Electronic structure and magnetic and electromagnetic wave absorption properties of BaFe12-xCoxO19 M-type hexaferrites

Crystal, electronic structures and the magnetic and electromagnetic wave absorption properties of BaFe_12-xCo_xO₁₉ (x = 0–2) M-type hexaferrites prepared by a co-precipitation technique were studied. The analyses of X-ray diffraction patterns indicated that the samples mainly crystallized in the P6₃/mmc hexagonal structure, with the additional constitution of Y-type hexaferrite as x > 0. The replacement of Co²⁺ for Fe³⁺ in BaFe_12-xCo_xO₁₉ changed the lattice constants and caused lattice distortions. Particularly, Co²⁺ doping also reduced magnetization and hard magnetic property of BaFe_12-xCo_xO₁₉. This is ascribed to magnetic moment of Co²⁺ smaller than that of Fe³⁺ and to the decrease of magnetocrystalline anisotropy. Having studied electromagnetic wave absorption properties in the frequency range f = 0.1–18 GHz, we found BaFe_12-xCo_xO₁₉ showing high reflection loss (RL) values at frequencies of 0.1–15 GHz, but fairly low RL values at higher frequencies. These features suggest that BaFe_12-xCo_xO₁₉ can be suitable to electronic devices working at GHz frequencies.     

Mn离子取代M型钡铁氧体的研究

本文对Mn离子取代M型钡铁氧体BaFe_12-xMn_xO₁₉作了较系统的研究。主要结论如下:(1)在我们的实验条件下,Mn的取代量x可达4,其中约有0.1—0.3的Mn²⁺存在,其余Mn为三价。(2)Mn离子主要进入12k和2a晶位。(3)BaFe_12-xMn_xO₁₉的各向异性常数K₁₉,居里温度T_c和饱和磁化强度σ_s均随x的增加而下降。(4)Mn引起BaFe_12-xMn_xO₁₉的非共线自旋结构。(5)Mn³⁺在12k和2a晶位中的平均零场劈裂因子D^h比尖晶石中八面体B位上的Mn³⁺之D^c值小近一个数量级。 关键词：     

Spin waves in MnO; from 4°K to temperatures close to TN

Spin waves have been measured in MnO by inelastic scattering of neutrons from 4 °K to a temperature 0·25 °K below T_N. The 4 °K spectrum is interpreted in the frame of linear spin wave theory with effective exchange integrals J₁^? = 0·321 meV, J₁⁺ = 0·424 meV, J₂¹ = 0·446 meV and a phenomenological parameter for anisotropy D₁ = 0·059 meV. The effect of the actual dipole-dipole Hamiltonian is shown to give a priori a very good account of the lifting of the degeneracy of spin waves near the Brillouin zone center. The Bloch model for interacting spin waves and theories based on Green function approximations have been adapted to the MnO case, in order to compute the main properties (mean magnetization of a sublattice, anisotropic deformation, extra isotropic contraction and magnon spectrum) at many temperatures. Comparison of these with experimental results tends to favour a generalized Callen renormalization model, which gives an overall fit from 4 °K, to temperalures close to T_N.     

Plasma enhanced atomic layer deposition of gallium oxide on crystalline silicon: demonstration of surface passivation and negative interfacial charge

Herein we report on the passivation of crystalline silicon by gallium oxide (Ga₂O₃) using oxygen plasma as the oxidizing reactant in an atomic layer deposition (ALD) process. Excess carrier lifetimes of 2.1 ms have been measured on 1.75 Ω cm p‐type silicon, from which a surface recombination current density J₀ of 7 fA cm^–2 is extracted. From high frequency capacitance‐voltage (HF CV) measurements it is shown that, as in the case of Al₂O₃, the presence of a high negative charge density Q_tot/q of up to –6.2 × 10¹² cm^–2 is one factor contributing to the passivation of silicon by Ga₂O₃. Defect densities at midgap on the order of ～5 × 10¹¹ eV^–1 cm^–2 are extracted from the HF CV data on samples annealed at 300 °C for 30 minutes in a H₂/Ar ambient, representing an order of magnitude reduction in the defect density compared to pre‐anneal data. Passivation of a boron‐diffused p⁺ surface (96 Ω/□) is also demonstrated, resulting in a J₀ of 52 fA cm^–2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ab initio determination of an extended Heisenberg Hamiltonian in CuO 2 layers

