The materials Fe���(Si,Ge)(S,Se)���, Cu���PS[subscript 4-x]Se[subscript x] (0 ��� x ��� 4), and Cu���PxAs[subscript 1-x]S��� (0 ��� x ��� 1) have been synthesized and studied as new earth-abundant absorbers for single and multijunction photovoltaic cells as well as solar fuel generation. The synthesis, single-crystal growth, and optical and electrical properties of these materials are described and discussed in Chapter 2, 3, and 4. Inspired by the photovoltaic absorber Cu���ZnSnS���, the new compound CuZnPS��� has been discovered; its structure and properties are discussed in Chapter 5, including a comparative analysis to Cu���PS���. The compound YZrF��� (Chapter 6) has been synthesized and evaluated for the first time as a new optical host for green up-conversion. / Graduation date: 2013

In this thesis, the preparation of new photoactive substances containing mono- and bipyridines coordinated to ruthenium is presented together with initial evaluations of their photoelectrochemical and photophysical properties. Complexes of the type Ru(bpy)2(4-X-py)2 (X = SH, COOH) were prepared and used in Grätzel-type solar cells based on ZnO. The results show that the thiol complex binds to the surface but give rather low solar cell efficiencies. Different routes to obtain Ru(bpy)2(4,4´-dithio-2,2´-bipyridine) were evaluated, among them substitution reactions on 4,4´-dichloro-2,2´-bipyridine coordinated to ruthenium. Due to reactivity issues, the target sulphur-containing complex has not yet been obtained. The synthesis of methanofullerenes, fulleropyrrolidines and –pyrazolines are presented, among them dyads containing Ru(bpy)n-units. A common feature for the dyads is the unusually short linkers between the fullerene and the ruthenium complex. Dyad preparations were in some cases simplified by carrying out the reactions in the presence of silver salts. A preliminary evaluation of the emission of the dyads showed almost complete quenching of the excited state of a pyrrolidine-based dyad, whereas emission remained from the pyrazoline-based ones. Whether this was due to incomplete quenching of the excited states of the ruthenium complex, or induced by the presence of hydrazones has yet to be revealed. The use of fullerene-substituted malonic acid and its ethyl ester as dyes in Grätzel-type solar cells resulted in even lower efficiencies (IPCE) than for bare TiO2. This could be due to electron transfer in the reverse direction compared to what is observed for ruthenium complexes. Thus, these fullerene derivatives are not suitable as sensitisers for Grätzel-type solar cells.

The urgent need for new, sustainable energy source intrigues scientists to provide the solution by developing new technology. Polymer solar cell appears to be the most promising candidate for its low cost, flexibility, and massive producibility. Novel polymers have been constantly synthesized and investigated, while the use of PCBM as acceptor seems to be the universal choice. Here, we studied the use of four dierent fullerene derivatives - [60]PCBM, [70]PCBM, and their bisadduct analogues - as acceptor in APFO-3 solar cells. A series of investigations were performed to study how the processing parameters - blend ratio, spin speed, and choice of solvent - influence the device performance. Using bisadduct fullerenes results in an enhanced Voc, as predicted by the up-shift of energy levels, but a strongly reduced Jsc, hence a poor PCE. Photoluminescence study indicates that all APFO-3:fullerene devices are limited by the inefficient dissociation of fullerene excitations, while it becomes more influential when bisadduct fullerenes were used as acceptor. The best device in this study was fabricated by using [70]PCBM as acceptor and chlorobenzene as solvent, exhibits a PCE of 2.9%, for the strong absorption, ne morphology, and comparatively strong driving force.

In this thesis, the microstructure of organic photovoltaic APFO-3:PC61BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, Tg, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC61BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above Tg. The temperature stability of APFO-3:PC61BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.   The crystallization of PC61BM was also investigated. Above Tg, PC61BM crystallization was found to commence, albeit slowly at temperatures close to Tg. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC61BM thin films above Tg affected PC61BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.

