Atomic reconfiguration among tri-state transition at ferroelectric/antiferroelectric phase boundaries in Pb(Zr,Ti)O3

Zhengqian Fu; Xuefeng Chen; Henchang Nie; Yanyu Liu; Jiawang Hong; Tengfei Hu; Ziyi Yu; Zhenqin Li; Linlin Zhang; Heliang Yao; Yuanhua Xia; Zhipeng Gao; Zheyi An; Nan Zhang; Fei Cao; Henghui Cai; Chaobin Zeng; Genshui Wang; Xianlin Dong; Fangfang Xu

doi:10.1038/s41467-022-29079-w

Atomic reconfiguration among tri-state transition at ferroelectric/antiferroelectric phase boundaries in Pb(Zr,Ti)O₃

Nat Commun. 2022 Mar 16;13(1):1390. doi: 10.1038/s41467-022-29079-w.

Authors

Zhengqian Fu^#¹, Xuefeng Chen^#¹, Henchang Nie^#¹, Yanyu Liu^#², Jiawang Hong³, Tengfei Hu¹, Ziyi Yu¹, Zhenqin Li¹, Linlin Zhang¹, Heliang Yao¹, Yuanhua Xia⁴, Zhipeng Gao⁵, Zheyi An⁶, Nan Zhang⁷, Fei Cao¹, Henghui Cai^{1

8}, Chaobin Zeng⁹, Genshui Wang^{10

11}, Xianlin Dong^{12

13

14}, Fangfang Xu^{15

16

17}

Affiliations

¹ State Key Laboratory of High Performance Ceramics and Superfine Microstructures & Key Lab of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China.
² School of Aerospace Engineering, Beijing Institute of Technology, Beijing, China.
³ School of Aerospace Engineering, Beijing Institute of Technology, Beijing, China. hongjw@bit.edu.cn.
⁴ Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, China.
⁵ Institute of Fluid Physics, China Academy of Engineering Physics, Mianyang, China.
⁶ Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education and International Center for Dielectric Research, School of Electronic and Information Engineering, Xi'an Jiaotong University, Xi'an, China.
⁷ Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education and International Center for Dielectric Research, School of Electronic and Information Engineering, Xi'an Jiaotong University, Xi'an, China. nzhang1@xjtu.edu.cn.
⁸ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, China.
⁹ Hitachi High-Tech (Shanghai) Co., Ltd., Shanghai, China.
¹⁰ State Key Laboratory of High Performance Ceramics and Superfine Microstructures & Key Lab of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China. genshuiwang@mail.sic.ac.cn.
¹¹ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, China. genshuiwang@mail.sic.ac.cn.
¹² State Key Laboratory of High Performance Ceramics and Superfine Microstructures & Key Lab of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China. xldong@mail.sic.ac.cn.
¹³ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, China. xldong@mail.sic.ac.cn.
¹⁴ School of Physical Science and Technology, ShanghaiTech University, Shanghai, China. xldong@mail.sic.ac.cn.
¹⁵ State Key Laboratory of High Performance Ceramics and Superfine Microstructures & Key Lab of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China. ffxu@mail.sic.ac.cn.
¹⁶ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, China. ffxu@mail.sic.ac.cn.
¹⁷ School of Physical Science and Technology, ShanghaiTech University, Shanghai, China. ffxu@mail.sic.ac.cn.

^# Contributed equally.

Abstract

Phase boundary provides a fertile ground for exploring emergent phenomena and understanding order parameters couplings in condensed-matter physics. In Pb(Zr_1-xTi_x)O₃, there are two types of composition-dependent phase boundary with both technological and scientific importance, i.e. morphotropic phase boundary (MPB) separating polar regimes into different symmetry and ferroelectric/antiferroelectric (FE/AFE) phase boundary dividing polar and antipolar dipole configurations. In contrast with extensive studies on MPB, FE/AFE phase boundary is far less explored. Here, we apply atomic-scale imaging and Rietveld refinement to directly demonstrate the intermediate phase at FE/AFE phase boundary exhibits a rare multipolar Pb-cations ordering, i.e. coexistence of antipolar or polar displacement, which manifests itself in both periodically gradient lattice spacing and anomalous initial hysteresis loop. In-situ electron/neutron diffraction reveals that the same parent intermediate phase can transform into either FE or AFE state depending on suppression of antipolar or polar displacement, coupling with the evolution of long-/short-range oxygen octahedra tilts. First-principle calculations further show that the transition between AFE and FE phase can occur in a low-energy pathway via the intermediate phase. These findings enrich the structural understanding of FE/AFE phase boundary in perovskite oxides.

Grants and funding

52002388, 51872312/National Natural Science Foundation of China (National Science Foundation of China)