Enhanced piezoelectric and ferroelectric properties of BiFeO3-BaTiO3 lead-free ceramics by optimizing the sintering temperature and dwell time

0.7BiFeO₃-0.3BaTiO₃ (BFO-0.3BT) ceramics were prepared to uncover the impacts of sintering temperature (T_S) and dwell time (t_d) on the microstructure and electrical properties. With increasing the T_S or t_d, the grain sizes increase along with the porosity decreases, which is in favor of the alignment of dipole. However, excess T_S or t_d are inclined to cause the volatilization of Bi₂O₃, which deteriorates piezoelectric properties. Because of the R-T two-phase coexistence, low defect ions concentration and porosity, as well as appropriate grain size, the excellent d₃₃?=?208?pC/N and k_p?=?35.46% as well as P_r?=?28.52?μC/cm² were achieved in BFO-0.3BT ceramics at T_S?=?1000?°C and t_d?=?6?h. In addition,large unipolar strain 0.13% and d₃₃*?=?256.2?pm/V also were obtained in BFO-0.3BT ceramics at T_S?=?1000?°C and t_d?=?6?h. This research indicates that the porosity and defect ion concentration as well as grain size also play an important role in piezoelectric properties in BFO-BT ceramics.     

A new method to improve the electrical properties of KNN-based ceramics: Tailoring phase fraction

Although both the phase type and fraction of multi-phase coexistence can affect the electrical properties of (K,Na)NbO₃ (KNN)-based ceramics, effects of phase fraction on their electrical properties were few concerned. In this work, through changing the calcination temperature of CaZrO₃ powders, we successfully developed the 0.96 K_0.5Na_0.5Nb_0.96Sb_0.04O₃-0.01CaZrO₃-0.03Bi_0.5Na_0.5HfO₃ ceramics containing a wide rhombohedral-tetragonal (R-T) phase coexistence with the variations of T (or R) phase fractions. It was found that higher T phase fraction can warrant a larger piezoelectric constant (d₃₃) and d₃₃ also showed a linear variation with respect to tetragonality ratio (c/a). More importantly, a number of domain patterns were observed due to high T phase fraction and large c/a ratio, greatly benefiting the piezoelectricity. In addition, the improved ferroelectric fatigue behavior and thermal stability were also shown in the ceramics containing high T phase fraction. Therefore, this work can bring a new viewpoint into the physical mechanism of KNN-based ceramics behind R-T phase coexistence.     

Long term stability of electrocaloric response in barium zirconate titanate

The stability of the electrocaloric effect under electric field cycling is an important consideration in the development of solid-state cooling devices. Here we report measurements carried out on Ba(Zr_0.2Ti_0.8)O₃ ceramics which reveal that the adiabatic temperature change, polarization-electric field hysteresis loops and dielectric permittivity/loss show stable behavior up to 10⁵ cycles. We further demonstrate that the loss in electrocaloric response observed after 10⁵ cycles is associated with the migration of oxygen vacancies. As a result, the electrical properties of the material are changed leading to an increase in leakage current and Joule heating. Reversing the polarity of the electric field after every 10⁵ cycles changes the migration direction of oxygen vacancies, thereby preventing charge accumulation at grain boundaries and electrodes. By doing so, the electrocaloric stability is improved and the adiabatic temperature remains constant even after 10⁶ cycles, much higher than achieved in commercially available barium titanate ceramics.     

Improved electric-field-induced strain and strong photoluminescence properties in novel Er3+-modified 0.93Bi0.5Na0.5TiO3-0.07BaTiO3 multifunctional ceramics

Recently, the progress of electronic devices toward miniaturization has strongly promoted development of multifunctional materials possessing multiple desirable properties. In this study, we develop and fabricate 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃-xEr multifunctional ceramics which show simultaneously considerable electric-field-induced strain and bright green light emission properties. With the introduction of Er³⁺, the ceramics gradually transform from non-ergodic relaxor phase to ergodic relaxor phase which could reversibly transform to ferroelectric phase under the electric field. As a result, with improving Er³⁺ content, the shape of the polarization-electric field loops of the ceramics become pinched, and it is obvious that the negative strain disappears while the positive strain gradually increases and reaches a maximum value 0.46% at x = 1.2 mol%. Besides, After the ceramics are poled, the light emission peak are greatly enhanced attributed to the decreased crystal symmetry and increased domain size, and is the strongest at x = 1.2 mol%. These results indicate that 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃-xEr ceramics are good candidates for developing multifunctional optoelectronic devices.     

