Interface engineering of ferroelectricity in thin films of thiophosphate ABP 2 X 6 (A = Cu, Ag; B = In, Bi, Cr, V; and X = S, Se)

TL;DR

This study demonstrates that interface engineering can effectively induce and control ferroelectricity in thiophosphate monolayers, enabling tunable electronic properties for advanced device applications.

Contribution

It introduces a novel interface engineering approach to switch ABP$_2$X$_6$ monolayers from antiferroelectric to ferroelectric states, supported by first-principles calculations.

Findings

AFEP CuInP$_2$Se$_6$ becomes FE when interfaced with certain 2D materials.

CuCrP$_2$S$_6$ remains AFE due to large energy difference, but can be driven into FE with MgO.

Electrical switching of AFE-FE transition and associated band-gap change observed.

Abstract

Two-dimensional ferroelectrics (FEs) are promising in the miniaturization of memory devices with ultra-high-density data storage and low power consumption. However, many thiophosphate monolayers, i.e., analogs of CuInP$_2$S$_6$ and referred to as ABP$_2$X$_6$, lose ferroelectricity and instead exhibit an antiferroelectric (AFE) or paraelectric ordering. We propose to tune the AFE ABP$_2$X$_6$ monolayers into the FE ordering through interface engineering. The mechanism is that there are couplings between the charge polarizations of the ABP$_2$X$_6$ monolayers and the local dipoles as well as the induced electronic polarizations in the substrate which have a tendency to stabilize the FE ordering. We further perform first-principles calculations for CuInP$_2$Se$_6$ and CuCrP$_2$S$_6$ monolayers and their van der Waals heterostructures. We find that an AFE CuInP$_2$Se$_6$ monolayer becomes FE as interfaced with graphene, MoS$_2$, and h-BN monolayers. In contrast, the CuCrP$_2$S$_6$ monolayer remains AFE since there is a large energy difference between the AFE and FE phases. Interfacing it with a MoTe$_2$ monolayer induces a metal-insulator transition for the heterostructure, whereas interfacing with a polar surface MgO(111) can drive it into FE. The interfacing effect can also be used to manipulate the FE properties of ABP$_2$X$_6$ multilayers. We further find that the AFE-to-FE transition is electrically switchable in these systems. In particular, it is accompanied by an indirect-direct band-gap transition for the CuInP$_2$Se$_6$ monolayer. Our study offers an effective approach to tune the FE and electronic properties of ABP$_2$X$_6$ thin films for applications in electronics and optoelectronics.