Accurate ab initio calculations on embedded Cu₄O₁₂ square clusters, fragments of the La₂CuO₄ lattice, confirm a value of the nearest neighbor antiferromagnetic coupling (J = 124 meV) previously obtained from ab initio calculations on bicentric clusters and in good agreement with experiment. These calculations predict non negligible antiferromagnetic second-neighbor interaction (J' = 6.5 meV) and four-spin cyclic exchange (K = 14 meV), which may affect the thermodynamic and spectroscopic properties of these materials. The dependence of the magnetic coupling on local lattice distortions has also been investigated. Among them the best candidate to induce a spin-phonon effect seems to be the movement of the Cu atoms, changing the Cu-Cu distance, for which the variation of the nearest neighbor magnetic coupling with the Cu-O distance is Δ J /Δ d _{Cu - O} ∼ 1700 cm^-1?^-1. Received 20 November 2000     

Application of the multireference equation of motion coupled cluster method,including spin–orbit coupling,to the atomic spectra of Cr,Mn, Fe and Co

The recently introduced multireference equation of motion (MR-EOM) approach is combined with a simple treatment of spin–orbit coupling, as implemented in the ORCA program. The resulting multireference equation of motion spin–orbit coupling (MR-EOM-SOC) approach is applied to the first-row transition metal atoms Cr, Mn, Fe and Co, for which experimental data are readily available. Using the MR-EOM-SOC approach, the splittings in each L-S multiplet can be accurately assessed (root mean square (RMS) errors of about 70 cm^?1). The RMS errors for J-specific excitation energies range from 414 to 783 cm^?1 and are comparable to previously reported J-averaged MR-EOM results using the ACESII program. The MR-EOM approach is highly efficient. A typical MR-EOM calculation of a full spin–orbit spectrum takes about 2 CPU hours on a single processor of a 12-core node, consisting of Intel XEON 2.93 GHz CPUs with 12.3 MB of shared cache memory.     

Indirect carbon–carbon spin–spin couplings across one,two and three bonds in pyridine and diazine systems: experiment and theory

An excellent linear correlation is found between a large body of experimental spin–spin carbon–carbon couplings, J(CC), across one, two and three bonds in pyridine and diazine ring systems and the corresponding B3PW91/6‐311++G(d,p)//B3PW91/6‐311++G(d,p) computations. The correlation does not differ significantly from the simplest relationship possible, J(CC)_exp. = J(CC)_calcd., within a small and random spread of about 1 Hz. There are 276 experimental values considered, and 124 out of these are new and come from the present work. The aromatic carbon–carbon couplings vary from ?7.6 through +78.5 Hz. It is shown that the correlation provides a reliable tool for predictions of the signs of aromatic J(CC)'s even if the magnitudes of the latter are of the order of 1 Hz. It is demonstrated, for the first time, that the relatively weak ² J(CC) couplings, in the heteroaromatic systems studied, can bear either sign and span a considerable range of about 11 Hz. The character of the correlation indicates that rovibronic effects on aromatic J(CC)'s and those of nuclear motions on aromatic J(CC)'s are practically negligible. All of this is in a perfect agreement with our recent extensive studies on aromatic J(CC)'s in analogous benzene ring system. Substituent effects on the aromatic J(CC)'s turn out to be significant not only for ¹J(CC)'s but also for most of ³J(CC)'s and ² J(CC)'s, and the computation neatly reciprocates these trends. Copyright © 2008 John Wiley & Sons, Ltd.     

Magnetic properties of barium ferrite synthesized using a microemulsion mediated process

Ultrafine barium ferrite particles have been synthesized using a microemulsion mediated process. The aqueous cores (typically 10–25 nm in size) of water-in-oil microemulsions were used as constrained microreactors for the precipitation of precursor carbonates of Ba²⁺ and Fe³⁺. These precursors (5–15 nm in size) when heated at 950°C, transformed to the hexagonal ferrite BaFe₁₂O₁₉ as confirmed by X-ray diffraction. This barium ferrite powder had an intrinsic coercivity of 5089 Oe and a saturation magnetization of 60.1 emu/g.     

