Co50Fe25-xMnxSi25系列合金的结构、磁性和半金属性研究

利用实验和能带计算相结合的方法,对介于两种预期的半金属Heusler合金Co₂FeSi和Co₂MnSi间的四元合金Co₅₀Fe_25-xMn_xSi₂₅的晶体结构、磁性、能带结构和半金属性进行了研究.采用考虑库仑相互作用的的广义梯度近似方法计算了系列合金的能带结构,通过与实验结果进行对比,揭示了成分变化过程中合金分子磁矩及原子磁矩的变化规律.研究发现, 关键词： 磁性 半金属 Heusler合金     

Optical Properties of Semiconducting Ruthenium Silicide

The optical properties of ruthenium silicide Ru₂Si₃ have been studied theoretically and experimentally. The energy band spectrum and optical properties were simulated with the aid of the firstprinciple selfconsistent method of linear attached plane waves. The spectral dependence of the absorption coefficient in the 0.52.2 eV energy range was measured experimentally by the photothermal refractive spectroscopy method. It is established that ruthenium silicide is a directgap semiconductor having an energy gap of 0.84 eV and a low oscillator strength of the first direct transition.     

Influence of Si substitution on structural,electronic and magnetic properties of Fe<Subscript>2</Subscript>MnGa Heusler compound

We investigate the electronic and magnetic properties of Fe₂MnGa_1?x Si _x alloy (x = 0, 0.25, 0.5, 0.75, and 1) using first-principles density functional theory within the generalized gradient approximation method. The lattice constant decreases linearly whereas bulk modulus increases with increasing Si content. The total magnetic moment varies linearly with increasing Si content, which follows the Slater-Pauling rule. Electronic band structure calculations indicate that the Fe₂MnGa_1?x Si _x exhibits half-metallic character for all the concentrations studied and the spin polarization and the spin-down band gap both increase with the Si content. Based on the magnetic properties calculations, the Heisenberg exchange coupling parameters give Fe-Mn ferromagnetic coupling and Mn-Mn antiferromagnetic coupling. The T _C first decreases and then increases with Si content, which is in well agreement with the experimental results.     

A Mössbauer spectroscopic study of cobalt-iron molybdates

Fe _x Co_1–x MoO₄ compounds prepared by coprecipitation were studied by XRD, electrical conductivity and mainly by absorption and emission Mössbauer spectroscopy. FeMoO₄ and CoMoO₄ samples were shown to contain Fe³⁺ and Co³⁺, respectively, in solid solution. Three kinds of Fe _x Co_1–x MoO₄ solids can be described. Forx0.16: one has a -Co(Fe²⁺, Fe³⁺)MoO₄ solid solution. For 0.17x0.25: one has the same solid solution with its surface rich in Fe³⁺. Forx0.26: one has the same solid solution with only bulk Fe³⁺, and ferric molybdate. Studies of reduction by hydrogen and of catalytic reaction of mechanical mixtures of CoMoO₄ and ferric molybdate support these statements.     

Electrical conductivity and thermopower in Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript> S sulfides

This paper reports on the results of investigations into the structural, electrical, and thermoelectrical properties of sulfides Co _x Mn_{1 ? x} S (0 ≤ x ≤ 0.4) in the temperature range 80–950 K. It is established that the thermopower coefficient α decreases significantly with an increase in the cobalt concentration in the lattice of the α-MnS compound. The Co _x Mn_{1 ? x} S compounds with cobalt concentrations in the range 0 ≤ x ≤ 0.3 are semiconductors with hole conduction (α > 0), whereas the compound with x = 0.4 exhibits metallic conduction (α < 0). It is found that the band gap E _g of the compounds under investigation varies in the range from 1.46 eV for α-MnS (x = 0) to 0.26 eV for Co _x Mn_{1 ? x} S (x = 0.4).     

Experimental and theoretical studies of Si/P substituted orthorhombic Fe2P

A Mössbauer spectroscopic study of orthorhombic Fe₂P_1–x Si _x withx 0.35 was performed. A large spread in magnetic hyperfine fields was found at the six Fe positions ranging from 10–26 T at 4.2 K. Small rearrangements in the crystal positions as compared to the hexagonal phase cause large changes in the magnetic field. Large changes in Fe magnetic moments have also been obtained in a spin-polarized LMTO band calculation performed on orthorhombic Fe₂P as compared to a similar calculation of hexagonal Fe₂P.     

