Structural,dielectric, vibrational and magnetic properties of Sm doped BiFeO3 multiferroic ceramics prepared by a rapid liquid phase sintering method

Rare earth Sm substituted Bi_1−xSm_xFeO₃ with x=0, 0.025, 0.05, 0.075 and 0.10 polycrystalline ceramics were synthesized by a rapid liquid phase sintering method. The effect of varying composition of Sm substitution on the structural, dielectric, vibrational, optical and magnetic properties of doped BiFeO₃ (BFO) ceramics have been investigated. X-ray diffraction patterns of the synthesized rare earth substituted multiferroic ceramics showed the pure phase formation with distorted rhombohedral structure with space group R3c. Good agreement between the observed and calculated diffraction patterns of Sm doped BFO ceramics in Rietveld refinement analysis of the X-ray diffraction patterns and Raman spectroscopy also confirmed the distorted rhombohedral perovskite structure with R3c symmetry. Dielectric measurements showed improved dielectric properties and magnetoelectric coupling around Néel temperature in all the doped samples. FTIR analysis establishes O–Fe–O and Fe–O stretching vibrations in BiFeO₃ and Sm-doped BiFeO₃. Photoluminescence (PL) spectra showed visible range emissions in modified BiFeO₃ ceramics. The magnetic hysteresis measurements at room temperature and 5 K showed the increase in the magnetization with the increase in doping concentration of Sm which is due to the structural distortion and partial destruction of spin cycloid caused by Sm doping in BFO ceramics.     

Substantial reduction of leakage currents in La/Er/Zn/Ti multielement-doped BiFeO3 multiferroic thin films

Multi-element doping is an effective method to suppress the leakage of BiFeO₃ (BFO). A systematic study on the effect of various elements (La, Er, Zn, Ti) doping on the leakage performance, mechanism and other electrical properties of BFO films was performed As the kinds of doping elements increases, the leakage current density of the BFO film gradually decreases. The leakage current density is gradually reduced from 5.78 × 10^?2 A/cm² doped with one element (La) to 1.25 × 10^?2 A/cm² doped with two elements (La, Ti), 4.13 × 10^?3 A/cm² doped with three elements (La, Ti, Zn), and 4.53 × 10^?4 A/cm² doped with four elements (La, Er, Zn, Ti). Finally, compared with pure BFO films, the leakage current density in doped BFO films is reduced by two orders of magnitude. Moreover, the conduction mechanism in doped BFO films is gradually changed from space charge limited current to ohmic conduction. This work provides an effective method to ameliorate the leakage of ferroelectric materials and lays a foundation for the practical application of BFO-based films.     

Ferroelectric switching and current characteristics dependence on ferroelectric polarization direction of microwave synthesized BiFeO3 nanocubes

Herein, we studied the ferroelectric switching and current characteristics of BiFeO₃ (BFO) nanocubes dispersed on the surface of a Nb-doped SrTiO₃ (Nb:STO) substrate based on the ferroelectric polarization orientation. The microwave synthesis method afforded BFO nanocubes with an average size of ～50 nm, which were dispersed on the Nb:STO substrate surface and the substrate was subsequently subjected to heat treatment at 500 °C for 1 h. The piezoelectric d₃₃ hysteresis loop, ferroelectric domain structure, and ferroelectric polarization switching characteristics of the 50-nm-sized BFO nanocubes were examined using piezoresponse force microscopy. Finally, atomic force microscopy confirmed the dependency of current characteristics on the ferroelectric polarization orientation of the BFO nanocubes, verifying the applicability of BFO nanocubes as storage media for ferroelectric polarization information.     

Solution-processed BiFeO3 thin films with low leakage current

Bismuth ferrite (BiFeO₃) is an attractive multiferroic material that shows strong ferroelectric and antiferromagnetic properties. Nevertheless, producing high-quality oriented BiFeO₃ on technology-important platinized silicon substrates by low-cost solution deposition methods is still challenging. In this work, polycrystalline Mn and Ti co-doped BiFeO₃ (BFO) thin films were fabricated on platinized silicon substrates by a solution deposition method. PbTiO₃ nanocrystals were used as a seed layer between the electrode and the BFO thin films to induce a preferential (100) pseudocubic orientation. We show that the introduction of a PbTiO₃ seed layer strongly reduces the leakage current. The films show excellent room-temperature ferroelectric properties at low frequencies (300 Hz), with epitaxial-like remanent polarization as high as 51 μC/cm² and coercive field of 500 kV/cm.     

