Temperature evolution of the crystal structure of Bi1 − x Pr x FeO3 solid solutions

The crystal structure of solid solutions in the Bi_{1 ? x} Pr _x FeO₃ system near the structural transition between the rhombohedral and orthorhombic phases (0.125 ≤ x ≤ 0.15) has been studied. The structural phase transitions induced by changes in the concentration of praseodymium ions and in the temperature have been investigated using X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. It has been established that the sequence of phase transformations in the crystal structure of Bi_{1 ? x} Pr _x FeO₃ solid solutions with variations in the temperature differs significantly from the evolution of the crystal structure of the BiFeO₃ compounds with the substitution of other rare-earth elements for bismuth ions. The regions of the existence of the single-phase structural state and regions of the coexistence of the structural phases have been determined in the investigation of the crystal structure of the Bi_{1 ? x} Pr _x FeO₃ solid solutions. A three-phase structural state has been revealed for the solid solution with x = 0.125 at temperatures near 400°C. The specific features of the structural phase transitions of the compounds in the vicinity of the morphotropic phase boundary have been determined by analyzing the obtained results. It has been found that the solid solutions based on bismuth ferrite demonstrate a significant improvement in their physical properties.     

Phase analysis of the system La1−x Ba x FeO3−y (0≦x≦0.70) by means of x—ray diffraction and Mössbauer spectroscopy

X-ray diffraction and Mössbauer measurements were performed on novelly synthesized La_1?x Ba _x FeO_3?y (0≤x≤0.70). Two phases were found in the system. La_1?x Ba _x FeO_3?y for 0≤x≤0.10 is an orthorhombic perovskite. La_1?x Ba _x FeO_3?y for 0.54≤x≤0.70 is a cubic perovskite. La_1?x Ba _x FeO_3?y for 0.10≤x≤0.54 consists of these two phases.     

Magnetic and piezoelectric properties of the Bi1 − x La x FeO3 system near the transition from the polar to antipolar phase

The crystal structure, piezoelectric and magnetic properties of the Bi_{1 ? x} La _x FeO₃ solid-solution system near the structural transition between the rhombohedral and orthorhombic phases (0.15 ≤ x ≤ 0.2) have been investigated. The regions of existence of the polar rhombohedral and orthorhombic phases have been determined, and the sequence of structural transitions as a function of the lanthanum ion concentration and temperature has been studied. The maximum piezoelectric signal is found for the solid solution with the composition x = 0.16, which has a single-phase rhombohedral structure. The relation between the type of crystal structure distortions and the increase in the magnetization upon the concentration-driven structural transition from the polar to antipolar phase has been established.     

Stabilization of Ferromagnetism in BiFeO<Subscript>3</Subscript>:Ho at Hydrostatic Pressure

The isothermal magnetization of the Bi_{1 – x}Ho _x FeO₃ (x = 0?0.2) multiferroic has been studied at a hydrostatic pressure up to 9 GPa in the range of room temperatures. A new anomaly at P_C ≈ 3.81 GPa related to intermediate phases between the structural transition R3c → Pnma has been found against the background of the pressure-induced antiferromagnetic ordering in BiFeO₃ (BFO) at P ≈ 2.59 GPa. It is established that the ferromagnetic behavior under pressure depends on the Ho impurity concentration: P_C decreases at 0.05 ≤ x ≤ 0.1 because of the decrease in R3c bond lengths in the structure, and the stabilization of ferromagnetism is implemented at 0.1 ≤ x ≤ 0.2 probably because of the coexistence of the R3c and Pnma phases. The results of studies indicate that, in Bi_{1 – x}Ho _x FeO₃ with x = 0.2, the transition pressure P_C = 3.7 GPa exceeds the values for BFO doped with other 4f elements (Eu, Y, Sm) in the region R3c → Pnma of the transition.     

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.     

