Mössbauer and TDPAC Studies on Fe/Mo Multilayers

Hyperfine fields at Fe and Mo layers in polyimide/Fe(10 nm)/[Mo(1.1 nm)/Fe(2.0 nm)]₁₂₀ and [Mo(1.3 nm) /Fe(2.0 nm)]₁₂₀ multilayers prepared by the electron-beam evaporation technique were measured at room-temperature by Mössbauer spectroscopy and perturbed-angular-correlation spectroscopy. The hyperfine fields in the Fe layers do not show a clear dependence on the Mo layer thickness. On the other hand, the hyperfine fields in the Mo layers show different magnetic structures in these samples. The difference suggests a variation of electron spin polarization in the Mo layers.     

X-ray properties and interface study of B4C/Mo and B4C/Mo2C periodic multilayers

We present a comparative study of B₄C/Mo and B₄C/Mo₂C periodic multilayer structures deposited by magnetron sputtering. The characterization was performed by grazing incidence X-ray reflectometry at two different energies and high resolution transmission electron microscopy. The experimental results indicate the existence of an interdiffusion layer at the B₄C-on-Mo interface in the B₄C/Mo system. Thus, the B₄C/Mo multilayers were modeled by an asymmetric structure with three layers in each period. The thickness of B₄C-on-Mo interfacial layer was estimated about 1.1 nm. The B₄C/Mo₂C multilayers present less interdiffusion and are well modeled by a symmetric structure without interfacial layers. This study shows that B₄C/Mo₂C structure is an interesting alternative to B₄C/Mo multilayer for X-ray optic applications.     

Mössbauer spectroscopical investigation of the exchange biased Fe/MnF2 interface

Two different Fe/MnF₂ samples have been prepared by e-beam evaporation on MgO(001) substrates. The Fe layer in the samples includes a 10 Å thick ⁵⁷Fe probe layer either at the Fe/MnF₂ interface (interface sample) or 35 Å away from the interface (center sample). The samples are characterized by X-ray diffraction, conversion electron Mössbauer spectroscopy (CEMS) and SQUID magnetometry. ⁵⁷Fe CEMS has been employed to study the depth dependent hyperfine interactions in Fe/MnF₂ as a function of temperature between 18 K to 300 K. The hyperfine field B _hf has been obtained for the interfacial and off-interfacial ⁵⁷Fe layers. At the interface, besides B _hf of bcc-Fe, the presence of a component with a distribution P(B _hf ) is observed. The latter is assigned to interfacial ⁵⁷Fe atoms, indicating some (～15%, equivalent to ～1 Fe atomic layer) intermixing at the Fe/MnF₂ interface and a decrease of the average hf > by 21%. The influence of the interface disappears as the ⁵⁷Fe probe layer is placed away from the interface. The temperature dependence of the average hf > of the interface has been measured. The Fe spins, at remanence, are found to lie in the film plane.     

Hyperfine interactions in nanocrystallized NANOPERM-type metallic glass containing Mo

NANOPERM-type alloy with chemical composition Fe₇₆Mo₈CuB₁₅ was studied by combination of ⁵⁷Fe Mössbauer spectroscopy and ⁵⁷Fe(¹⁰B, ¹¹B) nuclear magnetic resonance in order to determine distribution of hyperfine magnetic fields and evolution of relative concentration of Fe-containing crystalline phases within the surface layer and the volume of the nanocrystallized ribbons with annealing temperature. Differential scanning calorimetry revealed two crystallization stages at T_x1 ～ 510 ^°C and T_x2 ～ 640 ^°C, connected to precipitation of α-Fe and Fe(Mo,B) nanocrystals, respectively. The amorphous and partially crystalline state was obtained by annealing at several temperatures in the range 510-650 ^°C. The combination of conversion electron (CEMS) and transmission Mössbauer spectrometry (TMS) showed that annealing induces crystallization starting from both surfaces of the ribbons. For the as-quenched sample, scanning electron microscopy (SEM) and CEMS revealed significant differences in the “air” and “wheel” sides of the ribbons, crystallites were preferentially formed at the latter. While SEM micrographs of annealed samples showed various mean diameters of the crystals at opposite sides of the ribbons, the amounts of crystalline volume derived from the CEMS spectra approximately equaled. Mössbauer spectra of annealed samples contained narrow sextet ascribed to crystalline α-Fe phase, three sextets with distribution of hyperfine field assigned to the interface regions of the nanocrystals and the contribution of the amorphous phases. In-field TMS performed at 4.2 K with magnetic moments aligned by external magnetic field enabled to properly determine in particular the contribution of the amorphous phases in the samples. Resulting distributions of the hyperfine fields were compared with ⁵⁷Fe(¹⁰B, ¹¹B) nuclear magnetic resonance (NMR) spectra.     

