In this dissertation, we investigate two emerging strategies for enhancing the performance of organic photovoltaics. The first takes advantage of a process called singlet exciton fission, and the second embodies an exodus from the fullerene electron acceptors prominent in organic solar cells. Indeed, this versatile class of tunable small molecules are aptly termed nonfullerene acceptors. However, both strategies would benefit from a greater understanding of underlying principles. Singlet exciton fission is a photon-multiplying process in which a singlet exciton from a high-energy absorbed photon splits into two triplet excitons. The process could significantly reduce energy lost to heat in photovoltaic devices, but its mechanisms are still misunderstood. One model involves direct coupling between the singlet and triplet states, and another model involves an intermediate charge transfer state. Transient absorption spectroscopy allowed us to examine singlet fission in films of pentacene, fluorinated pentacene, and coevaporated blends of various mixing ratios. We directly observe an intermolecular charge transfer state during singlet fission in solid films of coevaporated pentacene and peruoropentacene, which supports the model of charge transfer state-mediated singlet fission. Furthermore, we successfully induced singlet fission in one blend by directly exciting the charge transfer state below the bandgap. We use various types of steady state and time-resolved spectroscopy to characterize two types of nonfullerene electron acceptors. The first type is a group of tetraazabenzodiuoranthene diimide (BFI) dimers and a BFI monomer. The BFI dimers were designed to have twisted, nonplanar 3-dimensional structures and have helped achieve power conversion efficiencies of over 8% in organic solar cells. The other type of nonfullerene acceptor is a calamitic small molecule, and we consider the BAF-4CN electron acceptor, which has also been used in a solar cell whose efficiency exceeded 8%. Spectroscopic studies give insight into the performances of these nonfullerene devices in relation to fullerene-derivative counterparts. We find that the nonfullerene blends suffer from more geminate charge recombination. However, despite this drawback, in some cases, slower rates of nongeminate recombination may lead to successful power conversion efficiencies in nonfullerene solar cells.

The perovskite family of materials is extremely large and provides a template for designing materials for different purposes. Among them, hybrid organic-inorganic perovskites (HOIPs) are very interesting and have been recently identified as possible next generation light harvesting materials because they combine low manufacturing cost and relatively high power conversion efficiencies (PCEs). In addition, some other applications like light emitting devices are also highly studied. This thesis starts with an introduction to the solar cell technologies that could use HOIPs. In Chapter 2, previously published results on the structural, electronic, optical and mechanical properties of HOIPs are reviewed in order to understand the background and latest developments in this field. Chapter 3 discusses the computational and experimental methods used in the following chapters. Then Chapter 4 describes the discovery of several hybrid double perovskites, with the formula (MA)$_2$M$^I$M$^{III}$X$_6$ (MA = methylammonium, CH$_3$NH$_3$, M$^I$ = K, Ag and Tl, M$^{III}$ = Bi, Y and Gd, X = Cl and Br). Chapter 5 presents studies on the variable presure and temperature response of formamidinium lead halides FAPbBr$_3$ (FA = formamidinium, CH(NH$_2$)$_2$) as well as the mechanical properties of FAPbBr$_3$ and FAPbI$_3$, followed by a computational study connecting the mechanical properties of halide perovskites ABX$_3$ (A = K, Rb, Cs, Fr and MA, X = Cl, Br and I) to their electronic transport properties. Chapter 6 describes a study on the phase stability, transformation and electronic properties of low-dimensional hybrid perovskites containing the guanidinium cation Gua$_x$PbI$_{x+2}$ (x = 1, 2 and 3, Gua = guanidinium, C(NH$_2$)$_3$). The conclusions and possible future work are summarized in Chapter 7. These results provide theoreticians and experimentalists with insight into the design and synthesis of novel, highly efficient, stable and environmentally friendly materials for solar cell applications as well as for other purposes in the future.

