Orientation dependence of electric field induced phase transitions in lead-free (Na0.5Bi0.5)TiO3-based single crystals

The orientation dependence of the electric field induced strain and phase transitions in 0.92(Na_0.5Bi_0.5)TiO₃–0.06BaTiO₃–0.02(K_0.5Na_0.5)NbO₃ (NBT–6BT–2KNN) single crystals has been investigated. The evolution of Raman spectra with electric field reveals that a tetragonal ferroelectric phase is initially induced at E = 14 kV/cm and completed above E = 25 kV/cm for [001] oriented single crystals. When the electric field is applied along [111] direction, a partial phase transition from pseudocubic to rhombohedral structure is triggered at E = 19 kV/cm, which is higher than that for inducing tetragonal ferroelectric phase along [001] direction. Both field-induced phase structures and stability of NBT–6BT–2KNN single crystal are strongly associated with the crystallographic orientations. These results provide a better understanding to the field-induced macroscopic strain in lead-free NBT-based ferroelectrics.     

Electric field induced splitting of the preferred orientation in PMN-PT textured ceramics

We have performed studies of the orientation distribution in <001>_C textured, 0.03(Na_1/2Bi_1/2)TiO₃ - 0.97[0.715Pb(Mg_1/3Nb_2/3)TiO₃ - 0.285PbTiO₃] (0.03NBT-0.97[PMN-28.5PT]) ceramics by a pole figure method, comparing the results to those for PMN-PT single crystal and polycrystal samples. The pole figures about the (001) zone are found to have monoclinic, Ma, phase for textured ceramics in the annealed condition and were similar to those for electrically poled single crystals. However, electrical poling of the textured ceramics resulted in a doublet splitting of the orientation distribution about the direction that defined the original grain texturing. Studies of pole figures about other high-symmetry zones also revealed the development of some degree of preferred orientation along the in-plane directions after poling. Our findings demonstrate that E-field induced phase transformation and domain textures superimpose with that of preferred grain orientations, giving rise to a unique texture symmetry for PMN-PT. The texture symmetry changes are driven by minimization of the elastic strain energy, and have an important effect upon the piezoelectric properties.     

Domain Structure and Enhanced Electrical Properties in Sodium Bismuth Titanate Ceramics Sintered from Crystals with Different Morphologies

Sodium bismuth titanate (Na_0.5Bi_0.5TiO₃, NBT) crystals with different morphology, wires, plates and cubes, were synthesized by hydrothermal method. The domain structure in as‐synthesized poled NBT ceramics was observed. The results demonstrate that the domain width of the poled NBT ceramics sintered from wire crystals is slightly larger than that of the NBT ceramics sintered from cube crystals, while the NBT ceramics sintered from plate crystals possess the largest domain width. In particular, the poled NBT ceramics sintered from plate crystals exhibit the optimum piezoelectric coefficient and remnant polarization of 87 pC/N and 36.7 μC/cm², respectively, which are 55% and 37% higher than those of the NBT ceramics sintered from cube crystals. The expanded domain width and large grain size are responsible for the improvement of ferroelectric, piezoelectric, and dielectric properties in NBT ceramics.     

Aging effect in Er3+-doped 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 ceramics

Usually, aging in poled ferroelectrics leads to degradation of certain physical properties. In this study, we found a remarkable aging effect in tetragonal Er³⁺-doped 0.5Ba(Zr_0.2Ti_0.8)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ (BZT-BCT) ceramics after poling. It is observed that the domains can spontaneously rotate to keep their spontaneous polarization direction similar to that of the poling electric field during aging for the poled ceramics. Furthermore, compared with freshly poled ceramics, the thermally stimulated current (TSC) peak of the aged ones shifts toward a higher temperature (10°C). And the temperature of the TSC peak in the aged ceramics is exactly equal to their Curie temperature. Such features indicate that aging for the poled ceramics could stabilize the alignment of ordered ferroelectric domains. Additionally, a downward TSC peak above Curie temperature is obtained in both poled and aged ceramics, demonstrating that poling and aging can lead to ordered alignment of defect dipoles. The aging mechanism of poled Er³⁺-doped BZT-BCT ceramics has proposed and discussed in this article.     

