Octahedral Distortion and Displacement-Type Ferroelectricity with Switchable 
Photovoltaic Effect in a 3d3 -Electron Perovskite System

Zhou, B. W.; Zhang, J.; Ye, X. B.; Liu, G. X.; Xu, X.; Wang, J.; Liu, Z. H.; Zhou, L.; Liao, Z. Y.; Yao, H. B.; Xu, S.; Shi, J. J.; Shen, X.; Yu, X. H.; Hu, Z. W.; Lin, H. J.; Chen, C. T.; Qiu, X. G.; Dong, C.; Zhang, J. X.; Yu, R. C.; Yu, P.; Jin, K. J.; Meng, Q. B.; Long, Y. W.

doi:10.1103/PhysRevLett.130.146101

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Octahedral Distortion and Displacement-Type Ferroelectricity with Switchable Photovoltaic Effect in a 3d³ -Electron Perovskite System

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Hu, Z. W.
Zhiwei Hu, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Zhou, B. W., Zhang, J., Ye, X. B., Liu, G. X., Xu, X., Wang, J., et al. (2023). Octahedral Distortion and Displacement-Type Ferroelectricity with Switchable Photovoltaic Effect in a 3d³ -Electron Perovskite System. Physical Review Letters, 130(14): 146101, pp. 1-6. doi:10.1103/PhysRevLett.130.146101.

Cite as: https://hdl.handle.net/21.11116/0000-000D-0261-3

Abstract

Because of the half-filled t2g-electron configuration, the BO6 octahedral distortion in a 3d3 perovskite system is usually very limited. In this Letter, a perovskitelike oxide Hg0.75Pb0.25MnO3 (HPMO) with a 3d3 Mn4+ state was synthesized by using high pressure and high temperature methods. This compound exhibits an unusually large octahedral distortion enhanced by approximately 2 orders of magnitude compared with that observed in other 3d3 perovskite systems like RCr3+O3 (R=rare earth). Essentially different from centrosymmetric HgMnO3 and PbMnO3, the A-site doped HPMO presents a polar crystal structure with the space group Ama2 and a substantial spontaneous electric polarization (26.5 μC/cm2 in theory) arising from the off-center displacements of A- and B-site ions. More interestingly, a prominent net photocurrent and switchable photovoltaic effect with a sustainable photoresponse were observed in the current polycrystalline HPMO. This Letter provides an exceptional d3 material system which shows unusually large octahedral distortion and displacement-type ferroelectricity violating the "d0-ness"rule. © 2023 American Physical Society.