Ce travail de thèse porte sur l’élaboration de matériaux polymères conjugués absorbants dans le proche infra-rouge. Il est issu du projet TAPIR financé par l’ANR dans lequel nous visons le développement de dispositifs d’interface Homme/Machine (IHM) pour des applications dans le secteur de la santé, afin de limiter la propagation des agents pathogènes. Les IHM étant contrôlées avec la main, sans contact, grâce à la réflectivité de la peau, (gamme spectrale 850-950 nm), il faut développer des matériaux absorbant dans cette gamme. Dans ce projet, notre rôle a été de synthétiser la partie active du photodétecteur infrarouge utilisé pour récupérer l’information. Une étude bibliographique et des calculs préliminaires ont permis une sélection judicieuse de différents monomères afin d’assurer une stabilité intrinsèque et obtenir les propriétés d’absorption requises. Différents monomères donneurs (D) et accepteurs (A) ont été combinés afin de synthétiser des copolymères alternés de types (D-A). Deux familles de copolymères absorbants dans le proche infrarouge ont ainsi été synthétisés Tous les copolymères ont été synthétisés via la polycondensation Stille. Leurs propriétés optiques, électroniques et leurs stabilités thermiques ont été étudiées. Par la suite, après avoir confirmé le rôle prépondérant de la force du monomère accepteur, par rapport à celle du donneur, sur les propriétés d’absorptions et les niveaux électroniques des différents copolymères obtenus, nous avons développé une approche originale très peu rapportée dans la littérature. Elle consiste en l’élaboration de copolymères de type (A-A). Ainsi, nous avons synthétisé six copolymères absorbants dans la gamme de longueurs d’onde souhaitée, et même au-delà. Enfin, certains copolymères ont pu être caractérisés en dispositifs OFET et photodétecteurs. / This thesis work focuses on the development of conjugated polymeric materials which absorb in the near infrared. It is the result of the TAPIR project funded by the ANR in which we aim to develop human-machine interface (HMI) devices for applications in the health sector, in order to limit the spread of pathogens. Since HMIs are controlled by hand, without contact, thanks to the reflectivity of the skin (spectral range 850-950 nm), it is necessary to develop materials which ansorb in this range. In this project, our role was to synthesize the active part of the infrared photodetector used to retrieve the information. A bibliographical study and preliminary calculations have allowed a judicious selection of different monomers to ensure intrinsic stability and obtain the required absorption properties. Different donor monomers (D) and acceptors (A) were combined to synthesize alternating copolymers of types (D-A). Two families of copolymers which absorb in the near infrared have been synthesized. All copolymers have been synthesized via Stille polycondensation. Their optical, electronic and thermal properties have been studied. Subsequently, after confirming the predominant role of the strength of the accepting monomer, compared to that of the donor, on the absorption properties and electronic levels of the various copolymers obtained, we developed an original approach that has been reported very rarely in the literature. It consists of the production of copolymers of the type (A-A). Thus, we have synthesized six copolymers which absorb in the desired wavelength range, and even beyond. Finally, some copolymers have been characterized as OFET devices and photodetectors.

