<p dir="ltr">The primary goal of this work is to gain a fundamental understanding on how growth conditions affect the morphology and crystallography orientation of CeO₂/Au vertically aligned nanocomposite (VAN) thin films. Focus has been placed on how the changes in morphology and crystallography translate to tunable optical properties. The morphological effects have been observed and analyzed via two main approaches: the change in morphology was observed at multiple points along the film thickness, and the morphology at the film/substrate interface has been analyzed with respect to total film thickness. The changes in Au crystallography orientations have been observed by measuring peak shift in XRD patterns and determining the resulting in- and out-of-plane strain. To observe additional effects of this morphology change, optical measurements have been taken for films at the bottom, middle, and top of the thickness range. Strong trends in transmittance, plasmonic absorption peak shifts and hyperbolic permittivity behavior are correlated with the film thickness. This tunability of optical properties likely arises from changes in both Au pillar phase morphology and crystal orientation. These findings demonstrate that changing film thickness may be a desirable method to easily tune the morphology and optical properties of VAN thin films.</p>

In this work, the mechanism of the corrosion behavior of laser-treated aluminum is studied. Two different laser techniques are used to fabricate the samples, direct laser interference patterning (DLIP) and direct laser writing (DLW), using nanosecond laser sources. The DLIP treatment uses a two-beam optical configuration producing line-like periodic structures. The DLW technique is employed to produce non-periodic structures on the Al-surface with the same cumulated fluences as in DLIP. The surface topography is analyzed by confocal microscopy, and the formation of oxide layers is investigated by scanning electron microscopy of cross-sections produced using a focused ion beam. Wetting measurements performed on the laser-treated samples exhibit a contrasting behavior, leading to either superhydrophobic or superhydrophilic states. In the case of the DLIP treatment, the static water contact angle is increased from 81° up to 158°, while for DLW, it decreases to 3°. Electrochemical tests demonstrate a decreased corrosion rate after laser treatment. Additionally, findings indicate no correlation between wettability and corrosion reduction. Therefore, the improvement in corrosion resistance is mainly attributed to the oxide layer formed by laser treatment. Although similar corrosion rates are achieved for both treatments, surfaces produced with DLIP can be beneficial when additional surface properties are required.

Yes / A novel process chain for serial production of polymer-based devices incorporating both micro- and nano-scale features is proposed. The process chain is enabled by the use of Zr-based bulk metallic glasses (BMG) to achieve the necessary level of compatibility and complementarity between its component technologies. It integrates two different technologies, namely laser ablation and focused ion beam (FIB) milling for micro-structuring and sub-micron patterning, respectively, thus to fabricate inserts incorporating different length scale functional features. Two alternative laser sources, namely nano-second (NS) and pico-second (PS) lasers, were considered as potential candidates for the first step in this master-making process chain. The capabilities of the component technologies together with some issues associated with their integration were studied. To validate the replication performance of the produced masters, a Zr-based BMG insert was used to produce a small batch of micro-fluidic devices by micro-injection moulding. Furthermore, an experimental study was also carried out to determine whether it would be possible by NS laser ablation to structure the Zr-based BMG workpieces with a high surface integrity whilst retaining the BMG's non-crystalline morphology. Collectively, it was demonstrated that the proposed process chain could be a viable fabrication route for mass production of polymer devices incorporating different length scale features.

