The work presented in this thesis describes both the thermal annealing of damage created in silicon due to low fluence ion implantation and the accumulation of that damage (to full amorphousness) at higher fluences. The technique utilised was in situ transmission electron microscopy (TEM).

In this thesis we apply a variety of computational methods based on density-functional theory (DFT) to the study of defect centres in bulk silicon and silicon nanostructures. Firstly, we discuss the system-size convergence of point defect properties in the supercell method for deep-level defects in bulk silicon; we consider both the vacancy and gold impurity. For the vacancy, we investigate systematically the main contributions to the finite size error that lead to the well-known slow convergence with respect to system size of defect properties, and demonstrate that different properties of interest can benefit from the use of different k-point sampling schemes. We also present a simple and accurate method for calculating the potential alignment correction to the valence band maximum of charged defect supercells by using maximally-localised Wannier functions, and show that the localised view of the electronic structure provided by them gives a clear description of the nature of the electronic bonding at the defect centre. For the gold impurity, we show that the system becomes a non-spin-polarised negative-U centre due to the effect of Jahn-Teller distortion, thus providing a simple explanation for the absent electron paramagnetic resonance signal for gold in silicon. The calculated transition levels are found to be in excellent agreement with experimental measurements. We then investigate the segregation of arsenic impurities in silicon close to an interface with amorphous silica. We employ a multiscale approach, generating a realistic disordered interface structure from Monte Carlo simulation, with a continuous random network model of the system parametrised from DFT. We calculate the segregation energy using DFT for a large number of substitutional sites encompassing all the oxidation states of silicon, and show that the results can be understood with a minimal model based only on the local strain and volume of the defect site.

Modification of solid surfaces provides a cost effective route for producing novel properties, such as adhesion, permeability, wettability, etc. The aim of this work was to modify polyolefin surfaces with silicon dioxide and ammonium salt overlayers. Silicon dioxide layers were formed by oxygen plasma treatment of polydimethylsiloxane (PDMS) rich polyolefin surfaces. PDMS enrichment at the surface was achieved by preparing polymer blends containing PDMS homopolymer or copolymer and polyolefin. The surface segregation behaviour of these blends was studied using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurements. Next, e-beam treatment of solvent-cast 3-(-2-aminoethylamino) propyltrimethoxy-silane (Z-6020 / pentaerythritol tetracrylate (PETA) / itaconic acid (ITA) mixtures onto polypropylene films was investigated. An enhancement in gas barrier was measured. This was attributed to the formation of ammonium salt, cross-linking, and siloxane networks. The findings of this work lead to the development of a novel solventless method for depositing ionically-interacting polymeric networks. This new approach comprised plasma co-polymerisation/deposition of monomers containing carboxylic, amine, and anhydride groups. The final part of this thesis describes the formation of highly fluorinated surfaces using CF4 plasma treatment of the polydimethylsiloxane / polyethylene (PDMS/PE), polydimethylsiloxane / polypropylene (PDMS/PP) blends, and pure PDMS films. The importance of plasma parameters such as the input power, duration, and of pulse duty cycle on the extent of fluorination was investigated.

This thesis is concerned with the possibility of producing novel materials by the sol-gel method that could be incorporated into a new sensing system to be used for the detection of hydrocarbons, in particular methane. Possibilities for a new system include coating optical fibres, at pre-determined points, with a material that causes some sort of disruption in the signal of the fibre when in contact with a hydrocarbon or specifically methane. Dip coating an optical fibre with a sol-gel would be a method for producing an optical fibre based system. This would provide variable chemistry, refractive index and hydrocarbon sensitivity. New silica-based sol-gel materials are presented and titania is incorporated to some of these materials in order to improve the catalytic potential of the system and to increase the refractive index. In order to increase the hydrophobicity and elasticity of the final coatings, organic modifiers are added. The sol-gel materials are characterised by a variety of techniques as both monoliths and thin films. Along with the characterisation, the samples are analysed to determine their potential to adsorb methane and water and the possibility of incorporating the samples in to an optical fibre sensor system utilising ultra-violet/visible spectroscopy. The presence of titania and/or organic modifiers in a silica based sol-gel system are seen to increase significantly the extent of methane adsorption and decrease the extent of water sorption at 293-298 K. It appears that having both titania and organic modifier gives a bigger effect on adsorption than either one alone. The reasons for this are considered in detail.