Cette thèse a pour but d'étudier le transport de charges pho- togénérées dans des matériaux hybrides composés de polymères π-conjugués et de nanocristaux de semi- conducteurs, conçus pour des applications en opto-électronique. La synthèse chimique permet d'obtenir des nanocristaux de CdSe à l'échelle du gramme ayant une faible polydispersité et des formes contrôlées (sphériques, branchées). Les ligands de surface des nanocristaux de CdSe sont échangés par de petites molécules (pyridine, éthanedithiol, phénylènediamine, butylamine, benzènedithiol) afin d'augmenter leur conductivité. L'échange de ligands modifie les niveaux énergétiques des nanocristaux, comme le montrent des études optiques et électrochimiques. Le poly(3-hexylthiophène) déposé sous forme de couches minces présente différents degrés de couplage intermoléculaire et de désordre énergétique selon la méthode de dépôt et le solvant utilisé. Dans les films hybrides, des mesures de diffraction de rayons X en incidence rasante montrent que la structuration cristalline de la matrice organique est modifiée par la présence des nanocristaux. Les mesures de Temps-de-Vol dans les couches hybrides montrent que les mobilités des trous et des électrons varient avec le contenu en nanocristaux, ainsi qu'avec leur forme et leurs ligands. De faibles fractions de nanocristaux provoquent une amélioration de la mobilité des trous, tandis que de plus grandes fractions la détériorent. Les mobilités électroniques sont soumises à une fraction-seuil, as- similable à un seuil de percolation. La fraction optimale de nanocristaux, du point de vue des mobilités des trous et des électrons, est de 36% en volume pour les nanocristaux sphériques avec les ligands de synthèse. Enfin, les simulations Monte-Carlo des courants transitoires photo-générés, dans un échantillon de poly(3-hexylthiophène) et dans un hybride, montrent d'une part que la distribution énergétique du poly(3-hexylthiophène) domine l'allure des courants simulés et d'autre part que les nanocristaux peuvent être assimilés à des sites difficilement accessibles du réseau cubique. / The aim of this work is the study of photogenerated charge transport in hybrid films composed of π-conjugated polymers and of semiconductor nanocrystals, designed for applications in optoelectronics. Chemical synthesis provides gram-scale samples of CdSe nanocrystals, of low polydispersity and con- trolled shapes (spherical, branched). In order to enhance their conductivity, the surface ligands of CdSe nanocrystals (stearic acid, oleylamine) are exchanged by smaller molecules, namely pyridine, ethanedithiol, phenylenediamine, butylamine and benzenedithiol. Optical and electrochemical studies show that the lig- and exchange modifies the nanocrystals' energy levels. Poly(3-hexylthiophene) thin films exhibit varying degrees of energetical disorder and of intermolecular coupling, depending on the processing method and on the solvent used. In hybrid films, the crystallinity of P3HT, probed by grazing incidence X-ray diffraction, is modified by the presence of nanocrystals. Time-of-Flight measurements of hybrid films show that elec- tron and hole mobilities vary with the content of nanocrystals, with their shape, and with their ligands. Small volume fractions of nanocrystals enhance the hole mobility, and large fractions degrade it. Electron mobilities are percolation-limited: they reach a stable value for a threshold fraction of nanocrystals. The optimal fraction of nanocrystals for electron and hole mobilities is 36 vol% in hybrids made of spherical nanocrystals with their synthesis synthesis ligands. Finally, Monte Carlo simulations of photogenerated current transients in pristine poly(3-hexylthiophene) and in a hybrid sample show on one hand that the energy distribution of poly(3-hexylthiophene) rules the shape of the simulated transients, and on the other hand that nanocrystals can be described as little accessible sites of the hopping lattice.

