Deposition of nanoscale thickness films is ubiquitous in micro- and nano-scale device manufacturing. Current techniques such as spin-coating and chemical vapor deposition are designed to create only uniform thin films, and can be wasteful in material consumption. They lack the ability to adaptively prescribe desired film thickness profiles. This dissertation presents a novel inkjet-based zero-waste polymer deposition process referred to as Jet and Coat of Adaptive Sustainable Thin Films or J-CAST. The core of this process is built on an experimentally validated multi-scale fluid evolution model, based on extensions of lubrication theory. This model involves a nano-scale fluid film sandwiched between two flat plates: a compliant superstrate and a rigid substrate, with spatial topography on both surfaces. Accounting for the flexural elasticity of the compliant superstrate, and describing the temporal evolution of the fluid film in the presence of different boundary conditions reveals that instead of seeking process equilibrium, non-equilibrium transients should be exploited to guide film deposition. This forms the first core concept behind the process. This concept also enables robust full-wafer processes for creation of uniform films as well as nanoscale films with prescribed variation of thickness at mm-scale spatial wavelengths. The use of inkjets enables zero-waste adaptive material deposition with the preferred drop volumes and locations obtained from an inverse optimization formulation. This forms the second core concept behind the process. The optimization is based on the prescribed film thickness profile and typically involves >100,000 integer parameters. Using simplifying approximations for the same, three specific applications have been discussed - gradient surfaces in combinatorial materials science and research, elliptical profiles with ~10km radius of curvature for X-ray nanoscopy applications and polishing of starting wafer surfaces for mitigation of existing nanotopography. In addition, the potential of extending the demonstrated process to high throughput roll-roll systems has also been mentioned by modifying the model to incorporate the compliance of the substrate along with that of the superstrate. / text

Ces travaux concernent l’étude expérimentale des textures se développant dans les ménisques de films smectiques de cristaux liquides thermotropes. Ces fluides complexes nous servent de système modèle pour l’étude des couplages élasto-capillaires qui se manifestent dans certaines conditions par des déformations périodiques de l’interface cristal liquide-air. Dans un premier temps, à partir de l’étude détaillée de la topographie de l’interface par une méthode interférométrique, nous caractérisons les différents types de structures, puis, identifions les principaux paramètres impliqués dans le processus d'apparition des défauts dans le ménisque de films libres suspendus. Ces résultats nous servent de base pour discuter des mécanismes physiques qui génèrent les différents types de défauts observés. Nous regardons en particulier, comment la diminution d’épaisseur de couche associée à une transition de phase va induire une instabilité mécanique responsable de l’apparition des ondulations de l’interface. Dans un deuxième temps, afin d’aller plus loin dans la compréhension des mécanismes, nous avons utilisé des films minces de cristaux liquides déposés sur des substrats solides microstructurés par des plots fabriqués par des techniques photolitographiques. Une telle géométrie permet de générer un ménisque autour de chaque plot et surtout de faire varier un plus grand nombre de paramètres comme par exemple l’ancrage sur le substrat via un traitement chimique de surface. L’ensemble de nos résultats apportent un éclairage nouveau sur la caractérisation et la compréhension des déformations spécifiques aux ménisques de fluides complexes. / The present work is an experimental study of the textures that appear in the meniscus of free standing smectic films with thermotropic liquid crystals. These complex fluids serve as model systems to investigate elasto-capillary phenomena which, under certain conditions, manifest themselves through periodic deformations of the liquid crystalair interface. In the first part of the thesis, we focus our attention on meniscus structures whose interfacial topographies are thoroughly characterized thanks to an in-house optical interferometry technique. Our study allows us to identify the main parameters involved in the development of meniscus structures and to discuss the physical mechanisms that are likely to be responsible for their formation. In particular, we show how a phase transition-induced layer shrinkage triggers a mechanical instability leading to interfacial undulations of the smectic free surface. In the second part of the manuscript, we address the case of thin liquid crystal films deposited on solid patterned solid substrates. The latter consist of regular arrays of microposts fabricated through photolithographic techniques. Such a geometry allows a meniscus to be formed around each micropost and makes it possible to examine the influence of other parameters such as the anchoring conditions on the solid substrate. The results gathered so far are able to shed some light on the characterization and the understanding of the specific deformations and textures that appear in the menisci of complex fluids.

