Crystal Structure of AgBi₂I₇ Thin Films

Synthesis of cubic-phase AgBi 2 I 7 iodobismuthate thin films and fabrication of air-stable Pb-free solar cells using the AgBi 2 I 7 absorber have recently been reported. On the basis of X-ray diffraction (XRD) analysis and nominal composition, it was suggested that the synthesized films have a cubic ThZr 2 H 7 crystal structure with AgBi 2 I 7 stoichiometry. Through careful examination of the proposed structure and computational evaluation of the phase stability and bandgap, we find that the reported “AgBi 2 I 7 ” films cannot be forming with the ThZr 2 H 7 -type structure, but rather more likely adopt an Ag-deficient AgBiI 4 type. Both the experimental X-ray diffraction pattern and bandgap can be better explained by the AgBiI 4 structure. Additionally, the proposed AgBiI 4 structure, with octahedral bismuth coordination, removes unphysically short Bi–I bonding within the [BiI 8 ] hexahedra of the ThZr 2 I 7 model. Our results provide critical insights for assessing the photovoltaic properties of AgBi 2 I 7 iodobismuthate materials.