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This study improved quality of CH₃NH₃PbI₃ (MAPbI₃) perovskite films by delaying thermal annealing in the spin coating process and introducing KI and I₂ to prepare MAPbI₃ films that were low in defects for high-efficiency perovskite solar cells. The influences of delayed thermal annealing time after coating the MAPbI₃ perovskite layer on the crystallized perovskite, the morphology control of MAPbI₃ films, and the photoelectric conversion efficiency of solar cells were investigated. The optimal delayed thermal annealing time was found to be 60 min at room temperature. The effect of KI/I₂ additives on the growth of MAPbI₃ films and the corresponding optimal delayed thermal annealing time were further investigated. The addition of KI/I₂ can improve perovskite crystallinity, and the conductivity and carrier mobility of MAPbI₃ films. Under optimized conditions, the photoelectric conversion efficiency of MAPbI₃ perovskite solar cells can reach 19.36% under standard AM1.5G solar illumination of 100 mW/cm².