Mössbauer-effect studies of multilayers and interfaces

The usefulness of Mössbauer spectroscopy for the investigation of magnetic multilayer systems is described. By applying ⁵⁷Fe Mössbauer spectroscopy, the behavior of ultrathin magnetic layers, such as FCC-like Fe films on Cu(0 0 1), is studied. Position-specified (depth-selective) information is available by preparing samples in which monatomic ⁵⁷Fe probe layers are placed at specific vertical positions, e.g. at interfaces or at the surface. As demonstrated for epitaxial chemically ordered Fe₅₀Pt₅₀ alloy films and polycrystalline nanostructured Tb/Fe multilayers, the Fe-spin structure can be determined directly, and a site-selective Fe-specific magnetic hysteresis loop can be traced in very-high-coercivity materials. For the studies of non-magnetic layers, on the other hand, hyperfine field observations by ¹⁹⁷Au and ¹¹⁹Sn probes are worthwhile. Spin polarizations in Au layers penetrating from neighboring ferromagnetic 3D layers are estimated ¹⁹⁷Au from Mössbauer spectra and are also studied by inserted ¹¹⁹Sn probes in Au/3D multilayers. In the Sn spectra for Cr/Sn multilayers, it was found that remarkably large spin polarization is penetrating into Sn layers from a contacting Cr layer, which suggests that Cr atoms in the surface layer have a ferromagnetic alignment.     

Raman spectroscopy of Limehouse porcelain sherds supported by Mössbauer spectroscopy and scanning electron microscopy

The Limehouse pot works, founded probably in the early 1745, was one of the earliest porcelain works established in England. It closed in June 1748. The factory site at 20 Fore Street Limehouse, London, was excavated by the Museum of London, Department of Greater London Archaeology in 1990, recovering 1402 sherds. A number of these sherds has now been examined by Raman spectroscopy, scanning electron microscopy and one by Mössbauer spectroscopy. Different porcellaneous formulations have been identified; namely, an experimental Si–Al body with a Si–Al–Ca glaze and a Si–Al–Ca body containing minor Pb and Mg and covered with a Si–Pb–Ca glaze. Several sherds were intermediate between these compositions. Most sherds failed to reach vitrification temperature and lack translucency. Mössbauer spectroscopy indicated that one sherd had been fired under mildly reducing conditions. These results have enabled conclusions to be reached in respect of the raw materials, body and glaze compositions and firing and glazing conditions used at Limehouse. Copyright © 2013 John Wiley & Sons, Ltd.     

Superconductivity in non-stoichiometric and tin-substituted La2CuO4: preparation, characterization, Mössbauer and microwave-absorption studies

Two samples of non-stoichiometric La₂CuO₄ were synthesized, one with La/Cu<2, and the other with 10% Sn substituting Cu. They were investigated by X-ray diffraction, Mössbauer spectroscopy, and microwave-absorption techniques. The microwave-absorption data indicated that they were both superconducting, with the transition temperatures T_c of 40.5 and 41.5 K, the one doped with Sn possessing the higher T_c. The Mössbauer spectra revealed that there exist two kinds of Sn(IV) atoms disordered with Cu. Their isomer shift, δ=−0.244(4) mm/s, is in agreement with Sn(IV) coordinated by oxygen. One site was characterized by a single Mössbauer line, being associated with a weakly distorted environment, wherein the Sn, coordinated more symmetrically, is surrounded by four Cu²⁺ ions. On the other hand, the other site, characterized by a Mössbauer doublet exhibited a quadrupole splitting Δ=1.07(2) mm/s, being associated with a highly distorted coordination, explained to be due to Sn occupying two adjacent cationic sites. To our knowledge, such a substitution for copper ions not resulting in a decrease of T_c has not been reported previously.     

Mössbauer analysis on the magnetic properties of Fe–Co nanoparticles synthesized by chemical vapor condensation process

The magnetic properties of Fe–Co nanoparticles synthesized by chemical vapor condensation (CVC) process were investigated. Effect of CVC processing variables on the magnetic properties was analyzed in detail, using Mössbauer spectroscopy, XRD, BET and HRTEM. The synthesized particles were nearly spherical, and their surfaces were identified to be -FeOOH, γ-FeOOH and Fe₃O₄, but not -Fe₂O₃. The magnetic properties were strongly influenced by CVC processing parameters. The increase of cobalt content had changed the magnetic property of the sample. However, when the decomposition temperature and the oxygen content in the carrier gas (Ar) were increased, the magnetic property reduced with decreasing the average particle size. Increasing the vacuum pressure in the chamber resulted in that the magnetic field reinforced with the increase of average particle size.     

