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Self-assembled monolayers (SAMs) of 4-aminothiophenol (4-ATP) has been successfully deposited onto nanometer-sized gold (Au) electrodes. The cyclic voltammograms obtained on a 4-ATP SAMs modified electrode show peaks and the peak height is proportional to the scan rate, which is similar to that on an electroactive SAMs modified macro electrode. The electrochemical behavior and mechanism of outer-sphere electron transfer reaction on the 4-ATP SAMs modified nanometer-sized electrode has also been studied. The 4-ATP SAMs modified electrode is further modified with platinum (Pt) nanoparticles. Electrochemical behaviors show that there is electrical communication between Pt nanoparticles and Au metal on the Pt nanoparticles/4-ATP SAMs/Au electrode. However, scanning electron microscopic image shows that the Pt nanoparticles are not evenly covered the electrode.

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Molecular self-assembly has recently attracted significant attention for possible application in organic electronic and optoelectronic devices, such as self-assembled monolayer field-effect transistors (SAMFETs) and functional self-assembled integrated circuits. Self-assembly combines the advantages of low temperature solution processability, regio-selective monolayer adsorption and nano-scale control of film thickness. Much progress has been made in improving device performance using self-assembled monolayers (SAMs). However, most SAMFET devices reported to date showed current modulation only with submicrometre channels, with low device yields and poor reproducibility as a result of limited lateral interconnection of the semiconducting layer.In an attempt to address these issues, this thesis presents an investigation of the synthesis and properties of conjugated SAM molecules for use as the charge transporting layer in SAMFETs. Chapter 1 gives a comprehensive introduction to SAM-based surface systems, organic semiconductors and their use in OFETs and SAMFETs. Chapter 2 discusses attempts to design and synthesise p-type conjugated molecules capable of self-assembly on oxide surfaces based on a phenylene-bithiophene semiconducting core. The optical and electrochemical properties, as well as the thermal behaviour of these molecules are studied in detail. This theme is carried over to Chapter 3, which describes the synthesis, chemical and physical characterisation of two families of n-type SAM molecules. These molecules consist of NTCDI cores with hexyl or cyclohexyl chains as end-capping groups. Incorporation of a selection of materials as the active layer in OFETs or SAMFETs to evaluate the charge transport is demonstrated in Chapter 4. Monolayer films based on p-type monochlorosilane-terminated SAM molecules are made using the solution assembly technique and characterised by contact angle and AFM. OFETs made from DH-PTTP by both thermal evaporation and spin coating show high mobilities comparable to the best values reported in the literature. Top-contact SAMFETs show a hole mobility of 1.1 × 10-3 cm2V-1s-1 in air, consistent with those of solution processed DH-PTTP based OFETs. Finally, an overview of the project and some suggestions for future work are presented in Chapter 5.

The development of metal-oxide-semiconductor field effect transistor (MOSFET) technology relies on new channel materials with higher carrier mobilities that allow faster switching but at lower voltages. III-V semiconductors are suitable for channel materials in n-type MOSFETs due to their higher electron mobility. However, the interface between the gate dielectric and the III-V surface shows defects that detriment the electrical performance of the transistor. These defects are attributed to interfacial oxides that create energy states in the band gap. Therefore, III-V oxides must be removed and the surface must be protected from reoxidation for the deposition of other functional layers. In this work, oxide etching and passivation of III-V semiconductors were studied to understand the oxide etching mechanism and to develop passivation techniques that allow the integration of these materials in device manufacturing. The etching of GaAs(100) was studied using aqueous HCl and H₂O₂ mixtures with and without the addition of alpha-hydroxy acids. Oxide etching depends on the strength of the acid. Without the addition H₂O₂, acetic, glycolic, tartaric and hydrochloric acids (pKₐ lower than 5) are able to remove oxides. Upon the addition of H₂O₂, only the stronger acids (glycolic, tartaric and hydrochloric) with a pKₐ lower than 4 are able to compete with H₂O₂ and etch the oxides. Oxide removal leaves an As-rich surface, and in the case of HCl, etching leaves a surface terminated with As-Cl species. As-As dimers are formed when oxides are etched with HCl and organic acids. After oxide removal with HF or HCl, the fresh GaAs and InP surfaces were passivated with a series of alkanethiols (C(n)H(2n+1)SH) to assess their effectiveness in protecting the substrate from reoxidation. Longer C chains provided increased protectiong due to their increased chain-chain interactions that allow them to form a denser and well-ordered monolayer. The surface is chemically passivated through S-X (where X = As, Ga for GaAs, and In for InP) bonding between the alkanethiolate layer and the surface. A layer formed by 1-eicosanethiol protected GaAs for 30 min, but prevented reoxidation of InP for at least 5 hours. Since the thickness of the alkanethiol layer is the same, the difference in protection is a result of the density of the layer and S bonding with the substrate.

