Highly degenerate 2D ferroelectricity in pore decorated covalent/metal organic frameworks
Lei Zhang1,2, Cheng Tang1,2, Stefano Sanvito3
1School of Chemistry and Physics, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD 4000, Australia. aijun.du@qut.edu.au.
Abstract:
Two-dimensional (2D) ferroelectricity, a fundamental concept in low-dimensional physics, serves as the basis of non-volatile information storage and various electronic devices. Conventional 2D ferroelectric (FE) materials are usually two-fold degenerate, meaning that they can only store two logical states. In order to break such limitation, a new concept of highly degenerate ferroelectricity with multiple FE states (more than 2) coexisting in a single 2D material is proposed. This is obtained through the asymmetrical decoration of porous covalent/metal organic frameworks (COFs/MOFs). Using first-principles calculations and Monte Carlo (MC) simulations, Li-decorated 2D Cr(pyz)2 is systematically explored as a prototype of highly degenerate 2D FE materials. We show that 2D FE Li0.5Cr(pyz)2 and LiCr(pyz)2 are four-fold and eight-fold degenerate, respectively, with sizable spontaneous electric polarization that can be switched across low transition barriers. In particular, the coupling between neighbouring electric dipoles in LiCr(pyz)2 induces novel ferroelectricity-controlled ferroelastic transition and direction-controllable hole transport channels. Moreover, three-fold and six-fold degenerate ferroelectricity is also demonstrated in P-decorated g-C3N4 and Ru-decorated C2N, respectively. Our work presents a general route to obtain highly degenerate 2D ferroelectricity, which goes beyond the two-state paradigm of traditional 2D FE materials and substantially broadens the applications of 2D FE compounds.
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