Defects-driven magnetism in bulk $\alpha$-Li$ _{3}$N

TL;DR

This study uses ab-initio calculations to explore how various defects and doping in bulk α-Li3N induce magnetism, revealing defect stability, electronic structure changes, and magnetic coupling behaviors.

Contribution

It provides new insights into defect-induced and dopant-induced magnetism in α-Li3N, highlighting the stability and electronic effects of Li and N vacancies and C doping.

Findings

Li vacancies induce magnetism with 1 μB magnetic moment.

Li-II vacancies are more thermodynamically stable than Li-I vacancies.

C doping can induce half-metallic magnetism and metallicity.

Abstract

\textit{Ab-initio} calculations based on density functional theory with local spin density approximation are used to study defects-driven magnetism in bulk $\alpha$-Li$ _{3}$N. Our calculations show that bulk Li$ _{3} $N is a non-magnetic semiconductor. Two types of Li vacancies (Li-I and Li-II) are considered, and Li-vacancies (either Li-I or Li-II type) can induce magnetism in Li$ _{3}$N with a total magnetic moment of 1.0 $\mu_{\rm B}$ which arises mainly due to partially occupied N-$p$-orbitals around the Li vacancies. The defect formation energies dictate that Li-II vacancy, which is in the Li$ _{2}$N plane, is thermodynamically more stable as compared with Li-I vacancy. The electronic structures of Li-vacancies show half-metallic behavior. On the other hand N-vacancy does not induce magnetism and has a larger formation energy than Li-vacancies. N vacancy derived bands at the Fermi energy are mainly contributed by the Li atoms. Carbon is also doped at Li-I and Li-II sites, and it is expected that doping C at Li-I site is thermodynamically more stable as compared with Li-II site. Carbon can induce metallicity with zero magnetic moment when doped at Li-I site, whereas magnetism is observed when Li-II site is occupied by the C impurity atom and C-driven magnetism is spread over the N atoms as well. Carbon can also induce half-metallic magnetism when doped at N site in Li$ _{3}$N, and has a smaller defect formation energy as compared with Li-II site doping. The ferromagnetic (FM) and antiferromagnetic (AFM) coupling between the C atoms is also investigated, and we conclude that FM state is more stable than the AFM state.