The β-phase,
in which the intermonomer torsion angle of a
fraction of chain segments approaches ∼180°, is an intriguing
conformational microstructure of the widely studied light-emitting
polymer poly(9,9-dioctylfluorene) (PFO). Its generation can in turn
be used to significantly improve the performance of PFO emission-layer-based
light-emitting diodes (LEDs). Here, we report the generation of β-phase
chain segments in a copolymer, 90F8:10BT, containing 90% 9,9-dioctylfluorene
(F8) and 10% 2,1,3-benzothiadiazole (BT) units and show that significant
improvements in performance also ensue for LEDs with β-phase
90F8:10BT emission layers, generalizing the earlier PFO results. The
β-phase was induced by both solvent vapor annealing and dipping
copolymer thin films into a solvent/nonsolvent mixture. Subsequent
absorption spectra show the characteristic fluorene β-phase
peak at ∼435 nm, but luminescence spectra (∼530 nm peak)
and quantum yields barely change, with the emission arising following
efficient energy transfer to the lowest-lying excited states localized
in the vicinity of the BT units. For ∼5% β-phase chain
segment fraction relative to 0% β-phase, the LED luminance at
10 V increased by ∼25% to 5940 cd m–2, the
maximum external quantum efficiency by ∼61 to 1.91%, and the
operational stability from 64% luminance retention after 20 h of operation
to 90%. Detailed studies addressing the underlying device physics
identify a reduced hole injection barrier, higher hole mobility, correspondingly
more balanced electron and hole charge transport, and decreased carrier
trapping as the dominant factors. These results confirm the effectiveness
of chain conformation control for fluorene-based homo- and copolymer
device optimization.