Cation ordering in perovskites

  • King G
  • Woodward P
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Although both A- and B-site cations have the same simple cubic topology
in the perovskite structure they typically adopt different patterns
of chemical order. As a general rule B-site cations order more readily
than A- site cations. When cation ordering does occur, rock salt
ordering of B/B' cations is favored in A(2)BB'X-6 perovskites, whereas
layered ordering of A/A' cations is favored in AA'B2X6 and AA'BB'X-6
perovskites. The unexpected tendency for A- site cations to order
into layers stems from the bond strains that would result at the
anion site if A and A' cations of different size were to order with
a rock salt arrangement. The bonding instabilities that are created
by layered ordering are generally offset either by anion vacancies
or second order Jahn-Teller distortions of a B-site cation. Novel
types of A- site cation ordering can be stabilized by a(+)a(+)a(+)
or a(+)a(+)c(-) tilting of the octahedra.

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