L'émergence des nouvelles applications dans le domaine de la micro et nanotechnologie requière de faibles coûts de fabrication et la caractérisation de dispositifs électroniques ayant des propriétés telles que la flexibilité, la portabilité, la légèreté, et des matériaux de faibles coûts. Les méthodes traditionnelles de fabrication impliquent de longues étapes de production, et des procédés de fabrication impliquant des étapes avec des produits chimiques. Le but de cette thèse est d'étudier la conception et la caractérisation de capteurs d'ammoniac et d'ozone sur support souple fabriqués par des processus de photolithographie et de gravure laser. Le support flexible est composé de Kapton avec des électrodes interdigitées de Ti/Pt pour la détection de gaz et un microchauffage. Les motifs du circuit ont été réalisés par photolithographie et gravure laser. L'utilisation de gravure laser sur support souple permet de réduire les coûts liés au temps de fabrication, aussi représente une excellente alternative aux processus chimiques. Des nanoparticles de ZnO déposées par gouttes ont été utilisées comme matériaux sensibles en raison de leurs excellentes propriétés dans la détection de gaz. Les conditions de détection de gaz ont été étudiées pour différentes concentrations d'ozone et d'ammoniac. Afin de tester une méthode de dépôt utilisée dans la production industrielle à grande échelle, un dépôt par spray ultrasonique a été effectué. Les capteurs réalisés montrent une large gamme de détection de 5 ppb à 500 ppb à 200 °C pour l'ozone et de 5 ppm à 100 ppm à 300 °C pour l'ammoniac avec une bonne reproductibilité, stabilité et de rapides temps de réponse et de retourn. / Nowadays the emerging of new applications in the micro and nanotechnology field required to reduce fabrication costand to improve electronic devices with properties such as flexibility, portability, lightweight, and low cost. Traditional methods involve expensive and long production steps, and chemical vapor deposition. The purpose of this work is to present the conception and characterization of flexible ammonia and ozone sensors fabricated by photolithography and laser ablation processes. The flexible platform is composed of Kapton substrate with interdigitated Ti/Pt electrodes for gas detection and a micro-heater device. The circuit patterns were realized by photolithography and laser ablation. Photolithography is a well-known and reliable patterning process used on rigid substrate. The application of laser ablation process not only reduces fabrication time, but also represents an excellent viable alternative instead of chemical processes. ZnO thin films deposited by drop coating have been used as sensitive materials due to their excellent properties in the gas detection. The gas sensing condition and the performances of the devices are investigated for ozone and ammonia at different gas concentrations and different thin film thicknesses. In order to test a deposit methodology used in large scale industrial production, an ultrasonic spray deposition was done. The sensor provides a wide range of detection from 5 ppb to 500 ppb for ozone and from 5 ppm to 100 ppm for ammonia. Their best sensibilities were obtained at 200°C for ozone and 300 °C for ammoniac with good repeatability, stability and fast response/recovery time.

Structural and optical properties of ZnO nanostructures synthesized by low energy ion implantation technique were examined. ZnO molecular ions were implanted into Si/SiO2 substrates at room temperature and then furnace annealed under different temperatures and environments. In all as-implanted samples only Zn nanostructures with varying diameters distributed into the Si/SiO2 matrices were observed. No trace of ZnO was found. The distributions of Zn nanostructures in Si/SiO2 closely matched results from Stopping and Range of Ions in Matter (SRIM) simulations. During annealing at 750 oC, Zn diffused both toward and away from the surface of the substrate and combine with oxygen to form ZnO nanostructures. At higher annealing temperatures ZnO bonding started to break down and transfer to zinc silicate (Zn2SiO4), and at 900 oC the ZnO was completely converted into Zn2SiO4. The average sizes of Zn/ZnO nanostructures depended on the ion fluence. If the fluence increased the average sizes of nanostructures also increased and vice versa. For room temperature photoluminescence (RT-PL), band-edge emission in the ultraviolet (UV) region was observed from all samples annealed at 700 oC/750 oC and were slightly blue shifted as compare to bulk ZnO. Donor-bound exciton (D,X) and acceptor-bound exciton (A,X) transitions were observed in low temperature photoluminescence (PL). The lifetime of both donor-bound excitonic emission (D, X) and acceptor-bound excitonic emission (A, X) were found to be in the picosecond (ps) range.

