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Entropy-Suppressed Ferroelectricity in Hybrid Lead-Iodide Perovskites

机译:混合碘化钙钛矿中的熵抑制铁电

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摘要

The actual nature of the electric polarization in hybrid lead-iodide perovskites is unveiled on the basis of ab initio and model results. A finite, albeit small electric polarization of few mu C/cm(2) is found to be pervasive in this system, due to the polar-uncompensated alignment of methylammonium dimers, at least for temperature lower than the activation energy of dimer rotations; however, the presence of a large number of structural local minima corresponding to differently oriented polarization directions counteracts the stabilization of an ordered ferroelectric phase at the macroscale. According to our estimate, only for temperatures lower than 40-50 K a clear ferroelectric behavior is displayed. At higher temperature the polarization is progressively suppressed and the ferroelectric ordering hindered by the large configurational entropy, giving rise to a superparaelectric-like behavior at the macroscale.
机译:根据从头算和模型结果揭示了杂化碘化铅钙钛矿中电极化的实际性质。由于甲基铵二聚体的极性无补偿排列,至少在低于温度低于二聚体旋转活化能的情况下,该系统中普遍存在几μC / cm(2)的有限电极化,尽管这种现象普遍存在。然而,对应于不同取向的极化方向的大量结构局部最小值的存在抵消了宏观上有序铁电相的稳定。根据我们的估计,仅当温度低于40-50 K时,才会显示清晰的铁电行为。在较高的温度下,极化被逐步抑制,铁电有序性因较大的构型熵而受阻,从而在宏观上产生类超顺电行为。

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