In dieser Arbeit wird ein grundlegender Rahmen für das Verständnis von photovoltaischer Ladungserzeugung an Grenzflächen zwischen einem Metalloxid und einem organischen Halbleiter geschaffen. Dabei wird gezeigt, dass hybride Ladungstransferzustände (HCTS) eine entscheidende Rolle im Energieumwandlungsprozess spielen. Vor ihrer endgültigen Trennung bleiben Elektronen und Löcher an gegenüberliegenden Seiten der Grenzfläche durch Coulomb-Interaktion aneinander gebunden. Nur wenn die Trennung eines solchen HCTS gelingt, kann es zu einem Photostrom beitragen. Die planaren Schichtsysteme ZnO/P3HT, ZnMgO/P3HT und SnO2/P3HT dienen als Modellsystem für eine ausführliche Studie über Energiestruktur der Grenzfläche, photovoltaische Energieumwandlung und die damit verbundenen Verluste. Es wird gezeigt, dass ein HCTS aus einem Elektron im Leitungsband des Metalloxids und einem Loch im HOMO des Polymers besteht. Folglich ist seine Entstehung eine intrinsische Eigenschaft von allen derartigen Grenzflächen. Elektrolumineszenzspektroskopie (EL) stellt sich als wirksame Methode zur Untersuchung von HCTS dar. Deren strahlende Rekombination produziert ein breites Signal im nahen Infrarotbereich. Spannungsabhängige EL-Messungen zeigen den hohen Grad an Delokalisierung von beiden Ladungsträgern in einem HCTS. EL-Spektren, die über einen weiten Temperaturbereich aufgenommen wurden, zeigen, dass nichtstrahlende Prozesse mit Abstand der dominierende Zerfallsmechanismus für HCTS bei Zimmertemperatur sind. Ein Modell aus mehreren Schritten für den Stromerzeugungsprozess kann aus temperaturabhängigen photovoltaischen Messungen abgeleitet werden. Hierbei wird deutlich, dass die Bindungsenergie von Elektron und Loch in einem HCTS keine bedeutende Einschränkung für die Leistungsfähigkeit einer Solarzelle darstellt. Die einflussreiche Rolle von nichtstrahlenden Zerfallsprozessen verursacht jedoch in allen untersuchten Materialsystemen schwere Verluste. / In this work, a fundamental framework for the understanding of photovoltaic charge generation at metal-oxide/organic hybrid interfaces is established. It is shown that hybrid charge transfer states (HCTS) play a crucial role in the power conversion process. Prior to full charge separation, pairs of electrons and holes situated at opposite sides of the heterojunction remain bound to each other by Coulomb interaction. Only if an HCTS is dissociated, a contribution to a photocurrent can be made. Planar heterojunctions of the material combinations ZnO/P3HT, ZnMgO/P3HT, and SnO2/P3HT serve as model systems for a broad investigation of interface energetics, photovoltaic power conversion and the loss processes therein. It is shown that an HCTS consists of an electron in the conduction band of the metal-oxide and a hole in the HOMO of the polymer. Consequently, its formation is an intrinsic property of all heterojunctions of that kind. Electroluminescence (EL) spectroscopy proves to be a powerful tool in the analysis of HCTS. Their radiative recombination produces a broad signal in the near-infrared spectral range. Voltage-dependent EL measurements reveal a high degree of delocalization of both carriers in an HCTS, whereas EL spectra recorded over a wide range of temperatures show that non-radiative processes are by far the dominant recombination channel for HCTS at room temperature. A multistep model of the charge generation process is derived from temperature-dependent photovoltaic measurements. It becomes apparent that the binding energy of electron and hole in an HCTS does not impose a significant limitation on device performance. The strong presence of non-radiative decay processes, however, causes severe losses for all material systems that are investigated in this work.

Les nanostructures périodiques jouent un rôle important dans le domaine des nanotechnologies, en particulier dans le contrôle des photons. Bien qu'il existe de nombreuses techniques d'usage général pour la fabrication et la simulation optique, nous avons développé une technique de fabrication sur mesure et une méthode de simulation optiques pour les structures périodiques pour accélérer le prototypage à l’échelle du laboratoire et la conception optique. Dans la première partie de cette thèse, nous décrivons une technique lithographique nommée « Laser Interference Lithography » (LIL) à faible coût pour la fabrication de nanostructures périodiques. La technique LIL est combinée avec gravure sèche, gravure humide et technique de gravure électrochimique pour réaliser, respectivement, des trous cylindriques, des pyramides inversées et des réseaux taux de pores bi-périodiques à facteur d’aspect élevé sur le substrat à base de silicium. Les modèles unidimensionnels sur des substrats en verre sont également utilisés comme nanofiltres dans la réalisation de la puce de pré-concentration à faible coût. Dans la deuxième partie, nous décrivons d'abord une méthode de calcul électromagnétique rigoureuse Rigorous Coupled-Wave Analysis (RCWA) conçu pour les structures périodiques. Une description détaillée est donnée pour expliquer la méthode numérique. Ensuite, nous combinons la méthode RCWA et une nouvelle approche proposée de la conception des modèles pseudo-désordonnée pour améliorer le piégeage des photons. A titre d'exemple, nous démontrons que, en ajoutant des structures désordonnées à petite échelle sur des arrangements périodiques à grande échelle, la performance quant à l’absorption des couches minces de silicium peut être grandement améliorée. / Periodic nanostructures play an important role in the domain of nanotechnology, especially in photon control. While there exist many general purpose techniques for fabrication and optical simulation, we show tailored fabrication and optical simulation methods for periodic structures to accelerate lab-scale prototyping and optical design. In the first part of this dissertation, we describe a low-cost lithographic technique named Laser Interference Lithography (LIL) for fabricating periodic nanostructures. LIL technique is combined with dry-etching, wet-etching and electrochemical etching technique to realize, respectively, cylindrical holes, inverted pyramids and high aspect ratio pore arrays on silicon based substrate. The one-dimensional patterns on glass substrates are also used as nanofilters in realizing low-cost preconcentration chip. In the second part, we first describe Rigorous Coupled-Wave Analysis (RCWA), a rigorous electromagnetic calculation method designed for periodic structures. A detailed derivation is given to explain the numerical method. Then, we combine the RCWA method and a new proposed pseudo-disordered patterns design approach to investigate photon control. As an example, we demonstrate that by adding ‘appropriate’ engineered fine stripes to each long period the absorption performance of thin silicon slab can be largely enhanced.

