Hidden chemical order in disordered Ba7Nb4MoO20 revealed by resonant X-ray diffraction and solid-state NMR

The chemical order and disorder of solids have a decisive influence on the material properties. There are numerous materials exhibiting chemical order/disorder of atoms with similar X-ray atomic scattering factors and similar neutron scattering lengths. It is difficult to investigate such order/disorder hidden in the data obtained from conventional diffraction methods. Herein, we quantitatively determined the Mo/Nb order in the high ion conductor Ba 7 Nb 4 MoO 20 by a technique combining resonant X-ray diffraction, solid-state nuclear magnetic resonance (NMR) and first-principle calculations. NMR provided direct evidence that Mo atoms occupy only the M 2 site near the intrinsically oxygen-deficient ion-conducting layer. Resonant X-ray diffraction determined the occupancy factors of Mo atoms at the M 2 and other sites to be 0.50 and 0.00, respectively. These findings provide a basis for the development of ion conductors. This combined technique would open a new avenue for in-depth investigation of the hidden chemical order/disorder in materials. Chemical order/disorder in materials can be difficult to determine for atoms with similar X-ray scattering factors and neutron scattering lengths. Here authors use resonant XRD and NMR to elucidate hidden Mo/Nb chemical order in disordered hexagonal perovskite Ba 7 Nb 4 MoO 20 , with Mo atoms found to be localized near the ion-conducting oxygen deficient layer.