Surface and interface properties of epitaxial Fe3O4 films studied by Mössbauer spectroscopy

Stoichiometric Fe₃O₄ films have formed epitaxially on -Al₂O₃ and MgO single-crystal substrates by a reactive vapor deposition method. In order to apply conversion electron Mössbauer spectroscopy depth-selectively, a 5–7 Åthick probe layer containing ⁵⁷Fe was formed at various depths in inactive ⁵⁶Fe₃O₄ matrix films. At the topmost surfaces and also at the interfaces, the essential electronic features of bulk Fe₃O₄ are retained, including a rapid electron hopping between the Fe²⁺ and Fe³⁺ ions at B sites. Minor depth-dependent changes are confined to a few outermost atomic layers, and the changes depend on the orientation and the lattice mismatch with the substrate. For (111) growth on -Al₂O₃, the surface layer seems to be strongly relaxed to reduced the electric polarization, while a high density of defects seems to be concentrated at the interface with -Al₂O₃. For (001) growth on MgO, the surface retains the spinel lattice though slightly oxidized, while the interface with MgO has good crystallinity and stoichiometry. An enhanced thermal fluctuation of the Fe³⁺-spins in contact with the MgO substrate and in the topmost surface layer can be seen in their reduced magnetic hyperfine field at 300 K.     

Mössbauer of γFe-Ni alloys

Mössbauer measurement performed as a function of temperature show quite different patterns for iron and nickel rich γ Fe-Ni alloys. Isotropic magnetic and additionally both anisotropic magnetic and electric contributions from neighbour atoms to the hyperfine interactions are considered. The temperature dependence of the isotopic contributions suggests the exchange integral J_FeFe to be not constant.     

Mössbauer investigations on Np3S5

The 59.5 keV Mössbauer resonance of ²³⁷Np has been measured in Np₃S₅ at 77 and 4.2 K. At 77 K, two different quadrupolar splittings are observed. The first one (δ₁ = −5(1) mm sec⁻¹/NpAl₂) is assigned to the Np⁴⁺ ions and the second one (δ₂ = 28(1) mm sec⁻¹/NpAl₂) is assigned to the Np³⁺ ions. At 4.2 K the spectrum gives a ratio of areas S(Np³⁺)/S(Np⁴⁺) of 2.0. These results clearly confirm the crystallographic data of this mixed-valence material.     

A Fe Mössbauer study of Mn2P

It is shown that ⁵⁷Fe substitutes for Mn(1) in Mn₂P. The Néel temperature is found to be 110 K and the magnetic moments for the iron atoms are estimated to be 0.63μ_B. All iron atoms have the same moment in contrast to what was found for Mn(1) atoms in an earlier neutron diffraction study by Yessik. A magnetic triangular substructure for Mn(1) is therefore proposed.     

Mössbauer studies of CoxFe1−xCr2S4

The mixed spinel systems Co_xFe_1−xCr₂S₄ has been studied using the Mössbauer effect. Spectra have been collected over the temperature range 83–300 K. The isomer shifts indicate that the charge states of Fe ions are ferrous in character throughout the series. Absence of quadrupole splitting above the magnetic ordering temperature T_c suggests that iron ions occupy only tetrahedral sites. It is notable that as the temperature decreases below T_c, both quadrupole shift and asymmetrical line-broadening appear and increase with decreasing temperature, suggesting the presence of electric field gradient and accompanying relaxation effects.     

Estimation of the exchange constants in the Fe sublattice of the Y2Fe17 and Y2Fe17N3−δ compounds from the analysis of Mössbauer measurements

From the analysis of Mössbauer data for Y₂Fe₁₇ and Y₂Fe₁₇N_3−δ at various temperatures the hyperfine fields for 4f, 6g, 12j, 12k iron sites were estimated as a function of temperature. The reduced magnetizations calculated from the values of the hyperfine fields are fitted with a mean field model for four interacting sublattices using a computer program. The estimated exchange interaction from the fitting procedure between the 4f sites is found strongly negative (antiferromagnetic) in Y₂Fe₁₇ whereas in Y₂Fe₁₇N_3−δ it increases and becomes weak negative following a modified Slater-Néel curve. The rest of the exchange interactions are found positive or weak negative depending on the distances between the Fe atoms.     

Tin hyperfine fields in Co2 VSn and Co2 NbSn from Mössbauer spectroscopy

The hyperfine fields at the Sn sites in the Heusler type alloys Co₂ VSn and Co₂NbSn have been measured by the Mössbauer effect at 4.2 K to be + 9.9 and + 15.0 kOe, respectively. These anomalously small values are discussed in terms of the outer electron structure of these alloys.     