Droplet evaporation is ubiquitous to multitude of applications such as microfluidics, surface patterning and ink-jet printing. In many of the process like food processing tiny concentrations of suspended particles may alter the behavior of an evaporating droplet remarkably, leading to partially viscous and partially elastic dynamical characteristics. This, in turn, may lead to some striking mechanical instabilities, such as buckling and rupture. In this thesis, we provide a comprehensive physical description of the vaporization, self-assembly, agglomeration and buckling kinetics of sessile nanofluid droplet pinned on a hydrophobic substrate in various configurations. We have deciphered five distinct regimes of droplet lifecycle. Regime I-III consists of evaporation induced preferential agglomeration that leads to the formation of unique dome shaped inhomogeneous shell with stratified varying density liquid core. Regime IV involves capillary pressure initiated shell buckling and stress induced shell rupture. Regime V marks rupture induced cavity inception and growth. We provide a regime map explaining the droplet morphology and buckling characteristics for droplets evaporating on various substrates. Specifically, we find that final droplet volume and radius of curvature at buckling onset are universal functions of particle concentration. Furthermore, flow characteristics inside the heated and unheated droplets are investigated and found to be driven by the buoyancy effects. Velocity magnitudes are observed to increase by an order at higher temperatures with self-similar flow profiles. With an increase in the surface temperature, droplets exhibit buckling from multiple sites over a larger sector in the top half of the droplet. In addition, irrespective of the initial nanoparticle concentration and substrate temperature, hydrophobicity and roughness, growth of daughter cavity (subsequent to buckling) inside the droplet is found to be controlled by the solvent evaporation rate from the droplet periphery. The results are of great significance to a plethora of applications like DNA deposition and nanofabrication. In the next part of the thesis, we deploy the droplet in a rectangular channel. The rich physics governing the universality in the underlying dynamics remains grossly elusive. Here, we bring out hitherto unexplored universal features of the evaporation dynamics of a sessile droplet entrapped in a 3D confined fluidic environment. Increment in channel length delays the completion of the evaporation process and leads to unique spatio-temporal evaporation flux and internal flow. We show, through extensive set of experiments and theoretical formulations, that the evaporationtimescale for such a droplet can be represented by a unique function of the initial conditions. Moreover, using same theoretical considerations, we are able to trace and universally merge the volume evolution history of the droplets along with evaporation lifetimes, irrespective of the extent of confinement. These results are explained in the light of increase in vapor concentration inside the channel due to greater accumulation of water vapor on account of increased channel length. We have formulated a theoretical framework which introduces two key parameters namely an enhanced concentration of the vapor field in the vicinity of the confined droplet and a corresponding accumulation lengthscale over which the accumulated vapor relaxes to the ambient concentration. Lastly, we report the effect of confinement on particle agglomeration and buckling dynamics. Compared to unconfined scenario, we report non-intuitive suppression of rupturing beyond a critical confinement. We attribute this to confinement-induced dramatic alteration in the evaporating flux, leading to distinctive spatio-temporal characteristics of the internal flow leading to preferential particle transport and subsequent morphological transitions. We present a regime map quantifying buckling & non-buckling pathways. These results may turn out to be of profound importance towards achieving desired morphological features of a colloidal droplet, by aptly tuning the confinement space, initial particle concentration, as well as the initial droplet volume. These findings may have implications in designing functionalized droplet evaporation devices for emerging engineering and biomedical applications.

