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 and valence states of iron ions in the Perovskite Bi<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>FeO<Subscript>3</Subscript>

Single-phase rhombohedral perovskites (Bi_0.9Sr_0.1)FeO₃ were studied by Mössbauer spectroscopy at temperatures of 293, 87, and 680 K. The Neel temperature T _N = 652 ± 2 K of the magnetic transition was measured. Three states of trivalent iron ions in the octahedral states were discovered. Substitution of Sr²⁺ for 0.1 mol % Bi³⁺ breaks the spatially spin-modulated structure.     

Studying local structural, valence, and magnetic states of iron ions in Bi0.9Ca0.1FeO3 perovskite

Mössbauer method was used to study a perovskite compound Bi_0.9Ca_0.1FeO₃ at T = 295 K and at temperature above T _N . It has been established that Bi_0.9Ca_0.1FeO₃ has a rhombohedral crystal structure similar to that of BiFeO₃. The substitution of Ca²⁺ for Bi³⁺ ions leads to the formation of three states of Fe³⁺ ions with an octahedral surroundings and one state with a tetrahedral oxygen surroundings with substantially different hyperfine magnetic fields. All Fe ions are in a trivalent state; the compensation of the charge deficit occurs via the formation of oxygen vacancies. Above T _N , two structurally nonequivalent states of Fe³⁺ ions exist in the Bi_0.9Ca_0.1FeO₃ sample, which correspond to the Fe³⁺ ions with an octahedral and tetrahedral oxygen coordination.     

Perovskites Bi0.8La0.2FeO3 and Bi0.8La0.2Fe0.95Cr0.05O3: Crystal structure and magnetic and charge states of iron ions

Perovskites of the Bi_0.8La_0.2Fe_{1 ? x} Cr _x O₃ system (x = 0, 0.05) were investigated by Mössbauer spectroscopy in the temperature range of 298–800 K. The samples were fabricated by solid-state synthesis and had a rhombic structure. Iron ions in Bi_0.8La_0.2FeO₃ and Bi_0.8La_0.2Fe_0.95Cr_0.05O₃ are situated in trivalent states. The magnetic transition temperatures (the Néel temperatures T _N ) T _N = 677.5 ± 2.5 K for Bi_0.8La_0.2FeO₃ and T _N = 647.6 ± 2.5 K for Bi_0.8La_0.2Fe_0.95Cr_0.05O₃ are measured. The substitution of trivalent iron ions from trivalent chromium ions in the amount x = 0.05 in Bi_0.8La_0.2Fe_0.95Cr_0.05O₃ perovskite decreases the hyperfine magnetic field at nuclei ⁵⁷Fe in Fe⁺³-O-Cr⁺³ chains by 30 kOe.     

Features of local crystallographic, magnetic, and valence states of iron ions in Bi1 − x Sr x FeO3 perovskites at x = 0–0.67

Perovskites of the Bi_{1 ? x} Sr _x FeO₃ system (x = 0–0.67) at T = 295 K and T > T _N are studied using the Mössbauer effect. When the strontium content x = 0.1–0.15, the structural transition from the rhombohedral to the cubic phase takes place. It is found that in samples of the Bi_{1 ? x} Sr _x FeO₃ system (x = 0.07–0.67), there are only two structurally nonequivalent states of iron ions that correspond to Fe³⁺ ions in octahedral and tetrahedral oxygen environments.     

Local states of iron ions in multiferroics Bi1−x La x FeO3

Mössbauer studies of perovskites Bi_1?x La _x FeO₃ (x = 0, 0.10, 0.20, 0.61, 0.90, 1.00) were conducted at 295 and 87 K. The spatial spin-modulated structure (SSMS) observed in perovskites BiFeO₃ and Bi_0.9La_0.1FeO₃ leads to a specific distribution of hyperfine fields P(B) with two peaks. Substitution of La for Bi (x = 0.2) destructs the SSMS. The concentration dependences of the hyperfine field (B), isomer shift (?) and quadrupole shift (δ) were measured. The iron ions are in the trivalent state. The local magnetic moments μ(Fe) of the Fe³⁺ ions are determined.     

