Temperature-induced A–B intersite charge transfer in an A-site-ordered LaCu3Fe4O12 perovskite.
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| Title: | Temperature-induced A–B intersite charge transfer in an A-site-ordered LaCu |
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| Authors: | Long, Y. W., Hayashi, N., Saito, T., Azuma, M., Muranaka, S., Shimakawa, Y. |
| Source: | Nature. 3/5/2009, Vol. 458 Issue 7234, p60-63. 4p. 1 Diagram, 3 Graphs. |
| Subjects: | Letters to the editor, Charge transfer |
| Abstract: | Changes of valence states in transition-metal oxides often cause significant changes in their structural and physical properties. Chemical doping is the conventional way of modulating these valence states. In ABO3 perovskite and/or perovskite-like oxides, chemical doping at the A site can introduce holes or electrons at the B site, giving rise to exotic physical properties like high-transition-temperature superconductivity and colossal magnetoresistance. When valence-variable transition metals at two different atomic sites are involved simultaneously, we expect to be able to induce charge transfer—and, hence, valence changes—by using a small external stimulus rather than by introducing a doping element. Materials showing this type of charge transfer are very rare, however, and such externally induced valence changes have been observed only under extreme conditions like high pressure. Here we report unusual temperature-induced valence changes at the A and B sites in the A-site-ordered double perovskite LaCu3Fe4O12; the underlying intersite charge transfer is accompanied by considerable changes in the material’s structural, magnetic and transport properties. When cooled, the compound shows a first-order, reversible transition at 393 K from LaCu2+3Fe3.75+4O12 with Fe3.75+ ions at the B site to LaCu3+3Fe3+4O12 with rare Cu3+ ions at the A site. Intersite charge transfer between the A-site Cu and B-site Fe ions leads to paramagnetism-to-antiferromagnetism and metal-to-insulator isostructural phase transitions. What is more interesting in relation to technological applications is that this above-room-temperature transition is associated with a large negative thermal expansion. [ABSTRACT FROM AUTHOR] |
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| Database: | Psychology and Behavioral Sciences Collection |
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