Synthesis and properties of random and alternating fluorene/carbazole copolymers for use in blue light-emitting devices

Random and alternating fluorene/carbazole (F/Cz) copolymers with various carbazole contents (20-50 mol %) have been designed and synthesized for use as the hole-transporting as well as light-emitting layer in blue light-emitting diodes (LEDs). DSC analysis has indicated the complete suppression of the crystallizability of these polymers by the introduction of 3,6-carbazole linkages into the polymer backbone, which also results in changes in their optical properties. The absorption maximum has been blue-shifted with an increase in the carbazole content due to the interruption in the main chain conjugation. Meanwhile, the photoluminescent properties have been influenced by the sequence distribution of the fluorene segments as well as the carbazole content. The emission maxima and vibronic features of the alternating copolymers have changed with carbazole content, reflecting the differences in the electronic structures of the repeat units. However, in the case of the random copolymers, the emission spectra remain almost unchanged and are similar to poly(9,9-dioetylfluorene) (PF), despite the fact that the carbazole content increases up to 33 mol %. This feature has been attributed to the existence of longer fluorene segments in the random copolymers, which would be expected to have lower energy gaps, and thus effectively collect excitons from other parts of the polymer backbone. Consequently, the light emitted from these energy traps is similar to that from PF. Electrochemical studies indicate that the introduction of carbazole units effectively raises the HOMO energy levels, thereby facilitating hole injection. Controlling the carbazole content between 20 and 33 mol % results in copolymers with stable and reversible p-doping and n-doping processes. A test for a LED device from P(F3-alt-Cz) indicates that the F/Cz copolymers could be a good candidate for blue light-emitting and hole-transporting materials.