Nos travaux de recherche ont été réalisés dans le but de développer de nouveaux nanomatériaux semi conducteurs transparents d‟alliages ZnxV1-xO en couches minces nanostructurées destinés aux applications dans les dispositifs optoélectroniques et en particulier dans les cellules photovoltaïques en couches minces à base de CIGS. L‟objectif principal recherché est de mettre en oeuvre des couches tampons/couches fenêtres à base de matériaux exempte de Cadmium et d‟Aluminium ou d‟Indium, comme le ZnxV1-xO respectivement à forte et à faible concentration de vanadium. L'originalité de mon travail est de réaliser à partir du même procédé de dépôt, deux éléments de la cellule CIGS en employant la technique PVD (rf-magnétron sputtering) dont les cibles de pulvérisation sont constituées de poudre nanocristallines préalablement synthétisées par voie sol-gel. Ce protocole d‟élaboration engendre une diminution conséquente du coût de production. Pour se faire, dans un premier temps des caractérisations structurales, morphologiques, optiques et électriques des films minces obtenus ont été menées et leurs paramètres physiques ont été mesurés pour déterminer les conditions optimales de dépôt des couches souhaitées. Les résultats obtenus montrent que des concentrations en vanadium de 20% et de 1% sont respectivement adéquates pour la réalisation des couches tampons et des Oxydes Transparents et Conducteurs (OTC) envisagés. Enfin, pour prévoir et améliorer les paramètres photovoltaïques, une nouvelle architecture de structure photovoltaïque de type Verre/(n+)Zn0.99V0.01O/(n)Zn0.80V0.20O/(p)Cu(In,Ga)Se2 /Mo a été définie et modélisée par simulation en utilisant les résultats expérimentaux déjà obtenus. Ce travail a permis de définir les critères auxquels doit répondre l‟absorbeur CIGS pour l‟obtention du meilleur rendement de conversion de la cellule proposée. / Our research work has been performed with the aim of developing new transparent semiconductor nanomaterials of ZnxV1-xO alloys in nanostructured thin films for applications in optoelectronic devices and in particular in photovoltaic cells in CIGS based thin films. Our main objective is to realize buffer layers/window layers based on materials not containing cadmium, aluminum nor indium, such as ZnxV1-xO at respectively high and low vanadium concentration. The originality of my work is in the realization, starting from the same deposition process, of two elements of the CIGS cell using the PVD (rf-magnetron sputtering) technique, in which the sputtering targets are based on nanocrystalline powders previously synthesized by the sol-gel process. This elaboration method gives rise to a significant decrease in the production cost. In order to achieve this, first of all structural, morphological, optical and electrical characterization of the thin films have been carried out and their physical parameters have been measured in order to determine the optimal conditions of deposition for the desired films. The obtained results exhibit that vanadium concentrations of 20% and 1% are respectively suitable for realizing the desired buffer layers and Transparent Conducting Oxides (TCO). Finally, in order to anticipate and improve the photovoltaic parameters, a new architecture of photovoltaic structure of the type Glass/(n+)Zn0.99V0.01O/(n)Zn0.80V0.20O/(p)Cu(In,Ga)Se2 /Mo has been defined and modeled by simulation using the experimental data already obtained. This work has allowed us to define the criteria which the CIGS absorber must respect in order to obtain the best conversion efficiency of the proposed cell.

The work described herein deals with the synthesis and characterization of lead chalcogenide thin films and nanocrystals. The first part of thesis describes the properties of semiconductors followed by an analysis on the chemical vapour deposition and nanoparticulate formation. In the next part of thesis, single-source precursors of type thioselenophosphinato, selenoureato, dithiocarbamato and dithiocarbanato complexes of lead have been synthesised and characterised. As-synthesised compounds have been utilised for the fabrication of lead sulfide and lead selenide thin films by aerosol-assisted chemical vapour deposition as well as nanocrystals by colloidal injection method. Lead sulfide thin films were also deposited by liquid-liquid interface from lead dithiocarbanato at room temperature. The as grown thin films of lead sulfide and lead selenide have been characterised by XRD, SEM and energy dispersive x-ray (EDX) analysis. In the second part of the thesis, preparation of lead sulfide and lead selenide nanocrystals in olive oil at low growth temperatures (50-60°C) is described and have shown that by controlling experimental conditions, well-defined particles with tunable emission in mid and far-infrared region can be synthesised. Furthermore, compositionally-tuned PbSxSe1-x nanocrystals has also been prepared by adding controlled amount of sulur and selenium ingredients into lead oxide. Homogenous distribution of sulfur and selenium within alloyed nanocrystals is confirmed by transmission electron microscope studies. Moreover, attempts have been made to prepare quaternary (PbTe/Se/S) nanocrystals of lead chalcogenides and depth (1.9-5.8 nm) profile analysis by x-ray photoelectron spectroscopy confirmed the formation of core/shell/shell type structure i.e. PbTe/S/Se.