Depuis une vingtaine d'années, des composants électroniques flexibles sont développés. Ces composants étant amenés à se tordre, à s'étirer et à se fléchir au cours de leur utilisation, le développement de composants ayant une bonne fiabilité mécanique est primordial. Ce travail s'est concentré sur les films métalliques d'argent déposés par impression jet d'encre ou sérigraphie sur des substrats de polyimide, servant à l’interconnexion électrique entre composants actifs. Deux mécanismes d’endommagement sont observables dans ces systèmes : la fissuration et le flambement par délaminage.Premièrement, pour caractériser expérimentalement ces deux phénomènes, des tests de traction sont réalisés sous microscope optique, afin de suivre l'évolution des fissures au cours de la déformation et sous interféromètre optique, afin de suivre les cloques de délaminage. Une analyse d'images est réalisée afin d'obtenir l'évolution de l'espacement entre fissures au cours de la déformation. L'existence de deux régimes de fissuration est observée : la fissuration longue et droite pour les films épais et la fissuration courte et en forme de zigzag pour les films minces. Le suivi des profils de cloques permet d'obtenir l'évolution de leur forme au cours de la déformation.Ensuite, afin d'éclairer les observations expérimentales, les phénomènes à l'étude sont modélisés par élément finis. Ainsi l'origine des deux régimes de fissuration est expliquée par un effet géométrique de l'épaisseur du film. Un modèle élastoplastique bidimensionnel de relaxation de contraintes dans le film permet d'obtenir un encadrement de l'espacement entre fissures au cours de la déformation. À partir du suivi des cloques, un modèle tridimensionnel permet de réaliser une identification des paramètres de la zone cohésive à l'interface film/substrat, où une énergie d'adhésion de 2 J.m-2, une contrainte critique de 20 MPa et un paramètre de mixité modale de 0,4 sont déterminés. Ces valeurs sont en accord avec la littérature. / Over the past 20 years, new improvements in materials and processes led to the development of printed flexible electronics. Flexible electronics devices subjected to bending, twisting, or stretching during their lifetime, the development of device with high reliability is therefore of great importance for the efficiency of electrical connection. This work investigates the mechanical reliability of inkjet or screen-printed Ag thin films on polyimide substrates dedicated to the electrical interconnection of active components. Expected mechanical failure modes are film cracking and buckling delamination.First of all, in order to characterized the two mechanisms, tensile tests are performed under an optical microscope to follow cracks and under an optical interferometer to follow buckles. In order to obtain crack spacing evolution during deformation, an image processing is realized. Two types of cracks are observed: long and straight cracking for thick films and small and zigzag shape cracking for thin films. The evolution of buckles shape with imposed tensile deformation is characterized.In a second time, in order to understand experimental observations, mechanical failure modes are analysed with finite elements models. The origin of the two types of cracking are explained by a geometrical effect of film thickness. A elastoplastic shear lag bidimensional model gives upper and lower bonds of crack spacing during deformation. A three-dimensional model allows identification of cohesive zone model parameters at film/substrate interface, from experimental buckle shape. An adhesion energy of 2 J.m-2 , a critical strength of 20 MPa and a mode mixity parameter of 0.4 are determined. These values are in good agreement with literature.

Numa primeira etapa, estudamos as conexões da VTA para o complexo VTA-substância negra (SN) utilizando a leucoaglutinina do Phaseolus vulgaris (PHA-L). Estas conexões são substanciais, topograficamente organizadas, com destaque para o pólo caudal da VTA que inerva bilateralmente toda a extensão deste complexo. Numa segunda etapa, estudamos as projeções da VTA para o hipotálamo. A VTA se projeta principalmente para a área pré-óptica lateral e área hipotalâmica lateral, a região subfornical posterior e o núcleo dorsomedial. Foram vistas poucas aposições entre varicosidades PHA-L+ e neurônios imunorreativos para orexina ou para hormônio concentrador de melanina. Por fim, estudamos a colocalização do substrato do receptor de insulina (IRS-1), IRS-1 fosforilado e fosfatidilinositol-3 quinase (PI3K) com tirosina hidroxilase (TH) ou com a subunidade B da toxina colérica (CTb) injetada no estriado. A maioria dos neurônios TH+ da VTA-SN expressa IRS-1; injeções de CTb no estriado resultaram em células duplamente marcadas para CTb/IRS-1, CTb/PI3K e CTb/IRS-1 fosforilado. / In a first step, we studied the connections of the VTA to the complex VTA-substantia nigra (SN) using the Phaseolus vulgaris leucoagglutinin (PHA-L). These connections are substantial, topographically organized, especially the caudal pole of the VTA, which innervates bilaterally throughout the length of this complex. In a second step, we studied the projections of the VTA to the hypothalamus. The VTA projected mainly to the lateral preoptic area, lateral hypothalamic area, posterior subfornical region and dorsomedial nucleus. Were observed few appositions between PHA-L+ varicosities and neurons immunoreactive for orexin or melanin-concentrating hormone. Finally, we studied the co-localization of the insulin receptor substrate-1 (IRS-1), IRS-1-phosphorylated and phosphatidylinositol-3 kinase (PI3K) with tyrosine hydroxylase (TH) or cholera toxin B subunit (CTb) injected into the striatum. Most TH+ neurons of the VTA-SN expressed IRS-1; CTb injections in the striatum resulted in cells double-labeled for CTb/IRS-1, CTb/PI3K and CTb/IRS-1 phosphorylated.