Influence of doping concentration on room-temperature ferromagnetism for Fe-doped BaTiO3 ceramics

Ba(Ti_1−xFe_x)O₃ ceramics (x=7, 30 and 70 at%) were prepared by solid-state reaction. All samples are single-phase with 6H-BaTiO₃-type hexagonal perovskite structure. Mössbauer spectra show all Fe atoms to be present as Fe³⁺ in BaTiO₃ lattice, occupying M1 octahedral and pentahedral sites. Room-temperature ferromagnetism is exhibited and saturation magnetization gradually decreases with increasing Fe content. The observed ferromagnetism is considered to be an intrinsic property of Ba(Ti_1−xFe_x)O₃, originating from super-exchange interactions between Fe³⁺ in different occupational sites associated with oxygen vacancies. The variation in magnetization with Fe content is related to the ratio of pentahedral to octahedral sites and oxygen vacancies.     

Effect of Sr concentration on microstructure and magnetic properties of (Ba1−xSrx)(Ti0.3Fe0.7)O3 ceramics

Fe-doped (Ba_1−xSr_x)TiO₃ ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti sites mediated by the O²⁻ ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe³⁺ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba_0.25Sr_0.75)TiO₃, is an order of magnitude higher than that of the Fe-doped BaTiO₃ system with similar Fe concentration and preparation conditions, which may indicate (Ba_1−xSr_x)TiO₃ as a more suitable matrix material for multiferroic research.     

Effect of annealing atmosphere on magnetism for Fe-doped BaTiO3 ceramic

Ba(Ti_0.3Fe_0.7)O₃ ceramic was prepared by solid-state reaction and post-annealed in vacuum and oxygen, respectively. The as-prepared and annealed samples are all single-phase, crystallizing in a 6H-BaTiO₃-type hexagonal perovskite structure. Room-temperature ferromagnetism is exhibited in all ceramics. For the as-prepared sample, the super-exchange interactions of Fe³⁺ in different occupational sites (pentahedral and octahedral sites) are expected to produce the ferromagnetism observed. After annealing in vacuum, the magnetization is reduced while the exchange mechanism remains unchanged. On the contrary, O₂ annealing can effectively enhance the magnetization due to the presence of Fe⁴⁺, an unusual valence for iron. The simultaneous presence of Fe³⁺ and Fe⁴⁺ allows new exchange mechanism responsible for the ferromagnetic interaction. The exchange couplings of Fe ions with mixed valences (Fe³⁺ and Fe⁴⁺) determine the magnetic behavior.     

Effects of cation size disorder and lattice distortion on metamagnetism in phase-separated manganites

The effects of A-site cation size disorder in ABO₃ type charge-ordered and antiferromagnetic Pr_0.5Ca_0.5MnO₃ system have been studied by substituting La³⁺, Sr²⁺ or Ba²⁺, while keeping the valency of Mn ions and the tolerance factor (t=0.921) constant in the substituted compounds. We find that the substitutions by these larger cations induce successive sharp step-like metamagnetic transitions at 2.5 K. The critical field for metamagnetism is the lowest for 3% Ba substituted compound, which has the largest A-site cation size disorder and the least distorted MnO₆ octahedra, among the compounds reported here. These cation substitutions give rise to ferromagnetic clusters within antiferromagnetic matrix, indicating phase-separation at low temperatures. The growth of the clusters is found to vary with the substitution amount. The local lattice distortion of MnO₆ octahedra enhances the charge ordering temperature and reduces the magnetization at high fields (>1 T) in these manganites.     

Sol-gel synthesis and dilute magnetism of nano MgO powder doped with Fe

Mg oxides doped with 1 % ⁵⁷Fe were prepared by a sol-gel method, and annealed at various temperatures. Nano-size Mg oxides were characterized by Mössbauer spectrometry, magnetization and XRD measurements. The crystalline size of MgO increases with increase of annealing temperature. Samples annealed at 600 °C and 800 °C gave only doublet peaks of paramagnetic Fe³⁺ in Mössbauer spectra although Fe³⁺ doping into MgO induced a distorted structure and showed weak ferromagnetism. It is considered that the magnetic property is due to defect induced magnetism by doping Fe³⁺ into MgO. For a sample heated at 1000 °C, it is found from low temperature Mössbauer spectra that Fe³⁺ species are located at the core and shell of fine MgFe₂O₄ grains and diluted in MgO matrix.     

