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Diamond is of interest as an advanced functional material, since the extreme physical properties of diamond, suggests it is ideally suited to a range of new demanding applications. In this context, the thesis explores basic surface chemical properties of diamond thin films, along with electrochemical, electronic and electron emission processes involving this material. New experiments are reported concerning the nature of surface conductivity on diamond. Measurements clearly show that the conductivity only arises if a hydrogenated diamond surface is exposed to water vapour, in the presence of chemical species capable of acting as electron acceptors. The conduction properties of surface conductive diamond in aqueous solution are also studied, and the first detailed electrochemical investigations of this material are described. Comparative electrochemical studies of nanocrystalline and boron-doped diamond have been performed. Investigations of electrode stability, and the accessible "potential window" are described, as well as the behaviour of a range of 'redox' systems, including transition metal complexes, metal deposition/stripping, and bio-related organic species. Significant differences between the behaviour of nanodiamond and microcrystalline boron-doped material are observed. A range of surface chemical and threshold photoemission studies of diamond thin films are reported. The results indicate that quantum photoyields (QPYs) are insensitive to the diamond "quality", although the wavelength selectivity is dependent on it. The adsorption of oxygen strongly reduces the QPY, although this only occurs slowly in the presence of O₂ because of a low reactive sticking probability. Much more rapid uptake of oxygen and consequent reduction of photoyield is observed in the presence of atomic O or electronically excited dioxygen O₂*. The presence of alkali metals on the diamond surface increases the QPY, and reduces the sensitivity of the QPY to surface oxygen. Significant differences between the surface chemical properties of Li, and other adsorbed akali metals (K and Cs) are observed.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2010. / Committee Chair: Breedveld, Victor; Committee Chair: Hess, Dennis; Committee Member: Aidun, Cyrus; Committee Member: Deng, Yulin; Committee Member: Singh, Preet. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Organic molecules such as porphyrins and alkanethiols are currently being investigated for applications such as sensors, light-emitting diodes and single electron transistors. Porphyrins are stable, highly conjugated compounds and the choice of metal ion and substituents bound to the macrocycle as well as other effects such as chemical surrounding and cluster size modulate the electronic and photonic properties of the molecule. Porphyrins and their derivatives are relatively non-toxic and their very rich photo- and electro-chemistry, and small HOMO-LUMO gaps make them outstanding candidates for use in molecularly-enhanced electronic applications. For these studies, self-assembled tri-pyridyl porphyrin thiol derivatives have been fully characterized on Au(111) surfaces. A variety of surface characterization techniques such as Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS) have been implemented in order to obtain information regarding the attachment orientation based on the angle and physical height of the molecule, conductivity which is determined based on the apparent height and current-voltage (I-V) measurements of the molecule, conductance switching behavior due to conformational or other effects as well as the stability of the molecular ensembles. Specifically, the transport properties of free base and zinc coordinated tri-pyridyl porphyrin thiol molecular islands inserted into a dodecanethiol matrix on Au(111) were investigated using STM and cross-wire inelastic electron tunneling spectroscopy (IETS). The zinc porphyrin thiol islands observed by STM exhibited reversible bias induced switching at high surface coverage due to the formation of Coulomb islands of ca. 10 nm diameter driven by porphyrin aggregation. Low temperature measurements (~ 4 K) from crossed-wire junctions verified the appearance of a Coulomb staircase and blockade which was not observed for single molecules of this compound or for the analogous free base. Scanning probe lithography via nanografting has been implemented to directly assemble nanoscale patterns of zinc porphyrin thiols and 16-mercapotohexadecanoic acid on Au surfaces. Matrix effects during nanopatterning including solvent and background SAMs have been investigated and ultimately ~ 10 nm islands of zinc porphyrins have been fabricated which is the optimal size for the observed switching effect.