Co x Ag1−x core–shell nanoparticles: magnetic and magneto-optical studies

The magneto-optical properties of 14-nm Co _x Ag_1?x core–shell nanoparticles (x=0.7, 0.8, and 0.35) deposited on different substrates are investigated at room temperature in the photon-energy range from 0.8 to 4.8 eV. Particles with low Ag content show spectra very similar to pure Co nanoparticles while particles with high Ag content have totally different features, where the Ag plasma edge dominates the spectra. The spectral features of the polar Kerr rotation depend on particle composition. The ageing process and development of an oxide layer influence the particles’ core–shell structures and magnetization curves. Co-rich particles exhibit lower resistance to the oxidation process as compared to Ag-rich ones. The quality of the nanoparticles was checked by transmission electron microscopy in respect of time scale.     

Magnetic properties of Co-ferrite-doped hydroxyapatite nanoparticles having a core/shell structure

The magnetic properties of Co-ferrite-doped hydroxyapatite (HAP) nanoparticles of composition Ca_10−3xFe_2xCo_x(PO₄)₆(OH)₂ (where x=0, 0.1, 0.2, 0.3, 0.4 and 0.5% mole) are studied. Transmission electron microscope micrograms show that the 90 nm size nanoparticles annealed at 1250 °C have a core/shell structure. Their electron diffraction patterns show that the shell is composed of the hydroxyapatite and the core is composed of the Co-ferrite, CoFe₂O₄. Electron spin resonance measurements indicate that the Co²⁺ ions are being substituted into the Ca(1) sites in HAP lattice. X-ray diffraction studies show the formation of impurity phases as higher amounts of the Fe³⁺/Co²⁺ ions which are substituted into the HAP host matrix. The presence of two sextets (one for the A-site Fe³⁺ and the other for the B-site Fe³⁺) in the Mössbauer spectrum for all the doped samples clearly indicates that the CoFe₂O₄.cores are in the ferromagnetic state. Evidence of the impurity phases is seen in the appearance of doublet patterns in the Mössbauer spectrums for the heavier-doped (x=0.4 and 0.5) specimens. The decrease in the saturation magnetizations and other magnetic properties of the nanoparticles at the higher doping levels is consistent with some of the Fe³⁺ and Co²⁺ which being used to form the CoO and Fe₂O₃ impurity phase seen in the XRD patterns.     

Exchange coupled magnetic nanocomposites of Sm(Co1−xFex)5 / Fe3O4 with core/shell structure

Magnetic nanocomposites of Sm(Co_1−xFe_x)₅/Fe₃O₄ (x≈0.1) with the core/shell type structure were successfully fabricated using a two-step polyol process, where as-prepared SmCo_5(1−x) nanoparticles were used as seeds for the ferrite coating. The core/shell composites are quite stable in air and show a typical hysteric behavior of single component, yielding an enhanced coercivity of 2.2 kOe with a saturated magnetization of 130 emu/g at 5 T. The magnetization data clearly reveal the presence of effective exchange coupling between the hard-magnetic Sm(Co_1−xFe_x)₅ core and soft-magnetic Fe₃O₄ shell, suggestive of a single-phase structure rather than a distinctive two-phase one.     

银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

Dependence of exchange bias on core/shell relative dimension in ferromagnetic/antiferromagnetic nanoparticles

We employ a modified Metropolis Monte Carlo simulation to study the effect of bimagnetic core/shell relative dimension on exchange bias in ferromagnetic/antiferromagnetic nanoparticles. The exchange bias field is inversely proportional to the ferromagnetic shell thickness in the antiferromagnetic (core)/ferromagnetic (shell) nanoparticles, while in the nanoparticles with an opposite core/shell structure the exchange bias behavior is complex and distinguished in different ranges of the ferromagnetic core radius. The work elucidates unambiguously how the core and shell dimensions optimize the exchange bias in nanoparticles.     

Preparation and photocatalytic properties of magnetically reusable Fe3O4@ZnO core/shell nanoparticles

Fe₃O₄@ZnO binary nanoparticles were synthesized by a simple two-step chemical method and characterized using various analytical instruments. TEM result proved the binary nanoparticles have core/shell structures and average particle size is 60 nm. Photocatalytic investigation of Fe₃O₄@ZnO core/shell nanoparticles was carried out using rhodamine B (RhB) solution under UV light. Fe₃O₄@ZnO core/shell nanoparticles showed enhanced photocatalytic performance in comparison with the as prepared ZnO nanoparticles. The enhanced photocatalytic activity for Fe₃O₄@ZnO might be resulting from the higher concentration of surface oxygen vacancies and the suppressing effect of the Fe³⁺ ions on the recombination of photoinduced electron–hole pairs. Magnetization saturation value (5.96 emu/g) of Fe₃O₄@ZnO core/shell nanoparticles is high enough to be magnetically removed by applying a magnetic field. The core/shell photocatalyst can be easily separated by using a commercial magnet and almost no decrease in photocatalytic efficiency was observed even after recycling six times.     

