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The actual role of transition metals like iron in the room temperature ferromagnetism (RTFM) of Fe doped ZnO nanoparticles is still an unsolved problem. While some studies concluded that the Fe ions participate in the magnetic interaction, others in contrast do not believe Fe to play a direct role in the magnetic exchange interaction. To contribute to the understanding of this issue, we have carefully investigated the structural, optical, vibrational and magnetic properties of sol-gel synthesized Zn1-xFexO (0 < x < 0.10) nanoparticles. No Fe(2+) was detected in any sample. We found that high spin Fe(3+) ions are substitutionally incorporated at the Zn(2+) in the tetrahedral-core sites and in pseudo-octahedral surface sites in ZnO. Superficial OH(-) was observed in all samples. For x ≤ 0.03, an increment in Fe doping concentration decreased a and c lattice parameters, average Zn-O bond length, average crystallite size and band gap; while it increased the degree of distortion and quadrupole splitting. Undoped ZnO nanoparticles exhibited very weak RTFM with a saturation magnetization (Ms) of ∼0.47 memu g(-1) and this value increased to ∼2.1 memu g(-1) for Zn0.99Fe0.01O. Very interestingly, the Ms for Zn0.99Fe0.01O and Zn0.97Fe0.03O increased by a factor of about ∼2.3 by increasing annealing for 1 h to 3 h. For x ≥ 0.05, ferrimagnetic disordered spinel ZnFe2O4 was formed and this phase was found to become more ordered with increasing annealing time. Fe does not contribute directly to the RTFM, but its presence promoted the formation of additional single charged oxygen vacancies, zinc vacancies, and more oxygen-ended polar terminations at the nanoparticle surface. These defects, which are mainly superficial, altered the electronic structure and are considered as the main sources of the observed ferromagnetism.

We report unusual observations in the magnetic behavior of Sn 1−x 57 Fe x O 2−␦ powders prepared by a sol-gel method. Mössbauer spectra showed three different sites for those irons in the SnO 2 lattice. The samples seem to exhibit many sources of ferromagnetism, and the dominance of one of them greatly depends upon the synthesis conditions. In one sample, prepared using citric acid solution of metal Fe and annealed at 500°C for two hours, we observed magnetization, but its room temperature Mössbauer spectrum did not show any magnetic component, suggesting that the ferromagnetism could not have originated from the iron ions but from magnetic defects. In another sample prepared from chloride acid solution of Fe 2 O 3 and annealed at 600°C for six hours, a large magnetization and a sextet with broad lines were observed and the ferromagnetism was ascribed to iron impurities. In another sample prepared from citric acid solution of metal Fe but annealed at 650°C for two hours, we observed an intensive magnetic sextet with sharp lines but small magnetization, suggesting the presence of hematite doped with tin.

In spite of the various theoretical and experimental efforts performed to understand the origin of ferromagnetism in Fe and Co codoped ZnO, there are still serious controversies in the reported data. While theoretical studies predicted the relative spin alignment and location of Co2+ and Fe2+ as the main source of magnetism, experimental studies have reported Co2+and superficial Fe3+. In this work, we performed a careful experimental study on Zn1–2xFexCoxO (x = 0, 0.01, 0.03, and 0.05) nanoparticles prepared by a sol–gel method and have found new interesting results. We detected only Fe3+ ions located in tetrahedral-core and pseudo-octahedral-surface sites. The Co ions displayed 2+ and 3+ oxidation states, with Co2+ ions in high spin state located mostly in the tetrahedral-core sites, while Co3+ in low spin states located presumably in pseudo-octahedral-surface sites. We detected isolated Fe3+ ions and weakly ferromagnetic coupled Co2+ ions. The most important finding is that the saturation magnetization (Ms) did not depend on the magnetic interactions involving the high spin Co2+or Fe3+; but Ms and Co3+ concentration increased systematically with x, indicating that multivalent ionic states may be playing a crucial role in the observed ferromagnetism

The Mössbauer spectra of akaganeite have always been interpreted considering both the tetragonal structure and the chlorine content. However, very recently it has been suggested that the crystallographic structure is not tetragonal but monoclinic, thus another interpretation for the Mössbauer spectra is required. For this purpose, we have prepared and characterized by several techniques synthetic akaganeite. Our results suggest that the two crystallographic sites required by the monoclinic symmetry are not distinguishable in the paramagnetic state as previously assumed, but they are only discernible in the low temperature magnetic region. At room temperature the spectrum is fitted with two doublets whose origin is related to the chlorine content, i.e. one Fe site assigned to Fe 3+ ions located close to chloride ions and the other Fe site to those located close to chloride vacancy sites. The low temperature spectra can be adequately fitted with four sextets, whose hyperfine parameters must be subjected to some constraints. The origin of these components is related to the two different crystallographic sites and to the chlorine content. In-field Mössbauer spectrometry at low temperature suggests that the magnetic structure behaves as a system which consists of two asperimagnetic-like structures antiferromagnetically coupled, and not as a collinear antiferromagnet as usually assumed.

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S U M M A R YIn this work, the magnetic properties of four non-stoichiometric goethites with varying total water content and surface area have been investigated. The samples were prepared using two different hydrothermal methods, deriving either from Fe(II) precursors or from Fe(III) precursors. The effects of both agitation during mixing solutions and drying time during synthesis upon the physical properties of the final products were also studied. The samples were characterized by XRD, TGA, BET, 57 Fe Mössbauer spectrometry at 300 K, 77 K and 4.2 K, ZFC and FC curves, and magnetization curves. The goethites synthesized from the Fe(II) precursors result less crystalline, contain higher water content than those prepared from the Fe(III) precursor. In addition, ferrous precursor goethites exhibit superparamagnetic relaxation effects, while the ferric precursor goethites exhibit magnetic ordering of clusters. It is found that the stirring process during synthesis can affect the total water content and the magnetic behaviour of the goethites. Our results suggest that structural water content decreases the magnetic hyperfine field at 4.2 K. The adsorbed water content also affects this parameter as suggested by in situ annealing cycles of the goethites in a Mössbauer cryofurnace. Finally, we propose an unique 2-D phase diagram to describe all the magnetic properties of present goethites observed as a function of temperature, surface area (or particle size) and total water content.

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