Ferroelectric Behavior in Exfoliated 2D Aurivillius Oxide Flakes of Sub-Unit Cell Thickness

Ferroelectricity in ultrasonically exfoliated flakes of the layered Aurivillius oxide Bi₅Ti₃Fe_0.5Co_0.5O₁₅ with a range of thicknesses is studied. These flakes have relatively large areas (linear dimensions many times the film thickness), thus classifying them as 2D materials. It is shown that ferroelectricity can exist in flakes with thicknesses of only 2.4 nm, which equals one-half of the normal crystal unit cell. Piezoresponse force microscopy (PFM) demonstrates that these very thin flakes exhibit both piezoelectric effects and that the ferroelectric polarization can be reversibly switched. A new model is presented that permits the accurate modeling of the field-on and field-off PFM time domain and hysteresis loop responses from a ferroelectric during switching in the presence of charge injection, storage, and decay through a Schottky barrier at the electrode–oxide interface. The extracted values of spontaneous polarization, 0.04(±0.02) C m⁻² and electrostrictive coefficient, 2(±0.1) × 10⁻² m⁴ C⁻² are in good agreement with other ferroelectric Aurivillius oxides. Coercive field scales with thickness, closely following the semi-empirical scaling law expected for ferroelectric materials. This constitutes the first evidence for ferroelectricity in a 2D oxide material, and it offers the prospect of new devices that might use the useful properties associated with the switchable ferroelectric spontaneous polarization in a 2D materials format.