Installed photovoltaic nameplate power have been growing rapidly around the worldin the last few years. But how much energy is returned to society (i.e. net energy) by this technology, and which factors contribute the most to the amount of energy returned? The objective of this thesis was to examine the importance of certain inputs and outputs along the solar panel production chain and their effect on the energy return on (energy) investment (EROI) for crystalline wafer-based photovoltaics. A process-chain model was built using publicly available life-cycle inventory (LCI) datasets. This model has been kept simple in order to ensure transparency. Univariate sensitivity analysis for processes and multivariate case studies was then applied to the model. The results show that photovoltaic EROI values are very sensitive to assumptions regarding location and efficiency. The ability of solar panels to deliver net energy in northern regions of the earth is questionable. Solar cell wafer thickness have a large impact on EROI, with thinner wafers requiring less silicon material. Finding an alternative route for production of solar-grade silicon is also found to be of great importance, as is introduction of kerf loss recycling. Equal system sizes have been found to yield an primary EROI between approximately 5.5-19 depending on location and assumptions. This indicates that a generalized absolute EROI for photovoltaics may be of little use for decision-makers. Using the net energy cliff concept in relation to primary EROI found in this thesis shows that primary EROI rarely decreases to less than the threshold of 8:1 in univariate cases. Crystalline photovoltaics under similar system boundaries as those in the thesis model does not necessarily constrain economic growth on an energetic basis.

The commercially available solar cells suffer from low conversion efficiency due to the thermalization and transmission losses arising from the mismatch between the band gap of the semiconductor materials and the solar spectrum. Advanced device architectures based on nanomaterial have been proposed and being successfully used to enhance the efficiency of the solar cells. Quantum dots (QDs) and nanowires (NWs) are the nanosclae structures that have been exploited for the development of the third generation solar cell devices and nanowire based solar cells, respectively. The optical and electrical properties of these materials can be tuned by their size and geometry; hence they have great potential for the production of highly efficient solar cell. Application of QDs and NWs with enhanced optoelectronic properties and development of low-cost fabrication processes render a new generation of economic highly efficient PV devices. The most significant contribution of this PhD study is the development of simple and cost effective methods for fabrication of nanowires and quantum dots for advanced solar cell architectures. In advanced silicon nanowires (SiNWs) array cell, SiNWs have been widely synthesised by the well-known vapor-liquid-solid method. Electron beam lithography and deep reactive ion etching have also been employed for fabrication of SiNWs. Due to the high price and complexity of these methods, simple and cost effective approaches are needed for the fabrication of SiNWs. In another approach, to enhance the cell efficiency, organic dyes and polymers have been widely used as luminescent centers and host mediums in the luminescent down shifting (LDS) layers. However, due to the narrow absorption band of the dyes and degradation of the polymers by moisture and heat, these materials are not promising candidates to use as LDS. Highly efficient luminescent materials and transparent host materials with stable mechanical properties are demanded for luminescent down shifting applications. In this project, simple fabrication processes were developed to produce SiNWs and QDs for application in advanced cell architectures. The SiNWs array were successfully fabricated, characterized and deployed in new cell architectures with radial p-n junction geometry. The luminescence down shifting of layers containing QDs in oxide and glass mediums was verified. The silica coated quantum dots which are suitable for luminescence down shifting, were also fabricated and characterized for deployment in new design architectures. Silicon nanowires were fabricated using two simplified methods. In the first approach, a maskless reactive ion etching process was developed to form upright ordered arrays of the SiNWs without relying on the complicated nano-scale lithography or masking methods. The fabricated structures were comprehensively characterized. Light trapping and photoluminescence properties of the medium were verified. In the second approach, combination of the nanosphere lithography and etching techniques were utilized for wire formation. This method provides a better control on the wire diameters and geometries in a very simple and cost effective way. The fabricated silicon nanowires were used for formation of the radial p-n junction array cells. The functionality of the new cell structures were confirmed through experimental and simulation results. Quantum dots are promising candidates as luminescent centers due to their tunable optical properties. Oxide/glass matrices are also preferred as the host medium for QDs because of their robust mechanical properties and their compatibility with standard silicon processing technology. Besides, the oxide layers are transparent mediums with good passivation and anti-reflection coating properties. They can also be used to encapsulate the cell. In this work, ordered arrays of QDs were incorporated in an oxide layer to form a luminescent down shifting layer. This design benefits from the enhanced absorption of a periodic QD structure in a transparent oxide. The down shifting properties of the layer after deployment on a crystalline silicon solar cell were examined. For this purpose, crystalline silicon solar cells were fabricated to use as test platform for down shifting. In order to examine the down-shifting effect, different approaches for formation of a luminescence down shifting layer were developed. The LDS layer consist of cadmium selenide- zinc sulfide (CdSe/ZnS) quantum dots in oxide and glass layers to act as luminescent centers and transparent host medium, respectively. The structural and optical properties of the fabricated layers were studied. The concept of spectral engineering was proved by the deployment of the layer on the solar cell. To further benefit from the LDS technique, quantum efficiency of the QDs and optical properties of the layer must be improved. Demand for the high quantum efficiency material with desired geometry leaded us to synthesis quantum dots coated with a layer of grown oxide. As the luminescence quantum efficiency of the QDs is correlated to the surface defects, one advantage of having oxide on the outer shell of the QDs, is to passivate the surface non-radiative recombination centers and produce QDs with high luminescent quantum yield. In addition, nanoparticles with desired size can be obtained only by changing the thickness of the oxide shell. This method also simplifies the fabrication of QD arrays for luminescence down shifting application, since it is easier to form ordered arrays from larger particles. QD superlattices in an oxide medium can be fabricated on a large area by a simple spin-coating or dip coating methods. The photonic crystal properties of the proposed structure can greatly increase the absorption in the QDs layer and enhance the effect of down shifting.

