Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles

This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI center dot NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI center dot PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 degrees C, 200 degrees C and 250 degrees C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 degrees C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses.

Optical third-harmonic spectroscopy of the magnetic semiconductor EuTe

EuTe possesses the centrosymmetric crystal structure m3m of rocksalt type in which the second-harmonic generation is forbidden in electric dipole approximation but the third-harmonic generation (THG) is allowed. We studied the THG spectra of this material and observed several resonances in the vicinity of the band gap at 2.2-2.5 eV and at higher energies up to 4 eV, which are related to four-photon THG processes. The observed resonances are assigned to specific combinations of electronic transitions between the ground 4f(7) state at the top of the valence band and excited 4f(6)5d(1) states of Eu(2+) ions, which form the lowest energy conduction band. Temperature, magnetic field, and rotational anisotropy studies allowed us to distinguish crystallographic and magnetic-field-induced contributions to the THG. A strong modification of THG intensity for the 2.4 eV band and suppression of the THG for the 3.15 eV band was observed in applied magnetic field. Two main features of the THG spectra were assigned to 5d(t(2g)) and 5d(e(g)) subbands at 2.4 eV and 3.15 eV, respectively. A microscopic quantum-mechanical model of the THG response was developed and its conclusions are in qualitative agreement with the experimental results.

Mn-doped cubic BN as an atomiclike memory device: A density functional study

We investigate the electronic properties of Mn(B) substitutional doping in cubic boron nitride (BN), for different charge states, using density functional theory (DFT) calculations. We show that the neutral Mn has a nonmagnetic ground state (S=0). Upon charge injection, it is unambiguously shown that the Mn(B)(-) has a high-spin configuration with a strong, localized magnetic moment of 5 mu(Bohr). We developed a simple model, parameterized by the DFT results, that allows us to interpret the rules played by the crystal-field and exchange-correlation splitting in the magnetization process.

Magnetic-field-induced transition in a wide parabolic well superimposed with a superlattice

We study a Al(x)Ga(x-1)As parabolic quantum well (PQW) with GaAs/Al(x)Ga(x-1)As square superlattice. The magnetotransport in PQW with intentionally disordered short-period superlattice reveals a surprising transition from electrons distribution over whole parabolic well to independent-layer states with unequal density. The transition occurs in the perpendicular magnetic field at Landau filling factor v approximate to 3 and is signaled by the appearance of the strong and developing fractional quantum Hall (FQH) states and by the enhanced slope of the Hall resistance. We attribute the transition to the possible electron localization in the x-y plane inside the lateral wells, and formation of the FQH states in the central well of the superlattice, driven by electron-electron interaction.

Optical second harmonic generation in the centrosymmetric magnetic semiconductors EuTe and EuSe

The magnetic europium chalcogenide semiconductors EuTe and EuSe are investigated by the spectroscopy of second harmonic generation (SHG) in the vicinity of the optical band gap formed by transitions involving the 4f and 5d electronic orbitals of the magnetic Eu(2+) ions. In these materials with centrosymmetric crystal lattice the electric-dipole SHG process is symmetry forbidden so that no signal is observed in zero magnetic field. Signal appears, however, in applied magnetic field with the SHG intensity being proportional to the square of magnetization. The magnetic field and temperature dependencies of the induced SHG allow us to introduce a type of nonlinear optical susceptibility determined by the magnetic-dipole contribution in combination with a spontaneous or induced magnetization. The experimental results can be described qualitatively by a phenomenological model based on a symmetry analysis and are in good quantitative agreement with microscopic model calculations accounting for details of the electronic energy and spin structure.

