XPS and Ag L3-edge XANES characterization of silver and silver gold sulfoselenides

Gold and silver sulfoselenides are of interest as materials with high ionic conductivity and promising magneto resistive, thermoelectric, optical, and other physico-chemical properties, which are strongly dependent on composition and structure. Here, we applied X-ray photoelectron spectroscopy and Ag L-3 X-ray absorption near edge structure (XANES) to study the electronic structures of low-temperature compounds and solid solutions Ag2SxSe1-x, (0 < x < 1), AgAuS, and Ag3AuSxSe2-x, (x = 0, 1, 2). Upon substitution of Se with S, a steady increase in the positive charge at Ag(I) sites and only minor changes in the local charge at chalcogen atoms were found from the photoelectron Ag 3d, S 2p, Se 3d, and Ag M4,5VV Auger spectra. The intensity of the Ag L-3-edge peak, which is known to correlate with hole counts in the Ag 4d shell having a formal d(10) configuration, was enhanced by 20-25% from Ag2Se to Ag2S and from Ag3AuSe2 to Ag3AuS2. The effect of gold is more pronounced, and the number of Ag d holes and the negative charge of S and Se notably decreased for Au-containing compounds; in particular, the Ag L-3-edge peak is about 35% lower for AgAuS relative to Ag2S. At the same time, the Au 4f binding energy and, therefore, charge at Au(I) sites increase with increasing S content due to the transfer of electron density from Au to Ag atoms. It was concluded that the effects mainly originate from shortening of the metal-chalcogen and especially the Au Ag interatomic distances in substances having similar coordination geometry.