In this thesis two issues in nanotechnology have been addressed. The first is the comprehensive characterization of engineered nanomaterials prior to their examination in toxicology and environmental studies. The second is the development of a method to produce nanostructure arrays over large areas and for low cost. A major challenge when assessing nanomaterial’s risks is the robust characterization of their physicochemical properties, particularly in commercial products. Such data allows the critical features for biological outcomes to be determined. This work focused on the inorganic oxides that were studied in powdered and dispersed forms as well as directly in consumer sunscreen products. The most important finding was that the commercial sunscreens that listed titania or zinc oxide as ingredients contained nanoscale materials. Cell free photochemical tests revealed that ZnO particles without any surface coating were more active at generating ROS than surface coated TiO2 nanoparticles. These studies make clear the importance of exposure studies that examine the native form of nanomaterials directly in commercial products. The second part of this thesis presents the development of a new method to fabricate gold nanoring and nanocrescent arrays over large areas; such materials have unique optical properties consonant with those described as metamaterials. A new shaped nanosphere lithography approach was used to manipulate the form of silica nanospheres packed onto a surface; the resulting array of mushroom structures provided a mask that after gold evaporation and etching left either golden rings or crescents over the surface. The structures had tunable features, with outer diameters ranging from 200 to 350 nm for rings and crescent gap angles of ten to more than a hundred degrees. The use of a double mask method ensured the uniform coverage of these structured over 1 cm2 areas. Experimental and theoretical investigations of the optical properties of the arrays revealed the optical resonances in the infrared region. Finally, in the course of developing the nanorings, etch conditions were developed to deposit large area arrays of polystyrene nanodoughnuts with diameters from 128 to 242 nm. These non-conductive structures provide an ideal template for further attachment of magnetic of optically emissive nanoparticles.

Content: ZnO nanoparticles were developed by 1:2 ratios of Zinc sulphate heptahydrate and Sodium hydroxide by using precipitation method. The structure, morphology of ZnO nanoparticles were investigated by using XRay Diffraction, Scanning Electron Microscopy and Transmission electron Microscopy. X-Ray Diffraction confirms the formation and average crystallite size of ZnO nanoparticles. Scanning Electron Microscopy studies shows the ZnO nanoparticles were in spherical in structure. These ZnO nanoparticles were used in different ratios along with conventional finishing formulations and coated on the leather surface. The performance properties such as water fastness, rub fastness and flexing resistance were evaluated. Application of ZnO nanoparticles in leather finishing showed significant improvement in overall performance properties than conventional finishing formulations. XRD confirms the formation of ZnO nanoparticles (wurtzite structure) at 36.67° (101) plane and the particles size was in the range of 43 nm. SEM image shows that the particles are in the spherical structure wheras EDAX investigate the stoichiometry and chemical purity of the samples to confirm the presence of zinc and oxygen. Optimum quantity up to 2-5 g/L of the season of ZnO nanoparticle is desirable for upgrading the value of leathers by improving color fastness to water, rub fastness and flexing resistance (wet & dry) properties significantly in cationic (wet), NC lacquer emulsions and PU top coat dispersions in finishing formulations. Take-Away: Optimum quantity up to 2-5 g/L of the season of ZnO nanoparticle is desirable for upgrading the value of leathers by improving color fastness to water, rub fastness and flexing resistance (wet & dry) properties significantly in cationic (wet), NC lacquer emulsions and PU top coat dispersions in finishing formulations.

