The photodarkening is observed in many chalcogenide glasses, while its mechanism remains controversial. There are few reports which discuss the whole process. We consider the mechanism through ab initio molecular-orbital calculations for the simplest systems, elemental S and Se clusters. The results manifest that valence-alternation pair (VAP) defects are unstable in the dark, thus it cannot be an origin. On the other hand, intimate VAPs can be quasi-stable, while those affect only band-edge states, which is contradictory with observed spectral modifications. By contrast, strains in van-der-Waals (VDW) distances are likely to broaden the lone-pair electron band. A refined bond-twisting model is able to trace such a process, including annealing stage. Quantitatively, the maximal red-shift of ∼0.1 eV can be related with quasi-stable strains containable in a medium-range volume of ∼1 nm3, which can be thermally released through atomic twisting motions over angular barriers with a height of ∼1 eV.
Read full abstract