Origin of Polarization in Bismuth Sodium Titanate-Based Ceramics.

The classical view of the structural changes that occur at the ferroelectric transition in perovskite-structured systems, such as BaTiO3, is that polarization occurs due to the off-center displacement of the B-site cations. Here, we show that in the bismuth sodium titanate (BNT)-based composition 0.2(Ba0.4Sr0.6TiO3)-0.8(Bi0.5Na0.5TiO3), this model does not accurately describe the structural situation. Such BNT-based systems are of interest as lead-free alternatives to currently used materials in a variety of piezo-/ferroelectric applications. A combination of high-resolution powder neutron diffraction, impedance spectroscopy, and ab initio calculations reveals that Ti4+ contributes less than a third in magnitude to the overall polarization and that the displacements of the O2- ions and the A-site cations, particularly Bi3+, are very significant. The detailed examination of the ferroelectric transition in this system offers insights applicable to the understanding of such transitions in other ferroelectric perovskites, particularly those containing lone pair elements.

High Thermoelectric Performance Related to PVDF Ferroelectric Domains in P-Type Flexible PVDF-Bi0.5 Sb1.5 Te3 Composite Film.

There is increasing demand to power Internet of Things devices using ambient energy sources. Flexible, low-temperature, organic/inorganic thermoelectric devices are a breakthrough next-generation approach to meet this challenge. However, these systems suffer from poor performance and expensive processing preventing wide application of the technology. In this study, by combining a ferroelectric polymer (Polyvinylidene fluoride (PVDF, ß phase)) with p-type Bi0.5 Sb1.5 Te3 (BST) a thermoelectric composite film with maximum is produced power factor. Energy filter from ferroelectric-thermoelectric junction also leads to high Seebeck voltage ≈242 µV K-1 . For the first time, compelling evidence is provided that the dipole of a ferroelectric material is helping decouple electron transport related to carrier mobility and the Seebeck coefficient, to provide 5× or more improvement in thermoelectric power factor. The best composition, PVDF/BST film with BST 95 wt.% has a power factor of 712 µW•m-1  K-2 . A thermoelectric generator fabricated from a PVDF/BST film demonstrated Pmax T 12.02 µW and Pdensity 40.8 W m-2 under 50 K temperature difference. This development also provides a new insight into a physical technique, applicable to both flexible and non-flexible thermoelectrics, to obtain comprehensive thermoelectric performance.

Structure and Conductivity in LISICON Analogues within the Li4GeO4-Li2MoO4 System.

New solid electrolytes are crucial for the development of all-solid-state lithium batteries with advantages in safety and energy densities over current liquid electrolyte systems. While some of the best solid-state Li+-ion conductors are based on sulfides, their air sensitivity makes them less commercially attractive, and attention is refocusing on air-stable oxide-based systems. Among these, the LISICON-structured systems, such as Li2+2xZn1-xGeO4 and Li3+xV1-xGexO4, have been relatively well studied. However, other systems such as the Li4GeO4-Li2MoO4 system, which also show LISICON-type structures, have been relatively little explored. In this work, the Li4-2xGe1-xMoxO4 solid solution is investigated systematically, including the solid solution limit, structural stability, local structure, and the corresponding electrical behavior. It is found that a γ-LISICON structured solution is formed in the range of 0.1 ≤ x < 0.4, differing in structure from the two end members, Li4GeO4 and Li2MoO4. With increasing Mo content, the ß-phase becomes increasingly more stable than the γ-phase, and at x = 0.5, a pure ß-phase (ß-Li3Ge0.5Mo0.5O4) is readily isolated. The structure of this previously unknown compound is presented, along with details of the defect structure of Li3.6Ge0.8Mo0.2O4 (x = 0.2) based on neutron diffraction data. Two basic types of defects are identified in Li3.6Ge0.8Mo0.2O4 involving interstitial Li+-ions in octahedral sites, with evidence for these coming together to form larger defect clusters. The x = 0.2 composition shows the highest conductivity of the series, with values of 1.11 × 10-7 S cm-1 at room temperature rising to 5.02 × 10-3 S cm-1 at 250 °C.

