Unraveling the structural and bonding nature of antimony sesquichalcogenide glass for electronic and photonic applications

Sb-Based phase-change materials have exhibited tremendous advantages in both data storage and reconfigurable photonic devices. Despite the intensive studies on their structures and properties in the crystalline state, the widely used amorphous phase remains elusive. Here, we investigate amorphous Sb2Te3, Sb2Se3, and Sb2S3 through ab initio calculations to link their unique properties to the local structure and bonding nature. We discover that Sb forms shorter and stronger bonds with Se and S than Te, and the average bonding angles of Se (92.0°) and S (94.1°) show larger distortion than that of Te (91.5°). This leads to larger Peierls-like distortion in Sb2Se3 and Sb2S3. On the other hand, more charge transfer and void fraction are presented, opening band gaps and leading to different electronic and optical properties. In contrast, Sb2Te3, due to its semiconducting behavior and low thermal stability, enables its application in phase-change memory. Our results reveal the physics of vastly different electronic and optical properties induced by S, Se, and Te alloying, providing an effective strategy for materials design.