Cette thèse s’intéresse à une technique de caractérisation particulièrement bien adaptée à l’étude de couches diélectriques ultra-minces sur semiconducteurs. La génération de seconde harmonique (SHG) est une méthode très prometteuse, basée sur l’optique non-linéaire. Un laser est focalisé sur l'échantillon à caractériser et le signal à deux fois la fréquence fondamentale est mesuré. Pour les matériaux centrosymétriques comme c-Si, SiO2 et Al2O3, le signal SHG est dû aux défauts et au champ électrique Edc d’interface (induit par les charges préexistantes Qox et/ou piégées au niveau des pièges d’interface Dit). La SHG donne ainsi accès à la qualité des interfaces entre diélectriques/semiconducteurs. Néanmoins, le signal SHG dépend aussi des phénomènes de propagation optique dans les structures multicouches. Pour cette raison, nous avons développé un programme de simulation qui prend en compte les phénomènes optiques et les champs électriques statiques aux interfaces. Nous avons utilisé la SHG pour analyser la qualité de passivation de structures Al2O3/Si préparées avec des procédés différents et nous avons montré une corrélation entre SHG et mesure de durée de vie des porteurs de charges. Les valeurs de Qox et Dit ont été extraites par des mesures de capacité-tension et elles ont permis de calculer le champ Edc. La simulation optique, avec les valeurs extraites de Edc a permis de reproduire les données expérimentales de SHG dans ces structures. La SHG a été utilisée également pour la caractérisation des substrats Silicium-sur-Isolant (SOI). Pour les structures SOI épaisses, la simulation et les résultats expérimentaux ont montré que la réponse SHG est dominée par les interférences optiques (faible impact de Edc). Pour les structures SOI ultraminces, les interfaces sont couplées électriquement et des valeurs de Edc sont nécessaires pour reproduire les données expérimentales par simulation. Cela implique que pour les SOI ultraminces, la SHG pourrait donner accès aux champs électriques au niveau des interfaces d’une manière non-destructive. / This PhD work was developed in the context of research for novel characterization methods for ultra-thin dielectric films on semiconductors and their interfacial quality. Second harmonic generation (SHG) is a very promising non-invasive technique based on nonlinear optics. A laser emitting at the fundamental frequency is incident upon the sample which responds through its 2nd order polarization, generating a signal at twice the fundamental frequency. For centrosymmetric materials such as c-Si, amorphous SiO2 or Al2O3, the SHG signal is mainly due to the defects and to the static electric field Edc present at the interface (due to pre-existing charges Qox and/or photo-injected charge trapping/detrapping at interface traps Dit). Thus, SHG measurement gives access to the quality of dielectric/semiconductor interfaces. Nevertheless, the SHG signal is also dependent on multilayer optical propagation phenomena. For this reason, we have developed a simulation program which accounts for the optical phenomena and the static electric fields at the interfaces. We have used SHG to monitor the passivation quality of Al2O3/Si structures prepared with different processes and showed a correlation between SHG and minority carrier lifetime measurements. Qox and Dit were extracted from capacitance-voltage measurements and helped calculating the Edc values. The optical simulation, fed with known Edc values reproduced the experimental SHG data in these structures. The SHG was also used for Silicon-on-Insulator (SOI) substrates characterization. In thick SOI structures, both simulations and experimental results show that the SHG response is mainly given by optical interferences (Edc has no impact). In ultrathin SOI, the interfaces are electrically coupled and Edc is needed as input in the simulation in order to reproduce the experimental SHG data. This implies that in ultrathin SOI, SHG can access the interface electric fields in a non-destructive way.

Neste trabalho, foi realizada a síntese de compostos do sistema PbO CrO3, em especial as composições PbCrO4 e Pb2CrO5, pelo método dos precursores poliméricos, avaliando sua aplicação como pigmentos. Para eliminar o aspecto negativo quanto à toxicidade dos materiais envolvidos, foi realizada a dispersão dos mesmos em SiO2, pelo método sol-gel. As amostras foram caracterizadas estruturalmente por difração de raios X, espectroscopia Raman e por microscopia eletrônica de varredura e transmissão. Pelos resultados de difratometria de raios X e espectroscopia Raman, foi verificado que o método dos precursores poliméricos possibilita a formação de Pb2CrO5 e PbCrO4 monofásicos para ambas as estequiometrias estudadas. Contudo, as imagens de microscopia eletrônica de varredura mostram que as partículas das duas composições apresentam forte coalescência e aglomeração. A caracterização óptica foi realizada pela técnica de reflectância difusa e coordenadas colorimétricas, em que foi determinado que as amostras de PbCrO4 possuem coloração verde-amarelada e que as amostras de Pb2CrO5 possuem coloração que varia do laranja escuro ao vermelho. A dispersão em SiO2 das partículas de Pb2CrO5 foi alcançada, no entanto, este processo provocou a formação de diferentes fases cristalinas, além de alterações na cor, as quais têm uma contribuição significativa da própria matriz SiO2, fato confirmado pela teoria de Kubelka-Munk. A incorporação dessas partículas em uma matriz polimérica de um copolímero de etileno e acetato de vinila (EVA) resultou em uma coloração homogênea da mesma, confirmando a eficácia destas partículas como pigmentos. / In this work, the synthesis of particles from the PbO-CrO3 system, in particular the PbCrO4 and Pb2CrO5 compositions were accomplished, by a polymeric precursor method, evaluating its application as pigments. In order to eliminate the negative toxic aspect of these materials, the dispersion of the same in SiO2 was achieved, by the sol-gel method. The samples were characterized structurally by X-Ray diffraction, Raman spectroscopy and scanning and transmission electron microscopy. From X-Ray diffraction and Raman spectra results it was verified that the polymeric precursors method is able to form single phase Pb2CrO5 and PbCrO4 for both studied stoichiometries. Although, scanning electron microscope images revealed that both compositions present strong coalescence and agglomeration of the particles. Optical characterization was carried out by diffuse reflectance technique and colorimetric coordinates. It was verified that the PbCrO4 samples possess green-yellowish coloration and the Pb2CrO5 samples presents coloration that varies from dark orange to red. The dispersion of Pb2CrO5 particles in SiO2 was reached, however, this process causes the formation of different crystalline phases, besides alteration in color, which have a significant contribution from the SiO2 matrix, confirmed by Kubelka-Munk theory. The incorporation of these particles in a polymeric matrix of ethylene vinyl acetate copolymer (EVA) resulted in the coloration of the same, confirming the efficiency of these particles as pigments.

