Magnetic, structural, and electronic properties of iron sulfide Fe3S4 nanoparticles synthesized by the polyol mediated process

  • I. S. Lyubutin
  • S. S. Starchikov
  • Chun-Rong Lin
  • Shin-Zong Lu
  • Muhammad Omar Shaikh
  • K. O. Funtov
  • T. V. Dmitrieva
  • S. G. Ovchinnikov
  • I. S. Edelman
  • R. Ivantsov
Research Paper

Abstract

Iron sulfide nanoparticles Fe3S4 with the spinel-type crystal structure were synthesized by the polyol mediated process. The particle size depends on preparation conditions and varies from 9 to 20 nm. Mössbauer data have revealed that the dominating fraction of iron ions in the 9-nm sample is in the high-spin ferric state. This implies an occurrence of the cation vacancies in nonstoichiometric greigite. The stoichiometric phase of greigite Fe3S4 dominates in the 18-nm-size nanoparticles. Magnetic measurements have shown a ferrimagnetic behavior of all samples at temperatures between 78 and 300 K. The estimated value of magnetic moment of the stoichiometric greigite nanoparticles is about 3.5 μB per Fe3S4 unit. The Mössbauer spectra indicate a superparamagnetic behavior of small particles, and some fraction of superparamagnetic phase is observed in all samples synthesized which may be caused by the particle size distribution. The blocking temperatures of T B ≈ 230 and 250 K are estimated for the 9 and 14 nm particles, respectively. The Mössbauer parameters indicate a great degree of covalency in the Fe–S bonds and support the fast electron Fe3+ ⇆ Fe2+ exchange in the B-sites of greigite. An absence of the Verwey transition at temperatures between 90 and 295 K is established supporting a semimetal type of conductivity. The temperature and magnetic field dependences of the magnetic circular dichroism (MCD) of optical spectra were measured in Fe3S4 for the first time. The spectra differ substantially from that of the isostructural oxide Fe3O4. It is supposed that the MCD spectra of greigite nanoparticles result from the collective electron excitations in a wide band with superimposed peaks of the dd transitions in Fe ions.

Keywords

Iron sulfides Fe3S4 Magnetic and electronic properties Mössbauer spectroscopy Magnetic circular dichroism 

Notes

Acknowledgments

This work is supported by Russian Foundation for Basic Research (grant no. 11-02-92001) and the Russian Academy of Sciences under the Program “Nanotechnology and Nanomaterials” (grant no. 24-3.1). We also thank the National Science Council of Taiwan (NSC100-2923-M-218-001-MY3) for financial support.

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Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • I. S. Lyubutin
    • 1
  • S. S. Starchikov
    • 1
  • Chun-Rong Lin
    • 2
  • Shin-Zong Lu
    • 2
  • Muhammad Omar Shaikh
    • 2
  • K. O. Funtov
    • 1
  • T. V. Dmitrieva
    • 1
  • S. G. Ovchinnikov
    • 3
    • 4
  • I. S. Edelman
    • 3
  • R. Ivantsov
    • 3
  1. 1.Shubnikov Institute of CrystallographyRussian Academy of SciencesMoscowRussia
  2. 2.Department of Mechanical Engineering, Institute of NanotechnologySouthern Taiwan University of Science and TechnologyTainanTaiwan, Republic of China
  3. 3.Kirensky Institute of PhysicsSiberian Branch of Russian Academy of SciencesKrasnoyarskRussia
  4. 4.Institute of Engineering Physics and RadioelectronicsSiberian Federal UniversityKrasnoyarskRussia

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