Les optiques utilisées pour les expérimentations utilisant la lumière blanche ou des lasers, sont généralement traitées afin de fonctionnaliser optiquement la surface pour, par exemple accroître leur faculté à réfléchir la lumière ou au contraire à la transmettre. Ceci est fait au moyen de machines de dépôt sous vide dans lesquelles différentes techniques de dépôt peuvent être utilisées. Dans tous les cas, de la matière est envoyée sur la surface de l'optique à traiter : des couches minces de différents matériaux sont alternativement déposées à leur surface. Cette amélioration des fonctions optiques exploite l'interférence des rayons lumineux qui sont réfléchis ou transmis par ces couches minces. Mais pour que le traitement soit efficace, il est nécessaire que les épaisseurs de chaque couche déposées respectent un schéma défini à l'avance : le design optique, il s'agit du plan de l'empilement des couches à déposer et de leurs épaisseurs théoriques.Différentes techniques de contrôle in-situ de l'épaisseur des couches minces existent. L'une d'elles, le contrôle quartz, est une technique de contrôle largement répandue pour sa simplicité de mise en œuvre mais possède une précision limitée à seulement quelques pourcents. Le sujet de cette thèse porte sur le développement et l'installation dans une machine de dépôt, prévue pour de grandes optiques, d'un système de contrôle basé sur l'analyse spectrale d'une lumière réfléchie par l'optique en cours de dépôt. Il s'agit d'un contrôle optique large-bande, technique mise en place dans la grande machine de dépôt du laboratoire afin de remplacer le contrôle quartz.Nous commencerons cette thèse par un aperçu des différentes techniques de dépôts utilisées au laboratoire puis des techniques de contrôle d'épaisseur les plus répandues dans le domaine des couches minces. Ensuite, nous continuerons sur le design et l'installation du système optique qui permet d'effectuer la mesure des couches en cours de dépôt. Enfin, nous monterons que les spécifications fixées sur les empilements de couches minces ont été atteintes avec précision et répétabilité / The optics that are generally used for the experiments using white light or lasers, have their surfaces usually treated in order to enhance their optical characteristics. This is done inside vacuum coating machines with different possible techniques. With all these techniques, some matter is deposited on the optical surface: several thin films of different materials are deposited in a stack. These improvements use the light interference properties of the beams that are reflected or transmitted by the thin films. But in order to make this effect the most efficient, it is necessary that the layer thicknesses respect an optical design: the layer stack and their theoretical thicknesses.Different in-situ thickness monitoring techniques exist. One of them, the quartz crystal microbalance technique, is widely used for its simplicity but it only allows an accuracy of a few percent. The thesis topic was the development and the installation of a thickness monitoring, in a large coating chamber used for large optics coating, in order to replace th quartz microbalance monitoring. . This is a broadband optical system performing a spectral analysis of the reflected beam from the optic during the coating. We will start this manuscript with a quick overviewof the deposition techniques available at the laboratory. Then, we will review the most widely used thickness monitoring methods in the domain of thin films. We will continue with the design and the installation of the optical system inside the coating chamber. Finally, we will show that the success criteria of the deposition tests were met with accuracy and repeatability

In this thesis, we report the various aspects of fabricating a Cold Atmospheric Plasma system, which can be used for Plasma Enhanced Chemical Vapour Deposition. The greatest advantage of this system is its vacuum free operation, which provides a cost e effctive alternative over conventional high vacuum systems. We have designed a reactor geometry for such a plasma system, in which, the contamination due to ambient air is kept at a minimum value using a low flow of Ar (500 sccm). Towards this end, we have modeled and simulated the flow pattern of Ar gas entering the reactor geometry and have studied its e effectiveness in removing air from the plasma zone. We have fabricated such a geometry and studied the contamination at different flow rates of Ar by observing the plasma optical emission. Further, the aspect of lamentation in atmospheric pressure plasma has been studied and we have identified a few process parameters which can convert a filamentary discharge to a diffused glow. Subsequently, a complete system was developed, including an in-house built high voltage power supply, to generate a plasma with low contamination and less number of laments. We have also carried out plasma diagnostics, specifically to estimate the Electron Energy Distribution Function (EEDF) of the plasma, by analysing the radiation emitted from an Ar plasma, acquired using an Optical Emission Spectroscope. The peaks in the spectrum were curve flatted with Voigt pro les and their widths and intensities were mapped to the electron number density and the EEDF of the plasma, using the mathematical models for Stark broadening and Corona population respectively. An optimization routine based on Nelder-Mead simplex algorithm was run to estimate the optimal values of these plasma parameters that produced a good match between the simulated spectrum and the experimentally acquired one. This analysis estimated that the value of electron number density in our plasma was in the range 0:82 1017 cm 3 to 3:56 1017 cm 3 and the electron temperature was in the range 0.36 eV -0.39 eV . It also predicted that the EEDF closely approximated a Maxwellian distribution. As a proof of concept, the fabricated reactor was used to deposit thin films of Polyacetylene over microscopic cover glass slides by polymerizing Acetylene gas in the cold plasma. Deposition rates as high as 1 m=min, were obtained during thin lm deposition of the polymer. The polymeric structure of the lm was studied using NMR and FT-IR. XPS measurement revealed 5% O2 inclusion in the samples. XRD showed no distinguishable peak, indicating the amorphous state of the films. The surface morphology investigated using SEM revealed highly porous broid kind of structures, which appeared to be agglomeration of particles with sizes in the order of few micrometers. P-type Polyacetylene lms were fabricated by doping them with 5.3% by atomic concentration of I2 vapours. The UV-Visible spectroscopy study revealed a bandgap of 2.05 eV for undoped and 1.49 eV for the doped Polyacetylene samples. The lms exhibited an increase in conductivity by two orders of magnitude; from 3:6 10 13 1cm 1 to 3:5 10 11 1cm 1 for un-doped and doped Polyacetylene samples respectively.

