Electromodulation of photoluminescence in vacuum-evaporated films of bathocuproine

Highlights: ► We report on optical properties of thin films of bathocuproine (BCP). ► We apply electromodulation of photoluminescence (EML) spectroscopy. ► The green photoluminescence band is attributed to the formation of dimers. ► The EML quenching effect for dimers is due to exciton dissociation. ► The EML results are explained in terms of the Onsager theory. -- Abstract: Electric field-modulated photoluminescence (EML) was measured in vacuum-evaporated films of bathocuproine (BCP), electron-transporting material commonly used in organic light-emitting diodes (OLEDs). The external electric field of 106 V/cm strength decreases long-wavelength photoluminescence (PL) up to 10% but the same effect on short-wavelength PL is above one order of magnitude smaller. The distinctive difference between the EML characteristics for the short-wavelength (mono-molecular) and long-wavelength (associative species) emission of BCP films is a result of the different nature of relevant emissive states. Absorption, PL, EML and atomic force microscopy (AFM) measurements can be consistently explained assuming existence of dimer species in solid BCP with their population increasing during aging process of the films. Besides ground state absorption dimer states are assumed to be populated indirectly from molecular (Frenkel type) excitons diffusing to defected domains of the films where dissociate through an intermediate stage of geminate (e–h) pairs. The EML data are analyzed applying various models of (e–h) pair dissociation based on Poole–Frenkel, Braun, Onsager and Sano-Tachiya-Noolandi-Hong (STNH) theories. The Onsager theory explains satisfactorily the observed EML quenching effect for dimer-type PL. The Stark effect on fluorescence quantum yield should be possibly invoked to explain the EML characteristics of monomolecular emission of BCP.