6 research outputs found
Tuning the Band Gap of Graphene Nanoribbons Synthesized from Molecular Precursors
A prerequisite for future graphene nanoribbon (GNR) applications is the ability to fine-tune the electronic band gap of GNRs. Such control requires the development of fabrication tools capable of precisely controlling width and edge geometry of GNRs at the atomic scale. Here we report a technique for modifying GNR band gaps <i>via</i> covalent self-assembly of a new species of molecular precursors that yields <i>n</i> = 13 armchair GNRs, a wider GNR than those previously synthesized using bottom-up molecular techniques. Scanning tunneling microscopy and spectroscopy reveal that these <i>n</i> = 13 armchair GNRs have a band gap of 1.4 eV, 1.2 eV smaller than the gap determined previously for <i>n</i> = 7 armchair GNRs. Furthermore, we observe a localized electronic state near the end of <i>n</i> = 13 armchair GNRs that is associated with hydrogen-terminated sp<sup>2</sup>-hybridized carbon atoms at the zigzag termini
Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework
We have characterized
the local electronic structure of a porphyrin-containing
single-layer covalent organic framework (COF) exhibiting a square
lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde
(DMA) and 5,10,15,20-tetrakisĀ(4-aminophenyl) porphyrin (TAPP) onto
a Au(111) surface in ultrahigh vacuum followed by annealing to facilitate
Schiff-base condensations between monomers. Scanning tunneling spectroscopy
(STS) experiments conducted on isolated TAPP precursor molecules and
the covalently linked COF networks yield similar transport (HOMOāLUMO)
gaps of 1.85 Ā± 0.05 eV and 1.98 Ā± 0.04 eV, respectively.
The COF orbital energy alignment, however, undergoes a significant
downward shift compared to isolated TAPP molecules due to the electron-withdrawing
nature of the imine bond formed during COF synthesis. Direct imaging
of the COF local density of states (LDOS) <i>via</i> d<i>I</i>/d<i>V</i> mapping reveals that the COF HOMO
and LUMO states are localized mainly on the porphyrin cores and that
the HOMO displays reduced symmetry. DFT calculations reproduce the
imine-induced negative shift in orbital energies and reveal that the
origin of the reduced COF wave function symmetry is a saddle-like
structure adopted by the porphyrin macrocycle due to its interactions
with the Au(111) substrate
Noncovalent Dimerization after Enediyne Cyclization on Au(111)
We
investigate the thermally induced cyclization of 1,2-bisĀ(2-phenylethynyl)Ābenzene
on Au(111) using scanning tunneling microscopy and computer simulations.
Cyclization of sterically hindered enediynes is known to proceed via
two competing mechanisms in solution: a classic C<sup>1</sup>āC<sup>6</sup> (Bergman) or a C<sup>1</sup>āC<sup>5</sup> cyclization
pathway. On Au(111), we find that the C<sup>1</sup>āC<sup>5</sup> cyclization is suppressed and that the C<sup>1</sup>āC<sup>6</sup> cyclization yields a highly strained bicyclic olefin whose
surface chemistry was hitherto unknown. The C<sup>1</sup>āC<sup>6</sup> product self-assembles into discrete noncovalently bound
dimers on the surface. The reaction mechanism and driving forces behind
noncovalent association are discussed in light of density functional
theory calculations
Experimentally Engineering the Edge Termination of Graphene Nanoribbons
The edges of graphene nanoribbons (GNRs) have attracted much interest due to their potentially strong influence on GNR electronic and magnetic properties. Here we report the ability to engineer the microscopic edge termination of high-quality GNRs <i>via</i> hydrogen plasma etching. Using a combination of high-resolution scanning tunneling microscopy and first-principles calculations, we have determined the exact atomic structure of plasma-etched GNR edges and established the chemical nature of terminating functional groups for zigzag, armchair, and chiral edge orientations. We find that the edges of hydrogen-plasma-etched GNRs are generally flat, free of structural reconstructions, and terminated by hydrogen atoms with no rehybridization of the outermost carbon edge atoms. Both zigzag and chiral edges show the presence of edge states
Bottom-Up Synthesis of <i>N</i> = 13 Sulfur-Doped Graphene Nanoribbons
Substitutional
doping of graphene nanoribbons (GNRs) with heteroatoms
is a principal strategy to fine-tune the electronic structure of GNRs
for future device applications. Here, we report the fabrication and
nanoscale characterization of atomically precise <i>N</i> = 13 armchair GNRs featuring regioregular edge-doping with sulfur
atoms (S-13-AGNRs) on a Au(111) surface. Scanning tunneling spectroscopy
and first-principle calculations reveal modification of the electronic
structure of S-13-AGNRs when compared to undoped <i>N</i> = 13 AGNRs
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Concentration Dependence of Dopant Electronic Structure in Bottom-up Graphene Nanoribbons
Bottom-up
fabrication techniques enable atomically precise integration
of dopant atoms into the structure of graphene nanoribbons (GNRs).
Such dopants exhibit perfect alignment within GNRs and behave differently
from bulk semiconductor dopants. The effect of dopant concentration
on the electronic structure of GNRs, however, remains unclear despite
its importance in future electronics applications. Here we use scanning
tunneling microscopy and first-principles calculations to investigate
the electronic structure of bottom-up synthesized <i>N</i> = 7 armchair GNRs featuring varying concentrations of boron dopants.
First-principles calculations of freestanding GNRs predict that the
inclusion of boron atoms into a GNR backbone should induce two sharp
dopant states whose energy splitting varies with dopant concentration.
Scanning tunneling spectroscopy experiments, however, reveal two broad
dopant states with an energy splitting greater than expected. This
anomalous behavior results from an unusual hybridization between the
dopant states and the Au(111) surface, with the dopantāsurface
interaction strength dictated by the dopant orbital symmetry