Visualizing the “Hidden” Triplet–Triplet Fusion Process to Fluorescence in Typical Organic/Polymer Light‐Emitting Diodes

Abstract Fluorescence emission of a typical poly(9,9‐dialkylfluorene) derivative (PF Green B)‐based polymer light‐emitting diodes (PLEDs) clearly demonstrates that it partially involves the contribution of triplet excitons by the triplet–triplet fusion (TTF) process through measuring the magneto‐electroluminescence (MEL) responses of devices at different bias conditions and temperatures. The TTF process to fluorescence intrinsically correlates with the concentration, lifetime, and polaron quenching of triplet excitons, as modulated by different bias regimes and conditions. Varying the cathode configurations of PLEDs by an additional exciton blocking layer and cathode buffer layers in PLEDs, such as a thin layer of bathocuproine, tetractylammonium bromide, or poly(ethylene glycol) dimethyl ether with metal cathodes, changes the carrier dynamics and regulates the magnitude of TTF process to fluorescence. The performance of the devices has increased due to the enhanced TTF process in fluorescence, as characterized by the measurement of MEL responses. The results in this work unveil the “hidden” component of fluorescence emission, which originates from the fusion of triplet excitons to singlet excitons in typical PLEDs. The results elucidate that TTF of triplet excitons to fluorescence emission can be a practicable mechanism that contributes to enhancing the performance of devices.