Modified electrical properties of chemical solution deposited epitaxial BiFeO3 thin films by Mn substitution

The effect of Mn substitution on microstructure and electrical properties of epitaxial BiFeO₃ (BFO) thin films grown by an all-solution approach was investigated. Raman analysis reveals that the Mn atoms substitution at Fe sites can result in Jahn-Teller distortion and thus lead to the weakness of long-range ferroelectric order. In addition, the break-down characteristics of BFO thin films are improved with the increase of Mn atoms content, although the leakage current is gradually increased. Meanwhile, the grain size, the dielectric constant and loss are also increased with the increase of Mn content. The P-E hysteresis loops and PUND results demonstrate that the intrinsic ferroelectric polarization is effectively improved with Mn atoms substitution as the grain size increased and Mn atoms play a role of nucleation sites. However, the ferroelectric properties are deteriorated with the excess substituted Mn content due to the higher leakage current.     

In situ study of electric-field-induced ferroelectric and antiferromagnetic domain switching in polycrystalline BiFeO3

Antiferromagnetic domain switching induced by ferroelectric polarization switching has previously been observed in situ in both multiferroic BiFeO₃ single crystals and thin films. Despite a number of reports on macroscopic magnetoelectric measurements on polycrystalline BiFeO₃, direct in situ observation of electric-field-induced antiferromagnetic domain switching in this material has not been addressed due to the lack of high-quality samples capable of electrical poling. Here, the electric field control of antiferromagnetic domain texture is identified in polycrystalline BiFeO₃ using in situ neutron diffraction, showing the resultant magnetic domain reorientation induced by an electric field. An antiferromagnetic domain reorientation to a value of 2.2-2.5 multiples of a random distribution (MRD) is found to be induced by an electric field that provides a non-180° ferroelectric-ferroelastic domain texture of 2.2-2.5 MRD along the field direction. The current results show well-controlled coupling of multiferroic domain texturing in single-phase polycrystalline BiFeO₃.     

Tunable multiferroic properties of Mn substituted BiFeO3 thin films

The current study explored the influence of Mn substitution on the electrical and magnetic properties of BiFeO₃ (BFO) thin films synthesized using low cost chemical solution deposition technique. X-ray diffraction analysis revealed that pure rhombohedral phase of BiFeO₃ was transformed to the tetragonal structure with P4mm symmetry on Mn substitution. A leakage current density of 5.7×10⁻⁴ A/cm² which is about two orders of magnitude lower than pure BFO was observed in 3% Mn doped BFO thin film at an external electric field >400 kV/cm. A well saturated (p-E) loops with saturation polarization (P_sat) and remanent polarization (2P_r) as high as 60.34 µC/cm² and 25.06 µC/cm² were observed in 10% Mn substituted BFO thin films. An escalation in dielectric tunability (n_r), figure of merit (K) and quality factor (Q) were observed in suitable Mn doped BFO thin films. The magnetic measurement revealed that Mn substituted BFO thin films showed a large saturation magnetization compared to pure BFO thin film. The highest saturation ~31 emu/cc was observed for 3% Mn substituted BFO thin films.     

Influence of Eu and Sr co-substitution on multiferroic properties of BiFeO3

Pure BiFeO₃ (BFO), and Eu-Sr co-substituted BFO samples were prepared by a sol–gel method. The effects of Eu and Sr codoped on the structural, morphological, magnetic and ferroelectric properties were systematically investigated. The X-ray diffraction and Fourier transform infrared spectroscopy reveal that substitution of Eu and Sr at the Bi site results in structural change and single phase formation. The maximum remnant magnetization of 0.287 emu/g and coercive field of 10.305 kOe are observed in the Bi_0.85Eu_0.05Sr_0.10FeO₃ sample. The suppression of spin cycloid caused from the structural distortion can play an important role in the improvement of magnetic properties. The Eu and Sr co-doped samples also exhibit good ferroelectric properties, which may be attributed to suppressing the formation of oxygen vacancies by Eu substitution.     