Determination of fine and hyperfine structure in Fe−Mo(W) dinuclear clusters

The fine and hyperfine structure of two dinuclear sulfide bridged Fe?Mo complex anions and their W homologues have been studied by magnetic susceptibility and Mössbauer measurements. It is shown that, by following a stepwise methodology, it is possible to derive from the low temperature magnetization data the value and sign of the fine structure parametersD andE/D. These parameters are further confirmed by an independent analysis of the Mössbauer data. Magnetic and electric hyperfine interaction parameters are also determined from the Mössbauer results. Both fine and hyperfine parameters point to a valence scheme, for all complexes, of Fe^II?Mo^VI(W^VI) with a varying degree of charge delocalization from the iron to the molybdenum (tungsten) site. The parameterD is negative with an orientation of itsz axis close to theV _zz axis.     

Mössbauer and XRD study of pulse plated Fe–P and Fe–Ni thin layers

⁵⁷Fe conversion electron Mössbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe–P and Ni–Fe coatings. XRD and ⁵⁷Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe–P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe–P deposits pulse plated at medium long deposition time (t _on?=?2 ms), with short relaxation time (t _off?=?9 ms) and low current density (I _p?=?0.05 Acm^?2) or at short deposition time (t _on?=?1 ms) with long relaxation time (t _off?=?250 ms) and high current density (I _p?=?1.0 Acm^?2). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni–Fe alloy with a very fine, 5–8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni–Fe and Fe–P pulse plated thin layers.     

237Np and 57Fe Mössbauer study of NpFeGa5

⁵⁷Fe and ²³⁷Np Mössbauer ōmeasurements have been performed for NpFeGa₅, which is one of the so-called neptunium 1-1-5 compounds. The ⁵⁷Fe Mössbauer spectra below T _N = 118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the ⁵⁷Fe nucleus is determined to be 1.98 ± 0.05 T at 10 K. From the ²³⁷Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the ²³⁷Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μ_B using the Np atomic magnetic moment of 0.86 μ_B determined by the neutron diffraction study.     

States in95Mo and99Mo populated in the (3He, α) reaction

The (³He,α) reaction on⁹⁶Mo and¹⁰⁰Mo targets has been studied at a bombarding energy of 18 MeV. Thel _n transfer assignments have been made on the basis of angular distribution patterns and on an analysis of the ratios of the experimental and theoretical cross-sections of (³He,α) and (d, t) reactions data leading to the same final states. New states are observed in⁹⁵Mo at 3373 keV (9/2⁺); spin and parity assignments are made to levels in⁹⁹Mo at 1621 keV 7/2⁺ (9/2⁺), 1778 keV (5/2^?) and 2078 keV (11/2^?).     

57Fe Mössbauer spectroscopy studies of Sr2Fe1−x Cr x Mo1−x W x O6 double perovskite compounds

Polycrystalline double perovskites Sr₂Fe_1?x Cr _x Mo_1?x W _x O₆ with x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30 have been prepared by sold state reactions. A continuous decrease of the tetragonal unit cell parameters α and c with increasing x values is observed. The highest Curie temperature T _C = 426 K is recorded for the x = 0.10 compound. ⁵⁷Fe Mössbauer spectroscopy measurements indicate a non-integral electronic configuration of ～3d^5.3 for the Fe ions at the ordered double perovskite structure for x ≤ 0.20, which reaches ～3d^5.4 for x = 0.30. Fe–Mo/W anti-site and anti-phase boundary defects are observed in all samples in equal concentrations of around 3% of the total number of Fe ions in their structure.     