Les performances électriques des cellules photovoltaïques à base de silicium sont fortement dégradées lorsque leur température augmente. Cette problématique, pourtant bien connue, n’est pas suffisamment prise en considération dans l’industrie du photovoltaïque. Pour parer à cette dégradation, deux voies d’améliorations peuvent être explorées : diminuer la température de fonctionnement des cellules ou réduire leurs coefficients de dégradation en température. Cette étude est d’autant plus importante pour les applications sous concentrations, un éclairement élevé favorisant l’échauffement des cellules. Pour les facteurs de concentration élevés, l’utilisation de systèmes de refroidissement actifs réduit drastiquement la température de fonctionnement. Pour les faibles éclairements, le refroidissement passif est préféré, bien moins coûteux en énergie. Ce travail de thèse est focalisé sur l’étude du comportement thermo-électrique des cellules sous faible concentration du rayonnement incident. Un banc de caractérisation innovant développé dans cette thèse a rendu possible la quantification des variations de la température de la cellule avec la tension de polarisation sous différents facteurs de concentration. Avec l’augmentation de la polarisation, une évolution du facteur d’émission thermique est observée du fait des variations de la concentration de porteurs de charge minoritaires. Le refroidissement radiatif est minimal au courant de court-circuit et est maximal à la tension de circuit ouvert : la température atteinte au point de court-circuit est supérieure à celle atteinte en circuit ouvert. Pour une cellule donnée, sous un éclairement de 3 soleils, un écart de température de 6.2 °C a pu être mesuré entre ces deux points. La fabrication de cellules avec des propriétés différentes nous a permis de confirmer l’importance du dopage de la base et de l’architecture sur l’augmentation du refroidissement radiatif avec la polarisation. De plus, la comparaison du comportement thermo-électrique des cellules de type de dopages différents a mis en avant de plus faibles coefficients de dégradation en température de la tension en circuit ouvert pour les cellules ayant un substrat de type n. Par exemple, pour une température de et sous un éclairement de 1 soleil, un coefficient de dégradation en température du Voc de −0.45% %·°C-1 a été mesuré sur une cellule de type n contre −0.49%·°C-1 pour une cellule de type p. / The electrical performances of silicon based solar cells strongly degrade when increasing their temperature. However, such a well-known issue is too scarcely considered in the phovoltaic industry. To prevent the degradation of silicon based solar cells, two ways of improvement can be explored : one can either decrease the cells’ functionning temperature or either reduce the temperature degradation coefficient. As light intensity tends to favor cell heating, the study is even more important under concentrated sunlight. Regarding high light intensities, active cooling systems can be used to drastically reduce the cell temperature. For low light intensities, passive cooling systems, such as radiative cooling, are more energetically savy. The thesis aims at studying the electro-thermal behavior of cells under low light intensities. An innovative experimental set-up has been developped during this thesis to quantify the variation of the cell temperature with the applied bias voltage. When increasing the bias, an evolution of the cell emissivity is observed because of a variation of the minorities carrier concentration. The radiative cooling is at its lowest at the short circuit current and peaks its highest value at the open circuit voltage : as a result, the reached temperature is higher at the short circuit current than at the open circuit voltage. For a given solar cell, under 3 suns, a temperature shift of 6.2 °C was measured between these two points. The control of the fabrication process gives the opportunity to analyse the influence of the base doping and cell architecture on the evolution of the radiative cooling with the applied bias. Furthermore, the comparison between the electro-thermal behaviors of solar cells, which are related to their type of doping, has shown a lower thermal degradation coefficient of the open circuit voltage for n-type based dope solar cells. For example, at 60°C and under 1 sun, we measured a thermal degradation coefficient BVoc = −0.45% %·°C-1 for a n type solar cell whereas the p type solar cell recorded BVoc = −0.49% %·°C-1.

