Thermally-activated charge reversibility of gallium vacancies in GaAs

TL;DR

This paper uses ab initio calculations to show that the charge state of gallium vacancies in GaAs reverses with temperature, reconciling conflicting experimental results through thermal effects on defect energetics.

Contribution

It introduces a temperature-dependent analysis of gallium vacancy charge states in GaAs, resolving previous experimental conflicts with a unified theoretical approach.

Findings

Charge state of Ga vacancies reverses with temperature.

Thermal effects explain conflicting experimental results.

Reproduces experimental vacancy concentrations accurately.

Abstract

The dominant charge state for the Ga vacancy in GaAs has been the subject of a long debate, with experiments proposing $-$1, $-$2 or $-$3 as the best answer. We revisit this problem using {\it ab initio} calculations to compute the effects of temperature on the Gibbs free energy of formation, and we find that the thermal dependence of the Fermi level and of the ionization levels lead to a reversal of the preferred charge state as the temperature increases. Calculating the concentrations of gallium vacancies based on these results, we reproduce two conflicting experimental measurements, showing that these can be understood from a single set of coherent LDA results when thermal effects are included.