R. Golovchak, O. Shpotyuk, J. Mccloy, B. Riley, C. Windisch, S. Sundaram, A. Kovalskiy, H. Jain.
Philosophical Magazine, vol. 90, No. 34, 2010, p. 4489–4501.
The structure of homogeneous bulk AsxS100-x (25 ≤ x ≤ 42) glasses, prepared by the conventional rocking–melting–quenching method, was investigated using high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. It is shown that the main building blocks of their glass networks are regular AsS3/2 pyramids and sulfur chains. In the S-rich domain, the existence of quasi-tetrahedral (QT) S=As(S1/2)3 units is deduced from XPS data, but with a concentration not exceeding 3–5% of total atomic sites. Therefore, QT units do not appear as primary building blocks of the glass backbone in these materials, and an optimally-constrained network may not be an appropriate description for glasses when x < 40. It is shown that, in contrast to Se-based glasses, the ‘chaincrossing’ model is only partially applicable to sulfide glasses.