Magnetic Study of Doped Ba Ferrites Prepared by Citrate Method

The M-type barium ferrite is doped with either Co²⁺-Ti⁴⁺ or Co²⁺-Zr⁴⁺ pairs to reduce its intrinsically high uniaxial magnetic anisotropy in order to make fine particles for magnetic recording. The magnetic parameters were investigated by magnetic measurements and the Mössbauer spectroscopy. Compounds (BaF) obtained from BaCo _x (Ti,Zr) _x Fe_12-2x O₁₉ with 0x1.0 have been prepared by the modified citrate method with the initial ratio of Ba:Fe equal to 1:10.8. The substitution of Co - Ti or Co - Zr for Fe³⁺ ions affects mainly the positions 2a and 4f ₂. Ba ferrite with the substitution x 0.8 is promising for perpendicular recording media applications.     

Energy levels of paired donor impurities in SixGe1−x alloys

The dependences on alloy compositionx of the bound and resonant deep energy levels of nearest-neighbor (P,P), (As, As), and (Sb, Sb) pairs in Si _x Ge_1–x alloys are predicted. Based on these predictions, it appears likely that (P, P) and (As, As) produce at least one deep level in the gap for allx, but that (Sb, Sb) does not for anyx.     

Mixed valence states in cobalt iron cyanide

Cobalt iron cyanide with both Co and Fe in mixed valence states were prepared and characterized. In this mixed valence system the cobalt atom is found both as high spin Co(2+) and low spin Co(III) while iron always appears in low spin state to form two solid solutions: Co(2+)Co(III) hexacyanoferrates (II,III), and Co(2+)Co(III) hexacyanoferrate (II). Such solid solutions have the following formula units: (Co²⁺)_x(Co^III)_1−xK[(Fe^II)_1−x(Fe^III)_x(CN)₆]·H₂O and (Co²⁺)_1.5x(Co^III)_1−xK[Fe^II(CN)₆]·yH₂O (0?x?1, 1?y?14). Compounds within these two series were characterized from Infrared, Mössbauer, X-ray diffraction and thermo-gravimetric data, and magnetic measurements at low temperature. A model for their crystal structure is proposed and the structure for a representative composition refined from XRD powder patterns using the Rietveld method. A simple and reproducible procedure to prepare these solid solutions is provided. Within hexacyanoferrates, such mixed valence states system in both metal centres shows unique features, which are discussed from the obtained data.     

Relation between the fine structure of the vibrational spectrum of the crystal lattice and the cation distribution in Co1+2xFe2−3xSbxO4 ferrites

The infrared reflection spectra in the region of lattice vibrations (1500–200 cm^–1) of ferrite spinels Co_1+2xFe_2–3xSb_xO₄ with x=0.0–0.4 are investigated. The permittivity spectra are calculated using the Kramers-Kronig relations. A dispersion analysis of the ₁(v); ₂(v) spectra, carried out using the multiscintillator model, enabled the fine structure of the bands of the spectra to be determined. It was found that for CoFe₂O₄ ferrite the short-wave band (v=590 cm^–1) consists of two components, while the long-wave band (v=375 cm^–1) consists of fur components. Since cobalt ferrite is inverted spinel, in which there are only Fe³⁺ ions in the tetra positions, the doublet structure with v=590 cm^–1 must obviously belong to vibrations of the ion groups FeO₆ and CoO₆, while the second band may belong to vibrations of the ion complexes consisting of the tetra-cation (Fe³⁺), oxygen and the three closest octa-cations [3Fe], [2Fe1Co], [2Co1Fe] and [3Co]. The replacement of some of the iron ions with antimony leads to the appearance of additional lines from the short-wave edge of both bands. The intensity of these lines increases as the value of the diamagnetic substitution increases, which enables the highest-frequency component to be uniquely related to the vibrations of the complex formed by the tetra-cations Fe³⁺ or Co²⁺, the anion and the three octa-cations Sb⁵⁺.V. I. Ul'yanov-Lenin Kazan State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 105–109, July, 1995.     

Magnetic hyperfine fields in Y2Fe17−x Si x compounds

Y₂Fe_17–x Si _x compounds withx=0, 0.5, 1.0, 1.5, 2.0, 2.5 and3.0 were investigated by magnetic measurement andNMR. It is found that with increasing Si content the Curie temperatureT _C increases while the average Fe magnetic moment _Fe decreases. NMR study indicates that Si preferentially substitute the Fe atoms at 4f sites, which is responsible for the increase ofT _C.     

