Niobium oxide dihalides NbOX2: a new family of two-dimensional van der Waals layered materials with intrinsic ferroelectricity and antiferroelectricity

Abstract

Two-dimensional (2D) ferroelectric (FE) materials displaying spontaneous polarizations are promising candidates for miniaturized electronic and memory devices. However, stable FE orderings are only found in a small number of 2D materials by experiment so far. In the current work, based on high-throughput screening of a 2D van der Waals layered materials database and first-principles calculations, we demonstrate niobium oxide dihalides NbOX₂ (X = Cl, Br and I), a group of experimentally synthesized yet underexplored van der Waals layered compounds, as a new family of 2D materials that simultaneously exhibit intrinsic in-plane ferroelectricity and antiferroelectricity. Similar to FE perovskite oxides, polar displacement of Nb cations relative to the center of the anion octahedral cage can lead to experimentally measurable FE polarizations up to 27 μC cm⁻² in layered NbOX₂. The presence of low-lying antiferroelectric (AFE) phases can effectively reduce the energy barrier associated with polarization switching, suggesting switchable ferroelectricity is experimentally achievable. In addition, the mechanism driving FE phase transitions in NbOX₂ monolayers around Curie temperature T_C is clearly revealed by our finite-temperature simulations. NbOCl₂ monolayer is predicted to be a stable ferroelectric with T_C above room temperature. Moreover, application of NbOBr₂ and NbOI₂ monolayers as 2D dielectric capacitors is further developed, where electrostatic energy storage of nearly 100% efficiency can be achieved in the 2D single-layer regime.