Dans cette thèse, nous nous intéressons à la problématique de l’intégration de capteurs plasmoniques performants et bas coût sur des dispositifs de type smartphone, en vue d’applications de diagnostic biomédical. A cette fin, nous proposons deux biocapteurs « smart ». Premièrement, un système de détection colorimétrique à base de nanoparticules d’or est mis en œuvre pour détecter de l’ADN. Le système intègre une détection synchrone logicielle mise en œuvre au sein du smartphone, où les signaux physiques transitent par la voie audio. Le processus de diagnostic prend moins de 15 minutes pour une limite de détection de 0.77 nM, approximativement 6 fois meilleure que la sensibilité usuelle d’un spectromètre UV-Vis conventionnel, à temps de mesure identique. Dans une seconde partie, un capteur à résonance plasmon de surface en configuration de Kretschmann, se distinguant par une sensibilité à la phase optique, est développé. Le design monolithique et compact repose sur un interféromètre à dédoublement latéral et une modulation de phase. Le contrôle et la lecture du prototype s’effectue également par smartphone. La modulation de phase est de type sinusoïdale et une sensibilité importante est obtenue, autour de 2,3 10-6 RIU avec une dynamique de 7 10-3 RIU, chiffres obtenus pour une puce optique standard et un temps d’intégration de 100 ms. Ce second dispositif est ensuite testé pour la détection de protéines (Troponine I cardiaque), en fonctionnalisant la surface par ADN Tro4 / In this thesis, we investigate the possibility and potential for integration of portable optical biosensor for diagnostic purposes. To this end, we propose two “smart” biosensor systems. In the first part of this thesis, a DNA biosensor combining single-wavelength colorimetry and digital Lock-in Amplifier within a smartphone is proposed. Utilizing full advantage of audio channel and digital signal processing capacity of a smartphone, we have built a handheld DNA AuNp colorimetry biosensor. Based on the results, the diagnostic process takes only 15 minutes of reaction time while offering a limit of detection around 0.77 nM which is 6 times better than a desktop UV-Vis spectrometer.In second part of the thesis, a Shearing interferometer based Surface Plasmon Resonance (SiSPR) biosensor is proposed. SiSPR allows for phase sensitive detection on conventional Kretschmann configuration. Its monolithic design reduces optical parts, costs and allows portable application. The essence of SiSPR is a reflective layer in addition to plasmonic layer. To extract phase information from SiSPR, a sinusoidal phase modulation is achieved by modulation of the laser injection current. For a 100 ms measurement and a standard optical chip, the sensitivity of the SiSPR is around 2.3x10-6 RIU with a dynamic range of 7.0x10-3 RIU, which is better than amplitude SPR devices. Finally, Tro4 DNA surface modification on the SiSPR chip is demonstrated for future cardiac Troponin I diagnostic

One antiaromatic polycyclic hydrocarbon (PH) with and without solubilizing tert-butyl substituents, namely s-indaceno[2,1-a:6,5-a′]dipyrene (IDPs), has been synthesized by a four-step protocol. The IDPs represent the longitudinal, peri-extension of the indeno[1,2-b]fluorene skeleton towards a planar 40 π-electron system. Their structures were unambiguously confirmed by X-ray crystallographic analysis. The optoelectronic properties were studied by UV/vis absorption spectroscopy and cyclic voltammetry. These studies revealed that peri-fusion renders the IDP derivatives with a narrow optical energy gap of 1.8 eV. The maximum absorption of IDPs is shifted by 160 nm compared to the parent indenofluorene. Two quasi-reversible oxidation as well as reduction steps indicate an excellent redox behavior attributed to the antiaromatic core. Formation of the radical cation and the dication was monitored by UV/vis absorption spectroscopy during titration experiments. Notably, the fusion of s-indacene with two pyrene moieties lead to IDPs with absorption maxima approaching the near infrared (NIR) regime.

