No description available.

Conjugated polymers are semiconducting materials that are currently being researched for numerous applications from chemical and biological sensors to electronic devices, including photovoltaics and transistors. Much of the novel research on conjugated polymers is performed in academic settings, where scientists are working to prepare conjugated polymers for commercially viable applications. By offering numerous advantages, inherent in macromolecular materials, conjugated polymers may hold the key to cheap and environmentally friendly manufacturing of future electronic devices. Mechanical flexibility, and solvent-based coating processes are two commonly cited advantages. Transitions in the backbone conformation of polythiophenes (PT) in organic solvents have been widely observed to influence thin-film morphology. However, conformational transitions of water-soluble PT derivatives, with respect to their intramolecular versus intermolecular origin, remain largely obscure. Here, conformational transitions of a water- soluble polythiophene in aqueous ionic surfactants are investigated by means of Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), ultraviolet-visible (UV-Vis) absorption and fluorescence spectroscopy, and various X-ray scattering techniques. As-prepared complexes exist as stable hydrogels. Upon dilution, a significant time-dependent chromism occurs spontaneously. A coil-to-rod conformational transition is identified in this mechanism and verified using small-angle x-ray scattering (SAXS). Study into the corresponding kinetics demonstrates an inverse first-order rate law. It is found that the conformational transition is thermally reversible and concentration-independent. The critical transition temperature is largely dependent on the surfactant formulation. A theoretical model is presented to explain this new phenomenon and the mechanisms behind its influence on the optoelectronic and solid-state morphological properties. A relationship between the dilute-solution processing with surfactants and the final properties of the system is substantiated.

All-polymer solar cells (APSC) are a class of organic solar cells in which hole and electron transporting phases are made of conjugated polymers. Unlike polymer/fullerene solar cell, photoactive material of APSC can be designed to have hole and electron transporting polymers with complementary absorption range and proper frontier energy level offset. However, the highest reported PCE of APSC is 5 times less than that of polymer/fullerene solar cell. The low PCE of APSC is mainly due to: i) low charge separation efficiency; and ii) lack of optimal morphology to facilitate charge transfer and transport; and iii) lack of control over the exciton and charge transport in each phase. My research work is focused towards addressing these issues. The charge separation efficiency of APSC can be enhanced by designing novel electron transporting polymers with: i) broad absorption range; ii) high electron mobility; and iii) high dielectric constant. In addition to with the above parameters chemical and electronic structure of the repeating unit of conjugated polymer also plays a role in charge separation efficiency. So far only three classes of electron transporting polymers, CN substituted PPV, 2,1,3-benzothiadiazole derived polymers and rylene diimide derived polymers, are used in APSC. Thus to enhance the charge separation efficiency new classes of electron transporting polymers with the above characteristics need to be synthesized. I have developed a new straightforward synthetic strategy to rapidly generate new classes of electron transporting polymers with different chemical and electronic structure, broad absorption range, and high electron mobility from readily available electron deficient monomers. In APSCs due to low entropy of mixing, polymers tend to micro-phase segregate rather than forming the more useful nano-phase segregation. Optimizing the polymer blend morphology to obtain nano-phase segregation is specific to the system under study, time consuming, and not trivial. Thus to avoid micro-phase segregation, nanoparticles of hole and electron transporters are synthesized and blended. But the PCE of nanoparticle blends are far less than those of polymer blends. This is mainly due to the: i) lack of optimal assembly of nanoparticles to facilitate charge transfer and transport processes; and ii) lack of control over the exciton and charge transport properties within the nanoparticles. Polymer packing within the nanoparticle controls the optoelectronic and charge transport properties of the nanoparticle. In this work I have shown that the solvent used to synthesize nanoparticles plays a crucial role in determining the assembly of polymer chains inside the nanoparticle there by affecting its exciton and charge transport processes. To obtain the optimal morphology for better charge transfer and transport, we have also synthesized nanoparticles of different radius with surfactants of opposite charge. We propose that depending on the radius and/or Coulombic interactions these nanoparticles can be assembled into mineral structure-types that are useful for photovoltaic devices.

No description available.

