A study has been made of a variety of factors influencing the efficiency and operational stability of front-wall CdS-Cu2S solar cells. In the course of this work -1 cm2 cells were fabricated with conversion efficiency of up to 8% without attempting to reduce reflection losses.The CdS films were produced by vacuum evaporation and the electrical and structural characteristics of these films were studied as a function of the rate and temperature of the deposition. Previously there had been some controversy concerning the nature of the CdS source material required for fabricating high performance CdS-based solar cells, but this work has shown that a variety of CdS sources can be employed successfully provided that the film deposition parameters are suitably chosen.A conventional chemical exchange technique was employed to convert the CdS film surface to Cu2SI with the thickness and stoichiometry of the resultant Cu2S layer being examined by means of electrochemical analysis.Changes in the electrical properties of the CdS-Cu2S cells due to post- fabrication anealing under a variety of different conditions were studied and correlated with structural changes monitored by means of Auger electron spectroscopy with the aid of argon ion etching. Depth profiles of the constituent element concentrations indicate that, for samples annealed in air, a deep penetration of copper into the CdS layer occurs together with a significant out-diffusion of cadmium from the CdS after only a few minutes at 1000C. In contrast, the copper penetration which results from vacuum or hydrogen annealing treatment is substantially less and no significant out-diffusion of cadmium is observed for annealing temperatures up to 4000C. Two different diffusion processes, one in the grain boundaries and one in the mid-grain regions, have been identified and their relative importance has been studied for annealing cycles performed under the same three different ambient atmospheres (air, vacuum or hydrogen). The normally rapid and undesirable grain boundary diffusion of copper was found to be significantly inhibited by the use of flowing hydrogen during annealing. A further technologically important observation concerns the effect of the deposition of a film of copper over the copper sulphide layer of a cell and subsequent annealing of it in air. The improved electrical stability which this treatment yields has been shown to be directly associated with reduced interdiffusion at the CdS-Cu2S interface. This interfacial diffusion has also been shown to be influenced by the CdS stoichiometry in the vicinity of the junction.Finally, a brief investigation was made into the use of the ion implantation technique as a means of doping the upper layer of the OdS film with copper without annealing the completed cell. The results have demonstrated the feasibility of this technique, with the best results being obtained using a copper ion fluence of 5.1014 ions cm-2 at 50 keV ion energy.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / This research describes the process of obtaining a photovoltaic cell, since getting electrical conductor glasses used for the flow of electrons coming from the photovoltaic effect until the deposition of thin films of semiconductor titanium dioxide (TiO2) and cadmium sulfide (CdS) at each of these glasses. The use of natural or synthetic dyes deposited on titanium dioxide layer has the objective to increase the absorption spectrum of the TiO2, since sunlight emits most of its energy in the frequency range of visible light. After joining the two glasses with thin films deposited over TiO2 plus dye and CdS, it was used a potassium triiodide electrolyte for regeneration and consequently the activation of photovoltaic solar cell. After mounting the cell concerned, tests of photoactivity have been performed by exposing the cells to sunlight collected for specified periods and the values of voltage and photocurrent generated. Theoretical studies have been conducted to mathematical modeling of the behavior of the solar cell mounted, and then we have analyzed the efficiency of converting solar energy into electrical energy. The constituents of the cell have been characterized by the techniques of X-ray diffraction (XRD) and scanning electron microscopy (SEM) for analyzing the porosity, uniformity and other physical parameters of thin films. / O presente trabalho descreve o processo de obtenÃÃo de uma cÃlula fotovoltaica, desde a obtenÃÃo de vidros condutores elÃtricos utilizados para o fluxo dos elÃtrons oriundos do efeito fotovoltaico, atà a deposiÃÃo dos filmes finos dos semicondutores diÃxido de titÃnio (TiO2) e sulfeto de cÃdmio (CdS) em cada um dos vidros. O uso de corantes naturais ou sintÃticos na camada depositada de diÃxido de titÃnio possuiu como objetivo aumentar o espectro de absorÃÃo do mesmo, uma vez que a luz solar emite uma grande parte de sua energia na faixa de frequÃncia da luz visÃvel. Depois de unir os dois vidros com os filmes finos depositados de TiO2 mais corante e o CdS, utilizou-se o eletrÃlito de tri-iodeto de potÃssio para a regeneraÃÃo e consequentemente a ativaÃÃo da cÃlula solar fotovoltaica. ApÃs a montagem da cÃlula em questÃo, foram realizados testes de fotoatividade, expondo as cÃlulas ao sol por perÃodos determinados e coletados os valores da fotocorrente gerada e a tensÃo, alÃm disso, foram realizados estudos teÃricos para modelagem matemÃtica do comportamento da cÃlula solar montada e em seguida analisou-se a eficiÃncia de conversÃo de energia solar em energia elÃtrica. Os constituintes da cÃlula foram caracterizados pelas tÃcnicas de difraÃÃo de raios-X (DRX) e microscopia eletrÃnica de varredura (MEV) para analisar a porosidade, uniformidade e outros parÃmetros fÃsicos dos filmes finos.

