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The perfect transmission of charge carriers through potential barriers in graphene (Klein tunneling) is a direct consequence of the Dirac equation that governs the low-energy carrier dynamics. As a result, localized states do not exist in unpatterned graphene, but quasibound states can occur for potentials with closed integrable dynamics. Here, we report the observation of resonance states in photoswitchable self-assembled molecular(SAM)-graphene hybrid. Conductive AFM measurements performed at room temperature reveal strong current resonances, the strength of which can be reversibly gated on- and off- by optically switching the molecular conformation of the mSAM. Comparisons of the voltage separation between current resonances (∼ 70-120 mV) with solutions of the Dirac equation indicate that the radius of the gating potential is ∼ 7 ± 2 nm with a strength ≥ 0.5 eV. Our results and methods might provide a route toward optically programmable carrier dynamics and transport in graphene nanomaterials.

Molecular self-assembly is a versatile nanofabrication technique with atomic precision en route to molecule-based electronic components and devices. Here, we demonstrate a three-dimensional, bicomponent supramolecular network architecture on an all-carbon sp(2)-sp(3) transparent platform. The substrate consists of hydrogenated diamond decorated with a monolayer graphene sheet. The pertaining bilayer assembly of a melamine-naphthalenetetracarboxylic diimide supramolecular network exhibiting a nanoporous honeycomb structure is explored via scanning tunneling microscopy initially at the solution-highly oriented pyrolytic graphite interface. On both graphene-terminated copper and an atomically flat graphene/diamond hybrid substrate, an assembly protocol is demonstrated yielding similar supramolecular networks with long-range order. Our results suggest that hybrid platforms, (supramolecular) chemistry and thermodynamic growth protocols can be merged for in situ molecular device fabrication.

On-surface chemistry for atomically precise sp(2) macromolecules requires top-down lithographic methods on insulating surfaces in order to pattern the long-range complex architectures needed by the semiconductor industry. Here, we fabricate sp(2)-carbon nanometer-thin films on insulators and under ultrahigh vacuum (UHV) conditions from photocoupled brominated precursors. We reveal that covalent coupling is initiated by C-Br bond cleavage through photon energies exceeding 4.4 eV, as monitored by laser desorption ionization (LDI) mass spectrometry (MS) and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) gives insight into the mechanisms of C-Br scission and C-C coupling processes. Further, unreacted material can be sublimed and the coupled sp(2)-carbon precursors can be graphitized by e-beam treatment at 500 °C, demonstrating promising applications in photolithography of graphene nanoarchitectures. Our results present UV-induced reactions on insulators for the formation of all sp(2)-carbon architectures, thereby converging top-down lithography and bottom-up on-surface chemistry into technology.