Philosophiae Doctor - PhD / When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell. A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon. In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity. The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped. A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity. / South Africa

Philosophiae Doctor - PhD / When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell.A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon.In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity.The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped.A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity.

Thin film chalcogenide solar cells are promising photovoltaic technologies. Cu(In,Ga)Se2 (CIGS)-based devices are already produced at industrial scale and record laboratory efficiency surpasses 22 %. Cu2ZnSn(S,Se)4 (CZTS) is an alternative material that is based on earth-abundant elements. CZTS device efficiency above 12 % has been obtained, indicating a high potential for improvement. In this thesis, in-line vacuum, sputtering-based processes for the fabrication of complete thin film chalcogenide solar cells on stainless steel substrates are studied. CIGS absorbers are deposited in a one-step high-temperature process using compound targets. CZTS precursors are first deposited by room temperature sputtering and absorbers are then formed by high temperature crystallization in a controlled atmosphere. In both cases, strategies for absorber layer improvement are identified and implemented. The impact of CZTS annealing temperature is studied and it is observed that the absorber grain size increases with annealing temperature up to 550 °C. While performance also improves from 420 to 510 °C, a drop in all solar cell parameters is observed for higher temperature. This loss is caused by blisters forming in the absorber during annealing. Blister formation is found to originate from gas entrapment during precursor sputtering. Increase in substrate temperature or sputtering pressure leads to drastic reduction of gas entrapment and hence alleviate blister formation resulting in improved solar cell parameters, including efficiency. An investigation of bandgap grading in industrial CIGS devices is conducted through one-dimensional simulations and experimental verification. It is found that a single gradient in the conduction band edge extending throughout the absorber combined with a steeper back-grading leads to improved solar cell performance, mainly due to charge carrier collection enhancement. The uniformity of both CIGS and CZTS 6-inch solar cells is assessed. For CZTS, the device uniformity is mainly limited by the in-line annealing process. Uneven heat and gas distribution resulting from natural convection phenomenon leads to significant lateral variation in material properties and device performance. CIGS solar cell uniformity is studied through laterally-resolved material and device characterization combined with SPICE network modeling. The absorber material is found to be laterally homogeneous. Moderate variations observed at the device level are discussed in the context of large area sample characterization. Power conversion efficiency values above 15 % for 225 cm2 CIGS cells and up to 5.1 % for 1 cm2 CZTS solar cells are obtained.

