Having conducted the research described in this thesis I found that there exists a possibility to produce polyelectrolyte nanostructures on hydrophobic surfaces by application of the moving contact line approach. It was demonstrated that the morphology of nanostructures displays a range of structure variations from root-like to a single wire structure with a high anisotropy and aspect ratio (providing diameters of several nanometers and the length limited by the sample surface dimensions). Such nanostructures can be produced exactly on the spot of interest or can be transferred from the surface where they were produced to any other surfaces by the contact printing technique. A model describing the polymer deposition during the moving contact line processes on hydrophobic surfaces has been proposed. The application of this model provides the ground for an explanation of all the obtained experimental data. Utilizing moving contact line approach aligned one-dimensional polycation structures were fabricated and these structures were used as templates for assembling amphiphile molecules. Quasiperiodic aligned and oriented nanostructures of polyelectrolyte molecules formed in moving droplets were utilized for fabrication of electrically conductive one-dimensional nanowires.

Thèse de doctorat : Électronique : Lille 1 : 2002. / N° d'ordre (Lille) : 3104. Résumé en français. Textes en français et en anglais. Notes bibliogr.

Thèse de doctorat : Electronique : Lille 1 : 2000. / Résumé en français. Textes en français et en anglais (publications). Bibliogr. en fin de chapitres.

An automatic implantable cardiac defibrillator (AICD) is a device that is implanted in the chest to constantly monitor and, if necessary, correct episodes of arrhythmia. While the longevity of the average AICD patient has increased to 10 years after implantation, only 5% of implants functioned for seven years, and this mismatch poses a significant and ever growing clinical and economic burden. Moreover, there are now efforts to “piggyback” devices on AICDs and BVPs for additional functionality, all of which require more power. An innovative approach towards generating power for AICDs is to harness the energy of the heart by embedding energy generators in AICD leads. The cardiovascular system as a source generator is appealing due to its ability to continuously deliver mechanical energy as long as the patient is alive. Herein a device incorporating nanostructured piezoelectrics was developed as a means to harvest the energy of heart. The generator system integrates inorganic piezoelectric nanomaterials, including aligned arrays of nanowires of crystalline zinc oxide (ZnO), with elastomeric substrates. The design combines several innovative structural configurations including a “wavy” flexible electrode and a layout where the nanowires are near or on the neutral mechanical plane. A wet synthetic strategy to reliably prepare piezoelectric ZnO nanostructures directly onto the devices was also developed and optimized to produce nanowires with high densities, large aspect ratios and high orientation. The elastomeric support permits direct integration within AICD leads and is small and flexible enough to not add resistance in systole. The flexible devices were integrated into a testbed mimicking the input a failing right ventricle and the results demonstrate progress towards energy harvesting from the cardiovascular system. A model was developed to gain insight as to how to structure the nanowire array within the latitude of the synthesis to boost the energy production. To further improve the output, the nanowires were passivated with dipolar molecules to change their resistivities and the barrier height of the Schottky contact. A novel low photon energy photoelectron spectroscopy tool was developed to measure the effects of the molecules on the individual nanowire properties. This concept of using nanostructured piezoelectrics as a means to convert the energy of the body may in the coming years represent a paradigm shift from battery dependant AICD modules to completely autonomous functional systems. / text

Many properties of the thin films are different from the bulk value and in many cases, depend dramatically on the film thickness. In the metallic ultra-thin films epitaxially grown on the semiconductor substrate, the conduction electrons are confined by the vacuum and metal-semiconductor interface. When the film thickness is comparable to the electron Fermi wavelength, this confinement will produce discrete energy levels known as quantum well states (QWS), which dramatically modify the electronic structures of the thin film and this is called quantum size effect (QSE). QSE will have a profound effect on a lot of physical properties of the thin films. Among various systems exhibiting QSE, Pb/Si (111) is the most widely studied one and exhibits the richest phenomena in QSE. In this study, a home made low temperature Scanning Tunneling Microscopy/Spectroscopy (LT-STM/S) was used to study the superconductivities of the Pb thin films. Quantum oscillations of the superconductivity have been observed for the films down to 4 monolayer and the oscillation amplitude increases as the film gets thinner. To resolve the discrepancies between the superconductivities measured with ex-situ transport and in-situ STS. We also studied the influence of Au overlay on the Pb thin films with LT-STM/S, and found out the deposition of Au on Pb dramatically roughened the Pb films. Finally, we successfully grew large scale near perfect 2ML Pb films. There are two types of films which exhibit different Moiré patterns. LT-STS studies revealed there is big difference in the superconductivity Tc of these two films, both of which decreased dramatically from that of the 4ML film. / text

