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Phase Transitions of Formamidinium Lead Iodide Perovskite under Pressure

The pressure-induced structural evolution of formamidinium-based perovskite FAPbI3 was investigated using in situ synchrotron X-ray diffraction and laser-excited photoluminescence methods. Cubic α-FAPbI3 (Pm3̅m) partially and irreversibly transformed to hexagonal δ-FAPbI3 (P63 mc) at a pressure less...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2018-10, Vol.140 (42), p.13952-13957
Main Authors: Jiang, Shaojie, Luan, Yiliang, Jang, Joon I, Baikie, Tom, Huang, Xin, Li, Ruipeng, Saouma, Felix O, Wang, Zhongwu, White, Timothy J, Fang, Jiye
Format: Article
Language:English
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Summary:The pressure-induced structural evolution of formamidinium-based perovskite FAPbI3 was investigated using in situ synchrotron X-ray diffraction and laser-excited photoluminescence methods. Cubic α-FAPbI3 (Pm3̅m) partially and irreversibly transformed to hexagonal δ-FAPbI3 (P63 mc) at a pressure less than 0.1 GPa. Structural transitions of α-FAPbI3 followed the sequence of Pm3̅m → P4/mbm → Im3̅ → partial amorphous during compression to 6.59 GPa, whereas the δ-phase converted to an orthorhombic Cmc21 structure between 1.26 and 1.73 GPa. During decompression, FAPbI3 recovered the P63 mc structure of the δ-phase as a minor component (∼18 wt %) from 2.41–1.40 GPa and the Pm3̅m structure of the α-phase becomes dominant (∼82 wt %) at 0.10 GPa but with an increased fraction of δ-FAPbI3. The photoluminescence behaviors from both the α- and δ-forms were likely controlled by radiative recombination at the defect levels rather than band-edge emission during pressure cycling. FAPbI3 polymorphism is exquisitely sensitive to pressure. While modest pressures can engineer FAPbI3-based photovoltaic devices, irreversible δ-phase crystallization may be a limiting factor and should be taken into account.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b09316