The manufacture of photovoltaic (PV) system components has a role to play in the industrialisation and poverty reduction strategies of developing countries. It has also been suggested that small scale local manufacture of balance of systems components has the potential to improve the maintenance, installation and use of the technology. However, PV is a complex technology and most developing countries have not been able to build the capabilities required to manufacture PV system components of an appropriate quality and price, either in the modern or small scale sectors. The factors that determine the success of PV manufacturers in developing countries are therefore of interest. Previous studies on learning in the PV industry have been focused on industry-wide concerns and have not explicitly addressed enterprise-level capability building or challenges specific to developing countries. In particular, there has been very little published about small scale PV manufacture. This thesis therefore aims to improve understanding of the factors that influence capability building, with a view to assisting decision making in relation to PV manufacture in developing countries. The aims of the study have been fulfilled by the development and assessment of a software simulation training tool for PV cell production line engineers, the development of an analysis framework, and application of it to several case study PV enterprises. Through the application of the framework to the case studies, it has been possible to assess the role of software simulations, the suitability of countries with different types of infrastructure for hosting PV manufacturing and the institutional arrangements or interventions that could be used to promote capability building for PV manufacturers in developing countries. While further case studies are required to make more than tentative conclusions, the framework developed and tested in this thesis may now be used as a tool to systematically and rapidly analyse the appropriateness of different types of PV manufacture in particular countries, to identify the weaknesses in their PV technological systems and therefore to suggest where resources should be invested and where appropriate institutional changes could be made. The simulation software has been demonstrated to be an effective capability building tool, thus providing one of the key elements required for successful manufacturing.

This thesis examines converter topologies suitable for Module Integrated Converters (MICs) in grid interactive photovoltaic (PV) systems, and makes a contribution to the development of the MIC topologies based on the two-inductor boost converter, which has received less research interest than other well known converters. The thesis provides a detailed analysis of the resonant two-inductor boost converter in the MIC implementations with intermediate constant DC links. Under variable frequency control, this converter is able to operate with a variable DC gain while maintaining the resonant condition. A similar study is also provided for the resonant two-inductor boost converter with the voltage clamp, which aims to increase the output voltage range while reducing the switch voltage stress. An operating point with minimized power loss can be also established under the fixed load condition. Both the hard-switched and the soft-switched current fed two-inductor boost converters are developed for the MIC implementations with unfolding stages. Nondissipative snubbers and a resonant transition gate drive circuit are respectively employed in the two converters to minimize the power loss. The simulation study of a frequency-changer-based two-inductor boost converter is also provided. This converter features a small non-polarised capacitor in a second phase output to provide the power balance in single phase inverter applications. Four magnetic integration solutions for the two-inductor boost converter have also been presented and they are promising in reducing the converter size and power loss.

No description available.

<p>Solar electricity is a promising energy technology for the future, and by using reflectors for concentrating solar radiation onto photovoltaic cells, the cost per produced kWh can be significantly reduced. The optical efficiency of a concentrating system determines the fraction of the incident energy that is transferred to the cells and depends on the optical properties of the system components. In this thesis, low-concentrating photovoltaic and photovoltaic-thermal systems with two-dimensional parabolic reflectors were studied and optimised, and a new biaxial model for the incidence angle dependence of the optical efficiency was proposed.</p><p>Concentration of light generally results in high cell temperatures, and the uneven irradiance distribution on cells with parabolic reflectors leads to high local currents and temperatures, which reduce fill-factor and voltage. Cooling the cells by means of water increases the voltage and makes it possible to utilize the thermal energy. The performance of a 4X concentrating photovoltaic-thermal system was evaluated. If operated at 50°C, this system would produce 250 kWh_electrical and 800 kWh_thermal per m² cell area and year. Optical performance can be increased by 20% by using better reflectors and anti-reflectance glazing.</p><p>Low-concentrating photovoltaic systems for façade-integration were studied and optimised for maximum annual electricity production. The optimisation was based on measured short-circuit currents versus solar altitude. Measurements were performed outdoors and in a solar simulator. It was found that the use of 3X parabolic reflectors increases the annual electricity production by more than 40%. High solar reflectance is crucial to system performance but by using a low-angle scattering reflector, the fill-factor and power are increased due to a more even irradiance on the modules.</p><p>Long-term system performance depends on the durability of the components. The optical properties and degradation of reflector materials were assessed using spectrophotometry, angular resolved scatterometry, Fresnel modelling, optical microscopy, and surface profilometry before and after ageing. The degradation of reflectors was found to be strongly dependent on material composition and environmental conditions. Back surface mirrors, all-metal reflectors, and polymer-metal laminates degraded in different ways, and therefore accelerated ageing must be tailored for testing of different types of reflector materials. However, new types of reflector laminates showed a potential for increasing the cost-effectiveness of low-concentrating solar energy systems.</p>