X-Ray Diffraction and Mössbauer Studies of the Structural Features of BiFe<Subscript>1 ‒ <Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> Multiferroics

The structure of ceramic BiFe_1?xZn_xO₃ multiferroic samples is investigated using the X-ray diffraction method and Mössbauer spectroscopy. X-ray diffraction analysis of the samples indicates the existence of the Bi₁₂(Bi_0.5Fe_0.5)O_19.5 impurity phase. High-temperature heating of the samples generates additional phases. The parameters of the Mössbauer spectra depend on the zinc concentration. In this case, for pure bismuth ferrite, the spectrum is a superposition between two Zeeman sextets and two paramagnetic doublets arising from two nonequivalent magnetic and electrical positions occupied by iron ions at the crystallattice sites of a sample. The replacement of iron ions with zinc ions substantially affects the spectrum parameters. This is probably related to changes in the spin-cycloid structure typical of multiferroics, the destruction of which stimulates the appearance of significant magnetoelectric interactions.     

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.     

Single or both site doped BiFeO3—Which is better candidate for profound electronic device applications?

Magnesium (Mg) and Zirconium (Zr) doped bismuth ferrite (BiFeO₃; BFO) such as Bi_1?xMg_xFeO₃ (Mg doped BFO; BMO), BiFe_1?xZr_xO₃ (Zr doped BFO; BZO) and Bi_1?xMg_xFe_1?xZr_xO₃ (both Mg and Zr doped BFO; BMZO) were synthesized by solid-state reaction techniques with dopant concentrations x?=?0 and 0.1, respectively. The distorted rhombohedral structures of doped BFO were confirmed by X-ray diffraction analysis. The microstructural analysis revealed that there were uniform dispersions and homogeneous distributions of ceramics in BMZO as compared to BMO, BZO and pure BFO. The presence of both grain and grain boundary in BMZO indicated its good electrical response than others as evidenced from impedance analysis and in agreement with AC conductivity study. The dielectric and ferroelectric measurement signified that BMZO possessed enhanced dielectric constant and high remanent polarization thus could be a better prominent candidate than others to be used in electronic devices.     

The crystal and grain structure and physical properties of Bi1 − x A x FeO3 (A = La, Nd) solid solutions

High-quality ceramics were synthesized on the basis of Bi_{1 ? x} A _x FeO₃ (A = La, Nd; 0.00 ≤ x ≤ 0.20) solid solutions. Their crystal and grain structure, Mössbauer spectra, and other dielectric and magnetic characteristics were studied. It was shown that an increase in the content of A elements in the studied samples considerably enhanced their magnetic susceptibility and magnetoelectric effect.     

Electrical behavior of high resistivity Ce-doped BiFeO3 multiferroic

Bi_1+xCe_xFeO₃ (Ce–BFO) for x=0, 0.05, 0.1, and 0.15 monophasic ceramic samples were successfully synthesized by conventional solid-state reaction routes. The influences of Ce doping on structural, dielectric, ferroelectric, leakage current and capacitive properties of BiFeO₃ ceramics were investigated intensively. At higher concentrations of x (x=0.1 and 0.15) the samples showed good crystallinity with almost impurity free phases. No structural phase transformation took place after partial doping of Ce ions and all ceramic bulk samples remain in their rhombohedral structure with space group R3c. The dielectric behavior of the samples improved significantly and the ferroelectric hysteresis loops changed their shape from rounded to a strongly nonlinear typical ferroelectric feature mainly originating from the domain switching and became enhanced with increase in doping concentration of cerium (Ce). Experimental results also suggested that partial doping of higher valence, smaller ionic radius Ce ions in BiFeO₃ forces the reduction of oxygen vacancies, resulting in a great suppression of leakage current. It is found that the sharp capacitance peak/discontinuity present in the C–V characteristics of Ce–BFO for different Ce doping concentrations is directly associated with the polarization reversal. Incorporation of excess bismuth in the presence of Ce in BiFeO₃ is expected to compensate Bi loss during high temperature sintering and caused structural distortion which also favors enhancement of ferroelectric properties in Ce-doped BFO.     

