Abstract
The effect of lanthanides that have positive association energies with oxygen vacancies, such as samarium and neodymium, and the elements with negative association energies, such as holmium and erbium, on ionization state of cerium and, consequentially, the oxygen vacancy concentration in doped ceria nanoparticles are investigated in this article. Structural and optical characterizations of the doped and undoped ceria nanoparticles, synthesized using chemical precipitation, are carried out using transmission electron microscopy, X-ray diffractometry, optical absorption spectroscopy, and fluorescence spectroscopy. It is deduced that the negative association energy dopants decrease the conversion of Ce+4 into Ce+3 and, hence, scavenge the oxygen vacancies, evidenced by the observed increase in the allowed direct bandgap, decrease in the integrated fluorescence intensity, and increased the size of doped nanoparticles. The opposite trends are obtained when the positive association dopants are used. It is concluded that the determining factor as to whether a lanthanide dopant in ceria acts as a generator or scavenger of oxygen vacancies in ceria nanoparticles is the sign of the association energy between the element and the oxygen vacancies. The ability to tailor the ionization state of cerium and the oxygen vacancy concentration in ceria has applications in a broad range of fields, which include catalysis, biomedicine, electronics, and environmental sensing.
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Acknowledgments
This study was funded in part by a NSF STTR Phase I grant with MW Photonics (award# 0930364). Shehata was funded through Virginia Tech Middle East and North Africa (VT-MENA) program. The authors thank Dr. Niven Monsegue, Dr. Jerry Hunter, and Andrew Giordani from the Nanotechnology Characterization and Fabrication Laboratory, Institute of Critical Technologies and Applied Science at Virginia Tech for their training and assistance with the TEM and XPS measurements. Also, the authors appreciate the support of Mr. Don Leber, manager of the Micron Technology Semiconductor Processing Laboratory at Virginia Tech.
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Shehata, N., Meehan, K., Hudait, M. et al. Control of oxygen vacancies and Ce+3 concentrations in doped ceria nanoparticles via the selection of lanthanide element. J Nanopart Res 14, 1173 (2012). https://doi.org/10.1007/s11051-012-1173-1
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DOI: https://doi.org/10.1007/s11051-012-1173-1