A combinatory ferroelectric compound bridging simple ABO<sub>3</sub> and A-site-ordered quadruple perovskite.

Zhao, Jianfa; Gao, Jiacheng; Li, Wenmin; Qian, Yuting; Shen, Xudong; Wang, Xiao; Shen, Xi; Hu, Zhiwei et al. · Nat Commun · 2021

basic_science · Level V

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Abstract

The simple ABO<sub>3</sub> and A-site-ordered AA'<sub>3</sub>B<sub>4</sub>O<sub>12</sub> perovskites represent two types of classical perovskite functional materials. There are well-known simple perovskites with ferroelectric properties, while there is still no report of ferroelectricity due to symmetry breaking transition in A-site-ordered quadruple perovskites. Here we report the high pressure synthesis of an A-site-ordered perovskite PbHg<sub>3</sub>Ti<sub>4</sub>O<sub>12</sub>, the only known quadruple perovskite that transforms from high-temperature centrosymmetric paraelectric phase to low-temperature non-centrosymmetric ferroelectric phase. The coordination chemistry of Hg<sup>2+</sup> is changed from square planar as in typical A-site-ordered quadruple perovskite to a rare stereo type with 8 ligands in PbHg<sub>3</sub>Ti<sub>4</sub>O<sub>12</sub>. Thus PbHg<sub>3</sub>Ti<sub>4</sub>O<sub>12</sub> appears to be a combinatory link from simple ABO<sub>3</sub> perovskites to A-site-ordered AA'<sub>3</sub>Ti<sub>4</sub>O<sub>12</sub> perovskites, sharing both displacive ferroelectricity with former and structure coordination with latter. This is the only example so far showing ferroelectricity due to symmetry breaking phase transition in AA'<sub>3</sub>B<sub>4</sub>O<sub>12</sub>-type A-site-ordered perovskites, and opens a direction to search for ferroelectric materials.