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The bottom-up approach to synthesize graphene nanoribbons strives not only to introduce a band gap into the electronic structure of graphene but also to accurately tune its value by designing both the width and edge structure of the ribbons with atomic precision. We report the synthesis of an armchair graphene nanoribbon with a width of nine carbon atoms on Au(111) through surface-assisted aryl-aryl coupling and subsequent cyclodehydrogenation of a properly chosen molecular precursor. By combining high-resolution atomic force microscopy, scanning tunneling microscopy, and Raman spectroscopy, we demonstrate that the atomic structure of the fabricated ribbons is exactly as designed. Angle-resolved photoemission spectroscopy and Fourier-transformed scanning tunneling spectroscopy reveal an electronic band gap of 1.4 eV and effective masses of ≈0.1 m for both electrons and holes, constituting a substantial improvement over previous efforts toward the development of transistor applications. We use ab initio calculations to gain insight into the dependence of the Raman spectra on excitation wavelength as well as to rationalize the symmetry-dependent contribution of the ribbons' electronic states to the tunneling current. We propose a simple rule for the visibility of frontier electronic bands of armchair graphene nanoribbons in scanning tunneling spectroscopy.

Abstract:The state of vanishing friction known as superlubricity has important applications for energy saving and increasing the lifetime of devices. Superlubricity detected with atomic force microscopy appears in examples like sliding large graphite flakes or gold nanoclusters across surfaces. However, the origin of the behavior is poorly understood due to the lack of a controllable nano-contact. We demonstrate graphene nanoribbons superlubricity when sliding on gold with a joint experimental and computational approach. The atomically well-defined contact allows us to trace the origin of superlubricity, unravelling the role played by edges, surface reconstruction and ribbon elasticity. Our results pave the way to the scale-up of superlubricity toward the realization of frictionless coatings.One Sentence Summary: Graphene superlubricity is investigated with atomic scale precision on nanoribbons anchored and dragged by a sharp tip on a gold surface.

Atomically precise graphene nanoribbons (GNRs) can be obtained via thermally induced polymerization of suitable precursor molecules on a metal surface. This communication discusses the atomic structure found at the termini of armchair GNRs obtained via this bottom-up approach. The short zigzag edge at the termini of the GNRs under study gives rise to a localized midgap state with a characteristic signature in scanning tunneling microscopy (STM). By combining STM experiments with large-scale density functional theory calculations, we demonstrate that the termini are passivated by hydrogen. Our results suggest that the length of nanoribbons grown by this protocol may be limited by hydrogen passivation during the polymerization step.

Narrow graphene nanoribbons exhibit substantial electronic bandgaps and optical properties fundamentally different from those of graphene. Unlike graphene-which shows a wavelength-independent absorbance for visible light-the electronic bandgap, and therefore the optical response, of graphene nanoribbons changes with ribbon width. Here we report on the optical properties of armchair graphene nanoribbons of width N ¼ 7 grown on metal surfaces. Reflectance difference spectroscopy in combination with ab initio calculations show that ultranarrow graphene nanoribbons have fully anisotropic optical properties dominated by excitonic effects that sensitively depend on the exact atomic structure. For N ¼ 7 armchair graphene nanoribbons, the optical response is dominated by absorption features at 2.1, 2.3 and 4.2 eV, in excellent agreement with ab initio calculations, which also reveal an absorbance of more than twice the one of graphene for linearly polarized light in the visible range of wavelengths.