The exchange bias in MnPd/Co1−xFex bilayers

A systematic study of exchange bias in MnPd/Co and MnPd/Co_1−xFe_x bilayers has been carried out. Very large unidirectional anisotropy constant of 2.2 erg/cm² and the appearance of double-shifted loops, ascribed to the coexistence of positive and negative exchange bias, have been observed. The dependence of exchange bias, unidirectional anisotropy constant and coercivity on thickness, temperature, annealing regime and Fe content has been investigated and discussed.     

Influence of B2O3 to the inhomogeneous broadening and spectroscopic properties of Er/Yb codoped fluorophosphate glasses

In a three-components fluorophosphate glass system, the introduction of H₃BO₃ brings some valuable influence to the spectroscopic and thermal properties of the glasses. With H₃BO₃ increases from 2 to 20 mol%, Ω₆, S_ed4I13/2, FWHM, T_g and fluorescence lifetime change from 3.21×10⁻²⁰ cm², 1.77×10⁻²⁰ cm², 45 nm, 480 °C and 8.8 ms to 4.66×10⁻²⁰ cm², 2.11×10⁻²⁰ cm², 50 nm, 541 °C and 7.4 ms, respectively. σ_abs, σ_emi, FWHM×τ_f×σ_emi has a maximum when H₃BO₃ is 11 mol%. T_g and T_x−T_g increases with H₃BO₃ introduction. Results showed that in fluorophosphate glasses, proper amount of B₂O₃ can be used as a modifier to suppress upconversion and improve spectroscopic properties, broadband property and crystallization stability of the glasses while keeps the fluorescence lifetime relatively high.     

Particle size dependence of exchange-bias and coercivity in CuO nanoparticles

For CuO nanocrystals of size 6.6-37 nm, the exchange bias H_eb and coercivity H_c are measured at 5 K in zero-field-cooled (ZFC) and field-cooled (FC at 50 kOe) samples and their variations investigated as a function of particle size D. The similar 1/D variations observed for the difference coercivity ΔH_c=H_c(FC)−H_c(ZFC) and the interfacial exchange energy Δσ=H_ebM_fD are discussed in terms of the ferromagnetic magnetization M_f being produced by the uncompensated surface Cu²⁺ spins in the otherwise antiferromagnetically ordered CuO nanoparticles. This leads to the observation that the experimentally measured ΔH_c provides a good measure of Δσ in nanoparticle systems, with H_eb/ΔH_c varying as 1/M_fD.     

Effect of anions on the phase stability of γ-FeOOH nanoparticles and the magnetic properties of gamma-ferric oxide derived from lepidocrocite

The effect of anions such as Cl⁻, SO₄²⁻, and HPO₄²⁻ on the phase stability of FeOOH (α or γ) during precipitation is investigated. Oxidation of Fe(OH)₂·xH₂O from FeCl₂ solution with high Cl⁻ concentration ([Cl⁻]/[Fe]=R_Cl≥8) or (NH₄)₂Fe(SO₄)₂ (FAS) with [HPO₄²⁻]/[Fe]=R_P≥0.02 yields phase-pure γ-FeOOH. In the medium ranges of R_Cl and R_P, mixed phases of α-FeOOH and γ-FeOOH are obtained. Replacement of OH⁻ by Cl⁻ with the bridging cations or strongly bonded HPO₄²⁻ ions in the matrix of the intermediate phase (Fe_x²⁺Fe_y³⁺(OH)_2x+2y−nz·xH₂O(A)_zⁿ⁻, where A is anions such as Cl⁻, SO₄²⁻, HPO₄²⁻, etc.), promoted the lower density γ-FeOOH. However, the particles are less developed and have poor crystallinity as evidenced from transmission electron microscope and thermogravimetry-differential thermal analysis of the precipitates. Whereas, monophasic, uniformly sized, nano-lath shaped particles with high aspect ratio >10 are obtained when morphology-controlling cation additives such as Pt⁴⁺, Pd²⁺ or Rh³⁺ are present in FeCl₂ (R_Cl≥8) solution. Preferential adsorption of additives on (0k0) and (h00) planes limits the growth in the perpendicular directions leading to high aspect ratios. The effect of these additives are suppressed by the phosphate ion, a strong complexing ligand, giving rise to fibrous aggregate with the length of individual particles as small as 10-30 nm. While most of the Cl⁻ ion is removed from the final precipitates on washing, phosphate remained as HPO₄²⁻ as evidenced from IR absorption spectra. Maghemite obtained by dehydroxylating γ-FeOOH contains randomly distributed micropores bringing in the relaxation effects of spins on the surface atoms as deciphered from Mössbauer spectroscopy. This leads to the low σ_s (44-48 emu/g) and H_c (120-130 Oe) for γ-Fe₂O_3−δ particles. Whereas nearly pore-free single crystalline particles obtained by reduction followed by reoxidation has high value of σ_s (73 emu/g) and H_c (320 Oe), which decreases to 30 emu/g and 75 Oe, respectively, for nanoparticles obtained from phosphate stabilized lepidocrocite. The mobility of iron ions and counter mobility of vacancies during the topotactic transformation of γ-FeOOH to magnetite to γ-Fe₂O_3−δ renders the particles pore-free.     