Effect of holmium substitution for the improvement of multiferroic properties of BiFeO3

This paper reports on multiferroic properties of Ho substituted BiFeO₃ (Bi_1−xHo_xFeO₃) ceramics. It is observed that for x=0.15, a prominent ferroelectric loop is seen at 300 K even if the system remains in rhombohedral (R3c) phase without appearance of any observable impurity phases. A well shaped M-H loop is observed at 10 K for x=0.15. However it showed ferromagnetism, confirming the contribution of Ho³⁺ towards enhancement of ferromagnetic properties of BiFeO₃ at 300 K. Suppression of impurity phases of pure BiFeO₃ bulk ceramic favors the reduction of mobile oxygen vacancies and reduces leakage current, due to which ferroelectric properties of BiFeO₃ is enhanced. We argue that Ho substitution at Bi site is likely to suppress the spiral spin modulation and at the same time increase the canting angle, which favors enhanced multiferroic properties. XRD, SEM, magnetization, polarization and chemical bonding analysis measurements were carried out to explain the multiferroic behavior.     

Heat capacity of BiFeO3-based multiferroics

The heat capacity of Bi_{1 ? x} Re _x FeO₃ (Re = La, Eu, Ho; x = 0, x = 0.05) multiferroics has been studied in the temperature range of 120–800 K. The substitution of a small amount of rare-earth elements for bismuth leads to a significant increase in the heat capacity in the broad temperature range studied. It is established that the temperature dependence of the excess heat capacity is related to the Schottky effect for three-level states certain that appear as a result of structure distortions in the rare-earth-doped compositions.     

Structural stability and magnetic properties of Bi1−xLa(Pr)xFeO3 solid solutions

In this work, X-ray diffraction data taken on Bi_1−xLa_xFeO₃ solid solutions are used to verify the following structural phase transitions: “polar rhombohedral-antipolar orthorhombic” at x≈0.16 and “commensurate-incommensurate” within the orthorhombic phase at x≈0.18. In contrast, in the Bi_1−xPr_xFeO₃ series, the polar rhombohedral phase transforms into an antipolar orthorhombic one at x≥0.13. The polar rhombohedral phase near the morphotropic phase boundary exhibits an isothermal transformation into an antipolar orthorhombic phase, though the transformation occurs much faster in the case of La-doped compounds. The incommensurate structural phase was not detected in Bi_1−xPr_xFeO₃ solid solutions. The ternary structural phase diagram is constructed for (Bi,La,Pr)FeO₃ systems. In addition, the polar rhombohedral phase exhibits a magnetic field-induced transition from the modulated antiferromagnetic state into a homogeneous weak ferromagnetic state whereas the antipolar phase is a weak ferromagnetic state in the absence of an external field.     

Specific features of the thermal,magnetic, and dielectric properties of multiferroics BiFeO<Subscript>3</Subscript> and Bi<Subscript>0.95</Subscript>La<Subscript>0.05</Subscript>FeO<Subscript>3</Subscript>

Thermophysical, magnetic, and dielectric properties of multiferroic BiFeO₃ and Bi_0.95La_0.05FeO₃ ceramic compounds were comprehensively studied. Anomalies of the permittivity near an antiferromagnetic phase transition related to the structural variations were detected. The temperature T _N was determined from the temperature dependences of the thermal expansion coefficient, heat capacity, and differential susceptibility. It is shown that the transition point is shifted to higher temperatures as the rare-earth La ion substitutes for Bi. It is established that an insignificant substitution of lanthanum for bismuth enhances the magnetic properties of bismuth ferrite and the magnetodielectric effect.     

Crystalline and magnetic structures of La1−x BixMnO3+δ manganites

The crystalline and magnetic structures and magnetic properties of La_1?x Bi_xMnO_3+δ (0.4 ≤ x ≤ 0.6, 0 ≤ δ ≤ 0.06) manganites have been studied. The solid solutions having the stoichiometric oxygen content are shown to be orbitally ordered A-type antiferromagnets. An increase in the oxygen content above the stoichiometric value is found to cause Mn⁴⁺ ions in the perovskite lattice, to remove the cooperative Jahn-Teller distortions, and to form a long-range ferromagnetic order. This order becomes broken as the concentration of the tetravalent manganese ions increases further. The tendency toward breaking the ferromagnetic order increases with the bismuth content. The magnetic properties are interpreted in terms of superexchange interactions on the assumption of local lattice distortions induced by anisotropy of the 6s ²(Bi³⁺)-2p ⁶(O^2?) chemical bonds.     