Dissertation deals with analysis and design of optoelectronic and photogrammetric measuring systems. Specific design of optoelectronic contactless flat object area meters with analysis of attainable measurement accuracy is described. Next part is dedicated to stereophotogrammetry - principles of 3D reconstructions, methods of camera self-calibration and matching points in images are described. The analysis of attainable accuracy of monitored parameters is discussed too. Finally, the test program with implemented described routines is introduced. This test program enables practical aplication of stereophotogrammetric system for taking spatial coordinates of 3D objects.

The doctoral thesis is aimed at research of application possibilities of low-temperature co-fired ceramics, especially its non-conventional usage. It deals with particular topics ensue from electronic chips package design. The thesis also touches optoelectronic sensor application of this ceramics.

The random fluctuations of signal phase of an oscillator limit the precision of time and frequency measurements. The noise and long-term stability of the system’s oscillator or clock is of major importance in applications such as optical and wireless communications, high-speed digital electronics, radar, and astronomy. The Optoelectronic Oscillator (OE Oscillator), a new class of time delay oscillator with promise as a low-phase noise source of microwave carriers, was introduced by Steve Yao and Lute Malek in 1996. The OE Oscillator combines into a closed loop an RF photonic link and an RF chain. The RF photonic link consists of a laser, electro-optic modulator, optical fibre delay line, and a photo-receiver that together provide an RF delay. An RF chain consists of one or more amplifiers and a RF resonator that together provide the sustaining amplification and the frequency selectivity necessary for single mode oscillation of the loop. The low loss of optical fibres enables the attainment of delays that correspond to optical fibre lengths of several kilometers. It is the long delay, unattainable in an all electronic implementations that is responsible for the superior phase noise performance of an OE Oscillator. In this thesis the fundamental principles of operation of an OE Oscillator are described and the principal sources of in-loop phase fluctuations that are responsible for phase-noise identified. This lays the ground for an exposition of the mechanism that describes the perturbation of a time delay oscillator by injection into the loop of a carrier that is detuned in frequency from the natural frequency of the oscillator. For sufficiently small detuning the oscillator can become phase locked to the injected carrier. The model presented in the thesis generalises the traditional Yao-Maleki and Leeson model to include all the important features that describe the injection locking dynamics of an OE Oscillator. In particular the common assumptions of single mode oscillation and weak injection are removed. This is important to correctly predict the effect of injection locking on the spurious peaks in the phase noise spectrum corresponding to the side-modes of a time delay oscillator. Simulation results are presented in order to validate the dynamics of the oscillator under injection and analytic results on the lock-in range and phase noise spectrum. A 10 GHz OE Oscillator with a single 5km delay line is used as an example in the simulation illustration.

Indiana University-Purdue University Indianapolis (IUPUI) / In the first part of this thesis, we investigate the propagation of quantum fluctuations in a nonlinear interferometer comprising under conditions of harmonic generation by computer simulations. This investigation assumes idealized conditions such as lossless and uniform nonlinear media, an ideal cavity and ideal photodetectors. After linearizing wave equations for harmonic generation with a coherent state input, we obtain equations for one dimensional spatial propagation of the mean field and quantum fluctuations for initial conditions set by arbitrary interferometer phase. We discover that fluctuations are de-squeezed in the X and Y quadratures as the interferometer phase is tuned. However, we discover that there is are quadratures P-Q obtained by rotating the X-Y quadratures for which squeezing is improved by factors of 10^9. We present a practical idea to implement rotation of X quadrature fluctuations to the Q quadrature by using an ideal empty optical cavity. Signal-to-Noise ratio of the nonlinear interferometer was calculated and compared with that of a linear interferometer with coherent state input. We calculated a maximum performance improvement of a factor of 60 for a normalized propagation length ζ0 = 3 under ideal conditions. In the second part of this thesis, we investigate experimentalarrangements to transfer atomic coherence from light to cesium atoms. We discuss the experimental arrangement to generate coherence under conditions of electromagnetically induced transparency (EIT). We measure a continuous wave EIT width of 7.18 MHz and present results for pulsed arrangements.