Sub-micron patterning is fundamental to the fabrication of numerous devices Traditional commercial manufacturing methods either lack the resolution needed to attain the appropriate size or are prohibitively expensive due to low throughput or the necessity of expensive equipment. Imprint lithography is a rapid, inexpensive alternative to making sub-micron features that can be tailored to work with a variety of materials. Imprint lithography, while traditionally used with pure polymers has been tailored to be used with nanoparticle-polymer hybrid films. This work has achieved high-fidelity pattern transfer onto polymer-nanoparticle hybrid films with feature sizes as small as 250 nm. The polymer-nanoparticle hybrid was fabricated by creating a liquid suspension of functionalized ZnO nanoparticles and poly(methyl methacrylate) (PMMA) in a solvent. The ZnO particles were functionalized by adding nonanoic acid in order to facilitate the dispersion of the particles in a non-polar solvent. This suspension was spread onto substrate, imprinted with a patterned stamp, allowed to dry, and was demolded. The final result was features ranging from 250 nm to 1 μm in size with good fidelity as determined by the accuracy of the feature replication and the surface roughness of the overall sample. The effect of the ZnO content as well as the method of combining the suspension components on the feature fidelity was studied. In general, it was found that feature fidelity is acceptable up to a dry-film composition of 15 vol% ZnO and that feature sizes above 500 nm were more tolerant of higher solids loading. The same imprint lithography method was also used to pattern a polymer-derived SiOC glass. The SiOC was shown to be have interesting shrinkage properties where the feature-level linear shrinkage was up to 5% more than that of the bulk. The features were shown to be stable during pyrolysis up to 1000°C and stable at operating temperatures up to 1000°C. A constant number Monte Carlo simulation was used to describe the suspension behavior to confirm the empirical results from the physical experiments. The effects of Van der Waals forces, steric stabilization, depletion flocculation, as well as the physical impediment of entangled polymer chains were considered. A similar agglomeration behavior was shown in the simulations compared to the physical experiments. This thesis shows that polymer-nanoparticle hybrid films are a compatible material for imprint lithography using appropriate suspension parameters. This is very important for a variety of applications and devices. Using imprint lithography to make these devices makes them cheaper and more accessible to the commercial market and can make a large number of theoretical devices a reality. / Ph. D. / Sub-micron patterning is an integral part of making many modern technologies such as memory storage devices or integrated circuits. As this technology becomes smaller and smaller, the limiting factor for making these devices has become the ability to manufacture effectively at the appropriate scale. Traditional commercial manufacturing methods lack the resolution needed to attain small enough features. Manufacturing methods that can make small enough features are often either extremely expensive or offer incomplete control of the feature morphology. Imprint lithography is a high-throughput, inexpensive alternative to making sub-micron features that can be tailored to work with a variety of materials. Imprint lithography is simple process in which a patterned stamp is pressed into a softened film of material in order to transfer the pattern of the stamp onto that material. Traditionally, imprint lithography works best with polymers and researchers have struggled to pattern nanoparticle-based materials. This work has achieved high-fidelity pattern transfer onto polymer-nanoparticle hybrid films with feature sizes on the same order as the polymer films found reported in literature. The polymer-nanoparticle hybrid was realized by creating a liquid suspension of functionalized ZnO nanoparticles and poly(methyl methacrylate) (PMMA) in a solvent. The ZnO particles were functionalized by adding nonanoic acid, allowing the normally polar particles to disperse in the non-polar solvent needed to dissolve the PMMA. This suspension was spread onto a glass substrate, imprinted with a patterned stamp, allowed to dry, and was demolded. The final result was the successful transfer of features ranging from 250 nm to 1 μm in size with good fidelity. The effect of the ZnO content as well as the method of combining the suspension components on the feature fidelity was studied. To help prove the broad applicability of this imprint method, it was adapted for use with polymer-derived ceramics. Additionally, a computer simulation was developed to help understand the behavior of the nanoparticle-polymer suspension during the imprint process.

