Hafsa Khurshid

Surface spin disorder and exchange-bias in hollow maghemite nanoparticles

We report a comparative study of the magnetic properties of polycrystalline hollow γ-Fe2O3 nanoparticles with two distinctly different average sizes of 9.2 ± 1.1 nm and 18.7 ± 1.5 nm. High-resolution transmission electron microscopy images reveal the presence of a shell with thickness of 2 nm and 4.5 nm for the 9.2 nm and 18.7 nm nanoparticles, respectively. The field-cooled hysteresis loops show interesting features of enhanced coercivity and horizontal and vertical shifts associated with the polarity of the cooling field for both types of nanoparticles. While the anomalously large horizontal shifts and open hysteresis loop in a field as high as 9 T observed for the 9.2 nm nanoparticles corresponds to a “minor loop” of the hysteresis loop, the loop shift observed for the 18.7 nm nanoparticles manifests an intrinsic “exchange bias” (EB). Relative to the 18.5 ± 3.2 nm solid nanoparticles, a much stronger EB effect is achieved in the 18.7 nm hollow nanoparticles. Our studies point to the importance of inner...

Mechanism and controlled growth of shape and size variant core/shell FeO/Fe3O4 nanoparticles

We report a novel synthesis approach for the growth of core/shell FeO/Fe3O4 nanoparticles with controlled shape and size. FeO particles were partially oxidized to form core/shell FeO/Fe3O4 structures, as evidenced from transmission electron microscopy, X-ray diffraction, and magnetometry analysis. We find that the molar ratios and concentrations of surfactants are the key parameters in controlling the particle size. The particles can grow in either isotropic or anisotropic shapes, depending upon a chemical reaction scheme that is controlled kinetically or thermodynamically. The competitive growth rates of {111} and {100} facets can be used to tune the final shape of nanoparticles to spherical, cubic, octahedral, octopod, and cuboctahedral geometries. FeO particles can also be oxidized chemically or thermally to form Fe3O4 nanoparticles. By following the same synthesis technique, it is possible to synthesize rods and triangles of Fe3O4 by introducing twinnings and defects into the crystal structure of the seed. The thermally activated first-order Verwey transition at ~120 K has been observed in all the synthesized FeO/Fe3O4 nanoparticles, indicating its independence from the particle shape. These core/shell nanoparticles exhibit a strong shift in field-cooled hysteresis loops accompanied by an increase in coercivity (the so-called exchange bias effect), but the low field-switching behavior appears to vary with the particle shape.

Anisotropy effects in magnetic hyperthermia: A comparison between spherical and cubic exchange-coupled FeO/Fe3O4 nanoparticles

Spherical and cubic exchange-coupled FeO/Fe3O4 nanoparticles, with different FeO:Fe3O4 ratios, have been prepared by a thermal decomposition method to probe anisotropy effects on their heating efficiency. X-ray diffraction and transmission electron microscopy reveal that the nanoparticles are composed of FeO and Fe3O4 phases, with an average size of ∼20 nm. Magnetometry and transverse susceptibility measurements show that the effective anisotropy field is 1.5 times larger for the cubes than for the spheres, while the saturation magnetization is 1.5 times larger for the spheres than for the cubes. Hyperthermia experiments evidence higher values of the specific absorption rate (SAR) for the cubes as compared to the spheres (200 vs. 135 W/g at 600 Oe and 310 kHz). These observations point to an important fact that the saturation magnetization is not a sole factor in determining the SAR and the heating efficiency of the magnetic nanoparticles can be improved by tuning their effective anisotropy.

Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 nanoparticles.

Disorder among surface spins is a dominant factor in the magnetic response of magnetic nanoparticle systems.

Synthesis and magnetic properties of core/shell FeO/Fe3O4 nano-octopods

We report the synthesis and magnetic properties of core/shell FeO/Fe3O4 nanoparticles with an average size of 30 nm in a complex quasi-octopod shape. FeO nanoparticles were synthesized by a wet chemical synthesis route followed by partial oxidation to form core/shell structured FeO/Fe3O4 octopods. X-ray diffraction and transmission electron microscopy confirmed the presence of iron oxide phases and the formed core/shell FeO/Fe3O4 morphology. Magnetic measurements revealed two distinct temperatures corresponding to the thermally activated Verwey transition (TV ∼ 120 K) of the ferrimagnetic Fe3O4 shell and the Neel temperature (TN ∼ 230 K) of the antiferromagnetic FeO core. The nanoparticles exhibited a strong horizontal shift in the field-cooled hysteresis loop (the so-called exchange bias (EB) effect) accompanied by enhanced coercivity. The Meiklejohn-Bean model has been implemented to quantify the amount of frozen spins that locate at the interface between FeO and Fe3O4 and are responsible for the observ...

