Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5426007 | Surface Science | 2006 | 9 Pages |
Conventional X-ray photoelectron spectroscopy (XPS) and synchrotron radiation XPS (SRXPS) were used to probe the chemical state properties of stibnite (Sb2S3), a large-band-gap semiconductor of complex structure. The conventional spectra were obtained with a Kratos Axis Ultra XPS with magnetic confinement charge neutralization, which is very effective in minimizing both uniform charging and differential charging on this large-band-gap semiconductor. The narrow linewidths (much narrower than previously obtained) for single doublet fits (e.g. Sb 4d5/2 of 0.57Â eV and S 2p3/2 of 0.63Â eV) enabled the observation of a small peak on the low binding energy side of the Sb 3d and Sb 4d lines. With the aid of the very surface-sensitive Sb 4d SRXPS spectra, these low energy peaks are assigned to small Sb metal clusters at the surface after cleavage; the signal for these clusters increases with X-ray dose on the sample.A detailed analysis of the Sb 4d and S 2p linewidths concludes that the Sb 4d5/2 linewidth is larger than expected based on the inherent linewidth of the instrument and the Sb 4d lifetime width, and on comparison with the As 3d linewidth (0.52Â eV) for the analogous As2S3. Also, the S 2p3/2 linewidth is substantially broader than the Sb 4d5/2 linewidth. These larger than expected linewidths are due to two structurally distinct Sb atoms and three structurally distinct S atoms in the Sb2S3 crystal structure. Accordingly, the Sb 4d and S 2p spectra have been fitted to two and three doublets respectively, and the linewidth for all peaks is 0.53Â eV. Using recent molecular orbital calculations, the doublets have been assigned to the different structural Sb and S sites.