The main goal of this work is to search for new stable porous carbon-based materials, which have the ability to accommodate and store hydrogen gas. Theoretical and experimental studies suggest a close relation between the nano-scale structure of the material and its storage capacity. In order to design materials with a high storage capacity, a compromise between the size and the shape of the nanopores must be considered. Therefore, a number of different carbon-based materials have been investigated: carbon foams, dislocated graphite, graphite intercalated by C60 molecules, and metal-organic frameworks. The structures of interest include experimentally well-known as well as hypothetical systems. The studies were focused on the determination of important properties and special features, which may result in high storage capacities. Although the variety of possible pure carbon structures and metal-organic frameworks is almost infinite, the materials described in this work possess the main structural characteristics, which are important for gas storage.

Die eingereichte Dissertation befasst sich mit Übergangsmetalloxid-Nanostrukturen, wobei quasi-eindimensionale Materialien im Mittelpunkt stehen, z.B. Nanoröhren und Nanostäbe. Mittels Suszeptibilitäts- bzw. EELS-Messungen wurden magnetische und elektronische Eigenschaften verschiedener Nanoverbindungen untersucht. Zur weiteren Charakterisierung der Proben wurden außerdem Magnetisierungsmessungen (VSM, Pulsfeld), optische Spektroskopie, AC-Suszeptibilitätsmessungen, Messungen der spezifischen Wärme sowie NMR- und ESR-Experimente durchgeführt. Ein Schwerpunkt dieser Arbeit sind Vanadiumoxid-Verbindungen, wobei Vanadiumoxid-Nanoröhren (VOxNT) aufgrund ihrer besonderen Morphologie eine Sonderstellung unter den vorgestellten Materialien besitzen. Suszeptibilitätsmessungen an den VOxNT offenbaren aktiviertes Verhalten bei Temperaturen T > 100 K, was auf V4+-Spindimere zurückgeführt werden kann. Zudem existieren quasi-freie V4+-Momente sowie längere Spinkettenfragmente, z.B. Trimere. Elektronische Anregungen im Valenzband können wahrscheinlich dem Platzwechsel von 3d-Elektronen zwischen V4+- und V5+-Plätzen innerhalb der gemischtvalenten V-O-Ebenen zugeschrieben werden. Durch Dotierung mit Alkalimetallen ist es möglich, die V 3d-Niveaus mit zusätzlichen Elektronen zu besetzen und dadurch die Vanadiumvalenz zu beeinflussen (V5+ -> V4+ -> V3+). Die dabei auftretenden stärkeren Coulombabstoßungen zwischen den V 3d-Elektronen beeinträchtigen die Mobilität der Ladungsträger. Ebenso wurde gezeigt, dass sich durch die Dotierung mit Ammoniak und anderen Übergangsmetallionen die Vanadiumvalenz sowie der Magnetismus der VOxNT beeinflussen lassen. Die Ergebnisse von weiteren Vanadiumoxid-Nanostrukturen - Co0.33V2O5, alpha-NaV2O5, VO2(B) sowie V3O7·H2O-Nanokristallen - zeigen, dass sehr unterschiedliches magnetisches Verhalten wie Paarbildung zwischen V4+-Spins, antiferromagnetisch gekoppelte Spinketten oder ein Phasenübergang zwischen zwei paramagnetischen Temperaturbereichen auf Nanoebene realisiert werden kann. Die magnetischen Eigenschaften von MnO2-Nanostäben sind durch starke Kopplungen und Frustration zwischen den Mn-Spins gekennzeichnet. Außerdem zeigt die Verbindung Merkmale eines Spinglases. Durch Dotierung mit Elektronen lässt sich bei diesem Material die Mn-Valenz verändern. Schließlich zeigen erste Charakterisierungsmessungen an übergangsmetalldotierten MoO3-Nanobändern paramagnetisches Verhalten dieser Systeme.

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.