Mössbauer study of the modulated magnetic structure of FeVO<Subscript>4</Subscript>

Mössbauer spectroscopy is used to study the FeVO₄ multiferroic, which undergoes two magnetic phase transitions at T _N1 ≈ 22 K and T _N2 ≈ 15 K. The first transition (T _N1) is related to transformation from a paramagnetic state into a magnetically ordered state of a spin density wave, and the second transition (T _N2) is associated with a change in the type of the spatial magnetic structure of the vanadate. The electric field gradient tensor at ⁵⁷Fe nuclei is calculated to perform a crystal-chemical identification of the partial Mössbauer spectra corresponding to various crystallographic positions of Fe³⁺ cations. The spectra measured in the range T _N2 < T < T _N1 are analyzed on the assumption about amplitude modulation of the magnetic moments of iron atoms μ_Fe. The results of model intersection of the spectra recorded at T < T _N2 point to a high degree of anharmonicity of the helicoidal magnetic structure of the vanadate and to elliptic polarization of μ_Fe. These features are characteristic of type-II multiferroics. The temperature dependences of the hyperfine interaction parameters of ⁵⁷Fe nuclei that were obtained in this work are analyzed in terms of the Weiss molecular field model on the assumption of orbital contribution to the magnetic moments of iron cations.     

Magnetic phase transitions and iron valence in the double perovskite Sr 2 FeOsO 6

The insulating and antiferromagnetic double perovskite Sr₂FeOsO₆ has been studied by ⁵⁷Fe Mössbauer spectroscopy between 5 and 295 K. The iron atoms are essentially in the Fe^3?+? high spin $( {t_{2\mathrm{g}}{^3} e_\mathrm{g}{^2} } )$ and thus the osmium atoms in the Os $^{5+} ( {t_{2\mathrm{g}}{^3} } )$ state. Two magnetic phase transitions, which according to neutron diffraction studies occur below T _N?= 140 K and T ₂?= 67 K, give rise to magnetic hyperfine patterns, which differ considerably in the hyperfine fields and thus, in the corresponding ordered magnetic moments. The evolution of hyperfine field distributions, average values of the hyperfine fields, and magnetic moments with temperature suggests that the magnetic state formed below T _N is strongly frustrated. The frustration is released by a magneto-structural transition which below T ₂ leads to a different spin sequence along the c-direction of the tetragonal crystal structure.     

Magnetic interaction in Tm3Fe5O12 studied by means of169Tm and57Fe Mössbauer spectroscopy

The temperature dependence of the hyperfine parameters of thulium iron garnet (Tm₃Fe₅O₁₂) powder was studied from 90 to 550 K using¹⁶⁹Tm and⁵⁷Fe Mössbauer spectroscopy (MB). The spectra were analyzed by least mean square fits to the transmission function. The temperature dependence of the magnetic fields of the thulium nuclei is well described by the mean field model. The coupling constants between the magnetic lattice occupied by the thulium atoms and the magnetic lattices occupied by the iron atoms were derived.     

Mössbauer studies of PbFe2/3W1/3O3 multiferroics

Mössbauer studies of ceramic samples of the antiferromagnetic perovskite PbFe_2/3W_1/3O₃ have been carried out. It has been established that the temperature of transition to the magnetically ordered state is T _N = 365 K. Iron ions in PbFe_2/3W_1/3O₃ are found to reside in the high-spin Fe³⁺ state. The Fe³⁺ ions occupy inequivalent positions differing in the nearest cation environment, or more precisely, tungsten and iron ions are distributed in a random manner over the sites of the octahedral sublattice. The inequivalent positions arise as a result of the Fe and W ions being statistically distributed over the octahedral sublattice. For T > 0 K, magnetic fields at the nuclei and, hence, the average thermodynamic values of the magnetic moments of Fe³⁺ ions occupying inequivalent positions are different and, at a given temperature, are determined by the number of the nearest magnetic neighbors, with the effective magnetic fields (H _eff) varying differently with temperature. As the temperature is lowered, the fields H _eff level off gradually in response to the effective magnetic fields of iron ions having different numbers of exchange bonds leveling off with decreasing temperature which lowers thermal excitation.     

The temperature dependence of the hyperfine parameters of YIG below the Curie point

The temperature dependence of the hyperfine parameters of the ⁵⁷Fe nuclei in yttrium iron garnet Y₃Fe₅O₁₂ (YIG) between room temperature and the Curie point was studied by means of conventional Mößbauer transmission spectroscopy. The critical exponent β, which describes the temperature dependence of the magnetic hyperfine field of ⁵⁷Fe in YIG, was found to be 0.29(1) and 0.33(1) in the [a]- and (d)-sublattice, respectively. In the temperature region just below the Curie point relaxation of the internal hyperfine fields could be observed. The phase transition at the Curie point shows a distinct dependence on the grain size in the sample.     

