Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

Abstract

Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositions in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. The computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.