Ce travail porte sur le traitement de surface de pigments, d'oxyde d'aluminium, de fer et de titane par des polyesters acrylique et l'analyse des propriétés qui en résultent. Les mesures d'angle de mouillage montrent que le traitement rend les pigments plus hydrophobes. Ces traitements sont ils complets, avec un recouvrement homogène de la surface et quels sont les types de liaisons formées ? L'analyse quantitative a été menée par thermogravimétrie et spectroscopie infrarouge après traitement et lavages par différents solvants. Les résultats cohérents montrent que les molécules sont fixées sur les trois oxydes de fer, une partie des molécules seulement sur l'oxyde de titane, avec une plus faible fraction fixée sur l'alumine. Des liaisons chimiques sont détectées par spectroscopie infrarouge, assisté par un modèle de mécanique quantique. Cependant l'AFM et l'XPS montrent que le traitement de la surface n'est pas homogène, le polymère se dépose sous forme d'îlots. L'observation directe par AFM sur des plaquettes d'alumine est décisive. Elle montre que ce mode de dépôt résulte de la conformation des molécules en pelotes. Cette hétérogénéité est inhérente à la structure macromoléculaire, dont la contribution entropique empêche le dépôt planaire sur la surface. Nous préconisons l'utilisation de molécules plus petites ou une polymérisation in-situ.

Les mémoires flash non volatiles - utilisées dans les ordinateurs, téléphones portables ou clés USB - peuvent être constituées de nanocristaux semiconducteurs (SC) insérées dans une matrice isolante. Elles nécessitent l'élaboration d'hétérostructures de type "oxyde/SC/oxyde/Si(00l)" et la maîtrise de chaque interface. Dans ce cadre, nous avons étudié les mécanismes de croissance initiale du Si et du Ge (SC) sur des substrats d'oxyde cristallins LaA1O3(001) à forte permittivité (high-k). Les propriétés chimiques et structurales ont été déterminées in-situ par photoémission X (XPS et XPD) et par diffraction d'électrons (RHEED et LEED) puis ex-situ par microscopies en champ proche (AFM) et en transmission (HRTEM). Le substrat LaAlO3(001) propre présente une reconstruction de surface c(2x2) attribuée à des lacunes d'O en surface. Les croissances de Si et Ge ont été réalisées par épitaxie par jet moléculaire (MBE), soit à température ambiante suivies de recuits, soit à haute température. L'épitaxie requiert des températures de dépôt supérieures à 550°C. Le mode de croissance est de type Volmer Weber caractérisé par la formation d'îlots cristallins de dimensions nanométriques et de forte densité. Ces îlots sont relaxés et présentent une interface abrupte avec le substrat. Quant aux îlots de Ge, ils ont majoritairement des orientations aléatoires avec néanmoins une relation d'épitaxie privilégiée, la même que celle du Si.

