Electronic structure and magnetism of transition metal doped Zn12O12 clusters: Role of defects

TL;DR

This study investigates how defects and transition metal doping influence the magnetic properties of ZnO clusters, revealing defect-induced ferromagnetism and unusual oxidation states that could advance spintronic nanodevices.

Contribution

It provides a detailed ab initio analysis of defect and dopant effects on magnetism in ZnO clusters, highlighting the role of charged defects in stabilizing ferromagnetism.

Findings

Antiferromagnetic interaction dominates in neutral, defect-free clusters.

Charged defects can induce ferromagnetism by stabilizing unusual oxidation states.

Defect-induced magnetism occurs even without transition metal doping.

Abstract

We present a comprehensive study of the energetics and magnetic properties of ZnO clusters doped with 3d transition metals (TM) using ab initio density functional calculations in the framework of generalized gradient approximation + Hubbard U (GGA+U) method. Our results within GGA+U for all 3d dopants except Ti indicate that antiferromagnetic interaction dominates in a neutral, defect-free cluster. Formation energies are calculated to identify the stable defects in the ZnO cluster. We have analyzed in details the role of these defects to stabilize ferromagnetism when the cluster is doped with Mn, Fe, and Co. Our calculations reveal that in the presence of charged defects the transition metal atoms residing at the surface of the cluster may have an unusual oxidation state, that plays an important role to render the cluster ferromagnetic. Defect induced magnetism in ZnO clusters without any TM dopants is also analyzed. These results on ZnO clusters may have significant contributions in the nanoengineering of defects to achieve desired ferromagnetic properties for spintronic applications.