Polarized X-ray absorption spectroscopy and XPS of TiS3:: S K- and Ti L-edge XANES and S and Ti 2p XPS

Sulfur and Ti 2p XPS and polarized S K- and L-2.3- and Ti L-2,L-3-edge XANES spectra have been obtained from oriented ribbon-like crystals of TiS3 grown by vapor transport. The S 2p XPS spectrum for (00 1) crystal faces has line widths of 0.53 eV and is completely accounted for by partially overlapped 2P(3/2)/2p(1/2) doublets for sulfide (S2-) and disulfide (S2-) 2 species, which are separate and independent entities in TiS3. Evidence of unsaturated surface states is lacking, consistent with a surface monolayer for the (00 1) growth face of disulfide atoms oriented with their charge-neutral sides outward. The S K-edge XANES spectra show pronounced anisotropy in the (00 1) plane of TiS3 crystals, associated with the photoelectron transition channel S 1s -> 3p(x)sigma(u) with the electric vector (E) parallel the a-axis (and the S-S bond of the disulfide group), and transitions to unoccupied antibonding orbitals of S-Ti bonds with E parallel to the b-axis (the direction of the well-known quasi-one-dimensional character of TiS3) The XPS and ultrasoft and soft X-ray region XANES spectra confirm the surface and near-surface structural integrity of TiS3. (c) 2005 Elsevier B.V. All rights reserved.