The fine control of iron oxide nanocrystal sizes within the nanometre scale (diameters range from 2.5 to 14 nm) allows us to investigate accurately the size-dependence of their structural and magnetic properties. A study of the growth conditions of these nanocrystals obtained by thermal decomposition of an iron oleate precursor in high-boiling point solvents has been carried out. Both the type of solvent used and the ligand/precursor ratio have been systematically varied, and were found to be the key parameters to control the growth process. The lattice parameters of all the nanocrystals deduced from X-ray diffraction measurements are consistent with a structure of the type Fe3-xO4, i.e. intermediate between magnetite and maghemite, which evolves toward the maghemite structure for the smallest sizes (x=1/3). The evolution of the magnetic behavior with nanoparticle sizes emphasizes clearly the influence of the surface, especially on the saturation magnetization Ms and the magneto-crystalline anisotropy K. Dipolar interactions and thermal dependence have been also taken into account in the study on the nanoscale size-effect of magnetic properties.
The effect of surface inorganic-organic interactions on magnetic and structural properties of iron oxide magnetic nanoparticles functionalized by lipophilic stilbene molecules has been investigated. The molecules have been grafted through either phosphonate or carboxylate coupling agents. Mo ¨ssbauer spectra recorded at 300 and 77K suggest a global composition of Fe 2.82 O 4 for the two types of functionalization. Complementary in-field Mo ¨ssbauer and SQUID measurements have demonstrated that the nanoparticles consist in a magnetite core surrounded by an oxidized layer. The oxidized shell exhibits a spin canting in the carboxylate case leading to a decrease of the net magnetization of the oxide nanoparticle. No canting occurs in the phosphonate case, and the magnetic properties are therefore preserved. The magnetic properties thus depend on the coupling agent, e.g., surface interactions. This result is of primary importance to tune the magnetic properties of functionalized nanoparticles for biomedical and high density storage media applications.
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