Interlayer Sliding-Induced Intralayer Ferroelectric Switching in Bilayer Group-IV Monochalcogenides

Abstract

Two-dimensional materials with ferroelectric properties break the size effect of conventional ferroelectric materials and unlock unprecedented potentials of ferroelectric-related application at small length scales. In this work, using density functional theory (DFT) calculations, we discover a tribo-ferroelectricity behavior in a group of bilayer group-IV monochalcogenides (MX, with M = Ge, Sn and X = S, Se). Upon interlayer sliding over an in-plane unit cell length, the top layer exhibits a reversible intralayer ferroelectric switching, leading to a reversible transition between the ferroelectric (electric polarization of 40$\hat{I}¼$C/cm${}^2$) and antiferroelectric states in the bilayer MXs. Our results show that the interlayer van der Waals interaction, which is usually considered to be weak, can actually generate an in-plane lattice distortion and thus cause the breaking/forming of intralayer covalent bonds in the top layer, leading to the observed tribo-ferroelectricity phenomenon. This unique property has several advantages for energy harvesting over existing piezoelectric and triboelectric nanogenerators. The interlayer sliding-induced polarization change is as high as 40$\hat{I}¼$C/cm${}^2$, which can generate an open-circuit voltage two orders of magnitude higher than that of MoS${}_2$-based nanogenerators. The polarization change occurs over a time period for interlayer sliding over a unit-cell length, leading to an ultrahigh polarization changing rate and thus an ultrahigh short-circuit current. The theoretical prediction of power output for the tribo-ferroelectric bilayer MXs at a moderate sliding speed 1 m/s is four orders of magnitude higher than the MoS${}_2$ nanogenerator, indicating great potentials in energy harvesting applications.

Manuscript: 19 pages including 4 figures