First-principles study of (Ba,Ca)TiO${}_3$ and Ba(Ti,Zr)O${}_3$ solid solutions

Abstract

(Ba,Ca)TiO${}_3$ and Ba(Ti,Zr)O${}_3$ solid solutions are the building blocks of lead-free piezoelectric materials that attract a renewed interest. We investigate the properties of these systems by means of first-principles calculations, with a focus on the lattice dynamics and the competition between different ferroelectric phases. We first analyze the four parent compounds in order to compare their properties and their different tendency towards ferroelectricity. The core of our study is systematic characterization of the binary systems (Ba,Ca)TiO${}_3$ and Ba(Ti,Zr)O${}_3$ within both the Virtual Crystal Approximation and direct supercell calculations. In the case of Ca doping, we find a gradual transformation from $A$-site to $B$-site ferroelectricity due to steric effects that largely determines the behavior of the system. In the case of Zr doping, in contrast, the behavior is eventually dominated by cooperative Zr-Ti motions and the local electrostatics. In addition, our comparative study reveals that the specific microscopic physics of these solid sets severe limits to the applicability of the Virtual Crystal Approximation for these systems.

References in corpus (2)

• EXAFS study of lead-free relaxor ferroelectric BaTi(1-x)Zr(x)O3 at the Zr K-edge
• Atomistic Description for Temperature-Driven Phase Transitions in BaTiO${}_3$

Cited by in corpus (8)

• Lattice dynamics and Raman spectrum of BaZrO3 single crystals
• Coexistence of local structural heterogeneities and long-range ferroelectricity in Pb-free (1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 ceramics
• On the microscopic mechanisms behind hyperferroelectricity
• Anharmonicity of the antiferrodistortive soft mode in barium zirconate BaZrO${}_3$
• Stability of the tetragonal phase of BaZrO3 under high pressure
• Effects of the antiferrodistortive instability on the structural behavior of BaZrO${}_3$ by atomistic simulations
• Towards machine learning for microscopic mechanisms: a formula search for crystal structure stability based on atomic properties
• Finite-temperature properties and the hidden ferroelectric $R3c$ phase of bulk CaTiO${}_3$ from second principles