P. Crespo

Giant magnetic anisotropy at the nanoscale: Overcoming the superparamagnetic limit

It has been observed for palladium and gold nanoparticles that the magnetic moment at a constant applied field does not change with temperature over the range comprised between 5 and 300 K. These samples, with sizes smaller than 2.5 nm, exhibit remanent magnetization up to room temperature. The existence of permanent magnetism up to so high temperatures has been explained as due to the blocking of a local magnetic moment by giant magnetic anisotropies. In this Brief Report we show, by analyzing the anisotropy of thiol capped gold films, that the orbital momentum induced at the surface conduction electrons is crucial to understand the observed giant anisotropy. The orbital motion is driven by a localized charge and/or spin through spin- orbit interaction, which reaches extremely high values at the surfaces. The induced orbital moment gives rise to an effective field of the order of 10(3) T that is responsible for the giant anisotropy.

Surface plasmon resonance and magnetism of thiol-capped gold nanoparticles

Surface plasmon resonance measurements and magnetic characterization studies have been carried out for two types of thiol-capped gold nanoparticles (NPs) with similar diameters between 2.0 and 2.5xa0nm and different organic molecules linked to the sulfur atom: dodecanethiol and tiopronin. In addition, Au NPs capped with tetraoctyl ammonium bromide have also been included in the investigation since such capping molecules weakly interact with the gold surface atoms and, therefore, this system can be used as a model for naked gold NPs; such particles presented a bimodal size distribution with diameters around 1.5 and 5xa0nm. The plasmon resonance is non-existent for tiopronin-capped NPs, whereas a trace of such a feature is observed for NPs covered with dodecanethiol molecules and a bulk-like feature is measured for NPs capped with tetralkyl ammonium salts. These differences would indicate that the modification of the surface electronic structure of the Au NPs depends on the geometry and self-assembling capabilities of the capping molecules and on the electric charge transferred between Au and S atoms. Regarding the magnetization, dodecanethiol-capped NPs have a ferromagnetic-like behaviour, while the NPs capped with tiopronin exhibit a paramagnetic behaviour and tetralkyl ammonium-protected NPs are diamagnetic across the studied temperature range; straight chains with a well-defined symmetry axis can induce orbital momentum on surface electrons close to the binding atoms. The orbital momentum not only contributes to the magnetization but also to the local anisotropy, giving rise to permanent magnetism. Due to the domain structure of the adsorbed molecules, orbital momentum is not induced for tiopronin-capped NPs and the charge transfer only induces a paramagnetic spin component.

sp magnetism in clusters of gold thiolates

Using first-principles calculations, we consider the bond between thiolate and small Au clusters, with particular emphasis on the resulting magnetic moment. The moment of pure gold clusters is 1µB for clusters with an odd number of Au atoms and zero for those with an even number. The addition of the thiolate, having an odd number of electrons itself, shifts the phase of the odd-even oscillations so that particles with an even number of Au atoms now have unit moment. Surprisingly, gold thiolate exhibits a dramatic and non- intuitive distribution of charge and spin moment. Our results show that the S-Au bond is such that sulfur does not get charge and an electron is transferred to the Au cluster. This extra electron is mainly sp in character and resides in an electronic shell below the Au surface. The calculations suggest that any thiolate- induced magnetism occurs in the gold nanoparticle and not the thiolate, and can be controlled by modifying the thiolate coverage.

Magnetometry and electron paramagnetic resonance studies of phosphine- and thiol-capped gold nanoparticles

In the last years, the number of studies performed by wholly independent research groups that confirm the permanent magnetism, first observed in our research lab, for thiol-capped Au nanoparticles (NPs) has rapidly increased. Throughout the years, the initial magnetometry studies have been completed with element-specific magnetization measurements based on, for example, the x-ray magnetic circular dichroism technique that have allowed the identification of gold as the magnetic moment carrier. In the research work here presented, we have focused our efforts in the evaluation of the magnetic behavior and iron impurities content in the synthesized samples by means of superconducting quantum interference device magnetometry and electron paramagnetic resonance spectrometry, respectively. As a result, hysteresis cycles typical of a ferromagnetic material have been measured from nominally iron-free gold NPs protected with thiol, phosphine, and chlorine ligands. It is also observed that for samples containing bot...

