Τα συστατικά μιας ευαισθητοποιημένης φωτοηλεκτροχημικής ηλιακής κυψελίδας μελετήθηκαν ξεχωριστά: ημιαγωγός, χρωστική και ηλεκτρολύτης. Παρασκευάστηκε και χαρακτηρίστηκε ένας στερεός ηλεκτρολύτης με βάση το υψηλού μοριακού βάρους πολυαιθυλενοξείδιο και νανοδομημένη τιτάνια. Ο ηλεκτρολύτης αυτός έφτασε σε ολικές αποδόσεις μετατροπής της ηλιακής ενέργειας σε ηλεκτρική της τάξεως του 4,55%, μία από τις μεγαλύτερες τιμές στη βιβλιογραφία. Χρήση άλλων ημιαγωγών πέρα του διοξειδίου του τιτανίου, όπως το οξείδιο του κασσιτέρου, δεν επέφερε αύξηση της παραπάνω απόδοσης. Νέα σύμπλοκα δισθενούς ρουθηνίου με διαφορετικούς πυριδινικούς υποκαταστάτες χρησιμοποιήθηκαν επίσης ως χρωστικές με αποδόσεις που έφτασαν μόλις το 1.74%. Επίσης, έγινε χρήση της φασματοσκοπίας micro-Raman για να θεμελιωθούν αρχικά συνθήκες συντονισμού και να μελετηθεί η χημειορρόφηση της χρωστικής στον ημιαγωγό. Τέλος μελετήθηκαν οι αλληλεπιδράσεις του οξειδοαναγωγικού ζεύγους με τη χρωστική κατά τη λειτουργία της κυψελίδας. / Τhe components of a dye-sensitized solar cell were thoroughly studied:semiconductor, dye and electrolyte. A novel electrolyte based on high molecular weight polyethylene oxide polymer filled with titania nanoparticles was prepared and characterized. The use of this electrolyte led to significantly high overall efficiencies (solar to electrical power) up to 4.55%, a value that is still one of the highest in literature. The use of different than titania conducting substrates, like tin oxide, did not improve the above efficiencies. Novel ruthenium(II) complexes with diver pyridine ligands were used leading to efficiencies up to only 1.74%. Micro-Raman spectrocopy was also used in order to establish resonance conditions to detect the dye chemisorption on the semiconductor substrate. Finally, the redox couple-dye interactions were thorouglh studied during the cell operation.

This thesis focuses on the effects of dopant compensation on the electrical properties of crystalline silicon relevant to the operation of solar cells. We show that the control of the net dopant density, which is essential to the fabrication of high-efficiency solar cells, is very challenging in ingots crystallized with silicon feedstock containing both boron and phosphorus such as upgraded metallurgical-grade silicon. This is because of the strong segregation of phosphorus which induces large net dopant density variations along directionally solidified silicon crystals. To overcome this issue, we propose to use gallium co-doping during crystallization, and demonstrate its potential to control the net dopant density along p-type and n-type silicon ingots grown with silicon containing boron and phosphorus. The characteristics of the resulting highly-compensated material are identified to be: a strong impact of incomplete ionization of dopants on the majority carrier density, an important reduction of the mobility compared to theoretical models and a recombination lifetime which is determined by the net dopant density and dominated after long-term illumination by the boron-oxygen recombination centre. To allow accurate modelling of upgraded-metallurgical silicon solar cells, we propose a parameterization of these fundamental properties of compensated silicon. We study the light-induced lifetime degradation in p-type and n-type Si with a wide range of dopant concentrations and compensation levels and show that the boron-oxygen defect is a grown-in complex involving substitutional boron and is rendered electrically active upon injection of carriers through a charge-driven reconfiguration of the defect. Finally, we apply gallium co-doping to the crystallization of upgraded-metallurgical silicon and demonstrate that it allows to significantly increase the tolerance to phosphorus without compromising neither the ingot yield nor the solar cells performance before light-induced degradation.