Enhancement of piezoelectric catalysis of Na0.5Bi0.5TiO3 with electric poling for dye decomposition

In this work, the performance of solid-phase sintered Na_0.5Bi_0.5TiO₃ ceramic powder catalyst is investigated for Rhodamine B (RhB) dye decomposition under different electric poling fields. As a result of the vibration excitation, the piezoelectric catalytic decomposition ratio of the poled Na_0.5Bi_0.5TiO₃ for RhB dye wastewater increases from 10.84% to 51.32% as the electric poling field increases from 0 to 0.5 kV/mm. The improved piezoelectric catalytic activity could be attributed to a rise in the piezoelectric performance of Na_0.5Bi_0.5TiO₃ after electric poling. The addition of the different types of radical scavengers in piezoelectric catalysis further proves that a large amount of superoxide-free radicals and a small number of hydroxyl radicals participate in the catalytic reaction. Our results demonstrate that electric poling, as a simple and effective method of improving piezoelectric catalysis, has potential applications in dye-containing wastewater treatment.     

Combining effects of TiO6 octahedron rotations and random electric fields on structural and properties in Na0.5Bi0.5TiO3

The structural and dielectric properties of Na_0.5Bi_0.5TiO₃ (NBT) ceramics and crystals have been investigated and are compared to that of Pb(Zr_0.55Ti_0.45)O₃ (PZT55/45) and Pb(Mg_1/3Nb_2/3)_0.72Ti_0.28O₃ (PMNT 72/28) ceramics. X-ray diffraction (XRD) profiles for (100), (110), (111), (200), (220), and (222) (referred to cubic structure) reveal that the monoclinic structure with Cc space group exists both in the NBT single crystal and ceramics. The diffraction profile obtained with high resolution laboratory XRD for the NBT single crystal can be well described, using Cc model instead of R3c model. The dielectric constant of NBT below T_hump shows some similarity to that of PZT45/55 ceramics below 50°C in which oxygen octahedron rotations cause the frequency dispersion of the dielectric constant. The temperature-dependent dielectric constant for NBT can be deconvolved into two independent processes. The lower temperature process shows a typical relaxor characteristic and follows the Vogel-Fulcher relationship. The other process at higher temperature shows less frequency-dependent behavior. Comparing the dielectric constant of NBT with that of PZT55/45 and PMNT72/28 reveals that both oxygen octahedral rotations and random electric fields play an important role in the frequency dispersion of the dielectric constant for NBT relaxor feroelectric.     

Effect of electric poling on structural,magnetic and ferroelectric properties of 0.8PbFe0.5Nb0.5O3-0.2BiFeO3 multiferroic solid solution