Hyperfine interactions in Sc<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript>x</Subscript>Fe<Subscript>2</Subscript> cubic Laves alloys

Effects of hybridization of 3d bands of iron with 3d bands of scandium and 4d bands of yttrium in Sc_1?xY_xFe₂ cubic Laves alloys (0≤_x≤1) are studied by the nuclear magnetic resonance method. The concentration dependences of the lattice parameters a, saturation magnetization σ, and hyperfine fields at the ⁵⁷Fe, ⁴⁵Sc, and ⁸⁹Y nuclei—as well as the ²⁷Al impurity nuclei, whose atoms substitute iron atoms in the lattices of these alloys—are measured. The “local” and “induced” contributions to hyperfine fields at the ⁵⁷Fe nuclei are separated and the magnetic moments at iron atoms are estimated. It is found that the hybridization effect leads to the formation of magnetic moments at Sc and Y atoms (whose direction is opposite to the direction of the magnetic moment at iron atoms) and is responsible for the ferrimagnetic structure in Sc_1?xY_xFe₂ alloys.     

Temperature dependence of the hyperfine parameters of a natural orthopyroxene Fe0.87Mg0.13SiO3

The Mössbauer parameters of an iron rich orthopyroxene Fe_xMg_1−xSiO₃ with x = 0.87 (natural compound named XYZ) have been analyzed in detail as a function of temperature in the paramagnetic and in the magnetic region. The magnetic ordering temperature obtained by Mössbauer spectroscopy is T_N = 27 ± 1 K. Above T_N, a quite different behaviour of the quadrupole interactions of the Fe²⁺ in the M1 and M2 sites has been observed as a function of temperature. It can be explained by the different energy splittings of the orbital states of the ⁵T₂ ground state of high spin iron (II). Below T_N, using simple level scheme considerations related to the low symmetry of the Fe²⁺ oxygen octahedra, one can assign unambiguously the values o of the hyperfine fields to Fe²⁺ in M1 and M2. In this low temperature range the Mössbauer spectra can be accounted for by a distribution of hyperfine fields P(H_h.f(M1)) and P(H_h.f(M2)) related to the various Fe²⁺-Mg²⁺ nearest neighbour configurations surrounding the Fe²⁺ probe located on the M1 or M2 site.     

Specific features of local structural,valence, and magnetic states of iron ions in the perovskite Bi0.5Ca0.5FeO3

The perovskite Bi_0.5Ca_0.5FeO₃ has been investigated using the Mössbauer effect at temperatures of 295 and 675 K. The measured temperature of the magnetic phase transition (Néel temperature) is T _N = 640 ± 10 K. Above the Néel temperature, there are two nonequivalent structural states of iron ions. In the perovskite Bi_0.5Ca_0.5FeO₃ at room temperature, there are seven most probable nonequivalent magnetic states of iron ions with significantly different values of the hyperfine interaction parameters. Four iron states correspond to Fe³⁺ ions in the octahedral oxygen environment, and three iron states correspond to Fe³⁺ ions in the tetrahedral oxygen environment.     

Magnetic states of iron ions in Bi<Subscript>0.75</Subscript>Si<Subscript>0.25</Subscript>FeO<Subscript>3 − <Emphasis Type="Italic">y</Emphasis></Subscript> perovskites

Hyperfine interactions on ⁵⁷Fe nuclei in cubic perovskite Bi_0.75Sr_0.25FeO_{3 ? y} in the temperature range 87–700 K are studied using Mössbauer spectroscopy. The temperature of the magnetic phase transition (the Neel point T _N ) of bismuth ferrite is T _N = 670(3) K. Below T _N , the experimental spectra demonstrate a partially resolved magnetic hyperfine structure with broadened lines, which is well described by superposition of four sextets. The values of the hyperfine magnetic field B and the isomer shift δ at room temperature initiated that all iron ions are in the trivalent state. Here, three sextets with the equal isomer shifts (δ₁ ≈ δ₂ ≈ δ₃ = 0.38 mm/s correspond to the iron ions in the octahedral oxygen environment; in the fourth sextet, the iron ions are in the square-pyramidal environment (δ₃ = 0.25 mm/s).     

Magnetic hyperfine fields of (Nd2Fe1-xCox)14B AT x = 0.25 between 100 and 780 K

The ⁵⁷Fe Mössbauer spectra are recorded in Nd₂(Fe_1-xCo_x)₁₄B at x = 0.25 in the temperature range 100 to 780 K. T_c the Curie temperature, B̄_hf, the magnetic hyperfine field average over various Fe nuclei of the unit cell and its temperature coefficient α(B̄_hf) in the vicinity of 300 K are found to be 760(5) K, 34.0(3) T and -0.08(1)% K^-1, respectively. The magnetic moment at Fe atoms is estimated to increase up to 12% as a result of the partial substitution by Co atoms. The dependence of the fields upon temperature is observed to be least at the j₂ and k₂ sites as compared to the other sites of Fe. The results for the variation of B_hf at all of the six sites of Fe with respect to temperature are given. A site preference of Fe atoms for the j₂ sites is observed.     