The solid oxide fuel cell (SOFC) is a potential high efficient electrochemical device for vehicles, auxiliary power units and large-scale stationary power plants combined heat and power application. The main challenges of this technology for market acceptance are associated with cost and lifetime due to the high temperature (700-1000 oC) operation and complex cell structure, i.e. the conventional membrane electrode assemblies. Therefore, it has become a top R&amp;D goal to develop SOFCs for lower temperatures, preferably below 600 oC. To address those above problems, within the framework of this thesis, two kinds of innovative approaches are adopted. One is developing functional composite materials with desirable electrical properties at the reduced temperature, which results of the research on ceria-based composite based low temperature ceramic fuel cell (LTCFC). The other one is discovering novel energy conversion technology - Single-component/ electrolyte-free fuel cell (EFFC), in which the electrolyte layer of conventional SOFC is physically removed while this device still exhibits the fuel cell function. Thus, the focus of this thesis is then put on the characterization of materials physical and electrochemical properties for those advanced energy conversion applications. The major scientific content and contribution to this challenging field are divided into four aspects except the Introduction, Experiments and Conclusions parts. They are: Continuous developments and optimizations of advanced electrolyte materials, ceria-carbonate composite, for LTCFC. An electrolysis study has been carried out on ceria-carbonate composite based LTCFC with cheap Ni-based electrodes. Both oxygen ion and proton conductance in electrolysis mode are observed. High current outputs have been achieved at the given electrolysis voltage below 600 oC. This study also provides alternative manner for high efficient hydrogen production.  Compatible and high active electrode development for ceria-carbonate composite electrolyte based LTCFC. A symmetrical fuel cell configuration is intentionally employed. The electro-catalytic activities of novel symmetrical transition metal oxide composite electrode toward hydrogen oxidation reaction and oxygen reduction reaction have been experimentally investigated. In addition, the origin of high activity of transition metal oxide composite electrode is studied, which is believed to relate to the hydration effect of the composite oxide. A novel all-nanocomposite fuel cell (ANFC) concept proposal and feasibility demonstration. The ANFC is successfully constructed by Ni/Fe-SDC anode, SDC-carbonate electrolyte and lithiated NiO/ZnO cathode at an extremely low in-situ sintering temperature, 600 oC. The ANFC manifests excellent fuel cell performance (over 550 mWcm-2 at 600 oC) and a good short-term operation as well as thermo-cycling stability. All results demonstrated its feasibility and potential for energy conversion. Fundamental study results on breakthrough research Single-Component/Electrolyte-Free Fuel Cell (EFFC) based on above nanocomposite materials (ion and semi-conductive composite) research activities. This is also the key innovation point of this thesis. Compared with classic three-layer fuel cells, EFFC with an electrolyte layer shows a much simpler but more efficient way for energy conversion. The physical-electrical properties of composite, the effects of cell configuration and parameters on cell performance, materials composition and cell fabrication process optimization, micro electrochemical reaction process and possible working principle were systematically investigated and discussed. Besides, the EFFC, joining solar cell and fuel cell working principle, is suggested to provide a research platform for integrating multi-energy-related device and technology application, such as fuel cell, electrolysis, solar cell and micro-reactor etc. This thesis provides a new methodology for materials and system innovation for the fuel cell community, which is expected to accelerate the wide implementation of this high efficient and green fuel cell technology and open new horizons for other related research fields. / <p>QC 20131122</p>

Cadmium sulfide (CdS) and cadmium telluride (CdTe) are two leading semiconductor materials used in the fabrication of thin film solar cells of relatively high power conversion efficiency and low manufacturing cost. In this work, CdS/CdTe solar cells with a varying set of processing parameters and device designs were fabricated and characterized for comparative evaluation. Studies were undertaken to elucidate the effects of (i) each step in fabrication and (ii) parameters like thickness, sheet resistance, light absorptivity solution concentration, inert gas pressure etc. Best results were obtained when the thickness of CdS planar film for the window layer was in the range of 150 nm to 200 nm. Also, CdS nanowires were fabricated for use as the window layer in CdS-CdTe solar cells. Their materials characteristics were studied with scanning electron microscopy (SEM) and X-ray Diffraction (XRD). Spectral absorption measurements on the planar CdS films and nanowire CdS layers were performed and results compared. It was established that the nanowire CdS design was superior because its absorption of sunlight was far less than that of planar CdS film, which would lead to enhanced performance in the CdS-CdTe solar cell through higher short circuit current density and higher open circuit voltage. Diode behavior of CdS-CdTe devices on planar CdS and nanowire CdS was analyzed and compared. KEYWORDS: Thin Film Solar Cell, Nanowire, UV Absorption, Open-circuit Voltage, Close Space Sublimation