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-07-21T11:39:31Z No. of bitstreams: 1 monalisadepaularocha.pdf: 972026 bytes, checksum: 1d1124c048f5e7456925bd61ed099336 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-22T15:28:17Z (GMT) No. of bitstreams: 1 monalisadepaularocha.pdf: 972026 bytes, checksum: 1d1124c048f5e7456925bd61ed099336 (MD5) / Made available in DSpace on 2016-07-22T15:28:17Z (GMT). No. of bitstreams: 1 monalisadepaularocha.pdf: 972026 bytes, checksum: 1d1124c048f5e7456925bd61ed099336 (MD5) Previous issue date: 2011-02-28 / Polybia platycephala (Richards, 1978) é uma vespa social enxameante que possui seu ninho constituído de várias filas de favos horizontais cobertos favo-a-favo por um envelope. Neste estudo caracterizou-se o padrão de fundação, arquitetura do ninho, o padrão de estocagem de recursos nas colônias, o ciclo colonial, a população, os estágios imaturos, e o número de ínstares larvais de P. platycephala. Além disso, o macho da espécie é descrito e ilustrado. No período de novembro de 2009 a novembro de 2010, foram estudadas 95 colônias em áreas antrópicas do município de Juiz de Fora, MG. Para descrição do padrão de fundação, foram realizadas observações ―ad libitum‖ em quatro enxames. Para analisar a arquitetura do ninho foram considerados os seguintes dados: coloração, comprimento e largura do orifício de entrada, e dimensões do ninho. O ângulo de orientação das colônias foi estabelecido com uma bússola posicionada abaixo dos ninhos. Através da dissecção de 15 colônias, foi verificada a fase de desenvolvimento e o número de: adultos, total de células, células vazias, ovos, larvas, e pupas. Foram mensuradas, a maior largura e o maior comprimento de 100 ovos, e a largura máxima da cápsula cefálica de 400 larvas e 120 pupas, sendo o número de ínstares larvais determinado de acordo com a Regra de Dyar. Foi possível determinar que antes da construção das primeiras células, P.platycephala constrói uma fina base de material vegetal sobre o substrato. O processo de construção inicial do ninho durou de 10 a 15 dias. A nidificação na vegetação foi maior do que em substratos construídos (x²= 53,063; p < 0,0001). Em média, os ninhos apresentaram 2115 ± 1234 (328 - 4723) células, podendo conter até oito favos, e estavam situados a cerca de 3,0 metros do solo. A distância média entre os favos foi de 0,67 ± 0,09 cm (0,53 - 0,85). Houve diferença sazonal no sentido de orientação dos ninhos fundados pela espécie, com ninhos na estação chuvosa orientados principalmente para o sul e ninhos na estação seca orientados para o norte. Os eventos de fundação e abandono das colônias ocorreram em todas as épocas do ano. As colônias produziram 510,26 ± 403,21 (71 – 1492) adultos e encontravam-se em diferentes fases do ciclo colonial. As oviposturas nos favos ocorreram geralmente do centro para a periferia, com pupas nas células centrais circundadas de larvas em diferentes ínstares, seguida de ovos e células vazias na periferia. Constatou-se a presença de casulos de parasitóides no interior das células de cinco ninhos. Foi observada a estocagem de substância açucarada em 80% das colônias (seis em fase de produção de operárias, três em fase de quiescência, duas na produção de machos e um na pré-emergência). O armazenamento ocorreu sempre em células vazias (92,63%), células com presas (4,88%), células com ovos (2,0%) ou células com larvas pequenas (0,5%). A estocagem de presas foi observada em duas colônias, dentro das células ou entre os favos dos ninhos. As larvas possuem cinco ínstares, com uma razão média de crescimento de 1,57. Os machos de P. platycephala distinguem-se das fêmeas por características como o clípeo amarelo com ou sem pilosidade prateada; antena não tão robusta, com 13 segmentos; gena estreita; gáster com 1-6 tergitos. / Polybia platycephala (Richards, 1978) is a social swarming wasp which has its nest constituted of several lines of horizontal combs covered each one of them by an envelope. In this study, it was characterized the foundation pattern, the nest architecture, the storage pattern of resources in the colony, the colonial cycle, the population, the immature stages, and the number of larval instars of P. platycephala. Furthermore, the male of the species is described and illustrated. During the period from November 2009 the November 2010, 95 colonies were studied in antropic areas of the city of Juiz de Fora, MG. For the description of the foundation pattern, some ―ad libitum‖ observations were performed on four swarms. For analyzing the architecture of the nest, the following data were considered: coloration, length and width of the entrance orifice, and nest dimensions. The orientation angle of the colonies was