De par leurs performances et leur fiabilité, la technologie Flash constitue, à l'heure actuelle, la référence en matière de mémoire non volatile. Cependant, ces mémoires étant en passe d'atteindre leurs limites de miniaturisation, plusieurs dispositifs alternatifs sont actuellement envisagés par les industriels du secteur, de manière à anticiper les demandes du marché ces prochaines années.Depuis 2003, des études ont été menées sur le remplacement de la grille flottante en silicium polycristallin des mémoires Flash par des nanocristaux. La modication du flot de procédés d'une mémoire à nanocristaux permet une réduction des coûts de fabrication, une amélioration de la fiabilité et une miniaturisation des dispositifs. L'intégration des nanocristaux dans une cellule mémoire de type Flash constitue donc un challenge pour l'industrie afin de repousser les limites de miniaturisation de cette architecture mémoire basée sur le transistor MOS, dispositif historique de l'industrie des semiconducteurs.Ce manuscrit présente les résultats de ma thèse qui porte sur les procédés de croissance de nanocristaux de silicium et leur caractérisation morphologique en vue d'une intégration dans des mémoires non volatiles.Les objectifs de la thèse sont :- Le transfert du procédé de fabrication des nanocristaux de silicium du CEA LETI vers l'usine de STMicroelectronics à Rousset ;- L'intégration des nanocristaux dans une cellule mémoire non-volatile ;- L'optimisation des procédés de fabrication en vue d'une industrialisation ;- Le développement d'outils de caractérisation de la chaîne de procédés ;- L'étude physique et physico-chimique avancée des nanocristaux de silicium. / By their performance and reliability, Flash technology is, today, the reference in nonvolatile memory . However, these memories being on track to reach their miniaturization limits , several alternative devices are currently being considered by the industrial sector, to anticipate market demands in the coming years .Since 2003, studies have been conducted on the replacement of the polysilicon floating gate by silicon nanocrystals in flash memory with nanocrystals to sustain this memory technology memory. Process flow modifications for nanocrystal integration allows a reduction of manufacturing costs, improving of reliability and miniaturization of devices . Integration of nanocrystals in a flash-like memory cell is therefore a challenge for the industry to extend the limits of miniaturization of the memory architecture based on the MOS transistor, historical device of the semiconductor industry.This manuscript presents the results of my thesis on the silicon nanocrystals growth process and morphological characterization for integration in a nonvolatile memory. The objectives of the thesis are :- Transfer of the manufacturing process of the silicon nanocrystals growth from CEA LETI plant to STMicroelectronics Rousset ;- Integration of nanocrystals in a non-volatile memory cell;- Optimization of manufacturing processes for industrialization ;- Development of tools to characterize the process chain ;- Physical and physico-chemical study of advanced silicon nanocrystals . and morphological characterization for integration in a nonvolatile memory.