In this thesis, two MFC based films Carboxymethylated-Microfibrillated Cellulose (MFC) and Enzymatic-MFC were characterized and metalized in order to improve the barrier properties at high relative humidity. Several methods were used for the characterization process, which were Atomic Force Microscopy (AFM), Contact Angle (CA), Energy Dispersive Spectra (EDS), Light Microscopy (LM), Scanning Electron Microscopy (SEM), and Oxygen Transmission Rate (OTR). Physical Vapor Deposition (PVD) system was used for the metalization of film, a thin layer of aluminium with a thickness of 200 nm was deposited on the films. The results revealed that ENZ-MFC exhibit a higher roughness and lower OTR values, compared to CM-MFC. The contact angle values proved that both non-metalized MFC films exhibited a hydrophilic surface with values around 50 degrees. SEM and EDS images showed that both films exhibited surface defects with dimensions in the order of a micrometer. The best barrier improvement by metalization was achieved for the metalized CM-MFC, where the OTR values were decreased by one order of magnitude after metalization. However, for ENZ-MFC metalization did not improve OTR at high RH. The protective layer was successfully protecting the MFC film as long as the surface roughness of the film was not too high. The limit is between 40 and 140nm (in root mean square roughness values). / I denna avhandling karakteriserades två MFC-baserade filmer Carboxymethylated-MFC och   Enzymatic-MFC som metalliserades för att förbättra barriäregenskaperna vid hög relativ fuktighet. Flera metoder har används för karaktäriseringsprocessen, vilka var Atomic Force Microscopy (AFM), Contact Angle (CA), Energy Dispersive Spectra (EDS), Light Microscopy (LM), Scanning Electron Microscopy (SEM), och Oxygen Transmission Rate (OTR). Physical Vapor Deposition (PVD) systemet användes för metalliseringen av filmerna, där ett tunt skikt aluminium med en tjocklek av 200 nm deponerades. Resultaten visade att ENZ-MFC har högreråhet och lägre OTR-värden jämfört med CM-MFC. Kontaktvinkelvärdena påvisade att bådaicke-metalliserade MFC-filmer har en hydrofil yta med värden omkring 50 grader. SEM- och EDS-bilder visade att båda filmerna har ytdefekter i storleksordningen en mikrometer. Den bästa barriärförbättringen genom metallisering uppnåddes för den metalliserade CM-MFC, där OTR-värdena minskade med en storleksordning efter metallisering. För ENZ-MFCförbättrade dock metallisering inte OTR vid hög RH. Det skyddande skiktet skyddar effektivt MFC-filmen så länge som filmens ytråhet inte var för hög. Gränsen är intervallet mellan 40 och140 nm (Kvadratiskt medelvärde för ytråhet).

Deposition of noble metal and semiconductor nanocrystalline thin films has received much attention. CdS and CdSe are important semiconductors used in optical devices. A wet chemical route which uses the interface of two immiscible liquids to control the growth and deposition of nanocrystalline thin films forms the basis of the current study. In this method, a metal precursor dissolved in toluene or decane is held in contact with a water layer containing a reducing or sulphiding agent. The reaction proceeds at the interface of the liquids and results in deposits adhering to the interfacial region. The products of such reactions typically consist of nanocrystals forming a thin film. Stable sols of Au, Ag were found to metathesize on contact with alkylamine in oil to form monolayer films that spread across large areas at the water/oil interface. The nature and properties of interfacial thin films depend on the alkylamine. Nanocrystalline thin films consisting of CdS adhering to the interface starting with a polydispersed aqueous sol of crystallites and alkylamine were obtained. The optical band gaps of the films formed are dependent on the alkylamine chain length, with the shortest chain yielding the largest gap. A systematic increase in particle diameters following adsorption is responsible for changes in the electronic structure of films. The formation of nanocrystalline films of CdS adhering at the interface using a toluene solution of cadmium diethyldithiocarbamate and aqueous Na2S solution, in the presence of tetraoctylammonium bromide (TOAB) in the aqueous phase, was investigated under various reaction parameters, while CdSe was obtained using Na2SeSO3 solution and the influences of deposition temperature and solution concentration were studied. A ternary water/decane/2-butoxyethanol /salt system was used to grow deposits of CdSe and CdS. Nanostructured thin films were obtained at the upper interface of the ternary system, between the emulsive middle layer and oil rich top phase. The influence of deposition conditions such as precursor concentrations and temperature, as well as the nature of the medium on the properties of the deposits was studied. Deposits grown using the ternary system were compared with those obtained using water/decane and water/toluene systems. Reaction parameters such as temperature, solution concentration and the size of CdS and CdSe were controlled. A thin film of CdS and CdSe nanocrystals was formed at the interface. The grain size was found to be dependent on reaction temperature and solution concentration, with higher temperatures and solution concentration resulting in larger grains. The nature of thin films obtained at the interface of two immiscible liquids and of a water/decane/2-butoxyethanol/salt ternary system were studied using Scanning and Transmission electron microscopy, X-ray diffraction and UV-visible spectroscopy.

