Synthesis of Extended Atomically Perfect Zigzag Graphene - Boron Nitride Interfaces.

The combination of several materials into heterostructures is a powerful method for controlling material properties. The integration of graphene (G) with hexagonal boron nitride (BN) in particular has been heralded as a way to engineer the graphene band structure and implement spin- and valleytronics in 2D materials. Despite recent efforts, fabrication methods for well-defined G-BN structures on a large scale are still lacking. We report on a new method for producing atomically well-defined G-BN structures on an unprecedented length scale by exploiting the interaction of G and BN edges with a Ni(111) surface as well as each other.

Intermolecular contrast in atomic force microscopy images without intermolecular bonds.

Intermolecular features in atomic force microscopy images of organic molecules have been ascribed to intermolecular bonds. A recent theoretical study [P. Hapala et al., Phys. Rev. B 90, 085421 (2014)] showed that these features can also be explained by the flexibility of molecule-terminated tips. We probe this effect by carrying out atomic force microscopy experiments on a model system that contains regions where intermolecular bonds should and should not exist between close-by molecules. Intermolecular features are observed in both regions, demonstrating that intermolecular contrast cannot be directly interpreted as intermolecular bonds.

Electronic states at the graphene-hexagonal boron nitride zigzag interface.

The electronic properties of graphene edges have been predicted to depend on their crystallographic orientation. The so-called zigzag (ZZ) edges haven been extensively explored theoretically and proposed for various electronic applications. However, their experimental study remains challenging due to the difficulty in realizing clean ZZ edges without disorder, reconstructions, or the presence of chemical functional groups. Here, we propose the ZZ-terminated, atomically sharp interfaces between graphene and hexagonal boron nitride (BN) as experimentally realizable, chemically stable model systems for graphene ZZ edges. Combining scanning tunneling microscopy and numerical methods, we explore the structure of graphene-BN interfaces and show them to host localized electronic states similar to those on the pristine graphene ZZ edge.

Sample corrugation affects the apparent bond lengths in atomic force microscopy.

Frequency modulation atomic force microscopy (AFM) allows the chemical structure of planar molecules to be determined with atomic resolution. Typically, these measurements are carried out in constant-height mode using carbon monoxide (CO) terminated tips. Such tips exhibit considerable flexibility, i.e., the CO molecule can bend laterally due to the tip-sample interaction. Using epitaxial graphene as a model system, we demonstrate experimentally that the apparent atomic positions measured by AFM depend on the sample corrugation. Using molecular mechanics simulations, we explain these observations by the interplay of the CO bending and the nonlinear background signal arising from the neighboring atoms. These effects depend nontrivially on the tip-sample distance and limit the achievable accuracy on the bond length determination based on AFM experiments.

Templated self-assembly and local doping of molecules on epitaxial hexagonal boron nitride.

Using low-temperature scanning tunneling microscopy, we show that monolayer hexagonal boron nitride (h-BN) on Ir(111) acts as ultrathin insulating layer for organic molecules, while simultaneously templating their self-assembly. Tunneling spectroscopy experiments on cobalt phthalocyanine (CoPC) reveal narrow molecular resonances and indicate that the charge state of CoPC is periodically modulated by the h-BN moiré superstructure. Molecules in the second layer show site-selective adsorption behavior, allowing the synthesis of molecular dimers that are spatially ordered and inaccessible by usual chemical means.

Molecular self-assembly on graphene on SiO2 and h-BN substrates.

One of the suggested ways of controlling the electronic properties of graphene is to establish a periodic potential modulation on it, which could be achieved by self-assembly of ordered molecular lattices. We have studied the self-assembly of cobalt phthalocyanines (CoPc) on chemical vapor deposition (CVD) grown graphene transferred onto silicon dioxide (SiO2) and hexagonal boron nitride (h-BN) substrates. Our scanning tunneling microscopy (STM) experiments show that, on both substrates, CoPc forms a square lattice. However, on SiO2, the domain size is limited by the corrugation of graphene, whereas on h-BN, single domain extends over entire terraces of the underlying h-BN. Additionally, scanning tunneling spectroscopy (STS) measurements suggest that CoPc molecules are doped by the substrate and that the level of doping varies from molecule to molecule. This variation is larger on graphene on SiO2 than on h-BN. These results suggest that graphene on h-BN is an ideal substrate for the study of molecular self-assembly toward controlling the electronic properties of graphene by engineered potential landscapes.

Quantum-confined electronic states in atomically well-defined graphene nanostructures.

Despite the enormous interest in the properties of graphene and the potential of graphene nanostructures in electronic applications, the study of quantum-confined states in atomically well-defined graphene nanostructures remains an experimental challenge. Here, we study graphene quantum dots (GQDs) with well-defined edges in the zigzag direction, grown by chemical vapor deposition on an Ir(111) substrate by low-temperature scanning tunneling microscopy and spectroscopy. We measure the atomic structure and local density of states of individual GQDs as a function of their size and shape in the range from a couple of nanometers up to ca. 20 nm. The results can be quantitatively modeled by a relativistic wave equation and atomistic tight-binding calculations. The observed states are analogous to the solutions of the textbook "particle-in-a-box" problem applied to relativistic massless fermions.