Formation and electrical interfacing of nanocrystal-molecule nanostructures

The objective of this thesis work is to develop methods for forming and interfacing nanocrystal-molecule nanostructures in order to explore their electrical transport properties in various controlled environments. This work demonstrates the potential of nanocrystal assemblies for laterally contacting molecules for electronic transport measurements. We first propose a phenomenological model based on rate equations for the formation of hybrid nanocrystal-molecule (respectively: 20 nm – 1.2 nm) nanostructures in solution. We then concentrate on nanocrystals (~ 60 nm) assembled between nano-gaps (~ 40 nm) as a contacting strategy for the measurement of electronic transport properties of thiophene-terminated conjugated molecules (1.5 nm long) in a two-terminal configuration, under vacuum conditions. Similar devices were also probed with a three-terminal configuration using thiophene-terminated oxidation-reduction active molecules (1.8 nm long) in liquid medium for the demonstration of the electrolytic gating technique. The experimental and modelling work presented in this thesis project brings into light physical and chemical processes taking place at the extremely narrow (~1 nm separation) and curved interface between two nanocrystals or one nanocrystal and a grain of a metallic electrode. The formation of molecular bridges at this kind of interface necessitates molecules to diffuse from a large liquid reservoir into the region in the first place. Molecular bonding must occur to the surface for both molecular ends: this is a low yield statistical process in itself as it depends on orientation of surfaces, on steric hindrance at the surface and on binding energies. On the other hand, the experimental work also touched the importance of the competition between potentially immiscible liquids in systems such that (organo-)metallic molecules solvated by organic solvent in water and organic solvent in contact with hydrated citrate stabilised nanocrystals dispersed in solutions or assembled between electrodes from both experimental and simulations point of view.

The effect of variability in the powder/liquid ratio on the strength of zinc phosphate cement

Aim: To investigate (a) variability in powder/liquid proportioning (b) effect of the extremes of any such variability on diametral tensile strength (DTS), in a commercial zinc phosphate cement. Statistical analyses (a = 0.05) were by Student's t-test in the case of powder/liquid ratio and one-way ANOVA and Tukey HSD for for pair-wise comparisons of mean DTS. The Null hypotheses were that (a) the powder-liquid mixing ratios observed would not differ from the manufacturer's recommended ratio (b) DTS of the set cement samples using the extreme powder/liquid ratios observed would not differ from those made using the manufacturer's recommended ratio. Methodology: Thirty-four undergraduate dental students dispensed the components according to the manufacturer's instructions. The maximum and minimum powder/liquid ratios (m/m), together with the manufacturer's recommended ratio (m/m), were used to prepare cylindrical samples (n = 3 x 34) for DTS testing. Results: Powder/liquid ratios ranged from 2.386 to 1.018.The mean ratio (1.644 (341) m/m) was not significantly different from the manufacturer's recommended value of 1.718 (p=0.189). DTS values for the maximum and minimum ratios (m/m), respectively, were both significantly different from each other (p<0.001) and from the mean value obtained from the manufacturer's recommended ratio (m/m) (p<0.001). Conclusions: Variability exists in powder/liquid ratio (m/m) for hand dispensed zinc phosphate cement. This variability can affect the DTS of the set material.

Precursor chemistry for oxide related materials

This thesis describes modelling, synthesis, spectroscopic and physical characterisation, as well as application of Magnesium, Calcium and Copper β-diketonate, β-ketoiminate, β-diiminate, Schiff base, amide and fluorenyl compounds. The selected compounds could potentially find application in materials deposition using Atomic Layer Deposition (ALD), MOCVD, CVD and Sol-Gel techniques. Quantum chemical modelling was used as a tool to perform the comprehensive and rapid study of magnesium and calcium precursor molecules in order to predict which of them would be more successful in ALD of metal oxides. Precursor chemistry plays a key role in ALD, since precursors must be volatile, thermally stable, chemisorb on the surface and react rapidly with existing surface groups. This Thesis describes one aspect of this, surface reactivity between ligands and hydroxyl groups, via a gas-phase model with energetics computed at the level of Density Functional Theory (DFT). A number of different synthetic strategies, both aerobic and anaerobic, were investigated for the synthesis of the described metal complexes. These included the use of different metal starting reagents such as, anhydrous and hydrated inorganic metal salts, metal alkyls and Grignard reagents. Some of previously unreported metal complexes of homoleptic and heteroleptic magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, amides and Schiff base type were synthesised and characterised: [Mg(hfpd)2(DipPa)], [Mg(hfpd)2(MapH)2], [Mg(hf-ebp)(THF)2], [Mg(tf-Pap)Cl(THF)2], [Ca(PhNacnac)2], [Cu(tf-Pap)2], [Cu(PhNacnac)2], [Cu(hf-ebp)], [Cu(DipPa)] and [Cu(DipPa)2(4,4’-bypy)]. A comprehensive study on the thermal properties of magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, Schiff base, amide and fluorenyl complexes was performed using TGA and sublimation of selected compounds. Atomic Layer Deposition of MgO using magnesium β-ketoiminate – [bis{(4-N-phenyl)-2-pentonato} magnesium] and β-diketonate - [bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)(THF)magnesium hydrate] was performed on Si(100) substrates at 180°C and 0.2 Torr using O2 plasma.