Layer-dependent ferroelectricity in 2H-stacked few-layer α-In₂Se₃

Atomically thin two-dimensional (2D) van der Waals materials have exhibited many exotic layer-dependent physical properties including electronic structure, magnetic order, etc. Here, we report a striking even-odd layer dependent oscillation in the ferroelectric polarization of 2H-stacked few-layer α-In₂Se₃ nanoflakes. As characterized by piezoresponse force microscopy (PFM), when the in-plane (IP) electric polarization of 2H-stacked α-In₂Se₃ films is electrically aligned, the out-of-plane (OOP) polarization of the odd-layer (OL) samples is obviously larger than that of the even-layer (EL) ones. Similarly, samples with electrically aligned OOP polarization also show even-odd layer dependent IP polarization. Such an even-odd oscillation, as confirmed by the density functional theory calculations, can be attributed to the strong intercorrelation of the IP and OOP electric polarization of the α-In₂Se₃ monolayers and the special 2H-stacking structure of a 180 degree IP rotation with respect to the adjacent layers. Moreover, a negative differential resistance, interestingly, is induced by the polarization flip with a small coercive field of ∼1.625 kV cm^-1, and its peak-to-valley ratio can be tuned up to ∼7 by the gate. This work demonstrates that the delicate stacking geometry of multilayer α-In₂Se₃ can bring an interesting even-odd ferroelectric effect, enriching the layer-dependent physical properties of the 2D materials family.