Effect of Substrate on Bottom-Up Fabrication and Electronic Properties of Graphene Nanoribbons

Abstract: Taking into account the technological demand for the controlled preparation of atomically precise graphene nanoribbons (GNRs) with well-defined properties, the present thesis is focused on the investigation of the role of the underlying metal substrate in the process of building GNRs using bottom-up strategy and on the changes in the electronic structure of GNRs induced by the GNR-metal interaction. The combination of surface sensitive synchrotron-radiation-based spectroscopic techniques and scanning tunneling microscopy with in situ sample preparation allowed to trace evolution of the structural and electronic properties of the investigated systems.Significant impact of the substrate activity on the growth dynamics of armchair GNRs of width N = 7 (7-AGNRs) prepared on inert Au(111) and active Cu(111) was demonstrated. It was shown that unlike inert Au(111) substrate, the mechanism of GNRs formation on Ag(111) and Cu(111) includes the formation of organometallic intermediates based on the carbon-metal-carbon bonds. Experiments performed on Cu(111) and Cu(110), showed that a change of the balance between molecular diffusion and intermolecular interaction significantly affects the on-surface reaction mechanism making it impossible to grow GNRs on Cu(110).It was demonstrated that deposition of metals on spatially aligned GNRs prepared on stepped Au(788) substrate allows to investigate GNR-metal interaction using angle-resolved photoelectron spectroscopy. In particular intercalation of one monolayer of copper beneath 7-AGNRs leads to significant electron injection into the nanoribbons, indicating that charge doping by metal contacts must be taken into account when designing GNR/electrode systems. Alloying of intercalated copper with gold substrate upon post-annealing at 200°C leads to a recovery of the initial position of GNR-related bands with respect to the Fermi level, thus proving tunability of the induced n-doping. Contrary, changes in the electronic structure of 7-AGNRs induced by the deposition of Li are not reversible.  It is demonstrated that via lithium doping 7-AGNRs can be transformed from a semiconductor into a metal state due to the partial filling of the conduction band. The band gap of Li-doped GNRs is reduced and the effective mass of the conduction band carriers is increased.