Tuning of BiFeO3 multiferroic properties by light doping with Nb

Bulk ceramic samples of BiFeO₃ were light doped (up to 1%) with Nb⁵⁺ in the place of Fe³⁺ (B-site doping) and their multiferroic properties were investigated using XRD, SEM, polarization (PMTS) and magnetization (SQUID) techniques. It is shown that even the small percentages of doping can notably change electric and magnetic behavior. Electric conductivity differs by two orders of magnitude between samples doped with 0.2% and 1% Nb. The ferroelectric behavior strongly depended on conduction mechanism, and transition from space-charge-limited current (SCLC) conduction to trap-filled limited (TFL) conduction regime reflected on a change in hysteresis patterns, particularly for the samples with 0.2% and 0.5% Nb. Separation of ZFC-FC magnetization curves occurred for all Nb concentrations and increased with Nb doping. Weak ferromagnetic behavior and the increase of remnant magnetization with Nb concentration was observed from the hysteresis measurements. Coercive field changed drastically compared to the pure BiFeO₃, namely, the sample with 1% Nb exhibited very high coercive magnetic field of ~ 10?kOe.     

Room temperature multiferroic properties of BiFeO3–MnFe2O4 nanocomposites

The novel functionalities of multiferroic magneto-electric nanocomposites have spawned substantial scope for fast-paced memory devices and sensor applications. Following this, herein we report the development of nanocomposites with soft ferromagnetic MnFe₂O₄ and ferroelectric BiFeO₃ to fabricate a system with engineered multiferroic properties. A modified sol-gel route called Pechini method is demonstrated for the preparation of the (1-x) BiFeO₃-x MnFe₂O₄ (x = 10%, 30%, 50%, 70%) nanocomposites. The crystallographic phase, structure, and morphology are characterized by XRD, FESEM, and HRTEM. The accurate crystallite size and lattice strain are determined by Williamson-Hall plot method and a comparative study with Scherer's equation is carried out. TEM image evidences the interface between BiFeO₃ and MnFe₂O₄ nanoparticles in the composite. The room temperature magnetic response reveals the strong dependence of magnetic saturation, remanent magnetization, and coercivity of the nanocomposites on MnFe₂O₄ addition. The dielectric response and impedance analysis of the prepared nanocomposites are observed. The electrical performance of the composite is affected by grain, grain boundaries, and oxygen vacancies. The unsaturated P-E loops exhibit the leaky ferroelectric behavior for the nanocomposite. The intrinsic magnetoelectric coupling between ferroelectric BiFeO₃ and ferromagnetic MnFe₂O₄ has been determined by varying H_dc/H_ac and its maximum coupling coefficient (α) is found to be 25.39 mV/cmOe for 70% BiFeO₃ -30% MnFe₂O₄ nanocomposite. These distinctive and achievable characteristics of the nanocomposite would enable the designing of magnetic field sensors, spintronic devices, and multiferroic memory devices.     

Enhancement in electrical and magnetodielectric properties of Ca‐ and Ba‐doped BiFeO3 polycrystalline ceramics

We carried out a comparative study on the electrical and magnetodielectric properties of polycrystalline BiFeO₃, Bi_0.9Ca_0.1FeO_2.95, Bi_0.9Ba_0.05Ca_0.05FeO_2.95, and Bi_0.9Ba_0.1FeO_2.95 ceramics. The two dielectric anomalies, near 25 K and 281 K, are observed for BiFeO₃. Interestingly, the anomaly near 25 K shifts towards a higher temperature above 60 K with Ca and/or Ba doping, attributed to the doping induced chemical pressure. In addition, the room temperature switchable magnetodielectric effect is witnessed for the doped BiFeO₃ compounds, due to the quadratic magnetoelectric coupling. This indicates the improved magnetoelectric coupling in BiFeO₃ with the Ca and Ba doping. This is essentially due to the enhanced magnetic ordering and reduced leakage current in BiFeO₃ after the doping.     