Spatially modulated magnetic structure of AgFeO2: Mössbauer study on 57Fe nuclei

The results of the Mössbauer study of ferrite AgFeO₂ manifesting multiferroic properties (at T ≤ T _N2) have been presented. The hyperfine interaction parameters of ⁵⁷Fe nuclei have been analyzed in a wide temperature range including the points of two magnetic phase transitions (T _N2 ≈ 7–9 K and T _N1 ≈ 15–16 K). It has been shown that the Mössbauer spectra of the ⁵⁷Fe nuclei are sensitive to the variations of the character of the magnetic ordering of Fe³⁺ ions in the studied ferrite. The results of the model identification of a series of spectra (4.7 K ≤ T ≤ T _N2) under the assumption of the cycloid magnetic structure of ferrite AgFeO₂ have been presented. The analysis of the results has been performed in comparison with the literature data for other oxide multiferroics.     

Structure of the local environment and hyperfine interactions of <Superscript>57</Superscript>Fe probe atoms in DyNiO<Subscript>3</Subscript> nickelate

The local structure of DyNiO₃ nickelate at both sides of the insulator (T < T _im) ? metal (T > T _im) phase transition was studied by probe ⁵⁷Fe Mössbauer spectroscopy. The character of change in the hyperfine parameters of probe iron atoms specifically near the phase-transition temperature (T ≈ T _im) was analyzed.     

SrTb2Fe2O7 studied by mössbauer spectra of 57Fe

The temperature dependence of the hyperfine parameters of ⁵⁷Fe in SrTb₂Fe₂O₇ gave a magnetic ordering temperature T_N=542 K, saturation effective magnetic fieldH_eff(0)=552 kGand Debye temperature θ_D=330 K. The princip al axis of the PFG tensorV_zzis angled at 9° to the crystallographic c axis. Mössbauer spectra at 4.2 K reveal reorientation of iron spin.     

Atomic and magnetic structures of Fe<Subscript>70</Subscript>Al<Subscript>5</Subscript>B<Subscript>25</Subscript> amorphous alloys

The short-range order around boron, aluminum, and iron atoms in Fe₇₅B₂₅ and Fe₇₀Al₅B₂₅ amorphous alloys has been studied by ¹¹B and ²⁷Al nuclear magnetic resonance at 4.2 K and ⁵⁷Fe Mössbauer spectroscopy at 87 and 295 K. The average magnetic moment of iron atoms μ(Fe) in these alloys has been measured by a vibrating sample magnetometer. It has been revealed that the substitution of aluminum atoms for iron atoms does not disturb μ(Fe) in the Fe₇₀Al₅B₂₅ alloy, gives rise to an additional contribution to the ¹¹B NMR spectrum in the low-frequency range, and shifts maxima of the distribution of hyperfine fields at the ⁵⁷Fe nuclei. In the Fe₇₀Al₅B₂₅ amorphous alloy, the aluminum atoms substitute for iron atoms in the nearest coordination shells of boron and iron atoms. This alloy consists of nanoclusters in which boron and iron atoms have a short-range order of the tetragonal Fe₃B phase type.     

57Fe Mössbauer study of Li x Fe1-y Co y PO4 (y = 0, 0.1, 0.2) as cathode material for Li-ion batteries

Lithium iron phosphates LiFe_1-y Co _y PO₄ (y = 0, 0.1, 0.2) exposed to a charging process were studied by ⁵⁷Fe Mössbauer spectroscopy taking into account XRD and SEM data. Hyperfine parameters of the spectra were determined above and below the magnetic ordering temperature for all the samples. It was shown that the presence of Co impurity atoms in lithium phosphates gives no effect on the hyperfine interaction of ⁵⁷Fe²⁺ cations. However, Co atoms in the nearest cation environment of Fe atoms lead to a significant change of the hyperfine interactions of ⁵⁷Fe³⁺ cations. The Co impurity atoms distribution over the positions of the iron atoms in the structure is found not to be statistical,but correlated.     

Hyperfine interactions of 57Fe impurity nuclei in TmNiO3 and YbNiO3 nickelates in the range of magnetic and structure phase transitions

Hyperfine interactions of ⁵⁷Fe impurity nuclei are studied by probe Mössbauer spectroscopy in TmNiO₃ and YbNiO₃ perovskite-like nickelates in the ranges of temperature transitions of an insulator (T < T _IM ) ? metal (T > T _IM ) and antiferromagnetic (T < T _N ) ? paramagnetic (T > T _N ). The changing behavior of hyperfine interaction parameters of ⁵⁷Fe nuclei in the ranges of phase transition temperatures (T _IM and T _N ) is analyzed. The results are interpreted in the context of the charge disproportionation of Ni³⁺ cations associated with the electronic localization in monoclinic-distorted nickelates at T < T _IM .     

