Herein, a deep blue emitter (PI-TPB-CN) with a synergistic effect of hybridized local and charge transfer excited state (HLCT) and aggregation-induced emission (AIE) properties is successfully designed and synthesized to improve the performance of deep blue organic light-emitting diodes (OLEDs). It is constructed using a 1,2,4,5-tetraphenylbenzene (TPB) as an π-conjugated AIE core being asymmetrically functionalized with a phenanthro[9,10-d]imidazole (PI) as a weak donor (D) and a benzonitrile (CN) as an acceptor (A), thereby formulating D-π-A type fluorophore. Its HLCT and AIE properties verified by theoretical calculations, solvatochromic effects, and transient photoluminescence decay experiments, bring about a strong blue emission (452 nm) with a high photoluminescence quantum yield of 74 % in the thin film. PI-TPB-CN is successfully employed as a blue emitter in OLEDs. Non-doped OLED with the structure of ITO/HAT-CN (6 nm)/NPB (30 nm)/TCTA (10 nm)/PI-TPB-CN (30 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm) demonstrates excellent electroluminescence (EL) performance with blue emission (451 nm) and maximum external quantum efficiency (EQEmax) of 7.38 %. The device with a thinner layer of PI-TPB-CN (20 nm) and TPBi (30 nm) exhibits a deeper blue emission (444 nm) with CIE coordinates of (0.156, 0.096), a low turn-on voltage of 3.0 V, and EQEmax of 6.45 %.
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