Structural,dielectric, magnetic,and ferroelectric properties of bismuth ferrite (BiFeO3) synthesized by a solvothermal process using hexamethylenetetramine (HMTA) as precipitating agent

Multiferroic BiFeO₃ (BFO) has been synthesized by the solvothermal technique for 4 h at 180 °C using Hexamethylenetetramine (HMTA) as a precipitating agent. Optimizations on HMTA concentration were performed to attain BFO in a narrow possible time using the solvothermal method. The effect of HMTA concentration on structural properties was investigated by XRD, FE-SEM, FT-IR, and Raman techniques. Moreover, the magnetic, ferroelectric, dielectric, and optical properties were studied by VSM, Ferroelectric analyser, Dielectric spectrometer, and UV–Vis–NIR spectrometer, respectively. The XRD data has unveiled the significant role of HMTA, as a precipitating agent, in obtaining the pure phase BFO at a particular concentration. A high concentration of HMTA (6 M) is found to be more favourable for producing pure phase BFO within the short reaction time of 4 h without any impurity phase formations. The FE-SEM images have shown the formation of granular structures that are inhomogeneously distributed throughout the powdered BFO with porosities. In addition, the magnetic measurements confirmed that the BFO synthesized with varying HMTA concentration exhibits a reasonable week ferromagnetic behaviour. However, the pure BFO powder synthesized at 6 M HMTA shows high magnetization value (0.72 emu/g) compared to the other samples synthesized at low concentrations of HMTA. Further, the dielectric measurements of all the synthesized BFO samples have shown a decrease in dielectric loss with an increase in frequency. Whereas the dielectric behaviour exhibited by the pure BFO synthesized at 6 M HMTA has shown a high dielectric constant value with moderate dielectric loss. A ferroelectric analyser studies the ferroelectric behaviour of BFO powder. The study revealed that pure phase BFO synthesized with 6 M HMTA exhibits a high value of remanent polarization with unsaturated P-E loops due to the high leakage current in the sample. The UV–Vis data shows that the BFO samples exhibited an excellent optical absorption in the visible range with narrow optical band gaps. Therefore, all the characterizations related to magnetic, structural, dielectric, ferroelectric, and optical properties of synthesized pure BFO have proven the significance of precipitating agent HMTA in the solvothermal synthesis method. Based on our findings, the synthesized pure phase BFO can be an excellent semiconducting photocatalyst for multiferroic based photocatalysis applications.     

The evolution of structure,properties and polar domains in rare earth and PbTiO3 co-substituted BiFeO3 ferroelectric ceramics

BiFeO₃ (BFO) based ferroelectric solid solutions attract long-lasting research interests due to their multi-functionalities including electric/multiferroic/energy-storage properties. However, achievement of large ferroelectric polarization is still highly challenging in BFO based bulk ceramics due to large leakage. In this work, the structure and electrical properties of rare earth Nd- and PbTiO₃ co-modified BFO ceramics have been explored. Based on high temperature in-situ X-ray diffraction and dielectric measurements, a preliminary ferroelectric phase diagram is established, depicting the morphotropic phase boundaries (MPB) and a critical temperature that cannot be correlated to any macroscopic phase transition. The effects of rare earth substitution on structure evolution have been investigated by comparing the results in this work and literature. The accomplishment of ferroelectric switching with giant ferroelectric polarization above 65 μC/cm² is successfully achieved without resorting to quenching treatment. The MPB compositions demonstrate the maximum piezoelectric coefficients and the lowest coercive field, suggesting the “softening” effects. The domain evolutions suggest two coexisting phases in MPB composition distribute separately in different grains.     