No / Zinc oxide (ZnO) nanoparticles are widely used in cosmetics and sunscreens. Human epidermal keratinocytes may serve as the first portal of entry for these nanoparticles either directly through topically applied cosmetics or indirectly through any breaches in the skin integrity. Therefore, the objective of the present study was to assess the biological interactions of ZnO nanoparticles in primary human epidermal keratinocytes (HEK) as they are the most abundant cell type in the human epidermis. Cellular uptake of nanoparticles was investigated by scanning electron microscopy using back scattered electrons imaging as well as transmission electron microscopy. The electron microscopy revealed the internalization of ZnO nanoparticles in primary HEK after 6 h exposure at 14 microg/ml concentration. ZnO nanoparticles exhibited a time (6-24 h) as well as concentration (8-20 microg/ml) dependent inhibition of mitochondrial activity as evident by the MTT assay. A significant (p < 0.05) induction in DNA damage was observed in cells exposed to ZnO nanoparticles for 6 h at 8 and 14 microg/ml concentrations compared to control as evident in the Comet assay. This is the first study providing information on biological interactions of ZnO nanoparticles with primary human epidermal keratinocytes. Our findings demonstrate that ZnO nanoparticles are internalized by the human epidermal keratinocytes and elicit a cytotoxic and genotoxic response. Therefore, caution should be taken while using consumer products containing nanoparticles as any perturbation in the skin barrier could expose the underlying cells to nanoparticles.

Neste trabalho, são discutidas as características de transistores de filmes finos (TFTs) nos quais nanopartículas de óxido de zinco (ZnO) são empregadas como material ativo na camada semicondutora. O crescimento contínuo do interesse por este componente está associado à busca pelo desenvolvimento da tecnologia de dispositivos eletrônicos flexíveis, transparentes e de baixo custo. TFTs integrados com nanopartículas de ZnO são apresentados, e uma extensa rotina de caracterização elétrica transiente é realizada para avaliar como estes dispositivos se comportam e degradam ao longo do tempo. Foram medidas, ao total, 80 amostras de transistores integrados em duas configurações distintas: inverted staggered e inverted coplanar. A partir das medidas analisadas foram identificados dois grupos de comportamentos elétricos dominantes, os quais foram classificados em: efeitos abruptos e efeitos de memória. A partir dos dados coletados, foram formuladas hipóteses para modelar o comportamento típico observado. Para tanto, utiliza-se dos mecanismos de atividade de traps, de interação da camada semicondutora com o meio ambiente, de polarização de dipolos e difusão de cargas móveis no dielétrico, de formação de caminhos percolados paralelos pelas nanopartículas e de difusão de vacâncias de oxigênio e íons metálicos que podem estar associados ao comportamento elétrico observado. / In this work, the characteristics of thin-film transistors (TFTs) employing nanoparticulated zinc oxide (ZnO) as the active semiconductor channel layer are discussed. The growing interest in this component is associated to the development of low-cost, flexible and transparent electronic devices. The TFTs integrated with ZnO nanoparticles are presented and an extensive transient electrical characterization campaign was performed in order to evaluate how these devices behave and degrade over time. The measurement was performed for 80 samples of two different integration setups: inverted staggered and inverted coplanar. In the performed tests two main disturbances were identified, which were classified as abrupt and memory effects. From the collected data, hypothesis to model the observed typical behavior are formulated. Trapping activity, ambient interaction, dielectric dipoles, mobile charges, formed parallel-paths, oxygen vacancies and metallic ions diffusion are mechanisms that may be associated to the observed behavior.

