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The aim of this work was to develop new, organic dyes, capable of harvesting photons in the red to near-IR region of the spectrum. A series of squaraine and tricarbocyanine dyes were produced and characterised and their optical and redox properties studied. The results of initial photovoltaic tests, followed by optimisations of cell performance, have also been presented. These clearly demonstrate the effectiveness of these dyes in solar cells. A total of 12 new squaraine dyes were successfully synthesised, seven of which were tested in "dye-sensitised" solar cells. The efficiencies ranged from 1.2%-3.7%, for the best dye [B1]. It was concluded that enhanced performance could be achieved in the presence of chenodeoxycholic acid (CDCA) and tetrabutylpyridine (TBP). These additives both help to prevent aggregation and increase the cell potential, limiting charge collection losses and enhancing performance. Three new tricarbocyanine dyes were also synthesised, two of which were used in solar cells. Unfortunately, due to the interaction of [B12] with the electrolyte, the dye proved to be unstable, as both the absorption maxima in UV-vis and fluorescence emission wavelengths were shifted to higher energies. Thus, the red response of the dye was significantly reduced and photovoltaic performance hindered. A limited photo-response of [B14] was also seen, although this dye appeared to be very stable in the presence of the electrolyte. To deduce the possible reasons for the poor performance of these dyes, their optical and electrochemical properties were investigated. Thus, cyclic voltametry was employed to identify the redox potentials of the dyes and their charge injection and recombination dynamics were studied through nanosecond time-resolved transient laser spectroscopy. It was concluded that the dyes theoretically possess the ideal characteristics for solar cell function and that the problem of [B14] lay in the purity of the dye. [B14] proved to be very difficult to purify as the dye was unstable in solution and decomposed on the columns employed in chromatography. Fortunately the dye appeared to be stable in the presence of an electrolyte when adsorbed on TiO2. The dye gave an IPCE of 12% between 800 – 900nm, which is particularly impressive, especially if the purity of the dye is considered. A new method of purification must be found however, if photovoltaic performance is to be enhanced. Finally, the effects of a compact blocking layer on device performance were studied. It was clearly demonstrated that a compact layer was essential. This was investigated and a relationship between the structure of the dye and the necessity of the blocking layer was established.
Urs Aeberhard, Beat Ruhstaller