Effect of Gd doping on structural, electrical and magnetic properties of BiFeO3 electroceramic

Room temperature multiferroic electroceramics of Gd doped BiFeO₃ monophasic materials have been synthesized adopting a slow step sintering schedule. Incorporation of Gd nucleates the development of orthorhombic grain growth habit without the appearance of any significant impurity phases with respect to original rhombohedral (R3c) phase of un-doped BiFeO₃. It is observed that, the materials showed room temperature enhanced electric polarization as well as ferromagnetism when rare earth ions like Gd doping is critically optimized (x=0.15) in the composition formula of Bi_1+2xGd_2x/2Fe_1−2xO₃. We believe that magnetic moment of Gd⁺³ ions in Gd doped BiFeO₃ tends to align in the same direction with respect to ferromagnetic component associated with the iron sub lattice. The dielectric constant as well as loss factor shows strong dispersion at lower frequencies and the value of leakage current is greatly suppressed with the increase in concentration of x in the above composition. Addition of excess bismuth and Gd (x=0.1 and 0.15) caused structural transformation as well as compensated bismuth loss during high temperature sintering. Doping of Gd in BiFeO₃ also suppresses spiral spin modulation structure, which can change Fe-O-Fe bond angle or spin order resulting in enhanced ferromagnetic property.     

Weak ferromagnetism and spin density distributions in thin films of Gd x Bi1 − x FeO3 solid solutions

Polycrystalline thin-film Gd _x Bi_{1 ? x} FeO₃ (x = 0, 0.05, 0.10, 0.15, or 0.20) samples are synthesized by means of thermal vacuum deposition. The concentrations, temperatures, and magnetic field dependences of specific magnetization are studied. Self-consistent calculations of the spin density distribution are performed for R3c BiFeO₃ and Pnma Gd_0.25Bi_0.75FeO₃ using the density functional theory in the LSDA approximation.     

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.     

Structure and multiferroic properties of Eu-substituted BiFeO3 ceramics

Polycrystalline Bi_1?x Eu _x FeO₃ (x=0.00–0.25) ceramics were synthesized by the solid state reaction method with the rapid liquid phase sintering process. The effects of Eu substitution on the structure, and ferroelectric and magnetic properties of BiFeO₃ ceramics were investigated. X-ray diffraction measurements reveal that the structure of BiFeO₃ was changed from rhombohedral to orthorhombic and the impurity phases were decreased both due to Eu substitution. Raman spectra results also confirm that a structure transition occurs in the Eu concentration range of 0.15–0.20. The SEM investigation has suggested that the Eu substitution hinders the grain growth. Vibrating sample magnetometer measurements indicate ferromagnetism in Eu-substituted BiFeO₃ ceramics. It is found that the room temperature magnetic moment increases with increasing Eu concentration due to the suppressed or broken cycloid spin structure. Ferroelectric measurements show that Eu substitution enhances the polarization due to the significant decrease of the electric leakage of the samples. Therefore, the Eu-substituted BiFeO₃, or more complicated substituted BiFeO₃ based on Eu substitution, will have great potential for many practical applications.     

On the prospects for technical applications of BiFeO<Subscript>3</Subscript> compounds substituted with rare-earth elements

Solid solutions of Bi_1-x Re _x FeO₃ (Re=La, Nd; x=0-0.2) compounds were synthesized, and their room-temperature magnetoelectric and magnetodielectric properties were studied. Amplification of magnetoelectric and magnetodielectric effects with increasing the rare-earth doping level was detected in the concentration range x under study. The results obtained confirm the prospects for applications of bismuth ferrite-based compounds as magnetoelectric converters and magnetic field sensors.