Mössbauer study of spin structure transformation from an incommensurate to a commensurate state

We present crystallographic and magnetic properties of NiCr_1.98 ⁵⁷Fe_0.02O₄ by using X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and Mössbauer spectroscopy. The lattice constants a₀ were determined to be 8.318 Å. The ferrimagnetic Neel temperature (T _N) for NiCr_1.98 ⁵⁷Fe_0.02O₄ is determined to be 90 K. The Mössbauer absorption spectra for all chromites at 4.2 K show two well developed sextets superposed with small difference of hyperfine fields (H _hf) caused by Cr^3?+? ions in two different magnetic sites. The values of the isomer shifts show that the charge states of Fe are Fe^3?+? for all temperature range. Ni-chromites Mössbauer spectra below T _N present aline broadening due to a Jahn–Teller distortion and show that spin structure behavior of Cr ions change from an incommensurate to a commensurate state.     

Mössbauer measurements on lattice and interstitial iron atoms in Fe1+xSb alloys

Mössbauer measurements on the Fe_1+xSb phase in seven samples of Fe : FeSb have been used to observe the independent magnetic ordering of lattice and interstitial iron atoms. An ordering temperature of (55 ± 5) K is deduced for the interstitial iron atoms. The anomalous behaviour of the lattice iron hyperfine fields at about the interstitial ordering temperature is attributed to the perturbation of the superexchange interaction between lattice atoms by the magnetic ordering of the interstitials.     

Mössbauer studies of magnetic behavior of 3d-doped REBa2Cu3−x Fe x O7+δ (RE=Y,Er, Dy,Gd)

A Mössbauer study has been made on⁵⁷Fe ions substituted into the Cu(1) site of REBa₂Cu_3?x Fe _x O_7+δ (RE=Y, Er, Dy, Gd;x=0.15, 0.30). At low temperature, the iron atoms antiferromagnetically order with a transition temperature which is dependent on the Fe concentration. The temperature dependence of the magnetic subspectra representing Fe ions with various local oxygen environments in YBa₂Cu_3?x Fe _x O_7+δ and ErBa₂Cu_3?x Fe _x O_7+δ fit a 2D-Ising model with a ratio of the anisotropic exchange between the two directions on the order of 0.5–1.0(10^?3) for the Y-compounds and on the order of 1 for the Er-compounds. The magnitude of the local dopant magnetization is related to a short-range chemical order which determines the magnetic chain size and defines the correlation lengths. For the Y-compound, the order is quasi-1D with strong intrachain but very weak interchain coupling. For the Er-compounds, the magnetic coupling is Ising 2D. The strong fluctuation behavior expected in low dimensional systems above and belowT _N is observed via characteristic relaxation in the Mössbauer linewidth nearT _N. For both the Dy- and Gd-compounds, the magnetic order is 3D. The magnitude of the rare-earth magnetic moments appears to affect the character of the magnetic interaction in the Cu(1)-site. However, a Mössbauer effect measurement at¹⁵⁵Gd nuclei in GdBa₂Cu_2.85Fe_0.15O_7+δ (T _N(Fe)～14 K) shows paramagnetic behavior at 4.9 K.     

Local atomic and magnetic structures of nanocrystalline Fe75Cr10B15 alloy

The crystal, local atomic and magnetic structures of Fe₇₅Cr₁₀B₁₅ alloys annealed at 440?C473°C for 5 min have been studied using X-ray diffraction and ⁵⁷Fe M?ssbauer spectroscopy. At the annealing temperature T _a = 440°C, nanocrystals of the ??-Fe phase (??1%) precipitate in the amorphous matrix of the alloy. The complete crystallization of the amorphous alloy occurs at T _a = 473°C with the formation of ??-Fe nanocrystals 26 ± 2 nm in size and nanocrystals of tetragonal boride t-Fe₃B 47 ± 2 nm in size. It has been found that chromium atoms are located in nanocrystals of the ??-Fe and y-Fe₃B types. The distribution functions of hyperfine fields in the nanocrystalline Fe₇₅Cr₁₀B₁₅ alloy reconstructed from the M?ssbauer spectra (at T _a = 473°C) show that there are three allowed states of iron atoms in the ??-Fe phase and three equally probable crystallographic nonequivalent states of iron in the t-(Fe,Cr)₃B phase. The chromium concentration x in the ??-Fe(Cr) phase is found to be ??10 at %. The substitution of chromium atoms for iron atoms in t-Fe₃B substantially decreases local magnetic moments of the iron atoms.