Tuning structure, stability and magnetism in vanadium doped zinc sulfide for spintronic applications: Insights from first-principles and Monte Carlo approaches

This work utilizes a multi-scale computational approach combining first-principles density functional theory (DFT) and Monte Carlo statistical simulations to provide fundamental insights into the impacts of vanadium (V) doping on the structural, electronic, magnetic, and thermodynamic properties of wurtzite zinc sulfide (ZnS). 2 × 2 × 2 ZnS supercells with controlled V doping concentrations from 12.5%–25% substituting zinc sites were constructed. The introduction of V dopants induces systematic expansions in lattice parameters and cell volume, attributed to the larger ionic radius of V2+ than Zn2+, while the average compressibility shows minimal variation. However, V incorporation is found to soften ZnS by over 15% at higher dopant contents, increasing compliance and anisotropy. Stable ferromagnetic spin couplings emerge, mediated by host carriers without precipitating V secondary phases. The band structure develops half-metallic electronic properties with the lifting of spin degeneracy and preferential spin-up band metallicity induced by V-3d and S-3p hybridization effects. This results in 100% spin polarization at the Fermi level. Monte Carlo simulations based on a tight-binding Hamiltonian constructed from maximally localized Wannier functions to accurately calculate the exchange interactions between V spins successfully reproduce the magnetic phase transition behavior. The results confirm high Curie temperatures exceeding 300 K at 25% V, attributable to the significant strengthening of short-range ferromagnetic couplings over antiferromagnetic interactions. The integrated computational approach provides fundamental insights into the microscopic origin of carrier-mediated ferromagnetism in V-doped wurtzite ZnS dilute magnetic semiconductors. The systematic first-principles calculations and statistical mechanics modeling establish clear structure–property relationships linking V doping configurations and concentrations to tuned mechanical response, enhanced stability, electronic structure modifications, spin polarization, and magnetic ordering temperatures in ZnS. The results present design pathways and predictive capabilities to guide experimental efforts toward emerging high-performance magnetic materials for spintronic technologies.