Synthesis and properties of multiferroic 0.7BiFeO3−0.3BaTiO3 thin films by Mn doping

Multiferroic BiFeO₃?BaTiO₃ thin films that simultaneously exhibit ferroelectricity and ferromagnetism at room temperature were prepared by chemical solution deposition. Perovskite single-phase 0.7BiFeO₃?0.3BaTiO₃ thin films were successfully fabricated in the temperature range 600–700 °C on Pt/TiO_x/SiO₂/Si substrates. As the crystallization temperature was increased, grain growth proceeded, resulting in higher crystallinity at 700 °C. Although the 0.7BiFeO₃?0.3BaTiO₃ thin films exhibited poor polarization (P)?electric field (E) hysteresis loops owing to their low insulating resistance. The leakage current at high applied fields was effectively reduced by Mn doping at the Fe site of the 0.7BiFeO₃?0.3BaTiO₃ thin films, leading to improved ferroelectric properties. The 5 mol% Mn-doped 0.7BiFeO₃?0.3BaTiO₃ thin films simultaneously exhibited ferroelectric polarization and ferromagnetic magnetization hysteresis loops at room temperature.     

Large strain and reduced hysteresis of BiFeO3-xBaTiO3 lead-free ceramic via multiphase coexistence and relaxor behaviors

Ferroelectric ceramics with large strain response, low hysteresis and high Curie temperature (T_C) are required for contemporary displacement actuator. In this work, (1-x)BiFeO₃-xBaTiO₃ ceramics were synthesized using traditional solid sintering technique. A high electric field-induced strain (0.25%), a relatively low hysteresis (22.5%) and a high Curie temperature (415 °C) were achieved in BiFeO₃-0.35BaTiO₃ ceramic. Meanwhile, the ceramics exhibited apparent relaxor behavior owing to the local structural heterogeneity. Aberration-corrected scanning transmission electron microscopy revealed that polar nano-regions with multiphase coexistence occur in the material, which is the microstructure origin of the enhanced strain and low hysteresis in BiFeO₃-0.35BaTiO₃ ceramics. This work indicates that BiFeO₃–BaTiO₃-based ceramics are good high-temperature ferroelectric materials and are promising candidates for high-precision actuator.     

Ferroelectric phase transition and electrical conduction mechanisms in high Curie-temperature PMN-PHT piezoelectric ceramics

Ferroelectric phase transition characteristic and electrical conduction mechanism of the high Curie-point (T_C) 0.15Pb(Mg_1/3Nb_2/3)O₃−0.4PbHfO₃−0.45PbTiO₃ (PMN-PHT) piezoelectric ceramics were studied by the temperature dependent Raman spectra and electrical properties. Sole first-order ferroelectric phase transition is demonstrated by the thermal hysteresis behavior of the temperature dependent dielectric constant and the dramatic drop of the derivative of inverse dielectric constant ξ= d(1/ε_r)/dT around T_C in the PMN-PHT ceramics. The temperature dependent Raman spectroscopy not only provides further evidence for the ferroelectric to paraelectric phase transition appearing around T_C in the PMN-PHT ceramics, but also reveals the successive phase symmetry changes of the polar nanoregions (PNRs), in which apparent anomalies appear in the Raman peaks' wavenumber, wavenumber distance, intensity, intensity ratio, and line width of some selected Raman modes upon heating. Typical sole cole-cole circle is obtained for the PMN-PHT ceramics in the temperature range of 440–560 °C, based on which the activation energy (E_a) of the electrical conduction is calculated being ~1.2 eV. Such low value of E_a indicates that the oxygen vacancies formed in the PHT-PMN ceramics induced by the evaporation of Pb during the sintering process dominate the high-temperature extrinsic electrical conduction.     

