Upper Bound Estimate of the Electronic Scattering Potential of a Weakly Interacting Molecular Film on a Metal

Thin organic films and two-dimensional (2D) molecular assemblies on solid surfaces yield the potential for applications in molecular electronics, optoelectronics, catalysis, and sensing. These applications rely on the intrinsic electronic properties of the hybrid organic/inorganic interface. Here, we investigate the energy dispersion of 2D electronic states at the interface between an atomically thin self-assembled molecular film, comprised of flat, noncovalently bonded 9,10-dicyanoanthracene (DCA) molecules, and a Ag(111) surface. Using Fourier-transformed scanning tunnelling spectroscopy (FT-STS), we determined that the 2D electronic wave functions with wavevectors within ∼80% of the first Brillouin zone (BZ) area close to the Γ-point are free-electron-like, suggesting a weak electronic interaction between the 2D molecular film and the metal surface. Via a perturbative second-order correction to the free electron energy dispersion, we further established an upper bound for the amplitude of the scattering potential resulting from the self-assembled molecular film that the interface electrons are subject to, on the order of 1.5 eV. Our approach allows for quantifying electronic interactions at hybrid 2D interfaces and heterostructures

Selective Activation of Aromatic C–H Bonds Catalyzed by Single Gold Atoms at Room Temperature

Selective activation and controlled functionalization of C–H bonds in organic molecules is one of the most desirable processes in synthetic chemistry. Despite progress in heterogeneous catalysis using metal surfaces, this goal remains challenging due to the stability of C–H bonds and their ubiquity in precursor molecules, hampering regioselectivity. Here, we examine the interaction between 9,10-dicyanoanthracene (DCA) molecules and Au adatoms on a Ag(111) surface at room temperature (RT). Characterization via low-temperature scanning tunneling microscopy, spectroscopy, and noncontact atomic force microscopy, supported by theoretical calculations, revealed the formation of organometallic DCA–Au–DCA dimers, where C atoms at the ends of the anthracene moieties are bonded covalently to single Au atoms. The formation of this organometallic compound is initiated by a regioselective cleaving of C–H bonds at RT. Hybrid quantum mechanics/molecular mechanics calculations show that this regioselective C–H bond cleaving is enabled by an intermediate metal–organic complex which significantly reduces the dissociation barrier of a specific C–H bond. Harnessing the catalytic activity of single metal atoms, this regioselective on-surface C–H activation reaction at RT offers promising routes for future synthesis of functional organic and organometallic materials

Direct Observation of 2D Electrostatics and Ohmic Contacts in Template-Grown Graphene/WS₂ Heterostructures

Large-area two-dimensional (2D) heterojunctions are promising building blocks of 2D circuits. Understanding their intriguing electrostatics is pivotal but largely hindered by the lack of direct observations. Here graphene–WS₂ heterojunctions are prepared over large areas using a seedless ambient-pressure chemical vapor deposition technique. Kelvin probe force microscopy, photoluminescence spectroscopy, and scanning tunneling microscopy characterize the doping in graphene–WS₂ heterojunctions as-grown on sapphire and transferred to SiO₂ with and without thermal annealing. Both p–n and n–n junctions are observed, and a flat-band condition (zero Schottky barrier height) is found for lightly n-doped WS₂, promising low-resistance ohmic contacts. This indicates a more favorable band alignment for graphene–WS₂ than has been predicted, likely explaining the low barriers observed in transport experiments on similar heterojunctions. Electrostatic modeling demonstrates that the large depletion width of the graphene–WS₂ junction reflects the electrostatics of the one-dimensional junction between two-dimensional materials