Enhanced energy storage performance in Sn doped Sr0.6(Na0.5Bi0.5)0.4TiO3 lead-free relaxor ferroelectric ceramics

SnO₂ doped Sr_0.6(Na_0.5Bi_0.5)_0.4TiO₃ (NBT-ST) ceramics were prepared by a conventional solid-state reaction method. Their phase structures, microstructures and electrical properties were characterized in details. It is found that SnO₂ doping could increase the lattice parameters, density and average grain size. A suitable amount of SnO₂ can improve dielectric properties, and affect the relaxor behavior of the NBT-ST matrix, thereby it can effectively reduce the energy loss and optimize the energy storage performance. Furthermore, the energy storage properties are improved with SnO₂ doping. Especially, the 1 at. % SnO₂ doped NBT-ST achieves a high recoverable energy density of 2.35 J/cm³, which is mainly attributed to large maximum polarization of 43.2 μC/cm², small remnant polarization of 5.83 μC/cm² and high breakdown strength of 180 kV/cm. Also, relatively good temperature stability for dielectric performance and excellent fatigue resistance are observed in this composition. These properties are attractive for lead-free energy storage applications.     

Direct measurement of electrocaloric effect in lead-free (Na0.5Bi0.5)TiO3-based multilayer ceramic capacitors

Multilayer ceramic capacitors (MLCCs) of lead-free NBT-based ceramics are produced and their electrocaloric effect (ECE) is characterised for the first time. Dense MLCCs with 97μm-thick active layers are successfully produced by tape casting. Dielectric permittivity measurements reveal the MLCCs to have properties similar with that reported for the corresponding bulk ceramics, including T_d∼50°C and T_S∼100°C. Direct ECE measurements also reveal agreement and confirm the previously reported tendency of the high-field ECE peak to shift towards T_S. The highest value of ECE, ΔT_max∼1.7K is measured at 90°C under 90kV/cm. A low breakdown strength of 93kV/cm needs to be solved to realise stronger electric fields and achieve commercially viable ECE values.     

Structural,ferroelectric, magnetic and magnetoelectric properties of (1-x) Ba0.85Ca0.15Zr0.1Ti0.9O3 -x La0.67Sr0.33MnO3 lead-free magnetoelectric composites

The influence of an additional La_0.67Sr_0.33MnO₃ (LSMO) magnetic phase on the structural, ferromagnetic, ferroelectric, and magnetoelectric properties of Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ (BCZT) ferroelectric phase was studied for composites of (1-x)BCZT -xLSMO (x = 0, 25, 50, 75 and 100%). The ferroelectric BCZT sample showed a perovskite single phase formation with a tetragonal crystal structure of the P4mm space group, and the magnetic phase of LSMO presented a rhombohedral crystal structure of R3c space group as shown by XRD. The composite sample with 25% LSMO exhibited large ferroelectric and piezoelectric properties with remnant, saturation polarization, and coercive electric field P_r ~7.74 μC/cm², P_s ~11.69 μC/cm² and E_C ~12.22 kV/cm with a piezoelectric coefficient d₃₃ ~ 231 pC/N. The magnetic characterization for the composites showed that the sample containing 75% of LSMO revealed the highest remnant, saturation magnetization, and coercive field of M_r ~1.358 emu/g, M_s ~19.17 emu/g, and H_C ~33.19 Oe, respectively. Moreover, it revealed the largest magnetoelectric coupling coefficient α_ME ~2.51 mV/cm.Oe with high coupling quality at a lower applied magnetic field. The results highlight the value of these composites as lead-free room temperature magnetoelectric sensors and actuators.     

Utilization of coordinating green solvents for high quality methylammonium bismuth iodide thin films for photovoltaic applications

Photovoltaic performances of the bismuth-based solar cells are profoundly affected by the thin film quality of the photoactive layer. Herein, we report on various green solvent system to obtain the highly crystalline, pinhole free and homogeneously methylammonium bismuth iodide (MBI) active layer. The MBI structure prepared with tetrahydrofuran:2-ethoxy-ethanol (THF-2ETO) solvent system was found to have the best film quality. Adding 0.05 M 2ETO as the co-solvent is sufficient to produce high quality BiI₃ and MBI thin films. According to the X-ray photoelectron spectroscopy (XPS) analyzes, we have demonstrated that there is an interaction between BiI₃ and 2ETO according to the concentration of 2ETO added to the main THF. Our study clarifies the importance of THF-2ETO solvent system that can accelerate the evolution of the Bi-based solar cells by creating high-quality BiI₃ or MBI thin films.     

Challenges and strategies of all-inorganic lead-free halide perovskite solar cells

Hybrid lead halide perovskite solar cells (PSCs) have experienced a rapid development in the past decade and a certified efficiency up to 25.5% has been achieved. However, the presence of toxic lead component and the inherent poor thermal stability of the organic cations in the hybrid lead halide perovskites obstruct the commercial applications of their corresponding photovoltaic devices. Therefore, fabricating high-efficient all-inorganic lead-free PSCs is a promising direction. This review summarizes the related research progress, which mainly focuses on the structural and optoelectronic properties of inorganic lead-free perovskites and devices. In particular, the strategies for improving the properties and stability of Cs–Sn perovskites, as well as enhancing the photovoltaic performance of the corresponding devices are highlighted. An outlook of challenges and future directions regarding to all-inorganic lead-free PSCs are also proposed.