… on-surface synthesis and assessment of band structure, flexibility, and information storage potential
With their extraordinary mechanical and electronic properties carbon-based nanomaterials are central in 21st century research and carry high hopes for future nanotechnology applications. Established sp2-hybridized scaffolds include carbon nanotubes (CNTs), graphene sheets, and graphene nanoribbons. Recently, the interest in carbon allotropes incorporating both sp2– and sp-hybridized atoms rose tremendously, especially for the most popular member, the so-called graphdiyne. According to theory, the related nanomaterials possess characteristics desirable for applications such as molecular electronics, energy storage, gas filtering and light harvesting. However, achieving the targeted materials with high quality remained challenging until now.
Here, we employed covalent on-surface synthesis on well-defined metal substrates under ultra-high vacuum (UHV) conditions to the homocoupling reaction of terminal alkyne compounds and fabricated the first functionalized graphdiyne (f-GDY) nanowires. Combining the substrate templating of the Ag(455) vicinal surface with specifically designed CN-functionalized precursors we achieved the controlled polymerization to atom-precise strands with their length reaching 40 nm. The left panel of Figure 1a depicts a scanning tunneling microscopy (STM) image of an area of the silver surface featuring two step edges where an example of such a f-GDY wire is lying at the lower side of the right step edge. The right panel displays a molecular model of the situation highlighting the structure of the nanowire adsorbed in the lower terrace (darker blue) consisting of covalently coupled monomers (red outline) with the CN moieties pointing towards the atoms of the upper terrace (brighter blue).
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Figure: (extract) Synthesis and characterization of functionalized graphdiyne nanowires. a) STM topograph of a f-GDY polymer covering the left step edge. b) ARPES data: Before annealing a non-dispersing feature originates from the HOMO of the monomer. After annealing a dispersing features (blue) can be identified. c) Schematic representation of the deduced intrinsic band structure of the f-GDY nanowires. d) STM topograph of a strongly bent nanowire. e) Information storage thru conformational cis-trans switching of benzonitrile units. Full image here.