Neste trabalho, são discutidas as características de transistores de filmes finos (TFTs) nos quais nanopartículas de óxido de zinco (ZnO) são empregadas como material ativo na camada semicondutora. O crescimento contínuo do interesse por este componente está associado à busca pelo desenvolvimento da tecnologia de dispositivos eletrônicos flexíveis, transparentes e de baixo custo. TFTs integrados com nanopartículas de ZnO são apresentados, e uma extensa rotina de caracterização elétrica transiente é realizada para avaliar como estes dispositivos se comportam e degradam ao longo do tempo. Foram medidas, ao total, 80 amostras de transistores integrados em duas configurações distintas: inverted staggered e inverted coplanar. A partir das medidas analisadas foram identificados dois grupos de comportamentos elétricos dominantes, os quais foram classificados em: efeitos abruptos e efeitos de memória. A partir dos dados coletados, foram formuladas hipóteses para modelar o comportamento típico observado. Para tanto, utiliza-se dos mecanismos de atividade de traps, de interação da camada semicondutora com o meio ambiente, de polarização de dipolos e difusão de cargas móveis no dielétrico, de formação de caminhos percolados paralelos pelas nanopartículas e de difusão de vacâncias de oxigênio e íons metálicos que podem estar associados ao comportamento elétrico observado. / In this work, the characteristics of thin-film transistors (TFTs) employing nanoparticulated zinc oxide (ZnO) as the active semiconductor channel layer are discussed. The growing interest in this component is associated to the development of low-cost, flexible and transparent electronic devices. The TFTs integrated with ZnO nanoparticles are presented and an extensive transient electrical characterization campaign was performed in order to evaluate how these devices behave and degrade over time. The measurement was performed for 80 samples of two different integration setups: inverted staggered and inverted coplanar. In the performed tests two main disturbances were identified, which were classified as abrupt and memory effects. From the collected data, hypothesis to model the observed typical behavior are formulated. Trapping activity, ambient interaction, dielectric dipoles, mobile charges, formed parallel-paths, oxygen vacancies and metallic ions diffusion are mechanisms that may be associated to the observed behavior.

Neste trabalho, são discutidas as características de transistores de filmes finos (TFTs) nos quais nanopartículas de óxido de zinco (ZnO) são empregadas como material ativo na camada semicondutora. O crescimento contínuo do interesse por este componente está associado à busca pelo desenvolvimento da tecnologia de dispositivos eletrônicos flexíveis, transparentes e de baixo custo. TFTs integrados com nanopartículas de ZnO são apresentados, e uma extensa rotina de caracterização elétrica transiente é realizada para avaliar como estes dispositivos se comportam e degradam ao longo do tempo. Foram medidas, ao total, 80 amostras de transistores integrados em duas configurações distintas: inverted staggered e inverted coplanar. A partir das medidas analisadas foram identificados dois grupos de comportamentos elétricos dominantes, os quais foram classificados em: efeitos abruptos e efeitos de memória. A partir dos dados coletados, foram formuladas hipóteses para modelar o comportamento típico observado. Para tanto, utiliza-se dos mecanismos de atividade de traps, de interação da camada semicondutora com o meio ambiente, de polarização de dipolos e difusão de cargas móveis no dielétrico, de formação de caminhos percolados paralelos pelas nanopartículas e de difusão de vacâncias de oxigênio e íons metálicos que podem estar associados ao comportamento elétrico observado. / In this work, the characteristics of thin-film transistors (TFTs) employing nanoparticulated zinc oxide (ZnO) as the active semiconductor channel layer are discussed. The growing interest in this component is associated to the development of low-cost, flexible and transparent electronic devices. The TFTs integrated with ZnO nanoparticles are presented and an extensive transient electrical characterization campaign was performed in order to evaluate how these devices behave and degrade over time. The measurement was performed for 80 samples of two different integration setups: inverted staggered and inverted coplanar. In the performed tests two main disturbances were identified, which were classified as abrupt and memory effects. From the collected data, hypothesis to model the observed typical behavior are formulated. Trapping activity, ambient interaction, dielectric dipoles, mobile charges, formed parallel-paths, oxygen vacancies and metallic ions diffusion are mechanisms that may be associated to the observed behavior.