Preparation and magnetic properties of the conductive Co(1−x)NixFe2O4/polyaniline microsphere composites

Core-shell Co_(1−x)Ni_xFe₂O₄/polyaniline nanoparticles, where the core was Co_(1−x)Ni_xFe₂O₄ and the shell was polyaniline, were prepared by the combination of sol-gel process and in-situ polymerization methods. Nanoparticles were investigated by Fourier transform spectrometer, X-ray diffraction diffractometer, Scanning electron microscope, Differential thermal analysis and Superconductor quantum interference device. The results showed that the saturation magnetization of pure Co_(1−x)Ni_xFe₂O₄ nanoparticles were 57.57 emu/g, but Co_(1−x)Ni_xFe₂O₄/polyaniline composites were 37.36 emu/g. It was attributed to the lower content (15 wt%), smaller size and their uneven distribution of Co_(1−x)Ni_xFe₂O₄ nanoparticles in the final microsphere composites. Both Co_(1−x)Ni_xFe₂O₄ and PANI/Co_(1−x)Ni_xFe₂O₄ showed superparamagnetism.     

Decrease of superparamagnetic fraction at room temperature in ultrafine CoFe2O4 particles by Ag doping

Co_1???x Ag _x Fe₂O₄ nanoparticles have been prepared by the combustion route. The average crystallite sizes for compositions with x = 0 and 0.2 are found to be 36 and 33 nm respectively from the XRD line broadening. Compared to the pure CoFe₂O₄, Ag-doping reduces the intrinsic magnetization values (M, M _r), but enhances coercivity (H _c). Mössbauer spectra show two sextets, indicating occupancies of tetrahedral and octahedral sites by Fe^3?+?. Hyperfine fields of 505 and 477 kOe in pure CoFe₂O₄ have been found for octahedral and tetrahedral sites respectively at liquid nitrogen temperature. The hyperfine field decreases with Ag-doping which also corroborates the magnetization studies. EPR study confirms the room temperature ferromagnetic behavior for Co_1???x Ag _x Fe₂O₄ (x = 0.2). The room temperature Mössbauer studies on x?=?0.0 and 0.2 show the ferromagnetic sextets (95%) along with superparamagnetic doublet (5%). However, x = 0.6 sample shows the ferromagnetic sextets only at room temperature. Highly Ag doped samples could be useful for the fabrication of the high-density magnetic materials as well as magnetic drug delivery.     

Estimate of the Degree of the Spin Polarization of a Ferromagnet from Data on the Superconductor/Ferromagnet Proximity Effect

The superconductor/ferromagnet proximity effect in the Pb/Co₂Cr_1–xFe _x Al bilayer systems has been studied. Thin films of the Heusler alloy Co₂Cr_1–xFe _x Al have been prepared at different substrate temperatures. It has been established using Andreev spectroscopy of point contacts that the degree of spin polarization of conduction electrons in the Heusler alloy is on the order of 30 and 70% for the films prepared at a substrate temperature of 300 and 600 K, respectively. It has been found that the dependence of the superconducting transition temperature on the thickness of the Pb layer at a fixed thickness of the Heusler layer is determined by the degree of spin polarization of the conduction band in the ferromagnetic layer.     

Epitaxial growth of bcc-FexCo100-x thin films on MgO(1 1 0) single-crystal substrates

Fe_xCo_100-x (x=100, 65, 50 at%) epitaxial thin films were prepared on MgO(1 1 0) single-crystal substrates heated at 300 °C by ultra-high vacuum molecular beam epitaxy. The film structure and the growth mechanism are discussed. FeCo(2 1 1) films with bcc structure grow epitaxially on MgO(1 1 0) substrates with two types of variants whose orientations are rotated around the film normal by 180° each other for all compositions. Fe_xCo_100-x film growth follows the Volmer Weber mode. X-ray diffraction analysis indicates the out-of-plane and the in-plane lattice spacings are in agreement with the values of respective bulk Fe_xCo_100-x crystals with very small errors less than ±0.4%, suggesting the strains in the films are very small. High-resolution cross-sectional transmission electron microscopy shows that periodical misfit dislocations are preferentially introduced in the film at the Fe₅₀Co₅₀/MgO interface along the MgO[1 1¯ 0] direction. The presence of such periodical dislocations decreases the large lattice mismatch of about −17% existing at the FeCo/MgO interface along the MgO[1 1¯ 0] direction.     

