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Title: Van der Waals epitaxy in graphene heterostructures
Author: Marsden, Alexander J.
ISNI:       0000 0004 5924 1140
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2015
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Graphene — a two-dimensional sheet of carbon atoms — has surged into recent interest with its host of remarkable properties and its ultimate thinness. However, graphene combined with other materials is starting to attract more attention. These heterostructures can be important for production routes, incorporating graphene into existing technologies, or for modifying its intrinsic properties. This thesis aims to examine the role of van der Waals epitaxy within these heterostructures. First, the graphene-copper interaction during chemical vapour deposition of graphene is investigated. Graphene is found to grow with a mismatch epitaxy of 8 relative to the [001] direction of the Cu(100) surface, despite a mismatch in symmetry and lattice parameter between two. Further, the electronic structure of both graphene and copper is unchanged by the interaction. This highlights the weak interaction between the two, owing to its van der Waals nature. Functionalised graphene is another important heterostructure, and is intensively studied for both graphene production routes and for altering graphene’s properties. Here, it is the change to the homogeneous graphene surface that makes it interesting for van der Waals epitaxy. The effect of functionalisation of graphene with atomic oxygen and nitrogen is presented next. In both cases, only small amounts of functionalisation ( 5 at%) is sufficient to significantly deteriorate the -band structure of the graphene through localisation. For small amounts of nitrogen functionalisation, and greater amounts of oxygen functionalisation, extended topological defects are formed in the graphene lattice. Unlike epoxide oxygen groups, these disruptions to the pristine graphene are found to be irreversible by annealing. Next, the interaction between graphene and the organic semiconducting molecule vanadyl-phthalocyanine (VOPc) is presented. As a result of the van der Waals nature of the graphene surface, VOPc molecules can form crystals microns in size when deposited onto a substrate with an elevated temperature of 155 C; at ambient temperatures, the crystals are only tens of nanometres across. In contrast, the functionalised graphene oxide surface prevents large crystal growth, even at elevated temperatures, because surface functionalities inhibit molecule diffusion. This highlights the importance of graphene as a substrate for molecular crystal growth, even when the growth is not epitaxial. Finally, the supramolecular assembly of trimesic acid (TMA) and terephthalic acid (TPA) is presented. Despite their chemical similarity they display different behaviour as they transition from monolayers to three-dimensional structures: for TMA, the epitaxial chicken wire structure seen at a monolayer templates up through the layers as molecules stack, until a thickness of 20 nm, when random in-plane orientations appear; on the other hand, TPA forms a brickwork structure at the monolayer, which quickly transitions to fibre-like crystals with a bulk structure for the thin films. However, the TPA orientation is still determined by the epitaxy with the graphene substrate, although this is significantly weaker than for TMA.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QC Physics