Raman‐induced Kerr effect spectroscopy of single‐wall carbon nanotubes aqueous suspensions in the range 0.1–10 and 100–250 cm−1

Here, we study a low (less than 0.1 µg/ml) concentration aqueous suspension of single‐wall carbon nanotubes (SWNTs) by Raman‐induced Kerr effect spectroscopy (RIKES) in the spectral bands 0.1–10 and 100–250 cm⁻¹. This method is capable of carrying out direct investigation of SWNT hydration layers. A comparison of RIKES spectra of SWNT aqueous suspension and that of milli‐Q water shows a considerable growth in the intensity of low wavenumber Raman modes. These modes in the 0.1–10 cm⁻¹ range are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed intensity increase as due to the production of hydrogen peroxide and the formation of a low‐density depletion layer on the water–nanotube interface. A few SWNT radial breathing modes (RBM)are observed (ω_RBM = 118.5, 164.7 and 233.5 cm⁻¹) in aqueous suspension, which allows us to estimate the SWNT diameters (∼2.0, 1.5, and 1 nm, respectively). Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of Magnetic Pulse Processing on the Structure and Magnetic Properties of Ferrites

The effect a pulsed magnetic field has on the crystal structure and macroscopic magnetic parameters of hexagonal ferrites BaFe₁₂O₁₉ and SrFe₁₂O₁₉ are studied. It is shown that changes in the physical properties of ferrites are due to the ordering of cation vacancies on the boundaries of hexagonal and spinel blocks that minimize local distortion of the oxygen polyhedrons. Violation of the collinear ordering of the magnetic moments of iron ions in the nonequivalent positions of SrFe₁₂O₁₉ ferrite is observed, due to the selective localization of such vacancies (and thus violations of the magnetic relationships in Fe–O–Fe).     

Effects of a single defect in composite gate insulators of carbon nanotube transistors

The polar phonon modes in BaFe₁₂O₁₉ single crystal are studied in the temperature range from 6 to 300 K by polarized infrared spectroscopy. The phonon spectrum of the crystal is strongly anharmonic and unstable with respect to long-wavelength fluctuations of the dielectric permittivity along the hexagonal axis. Our results suggests that in BaFe₁₂O₁₉ hexaferrite symmetry lowering to the polar phase with the space group P6₃ mc can be expected.     

Raman scattering in the magnetically frustrated double perovskite Sr2YRuO6

The spin correlations and excitations of the Sr₂YRuO₆ double perovskite are investigated by means of Raman scattering, complemented by synchrotron X‐ray diffraction measurements. Anomalous softening of a breathing mode of the oxygen octahedra is observed below ~200 K, much above the long‐range antiferromagnetic ordering temperature, T_N1 = 32 K, due to a spin‐phonon coupling mechanism in the presence of magnetic correlations. A diffusive Raman signal is also observed, possibly associated with spin excitations within magnetically correlated regions. Our results point to a characteristic energy and temperature scale of ~25 meV/200 K below which unusual behavior associated with magnetic correlations is observed in this material. Copyright © 2013 John Wiley & Sons, Ltd.     

Raman and infrared structural investigation of (PbO)x(ZnO)(0.6−x)(P2O5)0.4 glasses

The structure of ternary (PbO)_x(ZnO)_(0.6−x)(P₂O₅)_0.4glasses was investigated using Raman scattering and infrared spectroscopy over the compositional range x = 0–0.6. No significant change of the average chain length composed by PO₄ tetrahedral units with the substitution of zinc for the lead cation was observed. The linewidth and wavenumber variations of the Raman high‐wavenumber bands reflect the Zn/Pb substitution in these glasses and are correlated with the metal–oxygen force constant and local disorder. The infrared reflectivity spectra have been fitted with the four‐parameter dielectric function model. The variation in the 1000–1200 cm⁻¹wavenumber range has been attributed to an increase of the oscillator damping Γ_LO(PO₃)₂₋ as with PbO content vibrations rather than a variation of the chain length. Copyright © 2008 John Wiley & Sons, Ltd.     