Preparation of multiferroic composites of BaTiO3–Ni0.5Zn0.5Fe2O4 ceramics

Magneto-electric coupling in ceramic composites formed by ferroelectric and ferromagnetic phases can be obtained via an adequate mechanical coupling between the individual piezoelectric and magnetostrictive phases (product property). In the present work, the possibility of forming diphase ferroelectric–ferromagnetic ceramics has been investigated. Composites of xBaTiO₃–(1 − x)Ni_0.5Zn_0.5Fe₂O₄ with x = 0.5, 0.6 and 0.7 were prepared according two different procedures: (i) by direct mixing powders of perovskite BaTiO₃ and Ni_0.5Zn_0.5Fe₂O₄ spinel prepared by solid state and (ii) by coprecipitating Fe^III–Ni^II–Zn^II nitric salts in a NaOH solution in which the BaTiO₃ powders were previously dispersed. Optimum processing parameters for good homogeneity, densification and for a reduction of the chemical reactions at the interfaces ferroelectric-ferrite were found. A temperature and composition-dependent magnetic order is present in all the composites, with a dilution effect of the magnetisation due to the presence of the non-ferromagnetic phase. A diffuse ferroelectric–paraelectric transition due to the BaTiO₃ phase was identified by the temperature-dependence of the permittivity and losses, showing that at room temperature the material preserves a ferroelectric order. The interfaces play important roles in the dielectric properties, causing space charge effects and Maxwell–Wagner relaxation, particularly at low frequencies and high temperatures. The combined ferroelectric and magnetic ordering will result in magneto-electric coupling in this material; further investigations are necessary.     

When C3N4 meets BaTiO3: Ferroelectric polarization plays a critical role in building a better photocatalyst

Photogenerated electrons (e⁻) and holes (h⁺) easily undergo fast recombination in many semiconductors, limiting the further improvement of its photocatalytic efficiency. To solve this bottleneck problem, graphitic C₃N₄ was used to group tetragonal-phase BaTiO₃ ferroelectric and successfully constructed the g-C₃N₄/BaTiO₃ heterojunction via a facial mixing-calcination method. These composites exhibited an extraordinary improvement under visible-light irradiation, achieving a “1 + 1>2” performance compared with their single pristine components. It is because the formation of double-transfer structure promotes the fast transfer of photo-induced charge carriers in g-C₃N₄/BaTiO₃ composites. Synergy between the two materials, especially the ferroelectric polarization, plays a key role in facilitating the spatial separation of photo-excited e⁻/h⁺ pairs and improving the photocatalytic efficiency.     

A Novel BiFeO3–BaTiO3–BaZrO3 Lead‐Free Relaxor Ferroelectric Ceramic with Low‐Hysteresis and Frequency‐Insensitive Large Strains

A novel (0.67?x)BiFeO₃–0.33BaTiO₃–xBaZrO₃ lead‐free relaxor ferroelectric ceramic was developed by a solid‐state reaction method. Measurements of temperature‐dependent dielectric permittivity and the polarization/strain hysteresis loops demonstrated an obvious evolution of dielectric relaxor behavior at room temperature (RT) from nonergodic to ergodic states. A significantly enhanced electrostrain of ~0.37% at 7 kV/mm with a relatively small hysteresis of ~39% and a low‐frequency sensitivity was found at x = 0.04, showing large potential for actuator applications. This was basically attributed to a rapid response of forward and backward switching between ergodic and ferroelectric phases owing to similar free energies and large local random fields.     

Effect of Additives of Limited Solid Solubility on Ferroelectric Properties of Barium Titanate Ceramics

An experimental survey of additives to barium titanate shows that in addition to those which are readily soluble in the barium titanate lattice (class 1) and those which are insoluble (class 2) two other distinct classes of additive, with limited solid solubility (classes 3 and 4), can be distinguished. Class 3 additives give normal ferroelectric properties with particularly low electrical and mechanical losses, as exemplified by BaTiO₃ 2 mole % NiTiO₃ for which, after aging, tan δ= 10⁻³ and 1/Q = 4 X 10⁻⁴. Experimental results indicate that the ferroelectric loss, in high and low fields, is hysteresis loss associated with domain boundary movement and that in class 3 materials the losses are low because the domain boundaries are in particularly stable positions. Class 4 materials have useful dielectric properties associated with a crystallite size between 0.1 and 1 μ. For example, BaTiO₃.3 mole % NaNbO₃ has ε= 3200 × 200 between 0°C. and 120°C. with tan δ= 3 X 10⁻². The absence of a permittivity peak is attributed to a distribution of the Curie temperatures of individual crystallites and the enhanced permittivity at lower temperatures to inhibition of the spontaneous polarization by the mutual clamping, in the ceramic, of crystallites which are too small to divide into 90° domains.     

