The Fe-vacancy ordering patterns in the superconducting KxFe2-ySe2 and non-superconducting Kx(Fe,Co)2-ySe2 samples have been investigated by electron diffraction and high angle annular dark field scanning transmission electron microscopy. The Fe-vacancy ordering occurs in the ab plane of the parent ThCr2Si2-type structure, demonstrating two types of patterns. The superstructure I retains the tetragonal symmetry and can be described with the aI = bI = as{\surd}5 (as is the unit cell parameter of the parent ThCr2Si2-type structure) supercell and I4/m space group. The superstructure II reduces the symmetry to orthorhombic with the aII = as{\surd}2, bII = 2as{\surd}2 supercell and the Ibam space group. This type of superstructure is observed for the first time in KxFe2-ySe2. The Fe-vacancy ordering is inhomogeneous: the disordered areas interleave with the superstructures I and II in the same crystallite. The observed superstructures represent the compositionally-dependent uniform ordering patterns of two species (the Fe atoms and vacancies) on a square lattice. More complex uniform ordered configurations, including compositional stripes, can be predicted for different chemical compositions of the KxFe2-ySe2 (0 < y < 0.5) solid solutions.
Comment: This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials (copyright American Chemical Society) after peer review. To access the final edited and published work see Chem. Mater. 2011, 23, 4311-4316. 17 pages, 8 figures