La conversion photovoltaïque est un procédé très attractif pour la fourniture d’énergie propre et renouvelable. Cette filière est en plein essor grâce à une réduction constante des coûts de revient et des politiques incitatives de nombreux pays. Pourtant, l’ensemble des panneaux photovoltaïques installés ne produit qu’une faible part de la consommation mondiale en électricité. Les récents développements technologiques dans l’industrie photovoltaïque se sont surtout concentrés sur les cellules dites de seconde génération, à savoir les couches minces à base de CIGS, CdTe, a-Si, a-SiGe. Cette filière permet la fourniture d’électricité à coût inférieur à la technologie standard silicium, mais les rendements de conversion demeurent encore faibles, ce qui nécessite de larges surfaces disponibles. Il est à noter notamment que les cellules couches minces à base de matériaux semiconducteurs à gap direct comme le CIGS et le CdTe sont en plein essor puisqu’ils profitent en particulier d’une absorption accrue par rapport au silicium ; toutefois, ces matériaux sont présents en quantité limitée à la surface de la planète (In, Te). Dans ce contexte, les cellules à base de nanofils constituent une solution intéressante aux problèmes de l’absorption de la lumière, du transport et de la séparation des porteurs de charge photo-générés mais aussi de la quantité de matière utilisée. En effet, en utilisant une jonction radiale (i.e. entourant le nanofil), il est possible de séparer l’absorption de la lumière ( liée notamment à la longueur du nanofil) de la collecte des porteurs de charge (qui dépend du diamètre des nanofils). L’intérêt de ces structures réside également dans les propriétés de base des nanofils : la relaxation élastique favorable sur leur surface latérale ouvre le champ au dépôt de nanofils par hétéro-épitaxie sur tout type de substrat alors que la faible densité de défauts étendus en leur sein est propice à un transport efficace des porteurs de charges. Ainsi, la possibilité de réaliser des nanofils sur substrat souple en réduisant de manière importante la quantité de matière utilisée par rapport à une cellule en silicium cristallin massif peut être envisagée. Plusieurs laboratoires grenoblois ont déjà une expertise dans le domaine de la croissance des nanofils. Cette thèse a pour but de réaliser une analyse expérimentale approfondie des propriétés optoélectroniques des nanofils (par des mesures de réflectivité, de durée de vie des porteurs minoritaires et de recombinaisons en surface et aux interfaces) combinée à des simulations optiques (de type RCWA ou FDTD) et électriques (TCAD). L’objectif ultime étant de concevoir et de développer des cellules à base de nanofils de silicium et de ZnO/CdTe. Des démonstrateurs seront réalisés sur la base des simulations électro-optiques. Pour cela, les moyens d’élaboration, de caractérisation et de technologie des différents laboratoires et entités, ainsi que les compétences associées, seront mis en commun pour accompagner les travaux du doctorant. / Photovoltaic energy is a very attractive way to produce renewable energy. The current increase in the photovoltaic energy production mainly takes advantage of the continuous decrease in the solar cell cost as well as to incentive policy. However, installed photovoltaic panels only contribute to a very small part of the global electricity production. Therefore, important technological developments are dedicated to the second generation of solar cells (i.e. thin film solar cells) in order to reduce more their manufacturing cost despite the resulting lower conversion efficiency owing to a weaker structural and optical material quality. One alternative way to increase the solar cell efficiency is to fabricate nanowire-based solar cells since they may benefit from a higher light absorption and carrier collection efficiency. The light absorption is actually increased thanks to the high surface/volume ratio of nanowires but also to light trapping related to the nanowire length. Furthermore, the collection of minority charge carriers is more efficient in radial structures (i.e. core-shell structures) since the nanowire diameter is very small. This PhD thesis aims at investigating the optoelectronic properties of silicon and ZnO/CdTe nanowires (absorption, lifetime of minority charge carriers, bulk and surface recombination…) in order to design an optimised nanowire-based solar cell structure. Electromagnetic simulations will be first performed to define the best nanowire geometry for the absorbance, and then compared to experimental measurements of the absorption coefficient. Electrical characterisations (lifetime measurements, surface recombination…) will be also achieved to analyse the structural quality and to simulate the solar cell electrical properties. Some prototypes of optimised solar cells will eventually be fabricated.

