Synthesis and magnetic properties of the chromium-doped iron sulfide Fe1-xCrxS single crystalline nanoplates with a NiAs crystal structure.

Single crystalline iron sulfide nanoparticles doped with chromium Fe1-xCrxS (0 ≤x≤ 0.15) have been successfully prepared by a thermal decomposition method. The particles are self-organized into the single crystalline plates with the accurate hexagonal shape and dimensions up to 1 µ in plane and about 30-40 nm in thickness. The samples have the NiAs-type crystal structure (P63/mmc) at all Cr concentrations up to x = 0.15. Fe(57)-Mössbauer spectroscopy data reveal four nonequivalent iron sites in these nanocrystals related to the different number of cation vacancies in neighboring of the iron atoms. A 2C-type superstructure or a mixture of 2C and 3C superstructures of vacancy ordering can appear in these samples. It was established that in the Fe1-xCrxS series chromium prefers to replace iron in the cation layers containing vacancies at 0.00 < x < 0.10 and Cr atoms occupy both iron and vacant sites at x > 0.10. The specific magnetic properties, which can be tuned by chromium doping, enable potential applications of these nanoparticles in technical devices using the material with thermally activated magnetic memory, for example, switches or storages.

In situ synthesis and characterization of magnetic nanoparticles in shells of biodegradable polyelectrolyte microcapsules.

Hollow microcapsules with the shell composed of biodegradable polyelectrolytes modified with the maghemite nanoparticles were fabricated by in situ synthesis. The nanoparticles were synthesized from the iron salt and the base directly on the capsule shells prepared by "layer by layer" technique. An average diameter of the capsule was about 6.7 µm while the average thickness of the capsule shell was 0.9 µm. XRD, HRTEM, Raman and Mössbauer spectroscopy data revealed that the iron oxide nanoparticles have the crystal structure of maghemite γ-Fe2O3. The nanoparticles were highly monodisperse with medium size of 7.5 nm. The Mössbauer spectroscopy data revealed that the nanoparticles have marked superparamagnetic behavior which was retained up to room temperature due to slow spin relaxation. Because of that, the microcapsules can be handled by an external magnetic field. Both these properties are important for target drug delivery. Based on the Mössbauer spectroscopy data, the spin blocking temperatures TB of about 90K was found for the particles with size D≤5 nm and TB≈250 K for particles with D≥6 nm. The anisotropy constants K were determined using the superparamagnetic approximation and in the low temperature approximation of collective magnetic excitation.

Structural, magnetic, and electronic properties of iron selenide Fe6-7Se8 nanoparticles obtained by thermal decomposition in high-temperature organic solvents.

Iron selenide nanoparticles with the NiAs-like crystal structure were synthesized by thermal decomposition of iron chloride and selenium powder in a high-temperature organic solvent. Depending on the time of the compound processing at 340 °C, the nanocrystals with monoclinic (M)-Fe3Se4 or hexagonal (H)-Fe7Se8 structures as well as a mixture of these two phases can be obtained. The magnetic behavior of the monoclinic and hexagonal phases is very different. The applied-field and temperature dependences of magnetization reveal a complicated transformation between ferrimagnetic (FRM) and antiferromagnetic (AFM) structures, which can be related to the spin rotation process connected with the redistribution of cation vacancies. From XRD and Mössbauer data, the 3c type superstructure of vacancy ordering was found in the hexagonal Fe7Se8. Redistribution of vacancies in Fe7Se8 from random to ordered leads to the transformation of the magnetic structure from FRM to AFM. The Mössbauer data indicate that vacancies in the monoclinic Fe3Se4 prefer to appear near the Fe(3+) ions and stimulate the magnetic transition with the rotation of the Fe(3+) magnetic moments. Unusually high coercive force Hc was found in both (H) and (M) nanocrystals with the highest ("giant") value of about 25 kOe in monoclinic Fe3Se4. This is explained by the strong surface magnetic anisotropy which is essentially larger than the core anisotropy. Such a large coercivity is rare for materials without rare earth or noble metal elements, and the Fe3Se4-based compounds can be the low-cost, nontoxic alternative materials for advanced magnets. In addition, an unusual effect of "switching" of magnetization in a field of 10 kOe was found in the Fe3Se4 nanoparticles below 280 K, which can be important for applications.