XMCD studies of magnetic polarization at Mo atoms in CoMo alloy and magnetically coupled Co/Mo multilayers

Magnetic polarization of Mo atoms in Co₉₆Mo₄ alloy film and Co/Mo multilayered structures has been studied by X‐ray magnetic circular dichroism. Samples with Mo spacers of two different thicknesses (0.9 nm and 1.8 nm) were investigated. Mo atoms receive a magnetic moment of ?0.21μ_B in the alloy. In the multilayer with the thinner Mo spacer (d_Mo = 0.9 nm) the magnetic moment is much smaller (?0.03μ_B). In both cases the measured induced moment at the Mo site is oriented antiparallel to the moment at the Co atoms. The presence of the induced moment in the Mo spacer coincides with antiferromagnetic coupling between the Co component slabs. In contrast, neither measurable induced moment at the Mo site nor interlayer coupling between the Co layers has been found for the multilayer with the thicker Mo spacer. Possible mechanisms of the coupling associated with the induced moment are discussed in detail.     

Magnetization and Mössbauer studies of 57Fe doped SrCoO3

⁵⁷Fe (1%) doped SrCoO₃ obtained by high-pressure method, has been investigated by magnetization and Mössbauer spectroscopy studies (MS) in the temperature range 4.2 K to 300 K. The ferromagnetic ordering temperature T _C obtained is 272(2) K. Isothermal magnetization curves have been measured at various temperatures, from which the saturation moments (M _sat) have been deduced. The ⁵⁷Fe MS spectra display standard six-line patterns with an isomer shift typical of Fe^3?+? and a very small quadrupole splitting (QS = 0.14(1) mm/s above T _C). The magnetic hyperfine field at 4.2 K is 276(1) kOe. The temperature dependencies of the iron hyperfine field and M _sat (1.83 µ _B at 5 K) are almost identical. This shows that the Fe^3?+? is replacing Co^4?+?, both of the same electronic configuration. They also interact similarly, namely the Fe–Co exchange is almost identical to the Co–Co exchange.     

Half-lives of levels in99Nb and99Mo

The half-lives of the 469-keV level in⁹⁹Nb and the 236-keV state in⁹⁹Mo have been determined to (0.21±0.06) ns and (0.87±0.15) ns, respectively, fromβ,γ-delayed coincidences. Values ofB(E2)=(89±28)e ² fm⁴ andB(M1)=(0.017±0.003) μ _n ² are deduced for the 469-keV transition in⁹⁹Nb and the 138-keV transition in99Mo. The result for theE2-transition probability seems to be in accordance with the particle-core coupling interpretation of the low-lying levels in⁹⁸Nb if⁹⁸Zr is used as the core. TheM1 probability for⁹⁹Mo agrees with the systematics for “l-forbidden” 1g_7/2→2d _5/2 neutron transitions.     

Ground state hyperfine structure of95Mo and97Mo

The hyperfine structure of the ground state 4d ⁵ 5s ⁷ S ₃ of⁹⁵Mo and⁹⁷Mo has been measured by the atomic beam magnetic resonance technique with the following results:⁹⁵Mo:A=?208.582060(10)MHz,B=37.050 (100) kHzC=?30 (10) Hz,D=?3 (3) Hz⁹⁷Mo:A=? 212.980930 (10) MHz,B?69.990(140)kHzC=?5 (10) Hz,D=0 (3) Hz. After application of corrections calculated according to second order perturbation theory, the hyperfine structure constants became:⁹⁵Mo: A_c=?208.582560(290)MHz,B _c =16.920(4300)kHzC _c=?30(270) Hz,D _c =? 3 (50) Hz⁹⁷Mo: A_c=212.981450(300) MHz,B _c =?90.780(4400)kHzC _c=?6(270) Hz,D _c =0 (50) Hz. With the known ratio ofg _I(⁹⁵Mo)/g _I(⁹⁷Mo) [1] a calculation of the hyperfine anomaly yields:₉₅ Δ ₉₇=?0.01009(17)%. The ratio of the uncorrectedB factors isB(⁹⁷Mo)/B(⁹⁵Mo)=?1.8890(47). Because of the relatively large effects of second order hyperfine structure, the ratio of the correctedBfactors differs considerably from the ratio of the uncorrectedB factors. From the correctedB factors the electric quadrupole moments may be evaluated by means of calculated radial integrals [2]. The results are:Q (⁹⁵Mo)=?0.019(12)barns,Q(⁹⁷Mo)=0.102(39)barns.     

