Sayan Chandra

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.

Evidence of a canted magnetic state in self-doped LaMnO3+δ (δ = 0.04): a magnetocaloric study

We report a detailed investigation of the magnetocaloric properties of self-doped polycrystalline LaMnO(3+δ) with δ = 0.04. Due to the self-doping effect, the system exhibits a magnetic transition from a paramagnetic to ferromagnetic-like canted magnetic state (CMS) at ~120 K, which is associated with an appreciably large magnetocaloric effect (MCE). The CMS is an inhomogeneous magnetic phase developing due to a steady growth of antiferromagnetic correlation in its predominant ferromagnetic state below ∼120 K. The stabilization of CMS in this material is concluded from a comprehensive analysis of magnetocaloric data using Landau theory, which is in excellent agreement with our neutron diffraction study. The magnetic entropy change versus temperature curves for different applied fields collapse into a single curve, revealing a universal behavior of MCE. Our studies suggest that investigation of MCE is an effective technique to acquire fundamental understanding about the basic magnetic structure of a system with complex competing interactions.

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.

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.

Growth and physical property study of single nanowire (diameter ∼45nm) of half doped manganite

We report here the growth and characterization of functional oxide nanowire of hole dopedmanganite of La0.5Sr0.5MnO3 (LSMO). We also report four-probe electrical resistance measurement of a single nanowire of LSMO (diameter ∼45 nm) using focused ion beam (FIB) fabricated electrodes. The wires are fabricated by hydrothermal method using autoclave at a temperature of 270 °C. The elemental analysis and physical property like electrical resistivity are studied at an individual nanowire level. The quantitative determination ofMn valency and elemental mapping of constituent elements are done by using Electron Energy Loss Spectroscopy (EELS) in the Transmission Electron Microscopy (TEM) mode. We address the important issue of whether as a result of size reduction the nanowires can retain the desired composition, structure, and physical properties. The nanowires used are found to have a ferromagnetic transition (TC) at around 325K which is very close to the bulk value of around 330K found in single crystal of the same composition. It is confirmed that the functional behavior is likely to be retained even after size reduction of the nanowires to a diameter of 45 nm. The electrical resistivity shows insulating behavior within the measured temperature range which is similar to the bulk system.

Phase coexistence and magnetic anisotropy in polycrystalline and nanocrystalline LaMnO3+δ

We report on the phase coexistence and magnetic anisotropy in polycrystalline (bulk) and nanocrystalline (∼15 nm) LaMnO3+δ materials, which were prepared by solid state reaction and sol-gel methods, respectively. In addition to standard magnetization measurements, radio-frequency transverse susceptibility (TS) based on a very sensitive, self-resonant tunnel diode oscillator method was used to probe magnetic anisotropy and switching fields in the samples. The results revealed a coexistence of the ferromagnetic (FM) and antiferromagnetic (AFM) phases in both samples. For the bulk sample, the AFM phase significantly changed in volume fraction at ∼30 K and completely vanished around 120 K. Size reduction to the nanometer scale (∼15 nm) significantly suppressed the AFM phase while inducing surface spin disorder in the material. The large magnetic anisotropies were probed by TS experiments in both samples. Our studies showed that the magnetic properties of bulk LaMnO3+δ were strongly modified by size reduction.

Inverse magnetocaloric and exchange bias?effects in single crystalline La0.5Sr0.5MnO3 nanowires

We report the first observation of inverse magnetocaloric effect (IMCE) in hydrothermally synthesized single crystalline La0.5Sr0.5MnO3 nanowires. The core of the nanowires is phase separated with the development of double exchange driven ferromagnetism (FM) in the antiferromagnetic (AFM) matrix, whereas the surface is found to be composed of disordered magnetic spins. The FM phase scales with the effective magnetic anisotropy, which is directly probed by transverse susceptibility experiments. The surface exhibits a glassy behavior and undergoes spin freezing, which manifests as a positive peak (T(L) ~ 42 K) in the magnetic entropy change (-ΔS(M)) curves, thereby stabilizing the re-entrance of the conventional magnetocaloric effect. Precisely at T(L), the nanowires develop the exchange bias (EB) effect. Our results conclusively demonstrate that the mere coexistence of FM and AFM phases along with a disordered surface below their Néel temperature (T(N) ~ 210 K) does not trigger EB, but this develops only below the surface spin freezing temperature.

Magnetic entropy change in core/shell and hollow nanoparticles

The development of positive magnetic entropy change in the case of ferromagnetic (FM) nanostructures is a rare occurrence. We observe positive magnetic entropy change in core/shell (Fe/γ-Fe2O3) and hollow (γ-Fe2O3) nanoparticles and its origin is attributed to a disordered state in the nanoparticles due to the random distribution of anisotropy axes which inhibits any long range FM ordering. The effect of the energy barrier distribution on the magnetic entropy change and its impact on the universal behavior based on rescaled entropy change curves for core/shell and hollow nanostructures is discussed. Our study emphasizes that the magnetic entropy change is an excellent parameter to study temperature and field dependent magnetic freezing in such complex nanostructures.

Enhanced cryogenic magnetocaloric effect in Eu8Ga16Ge30 clathrate nanocrystals

We observe an enhanced magnetic entropy change (−ΔSM) at cryogenic temperatures (T < 20 K) in Eu8Ga16Ge30 clathrate (type-I) nanocrystals prepared by a ball milling method. With reduction in the crystal size to 15 nm, −ΔSM is enhanced at low temperatures, reaching the highest value (∼10 J/kg K) at 5 K for a field change of 5 T. For all samples investigated, there is a cross-over temperature (∼25 K) in −ΔSM (T) above which −ΔSM decreases with crystal size, opposite to that observed at low temperatures. A careful analysis of the magnetic and magnetocaloric data reveals that as the crystal size decreases the magnetic interaction between Eu2+ ions on the Eu2 site governing the primary ferromagnetic transition at ∼35 K becomes gradually weaker, in effect, altering the interaction between Eu2+ ions occupying the Eu1 and Eu2 sites responsible for the secondary ferromagnetic transition at 15 K. As a result, we have observed a strong change in magnetization and the enhancement of −ΔSM at low temperature.