Dielectric relaxation and enhanced multiferroic properties in YMn0.8Fe0.2O3 ceramics prepared by in situ spark plasma sintering

Dielectric characteristics of YMn_0.8Fe_0.2O₃ ceramics prepared by in situ spark plasma sintering (SPS) were evaluated over broad temperature and frequency ranges. An obvious dielectric relaxation was observed in the low temperature range, and it was a thermally activated process following the Arrhenius law. A regular ferroelectric hysteresis loop was detected at 153 K, and the weak ferromagnetic characteristic was observed at room temperature. These results indicated the enhanced multiferroic properties in the Fe-modified YMnO₃ ceramics.     

Oxygen‐Vacancy‐Related High Temperature Dielectric Relaxation in (Pb1−xBax)ZrO3 Ceramics

(Pb_1?xBa_x)ZrO₃ (x = 0, 0.025, 0.05, 0.075, 0.1) ceramics were synthesized by a traditional solid‐state reaction method, and the pure phase was obtained of all sintered samples. For all compositions, substitution of Pb²⁺ by Ba²⁺ reduced the phase transition temperature of antiferroelectric to ferroelectric and Curie temperature. Polarization–electric field hysteresis loops were conducted and typical ferroelectric hysteresis loops were observed in higher temperature range. Impedance and dielectric measurements were studied on the high temperature relaxation. Relaxation behavior could be suppressed after annealing treatment in oxygen atmosphere. Value of activation energy calculated from impedance was lower than that calculated from conduction measurements. It was concluded that short‐range hopping of oxygen vacancy contributes to the dielectric relaxation and long‐distance movement of doubly ionized oxygen vacancies contributes to the conduction.     

Enhanced electrocaloric response and energy storage performance of Li-substituted BaTiO3 ceramics

Recently, ferroelectric and antiferroelectric ceramic materials have gained a lot of interest for the development of environment-friendly highly-efficient electrocaloric refrigeration and energy-storage devices. In this work, lead-free Ba_1−xLi_xTiO₃ ceramics with x = 0, 0.01, 0.02, 0.03, 0.04, and 0.05 were synthesized by the conventional solid-state reaction method, and the effect of Li doping on dielectric, leakage current, ferroelectric, electrocaloric, and energy storage properties of BaTiO₃ ceramics was systematically investigated. The XRD and Raman studies confirmed that the structure of Ba_1−xLi_xTiO₃ remains tetragonal as for BaTiO₃. The Li substitution shifted the phase transition (T_C) of BaTiO₃ slightly towards the lower temperature side. Significant drop in leakage current was observed with an addition of Li content. The maximum values of the electrocaloric effect (ΔT), electrocaloric responsivity, and coefficient of performance were found to be 1.44 K, 0.24 × 10⁻⁶ K m/V, and 5.75, respectively, for x = 0.04 at an applied field of 60 kV/cm near the Curie temperature. The maximal value of energy storage density was found to be 0.42 J/cm³ with an energy storage efficiency of 60% for x = 0.05. Our results suggested that lead-free Ba_1−xLi_xTiO₃ ceramic material is a promising candidate for potential applications in solid-state refrigeration technology and high-efficiency energy storage devices.     

Enhanced energy storage performance and thermal stability in relaxor ferroelectric (1-x)BiFeO3-x(0.85BaTiO3-0.15Bi(Sn0.5Zn0.5)O3) ceramics

Lead-free (1-x)BiFeO₃-x(0.85BaTiO₃-0.15Bi(Sn_0.5Zn_0.5)O₃) [(1-x)BF-x(BT-BSZ), x=0.45-0.7] ceramic samples were prepared by solid phase sintering. It is revealed that the pure single-phase perovskite structure can be obtained in samples with x ≥ 0.6. With increasing x, the measured ferroelectric hysteresis loop becomes gradually slimmed in accompanying with reduced remnant polarization, and a clear ferroelectric-relaxor transition at x = 0.65 is identified. Furthermore, the measured electric breakdown strength can be significantly enhanced with increasing x, and the optimal energy storage performance is achieved at x = 0.65, characterized by the recoverable energy storage density up to ≈3.06 J/cm³ and energy storage efficiency as high as ≈92 %. Excellent temperature stability (25°C–110°C) and fatigue endurance (>10⁵ cycles) for energy storage are demonstrated. Our results suggest that the BF-based relaxor ceramics can be tailored for promising applications in high energy storage devices.     