Neste trabalho, foi realizada a síntese de compostos do sistema PbO CrO3, em especial as composições PbCrO4 e Pb2CrO5, pelo método dos precursores poliméricos, avaliando sua aplicação como pigmentos. Para eliminar o aspecto negativo quanto à toxicidade dos materiais envolvidos, foi realizada a dispersão dos mesmos em SiO2, pelo método sol-gel. As amostras foram caracterizadas estruturalmente por difração de raios X, espectroscopia Raman e por microscopia eletrônica de varredura e transmissão. Pelos resultados de difratometria de raios X e espectroscopia Raman, foi verificado que o método dos precursores poliméricos possibilita a formação de Pb2CrO5 e PbCrO4 monofásicos para ambas as estequiometrias estudadas. Contudo, as imagens de microscopia eletrônica de varredura mostram que as partículas das duas composições apresentam forte coalescência e aglomeração. A caracterização óptica foi realizada pela técnica de reflectância difusa e coordenadas colorimétricas, em que foi determinado que as amostras de PbCrO4 possuem coloração verde-amarelada e que as amostras de Pb2CrO5 possuem coloração que varia do laranja escuro ao vermelho. A dispersão em SiO2 das partículas de Pb2CrO5 foi alcançada, no entanto, este processo provocou a formação de diferentes fases cristalinas, além de alterações na cor, as quais têm uma contribuição significativa da própria matriz SiO2, fato confirmado pela teoria de Kubelka-Munk. A incorporação dessas partículas em uma matriz polimérica de um copolímero de etileno e acetato de vinila (EVA) resultou em uma coloração homogênea da mesma, confirmando a eficácia destas partículas como pigmentos. / In this work, the synthesis of particles from the PbO-CrO3 system, in particular the PbCrO4 and Pb2CrO5 compositions were accomplished, by a polymeric precursor method, evaluating its application as pigments. In order to eliminate the negative toxic aspect of these materials, the dispersion of the same in SiO2 was achieved, by the sol-gel method. The samples were characterized structurally by X-Ray diffraction, Raman spectroscopy and scanning and transmission electron microscopy. From X-Ray diffraction and Raman spectra results it was verified that the polymeric precursors method is able to form single phase Pb2CrO5 and PbCrO4 for both studied stoichiometries. Although, scanning electron microscope images revealed that both compositions present strong coalescence and agglomeration of the particles. Optical characterization was carried out by diffuse reflectance technique and colorimetric coordinates. It was verified that the PbCrO4 samples possess green-yellowish coloration and the Pb2CrO5 samples presents coloration that varies from dark orange to red. The dispersion of Pb2CrO5 particles in SiO2 was reached, however, this process causes the formation of different crystalline phases, besides alteration in color, which have a significant contribution from the SiO2 matrix, confirmed by Kubelka-Munk theory. The incorporation of these particles in a polymeric matrix of ethylene vinyl acetate copolymer (EVA) resulted in the coloration of the same, confirming the efficiency of these particles as pigments.

Doctor of Philosophy / Department of Civil Engineering / Yacoub M. Najjar / This study explored the potential use of ANNs for profiling and characterization of various environmental sites. A static ANN with back-propagation algorithm was used to model the environmental containment at a hypothetical data-rich contaminated site. The performance of the ANN profiling model was then compared with eight known profiling methods. The comparison showed that the ANN-based models proved to yield the lowest error values in the 2-D and 3-D comparison cases. The ANN-based profiling models also produced the best contaminant distribution contour maps when compared to the actual maps. Along with the fact that ANN is the only profiling methodology that allows for efficient 3-D profiling, this study clearly demonstrates that ANN-based methodology, when properly used, has the potential to provide the most accurate predictions and site profiling contour maps for a contaminated site. ANN with a back-propagation learning algorithm was utilized in the site characterization of contaminants at the Kansas City landfill. The use of ANN profiling models made it possible to obtain reliable predictions about the location and concentration of lead and copper contamination at the associated Kansas City landfill site. The resulting profiles can be used to determine additional sampling locations, if needed, for both groundwater and soil in any contaminated zones. Back-propagation networks were also used to characterize the MMR Demo 1 site. The purpose of the developed ANN models was to predict the concentrations of perchlorate at the MMR from appropriate input parameters. To determine the most-appropriate input parameters for this model, three different cases were investigated using nine potential input parameters. The ANN modeling used in this case demonstrates the neural network’s ability to accurately predict perchlorate contamination using multiple variables. When comparing the trends observed using the ANN-generated data and the actual trends identified in the MMR 2006 System Performance Monitoring Report, both agree that perchlorate levels are decreasing due to the use of the Extraction, Treatment, and Recharge (ETR) systems. This research demonstrates the advantages of ANN site characterization modeling in contrast with traditional modeling schemes. Accordingly, characterization task-related uncertainties of site contaminations were curtailed by the use of ANN-based models.

International Telemetering Conference Proceedings / October 25-28, 1999 / Riviera Hotel and Convention Center, Las Vegas, Nevada / Data from ARTM channel sounding test flights is examined to characterize the dynamic channel behavior of aeronautical telemetry channels. The dynamic behavior is characterized using the Doppler power spectrum. The width of the Doppler power spectrum is the Doppler bandwidth of the channel which indicates the required bandwidth of adaptive detection techniques such as adaptive equalization, adaptive modulation, adaptive channel selection and adaptive error control coding. Data collected from ARTM Flight 11 suggest a Doppler bandwidth exceeding 6.7 Hz for the channel, but greater accuracy and resolution will only be possible with more data.