High-temperature oxidation resistance and magnetic properties of Si-doped Sm2Co17-type magnets at 500 °C

The high-temperature oxidation resistance and magnetic properties of Si-doped Sm₂Co₁₇-type magnets at 500 °C were systematically investigated. The Sm(Co_0.76, Fe_0.1, Cu_0.1, Zr_0.04)₇Si_x (x=0–0.6) magnets were prepared by the conventional powder metallurgical technique. It is found that the addition of silicon in the Sm₂Co₁₇-type magnet can remarkably improve its oxidation resistance. Moreover, a small amount of silicon addition can also increase its high-temperature intrinsic coercivity. A maximum intrinsic coercivity of 6.7 kOe at 500 °C was obtained for the Sm₂Co₁₇-type magnet with Si content x=0.4, whose high-temperature maximum energy product loss was about 2.5 times smaller than pure Sm₂Co₁₇-type magnet after oxidation at 500 °C for 100 h, indicating the enhanced oxidation resistance. Its corresponding Curie temperature and saturation magnetization are about 723.9 °C and 7.4 kG, respectively.     

Mössbauer studies on the series La1-xSrxFeO3

Mössbauer spectra have been recorded at 4.2 and 300 K on the series La_1–x Sr _x FeO₃, wherex varies from 0 to 1.0 in steps of 0.1. Neutron diffraction experiments have shown that the crystal structure is orthorhombic for 0x<0.3, rhombohedral for 0.4x0.7, and cubic for 0.8<x1.0. Mössbauer spectra at 4.2 K are composed of magnetic sextet components arising from different charge states of iron ions. In the orthorhombic and rhombohedral phases, the charge states Fe³⁺ and Fe⁵⁺ coexist. In the cubic phase, iron is present as Fe³⁺ and Fe⁴⁺ states. At 300 K, the samples are magnetically ordered in the range 0 x0.3 and the coexistence of Fe³⁺ and Fe⁵⁺ remains. For samples 0.4x1.0, the samples are paramagnetic. Fits to these spectra require two components, one corresponding to an Fe⁴⁺ state, the other being best described as an Fe³⁺ ion forx0.7 but forx>0.7 having a mean charge state which increases to 3.5 forx=1.0.     

Synthesis and magnetic properties of Pr(Fe 1-xCo x) 2 and Pr 1-yTb y(Fe 0.4Co 0.6) 2 alloys

Measurement of X-ray diffraction, magnetization and magnetostriction was made on the Pr(Fe_1-xCo_x)₂ (x=0.4, 0.5 and 0.6) and Pr_1-yTb_y(Fe_0.4Co_0.6)₂ (y=0, 0.1, 0.2 and 0.3) alloy series. It was found that a cubic phase with the MgCu₂ structure can be obtained in the Pr(Fe_1-xCo_x)₂ series only at x=0.6. The Pr_1-yTb_y(Fe_0.4Co_0.6)₂ system has the cubic MgCu₂ structure over the studied range for y. The lattice constant and magnetization decrease and the Curie temperature increases with increasing y. At 7 K, Pr_1-yTb_y(Fe_0.4Co_0.6)₂ samples are found to have huge intrinsic coercivities, which are associated with narrow domain walls. It is also found from X-ray measurement that in Pr_1-yTb_y(Fe_0.4Co_0.6)₂ the spontaneous magnetostriction ₁₁₁ increases due to Tb substitution, while the saturation magnetostriction _s is much lower than ₁₁₁. This can be attributed to the large value of ₁₀₀ with an opposite sign to ₁₁₁, which may be caused by the filling of the d band due to Co substitution. PACS 75.80.-g; 61.10.-i; 75.60.-d     

Studying the properties of Fe and Fe–Co nanotubes in polymer ion-track membranes

Iron and iron–cobalt nanostructures are probed by means of Mössbauer spectroscopy combined with scanning electron microscopy, energy-dispersion analysis, and X-ray diffraction. The obtained nanostructures are single-phase Fe_{1 ? x}Co _x (0 ≤ x ≤ 1) nanotubes that have high degrees of polycrystallinity and a bcc lattice 12 μm long and 110 ± 3 nm in diameter, with walls 21 ± 2 nm thick. A random distribution of the orientations of the magnetic momenta of Fe atoms are observed for Fe nanotubes, while Fe–Co nanotubes are characterized by a magnetic texture along their axes.     

