The Pb(2)Fe(2)O(5) compound with a layered intergrowth structure has been prepared by a solid-state reaction at 700 °C. The incommensurate compound crystallizes in a tetragonal system with a = 3.9037(2) Å, c = 3.9996(4) Å, and q = 0.1186(4)c*, or when treated as a commensurate approximant, a = 3.9047(2) Å, c = 36.000(3) Å, space group I4/mmm. The crystal structure of Pb(2)Fe(2)O(5) was resolved from transmission electron microscopy data. Atomic coordinates and occupancies of the cation positions were estimated from high-angle annular dark-field scanning transmission electron microscopy data. Direct visualization of the positions of the oxygen atoms was possible using annular bright-field scanning transmission electron microscopy. The structure can be represented as an intergrowth of perovskite blocks and partially disordered blocks with a structure similar to that of the Bi(2)O(2) blocks in Aurivillius-type phases. The A-cation positions at the border of the perovskite block and the cation positions in the Aurivillius-type blocks are jointly occupied by Pb(2+) and Fe(3+) cations, resulting in a layer sequence along the c axis: -PbO-FeO(2)-PbO-FeO(2)-Pb(7/8)Fe(1/8)-O(1-x)-Fe(5/8)Pb(3/8)-O(2)-Fe(5/8)Pb(3/8)-. Upon heating, the layered Pb(2)Fe(2)O(5) structure transforms into an anion-deficient perovskite modulated by periodically spaced crystallographic shear (CS) planes. Considering the layered Pb(2)Fe(2)O(5) structure as a parent matrix for the nucleation and growth of CS planes allows an explanation of the specific microstructure observed for the CS structures in the Pb-Fe-O system.
© 2011 American Chemical Society