Precise determination of Mg/Fe ratios applicable to terrestrial olivine samples using Raman spectroscopy

The relationship between Mg# [ = 100 Mg/(Mg + Fe) in mol] and the Raman shift was analyzed precisely for olivine [(Mg, Fe)₂SiO₄] samples with Mg# between 100 and 62.8. Two prominent peaks at 826–820 cm⁻¹ (peak 1) and 858–849 cm⁻¹ (peak 2) and three subordinate peaks at 883–881 cm⁻¹ (peak 3), 920–914 cm⁻¹ (peak 4), and 967–951 cm⁻¹ (peak 5) were observed to shift monotonously to lower wavenumbers with decreasing Mg#. The ΔMg#( = Mg#_ref − Mg#) versus Δν(= ν_ref − ν) can be linearly regressed for each peak as ΔMg# = A Δν, where ν is a peak wavenumber of olivine with Mg# ranging from 100 to 62.8, and ν_ref is that of olivine with a reference value of Mg#, namely, Mg#_ref. We set Mg#_ref as 100 (i.e.pure forsterite Mg₂SiO₄) whereas A is a regression parameter (5.789, 4.294, 12.34, 6.348, and 2.09, respectively,for peaks 1, 2, 3, 4, and 5). This equation enables us to avoid small inter‐laboratory differences of wavenumber calibration. The equation for peak 2 yields estimations of Mg# in geologically satisfactory precision, ± 1 Mg# (1σ) in the Mg# range of 100–62.8. Copyright © 2011 John Wiley & Sons, Ltd.     

Exchange interactions in BaFe12O19

In the scope of the mean field approximation the nine nearest neighbour exchange interactions existing among the ferric ions in BaFe₁₂O₁₉ hexagonal ferrite have been determined from the experimental sublattice magnetizations. It is shown that these exchange interactions are well explained by means of the superexchange theory. It is also concluded that some direct exchange interaction does exist among the octahedral 4f _VI ions. The calculated magnetization, paramagnetic susceptibility, and Curie temperature are in good agreement with the corresponding experimental values. The stability of the collinear Gorter-type magnetic structure of BaFe₁₂O₁₉ is discussed as well.     

The dynamics of bipyramidal ions in magnetoplumbite-like hexagonal ferrite systems revisited

The dynamics of the bipyramidal 4e–Fe ions in the M-type hexagonal ferrite La_0.7Na_0.3Fe₁₂O₁₉ single crystal, is investigated by using Mössbauer spectroscopy. We show that a photon self-interference phenomenon can be used to explain the available experimental data. From this model we have deduced the jumping distance of the Fe(4e) ions. This model can also be succesfully used to investigate the existing data on the isomorphous CaAl₁₁FeO₁₉ and BaFe₁₂O₁₉ oxides. In all cases, the calculated jumping distances are in a excellent agreement with X-ray diffraction results. For CaAl₁₁FeO₁₉ and BaFe₁₂O₁₉ we have deduced the thermal dependence of the jumping distance. Any evidence of an atomic freezing is not found in the temperature range 80–300 K.     

Mössbauer investigation of In and Sc substituted barium hexaferrite

A detail Mössbauer analysis has been performed on polycrystalline samples of hexagonal ferrites with composition BaFe_12-x In _x O₁₉ (0x4) and BaFe_12-x ScxO₁₉ (0x3). The dependence on composition of the distribution of metallic cations among the five sublattices of the structure has been determined: these data confirm the strong preference of Sc and In ions for the sites belonging to the R block.As a consequence iron ions located in the main spin up sublattice (12k) with different number of neighbouring Fe³⁺ ions display different temperature dependences of the magnetization. The occurrence of non-collinear spin configurations, even for very low degrees of substitution of iron, has also been evidenced.     

On the Plasma Chemistry of an RF Discharge Containing Aluminium Tri‐Isopropoxide Studied by FTIR Spectroscopy