Cette thèse est consacrée au silicium polymorphe hydrogéné (pm-Si:H). Elle porte tout d'abord sur une étude du pm-Si :H puis sur une étude des cellules photovoltaïques fabriquées à partir de ce matériau. Le pm-Si:H est formé de couches minces nanostructurées et peut être déposé par PECVD conventionnelle. Les effets des différents paramètres de dépôt (mélanges gazeux, pression, puissance RF, température du substrat) sur les propriétés du matériau ont été étudiés pour optimiser sa qualité. La caractérisation des couches a été un enjeu primordial. Pour cela, nous avons choisi de combiner une palette très large de méthodes de caractérisation (ellipsomètrie spectroscopique, exodiffusion d'hydrogène, SIMS, FTIR, AFM, etc...). A cause de la contribution des nanoparticules de silicium dans le plasma, la nature du dépôt du pm-Si:H montre la différence contrairement au a-Si:H pour lequel le dépôt se fait par le biais de radicaux ionisés. L'étude des conditions du procédé nous a conduit à fabriquer des cellules solaires d'un rendement initial de 9.22 % avec un facteur de forme élevé (74.1), mais aussi de démontrer des effets de vieillissement inhabituels, tels que i) une dégradation initiale rapide, ii) une dégradation irréversible, et iii) de grands changements structuraux macroscopiques. Nous avons découvert que le principal problème se situe entre le substrat et la couche mince de silicium. L'hydrogène moléculaire diffuse et s'accumule à l'interface entre le substrat et la couche mince, ce qui introduit un délaminage local qui a pour conséquence une dégradation initiale rapide des performances des cellules. Nous avons trouvé que sous éclairement une structure PIN facilite l'accumulation d'hydrogène et le délaminage à l'interface entre le substrat et la couche dopée p. Cependant, l'utilisation d'une structure NIP empêche l'accumulation d'hydrogène et le délaminage. Cela nous a permis de fabriquer des cellules solaires pm-Si:H de structure NIP d'un rendement stable de 8.43 %, mais aussi de démontrer une degradation minimale (10 %) après un vieillissement de 500 heures.

Passivation of the crystalline silicon (c-Si) wafer surface and decreasing the number of interface defects are basic requirements for development of high efficiency a-Si:H/c-Si heterojunction solar cells. Surface passivation is generally achieved by development of detailed silicon wafer cleaning processes and the optimization of PECVD parameters for the deposition of intrinsic hydrogenated amorphous silicon layer. a-Si:H layers are grown in UHV-PECVD system. Solar cells were deposited on the p type Cz-silicon substrates in the structure of Al front contact/a-Si:H(n)/a-Si:H(i)/c-Si(p)/Al back contact. Solar cell parameters were determined under standard test conditions namely, using 1000 W/m2, AM 1.5G illumination at 25 oC. Growth of (i) a-Si:H, films on the clean wafer surface was investigated as a function of substrate temperature, RF power density, gas flow rate, hydrogen dilution ratio and deposition time and was characterized using SEM, HRTEM, AFM, SE, ATR-FTIR and I/V measurements. Structural properties of the films deposited on silicon wafer surface are directly effective on the solar cell efficiency. Morphological characterization of the grown films on the crystalline surface was found to be very complex depending on the deposition parameters and may even change during the deposition time. At 225 oC substrate temperature, at the beginning of the deposition, (i) a-Si:H films was found grown in epitaxial structure, followed by a simultaneous growth of crystalline and amorphous structure, and finally transforming to complete amorphous structure. Despite this complex structure, an efficiency of 9.2% for solar cells with total area of 72 cm2 was achieved. In this cell structure, TCO and back surface passivation do not exist. In the

Photovoltaic is a renewable energy technology that creates electricity by converting the energy of light. Photovoltaics are usually installed on buildings. In this pilot study, the viability of such an installation on the roof of the school Heby skola is examined with respect to produced electricity, economic potential and environmental impact. This is done with the software Solelekonomi, together with 11-years of solar irradiance data and measurements of the properties of the intended roof, which made it was possible to simulate the production patterns of a photovoltaic system. The simulations were made on two possible system sizes 50 m2 and 200 m2 with respectively 7.75 and 31 kWpeak installed power. Among other things, the results showed that 1.1% and 4.45% of the total electricity consumption could be replaced by the systems. A PV investment was found to be a good option with respect to the sections examined. Furthermore, considering PVinstallations, the school was found to be representative for schools in Sweden, and thus this essay can provide a basis for other PV pilot project on Swedish schools.