Thermoelectric (TE) materials, which can convert temperature gradients directly into electricity and vice versa, have received renewed interest for waste heat recovery and refrigeration applications. Higher manganese silicides (HMS) are promising p-type TE materials due to the abundance of the constituent elements, environmental friendliness, and good chemical stability. The objective of this dissertation is to establish a better understanding of the structure-TE properties relationship of HMS with a complex Nowotny chimney ladder structure. The focus of this work is on the investigations of the phonon dispersion of HMS crystals and the effects of chemical doping and nanostructuring on the TE properties of polycrystalline HMS. HMS crystals have been synthesized by the Bridgeman method for inelastic neutron scattering measurements of the phonon dispersion. In conjunction with density functional theory calculations, the results clearly show the presence of numerous low-lying optical phonon branches, especially an unusually low-energy optical phonon polarization associated with the twisting motions of the Si helical ladders in the Mn chimneys. The obtained phonon dispersion can be used to explain the low and anisotropic thermal conductivity of HMS crystals. (Al,Ge) double doping was found to be effective in modifying the electrical properties of HMS polycrystals. The peak thermoelectric power factor occurs at an optimized hole concentration of 1.8~2.2×10²¹ cm⁻³ at room temperature. On the other hand, Re substitution can suppress the lattice thermal conductivity to approach the calculated minimum value corresponding to the amorphous limit. Meanwhile, the thermoelectric power factor does not markedly change at low Re content of x ≤ 0.04 although it drops considerably with increasing Re content. Hence, the peak ZT has been improved to ~0.6 in both systems. The effects of nanostructuring on the TE properties have been studied in the cold-pressed samples and ball-milled samples. The thermal conductivity was reduced remarkably by decreasing the grain size. It is found that the grain size effects are more significant at low temperature. However, it is difficult to reduce the grain size to less than 50 nm without the formation of impurity phases by ball milling. These facts limit the ZT enhancement of the nanostructured HMS at high temperatures in this study. / text

Nanocomposite thin films with gold nanoparticles embedded in a host metal oxide prepared by spray pyrolysis deposition have been investigated. A single-step process has been developed using a one-pot solution containing precursors for both gold nanoparticles and host metal oxides. The films obtained display combined features of colouration, electrical conductivity and solar control. In this study two precursors for gold nanoparticles were used: preformed gold colloids and HAuCl₄. Three metal oxide host materials, TiO₂, SnO₂ and ZnO, were investigated. These films were deposited at a substrate temperature of 200-600 °C. Powder X-ray diffraction analysis reveals the presence of metallic gold. SEM inspection typically showed particulate gold of 5-20 nm in diameter, distributed at the surface or within the host matrix. Optical spectroscopy showed an intense absorption in the visible region due to the characteristic surface plasmon resonance (SPR) effects of gold nanoparticles. The wavelength of the SPR peaks varies depending on the refractive index of surrounding host material which is significantly influenced by the substrate deposition temperature. On the other hand, SnO₂ and ZnO, together with the introduction of dopants, were further investigated as suitable materials for transparent conducting oxides (TCO). SnO₂:F films were found to attain very low electrical resistivity, while ZnO films exhibit higher transparency in the visible. A double layered structure with a TCO layer of SnO₂:F on top of a layer embedded with gold nanoparticles has been employed to achieve the combined functionalities of conductivity and colouration. The electrical conductivity is significantly enhanced compared to a nanocomposite single layer film due to the introduction of the TCO top layer. In this thesis, spray pyrolysis deposition has demonstrated a simple and rapid approach to the production of a variety of thin films. It can be immediately integrated with current industrial coating equipment and scaled up for large-scale production process.

