Shearing mechanism in the Bi–Sr–Cu oxycarbonates: HREM study of a new collapsed phase Bi15Sr29Cu12(CO3)7O56

Abstract

A new oxycarbonate, Bi₁₅Sr₂₉Cu₁₂(CO₃)₇O₅₆, has been synthesized. It crystallizes in a monoclinic cell, a= 22.139(7)Å, b= 5.498(2)Å, c= 39.82(1)Å and β= 119.45(2)°, with the possible space groups A2/m, Am or A2. Its structure, determined by an HREM investigation, is derived from that of the single intergrowth (Bi₂Sr₂CuO₆)[Sr₂Cu(CO₃)O₂] by a shearing mechanism along the (010) plane, so that it can be described as an assembly of [2201]₁[S₂CC]₁ ribbons which are m= 7 CuO₆ octahedra wide and shifted by 12 Å with respect to each other. In fact, local substitutions exist such that the phase cannot be classified as a true shear structure, and for this reason it is referred to as ‘collapsed’. The detailed microstructural study allows other collapsed members (m= 8) oriented domains with chemical twins to be identified. New extended defects corresponding to the intergrowth of 2201-type ribbons in the oxycarbonate matrix along [001] and [01], are also observed. The correlation between the shearing mechanism in this structure and the amplitude of the modulation in the single intergrowth [2201]₁[S₂CC]₁ compounds is discussed.