Electronic structure of the wrong-bond states in amorphous germanium sulphides

First-principles calculations of the electronic structures of the wrong bonds were performed for amorphous germanium sulphides in order to explain their compositional dependence. Model cluster calculations of the density of states using a set of geometry similar to the crystalline-GeS₂ coordination can reproduce the peak structure of the experimental valence band photoemission spectra. The bonding and anti-bonding states of the covalent Ge-S bonds form valence and conduction band respectively, and the top of the valence band is occupied with S 3p lone-pair states. The bonding states are modified by S-S bonds and the anti-bonding states are modified by Ge-Ge bonds, mainly through their hybridization with the wrong-bond states between p-orbitals. The lone-pair states do not interact either of them to form a different band, and obscure the modification induced by the S-S wrong bonds. Therefore, we can conclude that the narrowing of the bandgap with increasing Ge content from GeS₂ composition is due to that of the conduction-band bottom with increasing germanium wrong bonds, though the narrowing with increasing S content is moderate due to the presence of the lone-pair states at the valence-band top.