamental requirement for the development of advanced electronic device architectures based on graphene nanoribbon (GNR) technology is the ability to modulate the band structure and charge carrier concentration by substituting specific carbon atoms in the hexagonal graphene lattice with p- or n-type dopant heteroatoms. Here we report the atomically precise introduction of group III dopant atoms into bottom-up fabricated semiconducting armchair GNRs (AGNRs). Trigonal-planar B atoms along the backbone of the GNR share an empty p-orbital with the extended π-band for dopant functionality. Scanning tunneling microscopy (STM) topography reveals a characteristic modulation of the local density of states along the backbone of the GNR that is superimposable with the expected position and concentration of dopant B atoms. First-principles calculations support the experimental findings and provide additional insight into the band structure of B-doped 7-AGNRs.

Physical Review Letters, 2015

Interfaces between organic molecules and solid surfaces play a prominent role in heterogeneous ca... more Interfaces between organic molecules and solid surfaces play a prominent role in heterogeneous catalysis, molecular sensors and switches, light-emitting diodes, and photovoltaics. The properties and the ensuing function of such hybrid interfaces often depend exponentially on molecular adsorption heights and binding strengths, calling for well-established benchmarks of these two quantities. Here we present systematic measurements that enable us to quantify the interaction of benzene with the Ag(111) coinage metal substrate with unprecedented accuracy (0.02 Å in the vertical adsorption height and 0.05 eV in the binding strength) by means of normal-incidence x-ray standing waves and temperature-programed desorption techniques. Based on these accurate experimental benchmarks for a prototypical molecule-solid interface, we demonstrate that recently developed first-principles calculations that explicitly account for the nonlocality of electronic exchange and correlation effects are able to determine the structure and stability of benzene on the Ag(111) surface within experimental error bars. Remarkably, such precise experiments and calculations demonstrate that despite different electronic properties of copper, silver, and gold, the binding strength of benzene is equal on the (111) surface of these three coinage metals. Our results suggest the existence of universal binding energy trends for aromatic molecules on surfaces.

Journal of physics. Condensed matter : an Institute of Physics journal, Jan 3, 2014

Temperature-programmed desorption measurements have been applied to investigate the binding energ... more Temperature-programmed desorption measurements have been applied to investigate the binding energies of four systems, namely the photochromic molecular compounds azobenzene and tetra-tert-butyl-azobenzene (TBA) adsorbed on the Au(1 1 1) and Ag(1 1 1) surfaces, respectively. The binding energy is a measure of the interaction strength between substrate and adsorbate. It therefore provides a suitable means for an investigation of the decoupling strategy pursued by adding the tert-butyl spacer groups and choosing the more inert gold substrate, which leads to TBA/Au(1 1 1), the only photoisomerizable system out of the four. Ironically, we find TBA/Au(1 1 1) to be the most strongly bound. The binding of TBA to Au(1 1 1) is almost 0.4 eV stronger than to Ag(1 1 1). On the other hand, azobenzene binds approximately equally strongly to both surfaces. These findings are consistent with and provide support for the recently proposed hybridization between the HOMO of TBA and the Au(1 1 1) d-band...

The Journal of Physical Chemistry C, 2013

Physical Review Letters, 2012

Femtosecond time-resolved two-photon photoemission spectroscopy is utilized to determine the elec... more Femtosecond time-resolved two-photon photoemission spectroscopy is utilized to determine the electronically excited states dynamics at the -sexithiophene ð6TÞ=Auð111Þ 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.

Physical Review B, 2012

Angle-resolved two-photon photoemission and high-resolution electron energy loss spectroscopy are... more 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.

Physical Review B, 2014

Bi possesses intriguing properties due to its large spin-orbit coupling, e.g. as a constituent of... more 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 ΓT -line where the electron dynamics have not been probed with time-resolved 2PPE so far.

Physical Chemistry Chemical Physics, 2010

We present large-scale density-functional theory (DFT) calculations and temperature programmed de... more 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.

New Journal of Physics, 2012

We use time-resolved two-photon photoemission to study two molecular photoswitches at the Au(111)... more 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.

Journal of Physics: Condensed Matter, 2011

Spiropyran is a prototype molecular switch which undergoes a reversible ring-opening reaction by ... more Spiropyran is a prototype molecular switch which undergoes a reversible ring-opening reaction by photoinduced cleavage of a C-O bond in the spiropyran (SP) to the merocyanine (MC) isomer. While the electronic states and switching behavior are well characterized in solution, adsorption on metal surfaces crucially affects these properties. Using two-photon photoemission and scanning tunneling spectroscopy, we resolve the molecular energy levels on a Au(111) surface of both isomeric forms. Illumination at various wavelengths does not yield any observable switching rate, thus evidencing a very small upper limit of the quantum efficiency. Electron-induced switching from the SP to the MC isomer via generation of a negative ion resonance can be detected with a quantum yield of (2.2 ± 0.2) × 10(-10) events/electron in tunneling spectroscopy. In contrast, the back reaction could not be observed. This study reveals that the switching properties of surface-bound molecular switches can be very different compared with free molecules, reflecting the strong influence of the interaction with the metal substrate.

The Journal of Chemical Physics, 2014

High conductivity and a tunability of the band gap make quasi-one-dimensional graphene nanoribbon... more 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.

ABSTRACT Along with the growing interest in graphene, other low-dimensional carbon nanostructures... more ABSTRACT Along with the growing interest in graphene, other low-dimensional carbon nanostructures are currently in the focus of research since these materials offer a wide variety of properties interesting e.g. for nanotechnology application. Among these carbon systems, quasi-one-dimensional graphene nanoribbons (GNR) introduce a possibility to tune the electronic structure - for example, GNRs exhibit a band gap which is inversely proportional to their width and can thus be adjusted over a wide range. While many theoretical studies have been published on the band structure of GNRs, experiments are usually limited by the quality of the GNRs' fabrication, e.g. using lithography or unzipping of carbon nanotubes. In order to avoid defects and irregular edges that are inevitable in these methods, lately a surface-assisted bottom-up synthesis has been demonstrated which yields quasi-perfect GNR structures. [1] In the present study we employ complementary surface-sensitive spectroscopies to investigate occupied and unoccupied bands and the band gap in an armchair GNR which has been synthesized on the Au(111) surface. DFT calculations were performed to obtain a thorough understanding of the nature of the observed states.[4pt] [1] J. Cai et al., Nature (London) 466, 470-473 (2010)

Angewandte Chemie International Edition, 2013

ABSTRACT A matter of doping: Graphene nanoribbons (GNRs) were generated through an on-surface bot... more ABSTRACT A matter of doping: Graphene nanoribbons (GNRs) were generated through an on-surface bottom-up synthesis and selectively doped at their edges by introducing nitrogen atoms in the precursor monomers. While the size of the band gap of 2.8 eV remains almost unchanged upon N substitution, a linear shift of the band structure is observed and corresponds to n-type doping (see picture; CB=conduction band and VB=valence band).

The Journal of Physical Chemistry C, 2016