<p>The sun provides us daily with large quantities of energy in the form of light. With the world’s increasing demand of electrical energy the prospect of converting this solar light into electricity is highly tempting. In the strive towards mass-production and low cost solar cells, new types of solar cells are being developed, e.g. solar cells completely based on organic molecules and polymers. These materials offer a promising potential of low cost and large scale manufacturing and have the additional advantage that they can be produced on flexible and light weight substrate which opens for new and innovating application areas, e.g. integration with paper or textiles, or as building materials. In polymer solar cells a combination of two materials are used, an electron donor and an electron acceptor. The three dimensional distribution of the donor and acceptor in the active layer of the device, i.e. the morphology, is known to have larger influence of the solar cell performance. For the optimal morphology there is a trade-off between sometimes conflicting criteria for the various steps of the energy conversion process. The dissociation of photogenerated excitons takes place at an interface between the donor and acceptor materials. Therefore an efficient generation of charges requires a large interface between the two components. However, for charge transport and collection at the electrodes, continuous pathways for the charges to the electrodes are required.</p><p>In this thesis, results from morphology studies by atomic force microscopy (AFM) and dynamic secondary ion mass spectrometry (SIMS) of spin-coated blend and bilayer thin films of polyfluorene co-polymers, especially poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-5,5-(4´,7´-di-2-thienyl-2´,1´,3´-benzothiadiazole)] APFO-3, and the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are presented. It is shown that by varying the blend ratio, the spin.-coating solvent, and/or the substrate, different morphologies can be obtained, e.g. diffuse bilayer structures, spontaneously formed multilayer structures and homogeneous blends. The connection between these different morphologies and the performance of solar cells is also analysed. The results indicate that nano-scale engineering of the morphology in the active layer may be an important factor in the optimization of the performance of polymer solar cells.</p>

<p>In this thesis, regioregularpoly( 3-hexylthiophene) (rr-P3HT) polymer was used as a light absorption and electron donating material, while the C60 fullerene and its derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were used as electron acceptor materials. The effect of solvent to control the degree of mixing of the polymer and fullerene components, as well as the domain size and charge transport properties of the blends were investigated in detail using P3HT:C60 films. The photo-physical, structural and electrical transport properties of the polymer blends were carried out according to their ratios. A distinctive photoluminescence (PL) quenching effect was observed indicating a photo-induced electron transfer. In this thesis, the effect of solvents on the crystallization and interchain interaction of P3HT and C60 fullerene films were studied using XRD, UV-vis, PL, Raman and FTIR spectroscopy. The polymer blends formed with non-aromatic solvents exhibited an improved crystallinity and polymer morphology than that formed with aromatic solvents. An improved ordering was demonstrated in the polymer films spin coated from non-aromatic solvents. This indicates that the limited solubility of rr P3HT in a marginal solvent such as non-aromatic solvents can offer a strategy to obtain highly ordered crystal structures and lead directly to optimal morphologies on the films.</p>

The sun provides us daily with large quantities of energy in the form of light. With the world’s increasing demand of electrical energy the prospect of converting this solar light into electricity is highly tempting. In the strive towards mass-production and low cost solar cells, new types of solar cells are being developed, e.g. solar cells completely based on organic molecules and polymers. These materials offer a promising potential of low cost and large scale manufacturing and have the additional advantage that they can be produced on flexible and light weight substrate which opens for new and innovating application areas, e.g. integration with paper or textiles, or as building materials. In polymer solar cells a combination of two materials are used, an electron donor and an electron acceptor. The three dimensional distribution of the donor and acceptor in the active layer of the device, i.e. the morphology, is known to have larger influence of the solar cell performance. For the optimal morphology there is a trade-off between sometimes conflicting criteria for the various steps of the energy conversion process. The dissociation of photogenerated excitons takes place at an interface between the donor and acceptor materials. Therefore an efficient generation of charges requires a large interface between the two components. However, for charge transport and collection at the electrodes, continuous pathways for the charges to the electrodes are required. In this thesis, results from morphology studies by atomic force microscopy (AFM) and dynamic secondary ion mass spectrometry (SIMS) of spin-coated blend and bilayer thin films of polyfluorene co-polymers, especially poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-5,5-(4´,7´-di-2-thienyl-2´,1´,3´-benzothiadiazole)] APFO-3, and the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are presented. It is shown that by varying the blend ratio, the spin.-coating solvent, and/or the substrate, different morphologies can be obtained, e.g. diffuse bilayer structures, spontaneously formed multilayer structures and homogeneous blends. The connection between these different morphologies and the performance of solar cells is also analysed. The results indicate that nano-scale engineering of the morphology in the active layer may be an important factor in the optimization of the performance of polymer solar cells.

