Understanding the White-Emitting CaMoO₄ Co-Doped Eu³⁺, Tb³⁺, and Tm³⁺ Phosphor through Experiment and Computation

In this article, the synthesis by means of the spray pyrolysis method, of the CaMoO₄ and rare-earth cation (RE³⁺)-doped CaMoO₄:xRE³⁺ (RE³⁺ = Eu³⁺, Tb³⁺, and Tm³⁺; and x = 1, 2, and 4% mol) compounds, is presented. The as-synthesized samples were characterized using X-ray diffraction, Rietveld refinement, field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and photoluminescence (PL) spectroscopy. To complement and rationalize the experimental results, first-principles calculations, at the density functional theory level, have been performed to analyze the band structure and density of states. In addition, a theoretical method based on the calculations of surface energies and Wulff construction was applied to obtain the morphology transformation of the CaMoO₄ and CaMoO₄:RE³⁺ microstructures. The experimental morphologies can be observed in the FE-SEM images. The PL behavior of the Co-doped samples exhibited well-defined bands in the visible region. The samples with 2 and 4% of RE³⁺ released white emission according to the chromaticity coordinates (0.34, 0.34) and (0.34, 0.33), respectively. The present results provide not only a deep understanding of the structure–property relationships of CaMoO₄-based phosphor but also can be employed as a guideline for the design of the electronic structure of the materials and the fabrication of photofunctional materials with optimal properties, which allows for the modeling of new phosphors for applications in solid-state lighting.