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The effect of voltage on Alq3 crystal growth in [C12mim][TFSI] was investigated. Theadditional voltage was applied through 1.0, 3.0, 5.0, 6.0, 8.0, 10.0 V. Cast iron and ITO were usedas two electrodes. Microstructure analysis revealed the rod shape of Alq3. When the appliedvoltage increases, the population of rod shape phases increases. The XRD analysis showed thatthe initial phase transited to and finally phases. The conventional growth methods of thevapor phase and the solution method need a high temperature of over 300 ℃, while the study’snew approaches can lower the heat-treatment temperature to 100 ℃. The phase transition waspromoted faster when the applied voltage increased from 0 to 10.0 V. The additional voltage isthought to play a vital role in promoting the phase transition due to lowering the activationenergy of nucleation. The phase and shape of OLED materials affect the performance of theOLED device. One can obtain various shapes and phases of Alq3 at a low temperature of 100 ℃,which is a promising technique for OLED material manufacturing. The results also suggest a newacademic point of view to understand the nucleation behavior of OLED materials with artificiallyapplied charges.