Above-Room-Temperature Ferroelectricity and Giant Second Harmonic Generation in 1D vdW NbOI₃.

Abstract

The realization of spontaneous ferroelectricity down to the one-dimensional (1D) limit is both fundamentally intriguing and practically appealing for high-density ferroelectric and nonlinear photonics. However, the 1D vdW ferroelectric materials are not discovered experimentally yet. Here, the first 1D vdW ferroelectric compound NbOI₃ with a high Curie temperature T_C > 450 K and giant second harmonic generation (SHG) is reported. The 1D crystalline chain structure of the NbOI₃ is revealed by cryo-electron microscopy, whereas the 1D ferroelectric order originated from the Nb displacement along the Nb-O chain (b-axis) is confirmed via obvious electrical and ferroelectric hysteresis loops. Impressively, NbOI₃ exhibits a giant SHG susceptibility up to 1572 pm V^-1 at a fundamental wavelength of 810 nm, and a further enhanced SHG susceptibility of 5582 pm V^-1 under the applied hydrostatic pressure of 2.06 GPa. Combing in situ pressure-dependent X-ray diffraction, Raman spectra measurements, and first-principles calculations, it is demonstrated that the O atoms shift along the Nb─O atomic chain under compression, which can lead to the increased Baur distortion of [NbO₂I₄] octahedra, and hence induces the enhancement of SHG. This work provides a 1D vdW ferroelectric system for developing novel ferroelectronic and photonic devices.