167 research outputs found
Giant edge state splitting at atomically precise zigzag edges
Zigzag edges of graphene nanostructures host localized electronic states that
are predicted to be spin-polarized. However, these edge states are highly
susceptible to edge roughness and interaction with a supporting substrate,
complicating the study of their intrinsic electronic and magnetic structure.
Here, we focus on atomically precise graphene nanoribbons whose two short
zigzag edges host exactly one localized electron each. Using the tip of a
scanning tunneling microscope, the graphene nanoribbons are transferred from
the metallic growth substrate onto insulating islands of NaCl in order to
decouple their electronic structure from the metal. The absence of charge
transfer and hybridization with the substrate is confirmed by scanning
tunneling spectroscopy (STS), which reveals a pair of occupied / unoccupied
edge states. Their large energy splitting of 1.9 eV is in accordance with ab
initio many-body perturbation theory calculations and reflects the dominant
role of electron-electron interactions in these localized states.Comment: 14 pages, 4 figure
Tunable Hydrophobicity in DNA Micelles:Design, Synthesis, and Characterization of a New Family of DNA Amphiphiles
This work describes the synthesis and characterization of a new family of DNA amphiphiles containing modified nucleobases. The hydrophobicity was imparted by the introduction of a dodec-1-yne chain at the 5-position of the uracil base, which allowed precise and simple tuning of the hydrophobic properties through solid-phase DNA synthesis. The micelles formed from these modified DNA sequences were characterized by atomic force microscopy, dynamic light scattering, and polyacrylamide gel electrophoresis. These experiments revealed the role of the quantity and location of the hydrophobic units in determining the morphology and stability of the micelles. The effects of hybridization on the physical characteristics of the DNA micelles were also studied; these results showed potential for the sequence-specific noncovalent functionalization of the self-assembled aggregates
Large-Cavity Coronoids with Different Inner and Outer Edge Structures
Coronoids, polycyclic aromatic hydrocarbons with geometrically defined cavities, are promising model structures of porous graphene. Here, we report the on-surface synthesis of C168 and C140 coronoids, referred to as [6]- and [5]coronoid, respectively, using 5,9-dibromo-14-phenylbenzo[m]tetraphene as the precursor. These coronoids entail large cavities (>1 nm) with inner zigzag edges, distinct from their outer armchair edges. While [6]coronoid is planar, [5]coronoid is not. Low-temperature scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy unveil structural and electronic properties in accordance with those obtained from density functional theory calculations. Detailed analysis of ring current effects identifies the rings with the highest aromaticity of these coronoids, whose pattern matches their Clar structure. The pores of the obtained coronoids offer intriguing possibilities of further functionalization toward advanced host-guest applications
Electron beam controlled covalent attachment of small organic molecules to graphene
Markevich A, Kurasch S, Lehtinen O, et al. Electron beam controlled covalent attachment of small organic molecules to graphene. NANOSCALE. 2016;8(5):2711-2719.The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion bending and twisting - caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography
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