Structural and electric properties of polycrystalline Bi1−xErxFeO3 ceramics

Polycrystalline Bi_1?xEr_xFeO₃ ceramics were synthesized by the solid state reaction method followed by rapid liquid phase sintering. The effects of Er substitution on the structure, morphology and electrical properties of the BiFeO₃ multiferroic ceramics were investigated. X-ray diffraction and Raman studies reveal that the structure of BiFeO₃ is changed from rhombohedral to orthorhombic in the Er concentration range of 0.10–0.15, and the impurity phases decrease both due to Er substitution. The X-ray photoelectron spectroscopy shows that Fe²⁺ could be suppressed by Er substitution. The SEM investigations suggest that the Er substitution could significantly reduce the grain sizes and increase the density of the samples. The leakage current is found to be decreased with increasing Er concentration. The dielectric and ferroelectric measurements show that dielectric constant, dielectric loss and ferroelectric properties are strongly dependent on the Er concentration. Er substitution can significantly improve the dielectric constant and remnant polarization, and decrease the dielectric loss by reducing the leakage current.     

Effect of (Zn,Mn) co-doping on the structure and ferroelectric properties of BiFeO3 thin films

BiFe_1-2xZn_xMn_xO₃ (BFZMO, with x = 0–0.05) thin films were synthesized via sol–gel method. Effects of (Zn, Mn) co-doping on the structure, ferroelectric, dielectric, and optical properties of BiFeO₃ (BFO) films were investigated. BFZMO thin films exhibit rhombohedral structure. Scanning electron microscopy (SEM) images indicate that co-doping leads to a decrease in grain size and number of defects. Leakage current density (4.60 × 10^?6 A/cm²) of BFZMO film with x = 0.02 was found to be two orders of magnitude lower than that of pristine BFO film. Owing to decreased leakage current density, saturated P–E curves were obtained. Maximum double remnant polarization of 413.2 μC/cm² was observed for BFZMO thin film with x = 0.02, while that for the BFO film was found to be 199.68 μC/cm². The reason for improved ferroelectric properties is partial substitution of Fe ions with Zn and Mn ions, which resulted in a reduction in the effect of oxygen vacancy defects. In addition, co-doping was found to decrease optical bandgap of BFO film, opening several possible routes for novel applications of these (Zn, Mn) co-doped BFO thin films.     

Enhanced magnetic and dielectric properties of Y doped bismuth ferrite nanofiber

Yttrium doped Bismuth ferrite (BFO) nanofiber was fabricated via a sol-gel-based electrospinning process with the fiber diameter in the range of 60–220 nm. The crystal structure, magnetic and dielectric properties were investigated at room temperature. The Rietveld refinement results indicate the phase transition from space group R3c to Pbnm by the Y doping. Dramatic increase of magnetization has been achieved in Y doped BFO nanofiber. Compared with BFO nanoparticle, the Bi_0.95Y_0.05FeO₃ nanofiber exhibits nearly eighteen-fold improved magnetization, which is the strongest in the reported Y doped BFO at the same doping level. The largely improved magnetization mainly originates from the serious suppression of spiral spin structure by the small crystal size of nanofiber structure. Moreover, the Bi_0.95Y_0.05FeO₃ nanofiber holds the lower dielectric loss and obvious dependence of the capacitance on bias voltage, indicating the improved ferroelectricity due to the decreased leakage current. The simultaneous enhancement of ferroelectricity and magnetization in Y doped BFO nanofiber suggests that nanofiber structure plays an important role in improving multiferroic performance.     

High-temperature dielectric properties and microwave absorption abilities of Bi1−xMgxFeO3 nanoparticles

BiFeO₃ (BFO) multiferroic nanoparticles have attracted increasing attention owing to the coexistence of ferroelectric and ferromagnetic properties. In this work, Bi_1−xMg_xFeO₃ (x = 0.05, 0.1, 0.15) multiferroic nanoparticles were synthesized by the sol-gel method. The electromagnetic properties and microwave absorption performance in the temperature range of 323–723 K at X-band were investigated. The qualified bandwidth (absorption intensity < −10 dB) of the Mg-doped BFO materials covers the whole X-band at 673 K, suggesting promising candidates as high-temperature electromagnetic absorbers.     

