201 research outputs found
Giant edge state splitting at atomically precise zigzag edges
Zigzag edges of graphene nanostructures host localized electronic states that
are predicted to be spin-polarized. However, these edge states are highly
susceptible to edge roughness and interaction with a supporting substrate,
complicating the study of their intrinsic electronic and magnetic structure.
Here, we focus on atomically precise graphene nanoribbons whose two short
zigzag edges host exactly one localized electron each. Using the tip of a
scanning tunneling microscope, the graphene nanoribbons are transferred from
the metallic growth substrate onto insulating islands of NaCl in order to
decouple their electronic structure from the metal. The absence of charge
transfer and hybridization with the substrate is confirmed by scanning
tunneling spectroscopy (STS), which reveals a pair of occupied / unoccupied
edge states. Their large energy splitting of 1.9 eV is in accordance with ab
initio many-body perturbation theory calculations and reflects the dominant
role of electron-electron interactions in these localized states.Comment: 14 pages, 4 figure
Electronic Band Dispersion of Graphene Nanoribbons via Fourier-Transformed Scanning Tunneling Spectroscopy
Atomically precise armchair graphene nanoribbons of width (7-AGNRs) are
investigated by scanning tunneling spectroscopy (STS) on Au(111). The analysis
of energy-dependent standing wave patterns of finite length ribbons allows, by
Fourier transformation, the direct extraction of the dispersion relation of
frontier electronic states. Aided by density functional theory calculations, we
assign the states to the valence band, the conduction band and the next empty
band of 7-AGNRs, determine effective masses of , and , respectively, and a band gap of eV.Comment: 20 pages, 7 figure
AgO investigated by photoelectron spectroscopy : Evidence for mixed valence
We present photoelectron spectroscopy investigations of in-situ prepared AgO. The sample was prepared by room temperature oxidation of Ag in an electron cyclotron resonance O2 plasma. In contrast to other measurements based on ex situ prepared AgO powder samples, our investigations show a distinct double peak structure of the O 1s signal with a remarkable chemical shift of 2.9 eV between the two O 1s components. These two components can not be motivated from a crystallographic point of view as the oxygen sites are all equivalent in the unit cell. We interpret this double peak structure as a characteristic feature of AgO and discuss it in terms of mixed valences
Coupled spin states in armchair graphene nanoribbons with asymmetric zigzag edge extensions
Carbon-based magnetic structures promise significantly longer coherence times
than traditional magnetic materials, which is of fundamental importance for
spintronic applications. An elegant way of achieving carbon-based magnetic
moments is the design of graphene nanostructures with an imbalanced occupation
of the two sublattices forming the carbon honeycomb lattice. According to
Lieb's theorem, this induces local magnetic moments that are proportional to
the sublattice imbalance. Exact positioning of sublattice imbalanced
nanostructures in graphene nanomaterials hence offers a route to control
interactions between induced local magnetic moments and to obtain graphene
nanomaterials with magnetically non-trivial ground states. Here, we show that
such sublattice imbalanced nanostructures can be incorporated along a large
band gap armchair graphene nanoribbon on the basis of asymmetric zigzag edge
extensions, which is achieved by incorporating specifically designed precursor
monomers during the bottom-up fabrication of the graphene nanoribbons. Scanning
tunneling spectroscopy of an isolated and electronically decoupled zigzag edge
extension reveals Hubbard-split states in accordance with theoretical
predictions. Investigation of pairs of such zigzag edge extensions reveals
ferromagnetic, antiferromagnetic or quenching of the magnetic interactions
depending on the relative alignment of the asymmetric edge extensions.
