Degradation-induced changes in the structural and optical properties of the polyfluorene-based blue emitting films and LEDs are examined using spectroscopic (FTIR, UV−vis, photo- and electroluminescence), analytical (FTIR and ESCA), and scanning probe microscopy techniques. The materials studied are oligomers (DP ∼ 10) of 9,9-di-n-hexylfluorene and its random copolymer with anthracene. In situ FTIR monitoring is used to characterize chemical changes in the active layer of operating LED devices. Two primary mechanisms of degradation are identified. In the first, photooxidation of the polymer matrix leads to the formation of an aromatic ketone, most likely fluorenone at the chain terminating monomer units, which quenches the fluorescence. The second process promotes aggregate formation, which then leads to loss of luminous intensity by exciton transfer and relaxation through excimers.

We study how changes in sidebranching in electroluminescent polymers affect the performance of polyfluorene-based light-emitting diodes with and without additional hole transport materials. We observe that light emission and device efficiency are determined more by the position of the exciton recombination zone than by changes in the polymer morphology induced by sidebranching. Consequently, we find that sidebranching mainly controls the relative emission between vibrational energy levels and has a minimal effect on polymer charge transport properties. Light outputs of 10 000 cd/m 2 and device efficiencies of 0.85 and 1.8 cd/A are obtained for single-and double-layer devices, respectively.