TY - JOUR
T1 - Effect of explicit cationic size and valence constraints on the phase stability of 1:2 B-site-ordered perovskite ruthenates
AU - Rijssenbeek, Job T.
AU - Saito, Takashi
AU - Malo, Sylvie
AU - Azuma, Masaki
AU - Takano, Mikio
AU - Poeppelmeier, Kenneth R.
PY - 2005/1/19
Y1 - 2005/1/19
N2 - The related parameters of cation size and valence that control the crystallization of Sr3CaRu2O9 into a 1:2 B-site-ordered perovskite structure were explored by cationic substitution at the strontium and calcium sites and by the application of high pressure. At ambient pressures, Sr3MRu2O9 stoichiometries yield multiphasic mixtures for M = Ni2+, Mg2+, and Y 3+, whereas pseudocubic perovskites result for M = Cu2+ and Zn2+. For A-site substitutions, an ordered perovskite structure results for Sr3-xCaxCaRu2O9, with 0 ≤ x ≤ 1.5. In contrast, Ba2+ substitution for Sr2+ is accompanied by a phase change to a hexagonal BaTiO3 structure type. At high pressures and temperatures, a 1:2 B-site-ordered perovskite structure is stabilized for Sr3-xBaxCaRu2O 9, with 0 ≤ x ≤ 3. The scarcity of B-site-ordered perovskite ruthenates at ambient pressure and the metastable nature of the high-pressure phases underscore the strict size and valence requirements that must be met by the constituent cations to achieve these uncommon ordered structures.
AB - The related parameters of cation size and valence that control the crystallization of Sr3CaRu2O9 into a 1:2 B-site-ordered perovskite structure were explored by cationic substitution at the strontium and calcium sites and by the application of high pressure. At ambient pressures, Sr3MRu2O9 stoichiometries yield multiphasic mixtures for M = Ni2+, Mg2+, and Y 3+, whereas pseudocubic perovskites result for M = Cu2+ and Zn2+. For A-site substitutions, an ordered perovskite structure results for Sr3-xCaxCaRu2O9, with 0 ≤ x ≤ 1.5. In contrast, Ba2+ substitution for Sr2+ is accompanied by a phase change to a hexagonal BaTiO3 structure type. At high pressures and temperatures, a 1:2 B-site-ordered perovskite structure is stabilized for Sr3-xBaxCaRu2O 9, with 0 ≤ x ≤ 3. The scarcity of B-site-ordered perovskite ruthenates at ambient pressure and the metastable nature of the high-pressure phases underscore the strict size and valence requirements that must be met by the constituent cations to achieve these uncommon ordered structures.
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U2 - 10.1021/ja044797w
DO - 10.1021/ja044797w
M3 - Article
C2 - 15643892
AN - SCOPUS:12944319337
VL - 127
SP - 675
EP - 681
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 2
ER -