established with a compass. Through the dissection of 15 colonies, it was verified the development phase and the number of adults, total of cells, vacant cells, eggs, larvae, and pupae. The largest width and the largest length of 100 eggs and the maximum width of the cephalic capsule of 400 larvae and 120 pupae were measured, and the number of larval instars is determined according to the Dyar’s Rule. It was possible to determinate that before the construction of the first cells, P. platycephala builds a slim base of vegetal material on the substrate. The initial process of construction has lasted from 10 to 15 days. The nidification in the vegetation was bigger than in constructed substrates (x²= 53.063; p < 0.0001). On average, the nests presented 2115 ± 1234 (328 - 4723) cells, which can contain up to eight combs, and they were situated about 3.0 meters above ground. The average distance between the combs was about 0.67 ± 0.09 cm (0.53 – 0.85). There was a seasonal difference in the orientation meaning of the nests founded by the species, with nests oriented mainly towards the south in the rainy season, and the north in the dry season. The events of foundation and abandonment of the colonies occurred all the year round. The colonies produced 510.26 ± 403.21 (71 – 1492) adults and these were found in different phases of the colonial cycle. The postures in the combs occurred generally from the center to the periphery, with pupae in the central cells surrounded by larvae in different instars, followed by eggs and vacant cells in the periphery. It was verified the presence of cocoons of parasitoids in the cells of five nests. It was observed the storage of sugary substance in 80% of the colonies (six in worker production stage, three in quiescence stage, two in the production of males and one in the pre-emergence). The storing always occurred in vacant cells (92.63%), cells with preys (4.88%), cells with eggs (2.0%) or cells with small larvae (0.5%). The storing of preys was observed in two colonies, inside the cells and between the combs of the nests. The larvae have five instars, with a a mean ratio of growth of 1.57. The males of P. platycephala differ from the females with characteristics like the yellow clypeus with or without silver hairiness; antenna not so robust, with 13 segments; narrow gena; gaster with 1-6 tergitos.

Les nanoparticules (NPs) d'Ag sont très utilisées dans le secteur de la santé, dans l'industrie alimentaire et dans les produits de consommation pour leurs propriétés antimicrobiennes. Le grand rapport surface sur volume des NPs d'Ag permet une augmentation importante du relargage d'Ag comparé au matériau massif et donc une toxicité accrue vis à vis des micro-organismes sensibles à cet élément. Ce travail de thèse présente une évaluation des propriétés antimicrobiennes de petites NPs d'Ag (<20 nm) enrobées dans des matrices de silice sur la photosynthèse d'algues vertes. Deux techniques d'élaboration par voie physique ont été utilisées pour fabriquer ces nanocomposites: (i) l'implantation ionique à basse énergie et (ii) la pulvérisation d'Ag couplée avec la polymérisation plasma. Les propriétés structurales et optiques de ces nanostructures ont été étudiées par microscopie électronique à transmission, réflectivité et ellipsométrie. Cette dernière technique, couplée à un modèle basé sur l'approximation quasi-statique de type Maxwell-Garnett, a permis la détection de petites variations dans la taille et la densité des NPs d'Ag. Le relargage d'argent de ces NPs d'Ag enrobées dans des diélectriques a été mesuré par spectrométrie de masse après immersion dans de l'eau tamponnée. La toxicité à court terme de l'Ag sur la photosynthèse d'algues vertes, Chlamydomonas reinhardtii, a été évaluée par fluorométrie. L'enrobage des nanoparticules dans un diélectrique réduit leur interaction avec l'environnement, et les protège d'une oxydation rapide. La libération d'Ag bio-disponible (impactant sur la photosynthèse des algues) est contrôlée par la profondeur à laquelle se trouvent les NPs d'Ag dans la matrice hôte de silice. Cette étude permet d'envisager le design de revêtements à effet biocide contrôlé. En couplant les propriétés antimicrobiennes de ces NPs d'Ag enrobées à leur qualité d'antenne plasmonique, ces nanocomposites peuvent être utilisés pour détecter et prévenir les premières étapes de la formation de biofilms sur des surfaces. Ainsi, une dernière partie de ce travail est dédiée à l'étude de la stabilité et de l'adsorption de protéines fluorescentes Discosoma rouges recombinantes (DsRed) sur ces surfaces diélectriques avec la perspective du développement de dispositifs SERS. / Silver nanoparticles (AgNPs) because of their strong biocide activity are widely used in health-care sector, food industry and various consumer products. Their huge surface-volume ratio enhances the silver release compared to the bulk material, leading to an increased toxicity for microorganisms sensitive to this element. This work presents an assessment of the biocide properties on algal photosynthesis of small (<20 nm) AgNPs embedded in silica layers. Two physical approaches were used to elaborate these nanocomposites: (i) low energy ion beam synthesis and (ii) combined silver sputtering and plasma polymerization. These techniques