Student Number : 0318623R - PhD thesis - School of Geosciences - Faculty of Science / Physical and chemical properties of atmospheric particles are fundamental but not necessarily easily accessible parameters. Uncertainties in these parameters are responsible for some uncertainties associated with radiative impacts of aerosol particles in global climate models. The uncertainties pertain to limitations of sampling and measurement devices, difficulties in modelling aerosols (source strengths, spatial and temporal variability) and in understanding microphysical and optical properties of aerosol particles. Physical and chemical properties can be obtained at single-particle level by microscopy analyses of individual particles. Using refined analytical and interpretative techniques to derive some of these fundamental properties, aerosol particles collected in various field campaigns and laboratory experiments were investigated using two high resolution microscopes. The particles were collected during the LBA-EUSTACH, Large-Scale Biosphere-Atmosphere Experiment part of European Studies on Trace Gases and Atmospheric Chemistry; SMOCC campaign, Smoke Aerosols, Clouds, Rainfall and Climate; CTBH II, Cape Town Brown Haze II campaign; and a controlled combustion experiment. Microscopy techniques were compared and complemented with conventional techniques to characterise particle sizes, shapes, chemical compositions and mixing states. Particle size distributions were compared between geometric equivalent sizes measured from microscopes and aerodynamic equivalent diameters, while taking into account particle densities. Large differences were found between the particle sizing techniques. Microscopy sizes (3D) were systematically lower than expected, and depended on the relative humidity during particle sampling. Differences were attributed to loss of mass, presumably water adsorbed on particles. Losses were high and could not be accounted for by known humidity growth factors suggesting losses of other volatile compounds adsorbed on particles as well. Findings suggest that there are inherent problems in defining particle sizes with different sizing techniques, despite accounting for humidity growth of particles and particle density. For collected particles, there are mass losses on individual particles, as opposed to particle losses to walls during sampling. These losses will inevitably bias observed mass distributions derived from collected particles and hence their number-size distributions. Relatively young aggregated soot particles from wood combustion were investigated for particle morphology (fractality, specific mass) and dynamic properties. Based on a procedure that has been validated on modelled aggregates, several important parameters to characterise geometry and drag-to-mass relationship of aggregates were derived. Three techniques were used to derive fractal dimension of soot aggregates. Averaged fractal dimension was found to be Df = 1.82 ± 0.08. Dynamic shape factors of soot particles were 1.7 to 2.5 and increasing with mass of aggregates. In the regime 0.2 < Kn < 0.7 (Knudsen number, Kn = 2#21;/dmob) the mobility diameter dmob was observed to be proportional to the radius of gyration with a ratio dmob/2Rg = 0.81 ± 0.07. Specific surface area of aggregates was determined to be 70 ± 10 m2g−1 based on SEM image analysis. These parameters can be used directly in modelling microphysical behaviour of freshly formed soot particles from biomass combustion with fractal dimension of Df ≈ 1.80. Chemical composition and size distributions of particles were investigated on filter samples collected during intense winter brown haze episodes in Cape Town. The sampling technique offered the capability to characterise highly heterogeneous aerosols over a polluted urban environment. Based on morphology and elemental composition, particles were categorised into seven particle groups of: aggregated soot particles, mineral dust, sulphates (SO2− 4 ), sea-salt, tar balls/fly ash, rod-shaped particles associated with soot agglomerates and those that could not be attributed to any of these groups were labelled as ‘others’. Apportionments of chemical species were highly variable both spatially and temporally. These variations indicate lack of lateral mixing and dependence of particle chemical compositions on localised and point sources within the Cape Town area. Sulphate and aggregated soot particles were externally mixed with fractional number concentrations of 0− 82% and 11%−46%, respectively. Aerosol complex refractive indices were derived from the chemical apportionment and particle abundance determined in microscopy analyses. The refractive indices were combined with in-situ measurements of number-size distribution to determine optical properties of aerosols. Single scattering albedo, !0, varied from 0.61 to 0.94 with a mean value of 0.72±0.08. The !0 is much lower than is generally reported in literature, and this was attributed to high concentrations of highly absorbing anthropogenic soot observed in SEM analysis. The mean extinction coefficient #27;ep was 194 ± 195 Mm−1. #27;ep and !0 clearly demonstrated and explained quantitatively the visibility reduction due to particles in the Cape Town atmosphere, reduction observed as the brown haze phenomenon. In all the three case studies, microscopy single particle analysis played a critical role in advancing knowledge of understanding properties of aerosol particles in the atmosphere.

