Structure of As2S3–Sb4S4 glasses by combined Raman spectroscopy and thermodynamic modeling approach

• As2S3–Sb4S4 glasses were described by the thermodynamic model of Shakhmatkin and Vedishcheva.
• The five components with significant abundance are As, Sb, As2S2, As2S3, and Sb2S3.
• Partial Raman spectra of As2S2, As2S3, and a spectral combination (0.15 As + 0.20 Sb + Sb2S3) were calculated.
• Spectra were decomposed by Malfait method. Experimental spectra were well reproduced.
• Obtained results confirmed the structural information acquired from the thermodynamic model.

The structure of chalcogenide glasses of the pseudo-binary system As2S3–Sb4S4 was investigated by comparing the results of the thermodynamic model of Shakhmatkin and Vedishcheva with the results obtained from the analysis of the Raman spectra of xAs2S3(100 − x)Sb4S4 (x = 100, 95, 90, 80, 70, 60, 50, 40) glasses performed by the Principal Component Analysis and the spectral decomposition by the method of Malfait. On the basis of the eigenvalues three independent components were identified in the studied spectral series. On the other hand, the thermodynamic modeling resulted in three components with significant abundance in the studied glasses, i.e. As2S2, As2S3, and Sb2S3. Moreover, the correlation analysis proved the strong linear dependence between the concentrations of As, Sb, and Sb2S3. Using the method of Malfait, partial Raman spectra of As2S2, As2S3, and the linear spectral combination (0.15 As + 0.20 Sb + Sb2S3) were calculated. The experimental spectra were well reproduced. The obtained results confirmed the structural information acquired from the thermodynamic model.