title: Octahedral tilt twinning and compositional modulation in NaLaMgWO(6).
abstract: A combination of selected-area electron diffraction (SAED), neutron powder diffraction (NPD) and high-resolution transmission electron microscopy (HRTEM) reveals a complex superstructure in the ordered perovskite NaLaMgWO(6). Through indexing of SAED patterns the unit-cell dimensions are found to be 46.8 x 7.8 x 7.9 A, which corresponds to a 12a(p) x 2a(p) x 2a(p) superstructure of the simple Pm3m perovskite unit cell. HRTEM images reveal the formation of an unmistakable stripe contrast that repeats with the same periodicity. Doubling of the b and c axes is brought about by a combination of layered ordering of Na and La, rock-salt ordering of Mg and W, and octahedral tilting. The a axis repeat distance results from a one-dimensional twinning of the octahedral tilts in combination with a compositional modulation. Modeling of the NPD pattern shows that the underlying tilt system is a(-)a(-)c(0) with tilt angles of approximately 8 degrees about the a and b axes. The octahedral tilt-twin boundaries run perpendicular to the a axis and are separated by 6a(p). Simulated HRTEM images show that octahedral tilt twinning alone cannot explain the stripes seen in the HRTEM images, rather a compositional modulation involving the A-site cations is necessary to explain the experimental images.
authors.affiliation: The Department of Chemistry, The Ohio State University, 100 West 18th Ave, Columbus, OH 43210, USA. gking@chemistry.ohio-state.edu
authors.forename: Graham
authors.initials: G
authors.lastname: King
authors.forename: Susana
authors.initials: S
authors.lastname: Garcia-Martin
authors.forename: Patrick M
authors.initials: PM
authors.lastname: Woodward