First-principles studies of the local structure and relaxor behavior of Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$-PbTiO$_3$-derived ferroelectric perovskite solid solutions

TL;DR

This study uses first-principles calculations to explore how transition metal dopants alter the local structure and relaxor behavior of Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$-PbTiO$_3$ ferroelectric perovskites, revealing dopant-specific effects on polarization and dielectric properties.

Contribution

It provides detailed insights into how various transition metal dopants influence local structure, polarization, and dielectric behavior in relaxor ferroelectric perovskites, a novel investigation in this material system.

Findings

Cu and Zn doping increase polarization and dielectric temperature.

Mo and Tc doping decrease polarization and dielectric temperature.

Dopants increase cation displacement disorder and affect temperature dispersion.

Abstract

We have investigated the effect of transition metal dopants on the local structure of the prototypical 0.75 Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$-0.25 PbTiO$_3$ relaxor ferroelectric. We find that these dopants give rise to very different local structure and other physical properties. For example, when Mg is partially substituted by Cu or Zn, the displacement of Cu or Zn is much larger than that of Mg, and is even comparable to that of Nb. The polarization of these systems is also increased, especially for the Cu-doped solution, due to the large polarizability of Cu and Zn. As a result, the predicted maximum dielectric constant temperatures ($T_m$) are increased. On the other hand, the replacement of a Ti atom with a Mo or Tc dramatically decreases the displacements of the cations and the polarization, and thus, the $T_m$ values are also substantially decreased. The higher $T_m$ cannot be explained by the conventional argument based on the ionic radii of the cations. Furthermore, we find that Cu, Mo, or Tc doping increase the cations displacement disorder. The effect of the dopants on the temperature dispersion ${\Delta}T_m$, which is the change of $T_m$ for different frequencies, is also discussed. Our findings lay the foundation for further investigations of unexplored dopants.