allow elaboration of a single layer of AgNPs embedded in silica films at defined nanometer distances (from 0 to 7 nm) beneath the free surface. The structural and optical properties of the nanocomposites were studied by transmission electron microscopy, reflectance spectroscopy and ellipsometry. This last technique, coupled to modelling based on the quasi-static approximation of the classical Maxwell-Garnett formalism, allowed detection of small variations over the size and density of the embedded AgNPs. The silver release from the nanostructures after immersion in buffered water was measured by inductively coupled plasma mass spectrometry. The short-term toxicity of Ag to the photosynthesis of green algae, Chlamydomonas reinhardtii, was assessed by fluorometry. Embedding AgNPs reduces their interactions with the buffered water, protecting the AgNPs from fast oxidation. The release of bio-available silver (impacting on the algal photosynthesis) is controlled by the depth at which AgNPs are located for the given host silica matrix. This provides a procedure to tailor the biocide effect of nanocomposites containing AgNPs. By coupling the controlled antimicrobial properties of the embedded AgNPs and their quality as plasmonic antenna, these coatings can be used to detect and prevent the first stages of biofilm formation. Hence, the last part of this work is dedicated to a study of the structural stability and adsorption properties of Discosoma recombinant red (DsRed) fluorescent proteins deposited on these dielectric surfaces with perspectives of development of SERS devices.

The research topic of liquid drop interaction with solid surfaces is being actively pursued to gain in-depth understanding of several practical cases such as the impingement of fuel spray droplets on surfaces like combustion chamber walls and piston top of an I.C. engine, heat transfer via spray impingement, ink-jet printing, etc. In most of the cases, the physical and flow properties of the liquid drop/spray may be fixed whereas it may be possible to tune the physical and chemical properties of the solid surface thereby enabling to control the interaction process. The present work belongs to the study of liquid drop-solid surface interaction process with special focus on the physical characteristics of solid surface. The thesis reports an experimental study of the dynamics of millimetric water drops impacted onto the junction of dual-textured substrates made of stainless steel. The dual-textured substrates consisted of hydrophobic (textured) and hydrophilic (smooth) portions. The entire textured portion comprised of parallel groove-like structures separated by solid posts/pillars. Two dual-textured substrates, which differ only in the geometry of their textured portions, were employed. Surface topography features of the dual-textured substrates were characterized using scanning electron microscopy (SEM) and optical surface profilometer. The wetting behavior of the textured and smooth portions of the substrates, quantified in terms of the equilibrium, advancing, and receding contact angles adopted by a water drop on the surface portions, was characterized experimentally through the methods of sessile drop formation, captive needle volume addition, and drop evaporation under ambient conditions. Free-falling water drops were impacted from a height onto the junction between the hydrophobic (textured) and hydrophilic (smooth) portions of the dual-textured substrates. A set of twelve different impact experiments were conducted on each of the target substrates with drop impact velocity (Uo) ranging from 0.37 to 1.50 m/sec. The dynamics of drop impact were captured using a high speed camera with frame rate ranging from 3000 to 10000 frames per second. From the captured frames, the temporal variations of the impacting drop parameters were measured using a MATLAB-assisted program. A systematic analysis of experimental data revealed the existence of four distinct regimes of drop dynamics on the dual-textured substrate: (a) early inertia driven drop spreading, (b) primary drop receding, (c) secondary spreading on the hydrophilic portion, and (d) final equilibrium regimes. It is shown that the drop impact dynamics during the early inertia driven impact regime remains unaffected by the dual-texture feature of the substrate. A larger retraction speed of impacting drop liquid observed on the hydrophobic portion of the substrate makes the drop liquid on the higher wettability/hydrophilic portion to advance further (secondary drop spreading). The net horizontal drop velocity towards the hydrophilic portion of the dual-textured substrate decreases with increasing drop impact velocity. The available experimental results suggest that the movement of bulk drop liquid away from the impact point during drop impact on the dual-textured substrate is larger for the impact of low inertia drops. A semi-empirical model, based on the balance of the wettability gradient, contact angle hysteresis, and viscous forces acting on impacted drop liquid on the substrate, is formulated to predict the movement of bulk drop liquid away from the impact point (ξ). A satisfactory comparison between the model predictions and the experimental measurements is reported for the variation of ξ with Uo.

