Diketopyrrolopyrrole derivatives for bulk heterojunction and dye sensitised solar cells

This thesis describes the synthesis and characterisation of a series of molecules for use in bulk heterojunction and dye sensitised solar cells. The target molecules were based on a central diketopyrrolopyrrole subunit. Molecules based on diketopyrrolopyrrole have a conjugated structure, allowing for π-π interaction. Diketopyrrolopyrrole molecules also have relatively low lying HOMO and LUMO levels and high absorption coefficients and exhibit efficient charge transport properties. Furthermore, their electron withdrawing properties have warranted their use as promising organic photovoltaic materials. A number of molecules were successfully synthesised and sent to collaborators for testing in organic photovoltaic devices and development of this series of molecules continues to be of interest within the research group.

The dehydrogenation reactions between LiH and organic amines for solid state hydrogen storage systems

Hydrogen is considered as an appealing alternative to fossil fuels in the pursuit of sustainable, secure and prosperous growth in the UK and abroad. However there exists a persisting bottleneck in the effective storage of hydrogen for mobile applications in order to facilitate a wide implementation of hydrogen fuel cells in the fossil fuel dependent transportation industry. To address this issue, new means of solid state chemical hydrogen storage are proposed in this thesis. This involves the coupling of LiH with three different organic amines: melamine, urea and dicyandiamide. In principle, thermodynamically favourable hydrogen release from these systems proceeds via the deprotonation of the protic N-H moieties by the hydridic metal hydride. Simultaneously hydrogen kinetics is expected to be enhanced over heavier hydrides by incorporating lithium ions in the proposed binary hydrogen storage systems. Whilst the concept has been successfully demonstrated by the results obtained in this work, it was observed that optimising the ball milling conditions is central in promoting hydrogen desorption in the proposed systems. The theoretical amount of 6.97 wt% by dry mass of hydrogen was released when heating a ball milled mixture of LiH and melamine (6:1 stoichiometry) to 320 °C. It was observed that ball milling introduces a disruption in the intermolecular hydrogen bonding network that exists in pristine melamine. This effect extends to a molecular level electron redistribution observed as a function of shifting IR bands. It was postulated that stable phases form during the first stages of dehydrogenation which contain the triazine skeleton. Dehydrogenation of this system yields a solid product Li2NCN, which has been rehydrogenated back to melamine via hydrolysis under weak acidic conditions. On the other hand, the LiH and urea system (4:1 stoichiometry) desorbed approximately 5.8 wt% of hydrogen, from the theoretical capacity of 8.78 wt% (dry mass), by 270 °C accompanied by undesirable ammonia and trace amount of water release. The thermal dehydrogenation proceeds via the formation of Li(HN(CO)NH2) at 104.5 °C; which then decomposes to LiOCN and unidentified phases containing C-N moieties by 230 °C. The final products are Li2NCN and Li2O (270 °C) with LiCN and Li2CO3 also detected under certain conditions. It was observed that ball milling can effectively supress ammonia formation. Furthermore results obtained from energetic ball milling experiments have indicated that the barrier to full dehydrogenation between LiH and urea is principally kinetic. Finally the dehydrogenation reaction between LiH and dicyandiamide system (4:1 stoichiometry) occurs through two distinct pathways dependent on the ball milling conditions. When ball milled at 450 RPM for 1 h, dehydrogenation proceeds alongside dicyandiamide condensation by 400 °C whilst at a slower milling speed of 400 RPM for 6h, decomposition occurs via a rapid gas desorption (H2 and NH3) at 85 °C accompanied by sample foaming. The reactant dicyandiamide can be generated by hydrolysis using the product Li2NCN.

Synthesis of novel organic semiconductors for optoelectronic devices

This thesis describes the synthesis and characterisation of novel conjugated organic materials with optoelectronic application. The first chapter provides an introduction about organic semiconductors and in particular about their working principle from a physical and chemical point of view. An overview of the most common types of solar cells is provided, including examples of some of the best performing materials. The second chapter describes the synthesis of a new library of flavin derivatives as potential active materials for optoelectronic applications. Flavins are natural redox-active molecules, which show potential application in optoelectronics, thanks to their stability and versatility. FPF-Flavins, for instance, could be used either as acceptor units in push-pull polyconjugated systems or as acceptor unit in dyes for DSSCs. In the same chapter a first attempt of synthesising bis-flavins to be used as N-type semiconductors in BHJ devices is described. The third chapter describes the successful synthesis and characterization of a series of conjugated organic molecules based on the benzothiadiazole moiety. Among these, three molecules containing ferrocene as donor unit were tested as sensitizers for DSSCs, reporting a PCE of 0.3% as the best result. Further studies indicated a significant problem of charge recombination which limits the performance. A near-infrared absorbing push-pull polymer, based on BbT as acceptor unit, was also synthesised and tested in BHJ devices as P-type semiconductor in blend with PC71BM, showing a VOC of 0.71 V. Finally, the last chapter describes the synthesis of several tetrathiafulvalene derivatives in order to explore this moiety as donor unit in dyes for DSSCs and as HTM for perovskite-based solar cells. In particular, two very simple dyes were synthesised and implemented in DSSCs reporting a PCE 0.2% and 0.4%, respectively. The low efficiency was associated to the tendency to aggregate at the solid state, with the absorption shifting from the visible to the infrared range. A conjugated molecule, containing a DPP core, was also synthesised and tested as HTM for perovskite solar cells. The best reported PCE of 7.7% was obtained without any additives. A case study about dehalogenation and “halogen dance” in TTF iodide is also presented.