Electron stimulated desorption of H3O from 316L stainless steel

Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr₂O₃. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p_3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H₂) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H₃O⁺ peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H₃O⁺, as well as its constituents (H⁺, O⁺ and OH⁺) and a small amount of fluorine as F⁻, but no F⁺ or F⁺ complexes (HF⁺, etc.). An electron stimulated desorption cross-section of σ⁺ ∼ 1.4 × 10⁻²⁰ cm² was determined for H₃O⁺ from 316L stainless steel for hydrogen residing in surface chromium hydroxide.     

Graphite nanosheets doped with Fe, Ni, and N, synthesized in one step, and their unique magnetic performance

Graphite nanosheets (GNs) doped with N, Fe, or Ni were synthesized by pyrolysis of metal tetrapyridinoporphyrazine (MPTpz, M=Fe²⁺, and Ni²⁺) and a mixture of MPTpzs in a chemical vapor deposition furnace. The products obtained were characterized by scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The magnetic properties of the GNs obtained were investigated at room temperature using a vibrating sample magnetometer with an applied field of −10 000-10 000 Gs. The results show the GNs obtained are terrace-like and ultra-thin, with very high aspect ratio. Fe, Ni and N atoms have been doped to the GNs successfully. There are two types of N atom that are introduced into pure carbon systems: pyrinidic and graphitic N atoms. The GNs obtained exhibit ferromagnetic behavior at room temperature. Sample S1, obtained by pyrolysis of a mixture of MPTpzs (M=Fe²⁺ and Ni²⁺), have the highest coercivity force. The saturation magnetization (M_s), remanent magnetization (M_r), and coercivity (H_c) values of sample S1 are 24.51 emu g⁻¹, 3.95 emu g⁻¹, and 207.34 Gs, respectively.     

Effect of Co underlayer on soft magnetic properties and microstructure of FeCo thin films

High saturation magnetization soft magnetic FeCo (=Fe₆₅Co₃₅) films were prepared using a thin Co underlayer. The FeCo/Co films exhibited a well-defined in-plane uniaxial anisotropy with easy axis coercivity (H_ce) of 10 Oe and hard axis coercivity (H_ch) of 3 Oe, and a half reduction of H_c with H_ce=4.8 Oe and H_ch=1.0 Oe was obtained when the composition was adjusted to 25 at% Co. The effective permeability of the films remains flat around 250 to 800 MHz. The saturation magnetostriction was 5.2×10⁻⁵ and the intrinsic stress was 0.8 GPa in FeCo single layer, both were slightly reduced by Co underlayer. The Co underlayer changed the preferred orientation of the FeCo films from (2 0 0) to (1 1 0) but more significantly, reduced the average grain size from ∼74 to ∼8.2 nm. It also reduced the surface roughness from 2.351 to 0.751 nm. The initial stage and interface diffusion properties were examined by TEM and XPS.     

The resonance decay function method in the determination of the pre-factor of the Néel relaxation time of single-domain nanoparticles

In its simple form, the relaxation time of the Néel relaxation process of the magnetic moment of single-domain particles is given by τ_N=τ_0Nexp(σ), σ being the ratio of anisotropy energy to thermal energy. The pre-factor, τ_0N, is normally given a value of 10⁻⁹ s, but values ranging from 10⁻⁸ to 10⁻¹² s have been reported in literature. Here, by means of the field and frequency dependence of the complex magnetic susceptibility, χ(ω,H)=χ′(ω,H)−iχ″(ω,H), of a magnetic fluid sample, in the MHz-GHz range, in conjunction with the determination of the sample decay function, b(t), the pre-factor τ_0N is determined. b(t) is readily obtained through the inverse Fourier transformation relationship, which exists between b(t) and χ″(ω).     