FexMn1-x合金在GaAs(001)表面外延的结构和磁性

报道了对于0≤x≤1的Fe_xMn_1-x合金在GaAs(001)表面上分子束外延的结构与磁性的实验结果,当x>0.8时,Fe_xMn_1-x合金以单晶体心立方结构生长;当x<0.35时,则以单晶面心立方结构生长;对于0.35xMn_1-x生长的结构比较复杂,而正是在这一区域中,该合金发生了从铁磁相到反铁磁相的转变. 关键词：     

Atomic scale models of $\mathsf{Co{-}Ag}$ mixed nanoclusters at thermodynamic equilibrium

The configurations at thermodynamic equilibrium of Co_xAg_201-x nanoparticles are explored for 0 < x < 201 by means of Metropolis Monte Carlo simulations with a semi-empirical embedded atom potential at temperatures from 100 K to 1000 K. Remarkable configurations are predicted in this temperature range. As a consequence of a competition between strain and Co binding at low temperature, for x < 20, Co is distributed just below the cluster surface layer into groups of no more than 5 atoms, favouring well-defined positions, and the cluster central area is avoided. To increase the temperature favours the clustering of these small groups. Their dissolution is predicted at temperatures higher than the melting temperature of the cluster. For x > 50, Co regroups at the centre of the cluster and intersects {111}-facets when Ag atoms are not numerous enough to form an entire surface shell. At these stoechiometries, temperature is not sufficient to mix Ag and Co, even above the melting point. At still smaller Ag concentrations, the Ag atoms are distributed at lowest coordination sites, along the edges of the cluster, avoiding the cluster facets as well as inner sites. At intermediate stoechiometries (20 < x < 50), either oblate Co groups below the surface or a compact group at the centre of the cluster are possible.Received: 1 October 2003, Published online: 27 January 2004PACS: 61.46. + w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals - 61.43.Bn Structural modeling: serial-addition models, computer simulation     

Ferromagnetic resonance of cobalt nanoparticles in the polymer shell

The magnetic properties of cobalt spherical nanoparticles (～ 5–9 nm in size) in a polymer shell are investigated using ferromagnetic resonance (FMR) spectroscopy. The metal-polymer complex is prepared through the frontal polymerization of the cobalt acrylamide (CoAAm) complex, followed by the thermolysis at a temperature of 643 K. Analysis of the ferromagnetic resonance spectra demonstrates that the material has a high blocking temperature of ～700 K. The anisotropy constant equal to 0.5 erg/cm³ is somewhat larger than the anisotropy constants characteristic of cobalt macrostructures. This difference is associated with the predominance of the surface anisotropy of nanoparticles. The surface anisotropy constant is calculated to be 0.17 erg/cm², and the anisotropy field is determined to be ～350 Oe. It is revealed that the polymer shell affects the magnetic properties of nanoparticles.     

利用激光烧蚀法制备表面等离子体可调谐的金核银壳层纳米颗粒胶体

利用激光烧蚀方法在水中制备了金核银壳层纳米颗粒胶体,发现这种复合胶体的等离子体振动吸收峰频率会随着激光烧蚀时间的不同而发生改变。利用等离子杂化理论定性解释了共振吸收峰可调谐的物理机制.     

Synthesis and characterization of CoxZn1−xFe2O4 magnetic nanoparticles via a PEG-assisted route

We present an investigation of properties of Co_xZn_1−xFe₂O₄ (x=0.0-1.0) nanoparticles synthesized by a polyethylene glycol (PEG)-assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and vibrating scanning magnetometry (VSM) were used to characterize the structural, morphological and magnetic properties. The particle size obtained from TEM and XRD are consistent with each other. It was observed that the lattice constant for each composition decreases with increasing Co substitution and follows Vegard's law. Magnetization measurements show that while the materials with high Zn substitution are superparamagnetic at room temperature, they are ferromagnetic at temperatures lower than the blocking temperature. The materials with less Zn substitution are ferromagnetic below room temperature. Magnetizations and the coercivities of the samples decrease with the Zn substitution. The resultant overall magnetic behavior of the superparamagnetic samples are found to be considerably different than that of conventional superparamagnetic systems due to the antiferromagnetic interactions both in intra- and inter-cluster spins, and size (effective moment) distribution of the particles.     

