Antiferroelectricity in a family of pyroxene-like oxides with rich polymorphism

Abstract

Antiferroelectrics have potential applications in energy conversion and storage, but are scarce, particularly among oxides that otherwise display rich ferroic behaviours. A question then arises whether potential antiferroelectrics are being overlooked, simply because their corresponding ferroelectric phase has not been discovered yet. Here we report a firstprinciples study suggesting that this is the case for a family of ABO 3 pyroxene-like materials, characterised by chains of corner-sharing BO 4 tetrahedra, a well-known member being KVO 3. The irregular tetrahedra have an electric dipole associated to them. In the most stable polymorph, the dipoles display an antipolar pattern with zero net moment. However, upon application of an electric field, half of the tetrahedra rotate, flipping the corresponding dipoles and reaching a ferroelectric state. We discuss the unique possibilities for tuning and optimisation of antiferroelectricity that these materials offer. We suggest that the structural features enabling this antiferroelectric behaviour can also be found in other all-important mineral families.

Antiferroelectric negative capacitance from a structural phase transition in zirconia

“…First predicted in 1951 6 , antiferroelectricity was subsequently discovered in the archetypal perovskite oxide, lead zirconate (PbZrO 3 ) 7 , 8 . Ever since, the range of materials has been expanded to two-dimensional hybrid perovskites 9 , interfacially engineered heterostructures and superlattices 10 , fluorite structure binary oxides 11 , 12 , and more have been predicted by first principles calculations 13 , 14 . However, compared to their ferroelectric counterparts, antiferroelectrics have remained less explored and understood so far, despite their intriguing properties and rich phase transition phenomena 14 – 16 .…”

“…Ever since, the range of materials has been expanded to two-dimensional hybrid perovskites 9 , interfacially engineered heterostructures and superlattices 10 , fluorite structure binary oxides 11 , 12 , and more have been predicted by first principles calculations 13 , 14 . However, compared to their ferroelectric counterparts, antiferroelectrics have remained less explored and understood so far, despite their intriguing properties and rich phase transition phenomena 14 – 16 . Therefore, antiferroelectric materials hold a large untapped potential for the discovery of emergent phases for example in antiferroelectric oxide heterostructures, which have been investigated in this work.…”