Temperature-dependent resistivity performance of Mn/Y-doped Ba1-xSrxTiO3 compositions with potential thermal control applications

Doped BaTiO₃ ceramics exhibit an attractive application prospect in the adaptive thermal control of electronic devices in spacecraft that originate from its remarkable positive temperature coefficient (PTC) characteristics. However, the Curie temperature of most current BaTiO₃-based PTC materials is much higher than the normal operating temperature range of electronic devices. In this work, we successfully synthesized Ba_1-xSr_xTiO₃ ceramics with a room temperature Curie point. The crystal structure, surface morphology and temperature dependence of resistivity are investigated. The Curie temperature where the crystal structure of the composition changes from a paraelectric phase to a ferroelectric phase is adjusted by increasing the doping level(x). In the temperature range 18–120 °C, the variation amplitude of resistivity exceeds 10⁴, and the positive temperature coefficient effect is as high as 10.7%/°C. The potential thermal control properties were discussed based on the experimental and theoretical analysis. The heating power of compositions can be automatically changed by varying the operating temperature. At the same initial heating power, the equilibrium temperature of the controlled equipment using the PTC heating element is lower than that when adopting an ordinary heater. Moreover, the effect of thermal control becomes more prominent as the resistivity-temperature coefficient increases.     

High temperature oxidation behavior of porous MoAlB ceramic from 800 °C to 1100 °C in air

MoAlB possesses the characteristics of both metals and ceramic materials, which has attracted extensive attention due to its excellent high-temperature oxidation resistance. For this reason, porous MoAlB is considered applicable to the practice of filtration under harsh environment. In this study, the high-temperature oxidation behavior of porous MoAlB ceramics is systematically studied at the temperatures ranging from 800 to 1100 °C. According to the results, the porous MoAlB exhibits good oxidation resistance at a maximum temperature of 1000 °C. The oxidation kinetics of porous MoAlB can be divided into three stages, and the estimated activation energies of the three stages are 253.83 kJ·mol⁻¹, 367.48 kJ·mol⁻¹ and 317.84 kJ·mol⁻¹, respectively. In the stable stage at 1000 °C, the quadratic mass gain per unit area shows linearity over time, and the oxidation rate of porous MoAlB reaches 37.31 mg²·cm⁻⁴·h⁻¹. As revealed by the analysis of the composition and microstructure of oxide layers, the main components of the oxide layer include MoO₃, MoO₂, Al₂O₃, B₂O₃. With the extension of oxidation time, the content of Al₂O₃ in the oxide films increases. The average pore size, permeability and open pore porosity of porous MoAlB show a trend of first decreasing and then tending to be stable. In addition, a discussion is conducted on the high-temperature oxidation mechanism of porous MoAlB.     

A novel route to produce BaTiO3 glass-ceramics with nanosized cubic BaTiO3 phase precipitating for high energy-storage applications

To meet requirements of miniaturization devices in high pulsed power technology, super dielectric energy storage performance, such as high dielectric breakdown strength (DBS), large energy storage density with high power density, is extremely important in dielectric materials. However, for BaTiO₃ based ceramics and glass ceramics, there is still a critical challenge to achieve high DBS and large energy storage density. Herein, a novel route was proposed to precipitate nanocrystals with cubic BaTiO₃ phase from glass matrix, which can elevate dielectric constant and meanwhile maintain high DBS compared to parent glass. A high recoverable energy storage density of ∼ 3.66 J cm⁻³ at 1000 kV cm⁻¹ and high discharge energy density of ∼3.57 J cm⁻³ with good thermal stability and ultra-high peak power density of ∼ 910 MW cm⁻³ can be achieved in BaTiO₃ glass ceramic, which implies this type of glass ceramics is suitable for high pulsed power technology application.     