Distinguishing the core from the shell in MnO(x)/MnO(y) and FeO(x)/MnO(x) core/shell nanoparticles through quantitative electron energy loss spectroscopy (EELS) analysis

The structural and chemical characterization of inverted bi-magnetic MnO_x(antiferromagnetic)/MnO_y(ferrimagnetic) and FeO_x(soft-ferrimagnetic)/MnO_x(hard-ferrimagnetic) core/shell nanoparticles has been carried out by means of scanning transmission electron microscopy with electron energy loss spectroscopy analysis, (S)TEM-EELS. Quantitative EELS was applied to assess the local composition of the nanoparticles by evaluating the local Mn oxidation state based on the Mn L₃/L₂ peak intensity ratio and the Mn L₃ peak onset. The analysis allows to unambiguously distinguish the core from the shell and to determine the nature of the involved manganese oxides in both cases. The results evidence that the structure of the nanoparticles is, in fact, more complex than the one designed by the synthesis parameters.     

Fe2+ localized excitations in the random antiferromagnet with competing spin anisotropies, Fe(1−x)CoxBr2

The Fe²⁺ localized magnetic excitations observed in the Co-rich antiferromagnetic phase of the randomly mixed system with competing Ising and XY spin anisotropies, Fe(_1?x)Co_xBr₂ have been analyzed quantitatively. The calculated frequency-field diagram reproduces well the experiments. The expectation values of the Fe²⁺ spin components in the ground state are calculated. It is shown that even in the Co-rich antiferromagnetic phase Fe²⁺ spins make an angle with the c-plane of the crystal in which Co²⁺ spins are confined.     

A facile strategy to synthesize bimetallic Au/Ag nanocomposite film by layer-by-layer assembly technique

A facile strategy has been developed for the preparation of bimetallic gold–silver (Au–Ag) nanocomposite films by alternating absorption of poly-(ethyleneimine)–silver ions and Au onto substrates and subsequent reduction of the silver ions. The composition, micro-structure and properties of the {PEI–Ag/Au}_n nanocomposite films were characterized by ultraviolet visible spectroscopy (UV–vis), transmisson electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), surface enhanced Raman scattering (SERS) and cyclic voltammetry (CV). The UV–vis characteristic absorbances of {PEI–Ag/Au}_n nanocomposite thin film increase almost linear with the number of bilayers, which indicates a process of uniform assembling. Appearance of a double plasmon bands in the visible region and the lack of apparent core–shell structures in the TEM images confirm the formation of bimetallic Au–Ag nanoparticles. The result of XPS also demonstrates the existence of Ag and Au nanoparticles in the nanocomposite films. TEM and FESEM images show that these Ag and Au nanoparticles in the films possess sphere structure with the size of 20–25 nm. The resulting {PEI–Ag/Au}_n films inherit the properties from both the metal Ag and Au, which exhibits a unique performance in SERS and electrocatalytic activities to the oxidation of dopamine. As a result, the {PEI–Ag/Au}_n films are more attractive compared to {PEI–Ag/PSS}_n and {PEI/Au}_n films.     

Tuning Carbon Content and Morphology of FeCo/Graphitic Carbon Core–Shell Nanoparticles using a Salt‐Matrix‐Assisted CVD Process

Large‐scale and tunable synthesis of FeCo/graphitic carbon (FeCo/GC) core–shell nanoparticles as a promising material for multipurpose biomedical applications is reported. The high‐quality graphitic structure of the carbon shells is demonstrated through high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), and Raman spectroscopy. A saturation magnetization of 80.2 emu g^?1 is reached for the pure FeCo/GC core–shell nanoparticles. A decrease in the saturation magnetization of the samples is observed with an increase in their carbon content with different carbon morphologies evolved in the process. It is also shown how hybrid nanostructures, including mixtures of the FeCo/GC nanoparticles and multi‐walled carbon nanotubes (MWNTs) or carbon nanorods (CNRs), can be obtained only by manipulation of the carbon‐bearing gas flow rate.     

Tunning exchange bias in inverted antiferromagnetic/ferromagnetic core/shell nanoparticles by binary alloy shells

A detailed investigation of exchange bias properties of an inverted nanoparticle with an antiferromagnetic core and a ferromagnetic binary alloy shell of the type $B_x{C}_{1?x}$ is presented by benefiting from Monte Carlo simulations. Exchange bias displays a non-monotonic behavior with the varying value of the concentration the type-B magnetic components, x. Coercivity exhibits a monotonic or a non-monotonic variation with x depending on the relative strength between unlike magnetic components in the shell. Particular attention has also been given to determine the effects of the cooling field process on the magnetic properties of the nanoparticle. Numerical results obtained in this work present a different physical mechanism and an alternative way for tuning the exchange bias and coercivity of bimagnetic core/shell nanoparticles.