Temperature Dependence of Self-diffusion in Cr2O3 from First Principles

TL;DR

This study uses high-accuracy density functional theory to model defect-mediated self-diffusion in Cr2O3, aligning theoretical predictions with experimental data and revealing temperature-dependent diffusion behaviors.

Contribution

It introduces hybrid functional DFT coupled with defect thermochemistry to accurately predict self-diffusion coefficients in Cr2O3, improving upon previous models.

Findings

Chromium has higher mobility at low temperatures and high oxygen pressures.

Oxygen diffusion dominates at high vacuum and high temperatures.

O vacancies are more mobile than Cr vacancies at interfaces.

Abstract

Understanding and predicting the dominant diffusion processes in Cr2O3 is essential to its optimization for anti-corrosion coatings, spintronics, and other applications. Despite significant theoretical effort in modeling defect mediated diffusion in Cr2O3 the correlation with experimentally measured diffusivities remains poor partly due to the insufficient accuracy of the theoretical approaches. Here an attempt to resolve these discrepancies is made through high accuracy density functional theory simulations coupled with grand canonical formalism of defect thermochemistry. In this approach, point defect formation energies were computed using hybrid exchange correlation functional. This level of theory proved to be essential for achieving the agreement with experimental self-diffusion coefficients. The analysis of the resulting self-diffusion coefficients indicate that chromium has higher mobility at low temperatures and high oxygen partial pressures, in particular at standard temperature and pressure conditions. At high vacuum, high temperature conditions, oxygen diffusion becomes dominant. At Cr/Cr2O3 interfaces O vacancies were found to be more mobile than Cr vacancies at all temperatures. Cr diffuses preferentially along the c-axis at low temperatures but switches to basal plane at higher temperatures. O diffusion is primarily bound to basal plane at all temperatures.