Amílcar Labarta

Finite-size effects in fine particles: magnetic and transport properties

Some of the most relevant finite-size and surface effects in the magnetic and transport properties of magnetic fine particles and granular solids are reviewed. The stability of the particle magnetization, superparamagnetic regime and the magnetic relaxation are discussed. New phenomena appearing due to interparticle interactions, such as the collective state and non-equilibrium dynamics, are presented. Surface anisotropy and disorder, spin-wave excitations, as well as the enhancements of the coercive field and particle magnetization are also reviewed. The competition of surface and finite-size effects to settle the magnetic behaviour is addressed. Finally, two of the most relevant phenomena in the transport properties of granular solids are summarized namely, giant magnetoresistance in granular heterogeneous alloys and Coulomb gap in insulating granular solids.

Finite-size and surface effects in maghemite nanoparticles: Monte Carlo simulations

Finite-size and surface effects in fine particle systems are investigated by Monte Carlo simulation of a model of a

Controlled Synthesis of Iron Oxide Nanoparticles over a Wide Size Range

\ensuremath{\gamma}\ensuremath{-}{\mathrm{Fe}}_{2}{\mathrm{O}}_{3}

Magnetic frustration and lattice dimensionality in SrCr8Ga4O19

(maghemite) single particle. Periodic boundary conditions for a large enough system have been used to simulate the bulk properties and the results compared with those for a spherical shaped particle with free boundaries to evidence the role played by the surface on the anomalous magnetic properties displayed by these systems at low temperatures. Several outcomes of the model are in qualitative agreement with the experimental findings. A reduction of the magnetic ordering temperature, spontaneous magnetization, and coercive field is observed as the particle size is decreased. Moreover, the hysteresis loops become elongated with high values of the differential susceptibility, resembling those from frustrated or disordered systems. These facts are a consequence of the formation of a surface layer with higher degree of magnetic disorder than the core, which, for small sizes, dominates the magnetization processes of the particle. However, in contradiction with the assumptions of some authors, our model does not predict the freezing of the surface layer into a spin-glass-like state. The results indicate that magnetic disorder at the surface simply facilitates the thermal demagnetization of the particle at zero field, while the magnetization is increased at moderate fields, since surface disorder diminishes ferrimagnetic correlations within the particle. The change in shape of the hysteresis loops with the particle size demonstrates that the reversal mode is strongly influenced by the reduced atomic coordination and disorder at the surface.

Role of surface disorder on the magnetic properties and hysteresis of nanoparticles

We report on the effect of using decanoic acid as capping ligand on the synthesis of iron oxide nanoparticles by thermal decomposition of an organic iron precursor in organic medium. This procedure allowed us to control the particle size within 5 nm and about 30 nm by modifying the precursor-to-capping ligand ratio in a systematic fashion and to further expand the particle size range up to about 50 nm by adjusting the final synthesis temperature. The nanoparticles also showed high saturation magnetization of about 80-83 emu/g at low temperature, almost size-independent and close to the value for the bulk counterpart. Decanoic acid-coated nanoparticles were transferred to water by using tetramethylammonium hydroxide, which allowed further coating with silica in a tetraethyl orthosilicate solution. Consequently, these iron oxide nanoparticles are tunable in size and highly magnetic, and they could become suitable candidates for various biomedical applications such as contrast agents for magnetic resonance imaging and magnetic carriers for drug delivery.

Magnetic domains and surface effects in hollow maghemite nanoparticles

Abstract DC magnetic susceptibility measurements of the magnetoplumbite-like compound SrCr 8 Ga 4 O 19 show that no magnetic phase transition occurs up to T=4.2K in spite of very high antiferromagnetic interactions making apparent a very high degree of magnetic frustration (O/Tg 117). The determination of a preferencial siblattice cation distribution by neutron diffraction allows us to interpret this effect as associated with an effective decrease of the lattice dimensionality.

Surfactant Organic Molecules Restore Magnetism in Metal-Oxide Nanoparticle Surfaces

We present the results of Monte Carlo simulations of a model of a single maghemite ferrimagnetic nanoparticle including radial surface anisotropy distinct from that in the core with the aim to clarify its role on the magnetization processes at low temperatures. The low-temperature equilibrium states are analysed and compared to those of a ferromagnetic particle with the same lattice structure. We have found that the formation of hedgehog-like structures due to increased surface anisotropy is responsible for a change in the reversal mechanism of the particles.

Microscopic origin of exchange bias in core/shell nanoparticles

In the present work, we investigate the magnetic properties of ferrimagnetic and non-interacting maghemite hollow nanoparticles obtained by the Kirkendall effect. From the experimental characterization of their magnetic behavior, we find that polycrystalline hollow maghemite nanoparticles exhibit low blocked-to-superparamagnetic transition temperatures, small magnetic moments, significant coercivities and irreversibility fields, and no magnetic saturation on external magnetic fields up to 5 T. These results are interpreted in terms of the microstructural parameters characterizing the maghemite shells by means of atomistic Monte Carlo simulations of an individual spherical shell. The model comprises strongly interacting crystallographic domains arranged in a spherical shell with random orientations and anisotropy axis. The Monte Carlo simulation allows discernment between the influence of the polycrystalline structure and its hollow geometry, while revealing the magnetic domain arranggement in the different temperataure regimes.

A high-sensitivity differential scanning calorimeter with magnetic field for magnetostructural transitions

The properties of magnetic nanoparticles tend to be depressed by the unavoidable presence of a magnetically inactive surface layer. However, outstanding magnetic properties with a room-temperature magnetization near the bulk value can be produced by high-temperature synthesis methods involving capping with organic acid. The capping molecules are not magnetic, so the origin of the enhanced magnetization remains elusive. In this work, we present a real-space characterization on the subnanometer scale of the magnetic, chemical, and structural properties of iron-oxide nanoparticles via aberration-corrected scanning transmission electron microscopy. For the first time, electron magnetic chiral dichroism is used to map the magnetization of nanoparticles in real space with subnanometer spatial resolution. We find that the surface of the nanoparticles is magnetically ordered. Combining the results with density functional calculations, we establish how magnetization is restored in the surface layer. The bonding with the acids O atoms results in O-Fe atomic configuration and distances close to bulk values. We conclude that the nature and number of molecules in the capping layer is an essential ingredient in the fabrication of nanoparticles with optimal magnetic properties.

Liver and brain imaging through dimercaptosuccinic acid-coated iron oxide nanoparticles

We report the results of Monte Carlo simulations with the aim to clarify the microscopic origin of exchange bias in the magnetization hysteresis loops of a model of individual core/shell nanoparticles. Increase of the exchange coupling across the core/shell interface leads to an enhancement of exchange bias and to an increasing asymmetry between the two branches of the loops which is due to different reversal mechanisms. A detailed study of the magnetic order of the interfacial spins shows compelling evidence that the existence of a net magnetization due to uncompensated spins at the shell interface is responsible for both phenomena and allows to quantify the loop shifts directly in terms of microscopic parameters with striking agreement with the macroscopic observed values.