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).     

Investigation of La1−x Ca x FeO3−y (0≦x≦0.50) by means of X—ray diffraction and Mössbauer spectroscopy

Compounds La_1?x Ca _x FeO_3?y (0≤x≤0.50) were prepared and characterized by X-ray diffraction and Mössbauer measurements. The diffraction patterns were defined to be orthorhombic. The lattice constants of orthorhombic perovskite La_1?x Ca _x FeO_3?y decrease linearly with increasingx. The Mössbauer spectra at room temperature indicate that the Néel temperature drops and the isomer shift decreases with increasingx. The spectrum of La_0.50 Ca_0.50 FeO_3?y at 80 K shows two hyperfine splitting patterns which may be related to the Fe³⁺ and Fe⁵⁺ ions.     

Valence and magnetic states of impurity iron ions in the La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Co<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> perovskite

The local magnetic and valence states of impurity iron ions in the rhombohedral La_0.75Sr_0.25Co_0.98 ⁵⁷Fe_0.02O₃ perovskite were studied using Mössbauer spectroscopy in the temperature range 87–293 K. The Mössbauer spectra are described by a single doublet at 215–293 K. The spectra contained a paramagnetic and a ferromagnetic component at 180–212 K and only a broad ferromagnetic sextet at T < 180 K. The results of the studies showed that, over the temperature range 87–295 K, the iron ions are in a single (tetrahedral) state with a valence of +3. In the temperature range 180–212 K, two magnetic states of Fe³⁺ ions were observed, one of which is in magnetically ordered microregions and the other, in paramagnetic microregions; these states are due to atomic heterogeneity. In the magnetically ordered microregions in the temperature range 87–212 K, the magnetic state of the iron ions is described well by a single state with an average spin S = 1.4 ± 0.2 and a magnetic moment μ(Fe) = 2.6 ± 0.4μ _B .     

Mössbauer spectroscopy as a probe of magnetic states in La0.5Ca0.5FeO3−δ perovskite

Charge disproportionation in La_0.5Ca_0.5FeO_3−δ perovskite has been detected by zero-field Mössbauer spectra from 20 K to room temperature. On the basis of the parameters of center shifts and hyperfine fields, Mössbauer spectra identified that the iron ionic states are Fe³⁺ and Fe⁵⁺ below 150 K, Fe³⁺, Fe⁴⁺ and Fe⁵⁺ in the intermediate temperature region, as well as Fe³⁺ and Fe⁴⁺ above 220 K. At low temperatures, the system exhibits a cluster-glass-like state resulting from competition between antiferromagnetic interaction of Fe³⁺–Fe³⁺ and ferromagnetic interaction of Fe³⁺–Fe⁵⁺.     

Charge disproportionation induced exchange bias in La0.5Ca0.5FeO3-δ

We observed an exchange bias effect in La0.5Ca0.5FeO3 perovskite compound.The exchange bias is associated with the charge disproportionation transition from Fe4+ions to Fe3+and Fe5+ions below 175 K.The competition between the ferromagnetic interaction of Fe3+and Fe5+ions and the antiferromagnetic one of Fe3+and Fe3+ions results in a unidirectional anisotropy in the cluster-glass system.An antiferromagnetically interfacial exchange coupling constant Ji1.95 meV at the cluster-glass region was yielded by fitting the cooling field-dependence of the exchange bias field.     

Electronic structures of Fe in La1−x Ba x FeO3−y (0≤x≤0.70)

Mössbauer spectra of La_1–x Ba _x FeO_3–y recorded at room temperature for various values of x show a six-line and/or a single-line subspectrum. The six-line subspectrum with IS=0.41 mm/s and H=52 T results from an orthorhombic perovskite containing only Fe³⁺ ions. The single-line subspectrum at 0.17 mm/s from a cubic perovskite can be assigned to neither Fe³⁺ nor Fe⁴⁺ but to an intermediate valence state, which may be due to electron hopping between the Fe³⁺ and Fe⁴⁺ ions on the identical octahedral sites. The temperature dependence of electron hopping in the compound La_0.40Ba_0.60FeO_3–y is presented.     