This work has centered on the interface dipoles arising at heterojunctions between metals, semiconductor nanoparticles, self-assembled monolayers, and organic semiconductor materials. Alkanethiol self-assembled monolayers, CdSe nanocrystals, and the organic semiconductors zinc phthalocyanine (ZnPc) and Buckminster fullerene (C60) were the basis of these investigations. UV photoemission spectroscopy has proven to be an invaluable tool to observe the vacuum level shifts for these analyses while using XPS to corroborate surface structure. With a full evaluation of these surfaces, the shifts in the vacuum level, valence ionizations, and core ionizations, the impact of these interfaces, as well as their influence on the subsequent deposition of organic semiconductor layers is established.Alkanethiols possessing varying dipole moments were examined on gold and silver substrates. The viability of these alkanethiols was demonstrated to predictively adjust the work function of these metals as a function of their intrinsic dipole moments projected to surface normal, and established differences between Ag--S and Au--S bonds. The capability of the SAMs to modify the work function of gold provided an opportunity for mixed monolayers of the alkanethiols to produce a precise range of work functions by minimal adjustments of solution concentration, which were examined with a simple point dipole model.Photoemission spectroscopy offers a thorough analysis of CdSe nanoparticle films. Despite a plethora of research on these nanocrystals, there still is controversy on the magnitude of the shift in the valence band with diameter. In our research we found the majority of the valence band shift could be attributed to the interface dipole, ignored previously. Meanwhile, the valence band tethered films was obscured by the sulfur of the thiol tether.Finally, organic semiconductor layers deposited on SAMs on gold exhibited various interface dipole effects at these heterojunctions. Charge transfer states of ZnPc did not favor energy level alignment on the SAM/Au substrates used; C60 demonstrated vacuum level shifts on C15 and C12ph alkanethiol monolayers consistent with the interface charge transfer (ICT) model. These results provide credibility to models recently demonstrated in the literature for other passivated metal surfaces, and include the viability of SAMs in these discussions.

A study to optimise an IgG based immunosensor is presented, that has been carried out by absorbing monolayers to a gold transducer surface at varying immersion times and temperatures. The theory and kinetics of monolayer adsorption are analysed and discussed. Existing mathematical models are reviewed and experimentally researched, to highlight gaps in knowledge that would facilitate high quality, cost effective immunosensor production. The creation of two mathematical models to predict monolayer adsorption kinetics and optimal immersion times are discussed. Details are provided of how the new mathematical models may be advanced, and how the production of immunosensors may be further improved. The first novel mathematical model (PTCS) has been created to model the presence of two sequentially forming structures on the surface of a substrate. It gives an insight into the percentages of each structure on the surface, along with the actual adsorption process. This model provides a good fit to all applicable experimental data and has allowed the deduction of optimum immersion times. The second novel model (PIF) provides a greater insight than existing models into the individual contributions to surface coverage by both random and island growth. This allows an insight into how the monolayer surface is covered, which is critical to determine the optimum conditions for adsorption. This model also provides a good fit to the isotherm data it has been applied to. To provide a thorough understanding of the bulk properties of monolayer formation over the gold transducer, and how these properties vary with immersion time and temperature, various measurement techniques have been employed. Electrochemical Impedance Spectroscopy (EIS) has been the principle measurement technique used to measure the bulk properties, but confirmation studies have also been carried out including, Contact angle measurements, FTIR microscopy with BSA molecular labels, Fluorescence microscopy for small adsorbed molecules and AFM for layers assembled from macromolecules. The data generated from the different techniques show consistency with the arguments discussed in each instance. Two different IgG adsorption processes have been compared. These include direct IgG addition and a multilayered streptavidin-based process. The results indicate that IgG molecules adsorbed via the streptavidin based multilayer process are more vertically orientated and have a higher packing density of IgG molecules. Keywords: Self Assembled Monolayer, impedance-based immunoassay, Streptavidin, biotinylated IgG, mathematical adsorption modelling.