Metallic Magnetic Nanoparticles

In this paper, we reviewed some relevant aspects of the magnetic properties of metallic nanoparticles with small size (below 4 nm), covering the size effects in nanoparticles of magnetic materials, as well as the appearance of magnetism at the nanoscale in materials that are nonferromagnetic in bulk. These results are distributed along the text that has been organized around three important items: fundamental magnetic properties, different fabrication procedures, and characterization techniques. A general introduction and some experimental results recently obtained in Pd and Au nanoparticles have also been included. Finally, the more promising applications of magnetic nanoparticles in biomedicine are indicated. Special care was taken to complete the literature available on the subject.

Influence of the Capping Molecule on the Magnetic Behavior of Thiol-Capped Gold Nanoparticles

Gold nanoparticles with an average particle size below 3 nm have been synthesized and stabilized with different thiol-derivatized molecules for studying the influence of the capping molecule on the magnetic behavior. Thiolated-alkane chains with different lengths as well as a thiol-containing biomolecule (tiopronin) have been selected as protecting shells for the synthesized NPs. Magnetic characterization indicates that the appearance of a ferromagnetic-like behavior is related not only with the formation of Au-S bonds linking the protective molecules to the nanoparticle surface but also with the formation of the nanoparticle itself as well as with the geometry of the capping molecule. The later seems to determine whether the protective monolayer shell is ordered or not. The simultaneous presence of Au-Au and Au-S bonds together with a reduced particle diameter, and the formation of an ordered monolayer protective shell, have been proved to be key parameters for the ferromagnetic-like behavior exhibited by thiol-functionalized gold NPs.

MAGNETIC PROPERTIES OF ORGANIC COATED GOLD SURFACES

We review here our recent results of experimental observation of room temperature magnetism in gold nanoparticles (NPs) and thin films. Capping gold surfaces with certain organic molecules leads to the appearance of magnetism at room temperature. The surface bonds between the organic molecules and Au atoms give rise to magnetic moments. These magnetic moments are blocked along the bond direction showing huge anisotropy. In the case of atomically flat surfaces, the magnetic moments are giants. An explanation of this orbital ferromagnetism is given. These results point out the possibility to observe magnetism at nanoscale in materials without typical magnetic atoms (transition metals and rare earths), and are of fundamental value to understand the magnetic properties of surfaces.

On the stability of AuFe alloy nanoparticles

AuFe nanoparticles with mean diameters d p xa0=xa013.2 nm have been prepared by inert-gas condensation. Conventional and high-resolution transmission electron microscopy and energy-dispersive x-ray spectroscopy investigations show that the particles are mostly icosahedra. Scanning transmission electron microscopy-energy-dispersive x-ray spectroscopy and scanning transmission electron microscopy-electron energy-loss spectroscopy show that the as-grown particles exhibit a core-shell structure. The shell is mainly composed of an amorphous FeO layer. Although Fe and Au are immiscible in the bulk, the particle cores are found to be homogeneously mixed at the atomic level with a local composition of around Au84Fe16 (at.%). AuFe nanoparticles exhibit a complex magnetic structure in which the core behaves as a spin glass with a freezing temperature of 35 K, whereas the amorphous FeO shell behaves as a ferro-ferrimagnetic system. On annealing above 300 °C, the AuFe icosahedra phases separate into their elemental constituents. Hence the as-grown AuFe icosahedra are metastable, thereby implying that the bulk phase diagram also applies for nanoscopic materials.

Giant diamagnetism of gold nanorods

The presence of giant diamagnetism in Au nanorods, NRs, is shown to be a possible consequence of field induced currents in the surface electrons. The distance, Δ, between quantum surface energy levels has been calculated as a function of the NRs radius. Note that those electrons occupying states for which Δ>kBT are steadily orbiting with constant orbital moment. The diamagnetic response induced when a field is turned on remains constant during the time the field is acting. As the NRs radius increases, Δ decreases and accordingly the electron fraction available to generate constant currents decreases, consequently the surface diamagnetic susceptibility decreases towards its bulk value. The surface electronic motion induced by the axial applied field on electrons confined into a cylindrical surface accounts with extremely good quantitative agreement for the giant diamagnetism recently measured and reported.