Dielectric properties and substitution preference of yttrium doped barium zirconium titanate ceramics

The dielectric properties of Ba(Zr_0.25Ti_0.75)O₃+xY ₂O₃ ceramics are investigated. We believe that, integrating with the lattice parameters, there is an alternation of substitution preference of yttrium ions for the host cations in perovskite lattice that is responsible for the Curie point. The T_c rises with the increase of Y ³⁺ doping when the doping content is less than 0.05 at%, owing to the replacement of Y ³⁺ ions for Ba²⁺ ions at the A-site; when the Y ³⁺ content is more than 0.05 at%, Y ³⁺ ions tend to occupy the B-site in perovskite lattice, causing a drop of T_c. Owing to the modifications of Y ³⁺ doping, the loss tangent of BZT ceramics is depressed remarkably, making it a superior candidate to replace widely used lead-contained ceramics.     

Rietveld analysis and multiferroic properties of Fe doped Ba0.95Bi0.05TiO3 ceramics

We report on the structural, magnetic and ferroelectric properties of Fe doped Ba_0.95Bi_0.05TiO₃ (Ba_0.95Bi_0.05Ti_1−yFe_yO₃ (0 ≤ y ≤ 0.1)) ceramics prepared by solid state reaction. Rietveld analysis shows that compounds with y ≤ 0.07 have a single phase-tetragonal structure (space group P4mm), and the tetragonality (c/a) decreases as x increases. Ba_0.95Bi_0.05Ti_0.93Fe_0.07O₃ ceramic shows ferromagnetic order with a Curie temperature of about 700 K and ferroelectric order at room temperature. These results indicate that the Ba_0.95Bi_0.05Ti_0.93Fe_0.07O₃ can be useful as a multiferroic material.     

The magnetoelectric coupling in rhombohedral–tetragonal phases coexisted Bi0.84Ba0.20FeO3

Ba doped Bi_1.04−xBa_xFeO₃ ceramics with x up to 0.30 have been prepared by the tartaric acid modified sol–gel method. The X ray diffraction patterns show that the structure transforms from rhombohedral to tetragonal with increasing the Ba substitution concentration from 10% to 30% and the coexistence of distorted rhombohedral and tetragonal phases in 20% Ba substituted BiFeO₃, which was further confirmed by the Raman spectra. Bi_0.84Ba_0.20FeO₃ exhibits the highest magnetization (1.6 emu/g under magnetic field of 12 kOe) compared with the other samples of different Ba substitution concentration. Significant enhancement of the ferroelectricity has been observed in 20% and 30% Ba substituted BiFeO₃ with saturate polarization close to 6.6 μC/cm² for Bi_0.74Ba_0.30FeO₃. The magnetoelectric coupling of Bi_0.84Ba_0.20FeO₃ has been measured and the maximum decrease of magnetization under magnetic field of 9.8 kOe was about 0.06 emu/g with increasing applied electric field to 11 kV/cm, and the magnetoelectric coefficient is 1.5×10⁻¹² s/m.     

The relationship between magnetic behaviour and local structure around Fe ions in Fe-doped TiO2 rutile

The magnetic and structural characterization of Ti_1−xFe_xO₂ (x=0.025, 0.05, 0.07, 0.125, and 0.15) samples prepared by mechano-synthesis using TiO₂ and Fe₂O₃ as starting materials are reported. XANES measurements performed at the Fe K-edge show that Fe ions are in 3+ oxidation state in the 7 at% Fe-doped sample and in a mixture of 2+ and 3+ oxidation states in the other samples. EXAFS results show the incorporation of Fe ions substituting Ti ones in the rutile TiO₂ structure. They also reveal a strong correlation between the number of oxygen nearest neighbours and the Fe²⁺ fraction, i.e the number of oxygen near neighbours decreases when the Fe²⁺ fraction increases. All samples present ferromagnetic-like behaviour at room temperature. We found a clear dependence between saturation magnetization and coercivity with the fraction of Fe²⁺ and/or the number of Fe near neighbour oxygen vacancies.     

Enhanced multiferroic characteristics in Fe-doped Bi4Ti3O12 ceramics

Modification of Bi₄Ti₃O₁₂ multiferroic ceramics prepared by a conventional solid state reaction method were investigated by substituting Ti partly with Fe. The introduction of Fe does not change the layered perovskite structure of Bi₄Ti₃O₁₂. Upon increasing Fe content, the remnant polarization of the samples is enhanced. The magnetism of the ceramics at room temperature develops from diamagnetism to weak ferromagnetism with increasing Fe doping. The largest variations of 15% and 6% in remnant polarization and magnetization, achieved in a Bi₄Ti₁Fe₂O_12?δ sample after poling it in a magnetic field at 1 T and a DC electric field at 30 kV/cm for 10 min, are evidence of magnetoelectric coupling between the electric dipoles and magnetic dipoles at room temperature. The present results suggest a new candidate for a room temperature multiferroic material with enhanced properties.     