Field-induced local magnetic moments in γ (FCC) Fe–Ni anti-Invar alloys

Mössbauer spectroscopy in longitudinal external fields (up to 7 T) and SQUID magnetometry (up to 5 T) measurements have been carried out on mechanically alloyed (MA) γ (FCC) Fe_100−xNi_x (x=21, 24, and 27 at%) alloys at room temperature. The zero-field Mössbauer spectra of these alloys show only singlets. The high field Mössbauer results indicate that large amounts of the material is in the paramagnetic state, giving rise to two spectral components with their effective fields almost linearly depend on the external field, but with slopes that are smaller than unity. The in-field Mössbauer spectra of the x=27 at% alloy show an additional component with a hyperfine field of ≈21 T, which is attributed to Ni-rich (>30 at% Ni) clusters (domains) of ferromagnetically ordered HM phase that behaves superparamagnetically at room temperature and shows a non-linear character in the magnetization (M–H) curves at low fields. This HM phase is also present in the x=21 and 24 at% samples but with smaller amounts. The results suggest induced hyperfine fields and hence induced moments in the paramagnetic components, which increases with increasing Ni contents. Taenite-enriched samples from the metal particles of two stony meteorites, Al Kidirate (H6) and New Halfa (L4), are also studied by high field Mössbauer spectroscopy and the results are compared to that of MA samples.     

The 57Fe Synchrotron Mössbauer Source at the ESRF

The design of a ⁵⁷Fe Synchrotron Mössbauer Source (SMS) for energy‐domain Mössbauer spectroscopy using synchrotron radiation at the Nuclear Resonance beamline (ID18) at the European Synchrotron Radiation Facility is described. The SMS is based on a nuclear resonant monochromator employing pure nuclear reflections of an iron borate (⁵⁷FeBO₃) crystal. The source provides ⁵⁷Fe resonant radiation at 14.4 keV within a bandwidth of 15 neV which is tunable in energy over a range of about ±0.6 µeV. In contrast to radioactive sources, the beam of γ‐radiation emitted by the SMS is almost fully resonant and fully polarized, has high brilliance and can be focused to a 10 µm × 5 µm spot size. Applications include, among others, the study of very small samples under extreme conditions, for example at ultrahigh pressure or combined high pressure and high temperature, and thin films under ultrahigh vacuum. The small cross section of the beam and its high intensity allow for rapid collection of Mössbauer data. For example, the measuring time of a spectrum for a sample in a diamond anvil cell at ～100 GPa is around 10 min, whereas such an experiment with a radioactive point source would take more than one week and the data quality would be considerably less. The SMS is optimized for highest intensity and best energy resolution, which is achieved by collimation of the incident synchrotron radiation beam and thus illumination of the high‐quality iron borate crystal within a narrow angular range around an optimal position of the rocking curve. The SMS is permanently located in an optics hutch and is operational immediately after moving it into the incident beam. The SMS is an in‐line monochromator, i.e. the beam emitted by the SMS is directed almost exactly along the incident synchrotron radiation beam. Thus, the SMS can be easily utilized with all existing sample environments in the experimental hutches of the beamline. Owing to a very strong suppression of electronic scattering for pure nuclear reflections (～10^?9), SMS operation does not required any gating of the prompt electronic scattering. Thus, the SMS can be utilized in any mode of storage ring operation.     

