RESUMO
The spatial spin modulated structure (SSMS) of the cycloid type present in bulk BiFeO3 prevents the linear magnetoelectric effect. One way to influence this structure is to reduce the crystal size to the nanoscale. Various opinions are circulating in the literature about the effect of nanocrystal size on SSMS, and to investigate this issue, we used a number of methods, with zero-field NMR (ZF NMR) spectroscopy at the forefront. ZF NMR spectroscopy enables the direct observation of the distribution profile of local fields on iron atoms and defines the SSMS presence and its properties. We also examined the synthesized samples using XRD, TEM, and magnetometry. We conclude that SSMS persists as the nanocrystal size decreases to the cycloid period and less, becoming more harmonic. This is accompanied by the change of the anisotropy type from an "easy axis" to an "easy plane". Magnetic measurements show a significant increase in the saturation magnetization, remanent magnetization, coercivity, and exchange bias of nanocrystals with sizes close to the cycloid period, which is probably associated with incomplete spin compensation in the case of an incomplete cycloid period. Despite the fact that SSMS is retained in the samples with decreased size, the magnetic properties experience a sharp increase up to applicable values.
RESUMO
The combustion method was used to prepare a precursor powder of an iron-gallium oxide compound which was further heat-treated in order to obtain a set of Fe1+xGa2-xO4 nanoparticles. All samples have a cubic spinel-type structure (space group Fd3[combining macron]m) and the particle size varies from 1.8 to 28.0 nm depending on the treatment conditions. From the comparative analysis by XRD, EDS, and Raman and Mössbauer spectroscopy the creation of a new spinel phase γ-FeGaO3, which was mainly located on the particle surface, was established. As a result, the composition consists of a FeGa2O4 core covered by a FeGaO3 shell. The relative content of FeGa2O4/FeGaO3 compounds in the composites can be varied by heat treatment. The maximum in the ZFC magnetization curves appeared in all samples at about 20-30 K corresponding to the spin-freezing temperature Tsg, which is much higher than in the bulk compound with a pure inverse spinel structure (Ga)[FeGa]O4. The values of effective Curie temperature ΘC for the Fe1+xGa2-xO4 nanoparticles are rather high and positive, indicating a ferromagnetic interaction between iron ions. The high values of the magnetic frustration parameter f = ΘC/Tsg (up to 7) indicate a high degree of magnetic frustration. The low temperature Mössbauer data reveal the magnetic ordering of Fe ions in all samples with the magnetic transition at about 20-26 K depending on the particle size. The specific features of the Mössbauer parameters indicate the properties of non-homogeneous magnetic systems with frustrated interactions specific to spin-glasses. The magnetic system behaves as a spin-glass below Tsg and it is superparamagnetic above Tsg. Such a system is called a "super-spin-glass". The anisotropy energy Eanis strongly depends on the content of Fe(2+) and Fe(3+) ions which contribute to the magnetocrystalline Ecryst and exchange Eex anisotropies, respectively. The anisotropy energy can be tuned by variation of the content of the (FeGaO3)-(FeGa2O4) phases in these complex composites.