Acousto-optic (AO) devices have great application potential in laser technology and network communication. Chalcogenide (ChG) glass is promising for AO devices because of its excellent infrared transparency and high AO figure of merit. Among them, As–S glasses represent the most typical and extensively studied ChG system. However, the correlation between the network structure of As–S glasses in the As-rich and S-rich regions and their AO properties remains to be investigated. In this work, the effect of glass composition and glass structure on the AO properties of As–S glasses was investigated. The gradual formation of homopolar As–As and S–S bonds leads to the weakening of the network crosslinking degree of the glass structure in the vicinity of As-rich and S-rich regions, which results in a reduction in the AO properties. In particular, the presence of long-chain As–S–As bonds in the As40S60 glass primarily causes its superior AO properties. The above results provide an important reference for the further investigation on the correlation between glass composition, structure, and AO properties and the development of As–S based AO media and devices.
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