Illuminating stability and spectral shifts: A DFT+U study of Eu-doped ZnWO4 for visible-light optoelectronics

Abstract

Tungstate-based oxides have attracted significant attention owing to their excellent structural stability, chemical robustness, and versatile optical properties, making them suitable for next-generation optoelectronic and phosphor applications. Among these, ZnWO₄ has emerged as a promising host matrix; however, the role of europium (Eu) substitution in modulating its optoelectronic behavior remains underexplored. In this work, we employ spin-polarized density functional theory (DFT) within the GGA + U framework to investigate the structural, electronic, and optical properties of pristine ZnWO₄ and Eu-doped ZnWO₄ systems. Phonon dispersion analysis confirms dynamical stability for both pristine and doped structures. Eu doping reduces the bandgap, introduces new localized states near the Fermi level, and significantly alters the density of states, thereby enhancing electronic transitions. The optical response reveals a broadened dielectric function, red-shifted absorption edge, and intensified extinction coefficient, consistent with the presence of Eu 4f states. Additionally, reflectivity and energy-loss spectra indicate improved photon–phonon coupling and optical tunability upon doping. These findings highlight that Eu incorporation not only stabilizes the ZnWO₄ lattice but also tailors its optoelectronic features, positioning Eu-doped ZnWO₄ as a potential candidate for white-light-emitting diodes (w-LEDs) and related optoelectronic technologies.