Epitaxial MoOx nanostructures on TiO2(1 1 0) obtained using thermal decomposition of Mo(CO)6

Stoichiometric and highly-defective TiO₂(1 1 0) surfaces (called as yellow and blue, respectively) were exposed to Mo(CO)₆ vapours in UHV and in a reactive O₂ atmosphere. In the case of yellow-TiO₂, an O₂ reactive atmosphere was necessary to obtain the Mo(CO)₆ decomposition at 450 °C with deposition of MoO_x nanostructures where, according to core level photoemission data, the Mo⁺⁴ state is predominant. In the case of blue-TiO₂ it was possible to obtain Mo deposition both in UHV and in an O₂ atmosphere. A high dose of Mo(CO)₆ in UHV on blue-TiO₂ allowed the deposition of a thick metallic Mo layer. An air treatment of this sample at 580 °C led to the elimination of Mo as MoO₃ and to the formation of a transformed layer of stoichiometry of Ti_(1−x)Mo_xO₂ (where x is close to 0.1) which, according to photoelectron diffraction data, can be described as a substitutional near-surface alloy, where Mo⁺⁴ ions are embedded into the titania lattice. This embedding procedure results in a stabilization of the Mo⁺⁴ ions, which are capable to survive to air exposure for a rather long period of time. After exposure of the blue-TiO₂(1 1 0) substrate to Mo(CO)₆ vapours at 450 °C in an O₂ atmosphere it was possible to obtain a MoO₂ epitaxial ultrathin layer, whose photoelectron diffraction data demonstrate that is pseudomorphic to the substrate.     

NiFe/Mo多层膜界面的电子显微学研究

用高分辨电子显微学方法研究了Ni₈₀Fe₂₀/Mo磁性多层膜，结果表明：(1)多层膜的结晶状态，随Mo非磁性层厚度而变化.当Mo层厚度为0.7nm时，多层膜基本为非晶；当Mo层厚度大于1.6nm时，Mo层和NiFe层内分别结晶为体心立方和面心立方多晶，层内晶粒尺寸为2—6nm.(2)在Mo层厚度为1.6和2.1nm的多层膜中，NiFe层和Mo层之间存在两种取向关系：(110)_Mo∥(111)_NiFe,［111］_关键词：     

Lack of oxygen substitution in the chevrel compound Mo6S8

We present results from x-ray powder diffraction and lithium intercalation cells on samples of nominal composition “Cu₂Mo₆S₆O₂” and “Mo₆S₆O₂”. Our results show that it is not possible to prepare these materials with any significant fraction of the sulfur substituted by oxygen as claimed by Umarji et al.¹ Instead, the high temperature (1250°C) products from starting materials of CuO, Cu, S, MoO₂ and/or Mo are MoO₂, Mo and Cu_yMo₆S₈ with y>2.     

Investigations of the Spin-Hamiltonian Parameters for the Rhombic Mo5+ Centers in Ca1−x Y x MoO4 Crystal

The spin-Hamiltonian parameters (g factors g _i and hyperfine structure constants A _i , where i = x, y, z) of the rhombic Mo⁵⁺ center in Ca_1?x Y _x MoO₄ crystal are calculated from the high-order perturbation formulas based on the two-mechanism model for the rhombic d¹ tetrahedral clusters with the ground state |d _z 2〉. In these formulas, besides the contributions due to the widely applied crystal-field (CF) mechanism concerning CF excited states, those due to the charge-transfer (CT) mechanism (which is omitted in CF theory) concerning CT excited states are considered. The calculated results are in reasonable agreement with the experimental values. The calculations show that because of the great relative importance of CT mechanism for the components of spin-Hamiltonian parameter along x and y axes, the accurate and complete calculations of spin-Hamiltonian parameters for Mo⁵⁺ and other high valence state dⁿ ions in crystals should take account of both the CF and CT mechanisms. The defect model of the rhombic Mo⁵⁺ center is also confirmed from the calculations.     

