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A study of electric field dependent spectra and the quantum electroluminescence yield of single-layer (SL) and double-layer (DL) light-emitting diodes (LEDs) based on a combination of an aromatic diamine (TPD) and an oxadiazole derivative (PBD) was carried out. It was shown that a high electric field weakens the recombination of Coulombically correlated electron-hole pairs in the bulk (SL LEDs) and enhances the process at the TPD-doped polymer/PBD interface (DL LEDs). The effects are discussed in terms of electric field mediated interplay between populations of localized (monomolecular) excitons, exciplexes and electroplexes in conjuction with their local environments.