The effect of electric poling on structure, magnetic and ferroelectric properties of 0.8PbFe_0.5Nb_0.5O₃-0.2BiFeO₃ (0.8PFN-0.2BFO) multiferroic was studied through XRD, Raman, magnetic and ferroelectric measurements. Single step solid state reaction method was adopted to synthesize single phase 0.8PFN-0.2BFO multiferroic at lower calcination and sintering temperature. Room temperature (RT) XRD pattern before and after poling confirmed the monoclinic structure with Cm space group. Rietveld refined XRD for poled and unpoled sample shows the influence of electric poling on Fe-O1, Fe-O2, Nb-O and Bi-O modes. There is a small variation in the lattice parameters after electric poling. The structural properties were also studied in detail for the poled and unpoled 0.8PFN-0.2BFO using Raman spectroscopy. Raman measurements were carried out over a wide range of temperature (250–550 K) for both poled and unpoled samples. At RT unpoled 0.8PFN-0.2BFO multiferroic exhibit 8 active modes at 211, 263, 440, 484, 571, 706, 785 and 1120 cm^-1 in the frequency range 100–1200 cm^-1. The Raman peaks exhibits significant changes in intensity as well as shape of the spectra at the characteristic temperature T_C (470 K) and T_N (310 K). Poled Raman spectra show major changes in the Fe/Nb-O modes intensities around T_N and are due to dynamic nature of spin phonon coupling. Changes observed in the temperature dependent magnetic measurements i.e. ZFC/FC and M − H loop evidence the existence of converse magneto-electric coupling (CME) and this is due to the poling effects on Fe-O, Nb-O active modes. Due to rotation of the oxygen octahedral the electric field induced strain will originate in the system. P-E loops after poling show an increase in remnant polarisation and coercive field due to an improvement in domain ordering. The potential tunability of magnetisation with electric poling is an ideal tool for realisation of application in practical devices.     

BiFeO3–(Na0.5Bi0.5)TiO3 butterfly wing scales: Synthesis,visible-light photocatalytic and magnetic properties

BiFeO₃–(Na_0.5Bi_0.5)TiO₃ (BFO–NBT) with ordered macropores was synthesized from Shirozu butterfly wings by a sol–gel method followed by calcination. The hierarchical structures were retained in the BFO–NBT replica, as evidenced directly by field-emission scanning electron microscope (FE-SEM) and transmission electron microscopy (TEM). The BFO–NBT replica showed a much higher visible-light photocatalytic properties in comparison with BFO–NBT powder without ordered macropores, attributing to the significantly higher surface area. It was found that the magnetic properties of the BFO–NBT replica were quite different with BFO–NBT powder without ordered macropores, probably due to the different grain sizes, and the hierarchical structures from Shirozu butterfly wings. It is expected that our method will open up new avenues for the synthesis of multiferroic materials with hierarchical structures, which may form applications as semiconductor visible-light photocatalyst and novel magnetoelectric devices.     

Enhanced pyroelectric response from domain-engineered lead-free (K0.5Bi0.5TiO3-BaTiO3)-Na0.5Bi0.5TiO3 ferroelectric ceramics

Enhanced pyroelectric response is achieved via domain engineering from [001] grain-oriented, tetragonal-phase, lead-free 0.2(2/3K_0.5Bi_0.5TiO₃-1/3BaTiO₃)-0.8Na_0.5Bi_0.5TiO₃ (KBT-BT-NBT) ceramics prepared by a templated grain growth method. The [001] crystallographic orientation leads to large polarization in tetragonal symmetry; therefore, texturing along this direction is employed to enhance the pyroelectricity. X-ray diffraction analysis revealed a Lotgering factor (degree of texturing) of 93 % along the [001] crystallographic direction. The textured KBT-BT-NBT lead-free ceramics showed comparable pyroelectric figures of merit to those of lead-based ferroelectric materials at room temperature (RT). In addition to the enhanced pyroelectric response at RT, an enormous enhancement in the pyroelectric response (from 1750 to 90,900 μC m^?2 K^?1) was achieved at the depolarization temperature because of the sharp ferroelectric to antiferroelectric phase transition owing to coherent 180° domain switching. These results will motivate the development of a wide range of lead-free pyroelectric devices, such as thermal sensors and infra-red detectors.     

