Experimental and theoretical study of the energetic, morphological, and photoluminescence properties of CaZrO3:Eu3+

Abstract

In this study, we present a combined experimental and theoretical study of the geometry, electronic structure, morphology, and photoluminescence properties of CaZrO₃:Eu³⁺ materials. The polymeric precursor method was employed to synthesize CaZrO₃:Eu³⁺ crystals, while density functional theory calculations were performed to determine the geometrical and electronic properties of CaZrO₃:Eu³⁺ in its ground and excited electronic states (singlet and triplet). The results were combined with X-ray diffraction (XRD) measurements to elucidate the local structural changes induced by the introduction of Eu³⁺ in the crystal lattice. This process results in the formation of intermediate levels in the band-gap (E_gap) region, narrowing its width. The PL emissions were rationalized by characterizing the electronic structure of the excited singlet and triplet electronic states, which provided deep insight into the main structural and electronic fingerprints associated with [CaO₈], [EuO₈], and [ZrO₆] clusters. In addition, the Wulff construction, obtained from the first-principles calculations, was used to clarify the experimental morphologies. These results extend our fundamental understanding of the atomic processes that underpin the Eu doping of CaZrO₃.