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La synthèse d’objets hybrides silice/latex constitue le coeur de ce travail de doctorat ; il s’agit de recouvrir partiellement des particules de polystyrène par de la silice nanométrique. Pour cela la polymérisation en émulsion de la phase organique in-situ en présence de nanoparticules de silice a été sélectionnée, en présence d’auxiliaires organiques pour rendre les surfaces amphiphiles. Les premières formulations mises en oeuvre avec des tensioactifs n’ont pas conduit à la décoration des latex parce que la présence de ces molécules aux interfaces favorise plutôt la dispersion des latex, empêchant l’adsorption de la silice. Par la suite, l’étude de deux systèmes composés respectivement d’une silice chargée négativement et du PEGMA, et d’une silice chargée positivement et du PSS, ont permis d’obtenir des latex « décorés » caractérisés par ATG et MET. Les mécanismes proposés s’appuient, selon les conditions, sur des mécanismes de nucléation homogène ou de nucléation en gouttelettes. Il apparait que la maîtrise des interactions pouvant être produites à la surface du latex est très importante pour permettre à la silice de se placer à sa surface. Ainsi, le choix de l’amorceur ou de l’auxiliaire organique est un paramètre clé pour obtenir des particules hybrides.Dans la dernière partie de cette étude, la silice a été introduite sous la forme d’objets hybrides silice/latex dans une suspension d’alumine pour procéder à l’hétérocoagulation des deux matériaux et à la granulation de l’alumine. La combinaison des propriétés des matériaux organique et inorganique constituant les particules hybrides a permis de conduire à l’amélioration de l’organisation microstructurale interne du granule lors de l’étape de séchage, en diminuant de manière significative les fissurations au sein des granules. / This work is centered on the silica/latex hybrid particles synthesis: the aim of the study is to partially cover the polystyrene beads with silica nanoparticles. For this purpose, in-situ emulsion polymerization of the organic phase with silica has been selected with organic auxiliaries to make the surfaces amphiphilic. The first compositions processed with surfactants did not lead to latex decoration because the presence of the molecules at the interface favors the dispersion of the latex impeding silica adsorption. Then, the study of two systems with, in one hand negatively charged silica and PEGMA, and in the other hand positively charged silica and PSS, allowed to get “decorated” latex characterized by TGA and TEM. The proposed mechanisms are based on the homogeneous nucleation or the droplet nucleation mechanisms depending on the conditions. It appears that the control of the interactions that could be produced at the surface of the latex is very important to allow the silica to go at the surface. Thus, the initiator or organic auxiliary choice is a key parameter to get hybrid particles.In the last part of this study, silica has been introduced via hybrid particles in an alumina suspension to proceed to heterocoagulation of both materials leading to alumina granulation. The combination of the properties of the organic and inorganic material that constitute the hybrid particles leads to the improvement of the microstructural organization inside the spheres during the drying step by reducing significantly the cracks in the spheres.

Στην παρούσα εργασία υπολογίστηκε η ενέργεια διαμορφώσεων γραφενίου στις οποίες τα άτομα άνθρακα αποκλίνουν από το επίπεδο εξαγωνικό πλέγμα. Η πρώτη περίπτωση που εξετάσθηκε ήταν η απόκλιση από το επίπεδο, των ατόμων του ενός εκ των δύο υποπλεγμάτων του γραφενίου, θεωρώντας μία άπειρη περιοδική δομή. Χρησιμοποιήσαμε τη θεωρία γραμμικού συνδυασμού ατομικών τροχιακών (Linear Combination of Atomic Orbitals-LCAO) προκειμένου να κατασκευάσουμε τις ενεργειακές ζώνες για τα s, px, py και pz τροχιακά των ατόμων άνθρακα στο γραφένιο και μελετήσαμε τη μορφή τους συναρτήσει της κατακόρυφης απόκλισης z των ατόμων του ενός υποπλέγματος από το επίπεδο. Στη συνέχεια, με προσαρμογή ab initio δεδομένων για την ενέργεια παραμόρφωσης του δεσμού άνθρακα-άνθρακα στο επίπεδο γραφένιο, εκτιμήσαμε τη συνάρτηση απωστικής ενέργειας μεταξύ των ατόμων άνθρακα. Έτσι, για την περίπτωση του άπειρου περιοδικού πλέγματος, υπολογίσαμε την ολική ενέργεια ανά άτομο συναρτήσει της κατακόρυφης απόστασης των δύο ατόμων της μοναδιαίας κυψελίδας. Στη συνέχεια, προκειμένου να μελετήσουμε ημιτονοειδείς κυματώσεις διαφορετικού μήκους κύματος και πλάτους, κατασκευάσαμε πλέγματα γραφενίου διαφορετικών μεγεθών και υπολογίσαμε την ολική ενέργεια για διάφορες διαμορφώσεις των πλεγμάτων αυτών. Προέκυψαν έτσι ορισμένες διαμορφώσεις πλέγματος ενεργειακά προτιμητέες σε σχέση με την επίπεδη διαμόρφωση του γραφενίου. Τέλος, μελετήθηκε η αλληλεπίδραση τύπου Van der Waals μεταξύ των ατόμων επίπεδου υποστρώματος SiO2 και των ατόμων του γραφενίου καθώς και η μεταβολή στην ολική ενέργεια των κυματώσεων του γραφενίου που προκύπτει από την αλληλεπίδραση αυτή. / In the present thesis, we studied cases of carbon atom deviations from planarity in graphene’s hexagonal lattice, with respect to graphene’s total energy. The first case studied, is the deviation of the atoms of the one crystal sublattice of graphene, in an infinite crystal lattice. Linear Combination of Atomic Orbitals (LCAO) was used in order to obtain the energy bands for the s, px, py and pz atomic orbitals in graphene. Graphene’s band structure was studied with respect to the deviation z ofthe atoms of the one crystal sublattice of graphene. In order to obtain an empirical formula for repulsive energy between carbon atoms in graphene, we fitted ab initio results for graphene bond stretching potential, in graphene’s plane. Subsequently, we calculated the total energy per carbon atom with respect to the distance z, for an infinite graphene lattice. In order to study ripples of sinusoidal form in graphene’s structure, we created graphene lattices of different sizes and then we calculated the electronic, the repulsive and the total energy for different ripple configurations. Configurations which are energetically more favourable with respect to flat graphene were found, providing thus a ground state with ripples at very low temperatures. Lastly, Van der Waals interaction between a flat SiO2 substrate and graphene lattices on top of it was studied, with respect to changes of graphene’s total energy that result from the graphene-substrate interaction.