Since its inception a quarter of a century ago, Kelvin probe force microscopy (KPFM) has enabled studying contact potential differences (CPDs) on the nanometre scale. However, current KPFM investigations are limited by the bandwidth of its constituent electronic loops to the millisecond regime. To overcome this limitation, pump-probe-driven Kelvin probe force microscopy (pp-KPFM) is introduced that exploits the non-linear electric interaction between tip and sample. The time resolution surpasses the electronic bandwidth and is limited by the length of the probe pulse. In this work, probe pulse lengths as small as 4.5 ns have been realized. These probe pulses can be synchronized to any kind of pump pulses. The first system investigated with pp-KPFM is an electrically-driven organic field-effect transistor (OFET). Here, charge carrier propagation in the OFET channel upon switching the drain-source voltage is directly observed and compared to simulations based on a transmission line model. Varying the charge carrier density reveals the impeding influence of Schottky barriers on the maximum switching frequency. The second system is an optically-modulated silicon homojunction. Here, the speed of surface photovoltage (SPV) build-up is accessed and compared to timeaveraged results. Due to slow trap states, the time-averaged method is found to lack comprehensiveness. In contrast, pp-KPFM exposes two intensity-dependent recombination times on the same timescale — high-level Shockley-Read-Hall recombination in the bulk and heat-dominated recombination in the surface layer — and a delay of the SPV decay with rising frequency, which is attributed to charge carrier retention at nanocrystals. The third system is a DCV5T-Me:C60 bulk heterojunction. The SPV dynamics is probed and compared to measurements via open-circuit corrected transient charge carrier extraction by linearly increasing voltage. Both methods reveal an exponential onset of the band bending reduction that is attributed to the charge carrier diffusion time in DCV5T-Me, and a double exponential decay, hinting at different recombination paths in the studied organic solar cell. The above-mentioned experiments demonstrate that pp-KPFM surpasses conventional KPFM when it comes to extracting dynamic device parameters such as charge carrier retention and recombination times, and prove that pp-KPFM is a versatile and reliable tool for studying electrodynamics on nanosurfaces.

Lipid bilayers form the basis of the membranes that serve as a barrier between a cell and its physiological environment. Their physical properties make them ideally suited for this role: they are extremely soft with respect to bending but essentially incompressible under lateral tension, and they are quite permeable to water but essentially impermeable to ions which allows the rapid establishment of the osmotic gradients. The function of membrane proteins, which are vital for tasks ranging from signal transduction to energy conversion, depends on their interactions with the lipid environment. Because of the complexity of natural membranes, model systems consisting of simpler lipid mixtures have become indispensable tools in the study of membrane biophysics. The objective of the work reported here is to develop a deeper understanding of the underlying physics of lipid bilayers through nanoscale measurements of the mechanical properties of mixed lipid systems including cholesterol, a key ingredient of cell membranes. Atomic force microscopy (AFM) has been used extensively to measure the topographical and elastic properties of supported lipid bilayers displaying complex phase behaviour and containing mixtures of important PC, PE lipids and cholesterol. Phase transformations have been investigated varying the membrane temperature, and the effects of cholesterol in controlling membrane fluidity, phase, and energetics have been studied. Elastic modulus measurements were correlated with phase behaviour observations. To aid in the nanoscale probing of lipid bilayers, AFM probes with a high aspect ratio and tip radii of $sim$4~nm were fabricated and characterised. These probes were used to investigate the phase boundary in binary and ternary lipid systems, leading to the discovery of a raised region at the boundary which has implications for the localisation of reconstituted proteins as well as the role of natural domains or lipid rafts. The electrical properties of the probes were examined to assess their potential application for combined structural and electrical measurements in liquid. A novel technique was developed to aid in the study of the physical properties of lipid bilayers. Membrane budding was induced above microfabricated substrates through osmotic pressure. Modification of the adhesion energy of the bilayer through biotin-avidin linking was successful in modulating budding behaviour of liquid disordered bilayers. The free energy of the system was modelled to allow quantitative information to be extracted from the data.