Temperature-dependent piezoelectric strain and resonance performance of Fe2O3-modified BiScO3-PbTiO3-Pb(Nb1/3Mn2/3)O3 ceramics

The piezoelectric strain and resonance performance of 0.37BiScO₃-0.6PbTiO₃-0.03Pb(Mn_1/3Nb_2/3)O₃ (BS-PT-PMN-xFe) ceramics with different amounts of Fe content addition were investigated from room temperature to 200 °C. Both the piezoelectric strain and resonance performance are improved by Fe addition in wide temperature range. Piezoelectric strain of BS-PT-PMN-xFe with 1 mol% Fe is 0.23%, which is comparable to that of BiScO₃-PbTiO₃ (BS-PT) ceramics, while the strain hysteresis is only one-third. At 200 °C, the high-field strain coefficient of BS-PT-PMN-Fe with 1 mol% Fe is as large as 700 pm/V. Variation of piezoelectric strain and hysteresis is clearly reducing by Fe addition. The maximum vibration velocity is enhanced up to approximately 1 m/s in 2 mol% Fe-modified BS-PT-PMnN-xFe ceramics, and the vibration velocity is stable from room temperature to 200 °C when the electric voltage magnitude was below 60 V_pp. These results indicate that BS-PT-PMN-xFe ceramics are potential candidates for high-temperature piezoelectric actuator application.     

Solution processing of morphotropic phase boundary BiFeO3-PbTiO3 thin films with reduced conductivity for high room temperature switchable polarization

The (1 – x)BiFeO₃-xPbTiO₃ (BFO-PTO) perovskite solid solution has great potential for being used in practical devices, as it exhibits significant ferroelectric response at its morphotropic phase boundary (MPB). However, the significant conduction, particularly high electrical leakage currents that BFO-PTO films show at room temperature, deteriorates their functionality. This is mainly associated with the presence of multivalent iron along with A-site and oxygen vacancies. Here, solution-derived BFO-PTO thin films have been crystallized at low temperature on Pt/TiO₂/SiO₂/Si substrates, by a rapid thermal annealing process to minimize Bi and Pb volatilization. X-ray analyses have revealed that textured films are obtained with a pseudocubic perovskite structure and without the formation of detectable second phases. Microstructural studies indicated a columnar growth of the films with grain size well above the nanometric range, which, therefore, should not produce an appreciable reduction of the ferroelectric response due to size effects. Because of the relatively low content of charged defects produced in these BFO-PTO films during processing, ferroelectric hysteresis loops can be measured at room temperature. The highest value of remnant polarizations (2P_R = 58 μC/cm²) was obtained for the 0.65BiFeO₃-0.35PbTiO₃ (65BFO-35PTO) films, which suggests that this film composition lies in the proximity of the MPB where the coexistence of a highly textured <100> tetragonal phase and a rhombohedral one seems to occur.     

Enhanced pyroelectric performance in potassium sodium niobate-based ceramics via multisymmetries coexistence design

Achieving excellent pyroelectric performance remains a challenge for lead-free piezoelectric ceramics. To meet the requirements of both an enhanced pyroelectric coefficient at room temperature and good thermal stability during the encapsulation of pyroelectric devices, (1–x)K_0.48Na_0.52NbO₃–xBi_0.5Ag_0.5ZrO₃–0.2%Fe₂O₃ (KNN–BAZ–Fe) lead-free ferroelectric ceramics with high Curie temperatures were prepared to obtain improved pyroelectric performance via the coexistence of multiple symmetries. The variation of BAZ content led to the formation of rhombohedral–orthorhombic–tetragonal phase boundary and promoted grain growth, resulting in the best pyroelectric coefficient (p = 5.09 × 10⁻⁴ C m⁻²°C⁻¹) and enhanced figures of merit (F_i = 0.2084 × 10⁻⁹ (m V⁻¹), F_v = 0.0142 m² C⁻¹, F_d = 0.0947 × 10⁻⁴ Pa^−1/2, and F_e = 17.66 J m⁻³ K⁻²) for infrared (IR) detection when x = 0.05. The room-temperature pyroelectric coefficient obtained in this study is approximately four times that of the pure KNN ceramic and is the maximum value reported for niobate-based piezoelectric ceramics. Moreover, compared with the poor thermal stability of barium titanate- and bismuth sodium titanate-based ceramics because of their ultralow Curie temperature or thermal depolarization temperature, the ceramics investigated here exhibit much better thermal stability because of their high Curie temperature (T_C > 300°C) and diffused phase-transition behavior, making them more adaptable for practical applications. These results suggest that KNN–xBAZ–Fe ceramics are attractive candidates for applications in the field of IR sensors.     

