Ce travail porte sur l'étude des propriétés optiques des composés à transition d'état de spin. Plus précisément, nous avons caractérisé le transition photo-induite de ce type de composé. Pour réaliser ces études, nous avons développé des montages basés sur la technique pompe-sonde résolue en temps. Nous avons alors caractérisé la cinétique de la transition photo-induite de composé du Fe(II) montant ainsi qu'un processus thermique est à l'origine de la transition et amorce un processus de type "nucléation/croissance". De plus, ces études ont été faites pour des poudres composées de particules dont la taille a été réduite. Par ailleurs, nous avons étudié les propriétés optiques de nanoparticules synthétisées sous forme de micelles. / This work deals with the study of optical properties of spin-state transition compounds. More precisely, we characterized the photo-induced transition of this complex. To make these studies, we have used two home-built experimental set ups based on time resolved pump-probe techniques. We have shown that thermal mechanism induces nucleation/growth process. Besides, we have studied the effect of particle size on the photo-induced transition. Finally, we have studied the optical properties of nanoparticles.

Il y a un besoin de nouvelles technologies photovoltaïques avec une efficacité de conversion lumière-électricité augmentée, qui puissent être des alternatives aux dispositifs plus traditionnels d’efficacité limitée et couteux à base de jonctions p-n. Dans ce contexte, la recherche sur les pérovskites ferroélectriques inorganiques ouvre des possibilités pour le développement de nouvelles approches pour augmenter l’efficacité, par exemple grâce à leur aptitude à séparer les charges électriques photoexcitées par le champ électrique intrinsèque (associé à leur polarisation) qui existe dans chaque maille élémentaire de ces matériaux. Pour profiter de cet avantage, un matériau doit posséder plusieurs propriétés comme la ferroélectricité, une bande interdite d’énergie relativement petite pour pouvoir absorber la lumière et une mobilité des porteurs de charges élevée. Ici, on a synthétisé et étudié des solutions solides Ba(Sn,Ti)O3, qui ont comme composants parents un ferroélectrique BaTiO3 et un paraélectrique BaSnO3. Les transitions de phases cristallographiques et la modification des états des dipôles sont caractérisées par les méthodes de diffraction et la spectroscopie diélectrique. La spectrométrie des photoélectrons X montre une corrélation entre l’évolution non-linéaire de la bande interdite pour les différentes compositions et entre l’évolution des charges locales dynamiques. Les propriétés optiques en température sont dominées par l’arrangement des dipôles dans les compositions ferroélectriques. Pour les autres compositions les propriétés sont plutôt guidées par les défauts. Il a été possible de déterminer les températures critiques des différents mécanismes à partir des caractérisations optiques. Dans ce système Ba(Sn,Ti)O3, les propriétés optiques et le photocourant sont fortement reliés à la structure locale particulière et la nature de la liaison chimique, comme nous avons mis en évidence par la spectroscopie Raman et la spectrophotométrie photoélectronique X. / There is an active search for new photovoltaic technologies with improved efficiency, since the traditional p-n junctions have either the limited efficiency or the increased cost. The research on inorganic ferroelectric perovskites offers opportunities to develop new approaches and increase photovoltaic efficiency, for instance due to capability of these materials to more efficiently separate the photoexcited charges due to the existence of an internal electric field within their unit cell. To profit from this advantage, the material must combine properties like ferroelectricity, relatively small band gap and high charge mobility. In this work, we have synthesized and studied compounds from Ba(Sn,Ti)O3 solid solution, having as end members ferroelectric BaTiO3 and paraelectric BaSnO3. Crystallographic phase transitions and changes of the polar states were characterized by diffraction techniques and dielectric spectroscopy. The non-linear evolution of the band gap for different compounds has been correlated to arise from evolution of the local dynamic charge existing in these compounds, as deduced from X-ray photoelectron spectroscopy. The temperature-dependent optical properties are dominated by polar order in ferroelectric compositions, while for the other compositions the defect-related mechanisms prevail. The critical temperatures for different mechanisms can be determined from optical characterization. In these compounds, the optical properties and photocurrent are strongly related to particularities of the local structure and chemical bonding deduced from Raman and X-ray photoelectron spectroscopies.

The innovative design of flat panel volume computed tomography (CT) systems has recently led to the emergence of a wide spectrum of new applications for both diagnostic and interventional purposes, such as ultra-high resolution bone imaging, image guided interventions, dynamic CT angiography, and interventional neuroradiology. Most of these applications require low X-ray dose to limit potential harm to the patient. One of the main challenges of low dose imaging is to maintain a quantum noise limited system to achieve the highest possible signal to noise ratio (SNR) at a given dose. One potential method to achieve a quantum noise limited system is to employ a high gain detector. Current flat panel CT technology is based on indirect conversion detectors that contain a scintillator and hydrogenated amorphous silicon (a-Si:H) p-i-n photodetectors which have a gain below unity and require a specialized p-layer. In this thesis, an alternative detector to the p-i-n photodetector, which can achieve gain above unity and thus aid in achieving quantum noise limited systems is investigated for large area flat panel imaging. The proposed detector is based on amorphous selenium (a-Se). Amorphous selenium is the most highly developed photoconductor for large area direct conversion X-ray imaging and is still the only commercially available large area direct conversion flat panel X-ray detector. However, the use of a-Se for indirect conversion imaging has not been significantly explored. Amorphous selenium has field dependent mobility and conversion efficiency, which increase with increasing electric field. It is also the only large area compatible avalanche-capable material; a property that was discovered more than 30 years ago. This unique property could be leveraged to provide the gain necessary for low dose medical imaging applications. The only current commercial avalanche capable a-Se optical detector uses electron beam readout in vacuum, which is not large area compatible and makes integration with pixelated readout electronics challenging. The detector structure proposed in this research seeks to address the challenges associated with integration of an avalanche capable a-Se detector with large area X-ray imager. One important aspect in the development of a-Se avalanche detectors is reducing the dark current and preventing a-Se breakdown as the electric field across the device is increased. A high dark current reduces the dynamic range of the detector, it increases the noise level, and it can lead to crystallization of the detector due to joule heating. To overcome the dark current problem, different blocking layers that allow for integration with large area flat panel imagers were investigated. Experimental results from fabricated devices provided the basis for the choice of the most suitable blocking layer. Two device structures are proposed using the selected blocking layer, a vertical structure and a lateral structure, each having associated benefits and drawbacks. It was shown that introducing a polyimide blocking layer brought down the dark current more than four orders of magnitude at high electric fields and does not deteriorate the charge transport properties of the detectors. The polyimide blocking layer also greatly minimizes physical stress related crystallization in a-Se improving reliability. Gain above unity was observed in the vertical structure and the initiation of impact ionization was verified by performing time-of-flight experiments. Although impact ionization was not verified in the lateral structure, this device structure was found to be highly sensitive to ultraviolet light due to the absence of a top contact layer. Devices were fabricated on several different substrates, including a CMOS substrate, to demonstrate their integration compatibility with large area readout electronics. The exhibited performance of the vertical device structure demonstrates that it is a suitable alternative to the p-i-n photodetector for low dose imaging applications.