X-ray photoelectron spectroscopic investigations on cubic BaTiO3, BaTi0.9Fe0.1O3 and Ba0.9Nd0.1TiO3 systems

X-ray photoelectron spectroscopic (XPS) studies were carried out on wet-chemically synthesized cubic BaTiO₃, Ba_0.9Nd_0.1TiO₃ and BaTi_0.9Fe_0.1O_3−δ powders. The compounds were prepared by hydrothermal and gel to crystallite conversion technique; and phases formed readily at 420 K. The phase purity of the powders was confirmed from X-ray diffractometry. Chemical state and chemical environment of the constituent elements in the compositions were examined by XPS. Ba²⁺ was found to exist in two different chemical environments in these titanates. The Ti 2p_3/2 photoelectron peak in BaTi_0.9Fe_0.1O_3−δ was found to be broadened after Fe³⁺ substitution. Any resolvable broadening was not observed distinctly in the Ti 2p peak for Ba_0.9Nd_0.1TiO₃, unsintered BaTiO₃ and BaTiO₃ annealed in hydrogen (8% H₂ + Ar) at 1000 K. The prevalence of mixed-valent titanium and iron in BaTi_0.9Fe_0.1O_3−δ composition was evident from the XPS results and was further supported by the enhanced electrical conductivity at 298-550 K for BaTi_0.9Fe_0.1O_3−δ in comparison to BaTiO₃ and Ba_0.9Nd_0.1TiO₃. Hydroxyl incorporation was facilitated by substituting Nd³⁺ in Ba-sublattice. The presence of hydroxyls was observed from the broadening of the O 1s peak in XPS studies of the compounds.     

Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.     

Anisotropy of hyperfine field in diamagnetically substituted YIG

The results of the nuclear magnetic resonance of ⁵⁷Fe in Al-, Ga- and In-substituted Y₃Fe₅O₁₂ garnets are reported. When diamagnetic Ga³⁺ or Al³⁺ ions are substituted for tetrahedral Fe³⁺ ions, four satellite lines in the NMR spectrum of octahedral Fe³⁺ ions appear. The substitution of In³⁺ ions for octahedral Fe³⁺ ions leads to three satellite lines in the spectrum of tetrahedral Fe³⁺ ions. The hyperfine fields of these satellites are explained using the independent bond model for the hyperfine interaction. Suprisingly large change of the anisotropic part of the hyperfine field relative to the isotropic one was found.     

Electromagnetic and microwave absorbing properties of Co2Z-type hexaferrites doped with La

Z-type ferrites doped with La³⁺, Ba_3−xLa_xCo₂Fe₂₄O₄₁ (x=0.00-0.30), were prepared by sol-gel method. The effect of the substitution La³⁺ rare-earth ions for Ba²⁺ ions on the microstructure, complex permeability, permittivity and microwave absorption of the samples was investigated. The results show that the major phase of the ferrites changed to Z-phase when sintering temperature was 1250 °C for 5 h. With the increase of the substitution ratio of La³⁺ ions from 0.0 to 0.3, the lattice parameters a and c increased gradually, which resulted in the change of the particle shape and size. The data of magnetism showed that the addition of La³⁺ ions make the ferrite a better soft magnetic material due to increase of magnetization (σ_s) and decrease of coercivity (H_c). The La³⁺ ions doped in the ferrite not only improved complex permeability and complex permittivity, but also microwave absorbency.     

Hyperfine field and relaxation effect in Li−Zn−Ti ferrites

⁵⁷Fe Mössbauer effect studies were made on titanium substituted Li?Zn ferrite with composition Li_0.45+0.5tZn_0.1 Ti_t Fe_2.45–1.5tO₄ (t=0.0 to 1.2) at 300K. The Mössbauer spectra for t≤0.4 show two well defined Zeeman sextets corresponding to the Fe³⁺ ions at tetrahedral (A) and octahedral (B) sites. The spectra for t=0.6, 0.8 and 0.9 show relaxation but can still be resolved into 2 sextets. The spectra for t=1.0, 1.2 show strong ferrimagnetic relaxation with the spectra for t=1.2 exhibiting an additional central doublet. The effect of Ti⁴⁺ substitution on the Isomer shift (I.S), Quadrupole splitting (Q.S.) and nuclear magnetic fields of Li?Zn ferrites have been reported in this paper. The I.S. was found to be independent of substitution level t, while the quadrupole splitting was observed to be negligible. The variation of hyperfine field with t has been explained on the basis of superexchange interaction and cation distribution.     