The absence of a cheap and easily scalable synthesis technique for nitrogen-vacancy (NV) centers enriched nanodiamonds (NDs) is a critical factor for the development of devices based on this very peculiar nanoparticle. Indeed, the combination between the unique NV fluorescence properties and NDs characteristics allow to obtain a tool having quantum sensing capabilities, with nanometric spatial resolution, which is able to operate in a wide range of temperature, pressures and in harsh chemical conditions. NVenriched NDs applications in nanothermometry, nanomagnetometry and in bio-imaging have already been reported. However, most of the standard fluorescent NDs production techniques present common drawbacks: poor control in NDs size distribution and in nitrogen concentration, as well as the need of post-synthesis process to clean the NDs surface from impurities and to increase the NV density. In this thesis, an alternative method for fluorescent NDs synthesis based on pulsed laser ablation (PLA) of graphite is demonstrated. After the introductory chapters on NV-centers physics and NDs properties (Chapter 2 and 3), the demonstration that PLA is a viable route for synthesis of NDs is given in Chapter 4. In particular, PLA of graphite and of diamond-like carbon is performed in water. Here, a thermodynamic model taking into account the peculiar physical processes occurring during PLA is developed to explain NDs formation. Then, synthesis of NV-enriched NDs is demonstrated through PLA of graphite in a nitrogen atmosphere (Chapter 5) and in liquid nitrogen (Chapter 6). In both chapters, the thermodynamic model is adapted to explain diamond phase formation in a gaseous environment and in a cryogenic liquid. Furthermore, NV centers optical properties are fully characterized with optically detected magnetic resonance (ODMR) spectroscopy. Finally, in Chapter 7, fluorescent NDs are produced by laser ablation of N-doped graphite in water. This particular target is then used for a quantitative comparison between the other fluorescent NDs laser-synthesis, with the aim of establishing in which condition the highest NV-center formation efficiency is achieved.

Two technologies, namely Laser Technology and Surface Modification Technology, have made rapid strides in the last few decades. The lasers have evolved from a simple laboratory curiosity to a matured industrial tool and its applications are limited only by imagination. Intense, coherent and monochromatic laser sources with power outputs ranging over several orders of magnitude have found innumerable applications in the realm of materials engineering. Reactive Pulsed Laser Deposition (PLD) is a powerful technique that utilises the power of a nanosecond pulsed laser for materials synthesis. Unlike conventional PLD, which require high density targets that are difficult to synthesize at a reasonable cost, the RPLD circumvents the need for one such ceramic target. This thesis presents a detailed and judicious use of this technique for synthesis of hard ceramic multilayer coatings using elemental metal targets. Transition metal nitrides having rock salt structure are known to exhibit superior properties such as hardness and wear resistance and hence formed the basis for the development of first generation coatings. Further improvements through alloying of these binary compounds with metal or metalloid components lead to the development of second generation coatings. As the demand for functional materials increased, surface modification technology alias surface engineering, grew in leaps and bounds. As the large number of coating requirements for optimal performance could not be fulfilled by a single homogeneous material, third generation coatings, comprising multilayer coatings, were developed. It is this aspect of combining the advantages of RPLD process to synthesize ceramic multilayer coatings, provides the main motivation for the present research work. In this thesis, a systematic study presented for synthesis of nanocrystalline and stoichiometric TiN and NbN thin films using RPLD through ablation of high purity titanium and niobium targets, in the presence of low pressure nitrogen gas. A novel Secondary Ion Mass Spectrometry (SIMS) based analysis was developed to effectively deduce the important process parameters in minimum trials to arrive at desired composition. The validity of this SIMS based method, for optimization of process parameters to get stoichiometric nitride films, was proved beyond any speculation by corroborative Proton Elastic Backscattering Spectrometric (PEBS) analysis. SIMS was also used to characterize the [NbN/TiN] multilayers. The feasibility of growing nanocrystalline multilayers with varying thicknesses has been demonstrated. Nanomechanical properties including hardness and adhesion strength of monolithic TiN and NbN films and multilayers were evaluated. The thesis is organised into six chapters. The first chapter gives a brief account on the history and development of ‘surface engineering’. The second chapter provides a comprehensive description of the experimental facility developed in-house to pursue research on PLD grown ceramic thin films and multilayers. Thin film synthesis procedure for ex-situ SIMS and TEM analyses is described. Brief introduction is also presented on the characterization techniques used in this study to investigate the surface, interface and microstructural aspects of PLD grown films with underlying basic principles. The third and fourth chapter describes the synthesis and characterization of titanium nitride and niobium nitride thin films using RPLD technique, respectively. SIMS was used in depth profiling mode, for optimization of three important process parameters, viz., nitrogen gas pressure, substrate temperature and laser pulse energy, to get stoichiometric nitride films. Further, films were characterized using GIXRD, TEM, XPS and PEBS for their structure and composition. AFM measurements were made to elucidate the surface morphological features. PEBS was effectively used to estimate the nitrogen concentration in a quantitative manner and the results corroborate well with the SIMS measurements. Having succeeded in synthesizing stoichiometric TiN and NbN films, further studies on the nanomechanical properties of monolithic TiN and NbN films and their multilayers were carried out and these results form the contents of the fifth chapter. The findings of the work reported in this thesis are concluded in Chapter 6 and few possible suggestions were presented as future directions. Both the monolithic TiN and NbN coatings showed a deposition pressure dependent hardness variation. The hardness of these monolithic films was found to be around 30 GPa, higher than the hardness values obtained by other conventional techniques. Keeping total thickness of the multilayers constant at 1 μm, [NbN/TiN] multilayers having bilayer periods ranging from 50 nm to 1000 nm, were synthesized. A systematic enhancement in hardness upto ~ 40 GPa was observed for [NbN/TiN]10 with the modulus of the multilayer remaining almost constant. The pileup observed around the indentation edge is indicative of toughening in multilayers. The tribological properties of multilayer films showed a better performance in terms of low coefficient of friction and regeneration of coating surfaces as revealed from the nanotribological studies. Overall, the multilayer coatings exhibited better performance in terms of hardness, toughness and adhesion with the substrate material.

