This thesis deals with polymer light-emitting diodes (LEDs) containing materials from the polyfluorene family, and investigates their behaviour when employed in device structures.

A study of poly(9,9’-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylenediamine) (PFB) by photothermal deflection spectroscopy (PDS) shows that the polymer undergoes a doping reaction with poly(styrene sulphonic acid). This is important because the two materials are found in intimate contact in LED structures. The conditions for reaction are investigated, and it is proposed that the reacted states are directly responsible for the drive-induced degradation of LEDs containing these two materials.

LEDs are studied which contain various combinations of poly(9,9’-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) and poly(9,9’-dioctylfluorene-co-benzothiadiazole) (F8BT), using pulsed electroluminescence. A strongly morphology-dependent spike-transient is observed in the electroluminescence at turn-on, and this is investigated by numerical modelling. Although not all features of the system can be well represented in the model, the spike transient is explicitly predicted without the need to impose any special conditions. The origin of this feature is elucidated by repeatedly running the model to a range of end-points and studying the time-evolution of space-charge distributions which result.

Finally, F8BT devices are considered on their own, in order to study the evolution of device performance under low-intensity electrical excitation. A phenomenon is investigated in which the quantum efficiency is dramatically increased during the early stages of driving. Ionic motions are ruled out, and the observations are attributed to the trapping of charge in the vicinity of the anode, leading to enhanced hole injection. The reverse-bias behaviour of the effect, in which a further enhancement is seen, is also examined. The analogy is made with polymer LEDs in general which increase in performance following a period of reverse bias, and it is suggested that the causes may be related.