Fourier Transform Emission Spectroscopy of the FΣ-XΣ System of RuN

Emission spectra of RuN have been recorded at high resolution in the region 12 000-35 000 cm⁻¹ using a Fourier transform spectrometer. The molecules were excited in a ruthenium hollow cathode lamp in the presence of about 2.5 Torr of Ne and 5 m Torr of N₂. New bands with origins near 17 758.1, 18 866.4, 19 800.4 and 20 721.5 cm⁻¹ have been assigned as the 0-1, 0-0, 1-0, and 2-0 bands of a new ²Σ⁺-²Σ⁺ system with the lower state as the ground state. This transition has been labeled as F²Σ⁺-X²Σ⁺, with the F²Σ⁺ state arising from the 1σ²2σ²1π⁴1δ⁴4σ¹ configuration. A rotational analysis of these bands has been carried out and spectroscopic constants have been extracted. The principal equilibrium constants for the ground state of RuN are ΔG(1/2)″=1108.3235(22) cm⁻¹, B_e″=0.5545023(42) cm⁻¹, α_e″=0.0034468(57) cm⁻¹, r_e″=1.5714269(60) Å, while the equilibrium constants for the excited state are ω_e′=946.8471(40) cm⁻¹, ω_ex_e′=6.4229(14) cm⁻¹, B_e′=0.50085(21) cm⁻¹, α_e′=0.00375(10) cm⁻¹, r_e′=1.65345(34) Å. This transition is analogous to the E²Σ⁺-X²Σ⁺ system of RhC (W. J. Balfour et al., J. Mol. Spectrosc.198, 393 (1999)).     

Thermal stability and switching field of hard/soft-stacked perpendicular media

The time dependence of remanence coercivity and thermal stability were investigated for hard/soft-stacked media consisting of a magnetically hard granular layer underneath a very thin soft layer with a large saturation magnetization, M_s. The values of remanence coercivity at measurement times t′=10³ and 10⁻⁵ s (pulse field) were measured, and defined as H_r and H_r^P. The remanence coercivity on the recording time scale, H_r (1 ns), and the energy barrier, ΔE/kT, were evaluated by fitting H_r and H_r^P to Sharrock's equation taking into account the power law variation of the energy barrier, n. The value of H_r (1 ns) for a (Co–Pt)–SiO₂ (9 nm)/Co–SiO₂ (2 nm) stacked medium with an interfacial coupling control layer was about 9 kOe, which was less than half of that of a (Co–Pt)–SiO₂ (9 nm) conventional medium (=21.3 kOe). The value of ΔE/kT for the stacked medium was about 111 (n=0.7), and was not significantly different from the conventional medium. Moreover, no significant difference in the rate of decrease of H_r with increasing temperature was observed between media with and without interlayers. These results indicate that the use of a thin soft layer with high M_s was effective at significantly reducing H_r with no notable change in thermal stability.     

High pressure behaviour of KHSO4 studied by electrical impedance spectroscopy

Measurements of the electrical conductivity were performed in KHSO₄ at pressures between 0.5 and 2.5 GPa and in the temperature range 120-350 °C by the use of the impedance spectroscopy. The temperatures of the α-β phase transition (T_Tr) and of the melting (T_m), determined from the Arrhenius plots ln(σT) vs. 1/T, increase with pressure up to 1.5 GPa having dT/dP∼+45 K/GPa. Above the pressure 1.5 GPa, the pressure dependencies of T_Tr and T_m are negative dT/dP∼−45 K/GPa. At pressures above 0.5 GPa, the reversible decomposition of KHSO₄ into K₃H(SO₄)₂+H₂SO₄ (and probably into K₅H₃(SO₄)₄+H₂SO₄) affects the electrical conductivity of KHSO₄, with the typical values of the protonic electrical conductivity, c. 10⁻¹ S/cm at 2.5 GPa.     