Στην παρούσα διατριβή μελετάται η σύμφωνη αλληλεπίδραση ημιαγώγιμων νανοδομών με ηλεκτρομαγνητικά πεδία. Κατά την αλληλεπίδραση αυτή μπορούν να προκύψουν ενδιαφέροντα φαινόμενα, με αρκετές τεχνολογικές εφαρμογές τόσο στο άμεσο όσο και στο προσεχές μέλλον. Οι σημαντικότερες από αυτές παρατηρούνται στη κβαντική τεχνολογία, στους κβαντικούς υπολογιστές και στις οπτικές επικοινωνίες δεδομένων. / In the present thesis is studied coherent interaction of semiconductor nanostructures with electromagnetic fields. Out of this interaction can result several interesting phenomena and this could be potentially useful in several areas of modern optical and quantum technology, such as quantum computers and optical communications.

L’auto-assemblatge de molècules en nano- i micro-estructures és una àrea de gran interès, sent els lípids particularment atractius en la formació de diverses estructures incloent els liposomes. Hi ha un gran número de mètodes reportats en la literatura per a la preparació de liposomes, però els inconvenients que limiten l’ús generalitzat dels liposomes són; els passos de preparació que requereixen de molt de temps donant lloc a poblacions heterogènies de liposomes de mida incontrolable, l’ús de solvents orgànics i la necessitat de passos per a reduir la mida dels liposomes. Per tant; l’objectiu d’aquest doctorat és la optimització d’un mètode ultra-ràpid per a la preparació de liposomes en un sol pas i lliure de dissolvents orgànics. Anomenat “Curvature tuned preparation method” ha estat implementat en diverses formulacions lipídiques per a la formació de liposomes i d’altres superestructures de lípids. Aquestes estructures s’han emprat en diverses aplicacions, com ara en nanoreactors i plantilles per a la síntesis a mida de nanopartícules d’or, liposomes per encapsular enzims com a potenciadors de senyal en el desenvolupament de immunosensors i finalment, com a vehicles per l’alliberament controlat de fàrmacs. / The self-assembly of molecules into nano- or microstructures is an area of intense interest, with lipids being particularly attractive in the formation several structures including liposomes. There are numerous methods reported for the preparation of liposomes, however, time-consuming preparative steps resulting in heterogeneous liposome populations of incontrollable size, the use of organic solvents and the need of further size-reducing steps are the drawbacks limiting wide-spread use of liposomes. Therefore; the main concern of this PhD thesis is optimization of a one-step, organic solvent-free, ultra rapid method for the preparation of liposomes. So called “Curvature tuned preparation method” was later implemented in several lipid formulations which resulted in liposomes and other lipid superstructures. Those structures were further used in several applications, such as nanoreactors and templates for tailored synthesis of gold nanoparticles, enzyme encapsulating liposomes as signal enhancers in immunosensor development, and finally as carriers for controlled release of drugs