Asymmetric hysteresis loops and its dependence on magnetic anisotropy in exchange biased Co/CoO core-shell nanoparticles

pendent magnetic response of the core and shell. This gives us information about the instantaneous magnetic state of the core and shell as asymmetry develops. In addition, our transverse susceptibility (TS) measurements provide a direct estimate of the magnetic anisotropy and its evolution with temperature as asymmetry sets in. Our analysis can be extended to core-shell nanoparticles with different compositions and suggests that it may be possible to selectively choose the material constituting the shell to gain control over the onset of asymmetry in a desired temperature range. We believe that knowledge about the presence or the absence of asymmetry in hysteresis loops may be used to advantage while designing future applications based on exchange bias.

FeCo nanowires with enhanced heating powers and controllable dimensions for magnetic hyperthermia

A detailed study of the magnetic properties and heating capacities of electrodeposited FeCo nanowires with varying lengths (2–40 μm) and diameters (100 and 300 nm) is reported. We find that specific absorption rate (SAR) increases rapidly with increasing wire length up to 10 μm, followed by a gradual increase for larger lengths. Magnetic and hyperthermia measurements have revealed the important effect of dipolar interactions between the nanowires on their magnetic and inductive heating responses. Both calorimetric and AC magnetometry methods consistently show that the physical movement contribution of the nanowires to the SAR is small, and that for applied fields exceeding the coercive field, the nanowires tend to align parallel to the field, thus enhancing the SAR. Maximum SAR values of ∼1500 W/g have been achieved for the largest wires at H = 300 Oe and f = 310 kHz.

Enhanced magnetism in highly ordered magnetite nanoparticle-filled nanohole arrays.

A new approach to develop highly ordered magnetite (Fe3O4) nanoparticle-patterned nanohole arrays with desirable magnetic properties for a variety of technological applications is presented. In this work, the sub-100 nm nanohole arrays are successfully fabricated from a pre-ceramic polymer mold using spin-on nanoprinting (SNAP). These nanoholes a then filled with monodispersed, spherical Fe3O4 nanoparticles of about 10 nm diameter using a novel magnetic drag and drop procedure. The nanohole arrays filled with magnetic nanoparticles a imaged using magnetic force microscopy (MFM). Magnetometry and MFM measurements reveal room temperature ferromagnetism in the Fe3O4-filled nanohole arrays, while the as-synthesized Fe3O4 nanoparticles exhibit superparamagnetic behavior. As revealed by MFM measurements, the enhanced magnetism in the Fe3O4-filled nanohole arrays originates mainly from the enhanced magnetic dipole interactions of Fe3 O4 nanoparticles within the nanoholes and between adjacent nanoholes. Nanoparticle filled nanohole arrays can be highly beneficial in magnetic data storage and other applications such as microwave devices and biosensor arrays that require tunable and anisotropic magnetic properties.

Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems

The exploration of exchange bias (EB) on the nanoscale provides a novel approach to improving the anisotropic properties of magnetic nanoparticles for prospective applications in nanospintronics and nanomedicine. However, the physical origin of EB is not fully understood. Recent advances in chemical synthesis provide a unique opportunity to explore EB in a variety of iron oxide-based nanostructures ranging from core/shell to hollow and hybrid composite nanoparticles. Experimental and atomistic Monte Carlo studies have shed light on the roles of interface and surface spins in these nanosystems. This review paper aims to provide a thorough understanding of the EB and related phenomena in iron oxide-based nanoparticle systems, knowledge of which is essential to tune the anisotropic magnetic properties of exchange-coupled nanoparticle systems for potential applications.

Laser Target Evaporation Fe 2 O 3 Nanoparticles for Water-Based Ferrofluids for Biomedical Applications

Maghemite spherical magnetic nanoparticles (MNPs) were prepared by laser target evaporation. X-ray diffraction, transmission electron microscopy, specific surface area, and dynamic light scattering studies were performed. For water-based suspensions prepared on the basis of obtained MNPs, the zeta potential was measured. Magnetic and microwave measurements were performed both for MNPs and ferrofluids. To estimate the inductive magnetic heating of electrostatically self-stabilized or electrostatically stabilized by adsorbed citrate ions ferrofluids, magneto-inductive heating experiments were performed that showed heating efficiency. For the study of cytotoxicity and maghemite MNPs accumulation process, two non-pathogenic Exophiala nigrum (black) and its mutant strain (red) yeasts were studied. In both cases, no significant alterations of cell morphology were observed.