Christopher Bronner

Aligning the Band Gap of Graphene Nanoribbons by Monomer Doping

Silicon-based field-effect transistors (FETs) are the building blocks of modern digital logic circuitry and therefore part of virtually every electronic device available today. Over the past decades, continuous downscaling of existing designs has met the rising performance requirements, but as the size of FETs approaches the regime of atomic structures, new concepts are required to maintain the current pace at which microelectronics is developing. At small gate channel lengths, the applicability of quantum mechanical principles results in several so-called short-channel effects (e.g. reduced carrier mobility). Since its experimental realization in 2004, graphene has been discussed intensively as a substitute for doped silicon in FETs because of its high charge carrier mobility and its unsurpassably low thickness. Graphene transistors have even been realized but cannot be put into the “off” state because of the lack of a band gap. However, there are concepts available for opening a band gap, for example, applying strain along the sheet or biasing bilayers of graphene. Also, lateral confinement in quasione-dimensional graphene nanoribbons (GNRs) leads to a band gap, which furthermore is highly sensitive to the width and edge shape of the GNR, thus opening possibilities to tailor the electronic properties of a device. Indeed, FETs built from nanoribbons show much higher on/off-ratios than graphene transistors, which makes them more suitable for integration into logic devices. However, the ability to control the electronic properties is essential: while the size of the gap can be engineered by varying the nanoribbon widths, the alignment of the GNR band structure with respect to the Fermi level of a metal electrode is equally important. Such a shifting of the entire band structure is observed both in two-dimensional graphene as well as in chemically synthesized or lithographically patterned GNRs upon doping, particularly with nitrogen atoms. Using present doping techniques, the distribution of dopant atoms will not be well-defined on the nanoscale and the band gap shift upon nitrogen doping depends on the site of the N atom, that is, the bonding configuration to neighboring carbon atoms. Generally, for doped and pristine GNRs, fabrication remains a challenge as well-established top-down approaches using lithography or unzipping of carbon nanotubes yield relatively wide ribbons with an undetermined edge structure. Particularly for small widths on the order of a few nanometers (where the band gap reaches a technologically relevant size) atomically precise edges are necessary and can be realized using Br-substituted precursor molecules, which are thermally activated on a surface and—in a bottom-up synthesis— covalently assemble to a specific nanostructure. In this study, we employed the latter approach to prepare GNRs with an atomically precise edge structure and doping pattern through polymerization of specific monomers directly on the Au(111) surface and studied the position and size of the band gap of these GNRs with surface-sensitive electron spectroscopies. Besides straight armchair edge GNRs, another type of chevron-shaped nanoribbons has previously been fabricated using an on-surface reaction. In this process adsorption of several layers of 6,11-dibromo-1,2,3,4-tetraphenyl-triphenylene (monomer 1 in Scheme 1) on Au(111) and heating at 250 8C leads to desorption of the second and higher layers as well as halogen dissociation and coupling of the resulting activated biradical monomers, yielding a sterically crowded and hence twisted polyphenylene. In a second heating step at 440 8C, this polymer undergoes a subsequent cyclodehydrogenation reaction providing access to the desired chevronshaped GNR with armchair edges. Selective substitution of the parent monomer 1 with either one or two N atoms provided monomers 2 and 3, respectively, which were used to generate GNRs with different doping levels (exemplarily shown for the doubly N doped GNR 5 in Scheme 1) and accordingly with potentially different electronic structure properties. Synthesis of the new monomers 2 and 3 was accomplished by Diels–Alder reactions of an appropriate cyclopentadienone with either mixed phenylpyridyl-acetylene or bispyridylacetylene, followed by immediate cheletropic CO extrusion (for details see the Supporting Information). [*] C. Bronner, S. Stremlau, A. Haase, Prof. Dr. P. Tegeder Fachbereich Physik, Freie Universit t Berlin Arnimallee 14, 14195 Berlin (Germany) E-mail: bronner@zedat.fu-berlin.de petra.tegeder@physik.fu-berlin.de

Site-Specific Substitutional Boron Doping of Semiconducting Armchair Graphene Nanoribbons

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.

Electronic structure of a subnanometer wide bottom-up fabricated graphene nanoribbon

(Received 10 November 2011; published 23 August 2012)Angle-resolvedtwo-photonphotoemissionandhigh-resolutionelectronenergylossspectroscopyareemployedto derive the electronic structure of a subnanometer atomically precise quasi-one-dimensional graphenenanoribbon(GNR)onAu(111).Weresolvedoccupiedandunoccupiedelectronicbandsincludingtheirdispersionand determined the band gap, which possesses an unexpectedly large value of 5.1 eV. Supported by densityfunctional theory calculations for the idealized infinite polymer and finite size oligomers, an unoccupiednondispersive electronic state with an energetic position in the middle of the band gap of the GNR couldbe 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.DOI: 10.1103/PhysRevB.86.085444 PACS number(s): 73

Switching ability of nitro-spiropyran on Au(111): electronic structure changes as a sensitive probe during a ring-opening reaction

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.

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.

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.

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.

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).

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

Adsorption energetics of azobenzenes on noble metal surfaces

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