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Title: Self-assembly of monolayers of aromatic carboxylic acid molecules on silver and copper modified gold surfaces at the liquid-solid interface
Author: Aitchison, Hannah
ISNI:       0000 0004 5364 7449
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 2015
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Exploiting coordination bonding of aromatic carboxylic acids at metal surfaces, this thesis explores new directions in the design and application of self-assembled monolayers (SAMs). The SAMs are investigated using a multi-technique approach comprising of a complementary combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In addition, the X-ray standing wave technique (XSW) was used to characterise the substrates. The process of layer formation and the final structures of the SAMs are found to be strikingly dependent on the combination of molecule and substrate, which is discussed in terms of the intermolecular and molecule-substrate interactions, bonding geometries and symmetry of the organic molecules. This is illustrated by the dramatic difference between molecular adsorption on Ag and Cu for molecules such as biphenyl-3,4',5-tricarboxylic acid and biphenyl-4-acetic acid. In the case of self-assembly on Cu, the molecule-substrate interactions play a decisive role in the resulting SAM structure, whereas on Ag, the intermolecular interactions dominate over the weaker molecule-substrate binding. This exploration of the balance of interactions that lead to the formation of these SAM structures lays the foundation for a systematic design of the structures and properties of aromatic carboxylic acid based monolayers. Finally, different applications and properties of some SAMs were investigated, namely coordination of a Pd(II) complex to a pyridine/pyrazole terminated molecule adsorbed on Ag. Evidence of coordination of Pd(II) to single molecules was provided by STM, XPS and NEXAFS spectroscopy. Additionally, controlled STM tip induced modification of local areas of a 1,3,5-tris(4-carboxyphenyl)benzene SAM on Ag was performed, opening an exciting prospect for nanoscale molecular manipulation.
Supervisor: Buck, Manfred Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Self-assembled monolayers ; Aromatic carboxylic acid ; Scanning tunneling microscopy ; X-ray photoelectron spectroscopy ; Near-edge X-ray absorption fine structure ; Nanotechnology ; X-ray standing wave spectroscopy ; QD509.M65A5 ; Monomolecular films ; Self-assembly (Chemistry) ; Carboxylic acids ; Coordination compounds