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Materials like iron, nickel, and cobalt consist of magnetic domains, within which the magnetic dipoles are arranged parallel to each other. The magnetic dipoles are rigidly aligned in the same direction within a domain by quantum mechanical coupling among the atoms. This coupling is so strong that even thermal agitation at room temperature cannot break it. The result is that each domain has a net dipole moment. However, some materials have weaker coupling, and are ferromagnetic at lower...
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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Fabrication of Spatially Confined Complex Oxides
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CaFeFeNbO6 - an iron-based double double perovskite.

K Ji1, J R Bedward1, Q Li1

  • 1Centre for Science at Extreme Conditions (CSEC) and School of Chemistry, The University of Edinburgh, EH9 3FD, UK. j.p.attfield@ed.ac.uk.

Chemical Communications (Cambridge, England)
|May 5, 2023
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Summary

The first Fe-based double perovskite, CaFeFeNbO6, exhibits spin glass magnetism due to cation disorder. Higher synthesis pressures are needed to create new ordered double perovskites with smaller A cations.

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Magnetism

Background:

  • Cation ordering in ABO3 perovskites influences material properties.
  • AA'BB'O6 double perovskites offer tunable electronic and magnetic characteristics.
  • Fe-based double perovskites are underexplored compared to other transition metals.

Purpose of the Study:

  • To synthesize and characterize the first Fe-based AA'BB'O6 double perovskite, CaFeFeNbO6.
  • To investigate the impact of cation disorder on magnetic properties.
  • To explore synthesis conditions for future double double perovskites.

Main Methods:

  • High-pressure synthesis techniques.
  • X-ray diffraction for structural analysis.
  • Magnetic susceptibility measurements to probe magnetic ordering.

Main Results:

  • CaFeFeNbO6 was successfully synthesized as an ordered double double perovskite.
  • Significant antisite disorder (37%) was observed between Fe3+ and Nb5+ cations.
  • Spin glassy magnetism was detected below a freezing transition at 12 K.
  • The CaMnFeNbO6 analogue also displayed cation disorder and spin glass behavior.

Conclusions:

  • Cation disorder significantly impacts magnetic properties in Fe-based double perovskites.
  • Achieving high cation order in related materials may require pressures of 14-18 GPa.
  • This work paves the way for discovering new double double perovskites with tailored magnetic functionalities.