The present work focuses on the growth and characterizations of GaN and InN layers and nanostructures on p-Si(100) and p-Si(111) substrates by plasma-assisted molecular beam epitaxy and the studies of GaN/p-Si and InN/p-Si heterojunctions properties. The thesis is divided in to seven different chapters. Chapter 1 gives a brief introduction on III-nitride materials, growth systems, substrates, possible device applications and technical background. Chapter 2 deals with experimental techniques including the details of PAMBE system used in the present work and characterization tools for III-nitride epitaxial layers as well as nanostructures. Chapter 3 involves the growth of GaN films on p-Si(100) and p-Si(111) substrates. Phase pure wurtzite GaN films are grown on Si (100) substrates by introducing a silicon nitride layer followed by low temperature GaN growth as buffer layers. GaN films grown directly on Si (100) are found to be phase mixtured, containing both cubic and hexagonal modifications. The x-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy studies reveal that the significant enhancement in the structural and optical properties of GaN films grown with silicon nitride buffer layer grown at 800 oC, when compared to the samples grown in the absence of silicon nitride buffer layer and with silicon nitride buffer layer grown at 600 oC. Core-level photoelectron spectroscopy of SixNy layers reveals the sources for superior qualities of GaN epilayers grown with the high temperature substrate nitridation process. The discussion has been carried out on the typical inverted rectification behavior exhibited by n-GaN/p-Si heterojunctions. Considerable modulation in the transport mechanism is observed with the nitridation conditions. The heterojunction fabricated with the sample of substrate nitridation at high temperature exhibites superior rectifying nature with reduced trap concentrations. Lowest ideality factors (~1.5) are observed in the heterojunctions grown with high temperature substrate nitridation which is attributed to the recombination tunneling at the space charge region transport mechanism at lower voltages and at higher voltages space charge limited current conduction is the dominating transport mechanism. Whereas, thermally generated carrier tunneling and recombination tunneling are the dominating transport mechanisms in the heterojunctions grown without substrate nitridation and low temperature substrate nitridation, respectively. A brief comparison of the structural, optical and heterojunction properties of GaN grown on Si(100) and Si(111) has been carried out. Chapter 4 involves the growth and characterizations of InN nanostructures and thinfilms on p-Si(100) and p-Si(111) substrates. InN QDs are grown on Si(100) at different densities. The PL characteristics of InN QDs are studied. A deterioration process of InN QDs, caused by the oxygen incorporation into the InN lattice and formation of In2O3/InN composite structures was established from the results of TEM, XPS and PL studies. The results confirm the partial oxidation of the outer shell of the InN QDs, while the inner core of the QDs remains unoxidized. InN nanorods are grown on p-Si(100), structural characterizations are carried out by SEM, and TEM. InN nanodots are grown on p-Si(100), structural characterizations are performed. InN films were grown on Si(100) and Si(111) substrates and structural characterizations are carried out. Chapter 5 deals with the the heterojunction properties of InN/p-Si(100) and InN/p-Si(111).The transport behavior of the InN NDs/p-Si(100) diodes is studied at various bias voltages and temperatures. The temperature dependent ZB BH and ideality factors of the forward I-V data are observed, while it is governed through the modified Richardson’s plot. The difference in FB BH and C-V BH and the deviation of ideality factor from unity indicate the presence of inhomogeneities at the interface. The band offsets derived from C-V measurements are found to be Δ EC=1.8 eV and Δ EV =1.3 eV, which are in close agreement with Anderson’s model. The band offsets of InN/p-Si heterojunctions are estimated using XPS data. A type-III band alignment with a valence band offset of Δ EV =1.39 eV and conduction band offset of ΔEC=1.81 eV is identified. The charge neutrality level model provides a reasonable description of the band alignment of the InN/p-Si interface. The interface dipole deduced by comparison with the electron affinity model is 0.06 eV. The transport studies of InN NR/p-Si(100) heterojunctions have been carried out by conductive atomic force microscopy (CAFM) as well as conventional large area contacts. Discussion of the electrical properties has been carried out based on local current-voltage (I-V) curves, as well as on the 2D conductance maps. The comparative studies on transport properties of diodes fabricated with InN NRs and NDs grown on p-Si(100) substrates and InN thin films grown on p-Si(111) substrates have also been carried out. Chapter 6 deals with the growth and characterizations of InN/GaN heterostructures on p-Si(100) and p-Si(111) substarets and also on the InN/GaN/p-Si heterojunction properties. The X-ray diffraction (XRD), scanning electron microscopy (SEM) studies reveal a considerable variation in crystalline quality of InN with grown parameters. Deterioration in the rectifying nature is observed in the case of InN/GaN/p-Si(100) heterojunction substrate when compared to InN/GaN/p-Si (111) due to the defect mediated tunneling effect, caused by the high defect concentration in the GaN and InN films grown on Si(100) and also due to the trap centers exist in the interfaces. Reduction in ideality factor is also observed in the case of n-InN/n-GaN/p–Si(111) when compared to n-InN/n-GaN/p–Si(100) heterojunction. The sum of the ideality factors of individual diodes is consistent with experimentally observed high ideality factors of n-InN/n-GaN/p–Si double heterojunctions due to double rectifying heterojunctions and metal semiconductor junctions. Variation of effective barrier heights and ideality factors with temperature are confirmed, which indicate the inhomogeneity in barrier height, might be due to various types of defects present at the GaN/Si and InN/GaN interfaces. The dependence of forward currents on both the voltage and temperatures are explained by multi step tunneling model and the activation energis were estimated to be 25meV and 100meV for n-InN/n-GaN/p–Si(100) and n-InN/n-GaN/p–Si(111) heterojunctions, respectively. Chapter 7 gives the summary of the present study and also discusses about future research directions in this area.