FMR studies in the TbFeCo/GdFeCoSi bilayers

Bilayers, TbFeCo/GdFeCoSi, made by sputtering on glass substrate with buffer and capping layers were studied by measuring the hysteresis loop and by ferromagnetic resonance (FMR). When the field H was applied along the film normal, a double H_C hysteresis loop related to the two sublayers was observed. In ferromagnetic resonance measurements, a peculiar out-of-plane angular dependence of FMR spectrum was obtained. When scanning field H was 0-637 kA/m less than the anisotropy field of TbFeCo sublayer, two FMR peaks were observed. One peak was characteristic of uniaxial and unidirectional anisotropy. The anisotropy constants were obtained by fitting the data with the theory of FMR, and this peak was considered to be related to the low anisotropy GdFeCoSi layer. The second peak appeared only when the dc field H was orientated in a limited angular range around 180°. This peak was considered to be related to an uncoupled interfacial GdFeCoSi sublayer near Al capping layer. However, when H was scanned between 0-1114 kA/m, only one peak is observed due to magnetization reversal of TbFeCo layer with uniaxial anisotropy.     

Elemental depth profiling of a-Si1−xGex:H films by elastic recoil detection analysis and secondary ion mass spectrometry

The hydrogen content in a-Si_1−xGe_x:H thin films is an important factor deciding the density and the optical band gap. We measured the elemental depth profiles of hydrogen together with Si and Ge by elastic recoil detection analysis (ERDA) combined with Rutherford backscattering (RBS) using MeV He²⁺ ions. In order to determine the hydrogen depth profiles precisely, the energy- and angle-dependent recoil cross-sections were measured in advance for the standard sample of a CH₃⁺-implanted Si substrate. The cross-sections obtained here are reproduced well by a simple expression based on the partial wave analysis assuming a square well potential (width: r₀ = 2.67 × 10⁻¹³ cm, depth: V₀ = −36.9 MeV) within 1%. For the a-Si_1−xGe_x:H films whose elemental compositions were determined by ERDA/RBS, we measured the secondary ions yields of HCs₂⁺, SiCs₂⁺, H⁻, Si⁻ and Ge⁻ as a function of Ge concentration x. As a result, it is found that the useful yield ratios of HCs₂⁺/SiCs₂⁺, H⁻/Si⁻ and Ge⁻/Si⁻ are almost constant and thus the elemental depth profiles of the a-Si_1−xGe_x:H films can be also determined by secondary ion mass spectrometry (SIMS) within 10% free from a matrix effect.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Properties of exchange interaction in Yb3Fe5O12 under extreme conditions

In Yb₃Fe₅O₁₂, the exchange effective field can be expressed as H_eff=−λ·M_Fe=−λχ_eff·H_e=−γ·H_e where γ is named as the exchange field parameter and H_e is the external magnetic field. Then, in this paper, by the discussions on the characteristics of the exchange field parameter γ, the properties of exchange interaction in ytterbium iron garnet (Yb₃Fe₅O₁₂) are analyzed under extreme conditions (high magnetic fields and low temperatures). Our theory suggests that the exchange field parameter γ is the function of the temperatures under different external magnetic fields, and γ=a+b·T+c·T², where the coefficients a, b, c are associated with the external magnetic fields and the magnetized directions. Thus, the temperature-dependence, field-dependence and anisotropic characteristics of the exchange interaction in Yb₃Fe₅O₁₂ are revealed. Also, excellent fits to the available experiments are obtained.     

Synthesis and magnetic properties of Au-coated amorphous Fe20Ni80 nanoparticles

Gold-coated nanoparticles of Fe₂₀Ni₈₀ (permalloy) have been synthesized by a microemulsion process. The as-prepared samples consist of ∼5 nm diameter particles of amorphous Fe₂₀Ni₈₀ that are likely encapsulated in B₂O₃. One or more Fe₂₀Ni₈₀@B₂O₃ particles are subsequently encapsulated in 8-20 nm gold nanospheres, as determined by TEM and X-ray powder diffraction (XRD) line broadening. The gold shells were found to be under expansive strain. Magnetic data confirm the existence of a superparamagnetic phase with a blocking temperature, T_B, of ∼33 K. The saturation magnetization, M_S, of the as-prepared, Au-coated sample is ∼65 emu g⁻¹ at 5 K and ∼16 emu g⁻¹ at 300 K. The coercivity, H_C, is ∼280 Oe at 5 K.     