Microstructures,magnetic, and dielectric properties of Ba-doped BiFeO3 nanoparticles synthesized via molten salt route

As the paradigm of magnetoelectric multiferroic materials, BiFeO₃ (BFO) has potential applications in spintronics, memory devices, sensors, and actuators. However, its large leakage current and small magnetism at room temperature restrict its practical applications. It is demonstrated that the substitutions of Bi by alkali earth elements at A-site of BFO can significantly reduce the leakage current and enhance the remanent magnetization of BFO. In this work, Ba-doped BFO nanoparticles Bi_1-xBa_xFeO₃ (x = 0, 0.05, 0.10, 0.15 and 0.20) were synthesized via molten salt route. X-ray diffraction patterns revealed that with increasing the Ba-doped content the formation of the impurity phase was depressed and the rhombohedral distortions of these nanoparticles were suppressed, as confirmed by Raman spectra. X-ray photoelectron spectroscopy measurements reveal that the Fe element in the nanoparticles exists in the dual valence states of Fe³⁺ and Fe²⁺, and two kinds of oxygen atoms (lattice oxygen atoms and the adsorbed oxygen atoms) exist in the nanoparticles. With increasing the Ba-doped content, the content ratios of Fe³⁺ to Fe²⁺ ions were generally increased, whereas the oxygen vacancy concentrations were decreased. The average particle sizes of the Ba-doped BFO nanoparticles were decreased as compared with that of nondoped BFO nanoparticles. In contrast, the room temperature magnetization of the Ba-doped BFO nanoparticles was greatly enhanced by Ba-substitution, as confirmed by the M-H loops. At room temperature, the remanent magnetization and coercive field of the Bi_0.8Ba_0.2FeO₃ nanoparticles were 0.51 emu/g and 1130 Oe, respectively. Furthermore, the leakage current density was reduced by one order of magnitude at x = 0.2 and the dielectric properties are also improved by Ba-substitution. The improvements on the remanent magnetization, leakage current density as well as dielectric properties of the Ba-doped BFO nanoparticles make them promising candidates for spintronics and dielectric energy storages.     

Rearrangement of Multiferroic BiFeO3 Nanodots Smaller than 15 nm Using Atomic Force Microscopy

In this study, we demonstrate an atomic force microscopy process for manipulating multiferroic BiFeO₃ nanodots smaller than 15 nm to desired positions on a Nb‐doped SrTiO₃ substrate. For formation of the BiFeO₃ nanodot array, nanocrystal movement was achieved using a +1.2 V biased conducting atomic force microscopy (CAFM) followed by nanocrystal attachment to the tip. Using this method, high‐density BiFeO₃ nanodot arrays with a density greater than 0.5 Tb/in.² can be achieved. Perfectly flipped ferroelectric polarization with an external electric field was observed for each BiFeO₃ nanodot, whose ferroelectric properties were confirmed using piezoelectric force microscopy.     

Effects of Nd3+ and high-valence Nb5+ co-doping on the structural,dielectric and magnetic properties of BiFeO3 multiferroics

Bi_0.90Nd_0.10Fe_1?xNb_xO₃ (0 ≤ x ≤ 0.05) multiferroics have been studied to reveal the effect of Nb doping on the physical properties of the neodymium modified BiFeO₃. These samples have been synthesized via conventional solid state reaction method. The structural characterization was performed by XRD technique and Rietveld refinement. Rietveld refinement results confirmed that all samples crystallized in rhombohedral symmetry. In the vicinity of anti-ferromagnetic Neel-temperature (T_N), an anomaly was observed in dielectric constant (?′) and loss tangent (tan δ) which indicates the existence of magnetoelectric coupling. It is observed that with Nb doping dielectric constant was reduced and Neel temperature shifted towards higher temperature. The impedance (Nyquist plots) and modulus spectroscopy revealed that materials possess non-Debye type of relaxation. The doping of donor ion is able to suppress the existence of oxygen vacancies which results in increase in resistivity. The B-site doping by higher valence ion suppresses the existing modulated spin structure by structural distortion, results in released net magnetization. The room temperature remanent magnetization increased with Nb doping and all powder samples possess weak ferromagnetism. The possible reasons for the notable magnetic and dielectric performance of prepared samples were discussed.