Facile synthesis of Sm3+/Eu3+ codoped CeO2 ultrafine nanocrystals and oxygen vacancy site dependent photoluminescence

• Sm3+/Eu3+ codoped CeO2 ultrafine nanocrystals are prepared by a simple method.
• Site symmetry of Sm3+ and Eu3+ in ceria matrix is studied.
• Influence of oxygen vacancy sites on luminescence properties of the material is investigated.
• Enhanced emission of Eu3+ by non radiative energy transfer from Sm3+→Eu3+ is established.

Ultrafine nanocrystals of Sm3+/Eu3+ codoped CeO2 have been prepared successfully by a simple and facile oxalate decomposition method. The structure, phase and size of the nanocrystals were characterized by X-ray diffraction and transmission electron microscope which confirmed that monodispersed nanocrystals of size below 5 nm are formed by this novel technique. Spectroscopic investigations of the synthesized phosphors are carried out with the help of photoluminescence excitation, emission and decay analysis. The studies revealed that oxygen vacancies introduced in the crystal lattice for charge compensation strongly influences the luminescence properties of the phosphor material. By investigating the luminescence characteristics of the material with different doping concentrations of Sm3+ and Eu3+, the position of the oxygen vacancies with respect to the dopant ion is determined. Also it can be revealed that symmetry of Eu3+ ions are perturbed by the oxygen vacancies at nearest neighbor site which produce strong electric dipole transition emissions in the luminescence spectra. In the case of Sm3+ ions oxygen vacancies are repelled to the next nearest neighbor site and hence the cubic symmetry of the ions is preserved. In addition, occurrence of non radiative energy transfer from Sm3+ to Eu3+ in the phosphor material is confirmed by the close examination of the luminescence spectra. Chromaticity coordinates evidenced that color purity of the synthesized nanophosphors is marginally increased by the proper addition of Sm3+.

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