Um den ständig steigenden Energiebedarf durch Kälteanlagen wie Kühlschränke oder Klimaanlagen zu verringern, sind in den vergangenen Jahren Kühlprozesse in den Mittelpunkt aktueller Forschungen gerückt, die auf Phasenumwandlungen in Festkörpern beruhen. Ein Beispiel dafür sind magnetokalorische Materialien, zu denen auch das in der vorliegenden Arbeit untersuchte Ni-Mn-Ga-Co gehört. In dieser Heusler-Legierung tritt eine Phasenumwandlung erster Ordnung von einer ferromagnetischen, kubischen Hochtemperaturphase (Austenit) in eine tetragonal verzerrte Tieftemperaturphase (Martensit) mit geringerer Magnetisierung auf. Der Unterschied in den Magnetisierungen beider Phasen erlaubt es auch, diese Phasenumwandlung durch ein Magnetfeld zu induzieren. Hierbei kühlt sich das Material durch eine Verringerung der Gitterentropie in dem System ab. Ein Nachteil von Phasenumwandlungen erster Ordnung ist die damit verbundene Hysterese. Außerdem lässt sich der magnetokalorische Effekt durch die scharfe Umwandlung nur in einem kleinen Temperaturbereich effektiv nutzen. Das Ziel dieser Arbeit besteht darin, anhand epitaktisch gewachsener Ni-Mn-Ga-Co-Schichten auf PMN-PT-Substraten zu untersuchen, ob und wie die Umwandlungstemperatur und damit auch die Hysterese der Heusler-Legierung durch mechanische Spannung beeinflusst werden kann. Dafür soll durch Anlegen eines elektrischen Feldes an das piezoelektrische Substrat die Ni-Mn-Ga-Co-Schicht reversibel mechanisch verspannt und die daraus resultierenden Veränderungen der strukturellen und magnetischen Eigenschaften untersucht werden. Im ersten Ergebnisteil wird zunächst gezeigt, dass epitaktische Ni-Mn-Ga-Co-Schichten auf PMN-PT wachsen können und diese einen strukturellen und magnetischen Phasenübergang zeigen. Eine Beeinflussung der bei Raumtemperatur vorliegenden Phase ist dabei über eine Variation der chemischen Zusammensetzung der Probe möglich. Im Anschluss werden die Auswirkungen eines angelegten elektrischen Feldes auf die strukturellen und magnetischen Eigenschaften analysiert. Röntgenuntersuchungen zeigen, dass die piezoelektrische Dehnung des Substrats vollständig auf das Ni-Mn-Ga-Co übertragen werden kann. Allerdings treten bei hohen Temperaturen aufgrund einer Phasenumwandlung im PMN-PT nichtlineare Dehnungseffekte auf. Eine Veränderung der Umwandlungstemperaturen durch die Dehnung des Ni-Mn-Ga-Co ist jedoch nicht möglich. Als wahrscheinliche Ursache dafür wird eine Besonderheit des martensitischen Gefüges der Ni-Mn-Ga-Co-Schichten diskutiert. Im Austenit wurde jedoch eine vollständig reversible Änderung der Magnetisierung um bis zu 7 % gemessen. Diese Magnetisierungsänderung bietet einen interessanten Anknüpfungspunkt für weitergehende Untersuchungen dieses Systems für multikalorische Anwendungen.

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Ce travail est une contribution à l'étude de l'interaction entre des couches minces de silicium amorphe hydrogéné (a-Si:H) et un plasma d'hydrogène, dans un réacteur de dépôt par PECVD (Plasma Enhanced Chemical Vapor Deposition). Le suivi in situ de la cinétique de gravure par l'hydrogène atomique est réalisé par ellipsométrie UV-visble. Les différents paramètres de plasma (température, puissance radiofréquence, pression du gaz H2, type de dopage du matériau) pouvant impacter cette cinétique ont été sondés. L'analyse des spectres d'ellipsométrie spectroscopique, à l'aide d'un modèle optique approprié, a permis de mettre en évidence leurs effets sur le temps de formation de la couche modifiée par l'hydrogène, son épaisseur et son excès d'hydrogène, ont été analysés. Le même traitement au plasma d'hydrogène appliqué à des jonctions i/p et i/n, révèle un comportement particulier de la cinétique de gravure dans la zone de jonction. Ce comportement a été interprété dans le cadre d'un modèle simple de diffusion de l'hydrogène sous champ électrique. / This work is a contribution to the study of the interaction between hydrogenated amorphous silicon (a-Si:H) thin films and hydrogen plasma in a PECVD (Plasma Enhanced Chemical Vapor Deposition) reactor. The kinetics of silicon etching by atomic hydrogen is monitored in situ by UV - visble ellipsometry .Several plasma parameters (temperature, RF power, H2 gas pressure, the doping of the material) that may impact the kinetics were probed. An analysis of the spectroscopic ellipsometry spectra, thanks to an appropriate optical model, allowed evidencing their effects on the time constant, the thickness and the hydrogen excess of the H-modified layer.The same hydrogen plasma treatment repeated on i/p and i/n H base junctions revealed a particular behavior of the etching kinetics in the junction zone. This effect is interpreted in the frame of a simple of hydrogen diffusion model under an electric field.