A study of Sm-substituted SrM magnets sintered using hydrothermally synthesised powders

Anisotropic SrM magnets with Sm substitution, which is observed to have the largest beneficial effect both on the coercivity and on the inhibition of grain growth at high temperature among the other elements such as La, Nd and Pr, were investigated. The average grain size of the samples decreases with increasing Sm/Sr ratio. All the magnets with Sm additions exhibit a bigger coercivity and remanence than those of the SrM magnet without Sm and the coercivity of the magnets increases with increasing Sm/Sr ratio. EDX quantitative analysis suggests that the solubility of Sm³⁺ in the SrM-type structure is very small and that the Sm³⁺ preferably goes into SrFeO_3−x, which is probably located around the SrM grain boundaries. The coercivity mechanism of the magnets is nucleation controlled. The formation and the distribution of the SrFeO_3−x phase around the SrM grain boundraies probably provides the inhibition of SrM grain growth, the reduction of the reverse domain nucleation at the grain surface and the isolation of the SrM grains. All these factors would contribute to the improvements of the coercivity of the magnets with Sm additions.     

Reactivity and XAFS study on (1−x)CeO2-xNiO (x=0.025-0.3) system in the two-step water-splitting reaction for solar H2 production

The redox reaction of Ce⁴⁺-Ce³⁺ promoted by the catalytic function of nickel ions in a (1−x)CeO₂-xNiO solid solution was investigated for solar H₂ production by the two-step water-splitting reaction. By irradiation using an infrared imaging lamp as a solar simulator, the O₂-releasing reaction with (1−x)CeO₂-xNiO solid solution proceeded at 1673-1873 K, and its reduced form was produced. The amounts of H₂ gas evolved by the reduced form were 1.2-2.5 cm³/g and the evolved gases amounts ratio of H₂/O₂ was nearly 2, which is equal to the stoichiometric value of the water-splitting reaction (H₂O=H₂+1/2O₂). The maximum amounts of evolved H₂ and O₂ gases were obtained at the Ce:Ni mole ratio of 0.95:0.05 (x=0.05) in the (1−x)CeO₂-xNiO system. The X-ray absorption fine structure (XAFS) measurement showed that the O₂-releasing and H₂-generation reactions with (1−x)CeO₂-xNiO solid solution were repeatable with the redox system of Ce⁴⁺-Ce³⁺, which was enhanced by the catalytic function of Ni²⁺-Ni⁰.     

Electrical and electromechanical properties of lead-potassium-yttrium-niobate ceramics—piezoelectric applications

Tungsten bronze (TB)-type oxide ceramic Pb_0.74K_0.13Y_0.13Nb₂O₆ (PKYN) has been synthesized by the standard solid state reaction method. Single phase formation, orthorhombic crystal structure was confirmed by X-ray diffraction (XRD). The substitution of Y³⁺ in Pb_0.74K_0.52Nb₂O₆ (PKN) decreased the unit cell volume and T_C=260 °C. PKYN exhibited the remnant polarization, P_r=8.5 μC/cm², and coercive field, E_c=28.71 kV/cm. Electrical spectroscopy studies were carried out over the temperature (35-595 °C) and frequency (45 Hz-5 MHz) ranges, and the charge carrier phenomenon, grain-grain boundary contribution and non-Debye-type relaxation were analyzed. The relaxation species are immobile charges in low temperature and oxygen vacancies at higher temperature. The theoretical values computed using the relations, ε′=ε_∞+sin(n(T)π/2)(a(T)/ε₀)(ω^n(T)−1); σ(ω)=σ_dc+Aωⁿ are fitted with the experimental one. The n and A parameters suggested that the charge carrier's couple with the soft mode and become mobile at T_C. The activation enthalpy, H_m=0.38 eV, has been estimated from the hopping frequency relation ω_p=ω_e exp(−H_m/k_BT). The piezoelectric constants K_t=35.4%, d₃₃=69×10⁻¹² C/N, d₃₁=−32×10⁻³ mV/N, S₁₁^E=17.8 pm²/N, etc., achieved in PKYN indicate the material is interesting for transducer applications. The activation energies from different formalisms confirmed the ionic-type conduction.