We report electroabsorption measurements of polymer light-emitting diodes, (LEDs), fabricated with poly(4-4-diphenylene diphenylvinylene), PDPV, as the emissive layer, Ca–Al cathodes, and indium tin oxide (ITO) anodes, with and without a doped conducting polymer hole injection/transport layer, namely poly(3,4-ethylene dioxythiophene), PEDOT, doped with poly(styrene sulfonate), PSS. In these structures, the bias at which the electroabsorption signal is null corresponds to the difference between the electrodes’ work functions. We find that such a built-in voltage increases by 0.5 V when a PEDOT:PSS film is incorporated between the ITO electrode and the emissive layer. This leads to a marked reduction of the anode barrier height at the hole-injecting interface, and accounts for a variety of improvements brought about by the PEDOT insertion, namely: (a) the increase of luminescence efficiency, (b) the reduction of the turn-on voltage, and (c) the increase of the device lifetime.

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