One of the key challenges in developing efficient organic light-emitting diodes (OLEDs) is overcoming the loss channel of triplet excitons. A common approach to mitigate these losses to enhance the external quantum efficiency of OLEDs is employing emitter molecules optimized for thermally activated delayed fluorescence (TADF) or triplet-triplet annihilation (TTA). However, achieving both in the solid state from the same organic chromophore poses a formidable challenge due to energetic and structural requirements needing to be met simultaneously. Here, we demonstrate TADF and TTA in donor-acceptor phthalimide derivatives by employing triphenylamine (TPA) or phenyl carbazole (PhCz) as a donor. Thin films of the TPA-substituted phthalimides doped in the poly(methyl methacrylate) matrix exhibit TADF emission from the singlet charge-transfer (CT) state. On the contrary, PhCz-substituted emitters display dominant TTA-induced delayed fluorescence in the neat film due to long-range molecular ordering that facilitates efficient triplet diffusion. The present study provides insight into how dual TADF-TTA delayed fluorescence can be realized in thin films of molecular semiconductors via rational molecular design.