Photoinduced electron transfer is a fundamentally interesting process; it occurs everywhere in the natural world. Studies on electron transfer shed light on questions about the interaction between molecules and how the dynamics of these can be utilized to steer the electron transfer processes to achieve a desired goal. The goal may be to get electrons to the electrode of a solar cell, or to make the electrons form an energy rich fuel such as hydrogen, and it may also be an input or output for molecular switches. The importance of electron transfer reactions will be highlighted in this thesis, however, the main motivation is to gain a better understanding of the fundamental processes that affect the rate and direction of the electron transfer. A study of photoinduced electron transfer (ET) in a series of metallophorphyrin/bipyridinium complexes in aqueous solution provided fresh insight concerning the intimate relationship between vibrational relaxation and electron transfer. The forward electron transfer from porphyrin to bipyridinium as well as the following back electron transfer to the ground state could be observed by femtosecond transient absorption spectroscopy. Both the reactant and the product states of the ET processes were vibrationally unrelaxed, in contrary to what is assumed for most expressions of the ET rates. This could be understood from the observation of unrelaxed ground states. The excess energy given by the initial excitation of the porphyrin does not relax completely during the two steps of electron transfer. This is an unusual observation, not reported in the literature prior the studies presented in this thesis. This study also gave the first clear evidence of electronically excited radical pairs formed as products of intramolecular electron transfer. Signs of electronically excited radical pairs were seen in transient spectra, and were further verified by the observation that the rates followed a Marcus normal region behavior for all excitation wavelengths, despite the relatively large excess energy of the second excited state. This thesis also concerns electron transfer in solar cell dyes and mixed valence complexes. In the ruthenium polypyridyl complex Ru(dcb)2(NCS)2, where dcb = 4,4’-dicarboxy-2,2’-bipyridine, inter-ligand electron transfer (ILET) in the 3MLCT state was followed by means of femtosecond transient absorption anisotropy that was probed in the mid-IR region. Unexpectedly, ILET was not observed because electron density was localized on the same bpy during the time-window allowed by the rotational lifetime.

Organic solar cells have the potential to become a low-cost photovoltaic technology. One approach to further increase the device efficiency aimsvto cover the near-infrared region of the sunvspectrum. However, suitable absorber materials are rare. This thesis focuses on the material class of aza-bodipy and dibenzo-aza-bodipy as near-infrared absorber materials for organic solar cells. Besides the synthesis of novel thiophene-substituted aza-bodipys, azadiisoindomethenes were prepared by the addition of Grignard reagents to phthalodinitrile an subsequent reduction with formamide. Starting from these azadiisoindomethenes as precursors, complexes with borondifluoride, boroncatechole and transition metals were synthesized. The optical and electrochemical properties of all compounds prepared were investigated by experimental and theoretical methods. The (dibenzo-)aza-bodipys are characterized by their electronic structure, comprising a central electron acceptor core and peripheral electron donor units. The substituents at the donor units offer a stronger impact on the HOMO energy than on the LUMO energy. Electron donating substituents at the donor units result in an overall decreased HOMO-LUMO gap. This allows to redshift the absorption maximum up to 800 nm. The corresponding dibenzo-analogues already demonstrate a bathochromic shift of the absorption compared to the (non-annulated) aza-bodipys. Yet, the central acceptor is weakened and a further redshift by substituents is less distinct. The compounds can be thermally evaporated in high vacuum. The required thermal stability is increased in some cases by boroncatechol compared to borondifluoride complexes, without significant influence on the optical and electrochemical properties. Besides the characterization of