Increasing emphasis has been placed on the use of renewable resources, on decreased reliance on petroleum in order to better utilize global energy needs. Biological structures available in nature have been a constant inspiration to the design and fabrication of the new line of functional biomaterials whose unique phenomena can be exploited in novel applications. In tissue engineering for example, a natural biomimetic material with close resemblance to the profile features existed in a native extracellular matrix could provide a temporary functional platform to regulate and control cellular interactions at a molecular level and to subsequently direct a tissue regeneration. However, the lack of rigidity of natural materials typically limits their mass production. One promising approach to address this shortcoming is to introduce a biomimetic composite material reinforced by high purity nanofibers found in nature. As an attractive reinforcing filler phase, cellulose nanowhiskers (CNWs) offer exceptional properties such as high aspect ratio, large interface area, and significant mechanical performance. As such, CNWs could integrate a viable nanofibrous porous candidate, resulting in superior structural diversity and functional versatility. Inspired by the fascinating properties of cellulose and its derivatives, we have designed two bio-inspired nanocomposite materials reinforced with CNWs in this work. The successful grafting of CNWs within the host matrix and their tendency to interconnect with one another through strong hydrogen bonding gave rise to the formation of a three-dimensional rigid percolating network, fact which imparted considerable mechanical strength and thermal stability to the entire structure with only a small amount of filler content, i.e. 3 wt.%. Also, the biocompatibility of the nanocomposite was probed by in-vitro incubation of human-bone-marrow-derived mesenchymal stem cells (MSCs), which resulted in the invasion and proliferation of MSCs around the nanocomposite at day 8 of culture. The green functional biomaterial with its unique features in this work could open new perspectives in the self-assembly of nanobiomaterial for tissue-engineered scaffolding, while it could make the design of the next generation of fully green functional biomaterial a reality.

International Telemetering Conference Proceedings / October 23-26, 2000 / Town & Country Hotel and Conference Center, San Diego, California / Data collected during July 1999 at Edwards EAFB by the Advanced Range Telemetry (ARTM) program is examined to characterize the dynamic behavior of multipath interference in an aeronautical telemetry channel. Multipath fade events are analyzed in the frequency domain to show how these fades appear, evolve, and disappear from the channel. A channel model and examples from the channel sounding data are used to show the dynamic nature of these fade events. The Doppler power spectrum is used to quantify the exact time-varying nature of the multipath fade events. The coherence time, or the amount of time the channel can be viewed as unchanging, is obtained from the Doppler power spectrum and is calculated to be 100 ms in the data sets examined in this paper. This implies that adaptive multipath mitigation techniques must have an adaptation bandwidth of 10 Hz.

Seepage from steelmaking coal mine waste rock dumps in the Elk Valley, British Columbia, Canada can contain selenium (Se), cadmium (Cd), and sulfate (SO42-) from the oxidation of sulfide minerals, and nitrate (NO3-) from blasting. The impact of these constituents of interest (CIs) on receiving groundwater systems and the potential for their natural attenuation is investigated. A 10.7 km2 mine-impacted research catchment (West Line Creek) was instrumented with 13 monitoring wells and 8 drivepoint wells to characterize the hydraulics and geochemistry of the aquifer system downgradient of the waste rock dump. These data were augmented with geophysical surveys and by characterizing the lithology, geotechnical properties, and geochemistry of core samples obtained during drilling. Furthermore, the groundwater monitoring program also facilitated the development of a conceptual model of hydrogeology in a small montane valley. An unconfined aquifer at the overburden/fractured bedrock interface, i.e. the basal alluvial aquifer was identified as the primary groundwater conduit for the migration of water and solutes from the waste rock dump toward Line Creek. Vertical and horizontal dispersion of CIs was confirmed with porewater analysis of core samples, with Se concentrations exceeding the BC water quality guideline (2.0 µg/L) in 98% of samples (n = 223). Residence time for groundwater in the overburden aquifers was determined using 3H/3He age dating (n = 3) and estimates of groundwater velocity to be less than three years across the 650 m study site. The chemistry of groundwater was compared with rock drain water samples to evaluate CIs from their source through to identified discharge locations. Linear correlation of CI concentrations with SO42- concentrations in water samples showed that Se and NO3- were conservative solutes, whereas Cd was non-conservative and may be undergoing mineral precipitation or adsorption reactions in the groundwater system. The distribution of CIs in the overburden aquifers was seasonally variable and dilution was determined to be the dominant mechanism controlling the concentrations of conservative CIs (Se, SO42- and NO3-) away from the toe of the waste rock dump and during the spring freshet. The basal alluvial aquifer downgradient of the waste rock dump was estimated to annually discharge 16% of the water and 7% of the SO42- load from the catchment.