Dielectric phase transition of an A2BX4-type perovskite with a pentahedral to octahedral transformation.


School of Chemical Engineering and Technology, Tianjin University, Yaguan Road 135, Tianjin 300350, China. [Email]


Organic-inorganic hybrid compounds that undergo reversible dielectric phase transitions are a very attractive class of smart materials due to their wide applications in data storage, data communication and signal sensing. Here, a piperidine ring, C5H11N, was introduced into the inorganic lead halide perovskite scaffold to obtain three hybrid perovskite compounds, [C5H12N]2PbCl4 (1), [C5H12N]2PbBr4 (2), and [C5H12N]PbI3 (3). When compound 2 and compound 3 feature static two-dimensional (2D) and one-dimensional (1D) perovskite structures, respectively, it is striking that compound 1 shows a reversible pentahedral to octahedral transformation. It undergoes an above-room-temperature dielectric phase transition at Tc≅ 352 K, wherein the high dielectric constant is more than twice the low dielectric constant. Structural analysis shows that 1 undergoes a phase transition from the space group Pnma at the low temperature phase (LTP) to C2/c at the high temperature phase (HTP). The phase transition originates from the order-disorder conversion of piperidinium cations. It is interesting to note that, the Pb2+ cations in the inorganic moieties change from five-coordinate at the LTP to six-coordinate at the HTP. The discovery of dielectric phase transition hybrid organic-inorganic lead halide perovskite materials further enhances the potential applications of high temperature responsive dielectric switchable materials.

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