Identification of bulk and surface sulfur impurities in Ti O2 by synchrotron x-ray absorption near edge structure

Synchrotron x-ray absorption near edge structure (XANES) measurements of Ti and S K edges, combined with first principles simulations, are used to characterize S-doped Ti O2 prepared by oxidative annealing of Ti S2 at various temperatures. Ti-edge XANES and x-ray powder diffraction data indicate that samples annealed above 300 °C have an anatase Ti O2 crystal structure with no trace of Ti S2 domains. S-edge XANES data reveal that the local structure seen by S atoms evolves gradually, from Ti S2 to a qualitatively different structure, as the annealing temperature is increased from 200 to 500 °C. For samples annealed at 500 °C, the spectrum appears to have features that can be assigned to S on the surface in the form of S O4 and S defects in the bulk (most likely S interstitials) of Ti O2

Mixed-Metal Cu-Zn Thiocyanate Coordination Polymers with Melting Behavior, Glass Transition, and Tunable Electronic Properties

The solid-state mechanochemical reactions under ambient conditions of CuSCN and Zn(SCN)2 resulted in two novel materials: partially Zn-substituted α-CuSCN and a new phase CuxZny(SCN)x+2y. The reactions take place at the labile S-terminal, and both products show melting and glass transition behaviors. The optical band gap and solid-state ionization potential can be adjusted systematically by adjusting the Cu:Zn ratio. Density functional theory calculations also reveal that the Zn-substituted CuSCN structure features a complementary electronic structure of Cu 3d states at the valence band maximum (VBM) and Zn 4s states at the conduction band minimum (CBM). This work shows a new route to develop semiconductors based on coordination polymers which are becoming technologically relevant for electronic and optoelectronic applications.</p