Lancaster delftware: a Raman spectroscopy,electron microscopy and Mössbauer spectroscopy compositional study

In 2008, excavations were conducted by the Northern Ceramic Society at the site of the former Lancaster delftware potworks, which operated between 1754 and about 1790. The recovered sherds have been non‐destructively examined by Raman and electron microscopies and the iron phases in the biscuit by Mössbauer spectroscopy. These methods have provided a new understanding of the mineralogy of the delftware produced at Lancaster using clay imported from Carrickfergus in Ireland and blended with the local ferruginous‐aluminous clays. This has implications for the attribution of delftware produced at Liverpool, Bristol, Scotland and Ireland. The Carrickfergus clay has been found to be highly dolomitic resulting in the body of the delftware forming diopside and the magnesian olivine forsterite, when fired. Brookite had not converted to rutile, nor had tridymite, nor cristobalite formed; the K‐feldspars did not undergo further chemical reactions, and the observation of metakaolin would suggest that the biscuit firing temperature was in the order of 800–900 °C. Chalcedony containing moganite was established as the silica source. A cobalt‐containing lead‐tin glaze was applied to the biscuit body and, after decorating, was fired. The mineralogy of the pigments used to decorate the objects indicate the yellow to be the PbSbSn triple oxide, the green to be a copper silicate mixed with lead‐tin yellow, the purple and browns to be manganese silicates and the blue to contain cobalt spinels and cobalt pyroxenes. Diopside crystals together with recrystallised tin agglomerates have been observed floating within the glaze. Copyright © 2015 John Wiley & Sons, Ltd.     

Mössbauer spectroscopy evidence of intrinsic non‐stoichiometry in iron telluride single crystals

The FeTe parent compound for iron‐superconductor chalcogenides was studied applying Mössbauer spectroscopy accompanied by ab initio calculations of electric field gradients at the iron nuclei. Room‐temperature (RT) Mössbauer spectra of single crystals have shown asymmetric doublet structure commonly ascribed to contributions of over‐stoichiometric iron or impurity phases. Low‐temperature Mössbauer spectra of the magnetically ordered compound could be well described by four hyperfine‐split sextets, although no other foreign phases different from Fe_1.05Te were detected by XRD and microanalysis within the sensitivity limits of the equipment. Density functional ab initio calculations have shown that over‐stoichiometric iron atoms significantly affect electron charge and spin density up to the second coordination sphere of the iron sub‐lattice, and, as a result, four non‐equivalent groups of iron atoms are formed by their local environment. The resulting four‐group model consistently describes the angular dependence of the single crystals Mössbauer spectra as well as intensity asymmetry of the doublet absorption lines in powdered samples at RT. We suppose that our approach could be extended to the entire class of FeSeTe_x compounds, which contain excess iron atoms.

     

57Fe Mössbauer spectroscopy on the cyclic spin-cluster Fe6(tea)6(CH3OH)6

We present ⁵⁷Fe Mössbauer spectroscopy experiments on the cyclic spin-cluster Fe₆(tea)₆(CH₃OH)₆ (tea = triethanolaminato(-3)). In former studies, the spin cluster has been treated as a homogenous, quasi-one-dimensional spin S=5/2 Heisenberg antiferromagnet. Our experiments reveal spectra, which consists of two different quadrupolar doublets. In consequence, there are two different Fe sites among the hexanuclear iron spin-cluster.     

Nuclear resonance reflectivity from a [57Fe/Cr]30 multilayer with the Synchrotron Mössbauer Source

Mössbauer reflectivity spectra and nuclear resonance reflectivity (NRR) curves have been measured using the Synchrotron Mössbauer Source (SMS) for a [⁵⁷Fe/Cr]₃₀ periodic multilayer, characterized by the antiferromagnetic interlayer coupling between adjacent ⁵⁷Fe layers. Specific features of the Mössbauer reflectivity spectra measured with π‐polarized radiation of the SMS near the critical angle and at the `magnetic' maximum on the NRR curve are analyzed. The variation of the ratio of lines in the Mössbauer reflectivity spectra and the change of the intensity of the `magnetic' maximum under an applied external field has been used to reveal the transformation of the magnetic alignment in the investigated multilayer.     

Surface morphology and local magnetic properties of electrodeposited thin iron layers

Thin iron layers with different thickness were prepared by electrodeposition on the polycrystalline substrate. The surface morphology of the layers, their structure and local magnetic properties were studied using scanning tunneling microscopy (STM), X-ray diffraction (XRD) and conversion electron Mössbauer spectroscopy (CEMS). STM studies revealed the granular structure of the surface of the electrodeposited iron layers with the roughness up to 10 nm. XRD analysis proved that these layers were highly strained. The CEMS spectra showed an in-plane magnetic anisotropy in the iron layers. Isomer shift of the electrodeposited iron was different than that of the -Fe. This difference was attributed to the internal stresses existing in the electrodeposited layers.     