<p>In this thesis, regioregularpoly( 3-hexylthiophene) (rr-P3HT) polymer was used as a light absorption and electron donating material, while the C60 fullerene and its derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were used as electron acceptor materials. The effect of solvent to control the degree of mixing of the polymer and fullerene components, as well as the domain size and charge transport properties of the blends were investigated in detail using P3HT:C60 films. The photo-physical, structural and electrical transport properties of the polymer blends were carried out according to their ratios. A distinctive photoluminescence (PL) quenching effect was observed indicating a photo-induced electron transfer. In this thesis, the effect of solvents on the crystallization and interchain interaction of P3HT and C60 fullerene films were studied using XRD, UV-vis, PL, Raman and FTIR spectroscopy. The polymer blends formed with non-aromatic solvents exhibited an improved crystallinity and polymer morphology than that formed with aromatic solvents. An improved ordering was demonstrated in the polymer films spin coated from non-aromatic solvents. This indicates that the limited solubility of rr P3HT in a marginal solvent such as non-aromatic solvents can offer a strategy to obtain highly ordered crystal structures and lead directly to optimal morphologies on the films.</p>

Philosophiae Doctor - PhD / In this thesis, regioregularpoly( 3-hexylthiophene) (rr-P3HT) polymer was used as a light absorption and electron donating material, while the C60 fullerene and its derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were used as electron acceptor materials. The effect of solvent to control the degree of mixing of the polymer and fullerene components, as well as the domain size and charge transport properties of the blends were investigated in detail using P3HT:C60 films. The photo-physical, structural and electrical transport properties of the polymer blends were carried out according to their ratios. A distinctive photoluminescence (PL) quenching effect was observed indicating a photo-induced electron transfer. In this thesis, the effect of solvents on the crystallization and interchain interaction of P3HT and C60 fullerene films were studied using XRD, UV-vis, PL, Raman and FTIR spectroscopy. The polymer blends formed with non-aromatic solvents exhibited an improved crystallinity and polymer morphology than that formed with aromatic solvents. An improved ordering was demonstrated in the polymer films spin coated from non-aromatic solvents. This indicates that the limited solubility of rr P3HT in a marginal solvent such as non-aromatic solvents can offer a strategy to obtain highly ordered crystal structures and lead directly to optimal morphologies on the films. / South Africa

Les cellules solaires organiques (OSC) apparaissent comme une technologie prometteuse pour les énergies renouvelables en raison de leur poids léger, leur grande flexibilité et leur processus de fabrication peu coûteux. Jusqu'à présent, la plupart des OPV ont utilisé des dérivés de Fullerene, tels que PCBM ou PC71BM, en tant qu'accepteur d'électrons dans la couche active, qui s'est avéré être un goulet d'étranglement pour cette technologie. Par conséquent, le développement d'accepteurs non-fullerene est devenu la nouvelle force motrice de ce domaine. Les cellules solaires tout-polymères (tous-PSC) qui ont les avantages de la robustesse, de la stabilité et de l'accessibilité ont déjà atteint PCE jusqu'à 9%. Ainsi, le développement de nouveaux matériaux accepteurs est impératif pour améliorer les performances de tous les PSC. / Organic solar cells (OSCs) appear as a promising technology for renewable energy owing to their light weight, great flexibility and low-cost fabrication process. So far most of the OPV shave been using fullerene derivatives, such as PCBM or PC71BM, as the electron acceptor in the active layer, which have been proven to a bottleneck for this technology. Therefore,developing non-fullerene acceptors has become the new driving force for this field. All-polymer solar cells (all-PSCs) that have the advantages of robustness, stability and tunability have already achieved PCE up to 9%. Thus, developing novel acceptor materials is imperative for improving the performance of all-PSCs.