One of the major challenges in the field of organic semiconductors is to develop molecular design rules and processing routes which optimise the charge carrier mobility, whilst independently controlling the radiative and non-radiative processes. To date there has existed a seeming trade-off between charge carrier mobility and photoluminescence efficiency, which limits the development of some devices such as electrically pumped laser diodes. This thesis investigates fluorescence enhancement strategies for high-mobility polymer semiconductor systems and the mechanisms by which they currently display poor emission properties. Four independent approaches were taken and are detailed as follows.

1. Solubilising chain engineering

It is shown that for the high mobility polymer poly(indacenodithiophene-co-benzothiadiazole), the addition of a phenyl- initiated side chain can enhance the solid-state fluorescence quantum yield, exciton lifetime and exciton diffusion length significantly in comparison to that without phenyl-addition.

1. Energy transfer to a highly fluorescent chromophore

It is shown that for the high mobility polymer poly(indacenodithiophene-co-benzothiadiazole) efficient energy transfer to a more emissive squaraine dye molecule is possible despite fast non-radiative decay short exciton diffusion lengths. This results in a significant fluorescence enhancement, which in turn facilitates an order of magnitude increase of the efficiency of polymer light emitting diodes made from this material combination.

1. Energy gap engineering

The well known Energy Gap Law predicts an increase in the non-radiative rate as the optical bandgap of an organic chromophore decreases in energy. In combination with this, almost all polymer semiconductors reported to date with high charge carrier mobility have low optical bandgaps. Therefore, molecular design principles which act to increase the optical bandgap of polymer semiconductors whilst retaining a high mobility were sought out. One specific system was successfully identified and showed a significant fluorescence enhancement compared to is predecessor poly(indacenodithiophene-co-benzothiadiazole) in both the solution and the solid state. It is found that the Frenkel exciton lifetime in this new system is a factor of four larger which also results in a significantly increased exciton diffusion length. An inter-chain electronic state is also identified and discussed.

1. Hydrogen substitution

For some low-bandgap material systems such as erbium chromophores, high energy vibrational modes such as the C-H stretching mode can act as non-radiative pathways. The effect of hydrogen substitution with deuterium and fluorine was therefore investigated in a series of polythiophene derivative families. It was found that in the solid state, fluorescence and exciton lifetime enhancement occurred when the backbone hydrogen atoms were replaced with fluorine. However, evidence is given that this was not owing to the initial hypothesis, and is more likely owing to structural differences which occur in these substituted material systems.