the molecular properties, promising materials were evaluated in thin fifilms and solar cell devices. The charge carrier mobility in the measured compounds were found to be between 10E-6 and 10E-4 cm2V-1s-1. The charge transport parameters were calculated on the basis of obtained single crystal structures. It was found that a high charge carrier mobility may be attributed to a better molecular overlap and a short intermolecular distance in the corresponding solid state structure. Selected materials were characterized in organic solar cells. In solution processed devices, the dibenzo-aza-bodipys reached efficiencies of 1.6 % and 2.1 %, as donor materials in combination with PC61BM and PC71BM as acceptor. The main limiting factor in these devices turned out to be the low fill factor of 30 %. From a series of vacuum processed devices with aza-bodipys and dibenzo-aza-bodipys, increased voltages were obtained with decreasing HOMO energy of the bodipy derivatives. A suitable near-infrared absorbing dibenzo-aza-bodipy exhibited a contribution to the photocurrent from 750 - 950 nm. / Die organische Photovoltaik hat das Potential eine kostengünstige Solarzellentechnologie zu werden. Ein Ansatz die Effizienz weiter zu steigern besteht darin den aktiven Spektralbereich in den nahen Infrarotbereich zu erweitern. Bisher gibt es jedoch nur wenige geeignete Materialien. In dieser Arbeit werden Verbindungen aus der Materialklasse der Aza-Bodipy und Dibenzo-Aza-Bodipy als Absorbermaterialien für den nahen Infrarotbereich zur Verwendung in organischen Solarzellen untersucht. Neben der Synthese von neuen Thiophen-substituierten Aza-Bodipys wurden Azadiisoindomethine durch die Addition von Grignardverbindungen an Phthalodinitril und anschließender Reduktion mit Formamid dargestellt. Ausgehend von den Azadiisoindomethinen sind neue Bordifluorid, Borbrenzcatechin und Übergangsmetallkomplexe synthetisiert worden. Alle Substanzen sind mit experimentellen und theoretischen Methoden auf ihre optischen und elektrochemischen Eigenschaften hin untersucht worden. Die elektronische Struktur der (Dibenzo-)Aza-Bodipys ist charakterisiert durch periphere Elektronendonoreinheiten um einen zentralen Elektronenakzeptor. Die langwelligste Absorptionsbande kann in beiden Systemen durch Elektronen schiebende Gruppen an den Donoreinheiten bathochrom, auf über 800 nm verschoben werden. Die Ursache liegt in einem stärkeren Einfluss der Substituenten auf das HOMO als auf das LUMO und einem damit einhergehenden stärkeren Anstieg der HOMO-Energie woraus eine verkleinerte HOMO-LUMO Lücke resultiert. Die Dibenzo-Aza-Bodipys zeichnen sich durch eine rotverschobene Absorption gegenüber den (nicht benzannulierten) Aza-Bodipys aus. Jedoch ist der Akzeptor in den Dibenzo-Aza-Bodipys abgeschwächt, so dass die Rotverschiebung durch die selben Substituenten weniger stark ausgeprägt ist und die Energieniveaus tendenziell höher liegen. Die Verbindungen lassen sich thermisch im Vakuum verdampfen. Die für das Verdampfen wichtige thermische Stabilität, kann durch Austausch von Bordifluorid mit Borbrenzcatechol erhöht werden, ohne die optischen und elektronischen Eigenschaften wesentlich zu beeinflussen. Neben der Charakterisierung der molekularen Eigenschaften, sind einige Verbindungen im Dünnfifilm auf ihre elektrischen Eigenschaften und in Solarzellen untersucht worden. Die Ladungsträgerbeweglichkeit liegt bei den gemessenen Verbindungen zwischen 10E-6 und 10E-4 cm2V-1s-1. Durch Berechnung der Ladungstransportparameter auf Basis erhaltener Kristallstrukturen ist eine höhere Beweglichkeit auf eine günstigere Packung und einen geringeren intermolekularen Abstand zurückgeführt worden. Ausgewählte Verbindungen sind als Donormaterialien in organischen Solarzellen charakterisiert worden. Aus Lösungsmittel prozessierte Solarzellen mit Dibenzo-Aza-Bodipys erreichen eine Effifizienz von 1.6 % mit PC61BM, und 2.1 % mit PC71BM als Akzeptor. Der Effizienz limitierende Faktor ist hierbei der niedrige Füllfaktor von ca. 30 %. In vakuumprozessierten Solarzellen mit planarem Dono-Akzeptor-Übergang von Aza-Bodipys und Dibenzo-Aza-Bodipys hat sich gezeigt, dass die erhaltene Spannung mit abnehmender HOMO Energie der Materialien gesteigert wird. Ein geeignetes Dibenzo-Aza-Bodipy Material ist mit einen Beitrag zum Photostrom im nahen Infrarotbereich, von 750 - 950 nm, gezeigt worden.

