Effect of carbazole–oxadiazole excited-state complexes on the efficiency of dye-doped light-emitting diodes

Interactions between hole-transporting carbazole groups and electron-transporting 1,3,4-oxadiazole groups were studied by photoluminescence and electroluminescence (EL) spectroscopy, in blends of poly(N-vinylcarbazole) with 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PVK:PBD) and in random copolymers with carbazole and oxadiazole groups attached as side chains. Different excited-state complexes form in the blends, which exhibit exciplexes, and in the copolymers, which manifest electroplexes, due to topological constraints on the position of carbazole and oxadiazole units in the polymer. Both types of complex red-shift the EL spectra of the matrices compared with pure PVK homopolymer, although the shift is significantly greater for the electroplex. The presence of these complexes has a profound effect on the external quantum efficiency of dye-doped organic light-emitting diodes employing the blends or copolymers as matrices, as it strongly affects the efficiency of Förster energy transfer from the matrix to the dye. Single-layer devices doped with either coumarin 47 (C47), coumarin 6 (C6), or nile red (NR) were compared. Among the three dye-doped PVK:PBD devices, C6 doping yields the highest efficiency, while NR doping produced the most efficient copolymer devices, consistent with the degree of overlap between the EL spectrum of the matrix material and the absorption spectrum of the dye.