L'efficacité des cellules photovoltaïques organiques est influencée par la morphologie du mélange composant la couche active. L'objectif de cette thèse a été d'élaborer un agent compatibilisant pour stabiliser la morphologie du mélange P3HT:PCBM. Nous avons choisi de synthétiser des copolymères alternant motifs C60 et polythiophène pour améliorer la miscibilité entre P3HT et PCBM. Les copolymères ont été réalisés par polycondensation d'un dérivé C60 avec plusieurs oligothiophènes régioréguliers de difonctionnalité contrôlée. Une attention particulière a été accordée aux conditions de polycondensation qui ont été optimisées pour favoriser de hauts degrés de polymérisation. Les caractérisations structurales, optiques et électrochimiques des matériaux ont été réalisées. Leur effet compatibilisant a été évalué en caractérisant la morphologie de la couche active par des mesures en cellules photovoltaïques, des observations par microscopie à force atomique et des calculs d'énergies de surface. / Efficiency of organic photovoltaic solar cells is influenced by the active layer's morphology. The aim of this thesis was to elaborate a compatibilising agent which could stabilise the morphology of the P3HT:PCBM blend. We chose to synthesize alternating copolymers based on fullerene and polythiophene blocks to improve compatibility between P3HT and PCBM. The synthesis of copolymers has been achieved by polycondensation of a fullerene derivative with several regioregular oligothiophenes for which difunctionality was well controlled. Particular care has been given to the optimisation of polycondensation conditions in order to favour high polymerisation degrees. Structural, optical and electrochemical characterisations have been realized. The compatibilising effect of our copolymers on the active layer morphology has been investigated on the basis of photovoltaic measurements, atomic force microscopy observations and surface energy calculations.

Vor dem Hintergrund der zukünftigen Notwendigkeit einer nachhaltigen Energieversorgung beschäftigt sich die vorliegende Arbeit mit Technologien der regenerativen Energiequelle Solarenergie, insbesondere Photovoltaik (PV). Systeme zur Nutzung der unerschöpflich verfügbaren, sauberen und im Prinzip “frei Haus” gelieferten Energie der Sonne können eine bedeutsame Rolle in einer umweltverträglicheren Zukunft spielen. Allerdings ist die Herstellung der erforderlichen Komponenten heute i.d.R. noch energie- und kostenintensiv, weshalb für eine korrekte Bewertung dieser Technologien der gesamte Lebenszyklus betrachtet werden muss. Zur tieferen Analyse der PV wird die Methodik des Environmental Life Cycle Costing (ELCC) auf der Grundlage von drei Grundideen eingeführt. Konkret sind dies die Ausgangspunkte: Nachhaltigkeit, Lebenszyklusdenken und die Drei-Dimensionalität dieses Instrumentes durch die gemeinsame Betrachtung ökologischer, ökonomischer und technischer Aspekte in ihrem Zusammenspiel. Ausgehend von theoretischen Elementen der Ökobilanzierung (Life Cycle Assessment) und des Life Cycle Costings, verbunden mit den technischen Eigenschaften der Photovoltaik werden wichtigste Anforderungen und Schritte für die Durchführung eines ELCC für PV beschrieben. Mittels einer softwaregestützten Inhaltsanalyse wird im Anschluss der definierte Rahmen für ein ELCC für PV getestet (und modifiziert) gegen eine Auswahl von 135 bereits existierender Studien, die sich mit dem Lebenszyklus von PV-Technologien aus ökologischer und ökonomischer Sicht beschäftigen. Im Ergebnis hieraus können die wichtigsten Elemente eines ELCC für PV, wie beispielsweise ökologische Wirkungskategorien oder ökonomische Indikatoren, identifiziert werden (methodisches Feedback). In einem nächsten Schritt werden die Studien hinsichtlich ihrer “Qualität” bezogen auf ökologische, ökonomische und übergreifende Inhalte eines ELCC für PV bewertet. Auf diese Weise kann ein Inventar von Lebenszyklusanalysen für PV erstellt werden, das nach den Technologien und der inhaltlichen Qualität bezüglich eines ELCC strukturiert ist und für weitere Analysen als Grundlage dienen kann. Aus den bisherigen Ergebissen kann eine erste Einschätzung zum aktuellen Stand des ELCC für PV in der Literatur vorgenommen werden: Es existiert bereits ein großer Pool von Studien, die sich mit dem Lebenszyklus der PV beschäftigen. Mit Blick auf die Anforderungen eines ELCC für PV besteht jedoch Nachholbedarf in der Verbindung und gemeinsamen Betrachtung von hot spots und trade offs aus ökologischer und ökonomischer Perspektive. Der definierte theoretische Rahmen für ein ELCC für PV, die kodierten Studien sowie das erstellte Inventar von Lebenszyklusanalysen der PV können nun als Grundlage für weitere Analysen dienen. Insbesondere eine inhaltliche Auswertung der konkreten Ergebnisse von Studien kann so einen