Improvement of Luminescence and Photocatalytic Performance of ZnO:Eu³⁺ Nanocrystals Activated by Na⁺ Ions

Abstract

Undoped and codoped (Eu/Na) ZnO nanocrystals (NCs) were successfully manufactured through an economical sol-gel method. X-ray diffraction (XRD) analysis demonstrated pure hexagonal wurtzite structure without secondary phases for all the samples. The size of the NCs was found to decrease with codoping by Eu3+/Na+ which is related to the existence of strain and stress in the lattice. The dominance of the E2(high) mode in Raman spectra indicates the good crystallinity of the samples. The study from the X-ray photoelectron spectroscopy (XPS) shows the successful insertion of both Eu3+ and Na+ ions into the ZnO lattice and the generation of the zinc and oxygen vacancies (Vo) defects. The band gap energy was reduced and the Urbach energy increased with Na+ content, proving the distortion of the lattice. From the photoluminescence (PL) study, the activation of the Eu3+ ions by Na+ ones was evidenced. Longer PL lifetimes were obtained from Eu3+ ions when they were sensitized by Na+, which may be beneficial to several applications. A process of excitation transfer from both the ZnO host and Na+ sensitizers to the Eu3+ ions was evidenced and discussed. As an application, we tested the performances of the prepared NCs as photocatalysts for Rhodamine B photodegradation under sunlight irradiation. The ZnO NCs codoped with 1% Eu/4% Na displayed the best photodegradation rate with a good stability and a high kinetic rate constant k of 0.021 min−1. The photocatalytic mechanism is discussed in terms of longer radiative recombination from Eu3+ and the generated oxygen vacancies.

Keywords

• ZnO nanocrystals
• rare earth ions
• photoluminescence
• charges transfer
• photocatalysis