In Ar and Ar/N₂ radio frequency (RF) discharges with admixtures of aluminium tri‐isopropoxide (ATI) the fragmentation of this metal‐organic precursor was studied by means of Fourier Transform Infrared (FTIR) spectroscopy using an optical long path cell providing an optical length of l = 17.2 m. The experiments were performed in an asymmetric capacitively coupled process plasma at a frequency of f = 13.56 MHz and at pres‐sure values in the range of p = 1–10.5 Pa. The discharge power was chosen between P = 10–100 W. Using FTIR spectroscopy the evolution of the concentrations of ATI and of six stable molecules, CH₄, C₂H₂, C₂H₄, C₂H₆, CO and HCN, was monitored under flowing conditions at gas flows of Φ_total = 0.5–14.5 sccm in the discharge. The concentrations of the reaction products were measured tobe between 2 x 10¹² molecules cm^–3 as e.g. found for C₂H₄and C₂H₆, and 5 x 10¹³ molecules cm^–3, as e.g. in the case of CO. In the plasma a complete dissociation of the precursor ATI was found at a power value of about P = 80 W independent on the admixture of Ar or N₂. The fragmentation efficiency (F_E) of the reaction products which originate from the ATI molecules ranges between 0.2 and 4 x 10¹⁶ molecules J^–1 while the fragmentation rate (F_R) reached up to 2.5 x 10¹⁸ molecules s^–1. The multi component detection ability of the spectrometer served to analyse the carbon balance of the by‐product formation. For all experiments, the carbon balance never exceeded 25%. Therefore, in the plasmas the majority of the provided carbon is most likely deposited at the reactor walls or forms dust particles or higher molecular C_xH_y. The conversion efficiencies (C_E) of the produced molecular species ranges between 0.1 x 10¹⁵ molecules J^–1 for C₂H₄ and 5 x 10¹⁵ molecules J^–1 for C₂H₆ depending on the discharge conditions of the RF plasma. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic anisotropy and saturation of LaFe12O19 and some related compounds

The saturation magnetization σ_s and uniaxial anisotropy constants K₁ and K₂ are measured on a polycrystalline, crystal-oriented sample of LaFe₁₂O₁₉ contaminated with known amounts of Fe₃O₄ and LaFeO₃. K₁ and K₂ increase strongly with decreasing temperature and the value of K₁ = (19–24) × 10⁵ erg/g at T = 0 shows that the substance is considerably more anisotropic than BaFe₁₂O₁₉ (K₁ ? 8·5 × 10⁵ erg/g) at low temperatures. The σ_s-T curve is more convex than that of BaFe₁₂O₁₉, so that σ_s is 11 per cent higher at room temperature but lower at T = 0. The value σ_s(T = 0) = 96·2 G cm³/g (19·2 μ_B/molecule) and the anisotropic behaviour are attributed to the presence of 1 Fe²⁺/molecule occupying the octahedral 2a sites in the magnetoplumbite lattice and having a uniaxial anisotropy of 10–15 cm^?1/ion.From measurements on polycrystalline, crystal-oriented samples of BaFe_10·8Fe²⁺_0·6Ti⁴⁺_0·6O₁₉ and BaFe_10·5Fe²⁺_1·0Sb⁵⁺_0·5O₁₉ it was found that, in comparison with LaFe₁₁Fe²⁺O₁₉, σ_s (T = 0) is smaller and K₁ is much smaller and much less temperature-dependent. The difference in anisotropic behaviour is attributed to a different distribution of the Fe²⁺ ions among the lattice sites due to the effective positive charge of the Ti⁴⁺ and Sb⁵⁺ ions.     

Substituent effects on indirect carbon–carbon couplings,J(CC), in substituted thiophenes,pyrroles, and furans studied by experiment and theory

An excellent linear correlation is found between a large set of experimental spin–spin carbon–carbon coupling constants, J(CC), in thiophene, pyrrole, and furan systems and the corresponding B3PW91/6‐311++G(2d,p)//B3PW91/6‐311++G(2d,p) calculated estimates. The correlation does not differ significantly from the simplest relationship possible, J(CC)_exp. = J(CC)_calcd., within a small and random spread of about 1 Hz. There are 285 experimental values considered, and 202 out of these are new and come from the present work. The character of the correlation indicates that rovibronic effects on aromatic J(CC)'s, and those of nuclear motions on aromatic J(CC)'s are practically negligible. All of this is in a perfect agreement with our recent extensive studies on aromatic J(CC)'s in pyridine and benzene ring systems. As has been shown by computations, not only large one‐bond couplings but also almost all long‐range ones occurring between the carbons of the heteroaromatic rings are, with a few exceptions, positive. Significant substituent effects experimentally observed in the one‐bond as well as long‐range couplings are very accurately reproduced by the computation. The experimental coupling magnitudes vary from ca. 1 to 98 Hz. The J(CC)'s computed for the model variously substituted trimethylsilyl and fluoro derivatives, which are not easily accessible experimentally, span a range of about 130 Hz, from ca. ?2 in up to ca. +125 Hz . Copyright © 2012 John Wiley & Sons, Ltd.