Magnetic properties of Fe(3)O(4) nanoparticles coated with oleic and dodecanoic acids

Magnetic nanoparticles (NP) of magnetite (Fe(3)O(4)) coated with oleic acid (OA) and dodecanoic acid (DA) were synthesized and investigated through transmission electron microscopy (TEM), magnetization M, and ac magnetic susceptibility measurements. The OA coated samples were produced with different magnetic concentrations (78%, 76%, and 65%) and the DA sample with 63% of Fe(3)O(4). Images from TEM indicate that the NP have a nearly spherical geometry and mean diameter similar to 5.5 nm. Magnetization measurements, performed in zero-field cooled (ZFC) and field cooled processes under different external magnetic fields H, exhibited a maximum at a given temperature T(B) in the ZFC curves, which depends on the NP coating (OA or DA), magnetite concentration, and H. The temperature T(B) decreases monotonically with increasing H and, for a given H, the increase in the magnetite concentration results in an increase in T(B). The observed behavior is related to the dipolar interaction between NP, which seems to be an important mechanism in all samples studied. This is supported by the results of the ac magnetic susceptibility chi(ac) measurements, where the temperature in which chi' peaks for different frequencies follows the Vogel-Fulcher model, a feature commonly found in systems with dipolar interactions. Curves of H versus T(B)/T(B) (H=0) for samples with different coatings and magnetite concentrations collapse into a universal curve, indicating that the qualitative magnetic behavior of the samples may be described by the NP themselves, instead of the coating or the strength of the dipolar interaction. Below T(B), M versus H curves show a coercive field (H(C)) that increases monotonically with decreasing temperature. The saturation magnetization (M(S)) follows the Bloch's law and values of M(S) at room temperature as high as 78 emu/g were estimated, a result corresponding to similar to 80% of the bulk value. The overlap of M/M(S) versus H/T curves for a given sample and the low H(C) at high temperatures suggest superparamagnetic behavior in all samples studied. The overlap of M/M(S) versus H curves at constant temperature for different samples indicates that the NP magnetization behavior is preserved, independently of the coating and magnetite concentration. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3311611]

Spin-wave fluctuations in ferrimagnetic Mg(x)Fe(3-x)O(4) nanoparticles

We have performed a systematic study of the magnetic properties of a series of ferrimagnetic nanoparticles of Mg(x)Fe(3-x)O(4) (0.8 <= x <= 1.5) prepared by the combustion reaction method. The magnetization data can be well fitted by Bloch's law with T(3/2). Bloch's constant B determined from the fitting procedure was found to increase with Mg content x from similar to 3.09 X 10(-5) K(-3/2) for x = 0.8 to 6.27 X 10(-5) K(-3/2) for x=1.5. The exchange integral J(AB) and the spin-wave stiffness constant D of Mg(x)Fe(3-x)O(4) nanoparticles were also determined as similar to 0.842 and 0.574 meV and 296 and 202 meV angstrom(2) for specimens with x=0.8 and 1.5, respectively. These results are discussed in terms of cation redistribution among A and B sites on these nanostructured spinel ferrites. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3359709]

Resistively detected NMR of the nu=1 quantum Hall state: A tilted magnetic field study

Previous resistively detected NMR (RDNMR) studies on the nu approximate to 1 quantum Hall state have reported a ""dispersionlike"" line shape and extremely short nuclear-spin-lattice relaxation times, observations which have been attributed to the formation of a skyrme lattice. Here we examine the evolution of the RDNMR line shape and nuclear-spin relaxation for Zeeman: Coulomb energy ratios ranging from 0.012 to 0.036. According to theory, suppression of the skyrme crystal, along with the associated Goldstone mode nuclear-spin-relaxation mechanism, is expected at the upper end of this range. However, we find that the anomalous line shape persists at high Zeeman energy, and only a modest decrease in the RDNMR-detected nuclear-spin-relaxation rate is observed.

Theory of near-gap second harmonic generation in centrosymmetric magnetic semiconductors: Europium chalcogenides

Second harmonic generation is strictly forbidden in centrosymmetric materials, within the electric dipole approximation. Recently, it was found that the centrosymmetric magnetic semiconductors EuTe and EuSe can generate near-gap second harmonics, if the system is submitted to an external magnetic field. Here, a theoretical model is presented, which well describes the observed phenomena. The model shows that second harmonic generation becomes efficient when the magnetic dipole oscillations between the band-edge excited states of the system, induced by the excitation light, enter the in-phase regime, which can be achieved by applying a magnetic field to the material.

