<p>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.</p>

<p>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, T_g, 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 T_g. 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.</p><p> </p><p>The crystallization of PC₆₁BM was also investigated. Above T_g, PC₆₁BM crystallization was found to commence, albeit slowly at temperatures close to T_g. 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 T_g affected PC₆₁BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.</p>

<p>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. </p><p>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.</p><p>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.</p><p>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.</p><p>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.</p>

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.

Dye-sensitized solar cells (DSCs) have attained considerable attention during the last decade because of the potential of becoming a low cost alternative to silicon based solar cells. Although efficiencies exceeding 10% in full sunlight have been presented, major improvements of the system are however limited. Electron transport is one of the processes in the cell and is of major importance for the overall performance. It is further a complex process because the transport medium is a mesoporous film and the pores are completely filled by an electrolyte with high ionic strength, resulting in electron-ion interactions. Therefore, present models describing electron transport include simplifications, which limit the practical use, in terms of improving the DSC, because the included model parameters usually have an effective nature. This thesis focuses in particular on the influence of the mesoporous film on electron transport and also on the influence of electron-ion interactions. In order to model diffusion, which is assumed to be the transport process for electrons in the DSC, Brownian motion simulations were performed and spatial restrictions, representing the influence of the mesoporous film, were introduced by using representative models for the structure. The simulations revealed that the diffusion coefficient is approximately half the value for electrons and ions in mesoporous systems. To study the influence of ions, a simulation model was constructed in where electric fields were calculated with respect to the net charge densities, resulting from the different charge carrier distributions. The simulations showed that electron transport is highly dependent on the nature of the ions, supporting an ambipolar diffusion transport model. Experimentally, it was found that the transport process is dependent on the wavelength of the incident light; we found that the extracted current was composed of two components for green light illumination, one fast and one slow. The slow component showed similar trends as the normal current. Also we found that the transport coefficient scaled linearly with film thickness for a fixed current, which questions diffusion as transport process. Other experiments, investigating various effects in the DSC, such as the effect of different cations in the electrolyte, are also presented. / QC 20100708

During the last decade, the dye sensitised solar cell (DSC) has attracted much attention. The technology has a potential to act as a new generation of photovoltaic device, it has also increased our knowledge within the field of photoelectrochemistry. The materials used in the DSC have been used in other technologies, such as electrochromic displays. This thesis examines how such systems can be analysed to understand their properties from their components. Both of the considered device technologies consist of a thin mesoporous semiconductor film immersed in an electrolyte. The study starts by investigating some of the fundamental properties of the mesoporous semiconductor and its interface with the electrolyte. This gives rise to the charge-voltage relationship for the devices, which is related to the chemical capacitance and electronic energy levels for the materials. In particular,special attention is given to the DSC and the properties of the charge carriers in the semiconductor. For the DSC, several techniques have been developed in order to understand the processes of transport and recombination for the charge carriers in the semiconductor film, which are vitally important for performance. In this thesis, particular focus is given to light modulation techniques and electrical analysis with impedance spectroscopy. The transportproperties show for both techniques a nonlinear behaviour, which is explained with the trapping model. The DSC solar cell is analysed in order to interpret the transport measurements for film thickness optimisation. DSC cells with new semiconductor materials, such as ZnO, were analysed with impedance measurements to provide new insights into the optimisation of the performance of the photoelectrochemical solar cell technology. / QC 20100804

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.