This thesis gives a detailed description of the design and synthesis of new organic sensitizers for Dye sensitized Solar Cells (DSCs). It is divided in 7 chapters, where the first gives an introduction to the field of DSCs and the synthesis of organic sensitizers. Chapters 2 to 6 deal with the work of the author, starting with the first publication and the other following in chronological order. The thesis is completed with some concluding remarks (chapter 7). The DSC is a fairly new solar cell concept, also known as the Grätzel cell, after its inventor Michael Grätzel. It uses a dye (sensitizer) to capture the incident light. The dye is chemically connected to a porous layer of a wide band-gap semiconductor. The separation of light absorption and charge separation is different from the conventional Si-based solar cells. Therefore, it does not require the very high purity materials necessary for the Si-solar cells. This opens up the possibility of easier manufacturing for future large scale production. Since the groundbreaking work reported in 1991, the interest within the field has grown rapidly. Large companies have taken up their own research and new companies have started with their focus on the DSC. So far the highest solar energy to electricity conversion efficiencies have reached ~12%. The sensitizers in this thesis are based on triphenylamine or phenoxazine as the electron donating part in the molecule. A conjugated linker allows the electrons to flow from the donor to the acceptor, which will enable the electrons to inject into the semiconductor once they are excited. Changing the structure by introducing substituents, extending the conjugation and exchanging parts of the molecule, will influence the performance of the solar cell. By analyzing the performance, one can evaluate the importance of each component in the structure and thereby gain more insight into the complex nature of the dye sensitized solar cell. / QC 20110505

Solar cells is one of the cleanest and most environmentally friendly ways to produce electricity. Västerås city has invested in a number of solar systems in public buildings as a step to solve the energy issues of the future and contribute to a sustainable environment. The purpose of this project is to compare the real system yield from Västerås city´s solar plants with simulations. Produces the solar plants as expected or not, and if not, what might be the cause. Data were collected about the solar cell installations, by Mälarenergi Elnät and Västerås city. The real system yield was calculated and then the solar plants were simulated in PVGIS (Photovoltaic Geographical Information System) to obtain the theoretical yield. This project shows that most of Västerås city´s solar plants have a yield that is as expected according to the simulations or higher. However, there are some solar plants with a low or very low yield compared to the simulations. The yield varies considerably during the year. For those plants where the yield has been studied monthly, the real yield is higher in the second half of the year compared with the first half. The self-consumption varies greatly between the different solar plants, but generally it is high. Some solar plants have a very high self-consumption of 100 % and some have a very low of 30-40 %. Some solar plants have a higher yield than expected and it may depends to the fact that the installed power is a few percent higher than what the manufacturer states. The simulations might be unsure, because losses, solar radiation and weather may vary. The solar plants that have a low yield compared to the simulations may have a broken or disconnected component, shading and dirt may also affect. To have as high self-consumption as possible is an economically advantage, as long as the plant is not under-dimensioned because the goal is to produce electricity. There is no clear pattern showing which of the four PVGIS simulations is best matched to reality.

This thesis investigated the possibility of integrating a small photovoltaic module in a wireless sensor network node prototype made for use in crop production, mainly in greenhouses. The main question was if the simple photovoltaic module could provide enough power to the prototype's recharge system in order to continuously recharge the battery and thereby reducing the time maintaining the device due to its power consumption. Through measurements, both of the energy supplied by the potential photo voltaic modules and the prototype's power demand, the conclusion was that the power would not be sufficient due to the concealing environment in which the device would be placed. However, suggestions for further work was given in how the proposed idea could be developed.