Co/Ni多层膜垂直磁各向异性的研究

采用直流磁控溅射法在玻璃基片上制备了Pt底层的Co/Ni多层膜样品, 对影响样品垂直磁各向异性的各因素进行了调制, 通过样品的反常霍尔效应系统的研究了Co/Ni多层膜的垂直磁各向异性. 结果表明, 多层膜中各层的厚度及周期数对样品的反常霍尔效应和磁性有重要的影响. 通过对多层膜各个参数的调制优化, 最终获得了具有良好的垂直磁各向异性的Co/Ni多层膜最佳样品Pt(2.0)/Co(0.2)/Ni(0.4)/Co(0.2)/Pt(2.0), 经计算, 该样品的各向异性常数K_eff 达到了3.6×10⁵ J/m³, 说明样品具备良好的垂直磁各向异性. 最佳样品磁性层厚度仅为0.8 nm, 样品总厚度在5 nm以内, 可更为深入的研究其与元件的集成性.     

Cu／Fe（CN）6^3—／4—界面的动态FT—IR光谱

采用现场FT-IR光谱电化学研究了Cu/Fe(CN)_6~(3-/4-)界面的化学反应、电化学反应及其随电位、时间的变化关系,并从C≡N基振动频率的改变详细分析和讨论了Cu与Fe(CN)_6~(3-/4-)的作用及成膜过程。     

Tunable in-plane spin orientation in Fe/Si(557) film by step-induced competing magnetic anisotropies

Although the spin-reorientation transition from out-of-plane to in-plane in Fe/Si film is widely reported, the tuning of in-plane spin orientation is not yet well developed. Here, we report the thickness-, temperature- and Cu-adsorptioninduced in-plane spin-reorientation transition processes in Fe/Si(557) film, which can be attributed to the coexistence of two competing step-induced uniaxial magnetic anisotropies, i.e., surface magnetic anisotropy with magnetization easy axis perpendicular to the step and volume magnetic anisotropy with magnetization easy axis parallel to the step. For Fe film thickness smaller than 32 monolayer(ML), the magnitudes of two effects under various temperatures are extracted from the thickness dependence of uniaxial magnetic anisotropy. For Fe film thickness larger than 32 ML, the deviation of experimental results from fitting results is understood by the strain-relief-induced reduction of volume magnetic anisotropy.Additionally, the surface and volume magnetic anisotropies are both greatly reduced after covering Cu capping layer on Fe/Si(557) film while no significant influence of Na Cl capping layer on step-induced magnetic anisotropies is observed.The experimental results reported here provide various practical methods for manipulating in-plane spin orientation of Fe/Si films and improve the understanding of step-induced magnetic anisotropies.     

Magnetic anisotropy and electronic structure of iron films on W(1 1 0) by spin-polarized two-electron spectroscopy

Low-energy spin-polarized two-electron spectroscopy was applied to study the spin-dependent electronic structure of 3 ML and 50 ML epitaxial iron films grown on single crystal W(1 1 0). Such films are known to show an in-plane rotation of the easy magnetization axis between thicknesses [M. Donath, Journal of Physics: Condensed Matter 11 (48) (1999) 9421; D. Sander, Journal of Physics: Condensed Matter (20) (2004) R603, O. Fruchart, J.P. Nozieres, D. Givord, Journal of Magnetism and Magnetic Materials 207 (1999) 158, H.J. Elmers, U. Gradmann, Applied Physics A: Materials Science & Processing 51 (3) (1990) 255]. Momentum distributions of correlated electron pairs I(k₁, k₂) excited from the films by 25 eV primary electrons were measured for two opposite polarizations of the incident beam. Energy and momentum conservation laws in the electron scattering events allow the extraction of information on the spin-dependent Bloch spectral density function of the valence electrons in iron films. The observed difference in the electronic structure of these two films is most likely due to the different crystal structures of the films.     