Structural and magnetic heterogeneities, phase transitions, 55Mn NMR, and magnetoresistive properties of La0.6Sr0.3 − x Bi x Mn1.1O3

The structural, resistive, magnetic, and magnetoresistive properties of the La_0.6Sr_{0.3 ? x} Bi _x Mn_1.1O₃ ceramics have been studied. The substitution of Bi ions for Sr ions increases the lattice parameter of the rhombohedral perovskite structure, decreases the metal-semiconductor and ferromagnet-paramagnet phase transition temperatures and the peak of the magnetoresistive effect, and increases the resistivity, approaching the system to the ferroelectric state. The ⁵⁵Mn NVR study indicates on the high-frequency Mn³⁺ ? Mn⁴⁺ superexchange and heterogeneity of the valence and magnetic states of manganese due to the nonuniformity of distribution of all ions and defects. The phase diagram has been constructed, which shows a strong correlation between the structural, magnetic, and magnetoresistive properties.     

Bismuth-induced enhancement of magneto-optical effects in iron garnets: A theoretical analysis

A semiquantitative model of circular magneto-optical effects in iron garnets is constructed within the concept of charge-transfer transitions and the existing qualitative notions. In the framework of the proposed model, the drastic enhancement of circular magneto-optical effects in R₃Fe₅O₁₂ iron garnets containing impurities of Bi³⁺ or Pb²⁺ ions is explained by the increase in the oxygen contribution to the spin-orbit coupling constant of the (FeO₆)^9? and (FeO₄)^5? complexes (the main magneto-optically active centers in iron garnets). This increase is associated with the covalent admixture of the Bi³⁺ (or Pb²⁺) 6p orbitals (with a giant one-electron spin-orbit coupling constant) to the oxygen 2p orbitals. The influence of the substitution does not reduce to an enhancement of the oxygen spin-orbit interaction alone but also leads to the appearance of the effective anisotropic tensor contributions to the spin-orbit interaction and circular magneto-optical effects. These contributions to the magneto-optical effects in garnets are estimated. The influence of an inhomogeneous bismuth distribution on the magneto-optical effects in Y_3?xBi_xFe₅O₁₂ garnets is investigated using computer simulation. Analysis of the available experimental data on the magneto-optical effects in garnets confirms the validity of the theoretical model proposed.     

On the Valence State of Iron in Sr0.52+Ca0.52+Fe0.54+ Me0.54+O32−

Powder samples of Sr_0.5Ca_0.5Fe_0.5Me_0.5O₃ (Me = Co, Zr or Mn) and Sr_0.3La_0.7FeO₃ are investigated by X-ray diffraction and Mössbauer effect spectroscopy. Analysis of the completely ordered spectra suggested three kinds of iron ions coexist in general where the resolution into the different valence state is clearly seen. The Mössbauer effect parameters values are found to be close to those expected for Fe³⁺, Fe⁴⁺ and Fe⁵⁺ indicating that some of the tetravalent iron ions in its high spin state disproportionate into Fe³⁺ and Fe⁵⁺ ions passing through temperature dependent intermediate valence states.     

