Chemical Short-Range Order in Selenide and Telluride Glasses.

The structure of Ge20SbxSe80-x (x = 5, 15, 20) glasses was investigated by neutron diffraction, X-ray diffraction, and extended X-ray fine structure measurements at the Ge, Sb, and Se K-edges. For each composition, large-scale structural models were obtained by fitting simultaneously the experimental data sets in the framework of the reverse Monte Carlo simulation technique. It was found that the structures of these glasses can be described mostly by the chemically ordered network model. Ge-Se and Sb-Se bonds are preferred; Se-Se bonds in the Se-poor composition (x = 20) and M-M (M = Ge, Sb) bonds in strongly Se-rich glass (x = 5) are not needed. The quality of the fits was significantly improved by introducing Ge-Ge bonding in the nearly stoichiometric composition (x = 15), showing a violation of chemical ordering. The structure of Ge20SbxSe80-x was compared to that of several glasses from the three analogous systems (Ge-As-Se, Ge-As-Te, Ge-Sb-Te), and it was found that chemical short-range order becomes more pronounced upon substituting As with Sb and Se with Te. Ge-As-Se glasses behave as random covalent networks over a very broad composition range. Chemical short-range order and disorder coexist in both Te-rich and Te-poor Ge-As-Te glasses, whereas amorphous Ge14Sb29Te57 and Ge22Sb22Te56 are governed by strict chemical preferences.

From selenium- to tellurium-based glass optical fibers for infrared spectroscopies.

Chalcogenide glasses are based on sulfur, selenium and tellurium elements, and have been studied for several decades regarding different applications. Among them, selenide glasses exhibit excellent infrared transmission in the 1 to 15 µm region. Due to their good thermo-mechanical properties, these glasses could be easily shaped into optical devices such as lenses and optical fibers. During the past decade of research, selenide glass fibers have been proved to be suitable for infrared sensing in an original spectroscopic method named Fiber Evanescent Wave Spectroscopy (FEWS). FEWS has provided very nice and promising results, for example for medical diagnosis. Then, some sophisticated fibers, also based on selenide glasses, were developed: rare-earth doped fibers and microstructured fibers. In parallel, the study of telluride glasses, which can have transmission up to 28 µm due to its atom heaviness, has been intensified thanks to the DARWIN mission led by the European Space Agency (ESA). The development of telluride glass fiber enables a successful observation of CO2 absorption band located around 15 µm. In this paper we review recent results obtained in the Glass and Ceramics Laboratory at Rennes on the development of selenide to telluride glass optical fibers, and their use for spectroscopy from the mid to the far infrared ranges.