An estimation of the magnetic disorder at Fe/Cr interfaces in coupled and non-coupled Fe/Cr multilayers

The antiferromagnetic coupling at the Fe/Cr interfaces, inferred from the orientation of the Cr magnetic moments, is used to estimate the magnetic disorder resulting from the interfacial roughness in Fe/Cr multilayers. A crossover from in-plane to out-of-plane orientation of Cr moments depends on the energy cost in either case: (i) to break the interfacial Fe–Cr antiferromagnetic coupling or (ii) having sites with frustrated Cr–Cr antiferromagnetic coupling in the Cr interlayers. A quantitative model of the magnetic frustration due to interfacial disorder in Fe/Cr multilayer systems is described. The step edge density, or terrace size, required to break the interfacial Fe–Cr coupling and destroy the Fe–Fe interlayer exchange coupling is estimated.     

Investigation of the static and dynamic magnetic properties of CoFe2O4 nanoparticles

We have investigated the magnetic behavior of cobalt ferrite nanoparticles with a mean diameter of 7.2 nm. AC susceptibility of colloidal cobalt ferrite nanoparticles was measured as a function of temperature T from 2 to 300 K under zero external DC field for frequencies ranging from f=10 to 10,000 Hz. A prominent peak appears in both χ′ and χ″ as a function of T. The peak temperature T₂ of χ″ depends on f following the Vogel–Fulcher law. The particles show superparamagnetic behavior at room temperature, with transition to a blocked state at T_B^m94 K in ZFC and 119 K in AC susceptibility measurements, respectively, which depends on the applied field. The saturation magnetization and the coercivity measured at 4.2 K are 27.3 emu/g and 14.7 kOe, respectively. The particle size distribution was determined by fitting a magnetization curve obtained at 295 K assuming a log-normal size distribution. The interparticle interactions are found to influence the energy barriers yielding an enhancement of the estimated magnetic anisotropy, K=6×10⁶ erg/cm³. Mössbauer spectra obtained at higher temperatures show a gradual collapse of the magnetic hyperfine splitting typical for superparamagnetic relaxation. At 4.2 K, the Mössbauer spectrum was fitted with two magnetic subspectra with internal fields H_int of 490, 470 and 515 kOe, corresponding to Fe³⁺ ions in A and B sites.     

Coexisting antiferromagnetism and ferromagnetism in mechanically alloyed Fe-rich Fe–Ni alloys: implications regarding the Fe–Ni phase diagram below 400°C

Fe–Ni alloys below the Invar region with compositions Fe_100−xNi_x (x=21, 24, and 27 at%) were prepared by high-energy ball milling technique (mechanical alloying). The as-milled samples, characterized by X-ray diffraction and Mössbauer spectroscopy, contain a mixture of (BCC) and γ (FCC) phases, whereas the samples annealed at 650°C for 0.5 h show a single γ (FCC) phase displaying a single line Mössbauer spectrum at room temperature (RT). At low temperature, the Mössbauer spectra of annealed Fe₇₆Ni₂₄ and Fe₇₃Ni₂₇ alloys show the existence of a magnetically split pattern together with a broad singlet, which are ascribed to a high-moment ferromagnetic Ni-rich phase and a low-moment Fe-rich phase, respectively. The Fe-rich phase in annealed Fe₇₆Ni₂₄ alloy, which is paramagnetic at RT, undergoes antiferromagnetic ordering at 40 K, estimated from the dramatic line broadening of its spectrum, giving rise to a small hyperfine field (e.g. 2 T at 6 K). The coexistence of these phases is attributed to phase segregation occurring in these alloys as a result of enhanced atomic diffusion. The stability of these alloys towards martensitic (FCC→BCC) transformation at low temperatures is discussed in connection with the Fe–Ni phase diagram below 400°C.     

Mössbauer study of the invar Fe–Ni and Fe–Ni–C alloys in magnetic field

F.C.C. Fe–30.3%Ni and Fe–30.5%Ni–1.5%C (wt.%) alloys were studied by means of Mössbauer spectroscopy in external magnetic field B _ext?=?2.5, 5, 7 T parallel to the gamma-beam. It is shown that distribution of effective magnetic field in the alloys is broad and that carbon expands the range of B _eff. The external magnetic field increases B _eff in the Fe–Ni alloy and decreases it more evidently in the Fe–Ni–C alloy. Antiferromagnetic spin coupling along the ferromagnetic component is proposed to explain data.