Solar photovoltaic has become one of the potential solutions for current energy needs and for combating greenhouse gas emissions. The photovoltaics (PV) industry is booming, with a yearly growth rate well in excess of 30% over the last decade. This explosive growth has been driven by market development programs to accelerate the deployment of sustainable energy options and rapidly increasing fossil fuel prices. Currently, the PV market is based on silicon wafer solar cells (thick cells of around 150–300 μm made of crystalline silicon). This technology, classified as the first-generation of photovoltaic cells. The second generation of photovoltaic materials is based on the introduction of thin film layers of semiconductor materials. Unfortunately, the conversion efficiency of the current PV systems is low despite the lower manufacturing costs. Nevertheless, to achieve highly efficient silicon solar cell devices, the development of new high quality materials in terms of structure and electrical properties is a must to overcome the issues related to amorphous silicon (a -Si:H) degradation. Meanwhile, to remain competitive with the conventional energy sources, cost must be taken into consideration. Moreover, novel approaches combined with conventional mature silicon solar cell technology can boost the conventional efficiency and break its maximum limits. In our approach, we set to achieve efficient, stable and affordable silicon solar cell devices by focusing on the development of a new device made of epitaxial films. This new device is developed using new epitaxial growth phosphorous and/or boron doped layers at low processing temperature using plasma enhanced chemical vapor deposition (PECVD). The junction between the phosphorous or boron-doped epitaxial film of the device is formed between the film and the p or n-type crystalline silicon (c-Si) substrate, giving rise to (n epi-Si/p c-Si device or p epi-Si/n c-Si device), respectively. Different processing conditions have been fully characterized and deployed for the fabrication of different silicon solar cells architectures. The high quality epitaxial film (up to 400 nm) was used as an emitter for an efficient stable homojunction solar cell. Extensive analysis of the developed fine structure material, using high resolution transmission electron microscope (HRTEM), showed that hydrogen played a crucial role in the epitaxial growth of highly phosphorous doped silicon films. The main processing parameters that influenced the quality of the structure were; radio frequency (RF) power density, the processing chamber pressure, the substrate temperature, the gas flow rate used for deposition of silicon films, and hydrogen dilution. The best result, in terms of structure and electrical properties, was achieved at intermediate hydrogen dilution (HD) regime between 91 and 92% under optimized deposition conditions of the rest of the processing parameters. The conductivity and the carrier mobility values are good indicators of the electrical quality of the silicon (Si) film and can be used to investigate the structural quality indirectly. The electrical conductivity analyses using spreading resistance profile (SRP), through the detection of active carriers inside the developed films, are presented in details for the developed epitaxial film under the optimized processing conditions. Measurements of the active phosphorous dopant revealed that, the film has a very high active carrier concentration of an average of 5.0 x1019 cm-3 with a maximum value of 6.9 x 1019 cm-3 at the interface between substrate and the epitaxial film. The observed higher concentration of electrically active P atoms compared to the total phosphorus concentration indicates that more than half of dopants become incorporated into substitutional positions. Highly doping efficiency ηd of more than 50 % was calculated from both secondary ion mass spectroscopy (SIMS) and SRP analysis. A variety of proposed structures were fabricated and characterized on planar, textured, and under different deposition temperatures. Detailed studies of the photovoltaic properties of the fabricated devices were carried out using epitaxial silicon films. The results of these studies confirmed that the measured open circuit voltage (Voc) of the device ranged between 575 and 580 mV with good fill factor (FF) values in the range of 74-76 %. We applied the rapid thermal process (RTP) for a very short time (60 s) at moderate temperature of 750oC to enhance the photovoltaic properties of the fabricated device. The following results were achieved, the values of Voc, and the short circuit current (Isc) were 598 mV and 27.5 mA respectively, with a fill factor value of up to 76 % leading to an efficiency of 12.5 %. Efficiency enhancement by 13.06 % was achieved over the reference cell which was prepared without using RTP. Another way to increase the efficiency of the fabricated device is to reduce the reflections from its polished substrate. This was achieved by utilizing the light trapping technique that transforms the reflective polished surface into a pyramidical texturing using alkaline solutions. Further enhancements of both Voc and Isc were achieved with values of 612 mV and 31mA respectively, and a fill factor of 76 % leading to an increase in the efficiency by up to 13.8 %. A noticeable efficiency enhancement by ~20 % over the reference cell is reported for the developed devices on the textured surfaces. Moreover, the efficiency of the fabricated epitaxial silicon solar cells can be boosted by the deployment of silicon nanocrystals (Si NCs) on the top surface of the fabricated devices. In the course of this PhD research we found a way to achieve this by depositing a thin layer of Si NCs, embedded in amorphous silicon matrix, on top of the epitaxial film. Structural analysis of the deposited Si NCs was performed. It is shown from the HRTEM analysis that the developed Si NCs, are randomly distributed, have a spherical shape with a radius of approximately 2.5 nm, and are 10-20 nm apart in the amorphous silicon matrix. Based on the size of the developed Si NCs, the optical band gap was found to be in the region of 1.8-2.2 eV. Due to the incorporation of Si NCs layer a noticeable enhancement in the Isc was reported.