Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature. Two phase transformations below 2 GPa (from Pm3̅m to Im3̅, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively. The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.
A pyridinium-carboxylate compound undergoes reversible color change under pressure owing to the formation of radicals via electron transfer; dehydration and hydration can also trigger electron transfer.
Angle-dispersive synchrotron X-ray diffraction measurements were performed on vaterite-type YBO3/Eu3+, GdBO3, and EuBO3, respectively, up to 41 GPa at room temperature using a diamond-anvil cell. Pressure-induced amorphization was observed in hexagonal GdBO3 with a significant compression along the c-axis. Compared to the ions of the distorted GdBO3 phase, its anions may lose their long-range order prior to the cations at high pressures. Based on the experimental pressure-volume data, the obtained bulk moduli of YBO3/Eu3+ and GdBO3 are 329 and 321 GPa, respectively, which are more than 90% larger than that of EuBO3 (167 GPa) and are presumably attributed to Gd3+ and Y3+ with a high density of d valence electrons.
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