The upconversion luminescence modulation and its enhancement in Er3+‐doped Na0.5Bi0.5TiO3 based on photochromic reaction

A large and reversible upconversion (UC) luminescence modulation has been found in the Na_0.498Bi_0.498TiO₃:0.002Er (NBT:0.002Er) based on the photochromic reaction. The dependence of luminescence modulation of the ceramics on the wavelength of irradiation light and sintering temperature was investigated. It was found that the optimized sintering temperature and irradiation wavelength were 1130°C and 405 nm, respectively. The highest ΔR_t (defined as: ΔR_t = (R₀ – R_t)/R₀×100(%), where R₀ and R_t are the initial emission intensity and that after different irradiation time, respectively) value of 44.9% was obtained for the ceramics sintered at 1130°C after irradiation at 405 nm. More importantly, for the poled ceramics, ΔR_t value was promoted to a high value of 75.5%, which was 168% of that of the unpoled ones. The mechanism of luminescence modulation and its enhancement via electric field poling were discussed. This study demonstrated that electric field poling was an effective strategy to enhance the PC reaction in the NBT ceramics.     

Grain size engineered Ba0.9Sr0.1Ti0.9Hf0.1O3-Na0.5Bi0.5TiO3 relaxor ceramics with improved energy storage performance

Novel lead-free diphasic (1-x)Ba_0.9Sr_0.1Ti_0.9Hf_0.1O₃-xNa_0.5Bi_0.5TiO₃ (BSTH-NBT) ceramic nanocomposites were synthesized via an economically viable modified mechano-chemical activation technique. In the present investigation, we have developed an energy storage composite material by systematically optimizing the charge transport behavior and charge storage characteristics between the ferroelectric BSTH and piezoelectric NBT phase. The composite with x = 0.09 NBT concentration has shown the best energy storage properties with 1.61 J/cm³ discharge energy density along with 80.1% energy efficiency. The BSTH and NBT had a synergetic effect on the ferroelectric properties of the composites. The improvement in ferroelectric and piezoelectric properties along with excellent aging characteristics in composite materials is mainly attributed to enhancement in microstructural density, grain boundary interface, and stress effects. The improved dispersibility and excellent compatibility between BSTH and NBT phase have resulted in approximately 20% enhancement in breakdown strength of composite compared to pure BSTH ceramic.     

Phase-composition dependent domain responses in (K0.5Na0.5)NbO3-based piezoceramics

Lead-free (K_0.5Na_0.5)NbO₃-based (KNN) piezoceramics featuring a polymorphic phase boundary (PPB) between the orthorhombic and tetragonal phases at room temperature are reported to possess high piezoelectric properties but with inferior cycling stability, while the ceramics with a single tetragonal phase show improved cycling stability but with lower piezoelectric coefficients. In this work, electric biasing in-situ transmission electron microscopy (TEM) study is conducted on two KNN-based compositions, which are respectively at and off PPB. Our observations reveal the distinctive domain responses in these two ceramics under cyclic fields. The higher domain wall density in the poled KNN at PPB contributes to the high piezoelectric properties. Upon cycling, however, a new microstructure feature, “domain intersection”, is directly observed in this PPB composition. In comparison, the off-PPB KNN ceramic develops large domains during poling, which experience much less extent of disruption during cycling. Our comparative study provides the basis for understanding the relation between phase composition and piezoelectric performance.     

Greatly enhanced photocurrent in inorganic perovskite [KNbO3]0.9[BaNi0.5Nb0.5O3‐σ]0.1 ferroelectric thin‐film solar cell

Inorganic perovskite [KNbO₃]_0.9[BaNi_0.5Nb_0.5O_3‐σ]_0.1 (KBNNO) ferroelectric thin films with narrow band gap (1.83 eV) and high room‐temperature remnant polarization (Pr = 0.54 μC/cm²) was grown successfully on the Pt(111)/Ti/SiO₂/Si(100) substrates by pulsed laser deposition. Ferroelectric solar cells with a basic structure of ITO/KBNNO/Pt were further prepared based on these thin films, which exhibited obvious external‐poling dependent photovoltaic effects. When the devices were negatively poled, the short‐circuit current and open‐circuit voltage were both significantly higher than those of the devices poled positively. This is attributed to enhanced charge separation under the depolarization field induced by the negative poling, which is superimposed with the built‐in field induced by the Schottky barriers at the interfaces between KBNNO and the two electrodes. When a poling voltage of ‐1 V was applied, the device showed a short‐circuit current as high as 27.3 μA/cm², which was by two orders of magnitude larger than that of the KBNNO thick‐film (20 μm) devices reported previously. This work may inspire further exploration for lead‐free inorganic perovskite ferroelectric photovoltaic devices.     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

