Association of oxygen vacancies with impurity metal ions in lead titanate

TL;DR

This study uses first principles calculations to explore how copper and iron impurities interact with oxygen vacancies in lead titanate, revealing their preferred configurations and implications for material degradation.

Contribution

It provides the first detailed atomic-level analysis of impurity-vacancy complexes in lead titanate, linking electronic structure to ferroelectric degradation.

Findings

Copper and iron form stable defect complexes with oxygen vacancies.

The most stable defect configurations align with the material's polarization axis.

Results explain experimental observations and degradation mechanisms.

Abstract

Thermodynamic, structural and electronic properties of isolated copper and iron atoms as well as their complexes with oxygen vacancies in tetragonal lead titanate are investigated by means of first principles calculations. Both dopants exhibit a strong chemical driving force for the formation of M_Ti-V_O (M = Cu, Fe) defect associates. The most stable configurations corresponds to a local dipole aligned along the tetragonal axis parallel to the spontaneous polarization. Local spin moments are obtained and the calculated spin densities are discussed. The calculations provide a simple and consistent explanation for the experimental findings. The results are discussed in the context of models for degradation of ferroelectric materials.