Influence of the Rare Earth Cation on the Magnetic Properties of Layered 12R-Ba4M4+Mn3O12 (M = Ce, Pr) Perovskites

Michael Dzara, Arthur Campello, Aeryn Breidenbach, Nicholas Strange, James Park, Andrea Ambrosini, Eric Coker, David Ginley, Young Lee, Robert Bell, Rebecca Smaha

Research output: Contribution to journalArticlepeer-review


Material design is increasingly used to realize desired functional properties, and the perovskite structure family is one of the richest and most diverse: perovskites are employed in many applications due to their structural flexibility and compositional diversity. Hexagonal, layered perovskite structures with chains of face-sharing transition metal oxide octahedra have attracted great interest as quantum materials due to their magnetic and electronic properties. Ba4MMn3O12, a member of the "12R" class of hexagonal, layered perovskites, contains trimers of face-sharing MnO6 octahedra that are linked by a corner-sharing, bridging MO6 octahedron. Here, we investigate cluster magnetism in the Mn3O12 trimers and the role of this bridging octahedron on the magnetic properties of two isostructural 12R materials by systematically changing the M4+ cation from nonmagnetic Ce4+ (f0) to magnetic Pr4+ (f1). We synthesized 12R-Ba4MMn3O12 (M= Ce, Pr) with high phase purity and characterized their low-temperature crystal structures and magnetic properties. Using substantially higher purity samples than previously reported, we confirm the frustrated antiferromagnetic ground state of 12R-Ba4PrMn3O12 below TN approximately 7.75 K and explore the cluster magnetism of its Mn3O12 trimers. Despite being atomically isostructural with 12R-Ba4CeMn3O12, the f1 electron associated with Pr4+ causes much more complex magnetic properties in 12R-Ba4PrMn3O12. In 12R-Ba4PrMn3O12, we observe a sharp, likely antiferromagnetic transition at T2 approximately 12.15 K and an additional transition at T1 approximately 200 K, likely in canted antiferromagnetic order. These results suggest that careful variation of composition within the family of hexagonal, layered perovskites can be used to tune material properties using the complex role of the Pr4+ ion in magnetism.
Original languageAmerican English
Pages (from-to)2810-2818
Number of pages9
JournalChemistry of Materials
Issue number6
StatePublished - 2024

NREL Publication Number

  • NREL/JA-5K00-87867


  • magnetism
  • perovskite
  • quantum material


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