Benchmark und Orientierung für neue Lebenszyklusanalysen für PV-Technologien liefern. / The special need of a sustainable energy supply in mind the technologies of the renewable source solar energy, especially photovoltaics (PV) is main subject of the present thesis. Using the inexhaustible, clean and “freely delievered” power from the sun solar devices may play a major role in a cleaner future, but, on the other hand, they are still energy consuming and expensive in their production which consequently demands a whole life cycle perspective when assessing this technology. For a closer look at PV the methodology of Environmental Life Cycle Costing (ELCC) is introduced by following three theoretical points of view. Namely these are sustainability, life cycle thinking and the three dimensional nature of this tool by regarding environmental, economic and technical aspects in their interaction. Based on theoretical elements of Life Cycle Assessment and Life Cycle Costing in combination with the technical background of photovoltaics main requirements and steps for performing an ELCC for PV are described. By executing software based content analysis the defined framework is checked (and modified) against a choice of 135 existing studies analyzing the life cycle of PV technologies from an environmental or economic perspective. As a result the main elements of an ELCC for PV, e.g. environmental impact categories and economic indicators, are identified (methodological feedback). Within the next step the existing studies are rated by their “quality” regarding the environmental, economic and more general parts of an ELCC for PV in order to create an inventory of life cycle studies for PV. This inventory is structured by technologies as well as quality of content respecting ELCC and might be used for further analyses. At this stage the results propose the possibility of a first estimate of the present status of ELCC for PV: until now there is a good pool of existing analyses of the life cycle of PV systems. But from an ELCC perspective the examination of common hot spots and trade offs between economic and environmental aspects should be expanded. The theoretical framework of ELCC for PV, the encoded studies and the inventory of life cycle analyses for PV are now the starting point for further analyses, especially of the individual outcome within studies, which will then pose a benchmark for new life cycle studies of PV technology.

Semiconductors such as CuInGaSe2 and CdTe have been investigated as absorber layer materials for thin film solar cells since their band gap matches with the solar spectrum. Films as thin as 2m are sufficient for the absorption of the visible part of solar radiation, because they are characterized by a high absorption coefficient. However, the scarcity and high costs of Indium, Gallium and Tellurium have led to concerns on the sustainability of these technologies. The semiconductor Cu2ZnSnS4 (Copper Zinc Tin Sulphide) consisting of abundantly available elements promises to be an excellent photovoltaic absorber material. The present study is focused on the growth and characterization of CZTS/ZnS thin film heterostructure suitable for PV applications. Ultrasonic Spray Pyrolysis (USP), a variation of Spray Pyrolysis is a thin film deposition technique where the solution to be sprayed is atomized by ultrasonic frequencies. The details of the USP experimental set up and the deposition principle are presented in the thesis. The active layers of the solar cell, viz. the CZTS absorber layer and ZnS emitter layer were grown by this technique. The metal top contact was deposited using e-beam evaporation. The effects of copper concentration and sodium diffusion on the Cu2ZnSnS4 film properties were investigated. The films have shown preferred orientation along (112) direction confirming kesterite structure. The optical studies revealed that a reduction of copper in the films will bring the band gap energy to 1.5eV, which will match with the solar spectrum. Sodium diffusion in the CZTS films is found to passivate the grain boundaries and enhance the electrical conductivity. These properties render CZTS films as good photovoltaic absorber layers. ZnS has a high band gap and is non toxic unlike CdS. The influences of variation in substrate temperature and spray duration on the ZnS film properties were examined. The optical studies conducted on ZnS films revealed that they are highly transparent in the visible region of the solar spectrum. The films were found to possess a band gap of 3.5 eV. These properties make them potential candidates as solar cell emitter layers. The CZTS/ZnS heterojunction solar cell was fabricated and subjected to electrical characterization in dark and illuminated conditions. A conversion efficiency of 1.16% was achieved for the device.