A valence states approach for luminescence enhancement by low dopant concentration in Eu-doped ZnO nanoparticles

The paper presents a simple, reproducible, controllable, and direct wet chemical synthesis method for Zn1−x Eu x O nanoparticles. The full understanding of decomposition mechanism of the as-obtained oxalate precipitate was achieved based on the thermal analysis correlated with the evolved gas analysis and FTIR spectroscopy. The structure, morphology, and optical luminescent properties of the Zn1−x Eu x O nanoparticles have been investigated by X-ray diffraction, Raman spectroscopy, HRTEM, SAED, XPS, and PL. The XRD studies reveal the formation of a hexagonal wurtzite-type structure. The presence of Eu2O3 cubic structure can be observed up to 0.5 mol% Eu, suggesting that the solubility of the divalent or trivalent Eu into the ZnO lattice is limited. The formation of Eu2O3 secondary phase at higher Eu concentration is sustained by Raman spectroscopy and XPS, as well. The TEM investigations of the Eu-doped ZnO samples illustrate the presence of aggregates with different shapes and dimensions formed by agglomerated spherical and polyhedral nanoparticles with sizes ranging from 20 to 120 nm. The effect of europium concentration on the structural and morphological characteristics, as well as on the luminescent properties was studied with special emphasis on the europium chemical states—Eu2+ and Eu3+. The PL measurements sustain the presence of both divalent and trivalent europium ions into the ZnO host lattice and, at the same time, an increase of its defects density induced by the dopant presence.