Ferromagnetic Order from p-Electrons in Rubidium Oxide

Syarif Riyadi, Shivakumara Giriyapura, Robert A. de Groot, Antonio Caretta, Paul H. M. van Loosdrecht, Thomas T. M. Palstra, Graeme R. Blake*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

Magnetic dioxygen molecules can be used as building blocks of model systems to investigate spin-polarization that arises from unpaired p-electrons, the scientific potential of which is evidenced by phenomena such as spin-polarized transport in graphene. In solid elemental oxygen and all of the known ionic salts comprised of magnetic dioxygen anions and alkali metal cations, the dominant magnetic interactions are antiferromagnetic. We have induced novel ferromagnetic interactions by introducing oxygen deficiency in rubidium superoxide (RbO(2)). The anion vacancies in the resulting phase with composition RbO(1.72) provide greater structural flexibility compared to RbO(2) and facilitate a Jahn-Teller-driven order-disorder transition involving the anion orientations at similar to 230 K, below which their axes become confined to a plane. This reorganization gives rise to short-range ferromagnetic ordering below similar to 50 K. A ferromagnetic cluster-glass state then forms below similar to 20 K, embedded in an antiferromagnetic matrix that orders at similar to 5 K. We attribute this inhomogeneous magnetic order to either subtly different anion geometries within different structural nanodomains or to the presence of clusters in which double exchange takes place between the anions, which are mixed-valence in nature. We thus demonstrate that nonstoichiometry can be employed as a new route to induce ferromagnetism in alkali metal oxides.

Original languageEnglish
Pages (from-to)1578-1586
Number of pages9
JournalChemistry of Materials
Volume23
Issue number6
DOIs
Publication statusPublished - 22-Mar-2011

Keywords

  • ferromagnetism
  • p-electrons
  • superoxide
  • Jahn-Teller
  • cluster glass
  • NONMONOTONIC FIELD-DEPENDENCE
  • MAGNETIC NANOPARTICLES
  • SUPEROXIDE COMPOUNDS
  • PHASE-TRANSITIONS
  • OPEN QUESTIONS
  • O-2 MOLECULES
  • SOLID-STATE
  • SPIN
  • HYPEROXIDES
  • TEMPERATURE

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