Chapter 1. A Brief Overview of Low Molecular Mass Gels and their Applications This chapter deals with molecular gels derived from the self-assembly of small organic molecules (typical molecular weight < 2000 daltons), endowed with appropriate functions to promote anisotropic growth of supramolecular aggregates, by means of various non-covalent interactions like van der Waals, π-πstacking, H-bonding etc., leading to a self-assembled fibrillar network (SAFIN). Several representative examples from the literature (Chart 1) are discussed to demonstrate the structural diversity of the gelator molecules which form self-assembled organogels or hydrogels. Chart 1 Besides emphasizing on the diverse molecular structures of the gelators, applications of gel phase materials as functional nanostructures are also discussed (Scheme 1). Some of the aspects that have been elaborated in this context include the use of gels as reaction media, as sensors, in light harvesting, as biomaterials and in optoelectronic applications. Scheme 1 Chapter 2. Supramolecular Chirality in Organogels: Spectroscopic, Morphological and Rheological Investigations of Gels/Xerogels derived from Alkyl Pyrenyl Urethanes This chapter addresses the formation of chiral supramolecular structures in the organogels derived from chiral 1R (or 2R), and its mixture with its enantiomer (1S) and a series of achiral analogues (3-9) by extensive circular dichroism (CD) spectroscopic measurements (Chart 2). Morphological studies by atomic force microscopy (AFM) and scanning electron microscopy (SEM) were complemented by the measurements of their bulk properties by thermal stability and rheological studies. Specific molecular recognition events (1/3 vs 2/3) and solvent effects (isooctane vs dodecane) were found to be critical in the formation of the chiral aggregates. Computational studies were carried out to understand the interactions responsible for the formation of chiral superstructures. Chapter 3. Self-assembled Composite Organogels based on a Thermo-reversible Photoactive n-Acene Fibrillar Scaffold and Organic Ligand stabilized ZnO Nanoparticles Organic/inorganic composite organogels were obtained in n-BuOH by the self-assembly of 2,3-di-n-decyloxyanthracene (DDOA, Chart 3) in this solvent in the presence of ZnO nanoparticles (NPs) capped with different organic ligands (Chart 4). When ligands (oleic acid or 2,3-substituted anthracenic acid/oleic acid mixed shell) having structural similarity with the gelator molecule were used to cap the NPs, a homogeneous dispersion of the NPs in the gel matrix was obtained, as confirmed by microscopy (TEM and confocal fluorescence microscopy) experiments. The efficient integration of these NPs into the gel fibers resulted in a significant quenching (20-25%) of DDOA emission, even with extremely small loading of these NPs (~ 10-4mol% compared to DDOA) into the gel fibers. The mechanical properties (rheology were unaffected relative to the pristine DDOA organogel. However, the presence of the NPs lowered the critical gelation concentration and accelerated the gelation kinetics. Attempts to disperse these NPs (the ones without fluoro capping) on the aerogel fibers of DDOA by dissolving both DDOA and the NPs in supercritical (sc) CO2 were not successful (Fig. 1), since the NPs could not be dissolved in scCO2. Figure 1. (a) TEM images of DDOA aerogels obtained from scCO2, containing A23-NPs, scale bar 200 nm; (b) SEM image of DDOA aerogel obtained in the presence of OL-NPs, scale bar 10 µm. Chapter 4. Donor-Acdeptor Interaction Promoted Gelation Of Organic Fluids by Anthracene Carboxamides/2,4,7-Trinitrofluorenone Tris Carboxamides of anthracene were found to form charge-transfer driven organogels in a range of aliphatic alcohols in the presence of an equivalent of (electron-deficient) 2,4,7-trinitrofluorenone (TNF) (Chart 5). Intense color developed in the gel state during the sol to gel phase transition process (Fig 2) Besides, none of these carboxamides were able to form gel in the absence of TNF, suggesting the importance of charge-transfer interaction in the gel formation. Importantly, most of these gels formed only through rapid cooling of the hot solution, otherwise, leading to the precipitation of the CT complex from the solvent. This result indicated that the kinetics is very important for the formation of these gels. Optimum stoichiometry of the donor and acceptor was found to be 1:1. At this molar ratio of the donor and the acceptor, the gels not only showed the highest thermal stability (thermal gel melting experiments), they also displayed the highest values of the mechanical strength and the yield stress (rheology experiments). All the gels showed extensive quenching of the emission of the monomeric anthracenic donor. For the gels derived from the 2-substituted donor, a low energy emission at high wavelength indicated the formation of an emissive CT exciplex. X-ray powder diffraction studies of these xerogels revealed the presence of layered, fibrillar structures in the xerogel phase. (For structural formula pl see the abstract file)