Enhanced room temperature ferromagnetism in porous BiFeO3 prepared using cotton templates

Porous BiFeO₃ has been prepared using cotton templates. Strongly enhanced ferromagnetism with saturate magnetization of 3 emu/g at 300 K has been observed. An energy band gap of 2.21 eV was determined from the UV-visible diffuse reflectance spectrum. The Raman and X-ray photoelectron spectroscopy measurements indicate the existence of Fe²⁺ and the suppression of the oxygen octahedral tilts. The enhanced ferromagnetism has been attributed to the enhanced double exchange interaction with increased angle of Fe^{2 +}-O-Fe^{3 +}.     

Abnormal Raman spectra in Er‐doped BaTiO3 ceramics

Greatly enhanced and abnormal Raman spectra were discovered in the nominal (Ba_{1 − x}Er_x)Ti_{1 − x/4}O₃ (x = 0.01) (BET) ceramic for the first time and investigated in relation to the site occupations of Er³⁺ ions. BaTiO₃ doped with Ti‐site Er³⁺ mainly exhibited the common Raman phonon modes of the tetragonal BaTiO₃. Er³⁺ ions substituted for Ba sites are responsible for the abnormal Raman spectra, but the formation of defect complexes will decrease spectral intensity. A large increase in intensity showed a hundredfold selectivity for Ba‐site Er³⁺ ions over Ti‐site Er³⁺ ions. A strong EPR signal at g = 1.974 associated with ionized Ba vacancy defects appeared in BET, and the defect chemistry study indicated that the real formula of BET is expressed by (Ba_{1 − x}Er_3x/4)(Ti_{1 − x/4}Er_x/4)O₃. These abnormal Raman signals were verified to originate from a fluorescent effect corresponding to ⁴S_3/2→⁴I_15/2 transition of Ba‐site Er³⁺ ions. The fluorescent signals were so intense that they overwhelmed the traditional Raman spectra of BaTiO₃. The significance is that the abnormal Raman spectra may act as a probe for the Ba‐site Er³⁺ occupation in BaTiO₃ co‐doped with Er³⁺ and other dopants. A new broad EPR signal at g = 2.23 was discovered, which originated from Er³⁺ Kramers ions. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and magnetic properties of hexagonal Y(Mn,Cu)O3 multiferroic materials

Single-phase hexagonal-type solid solutions based on the multiferroic YMnO₃ material were synthesized by a modified Pechini process. Copper doping at the B-site (YMn_1−xCu_xO₃; x<0.15) and self-doping at the A-site (Y_1+yMnO₃; y<0.10) successfully maintained the hexagonal structure. Self-doping was limited to y(Y)=2 at% and confirmed that excess yttrium avoids formation of ferromagnetic manganese oxide impurities but creates vacancies at the Mn site. Chemical substitution at the B-site inhibits the geometrical frustration of the Mn³⁺ two-dimensional lattice. The magnetic transition at T_N decreases from 70 K down to 49 K, when x(Cu) goes from 0 to 15 at%. Weak ferromagnetic Mn³⁺-Mn⁴⁺ interactions created by the substitution of Mn³⁺ by Cu²⁺, are visible through the coercive field and spontaneous magnetization but do not modify the overall magnetic frustration. Presence of Mn³⁺-Mn⁴⁺ pairs leads to an increase of the electrical conductivity due to thermally-activated small-polaron hopping mechanisms. Results show that local ferromagnetic interactions can coexist within the frustrated state in the hexagonal polar structure.     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

Magnetic property and Mössbauer analysis of SrSn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Bold">x</Emphasis></Subscript>O<Subscript>3</Subscript> prepared by a sol-gel method

The dilute magnetic properties of SrSn_1?xFe_xO₃ (x = 0.01 ? 0.15) prepared by sol-gel and thermal decomposition methods were investigated by ⁵⁷Fe Mössbauer spectrometry, magnetometry, and X-ray diffractometry. It was found that SrSnO₃ doped with 2–8 % Fe show weak ferromagnetism although only paramagnetic doublets are observed in ⁵⁷Fe Mössbauer spectra at room temperature (RT), whereas SrSnO₃ doped with 10–15 % Fe show relatively strong ferromagnetism, and the sextets are additionally observed in the ⁵⁷Fe Mössbauer spectra at RT. The weak ferromagnetism by doping 2–8 % Fe is considered to be caused by the induced magnetic defects, and the ferromagnetism by doping 10–15 % Fe are considered mainly due to the magnetic coupling between dilute Fe ³⁺ partially substituted at Sn ⁴⁺ sites in the orthorhombic structure of SrSnO_3?δ accompanying the oxygen deficiencies. It is further remarkable that poor crystalline 8 % Fe doped SrSnO_3?δ obtained by annealing at 600 ^°C shows relatively high saturation magnetization and low coercivity.