Correlations between structure and optoelectronic properties of conjugated polymers

An understanding of the fundamental processes that govern the electro-optical properties of conjugated polymers is essential for the improvement of polymer light-emitting diodes (PLEDs). The majority of the work in this thesis comprises a study on a group of sterically congested poly(para-phenylenevinylene)s (PPVs). It deals initially with the discovery and development of a highly ordered crystalline phase of a chloro-derived n-butyl analogue. A thorough structural characterisation of this phase is then made from the results of X-ray Diffraction, FT-IR and Raman scattering spectroscopies. The effective conjugation length of the chains that comprise the crystalline sample is longer than that found in two relatively disordered films, one that was prepared by spin-coating and the other by drop-casting. The spin-coated film was found to exhibit a higher photoluminescence quantum efficiency (PLQE) value than the drop-cast film, which has been attributed to the presence of lower density of aggregate states in the former. The PLQE of the crystalline sample is considerably lower than that of both of the films and this is ascribed to the rapid migration of excitons to defect sites e.g. grain boundaries. PLE measurements for all the samples strongly suggest that singlet exciton quenching is intimately related to energy migration processes. Through the study of a novel, reversible, light-induced photoluminescence quenching effect, it was concluded that photogenerated polaronic species can be trapped sufficiently deeply that they can stabilise for periods in excess of hours at low temperatures. Furthermore, it is demonstrated that the photogenerated polaronic species are less stable in the crystalline sample, yet most stable in the most disordered spin-cast film. It is shown by excitation into the tail states of the crystalline sample that the first vibronic feature in the quasi-resonantly excited PL spectrum undergoes gain. This phenomenon is not observed in the more amorphous films. Finally, a detailed investigation of the effect of oxidation on the structural and optical properties of poly(9,9-diocylfluorene) (PFO) is presented. It is shown that the appearance of a broad-red-shifted emission feature in oxidised PFO films arises from interchain excimer radiation. It is proposed that the effect arises from an interchain triplet-triplet annihilation process associated with the formation of ketone moieties along the polymer backbone. (author)Available from British Library Document Supply Centre- DSC:DXN060439 / BLDSC - British Library Document Supply CentreSIGLEGBUnited Kingdo