Preserving a robust CsPbI(3) perovskite phase via pressure-directed octahedral tilt

通过压力导向的八面体倾斜来保持稳定的CsPbI₃钙钛矿相。

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Abstract

Functional CsPbI(3) perovskite phases are not stable at ambient conditions and spontaneously convert to a non-perovskite δ phase, limiting their applications as solar cell materials. We demonstrate the preservation of a black CsPbI(3) perovskite structure to room temperature by subjecting the δ phase to pressures of 0.1 - 0.6 GPa followed by heating and rapid cooling. Synchrotron X-ray diffraction and Raman spectroscopy indicate that this perovskite phase is consistent with orthorhombic γ-CsPbI(3). Once formed, γ-CsPbI(3) could be then retained after releasing pressure to ambient conditions and shows substantial stability at 35% relative humidity. First-principles density functional theory calculations indicate that compression directs the out-of-phase and in-phase tilt between the [PbI(6)](4-) octahedra which in turn tune the energy difference between δ- and γ-CsPbI(3), leading to the preservation of γ-CsPbI(3). Here, we present a high-pressure strategy for manipulating the (meta)stability of halide perovskites for the synthesis of desirable phases with enhanced materials functionality.

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