Effect of meta-linkages on the photoluminescence and electroluminescence properties of light-emitting polyfluorene alternating copolymers

Alternating copolymers poly[9,9-dihexylfluorene-alt-(1,3-phenylene)(x)(1,4- phenylene) (1-x)] (x = 0, 0.05, 0.1, 0.25, 0.5, 0.75, 1.0) were prepared, and the absorption spectra showed the expected hypsochromic shift with increasing meta linkages. In the solution photoluminescence (PL) emission spectra, all but the all-meta polymer (x = 1) showed a spectrum similar to the all-para polymer, indicating rapid intrachain energy transfer to para-linked segments. Similar spectra were observed from thin films in which inter-chain energy transfer is also available. Annealing of the thin films in air above the T-g of the polymer for several hours led to an increase in long wavelength emission, but the increase was smaller for the polymers containing more meta linkages. IR experiments confirmed the formation of fluorenone defects during the annealing process. For those polymers with high meta-linkage incorporation (i.e. 75% and 100% meta) the long wavelength emission is suppressed. This suggests that when the conjugation length of the polymer is reduced then energy transfer to fluorenone defects is less likely, due to lower exciton delocalisation and mobility. The long wavelength emission was more prominent in the electroluminescence (EL) spectra of devices prepared from the polymer, and, while initially less intense in the high meta linkages polymers, became dominant even for the all-meta linked polymer after a few minutes of operation. In summary, the meta linkages had a beneficial effect in suppressing the undesirable long wavelength emission in both the PL and EL output.