Role of dipolar interactions in a system of Ni nanoparticles studied by magnetic susceptibility measurements

The role of dipolar interactions among Ni nanoparticles (NPs) embedded in an amorphous SiO(2)/C matrix with different concentrations has been studied performing ac magnetic susceptibility chi(ac) measurements. For very diluted samples, with Ni concentrations < 4 wt % Ni or very weak dipolar interactions, the data are well described by the Neacuteel-Arrhenius law. Increasing Ni concentration to values up to 12.8 wt % Ni results in changes in the Neacuteel-Arrhenius behavior, the dipolar interactions become important, and need to be considered to describe the magnetic response of the NPs system. We have found no evidence of a spin-glasslike behavior in our Ni NP systems even when dipolar interactions are clearly present.

In-field Mossbauer study of disordered surface spins in core/shell ferrite nanoparticles

Magnetization and Mossbauer spectroscopy measurements are performed at low temperature under high field, on nanoparticles with a nickel ferrite core and a maghemite shell. These nanoparticles present finite size and surface effects, together with exchange anisotropy. High field magnetization brings the evidences of a monodomain ordered core and surface spins freezing in disorder at low temperature. Mossbauer spectra at 4.2 K present an extra contribution from the disordered surface which is field dependent. Field and size dependences of this latter show a progressive spin alignment along the ferrite core which is size dependent. The weak surface pinning condition of the nanoparticles confirms that the spin disorder is localized in the external shell. The underfield decrease in the mean canting angle in the superficial shell is then directly related to the unidirectional exchange anisotropy through the interface between the ordered core and the disordered shell. The obtained anisotropy field H(Ea) scales as the inverse of the nanoparticle diameter, validating its interfacial origin. The associated anisotropy constant K(Ea) equals 2.5 x 10(-4) J/m(2). (C) 2009 American Institute qf Physics. [doi: 10.1063/1.3245326]

Emergent and reentrant fractional quantum Hall effect in trilayer systems in a tilted magnetic field

Magnetotransport measurements in triple-layer electron systems with high carrier density reveal fractional quantum Hall effect at total filling factors nu>2. With an in-plane magnetic field we are able to control the suppression of interlayer tunneling which causes a collapse of the integer quantum Hall plateaus at nu=2 and nu=4, and an emergence of fractional quantum Hall states with increasing tilt angles. The nu=4 state is replaced by three fractional quantum Hall states with denominator 3. The state nu=7/3 demonstrates reentrant behavior and the emergent state at nu=12/5 has a nonmonotonic behavior with increasing in-plane field. We attribute the observed fractional quantum Hall plateaus to correlated states in a trilayer system.

Magnetoconfined levels in a parabolic quantum dot: An analytical solution of a three-dimensional Fock-Darwin problem in a tilted magnetic field

The energy spectrum of an electron confined in a quantum dot (QD) with a three-dimensional anisotropic parabolic potential in a tilted magnetic field was found analytically. The theory describes exactly the mixing of in-plane and out-of-plane motions of an electron caused by a tilted magnetic field, which could be seen, for example, in the level anticrossing. For charged QDs in a tilted magnetic field we predict three strong resonant lines in the far-infrared-absorption spectra.

Zero-phonon emission and magnetic polaron parameters in EuTe

A phonon structure in the photoluminescence of EuTe was discovered, with a well-defined zero-phonon emission line (ZPL). The ZPL redshifts linearly with the intensity of applied magnetic field, indicating spin relaxation of the photoexcited electron, and saturates at a lower magnetic field than the optical absorption bandgap, which is attributed to formation of magnetic polarons. From the difference in these saturation fields, the zero-field polaron binding energy and radius are estimated to be 43 meV and 3.2 (in units of the EuTe lattice parameter), respectively. (C) 2011 American Institute of Physics. [doi:10.1063/1.3634030]

Spin-Induced Optical Second Harmonic Generation in the Centrosymmetric Magnetic Semiconductors EuTe and EuSe

Spectroscopy of the centrosymmetric magnetic semiconductors EuTe and EuSe reveals spin-induced optical second harmonic generation (SHG) in the band gap vicinity at 2.1-2.4 eV. The magnetic field and temperature dependence demonstrates that the SHG arises from the bulk of the materials due to a novel type of nonlinear optical susceptibility caused by the magnetic dipole contribution combined with spontaneous or induced magnetization. This spin-induced susceptibility opens access to a wide class of centrosymmetric systems by harmonics generation spectroscopy.