Stacking-Engineered Ferroelectricity and Multiferroic Order in van der Waals Magnets

Two-dimensional (2D) materials that exhibit spontaneous magnetization, polarization, or strain (referred to as ferroics) have the potential to revolutionize nanotechnology by enhancing the multifunctionality of nanoscale devices. However, multiferroic order is difficult to achieve, requiring complicated coupling between electron and spin degrees of freedom. We propose a universal method to engineer multiferroics from van der Waals magnets by taking advantage of the fact that changing the stacking between 2D layers can break inversion symmetry, resulting in ferroelectricity as well as magnetoelectric coupling. We illustrate this concept using first-principles calculations in bilayer NiI2, which can be made ferroelectric upon rotating two adjacent layers by 180 degrees with respect to the bulk stacking. Furthermore, we discover a novel strong magnetoelectric coupling between the interlayer spin order and interfacial electronic polarization. Our approach is not only general but also systematic and can enable the discovery of a wide variety of 2D multiferroics with strong magnetoelectric coupling.