Influence of photoexcitation on the EPR spectra of Mo5+ in Li2Zn2(MoO4)3: Ce3+,Cu2+ crystals annealed in a CO2 atmosphere

The influence of recovery annealing in a CO₂ atmosphere at 700°C on the properties of Li₂Zn₂(MoO₄)₃ crystals doped with cerium and copper ions has been studied. The EPR investigation of Li₂Zn₂(MoO₄)₃ crystals annealed in a CO₂ atmosphere has revealed that the annealing leads to the formation of oxygen vacancies in positions adjacent to the oxygen octahedron of lithium, M3, and the oxygen tetrahedron of molybdenum, Mo1. In this case, the charge state of molybdenum becomes Mo⁵⁺ and appears in the EPR spectra in the form of one magnetically nonequivalent position. The analysis of the angular dependence of the EPR spectrum of Mo⁵⁺ made it possible to calculate the spectral parameters g _∥ = 1.862, g _⊥ = 1.933, A _∥ = 71.8 G, and A _⊥ = 34.1 G. The cross relaxation on the hyperfine structure from the molybdenum isotope ⁹⁷Mo is found in the EPR spectra. The photoexcitation of Li₂Zn₂(MoO₄)₃ crystal doped with cerium ions leads to the saturation of the EPR spectrum of Mo⁵⁺ and to the formation of the hyperfine structure from one lithium ion with a hyperfine structure constant of 14 G. For Li₂Zn₂(MoO₄)₃ crystals doped with copper ions, a very weak EPR spectrum of Mo⁵⁺ is observed in the initial crystals. As a result of the photoexcitation, an increase in the intensity of this spectrum by an order of magnitude and manifestation of the EPR spectrum of Cu²⁺ ions take place. It is assumed that such a behavior of the EPR spectra of molybdenum ions in Li₂Zn₂(MoO₄)₃ crystals doped with cerium and copper ions under photoexcitation is caused by different positions of the energy levels of cerium and copper ions with respect to the energy level of the molybdenum ion.     

Magnetic annealing of the ion-beam sputtered IrMn/CoFeB bilayers – positive exchange bias and coercivity behaviour

The effect of optimum dilution of antiferromagnetic (AF)/ferromagnetic (FM) interface necessary for observance of positive exchange bias in ion-beam sputtered Si/Ir₂₂Mn₇₈ (t _AF = 12, 18, 24 nm)/Co₂₀Fe₆₀B₂₀(t _FM = 6,9,15 nm) exchange coupled bilayers is investigated by magnetic annealing at 380, 420 and 460 °C for 1 h at 5 × 10^-6 Torr in presence of 500 Oe magnetic field. While the coercivity of the exchange coupled FM layer decreases with the increase in annealing temperature irrespective of the value of t _AF or t _FM, the hysteresis loops however shift by ≈+ 10 Oe whenever the coercivity drops in the 10–15 Oe range. This is consistent with the phase diagram of exchange bias field and coercivity derived from Meiklejohn and Bean model. The X-ray diffraction and X-ray reflectivity measurements confirmed that the texture, grain size and interface roughness of IrMn/CoFeB bilayers are thickness dependent and are correlated to the observed magnetic response of the bilayers. The results establish that optimum dilution of the IrMn/CoFeB interface by thermally diffused Mn-spins is necessary in inducing the effective coupling between the IrMn domains and diluted CoFeB layer. It is further shown that the annealing temperature required for the optimum dilution of the CoFeB interface critically depends on the thickness of the layers.     

The hyperfine field of99Tc in iron

The magnetic hyperfine field at⁹⁹Tc impurities in Fe has been measured to be ¦H _hf¦=325 (7) kGauss at 298 °K. The technique of time-differential perturbed angular correlations on the 181 keV state of⁹⁹Tc was used.