Molecules that contain linear alkane chains self-assemble on a variety of surfaces changing the degree of wetting, lubricity, and reactivity. We report on the reoxidation of GaAs(100) in air after adsorbing five alkanethiols (C$_n$H$_{2n+1}$-SH where $n=$ 3, 6, 12, 18, 20) and one alkanedithiol (HS-(CH$_2$)$_8$-SH) deposited from the liquid phase. The alignment of the alkane chains forms a self-assembled layer, however, air diffuses readily through the carbon layer and reaches the surface. The impact of alignment is to improve the bonding of sulfur with the surface atoms which reduces the oxidation rate based on fitting the data to a reaction-diffusion model. The layer thickness and molecular density scale linearly with the number of carbon atoms in the alkane chain. The thickness of the alkanethiolate (RS$^{-}$) layer grows by $0.87 \pm 0.06$ {\AA} for each C atom in the chain and the surface density by $0.13 \pm 0.03$ molecule per nm$^2$ per C atom up to a coverage of 5.0 molecules/nm$^2$ for $n=20$ or 0.8 monolayer. The surface coverage increases with length because interactions between methylene (CH$_2$) groups in neighboring chains reduce the tilt angle of the molecules with the surface normal. The tight packing yields areas per alkanethiolate as low as 20 \AA$^2$ for $n=20$. The amount of C in the layer divided by the chain length is approximately constant up to $n=12$ but increases sharply by a factor of 2-4$\times$ for $n=18$ and 20 based on the C 1s x-ray photoelectron spectroscopy (XPS) peak. Fourier transform infrared (FTIR) spectroscopy shows that the asymmetric methylene stretch shifts continuously to lower wavenumber and the relative peak area increases sharply with the length of the alkane chain. Fitting the data to a reaction-diffusion model shows that for times less than 30 min the surface oxide coverage does not depend on the thickness of the self-assembled layer nor the diffusivity of oxygen through the layer. Instead increasing the layer thickness makes more S available for bonding with the predominately As termination and reduces the rate coefficient for reaction of oxygen with the GaAs surface.

This thesis is an investigation of infrared electro-absorption at room temperature in electrochemically self assembled Cadmium Sulfide quantum dots produced by electrodepositing the semiconductor in 50nm pores of an anodic alumina film. Infrared absorption in these systems is associated with real space transitions of electrons between electronic states in the Cadmium Sulfide quantum dots and trap states in the surrounding alumina. When an electric field is applied on a quantum dot, it modulates the absorption by altering the overlap between the wavefunctions of dot states and the trap states in the alumina. This results in a change in the matrix element for absorption. Such a phenomenon is reminiscent of the quantum confined Stark effect. The ability to electrically modulate absorption in these structures can result in inexpensive infrared signal processing devices operating at room temperature.

