First Principles Insights into Phase Transitions, Disorder and Electronic Properties of Lead-Free Ba-Based Tetragonal Tungsten Bronzes

Tetragonal tungsten bronzes (TTBs), with the general formula A2₄A1₂C₄B1₂B2₈O₃₀, are a family of ferroelectric materials, which, due to their broad compositional space and structural flexibility make them a suitable framework for tuneable lead-free oxide ferroelectrics.

The Ba-containing TTBs such as Ba₄Na₂Nb₁₀O₃₀ (BNN) with a T_c of ~560^oC[1] is of particular interest in high temperature applications where there is a lack of suitable materials. Previous experimental work on substituting the A-site Na cation with larger alkali metals: K and Rb, show a systematic decrease in Tc in addition to uncovering the integral role that cation disorder plays on the structural parameters of these systems.[1]

However, there is little in terms of mechanistic understandings of these compositions using first principles characterisation techniques. In this work, density functional theory (DFT) calculations using both standard and hybrid functionals are performed on BNN-based compositions: Ba₄A₂M₁₀O₃₀ (A = Na, K, Rb ; M = Nb, Ta). In particular, we probe the origin of the high Tc as well as the thermodynamics of disorder. In particu

and the trends associated with the compositional engineering, as well as the thermodynamics of disorder and its effect on structural and electronic properties. The effects of this study are discussed in line with experimental work done in parallel as well as implications for the future direction of these materials.