Superior ferroelectricity and nonlinear optical response in a hybrid germanium iodide hexagonal perovskite.

Ding, Kun; Ye, Haoshen; Su, Changyuan; Xiong, Yu-An; Du, Guowei; You, Yu-Meng; Zhang, Zhi-Xu; Dong, Shuai et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Abundant chemical diversity and structural tunability make organic-inorganic hybrid perovskites (OIHPs) a rich ore for ferroelectrics. However, compared with their inorganic counterparts such as BaTiO<sub>3</sub>, their ferroelectric key properties, including large spontaneous polarization (P<sub>s</sub>), low coercive field (E<sub>c</sub>), and strong second harmonic generation (SHG) response, have long been great challenges, which hinder their commercial applications. Here, a quasi-one-dimensional OIHP DMAGeI<sub>3</sub> (DMA = Dimethylamine) is reported, with notable ferroelectric attributes at room temperature: a large P<sub>s</sub> of 24.14 μC/cm<sup>2</sup> (on a par with BaTiO<sub>3</sub>), a low E<sub>c</sub> below 2.2 kV/cm, and the strongest SHG intensity in OIHP family (about 12 times of KH<sub>2</sub>PO<sub>4</sub> (KDP)). Revealed by the first-principles calculations, its large P<sub>s</sub> originates from the synergistic effects of the stereochemically active 4s<sup>2</sup> lone pair of Ge<sup>2+</sup> and the ordering of organic cations, and its low kinetic energy barrier of small DMA cations results in a low E<sub>c</sub>. Our work brings the comprehensive ferroelectric performances of OIHPs to a comparable level with commercial inorganic ferroelectric perovskites.