Blue shifts corresponding to the absorption edge in the UV-A (310–400 nm) range are obtained from ultraviolet (UV) absorption spectra of monodisperse CeO2−x (0<x<0.5) nanoparticles, which are produced as toluene suspensions by a successive microemulsification method. The blue shift of the nanoparticles is inversely proportional to the 2.2 power of the particle size for a direct transition, but no relation is found for an indirect transition. In contrast, the shift for thin films of 100–200 nm thickness exhibits a relation nearly inverse proportional to the square root of the thickness for the direct transition. These relations are different from that for the quantum size effect, though the difference is small for the nanoparticles. A possible explanation for the blue shift is a valence change of the Ce ions.
Anomalous lattice expansions have been measured for the first time in monodisperse CeO2-x nanoparticles and in BaTiO3 single nanoparticles by electron diffraction. X-ray photoelectron spectroscopy studies on CeO2-x nanoparticles and ab initio computer simulation on BaTiO3 clusters show that the origin of expansion is the decrease of electrostatic force caused by valence reduction of Ce ions and the increase in ionicity of Ti ions, respectively. The lattice constant change of oxide (ionic) nanoparticles with the increase in ionicity would depend on the structure of the particles. Hence, first-principles calculations of large ionic clusters are indispensable.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.