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| Home > Publications database > Structural order in (As$_{2}$S$_{3}$)x(GeS$_{2}$)$_{1-x}$ glasses |
| Journal Article | PUBDB-2021-03959 |
; ; ; ; ; ;
2021
Elsevier Science
Amsterdam [u.a.]
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Please use a persistent id in citations: doi:10.1016/j.jnoncrysol.2021.121075
Abstract: Structural order in the chalcogenide glasses of (As$_2$S$_3$)$_x$(GeS$_2$)$_{1−x}$ (x = 0.0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0) system is examined in terms of the parameters of local atomic structure as a function of composition x, obtained using high-resolution Raman spectroscopy, high-energy synchrotron X-ray diffraction, extended X-ray absorption fine structure spectroscopy and reverse Monte-Carlo modeling of diffraction data. As a result of the research carried out it is revealed that the structural order of As-rich (x > 0.4) and Ge-rich (x < 0.4) glasses is organized by the main As−S and Ge−S structural motifs based on pyramidal AsS$_3$ and tetrahedral GeS$_4$ units linked by =As−S−As= and triple bondGe−S−Getriple bond structural configurations, respectively; while for the intermediate compound with x = 0.4 the structural network seems to be better homogeneous on the nanoscale due to appearance of triple bondGe−S−As= mixed structural configurations resulting in misbalance between corner-shared and edge-shared tetrahedral units in comparison with their predicted ratio for binary GeS$_2$ glass and the structure of this alloy is similar to the structure of the stoichiometric glass Ge$_{18.2}$As$_{18.2}$S$_{63.6}$ (i.e., x = 0.455) consisting of a coner-shared network of homogeneously mixed GeS$_4$ tetrahedra and AsS$_3$ pyramids. Based on the structural studies, it is also established that the balance between corner-shared and edge-shared GeS$_4$ tetrahedra in the glass backbone of the investigated GeS$_2$-based glasses seems to be responsible for the interconnectivity between two speculative Raman modes at 370 and 430 cm$^{−1}$. Compositional changes in studied glasses result in the evolution of the observed Raman bands. Such dependences of characteristic constituent Raman bands’ intensities showed that (As$_2$S$_3$)$_x$(GeS$_2$)$_{1−x}$ samples contain different nanophases whose concentration is changing along chosen compositional cross-section.
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