Raman spectra of MCl-Ga2S3-GeS2 (M = Na, K, Rb) glasses

Raman spectra of (MY)( x )(Ga2S3)(0.2-0.2x )(GeS2)(0.8-0.8x ) pseudo-ternary glassy systems (M = Na, K, Rb; Y = Cl, Br, I) were investigated systematically as a function of MY nature and alkali content. Raman spectroscopy of the Ga3S3-GeS2 glassy matrix shows a complicated local structure: corner-sharing CS- and edge-sharing ES-GeS4/2 tetrahedra, Ga-S triclusters and ETH-Ga2S6/2 ethane-like units. The Ga2S6/2 population decreases with increasing x related to a substitution of some bridging sulfur atoms around central Ga by terminal Y species with a respective decrease of the network rigidity. The formation of mixed Ga-(S,Y) environment is affected by the M+ ion size and the MY concentration.