No description available.

Le domaine de l’enregistrement magnétique est en constante évolution pour repousser davantage les limites de stockage de l’information, une approche prometteuse étant l’enregistrement perpendiculaire. Le matériau faisant l’objet de ce manuscrit est le ferrite de cobalt CoFe2O4 (= CFO). Ses propriétés font de lui un candidat prometteur pour la réalisation de dispositif à enregistrement perpendiculaire, cela passant par le contrôle de sa direction de facile aimantation.Ce travail de thèse traite ainsi de la modification de l’anisotropie magnétocristalline du CFO en couche mince par dopage aux éléments de terres rares. Nous avons démontré la possibilité de moduler la direction de facile aimantation du CFO non dopé, en modifiant la pression partielle en O2/N2 lors de l’élaboration. Nous avons également mis en évidence l’insertion des éléments lanthanides dans la structure du CFO ainsi que l’impact de l’anisotropie de la terre rare sur les propriétés magnétiques du matériau. / The field of magnetic storage is in constant progress to constantly push further the storage capacity of the device. A promising approach is the perpendicular magnetic recording of datas. The material presented in this manuscript is cobalt ferrite. It is an excellent candidate for the realization of perpendicular storage device due to its properties. The present work deals with the modification of the magnetic anisotropy by doping the ferrite cobalt thin films with rare earth elements. We have demonstrated the possibility to modulate the easy magnetization axis of undoped cobalt ferrite by changing the partial pressure of O2/N2 during the elaboration of the thin films. We have also highlighted the insertion of rare earth elements into the structure of the cobalt ferrite although their important ionic radii. The impact of the rare earth anisotropy on the magnetic properties of the ferrite cobalt has also been observed.