Investigation of the mechanism of domain switching in different Na0.5Bi0.5TiO3 microstructures

Several researches have studied the physical properties of hydrothermally-synthesized low dimensional piezoelectric nanostructures. However, the obtained piezoelectric coefficient is not high and the relationship between physical properties and microstructures is still neglected. Here we report the piezoelectric and ferroelectric properties of different lead-free sodium bismuth titanate (Na_0.5Bi_0.5TiO₃, NBT) microstructures synthesised with hydrothermal routes and give visualization of domain structures using piezoresponse force microscopy. The NBT nanowire exhibits better local piezoelectric response compared with NBT spherical aggregates and microcubes and other one-dimensional materials prepared by hydrothermal method and the large piezoelectric coefficient of nanowire was explained by observed regular stripe domain structures. Moreover, it is found that there are different domain configurations at the top and side of the nanowire under the external electrical fields, which don't change the regular stripe domain structure but lead to the movement of domain boundaries. By finite element modeling, it attributes to the different electric potential distributions from tip within the nanowire.     

Optimizing Na0.5Bi0.5TiO3 electrolyte fuel cell through constructing heterostructures

Heterostructure materials deliver special properties comparing with single phase materials. In this study, the performance of Na_0.5Bi_0.5TiO₃ (NBT) electrolyte fuel cell is proved to be optimized by constructing heterostructures with other materials. SOFC based on NBT single phase electrolyte exhibits poor stability and low power output. By mixing NBT with electronic conductor La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF), improved performance is obtained and power output is observed to be dependent on the weight ratio of NBT to LSCF. It is interesting that the best performance is obtained in the cell with an optimized weight ratio of 30 wt% NBT - 70 wt% LSCF, in which the amount of electronic conductor exceeds that of ionic conductor. However, the stability of SOFC based on NBT-LSCF composite electrolyte still needs to be improved. In addition, the composition of sodium carbonate and lithium carbonate is added to the NBT-LSCF composite electrolyte for the purpose of creating amorphous shells around the NBT-LSCF particles, which is expected to protect the NBT-LSCF particles from reducing by hydrogen. Improved stability of the cell is then observed. This study provides an effective way to enhance the ionic conductivity and stability of electrolyte by constructing heterostructures.     

Dielectric properties of some low-lead or lead-free perovskite-derived materials: Na0.5Bi0.5TiO3–PbZrO3, Na0.5Bi0.5TiO3–BiScO3 and Na0.5Bi0.5TiO3–BiFeO3 ceramics

Na_0.5Bi_0.5TiO₃ (NBT) and its modifications are known to be new lead-free ferroelectric materials and are promising for environment friendly devices. The systems under investigation were (i) NBT (trigonal/ferroelectric)–PbZrO₃ (orthorhombic/antiferroelectric); (ii) NBT (trigonal/ferroelectric)–BiScO₃ (trigonal/paraelectric); and (iii) NBT (trigonal/ferroelectric)–BiFeO₃ (trigonal/antiferromagnetic).The lattice parameters change as expected from the respective ionic radii values. For NBT–PZ, the dielectric permittivity shows a large frequency and temperature dispersion suggesting a relaxor-like behaviour dependent on the thermal annealing of the samples. For NBT–BS, the Curie temperature increases with BS content as well as the diffuseness of the phase transition, connected with the introduced disorder. For NBT–BF, the overall behaviour of the permittivity of NBT is maintained up to 50% BF but anomalies of the permittivity appeared close to 600 °C, which might be connected with the onset of magnetic influence for high BF content.     

