30 research outputs found
Electronic structure, charge transfer, and intrinsic luminescence of gadolinium oxide nanoparticles: Experiment and theory
The cubic (c) and monoclinic (m) polymorphs of Gd2O3 were studied using the
combined analysis of several materials science techniques - X-ray diffraction
(XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy
(XPS), and photoluminescence (PL) spectroscopy. Density functional theory (DFT)
based calculations for the samples under study were performed as well. The
cubic phase of gadolinium oxide (c-Gd2O3) synthesized using a precipitation
method exhibits spheroidal-like nanoclusters with well-defined edges assembled
from primary nanoparticles with an average size of 50 nm, whereas the
monoclinic phase of gadolinium oxide (m-Gd2O3) deposited using explosive
pyrolysis has a denser structure compared with natural gadolinia. This phase
also has a structure composed of three-dimensional complex agglomerates without
clear-edged boundaries that are ~21 nm in size plus a cubic phase admixture of
only 2 at. % composed of primary edge-boundary nanoparticles ~15 nm in size.
These atomic features appear in the electronic structure as different defects
([Gd...O-OH] and [Gd...O-O]) and have dissimilar contributions to the
charge-transfer processes among the appropriate electronic states with
ambiguous contributions in the Gd 5p - O 2s core-like levels in the valence
band structures. The origin of [Gd...O-OH] defects found by XPS was
well-supported by PL analysis. The electronic and atomic structures of the
synthesized gadolinias calculated using DFT were compared and discussed on the
basis of the well-known joint OKT-van der Laan model, and good agreement was
established.Comment: 27 pages, 10 figures, accepted in Appl. Surf. Sc