Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO2 nanoparticles using Raman spectroscopy



Ni-doped SnO2 nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO2) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO2 nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A1g mode with the Ni content, a solubility limit at ∼2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above ∼2 mol% Ni, the redshift of A1g mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright © 2010 John Wiley & Sons, Ltd.