Structure and ferroelectric behaviour of Na0.5Bi0.5TiO3-KNbO3 ceramics

Lead-free piezoelectric ceramics, (1?x)Na_0.5Bi_0.5TiO₃-xKNbO₃ (NBT-xKN), with x?=?0.02–0.08 were fabricated by solid-state reaction and sintering. The crystal structures and dielectric properties were measured for different KN contents. All compositions in the unpoled, as-sintered state were found to be single-phase pseudo-cubic. However, typical ferroelectric behaviour, with well-saturated polarisation-electric field hysteresis loops, was observed for certain compositions at high electric field levels. It is shown using high-energy synchrotron X-ray diffraction that the application of the electric field induced an irreversible structural transformation from the nano-polar pseudo-cubic phase to a ferroelectric rhombohedral phase. The changes in lattice elastic strain and crystallographic texture of a poled NBT-0.02KN specimen as a function of the grain orientation, ψ, conform well to those expected for a conventional rhombohedrally distorted perovskite ferroelectric ceramic. The dielectric permittivity-temperature relationships for all compositions exhibit two transition temperatures and a frequency-dependent behaviour that is typical of a relaxor ferroelectric. The transition temperatures and grain size decrease with the increasing KN content.     

Enhancing the dielectric and energy storage properties of lead-free Na0.5Bi0.5TiO3–BaTiO3 ceramics by adding K0.5Na0.5NbO3 ferroelectric

A novel strategy of enhancing the dielectric and energy storage properties of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) ceramics by introducing a K_0.5Na_0.5NbO₃ (KNN) ferroelectric phase is proposed herein, and its underlying mechanism is elucidated. The lead-free KNN ceramic decreases the residual polarisation and increases the electric breakdown strength of the NBT–BT matrix through the simultaneous modification of its A-sites and B-sites. The obtained NBT?BT?x?KNN ceramics have a perovskite structure with unifying grains. A bulk 0.9NBT–BT–0.1KNN ceramic sample with a thickness of 0.2 mm possesses a high energy storage density of 2.81 J/cm³ at an applied electric field of 180 kV/cm. Moreover, it exhibits good insulation properties and undergoes rapid charge and discharge processes. Therefore, the obtained 0.9NBT–BT–0.1KNN ceramic can be potentially used in high-power applications because of its high energy density, good insulation properties, and large discharge rate.     

Conformational polymorphism on styrl quinolinium salts of 2-[(E)-2-(4-hydroxy-3-methoxystyrl)-1-methyl]-quinolinium 4-chlorobenzenesulfonate (HMQ-CBS): Potential nonlinear optical crystals for terahertz application

Polymorphism is an important phenomenon to investigate the relationship between the chemical structures and properties of functional materials. Here, we demonstrate the existence of conformational polymorphism in the terahertz (THz) compounds of 2-[(E)-2-(4-hydroxy-3-methoxystyrl)-1-methyl]-quinolinium 4-chlorobenzenesulfonate (abbreviated as HMQ-CBS). There are two different crystalline phases (I and II, respectively). X-ray structural analyses reveal that HMQ-CBS crystallizes in the monoclinic crystallographic system with the non-centrosymmetric space group P_c for phase-I, and centrosymmetric space group of P2₁/n for phase-II. These two different crystalline phases exhibit the distinct anionic orientations and crystal packings, leading to significantly different nonlinear optical (NLO) properties. Second harmonic generation (SHG) measurements reveal that crystals in phase-I possess the SHG efficiency of about 0.5 times that of N, N-dimethylamino-N-methylstilbazolium p-toluenesulphonate (DAST), which indicates that HMQ-CBS in phase-I might be a potential NLO crystal for THz application. In contrast, crystals in the phase-II show no SHG responses. Comparison of their crystal structures and NLO properties enables us to understand the correlation between molecular conformational changes and bulk NLO properties, and sheds light on the design of organic THz materials.