Moreover, a ferromagnetic spin chain is demonstrated for a periodic pattern of
zigzag edge extensions along the nanoribbon axis. This work opens a route
towards the design and fabrication of graphene nanoribbon-based spin chains
with complex magnetic ground states
On-Surface Hydrogen-Induced Covalent Coupling of Polycyclic Aromatic Hydrocarbons via a Superhydrogenated Intermediate
The activation and subsequent covalent coupling of polycyclic aromatic
hydrocarbons (PAHs) are of great interest in fields like chemistry, energy,
biology, or health, among others. However, this is not a trivial process. So
far, it is based on the use of catalysts that drive and increase the efficiency
of the reaction. Here, we report on an unprecedented method in which the
dehydrogenation and covalent coupling is thermally activated in the presence of
atomic hydrogen and a surface. This mechanism, which requires of the
superhydrogenation of the PAHs, has been characterized by high-resolution
scanning tunnelling microscopy (STM) and rationalized by density functional
theory (DFT) calculations. This work opens a door toward the formation of
covalent, PAH-based, macromolecular nanostructures on low-reactive surfaces,
thus facilitating its applicability.Comment: This manuscript version is made available under the CC-BY-NC-ND 4.0
licens
Structure-dependent electrical properties of graphene nanoribbon devices with graphene electrodes
Graphene nanoribbons (GNRs) are a novel and intriguing class of materials in
the field of nanoelectronics, since their properties, solely defined by their
width and edge type, are controllable with high precision directly from
synthesis. Here we study the correlation between the GNR structure and the
corresponding device electrical properties. We investigated a series of field
effect devices consisting of a film of armchair GNRs with different structures
(namely width and/or length) as the transistor channel, contacted with narrowly
spaced graphene sheets as the source-drain electrodes. By analyzing several
tens of junctions for each individual GNR type, we observe that the values of
the output current display a width-dependent behavior, indicating electronic
bandgaps in good agreement with the predicted theoretical values. These results
provide insights into the link between the ribbon structure and the device
properties, which are fundamental for the development of GNR-based electronics.Comment: Published in Carbon (2019
Observation of the Magnetic Ground State of the Two Smallest Triangular Nanographenes.
Fusion of three benzene rings in a triangular fashion gives rise to the smallest open-shell graphene fragment, the phenalenyl radical, whose π-extension leads to an entire family of non-Kekulé triangular nanographenes with high-spin ground states. Here, we report the first synthesis of unsubstituted phenalenyl on a Au(111) surface, which is achieved by combining in-solution synthesis of the hydro-precursor and on-surface activation by atomic manipulation, using the tip of a scanning tunneling microscope. Single-molecule structural and electronic characterizations confirm its open-shell S = 1/2 ground state that gives rise to Kondo screening on the Au(111) surface. In addition, we compare the phenalenyl's electronic properties with those of triangulene, the second homologue in the series, whose S = 1 ground state induces an underscreened Kondo effect. Our results set a new lower size limit in the on-surface synthesis of magnetic nanographenes that can serve as building blocks for the realization of new exotic quantum phases of matter
Quantum Electronic Transport Across "Bite" Defects in Graphene Nanoribbons
On-surface synthesis has recently emerged as an effective route towards the
atomically precise fabrication of graphene nanoribbons of controlled topologies
and widths. However, whether and to which degree structural disorder occurs in
the resulting samples is a crucial issue for prospective applications that
remains to be explored. Here, we experimentally identify missing benzene rings
at the edges, which we name "bite" defects, as the most abundant type of
disorder in armchair nanoribbons synthesized by the bottom-up approach. First,
we address their density and spatial distribution on the basis of scanning
tunnelling microscopy and find that they exhibit a strong tendency to
aggregate. Next, we explore their effect on the quantum charge transport from
first-principles calculations, revealing that such imperfections substantially
disrupt the conduction properties at the band edges. Finally, we generalize our
theoretical findings to wider nanoribbons in a systematic manner, hence
establishing practical guidelines to minimize the detrimental role of such
defects on the charge transport. Overall, our work portrays a detailed picture
of "bite" defects in bottom-up armchair graphene nanoribbons and assesses their
effect on the performance of carbon-based nanoelectronic devices
Edge Disorder in Bottom-Up Zigzag Graphene Nanoribbons: Implications for Magnetism and Quantum Electronic Transport
We unveil the nature of the structural disorder in bottom-up zigzag graphene
nanoribbons along with its effect on the magnetism and electronic transport on
the basis of scanning probe microscopies and first-principles calculations. We
find that edge-missing m-xylene units emerging during the cyclodehydrogenation
step of the on-surface synthesis are the most common point defects. These
"bite'' defects act as spin-1 paramagnetic centers, severely disrupt the
conductance spectrum around the band extrema, and give rise to spin-polarized
charge transport. We further show that the electronic conductance across
graphene nanoribbons is more sensitive to "bite" defects forming at the zigzag
edges than at the armchair ones. Our work establishes a comprehensive
understanding of the low-energy electronic properties of disordered bottom-up
graphene nanoribbons
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