Vacancy defect in bulk and at (10$\overline{1}$0) surface of GaN: A combined first-principles theoretical and experimental analysis

TL;DR

This study combines first-principles calculations and experimental evidence to analyze native point defects in GaN, revealing that nitrogen vacancies are energetically favored and significantly influence its electronic and conductive properties.

Contribution

It provides a comprehensive atomic and electronic structure analysis of vacancies in GaN using DFT and correlates findings with experimental spectroscopy and conductivity measurements.

Findings

N-vacancies have lower formation energy than Ga-vacancies.

N-vacancies cause metallic behavior in GaN nanostructures.

Clustering of vacancies enhances electrical conductivity.

Abstract

We determine atomic and electronic structure, formation energy, stability and magnetic properties of native point defects, such as Gallium (Ga) and Nitrogen (N) vacancies in bulk and at non-polar (10$\overline{1}$0) surface of wurtzite Gallium Nitride (\textit w-GaN) using, first-principles calculations based on Density Functional Theory (DFT). Under both Ga-rich and N-rich conditions, formation energy of N-vacancies is significantly lower than that of Ga-vacancies in bulk and at (10$\overline{1}$0) surface. Experimental evidence of the presence of N-vacancies was noted from electron energy loss spectroscopy measurements which further correlated with the high electrical conductivity observed in GaN nanowall network. We find that the Fermi level pins at 0.35 $\pm$0.02 eV below Ga derived surface state. Presence of atomic steps in the nanostructure due to formation of N-vacancies at the (10$\overline{1}$0) surface makes its electronic structure metallic. Clustering of N-vacancies and Ga-Ga metallic bond formation near these vacancies, is seen to be another source of electrical conductivity of faceted GaN nanostructure that is observed experimentally.