Photochemical functionalization of diamond surfaces

Diamond surfaces are excellent substrates for potential applications in fields such as biotechnology, molecular sensing, and molecular electronics. In order to develop new diamond-based technologies, it is important to develop a fundamental understanding of diamond surface chemistry. Previous work in the Hamers group has demonstrated covalent functionalization of hydrogen-terminated diamond surfaces with molecules bearing a terminal vinyl group via a photochemical process using sub-bandgap light at 254 nm. While the reaction was shown to occur reproducibly with self-terminating monolayer surface coverage, the mechanism was never fully understood. This thesis investigates the photochemical modification of hydrogen-terminated surfaces of diamond. The results show that this reaction is a surface-mediated radical process initiated by the UV-assisted photoejection of electrons from the diamond surfaces into the liquid phase.; To develop a better understanding of the photochemical mechanism, an electrical bias was applied to the diamond samples during the photochemical reaction. Applying a 1 volt potential between two diamond electrodes significantly increases the rate of functionalization of the negative electrode. Cyclic voltammetry and electrochemical impedance measurements show that the applied potential induces downward band-bending within the negative diamond film electrode. At higher voltages a Faradaic current is observed, with no further acceleration of the functionalization rate. The bias-dependent changes in rate are attributed to a field effect; the applied potential induces a downward band-bending on the negative electrode and facilitates electron ejection into the adjacent organic fluid. The ability to directly organically photopattern the surface on length scales of <25 microns has also been demonstrated using simple photomasking techniques.; Techniques for the functionalization of diamond may be applied to other 'unreactive' surfaces. The activation of a gallium nitride surface with a hydrogen plasma treatment has been achieved; this hydrogen-treated surface has been shown to be photochemically reactive under 254 nm light.; Preliminary studies into the use of diamond as a photocatalytic substrate suggest that diamond can be used for the photo-induced breakdown of small organics. The stability of the diamond surfaces in these environments remains to be examined.