Structural and electric-dielectric properties of some bismuth -phosphate glasses

In the present study, glasses with composition XBi₂O₃ (60?X)P₂O₅ 20Fe₃O₄ 20Li₂O (0≤X≤15) mol% have been prepared by the conventional melt quenching technique. The IR studies show the presence of FeO₄, FeO₆, BiO₆, PO₃, PO and PO₄ structural groups. The hyperfine structure of these glasses is investigated using Mössbauer spectroscopy. ME spectroscopy indicated the presence of two different oxidation states of iron (Fe²⁺ and Fe³⁺). The ferrous ions Fe²⁺ occupied tetrahedral coordination states, while the ferric ions Fe³⁺ occupied both tetrahedral and octahedral coordination states. The effect of partial replacement of P₂O₅ by Bi₂O₃ on the electric-dielectric properties is studied in more details. It is found that, unmonotonic variation in the σ_dc, (θ_D/2), σ_ac(ω), ε₁(ω), and ε₂(ω), as a function of Bi₂O₃ contents. Also it is found that, the power law exponent, s, is temperature dependent and the CBH model is the most applicable conduction mechanism in all glass samples. Pseudo Cole-Cole diagram of the investigated glassy samples exhibit similar behavior where all plots show a single semicircle indicating a single relaxation process.     

Luminescence of La and Sc impurity centers in YAlO3 single-crystalline films

The luminescence of La_Y³⁺ and Sc_Y³⁺ and Sc_Al³⁺ centers created by lanthanum and scandium ions at Y³⁺ and Al³⁺ cation sites of YAlO₃ perovskite lattice was investigated. The features of emission of excitons localized at the mentioned centers in YAlO₃:La and YAlO₃:Sc single-crystalline films were analyzed by means of time-resolved emission spectroscopy and luminescence decay kinetics measurements under excitation by synchrotron radiation at 9 and 300 K.     

Structural and magnetic properties in the self-doped perovskite manganites with nominal composition La0.7Sr0.3−xMnO3−δ

Perovskite manganites with nominal composition La_0.7Sr_0.3−xMnO_3−δ (0.00≤x≤0.20) have been prepared by the sol-gel method with the highest heat treatment temperature being 1073 K. The XRD patterns indicate that when the doping level is x≤0.10 the samples have only a single phase, with the R3?c perovskite structure, while for x>0.10, the samples have two phases with the R3?c perovskite being the dominant phase and Mn₃O₄ being the second phase. A quantitative analysis and Rietveld fitting of the X-ray powder diffraction data indicate that on the basis of the thermal equilibrium theory of crystal defects there are Mn²⁺ ions at the A sites and Mn³⁺ plus Mn⁴⁺ ions at the B sites in the ABO₃ perovskite phase. The curves of magnetization versus applied magnetic field at 10 K showed that the magnetic moments of the Mn²⁺ ions at the A sites are antiparallel to those of the Mn³⁺ and Mn⁴⁺ ions at the B sites.     

Structural properties of Bi1-xLaxFeO3 studied by micro-Raman scattering

This paper reports that La-doped BiFeO 3(Bi1-x La x FeO3,x = 0,0.1,0.2,0.3,0.6,0.8 and 1.0) were studied by using micro-Raman spectroscopy and x-ray diffraction(XRD).The XRD patterns indicate that the structure of Bi1-xLaxFeO 3 changes from rhombohedral BiFeO3 to orthorhombic LaFeO3.The results of Raman spectroscopy show good agreement with the XRD results.Strikingly,the phonon peak at around 610 cm-1 and the two-phonon peaks in the high frequency range exist in all compounds and enhance with increasing La substitution.The increasing intensity of the 610 cm-1 peak is attributed to the changes in the FeO 6 octahedron during the rhombohedral-orthorhombic phase transition.The enhancements of the two-phonon peaks are associated with the breakdown of the cycloid spin configuration with the appearance of the orthorhombic structure.These results indicate the existence of strong spin-phonon coupling in Bi1-xLax FeO3,which may provide useful information for understanding the effects of La content on the structural and magnetic properties of Bi1-xLaxFeO3.     

Chemical disorder of La and Sr ions in the block layer of LaSrFeO4

⁵⁷Fe Mössbauer spectroscopic studies were carried out on the single layered perovskite, LaSrFeO₄, in the temperature range 15-380 K. The observed line width asymmetries in the line shapes of the spectra were understood to arise from a chemical disorder of La³⁺ and Sr²⁺ ions in the block layer of the perovskite structure. The temperature dependence of the hyperfine magnetic field, quadrupole interaction, and isomer shift observed for the system was also analyzed in terms of the local environment of Fe atoms in this structure.