Organic π-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structureactivity relationships useful for technological innovations. In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the iv efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchangecorrelation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different v semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations. In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1 † ) excitons, positive (P+ ) and negative (P- ) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particlehole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium. In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P + and Pis determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1 † ) mostly follows their lattice distortions. Geometry vi relaxation plays an important role in the localization of the S1 and T1 † excitons owing to the nonvariational construction of the excited state wavefunction. While, mean-field calculated P + , Pand T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and Pformation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LCwPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure. In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P + and Pexcitations in PPV and MEHPPV. We observe that the extent of self-trapping for P+ and Ppolarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.

Les dispositifs optoélectroniques sont devenus un élément essentiel de la technologie moderne visant à exploiter des applications de niche pour l'électronique flexible à base de composés organiques. Jusqu'à présent, les films minces préparés à partir de composés polymères conjugués ont été les principaux concurrents pour les dispositifs optoélectroniques organiques. Avec l'apparition de nouvelles méthodes de mise en œuvre et de nouveaux besoins électroniques, les méthodes de fabrication additive des matériaux optoélectroniques suscitent de plus en plus d'intérêt. Malgré l'intérêt croissant et la variété des méthodes de mise en œuvre tridimensionnelles, on comprend encore mal l'impact de la technique de mise en œuvre sur l'organisation moléculaire des échantillons. Ici, une étude est présentée impliquant l’impression 3D assistée par évaporation de solvant et le poly(3-hexylthiophène) (P3HT) qui est bien décrit dans la littérature, et, dans ce cas-ci, mélangé à diverses matrices thermoplastiques. Dans un premier temps, les matrices thermoplastiques employées, i.e. le polystyrène (PS), le polypropylène carbonate (PPC), le polyméthacrylate de méthyle (PMMA) et le polyoxyéthylène (PEO) sont évaluées en fonction de leurs propriétés rhéologiques et de leur imprimabilité en 3D, qui ne sont que très peu affectées par l'introduction du P3HT. Par la suite, le P3HT à régiorégularité élevée et faible est mélangé dans chacune des matrices thermoplastiques. L'organisation moléculaire des deux composantes dans les architectures imprimées a été évaluée par des techniques de spectroscopie UV-visible et de fluorescence. Les phases en présence ont été analysées à l'aide d’analyse calorimétrique différentielle à balayage, de microscopie optique polarisée et de diffraction des rayons X, ce qui a également permis d'analyser l'état d'agrégation du P3HT par rapport à celui retrouvé dans les films minces. Il est intéressant de noter que les propriétés optiques montrent peu ou pas de différence entre les architectures 3D et les films minces, ce qui indique vraisemblablement que l'efficacité d'un dispositif optoélectronique imprimé en 3D ne serait pas affectée par l’impression 3D assistée par évaporation de solvant. Cette étude pourrait permettre de mieux comprendre comment il serait possible de mettre au point des dispositifs optoélectroniques, y compris des photoconducteurs, des photovoltaïques organiques, des transistors à effet de champ organiques, etc. à l’aide de techniques de fabrication additive, ce qui ouvrira la voie à une nouvelle ère en électronique organique imprimée en trois dimensions. / Optoelectronic devices have become a staple in modern day technology which aims to transition to flexible electronics that are developed from organic compounds. To date, 2-dimensional films of conjugated polymer compounds have been the main contender for organic optoelectronic devices. As new processing methods and electronic needs become present in the modern day, a focus on 3-dimensional processing methods of optoelectronic materials have become increasingly of interest. With the increasing interest and variety of 3-dimensional processing methods, there is little understanding of how the processing technique molecularly affects the final product. Herein is presented a study on the extrusion-based, direct-ink writing of the well understood poly(3-hexylthiophene-2,5-diyl) (P3HT) blended into a variety of thermoplastic matrices. Initially the pristine thermoplastics of polystyrene (PS), poly(propylene carbonate) (PPC), poly(methyl methacrylate) (PMMA), and poly(ethylene oxide) (PEO) were evaluated based on their rheological and printable properties which are negligibly affected by the introduction of P3HT. Subsequently, after the blending of both high and low regioregular P3HT into each of the thermoplastic matrices, the printed architectures were further analyzed by X-Ray diffraction, UV-vis, and fluorescence techniques to assess the aggregation state of P3HT in comparison to 2-dimensional processed films. Interestingly, the electronic properties show little to no difference between 3-dimensional architectures and 2-dimensional films, which presumably indicates that the efficiency would not be affected by the direct-ink writing technique. This study could contribute to the beginning of producing optoelectronic devices, including photoconductors, organic photovoltaic and organic field effect transistors, in 3-dimensions resulting in a new age of electronics.