A Review on the Effects of Fe and Mg Doping on the Properties of ZnO Nanomaterials: A DFT Perspective
DOI:
https://doi.org/10.33003/fjs-2026-1014-5734Keywords:
density functional theory, zinc oxide, Fe doping, Mg doping, dilute magnetic semiconductors, optoelectronics, band-gapAbstract
Wurtzite zinc oxide is a reference wide-band-gap oxide for optoelectronics, yet density functional studies of its cation substitution remain fragmented and contradictory. This review critically synthesises first-principles results on Fe- and Mg-doped ZnO, two substituents of opposing chemistry: Fe, an open-shell 3d ion introducing localised spins, and Mg, a closed-shell cation whose effect is band-edge tuning. Doped-system claims are benchmarked against polymorph-resolved host calculations: GGA-PBE places the wurtzite, zinc-blende, and rocksalt gaps at 0.749, 0.637, and 0.817 eV against the experimental 3.37 eV, GGA+U raises them to 1.12, 1.00, and 1.11 eV, and hybrid functionals with the mBJ potential restore quantitative agreement for the tetrahedral phases. Against this baseline, Fe substitution yields a non-monotonic optical gap — Burstein–Moss widening at low concentration giving way to sp–d exchange narrowing at higher content and total magnetisations rising only weakly from 4.12 to 4.25 μB per supercell between 3 and 6 at% Fe, well below the 2 μB expected per added Fe atom. The ferromagnetism literature is coherently explained by bound magnetic polarons; intrinsic bulk-lattice room-temperature ferromagnetism remains unsupported. Mg widens the direct gap predictably, DFT+U tracking experiment from 3.37 to 3.57 eV up to 8.33% Mg, before the wurtzite-to-rocksalt transition caps single-phase solubility near 40 at% Mg and limits the gap to about 4.3 eV. The exchange-correlation choice, rather than the dopant alone, governs most reported trends; finite-temperature, disorder, and self-consistent-U treatments remain the decisive open frontiers.
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