L’accumulation de lipides chez une espèce levurienne Yarrowia lipolytica souche sauvage a été caractérisée par l’analyse dynamique et systémique des différents états métaboliques identifiés lors des cultures sous conditions environnementales parfaitement maitrisées, à hautes densités cellulaires selon deux stratégies bien distinctes. En premier lieu sur substrat osidique avec le phosphore comme élément inducteur de l’accumulation de lipides, stratégie originale pour déclencher l’accumulation de lipides chez cette souche. Et deuxièmement sur co-susbtrats glucose et oléate et sans aucune limitation nutritionnelle.Ces stratégies de conduites ont permis de dégager les points suivants :- La limitation phosphore déclenche une accumulation en lipides mais aussi en polysaccharides de réserves mobilisables mais non transitoire contrairement à la limitation azote.- La teneur en phosphore de la biomasse catalytique est très variable. De ce fait, le taux de croissance de la biomasse catalytique n’est pas contrôlable par le débit en phosphore.- Le phosphore joue un rôle dans la régulation de l’entrée de glucose dans la cellule, et permet d’éviter la production de citrate lorsque les voies de production de biomasse et de lipides sont en débordement sur une large gamme de rapport C/P (de 0 à 8000 Cmole.mole-1).- La capacité maximale d’accumulation en réserves carbonées chez Y. lipolytica wT est identique quelle que soit la méthode d’accumulation (limitation azote, limitation phosphore, co-substrats glucose / oléate) et est égale à 0,5 Cmole/CmoleX-1. Il existe donc un phénomène de régulation de la levure encore inconnu et limitant l’accumulation en réserves carbonées chez cette souche.Ces résultats ont permis d’identifier des points clés dans l’accumulation en réserves carbonées de cette espèce levurienne et de proposer un mode de conduite original faisant l’objet d’un dépôt de brevet / Lipid accumulation by the yeast Yarrowia lipolytica wT was characterized by dynamic and systemic analysis of different metabolic states in a microbial culture under fully controlled environmental conditions with high cell concentration and under two different strategies:Glucose as the substrate and phosphorus limitation as an inducer of lipid accumulation, an original strategy for lipid accumulation in Y. lipolytica wT.A co-substrate strategy with glucose and oleic acid and without any nutritional limitation.These strategies allowed showing the following points:- Phosphorus limitation triggers a lipid accumulation and a non-transient accumulation of reserve polysaccharide that can be consumed by biomass when necessary, contrary to nitrogen limitation- Phosphorus rate in catalytic biomass shows great variations. Catalytic growth rate cannot be governed by phosphorus input. - Phosphorus has a role in regulating cellular glucose uptake and allows avoiding citric acid production due to overflow of carbon input over a large range of C/P ratios (0 to 8000 Cmol.mol-1)- Maximum capacity of reserve carbon accumulation in Y. lipolytica wT is similar for any culture strategy tested (under nitrogen limitation, phosphorus limitation or with glucose and oleic acid co-substrates) and is equal to 0,5 Cmol/CmolX-1. There is an unknown phenomenon of carbon regulation limiting reserve carbon accumulation in Y. lipolytica wT. Results allowed identifying key points in reserve carbon accumulation in this particular yeast strain and suggesting an original process, claim of a patent