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

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${}_3$, their ferroelectric key properties, including large spontaneous polarization ($P_s$), low coercive field ($E_c$), and strong second harmonic generation (SHG) response, have long been great challenges, which hinder their commercial applications. Here, a quasi-one-dimensional OIHP DMAGeI${}_3$ (DMA=Dimethylamine) is reported, with notable ferroelectric attributes at room temperature: a large $P_s$ of 24.14 $\hat{I}¼$C/cm${}^2$ (on a par with BaTiO${}_3$), a low $E_c$ below 2.2 kV/cm, and the strongest SHG intensity in OIHP family (about 12 times of KH${}_2$PO${}_4$ (KDP)). Revealed by the first-principles calculations, its large $P_s$ originates from the synergistic effects of the stereochemically active $4s^2$ lone pair of Ge${}^{2+}$ and the ordering of organic cations, and its low kinetic energy barrier of small DMA cations results in a low $E_c$. Our work brings the comprehensive ferroelectric performances of OIHPs to a comparable level with commercial inorganic ferroelectric perovskites.