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Engineering the electronic structure of atomically-precise graphene nanoribbons

Abstract

Graphene nanoribbons (GNRs) have recently attracted great interest because of their novel electronic and magnetic properties, as well as their significant potential for device applications. Although several top-down techniques exist for fabricating GNRs, only bottom-up synthesis of GNRs from molecular precursors yields nanoribbons with atomic-scale structural control. Furthermore, precise incorporation of dopant species into GNRs, which is possible with bottom-up synthesis, is a potentially powerful way to control the electronic structure of GNRs. However, it is not well understood how these dopants affect the electronic structure of GNRs. Are these effects dependent on the dopant site? Can the band gap be tuned by doping? This dissertation helps to answer these questions through studying the electronic structure of bottom-up grown GNRs with controlled atomic dopants. The effects of edge and interior doping with different atomic species such as sulfur, boron and ketone were investigated and showed significant site dependence. Topographic and local electronic structure characterization was performed via scanning tunneling microscopy & spectroscopy (STM & STS) and compared to first-principle calculations. The chemical structure of GNRs and GNR heterojunctions was characterized by CO-tip-functionalized non-contact atomic force microscopy (nc-AFM) as well as by a newly developed technique of bond-resolved STM (BRSTM).

In an effort to develop a new method for directly synthesizing GNRs on an insulating substrate, we also studied light-induced photo-isomerization of azobenzene molecules adsorbed on an insulating surface of CVD-grown monolayer boron nitride (BN) on Cu(111). This study provides important insights into molecular behavior on an insulating surface, how to couple light to an STM system, and how to utilize local field enhancement effects due to surface plasmon resonance.

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