Increase in the magnetostrictive susceptibility of Tb0.3Dy0.67Ho0.03Fe2−x Co x alloys upon substitution of cobalt for iron

This paper reports on the results of investigations into the concentration dependences of the magnetostrictive susceptibility, the magnetostriction, the magnetization, and the Curie temperature for Tb_0.3Dy_0.67Ho_0.03Fe_2?x Co _x alloys upon substitution of cobalt for iron. It is revealed that the temperature of the spin-reorientation transition shifts toward room temperature with an increase in the cobalt content in the range 0 ≤ x ≤ 1.3. Substitution of cobalt for iron in the alloys leads to a decrease in the contribution of the 3d transition metal sublattice to the magnetic anisotropy owing to the opposite signs of the single-ion anisotropy constants for iron and cobalt. The decrease observed in the magnetocrystalline anisotropy compensated in both rare-earth and 3d transition metal sublattices is responsible for the high magnetostrictive susceptibility of the studied compounds at a high cobalt content (x = 1.3) in the room-temperature range.     

Formation of interfacial iron silicides on the oxidized silicon surface during solid-phase epitaxy

The early stages of iron silicide formation in the Fe/SiO _x /Si(100) ternary system during solid-phase epitaxy are studied by high-resolution (～100 meV) photoelectron spectroscopy using synchrotron radiation. The spectra of core and valence electrons taken after a number of isochronous heat treatments of the samples at 750°C are analyzed. It is found that the solid-phase reaction between Fe and Si atoms proceeds in the vicinity of the SiO _x /Si interface, which metal atoms reach when deposited on the sample surface at room temperature. Iron silicide starts forming at 60°C. Solid-phase synthesis is shown to proceed in two stages: the formation of the metastable FeSi interfacial phase with a CsCl-like structure and the formation of the stable β-FeSi₂ phase. During annealing, structural modification of the silicon oxide occurs, which shows up in the growth of the Si⁺⁴ peaks and attenuation of the Si⁺² peaks.     

Pulsed laser deposition of magnetic films by ablation of Co- and Fe-based amorphous alloys

Magnetic films were prepared by pulsed laser ablation of amorphous magnetic ribbons (composition Co₆₇Cr₇Fe₄Si₈B₁₄, Fe_73.5Nb₃Cu₁Si_13.5B₉, and Fe₄₀Ni₄₀B₂₀) and permalloy foils (composition Fe_xNi_1-x with x=22,50). Depositions were performed in a vacuum of (2–4)×10^-5 Pa by KrF excimer laser pulses at fluences of between 2 and 7 Jcm². Films were deposited on oxidized silicon wafers, placed 60–80 mm apart from the target. Films were analyzed by SEM, XRD, RBS, and EDS. Ferromagnetic resonance (FMR) spectra were studied at GHz frequencies. From RBS and EDS measurements it follows that the stoichiometry of the targets is preserved in the films to a large extent. The films deposited from amorphous targets remain amorphous. From FMR studies it follows that Fe and Fe-Ni rich films exhibit properties close to those of bulk alloys, having very low magnetization motion damping parameter () of 7.0–7.8×10⁷ rad/s, which are appropriate for fast magnetic sensors. PACS 79.20.Ds; 75.50.Kj; 75.70.-i     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Optical properties of semiconducting iron disilicide thin films

The iron silicides samples were prepared by annealing of iron films evaporated onto silicon wafers and capped with amorphous silicon thin overlayers. Semiconducting FeSi₂ phase is formed by annealing at the temperatures from 550°C to 850°C. The optical properties of the FeSi₂ layers have been deduced from reflectance and transmittance measurements carried out in the temperature range of (77–380) K. The spectral dependence of the absorption coefficient favours direct allowed transitions with forbidden energy gap of 0.87eV at the room temperature. The application of a simple three-parameter semiempirical formula to the temperature dependence of the direct energy gaps leads to the following best fit parameters: the band gap at zero temperature E _g (0) = (0.895 ± 0.004)eV, the dimensionless coupling parameter S = 2.0 ± 0.3, and the average phonon energy <hw> = (46 ± 8)meV. By examining all the reported triplets of parameters for -FeSi₂ fabricated by different techniques and thermal processes, an obvious discrepancy can be found for the lattice coupling parameter and average phonon energy, although the bandgaps at 0 K are very similar. Unlike the theoretical prediction and the earlier reported result, our results do not show any evidence of a particularly strong electron-phonon interaction, which would give the lower carrier mobilities. -FeSi₂ seems to be an intriguing material where states with energies near the band edges permit ambiguous interpretation of the character of transitions. From optical model for the thin film-substrate system we found the index of refraction to be (5–5.9) in the photon energy interval from 0.65 to 1.15eV. There is also indication of an additional higher-energy absorption edge at l.05eV.