Large pyroelectricity via engineered ferroelectric-relaxor phase boundary

With growing demand for high-sensitivity infrared detectors in industrial temperature monitoring and medical systems, high-performance pyroelectric materials are vitally required. In this work, large pyroelectric performance is achieved in (1 − x)Pb_0.99Nb_0.02[(Zr_0.57Sn_0.43)_0.937Ti_0.063]_0.98O₃–xBaTiO₃ (1 − x)PNZST–xBT ceramics by tuning the ferroelectric (FE)-relaxor phase boundary near room temperature. The FE- and ergodic-relaxor phase boundaries are engineered by breaking the long-range antiferroelectric order with the introduction of BaTiO₃. It is found that the ceramics with x = 0.15 exhibit a large pyroelectric coefficient of 11.3 × 10^–4 C m^–2 K^–1 and figures of merit of F_i = 20.1 × 10^–10 m V^–1, F_v = 3.44 × 10^–2 m² C^–1, and F_d = 3.87 × 10^–5 Pa^–1/2 around room temperature due to engineered phase boundary. Our results provide the potential technological application for ultrasensitive infrared detector and scientific insights into pyroelectric ceramic design.     

Local Structure Investigation in Multiferroic BiFeO3–BaTiO3 Ceramics by XAS Technique and Their Relevant Properties

The (1?x)BiFeO₃‐xBaTiO₃ (with x = 0.1, 0.2, 0.3, and 0.4) ceramics were fabricated successfully by solid‐state reaction method. Single‐phase perovskite was obtained in all ceramics, as confirmed by XRD technique. It was observed that 0.7BiFeO₃–0.3BaTiO₃ was the morphotropic phase boundary (MPB) between rhombohedral and cubic phases, as also revealed from ferroelectric and magnetic properties. The simulated and experimental X‐Ray Absorption Spectroscopy (XAS) study revealed that BT in 0.75BF‐0.25BT is possibly taken a rhombohedral structure. Furthermore, the rounded ferroelectric hysteresis loops observed for 0.9BiFeO₃–0.1BaTiO₃ and 0.8BiFeO₃–0.2BaTiO₃ compositions could be attributed to their microstructure and surface charge effects and electron transfer between Fe³⁺ and Fe²⁺ ions. It was also found that high dielectric constant of 0.9BiFeO₃–0.1BaTiO₃ composition was a result of grain and grain‐boundary effects, as observed in SEM micrographs. In addition, a strong signature of dielectric relaxation behavior was observed in this ceramic system with the activation energy 0.467 eV obtained from the Arrhenius' law. Finally, the local structure investigation with XAS technique provided additional information to better understand the electric and magnetic properties in the BF‐BT ceramic system.     

Enhancement of piezoelectric and ferroelectric properties of BaTiO3 ceramics by aluminum doping

Ferroelectric and piezoelectric properties of BaTiO₃ and Al-doped BaTiO₃ ceramics were investigated. The ferroelectric study demonstrated that, by doping Al³⁺ ions in the A-site of BaTiO₃, the polarization–electric field loop exhibited enhanced remnant polarization (from 12 to 17.5  μC/cm²), saturation and switching. In addition, the piezoelectric constant (d₃₃) increased with Al-doping for both static and dynamic strain values (from 75 to 135 and from 29.2 to 57.9 pC/N, respectively, at a maximum applied electric field of 16 kV/cm). Furthermore, the dielectric constant values increased and both the dielectric loss factor and leakage current decreased, even though the transition temperature shifted to lower temperature (from 121 to 113 °C) for the Al-doped sample. Therefore, the Al-doped BaTiO₃ has adjustable piezoelectric and ferroelectric properties.