Les composants électroniques utilisés pour des applications spatiales sont soumis à des rayonnements susceptibles de les rendre inopérants. Pour se prémunir de tels effets, leur sensibilité est testée au sol dans des accélérateurs de particules, onéreux et complexes à mettre en œuvre. Ce travail de thèse porte sur l’utilisation d’impulsions laser pour reproduire sous certaines conditions les effets des ions lourds. Le déclenchement de phénomènes parfois destructifs sur plusieurs types de composants de niveaux d’intégration différents a été obtenu sur le banc laser développé pendant cette thèse. Cela ouvre la voix à l’utilisation du laser comme outil de diagnostic en tirant partie de ses avantages en termes d’accessibilité, de coûts et de compréhension fine des effets. / Electronic components used for space applications may exhibit failures under radiation. To prevent uch effects, the radiation sensitivity is evaluated using particle accelerators. Since those facilities are nly few around the world and expensive, complementary tests are needed to analyse radiation ensitivity. This work contributes to the use of laser pulses to reproduce under given conditions the ffects of heavy ions. Using the laser set-up developed during this thesis, single events which may be estructive were triggered on several types of electronic components. This paves the way to the use of aser as a diagnostic tool, given its advantages in terms of accessibility, costs and detailed analysis

Laser Diodes (LDs) are semiconductor coherent lightening devices which are widely used in many fields such as defence, industry, medical and optical communications. They have advantageous characteristics such as having higher electrical-to-optical and optical-to-optical conversion efficiencies from pump source to useful output power when compared to flash lamps, which makes them the best devices to be used in range finding applications. Optical output power of lasers depends on current through LDs. Therefore, there is a relationship between operating life and work performance of LDs and performance of drive power supply. Even, weak drive current, small fluctuations of drive current can result in much greater fluctuations of optical output power and device parameters which will reduce reliability of LDs. In this thesis, a hardware for a fast and high power pulsed LD driver is designed for laser range finder and is based on linear current source topology. The driver is capable of providing pulses up to 120A with 250&mu / s pulse width and frequencies ranging from 20Hz to 40Hz. It provides current pulses for two LD arrays controlled with a proportional-integral (PI) controller and protect LDs against overcurrents and overvoltages. The proposed current control in the thesis reduces current regulation to less than 1% and diminishes overshoots and undershoots to a value less than 1% of steady-state value, which improves safe operation of LDs. Moreover, protection functions proposed in the thesis are able to detect any failure in driver and interrupt LD firing immediately, which guarantees safe operation of LDs.

The thesis consists of two parts. Part 1 deals with the preparation of thin films and sub-micron powders of complex metal oxides by nebulized spray pyrolysis (NSP) and Part 2 consists of Brillouin scattering studies of solid materials exhibiting interesting phase transitions. The simple technique of NSP has been employed to prepare thin films of A12O3, PbTiO3, Pb(Zr0.5Ti0.5)O3 (PZT) and PbZrO3 on single crystal substrate. The films were characterized by various techniques for their composition, structure, morphology and dielectric properties. Ferroelectric (FE) films of the configuration FE/LaNiO3/SiO2/Si (FE = PbTiO3 and PZT), wherein the LaNiO3 barrier electrode was also deposited on the SiO2/Si substrate by NSP, have been investigated. The films exhibit satisfactory ferroelectric properties. PbZrO3 films deposited on LaNiO3/SiO2/Si substrates show good features, including a reversible AFE ↔ FE transition. Sub-micron particles of TiO2, ZrO2, Pb(Zr0.5Ti0.5)O3, Al2O3, S1O2 and mullite have been prepared by NSP and characterized by various techniques. Brillouin scattering has been used, for the first time, not only to characterize the Peierls transition but also the incommensurate to commensurate transition in the one-dimensional blue bronze, K0.3M0O3. The charge density wave transition in NbSe2 has also been investigated by Brillouin scattering. The charge ordering and antiferromag-netic transitions in single crystals of the rare earth manganates, Nd0.5Ca0.5MnO3 and Pr0.63Ca 0.37MnO3, have been investigated by Brillouin scattering. It is noteworthy that the temperature variation of the Brillouin shift and intensity parallel to that of the magnetization, thereby throwing light on magnetic excitations in charge-ordered state. Brillouin scattering investigations of C60 and C70 films have yielded values of the elastic moduli.