Study of the magnetism and the magnetic anisotropy of Fe layers in Ni/Fe/Ni(1 1 1) by Mössbauer spectroscopy

The hyperfine field and the magnetic anisotropy of a Fe layer as a function of thickness have been investigated in several Ni/⁵⁷Fe_x/Ni(1 1 1) trilayers with relatively thick Ni layers by Mössbauer spectroscopy. For Fe layers with thickness below 16 Å, the Mössbauer spectra show always the presence of two ferromagnetic phases with high-spin state. In the range between 6 and 8 Å, also a ferromagnetic phase with low-spin state and a paramagnetic phase have been found. The evolution of the mean hyperfine field of the ⁵⁷Fe nuclei is used to study the Fe growth. A structural FCCBCC phase transition is found to begin with an iron thickness of 8 Å. The easy direction of the magnetization is found out-of-plane for Fe interlayer with FCC structure, and perfectly in plane for Fe interlayer with BCC structure.     

High field Mössbauer investigations of paramagnetic Y(Fe, Al)2

⁵⁷Fe Mössbauer measurements in external fields up to 13.5 T in the temperature range 4–300 K are reported for Y(Fe_xAl_1−x)₂. A negative sign was found for the quadrupole splitting. In the paramagnetic state different induced hyperfine fields for different Fe environments were observed.     

Identification of the intercalant species in SbCl5-graphite using Mössbauer spectroscopy

¹²¹Sb Mössbauer spectra of SbCl₅-graphite have been obtained. The spectra provide clear evidence for the presence of the acceptor molecular ion SbCl₆^-(Sb⁵⁺ and neutral SbCl₃(Sb³⁺ in the intercalate layers, with weak evidence for neutral intercalated SbCl₅. Lineshape analyses of the Sb³⁺ region of the spectra further indicate that two chemical Sb³⁺ sites fit the data significantly better than one site. We attribute the second Sb³⁺ site to SbCl₄^- and find the concentration ratio [SbCl₄^-]/[SbCl₃] 0.25. Samples prepared by the reaction of graphite with vapor mixtures of SbCl₅ and SbCl₃ were found to exhibit dramatically higher concentrations of SbCl₃ than those samples prepared from a reaction with SbCl₅ alone. This latter result is interesting in view of the fact that the reaction of graphite with SbCl₃ vapor does not lead to an intercalation compound.     

Magnetic and Mössbauer data of Fe in K2ZnF4, analyzed in the spin Hamiltonian formalism

Magnetic measurements on single crystals and Mössbauer spectra of powders under magnetic field, recorded on Fe²⁺ doped K₂ZnF₄, have been analyzed in the spin Hamiltonian formalism. The data slightly depart from the expectations of a spin 2 in D_4h symmetry. The occurrence of vibronic effects is discussed.     

A pulsed synthesis of β-FeSi2 layers on silicon implanted with Fe ions

Continuous layers and fine-grained films of β-FeSi₂ were synthesized using the implantation of Fe⁺ ions into Si (1 0 0) with subsequent pulsed nanosecond ion-beam treatment of the implanted layers. The X-ray diffraction studies showed that the pulsed ion-beam treatment brings about the formation of a mixture of two phases: FeSi and β-FeSi₂ with strained crystal lattices. Subsequent rapid thermal annealing led to the complete transformation of the FeSi phase into the β-FeSi₂ phase with the formation of a textured layer. The data obtained using Raman spectroscopy corroborate the formation of the β-FeSi₂ phase with a high degree of silicon crystallinity.The results of measuring the optical absorption point to the formation of β-FeSi₂ layers and precipitates with a direct-gap structure, an optical gap of E_g≈0.83 eV. The photoluminescence band peaked at λ≈1.56 μm and caused by direct band-to-band transitions in β-FeSi₂ was observed at temperatures lower than 210 K.     

The role of Sb in the structure of Sb2O3–B2O3 binary glasses—an NMR and Mössbauer spectroscopy study

Glasses of general formula xSb₂O₃ (1−x)B₂O₃ (0x0.8) have been prepared by conventional melt- quenching. Mössbauer spectroscopy shows that a fraction of the Sb³⁺ is converted to Sb⁵⁺ and this fraction increases with x. High-field ¹¹B MAS NMR gives well-resolved resonances from boron atoms which are 3- and 4-coordinated to oxygen. The fraction of 4-coordinated boron, N₄, goes through a maximum value of 0.12±0.01 at x=0.5. The position of the maximum in N₄ is consistent with the cation potential for Sb³⁺, as observed for other systems. However, the low value of N₄ at this maximum is not so readily explained. The values are similar to those predicted if [BO₄]⁻ were stabilised by [SbO₄]⁺ but the trends with composition are different.     

