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    Fe57 Mössbauer spectral and muon spin relaxation study of the magnetodynamics of monodispersed γ−Fe2O3 nanoparticles

    Leïla Rebbouh, Raphaël P. Hermann*, and Fernande Grandjean†

    Taeghwan Hyeon‡ and Kwangjin An

    Alex Amato§

    Gary J. Long∥

    • Department of Physics, University of Liège, B5, B-4000 Sart-Tilman, Belgium

    • National Creative Research Initiative Center for Oxide Nanocrystalline Materials and the School of Chemical and Biological Engineering, Seoul National University, Seoul 151-744, Korea

    • Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institut, CH-5232 Villigen, Switzerland

    • Department of Chemistry, University of Missouri–Rolla, Rolla, Missouri 65409-0010, USA

    • *Present address: Institut für Festkörperforschung, Forschungszentrum Jülich, Jülich GmbH, D-52425 Jülich, Germany.
    • †fgrandjean@ulg.ac.be
    • ‡thyeon@snu.ac.kr
    • §alex.amato@psi.ch
    • ∥glong@umr.edu

    Phys. Rev. B 76, 174422 – Published 13 November, 2007

    DOI: https://doi.org/10.1103/PhysRevB.76.174422

    Abstract

    The Mössbauer spectra of monodispersed iron oxide nanoparticles with diameters of 4, 7, 9, and 11nm have been measured between 4.2 and 315K and fitted within the formalism for stochastic fluctuations of the hyperfine Hamiltonian. In this model, the hyperfine field is assumed to relax between the six ±x, ±y, and ±z directions in space with a distribution of relaxation rates that is temperature dependent. Muon spin relaxation measurements have been carried out on the 9nm particles between 4.2 and 295K. Both techniques reveal three regimes in the magnetic dynamics of these nanoparticles. In the low-temperature regime, between 4.2 and ∼30K, the nanoparticle magnetic moments are blocked and a spin-glass-like state is observed with nearly static hyperfine fields, as is indicated by the well resolved magnetic Mössbauer spectra and the slow exponential decay of the muon asymmetry functions. In the high-temperature regime, above ∼125K, the nanoparticle magnetic moments and, hence, the hyperfine fields, relax rapidly and a typical thermally activated superparamagnetic behavior is observed, as is indicated by the Mössbauer doublet line shape and the muon asymmetry functions that are unquestionably characteristic of monodispersed nanoparticles. In the intermediate regime between ∼30 and 125K, the Mössbauer spectra are the superposition of broad sextets and doublets and the muon asymmetry functions have been fitted with a sum of two terms, one relaxing term similar to that observed at and above 125K and one term characteristic of static local fields. Hence, in this intermediate regime, the sample is magnetically inhomogeneous and composed of nanoparticles rapidly and slowly relaxing as a result of interparticle interactions. The magnetic anisotropy constants determined from both the Mössbauer spectral and magnetic susceptibility results decrease by a factor ∼4 with increasing diameter from 4to22nm and increase linearly with the percentage of iron(III) ions present at the surface of the nanoparticles. The interparticle interaction energy is estimated to be between 89 and 212K from the temperature dependence of the magnetic hyperfine field measured on the 9nm nanoparticles.

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