Secondary Exciplex by Electromer Mediated Charge Transfer for Multiband Electroluminescence

Charge-transfer states have been observed extensively in heterojunctions of organic semiconductors, which are also referred to as exciplexes in polymer blends. Such mechanisms have been well understood in the conventional material systems. However, electromer states may be produced only in some polymeric molecules with folded chains. We report here the interaction between exciplex and electromer states, which facilitates the formation of a new electrically excited state that we define as a secondary exciplex. This is an indirect process understood as an electromer-mediated heterojunction. We discovered such an optoelectronic mechanism in the blend film of poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-pheny-l,4-phenylene-diamine) (PFB) and poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT). Four emission bands can be resolved from the electroluminescence spectrum, including those based on the excitons, the electromers, and the primary and secondary exciplexes. The whole electroluminescence spectrum thus extends from the green (500 nm) to the near-infrared (900 nm) with a full bandwidth of 400 nm. These new discoveries with the conventional light-emitting polymers are important not only for polymeric optoelectronics, but also for the development of broadband light-emitting devices.