There are a number of factors that influence both the physical and the economical performance of a photovoltaic solar energy (PV) installation. The aim of this project was to develop a simulation and optimization model with which these factors could be analyzed and the PV installation optimized. By supplying the model with meteorological data, electricity consumption data and available building surfaces the model finds the optimum PV installation. The output consists of both physical and economical performance as well as information on how to distribute and install the PV modules on the available building surfaces. The model was validated using annual and hourly measurement data from Swedish PV installations. The validation shows that the model is a reliable tool for simulating the electricity generation from a PV system. In the second part of the project the model was used to evaluate the PV potential at two different hospitals and one health care center within the Uppsala County, Sweden. The model was also used to study the effect of different house orientations on the PV potential in Swedish neighborhoods. The physical and economical PV potentials are high for the hospitals and the health carecenter. This is mainly due to a high electricity demand but also due to a good match between the load profile and the PV electricity generation profile. The study on different neighborhoods shows that for gable roof buildings it might be more favorable to plan the houses so that the roofs face east-west rather than north-south. / Det är många faktorer som påverkar de fysikaliska och ekonomiska resultaten av en planerad solcellsinstallation. Syftet med det här projektet var att utveckla en simulerings- och optimeringsmodell med vars hjälp det skulle gå att analysera dessa frågor och hitta det bästa installationsalternativet i varje enskilt fall. Modellen som togs fram i detta projekt kan både studera ett givet installationsalternativ och räkna ut den mest optimala installationen utifrån de av användaren specificerade målen och begränsningarna. För att kunna göra detta behöver modellen förses med meteorologiska data för den aktuella platsen, elkonsumtionsdata från det aktuella objektet samt mått och orienteringar för de tillgängliga byggnadsytorna. Dessutom behöver användaren ange vissa ekonomiska parametrar såsom exempelvis avbetalningstid, ränta och aktuellt solcellspris. Resultatet från modellen består av både fysikaliska och ekonomiska resultat, exempelvis timvis nettoflöde av elektricitet, avbetalningstid och genomsnittligt elpris från solcellssystemet. I optimeringsresultatet redovisas hur solcellerna bör fördelas och installeras på de olika byggnadsytorna för att ge bäst resultat enligt målspecifikationen. För att validera modellen jämfördes dess simuleringsresultat med årliga och timvisa mätvärden från svenska solcellsanläggningar. Dessutom jämfördes modellens resultat med motsvarande resultat från andra simuleringsverktyg för solceller. Valideringsresultaten visar att modellen är ett pålitligt verktyg för att simulera elgenereringen från solcellsystem med olika moduler, växelriktare och installationssätt. Som ett delresultat vid modellutvecklingen simulerades ett stort antal olika solcellssystempå platta och svagt lutande tak. Utifrån dessa simuleringar utformades ett antal tumregler för hur uppvinklade moduler på platta eller svagt lutande tak skall monteras. Tumreglerna visar vilket avstånd mellan modulraderna och vilken vinkel på modulerna som ger den högsta taktäckningsgarden (största installationen) vid olika övre gränser för de interna skuggningsförlusterna. I projektets andra del användes modellen för att utvärdera solcellspotentialen på Akademiska sjukhuset, Enköpings lasarett och Tierps vårdcentral. Resultaten som levererades till Landstinget i Uppsala län visar att både den tekniska och den ekonomiska solcellspotentialen är stor på dessa enheter. Huvudanledning till den höga potentialen är att elbehovet är väldigt stort på dessa enheter samt att solcellernas elgenereringsprofil stämmer mycket väl överens med när elbehovet är som störst. Modellen användes även för att studera hur olika byggnadsorienteringar påverkar solcellspotentialen i olika tänkbara svenska bostadsområden. De olika resultaten från dessa studier visar att det i många fall är bättre att orientera byggnader med sadeltak så att taken pekar i östlig och västlig riktning snarare än mot syd och nord. Därmed föreslås en översyn avde nu rådande rekommendationerna att optimera huvudorienteringarna av taken mod syd vid detaljplanering av stadsdelar.