Fingerprint of local disorder in long range ordered isometric pyrochlores

The detailed characterization of local order and disorder in isometric A₂B₂O₇ crystalline pyrochlores is of significant importance in view of their wide range and sensitive technological applications. Nevertheless, much remains to be understood concerning their atomic scale structures. Here we specifically pinpoint local order and disorder in four stoichiometric Ln₂Zr₂O₇ (Ln = La, Nd, Sm and Eu) pyrochlores using a combination of three standard easily available laboratory techniques: XRD, ¹⁷O solid-state MAS NMR and Raman spectroscopy. The evolution of the oxygen sub-lattice identifies specific features (extra ¹⁷O NMR signals and Raman bands) which undoubtedly reveal local oxygen order and disorder in these stoichiometric long range ordered crystalline pyrochlores. These results complete the understanding of the atomic scale in these stoichiometric pyrochlores necessitating the need for new microscopic structural models.