First principle thermodynamic study of oxygen vacancy at metal/oxide interface

TL;DR

This study uses ab initio thermodynamics to analyze how oxygen vacancies at metal/oxide interfaces affect the system's thermodynamic properties, impacting device performance.

Contribution

It provides a detailed thermodynamic analysis of oxygen vacancies at interfaces, highlighting the importance of vacancy location, temperature, and partial pressure effects.

Findings

Oxygen vacancies near interfaces alter bonding and thermodynamic properties.

Vacancy location significantly influences energy and entropy changes.

Temperature and partial pressure affect oxygen vacancy formation energy.

Abstract

The oxygen vacancy is a crucial intrinsic defect in metal-ultrathin oxide semiconductor heterostructures, and its formation at an interface is of great importance in determining the device performance and degradation. This paper presents an ab initio thermodynamic study of oxygen vacancies at metal/oxide interfaces. Electronic energies and entropies are calculated for defective interface systems, as a function of interface-vacancy distance. The study indicates that oxygen vacancies near the interface modify its bonding structure, and significantly change the thermodynamic properties of the system (i.e., electronic energy and entropy) compared to bulk-like oxygen vacancies. We illustrate that different factors, including the vacancy location dependence on the energy and entropy, the temperature dependence on the entropy, and the temperature and partial pressure dependence on the oxygen chemical potential, are all important in determining the Gibbs free energy of formation of oxygen vacancy.