Doppler-limited spectroscopy of the 3ν3 band of SF6

The strongest portion of the 3ν₃ band of SF₆ has been recorded at T = 160 and 295 K with Doppler-limited resolution using a tunable laser difference-frequency spectrometer. The structure in this band has been identified with the P, Q, and R branches of one F_1u sublevel (with essentially l = 1 character) within the 3ν₃ vibrational manifold. Preliminary effective rotational constants have been obtained for this band from which the anharmonic parameters X₃₃, G₃₃, and T₃₃ can be estimated. The role of hot bands and of the other anharmonic sublevels is discussed in relation to prior interpretations of low resolution spectra and of the initial isotope selective stages of CO₂ laser photo-dissociation of SF₆.     

Lattice sternheimer factor of Eu(OH)3 from Mössbauer spectral study

The Mössbauer spectra of powdered Eu(OH)₃ were recorded between 300 and 4.2 K, with ¹⁵¹SmF₃ as source. The spectra showed one single absorption line having definite width but without any fine structure. The lattice Sternheimer factor γ_∞ of ¹⁵¹Eu in Eu(OH)₃ was estimated with the help of these spectra as well as by using the values of some physical parameters obtained from spectral and magnetic susceptibility measurements on pure single crystal of Eu(OH)₃, The value of lattice Sternheimer factor (= -87) thus evaluated is slightly larger than that value ( = - 80) for ¹⁵⁴Eu in ethylsulphate host. This result is consistent with the γ_∞ values of other rare-earth ions and also with the results obtained from magnetic and optical experiments on Eu(OH)₃.     

Spin excitations in a K0.84Fe1.99Se2 superconductor as studied by Mössbauer spectroscopy

Mössbauer spectroscopy was used to probe the site-specific information of a K_0.84Fe_1.99Se₂ superconductor. A spin excitation gap, ΔE ≈5.5 meV, is observed by analyzing the temperature dependence of the hyperfine magnetic field (HMF) at the iron site within the spin wave theory. Using the simple model suggested in the literature, the temperature dependence of the HMF is well reproduced, suggesting that, below room temperature, the alkali metal intercalated iron-selenide superconductors can be regarded as ferromagnetically coupled spin blocks that interact with each other antiferromagnetically to form the observed checkerboard-like magnetic structure.     

Tm Mössbauer effect and magnetic study of Tm6Mn23 and its ternary hydride

The magnetic properties and the lattice constants of Tm₆Mn₂₃ were determined before and after hydrogen absorption. The compound Tm₆Mn₂₃ is ferrimagnetic with an ordering temperature T_c = 404 K. After hydrogen absorption the magnetization is strongly reduced and does not point to the occurrence of magnetic ordering. The strongly increasing hyperfine splitting observed by means of ¹⁶⁹Tm Mössbauer spectroscopy in the hydride for temperature below 60 K, however, shows that the Tm sublattice becomes magnetically ordered after H₂ absorption as well. In uncharged and charged Tm₆Mn₂₃ the values of the Tm moments are close to the free ion values.     

Low temperature magnetocaloric effects in Dy1Ba2Cu3O7−δ and Y1Ba2Cu3O7−δ high-Tc single crystals

The heat release has been measured in high temperature superconductors during and after a change of the external magnetic field μ₀H_a ≤ 0.5 T applied parallel to the c-axis at 0.1 K ≤ T ≤ 0.45 K. Two Y123 and one Dy123 twinned single crystals were investigated. An analysis of the heat release based on the Bean model and on a model for thin superconductors in perpendicular geometry recently proposed by Brandt et al. has been carried out. During field sweep we measured ∝ H_a²dH_a/dt. This dependence can be understood within the Bean model for longitudinal geometry. The critical current densities obtained with this method are in good agreement with those from magnetization measurements. We also present measurements, and a first quantitative analysis, of dissipation due to the time relaxation of the flux line lattice after a field sweep. For the heat release a t⁻¹ dependence has been found which corresponds to a logarithmic time dependence of the magnetization. The normalized relaxation rate we obtained is in agreement with literature values.     

Relaxation effects and evidence for one dimensional ordering in KFeCl3 studied by Mössbauer spectroscopy

Mössbauer measurements of KFeCl₃ over the temperature range 4.2–293°K show a transition to a magnetically ordered phase at T_N ? 18.5°K and evidence for one-dimensional order above T_N. In the region 10–25°K striking relaxation effects appear. An approximate analysis of the quadrupole splitting data was used for the determination of the fine structure of the ⁵D levels below T_N which in turn was used for a theoretical reproduction of the relaxation spectra between 10–25°K.