Computational prediction and experimental confirmation of rhombohedral structures in Bi1.5CdM1.5O7 (M = Nb, Ta) pyrochlores

Abstract

In this study, computationally predicted band gaps and structures using density functional theory (DFT) in Bi1.5CdM1.5O7 (M = Nb, Ta) pyrochlores are confirmed by experimental data on synthesized samples. Ordered Cd substitutions in the B-site of the pyrochlore structures are required to achieve electronic band gaps in the calculated energy band structures, when using full plane waves for DFT calculations, which are supported by a significantly lower total enthalpy. The computationally predicted band gap values are closely matched to experimental band gaps estimated from optical absorption spectra in the UV-Vis. In addition to the prediction of electronic structures, the models also indicate that the large ionic radius of the Cd-cation leads to symmetry modification from the archetypal cubic pyrochlore structure in Bi1.5CdM1.5O7 (M = Nb, Ta). A rhombohedral structure and localized superlattice order are confirmed using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. Energy dispersive X-ray spectroscopy profiles across the superlattice domain interfaces, which are constant within experimental uncertainty, indicate that domain formation is not compositionally driven but likely a mechanism to alleviate strain build up. Raman and FTIR spectroscopy analyses on these two compounds display strong similarities suggesting that peaks and activities belong to the same structure type.