Dans le cadre du développement de nouvelles technologies pour la protection environnementale, et tout particulièrement pour la dépollution de l’eau ou de l’air, le présent travail de thèse porte sur la mise en œuvre de matériaux semiconducteurs à morphologies contrôlées, susceptibles d’activités photocatalytiques permettant la dégradation ou la transformation de molécules en milieux aqueux. Plusieurs types de synthèses conduisant à des morphologies diversifiées ont été mises en œuvre. Chaque matériau a été caractérisé par diffraction de rayons X, microscopies électroniques à balayage et en transmission, et parspectroscopie Raman. La réflectance diffuse a été utilisée pour déterminer les énergies de bandes interdites des matériaux. Compte tenu des propriétés déjà connues pour les tungstates de type MWO4, notre choix s’est orienté vers trois matériaux : le trioxyde WO3, le tungstate SrWO4 et un nouveau tungstate NaCe(WO4)2 ou Na0,5Ce0,5WO4. L’oxyde WO3 a été choisi comme matériau de référence. Pour ce matériau, deux types de morphologies ont été obtenues : des nanoplaquettes et des nanosphères. Le tungstate SrWO4 de structure scheelite a été synthétisé sous deux formes microstructurales : des sphères et des navettes. Un nouveau matériau a été synthétisé et caractérisé : le tungstate double Na0,5Ce0,5WO4 de structure scheelite. Pour cette nouvelle phase, trois morphologies 3D hiérarchisées ont été élaborées en utilisant la méthode hydrothermale en présence d’EDTA. Pour chaque morphologie observée, un mécanisme de germination-croissance est proposé. Les performances photocatalytiques des différentes formes morphologiques ont été évaluées lors de la dégradation de la rhodamine B (RhB) et du bleu de méthylène (BM), sous rayonnements UV et visible. L’efficacité photocatalytique des différentes microstructures a été étudiée en fonction du pH du milieu réactionnel. À partir des résultats obtenus, nous avons pu montrer la forte corrélation entre largeur de bande interdite et réactivité photocatalytique, mais aussi entre morphologies, tailles et propriétés photocatalytiques. Il est apparu que la dégradation reposesur deux mécanismes complémentaires : l’adsorption des molécules due à la porosité des microstructures et à leur morphologie, et la réaction photocatalytique due aux radicaux actifs générés par les paires e-/h+ photogénérées. Ainsi, la RhB se décompose en présence de SrWO4 et WO3 sous UV-C (254 nm) et UV-Vis (365 nm) respectivement. Le bleu de méthylène se dégrade en présence de NaCe(WO4)2 sous rayonnement solaire UV-Vis. / In the framework of the development of new technologies for environmental protection, andmore specially for the depollution of water or air, this work deals with the implementation ofsemiconductor materials with controlled morphologies, likely photocatalytic activities andtheir enabling the degradation or transformation of organic molecules in aqueous media.Several types of syntheses leading to diversified morphologies have been implemented. Eachmaterial was characterized by X-ray diffraction, scanning and transmission electronmicroscopies, and Raman spectroscopy. Diffuse reflectance was used to determine the bandgap of the materials. Given the properties already known for MWO4 tungstates, we chosethree materials: WO3 trioxide, SrWO4 tungstate and a new tungstate NaCe(WO4)2 orNa0.5Ce0.5WO4. The oxide WO3 was chosen as the reference material. For this material, twotypes of morphologies were obtained: nanoplates and nanospheres. The tungstate SrWO4 withscheelite structure was synthesized in two microstructural forms: spindles and spheres. A newmaterial was synthesized and characterized: double tungstate of Na0.5Ce0.5WO4 with scheelitestructure. For this new phase, three hierarchical 3D morphologies were developed using thehydrothermal method in the presence of EDTA. For each observed morphology, agermination-growth mechanism is proposed. The photocatalytic performances of the differentmorphological forms were evaluated during the degradation of rhodamine B (RhB) andmethylene blue (MB), under UV and visible radiation. The photocatalytic efficiency of thedifferent microstructures was studied as a function of the pH of the reaction medium. Fromthe results obtained, we have been able to show the strong correlation between band gap andphotocatalytic reactivity, but also between morphologies, sizes and photocatalytic properties.It has been shown that the degradation is based on two complementary mechanisms: theadsorption of molecules due to the porosity of the microstructures and their morphology, andthe photocatalytic reaction due to the active radicals generated by the photogenerated e-/ h+pairs. Thus, RhB decomposes in the presence of SrWO4 and WO3 under UV-C (254 nm) andUV-Vis (365 nm) respectively. Methylene blue degrades in the presence of NaCe(WO4)2under UV-Vis solar radiation.