The dynamic properties of several rectangular and V-shaped microcantilevers were investigated. Particular attention was paid to the higher flexural eigenmodes of oscillation. The potential of the higher flexural modes was demonstrated through the use of cantilevers as standalone sensors for adsorbed mass. The mass adsorbed on the surface of a cantilever was in the form of a homogeneous water layer measured as a function of relative humidity. The minimum detectable water layer thicknesses were 13.7 Å, 3.2 Å, 1.1 Å, and 0.7 Å for the first four modes of a rectangular cantilever, clearly demonstrating enhanced accuracy for the higher eigenmodes of oscillation. These thicknesses correspond to minimum detectable masses of 33.5 pg, 7.8 pg, 2.7 pg and 1.7 pg for the first four modes. For quantitative applications the spring constants of each cantilever must be determined. Many methods exist but only a small number can calibrate the higher flexural eigenmodes. A method was developed to simultaneously calibrate all flexural modes of microcantilever sensors. The method was demonstrated for the first four eigenmodes of several rectangular and V-shaped cantilevers with nominal fundamental spring constants in the range of 0.03 to 1.75 N/m. The spring constants were determined with accuracies of 5-10 %. Spring constants of the fundamental mode were generally in agreement with those determined using the Sader method. The method is compatible with existing AFM systems. It relies on a flow of gas from a microchannel and as such poses no risk of damage to the cantilever beam, its tip, or any coating. A related method was developed for the torsional modes of oscillation. Preliminary results are shown for the fundamental mode of a rectangular cantilever. The method can be easily extended to the higher torsional modes, V-shaped cantilevers, and potentially, the flapping modes of the legs of V-shaped microcantilevers.

This work aimed at studying biophysical properties of two membrane proteins, one of potential nanotechnological use, bacteriorhodopsin, and one potential drug target, the NTS1 neurotensin receptor, at the single molecule scale. Bacteriorhodopsin (BR) is the only protein in the purple membrane (PM) of the halophilic organism Halobacterium salinarium. It is a light-driven proton pump converting light into a transmembrane proton gradient through isomerization of its retinal chromophore. Its stability, as well as its photoactivity remaining in dry protein layers, has made BR an attractive material for biomolecular devices. Numerous studies have been published on this topic; however, they have all used BR within the PM, on relatively large (µm-wide) surfaces. Here, conducting-probe atomic force microscopy (C-AFM) analysis was performed after removing most of the membrane lipids. For the first time, it was shown that the molecular conductance of BR can be reversibly photoswitched with predictable wavelength sensitivity. Intimate and robust coupling to gold electrodes was achieved by using a strategically engineered cysteine which, combined with partial delipidation, generated protein trimers homogenously orientated on the surface. Numerous controls using biophysical (SPR, ellipsometry, Kelvin-probe AFM) and chemical (photocurrent, cyclic voltammetry) techniques confirmed the wavelength specificity of the photoswitch, the anchoring role of the mutation and the homogenous orientation of the protein on the gold surface. Neurotensin is a brain and gastrointestinal 13 amino acid peptide acting as a neuromodulator in the central nervous system and as a hormone in the periphery. Its wide range of biological activities is primarily mediated through its binding to the neurotensin type 1 receptor (NTS1). NTS1 expressed in E.coli was purified and inserted into 100 nm brain polar lipid liposomes in a conformation which retained its ligand-binding capabilities. Initial AFM characterisation was performed as a prelude for ligand-receptor interaction studies, including high resolution imaging, force spectroscopy and solid state NMR approaches.

Patterned silver (Ag) columnar nanorods were prepared by the glancing angle physical vapor deposition method. The Ag columnar nanorods were grown on a Si (100) substrate patterned with posts in a square “lattice” of length 1 μm. An electron beam source was used as the evaporation method, creating the deposition flux which was oriented 85˚ from the substrate normal. A Dimension Icon with NanoScope V controller atomic force microscope was used to measure the spring constant in 10 nm increments along the long axis of five 670 nm long Ag nanorod specimens. The simple beam bending model was used to analyze the data. Unexpected behavior of the spring constant data was observed which prevented a conclusive physically realistic value of the Young’s modulus to be calculated.

Because the surface plays an important role in the electrical and optical properties of GaN devices, an improved understanding of surface effects should help optimize device performance. In this work, atomic force microscopy (AFM) and related techniques have been used to characterize three unique sets of n-type GaN samples. The sample sets comprised freestanding bulk GaN with Ga polar and N polar surfaces, epitaxial GaN films with laterally patterned Ga- and N-polar regions on a common surface, and truncated, hexagonal GaN microstructures containing Ga-polar mesas and semipolar facets. Morphology studies revealed that bulk Ga-polar surfaces treated with a chemical-mechanical polish (CMP) were the flattest of the entire set, with rms values of only 0.4 nm. Conducting AFM (CAFM) indicated unexpected insulating behavior for N-polar GaN bulk samples, but showed expected forward and reverse-bias conduction for periodically patterned GaN samples. Using scanning Kelvin probe microscopy, these same patterned samples demonstrated surface potential differences between the two polarities of up to 0.5 eV, where N-polar showed the expected higher surface potential. An HCl cleaning procedure used to remove the surface oxide decreased this difference between the two regions by 0.2 eV. It is possible to locally inject surface charge and measure the resulting change in surface potential using CAFM in conjunction with SKPM. After injecting electrons using a 10 V applied voltage between sample and tip, the patterned polarity samples reveal that the N-polar regions become significantly more negatively charged as compared to Ga-polar regions, with up to a 2 eV difference between charged and uncharged N polar regions. This result suggests that the N-polar regions have a thicker surface oxide that effectively stores charge. Removal of this oxide layer using HCl results in significantly decreased surface charging behavior. A phenomenological model was then developed to fit the discharging behavior of N-polar GaN with good agreement to experimental data. Surface photovoltage (SPV) measurements obtained using SKPM further support the presence of a thicker surface oxide for N polar GaN based on steady state and restoration SPV behaviors. Scanning probe microscopy techniques have therefore been used to effectively discriminate between the surface morphological and electrical behaviors of Ga- vs. N-polar GaN.

Corrosion is the destructive result of chemical reaction between a metal or metal alloy and its environment. Airplanes, power generating plants, chemical process and manufacturing plants, concrete structure, and many others which widely uses aluminum alloy and stainless steel alloys are subjected to corrosion. The estimated cost of corrosion damage is in order of 3 to 5 percent of gross national product (GNP). Out of all forms of corrosion, pitting corrosion is most commonly observed in aluminum alloy 2024 and stainless steel type 316. There is a need to study the stress environment around the pits in order to predict the nucleation of the crack. The objective of this thesis is to investigate the correlation between pits and stresses in AA2024 and SS316 alloys under different types of loading. Corrosion experiments were carried out on both alloys samples for a fixed time interval and were imaged on optical and AFM. The optical microscope provided the information on forms of corrosion expected on the surface while the AFM provided the pit profile on the surface. An analysis procedure was developed using CAD and finite element analysis to predict stresses resulting from corrosion pits under different types of loadings. The average corrosion rate of AA2024 is six times higher than that of SS316 in 2 Molar NaCl corrosive environment. Based on the results from the optical microscope, AA2024 usually initiated with localized corrosion along with pitting and localized regions grows in size and soon uniform corrosion is observed. However, the stainless steel SS316 usually initiated with pitting corrosion and soon followed by film forming corrosion. Based on the analysis, it was observed that the stress distribution and levels on the corroded surface varied due to irregularities in the corrosion process. From the stress analysis result of AA2024 under bending, it was observed that there was 80% stress increase during first 30 min of corrosion and then the increase was about 6% from 30min to 60 min and then soon reaches a plateau. Similar results were obtained for both AA2024 and SS316 materials under different type of loadings. Initially, the stress increases sharply as time increases but the amount of stress increase demises as time progress and soon reaches a plateau. There was a sharp increase of Bending and shear loading are induces higher level of stresses compared to tension loading. From these stresses it is possible to estimate the initiation of crack, from which the life can be estimated for failure in the material.