Antiferroelectric-like Behavior in a Lead-Free Perovskite Layered Structure Ceramic.

Antiferroelectric (AFE) materials have been intensively studied due to their potential uses in energy storage applications and energy conversion. These materials are characterized by double polarization-electric field (P-E) hysteresis loops and nonpolar crystal structures. Unusually, in the present work, Sr1.68La0.32Ta1.68Ti0.32O7 (STLT32), Sr1.64La0.36Ta1.64Ti0.36O7 (STLT36), and Sr1.85Ca0.15Ta2O7 (SCT15), lead-free perovskite layered structure (PLS) materials, are shown to exhibit AFE-like double P-E hysteresis loops despite maintaining a polar crystal structure. The double hysteresis loops are present over wide ranges of electric field and temperature. While neutron diffraction and piezoresponse force microscopy results indicate that the STLT32 system should be ferroelectric at room temperature, the observed AFE-like electrical behavior suggests that the electrical response is dominated by a weakly polar phase with a field-induced transition to a more strongly polar phase. Variable-temperature dielectric measurements suggest the presence of two-phase transitions in STLT32 at ca. 250 and 750 °C. The latter transition is confirmed by thermal analysis and is accompanied by structural changes in the layers, such as in the degree of octahedral tilting and changes in the perovskite block width and interlayer gap, associated with a change from non-centrosymmetric to centrosymmetric structures. The lower-temperature transition is more diffuse in nature but is evidenced by subtle changes in the lattice parameters. The dielectric properties of an STLT32 ceramic at microwave frequencies was measured using a coplanar waveguide transmission line and revealed stable permittivity from 1 kHz up to 20 GHz with low dielectric loss. This work represents the first observation of its kind in a PLS-type material.

Structural Evolution in BiNbO4.

The sequence of transitions between different phases of BiNbO4 has been thoroughly investigated and clarified using thermal analysis, high-resolution neutron diffraction, and Raman spectroscopy. The theoretical optical phonon modes of the α-phase have been calculated. Based on thermoanalytical data supported by density functional theory (DFT) calculations, the ß-phase is proposed to be metastable, while the α- and γ-phases are stable below and above 1040 °C, respectively. Accurate positional parameters for oxygen positions in the three main polymorphs (α, ß, and γ) are presented and the structural relationships between these polymorphs are discussed. Even though no significant changes, only relaxation phenomena, are observed in the dielectric behavior of α-BiNbO4 below 1000 °C, evidence of two further subtle transitions at ∼350 and 600 °C is presented through careful analysis of structural parameters from variable temperature neutron diffraction measurements. Such phase variations are also evident in the phonon modes in Raman spectra and supported by changes in the thermoanalytical data. These subtle transitions may correspond to the previously proposed antiferroelectric to ferroelectric and ferroelectric to paraelectric phase transitions, respectively.

Dielectric probing of low-temperature degradation resistance of commercial zirconia bio-ceramics.

OBJECTIVES: To investigate the effect of the stability of oxygen vacancies on the low-temperature degradation (LTD) resistance of two kinds of commercial zirconia-based materials (3Y-TZP ceramics and Ce-TZP/Al2O3 composites) via the dielectric probing methods. METHODS: The commercial 3Y-TZP ceramics and Ce-TZP/Al2O3 composites were prepared via conventional solid-state methods. Density, phase content, microstructure, strain, and biaxial flexural strength (BFS) of two materials were investigated using Archimedes method, XRD, SEM, strain-electric field (S-E) loops and ball-on-ring methods, respectively. The concentration of oxygen vacancies before and after LTD of two materials were evaluated using dielectric probing and XPS methods. RESULTS: The XRD analysis revealed that compared to the 3Y-TZP ceramics, the Ce-TZP/Al2O3 composites showed better LTD resistance, without clear LTD. The greater LTD resistance for Ce-TZP/Al2O3 composites was associated with their stability of oxygen vacancies, by higher activation energy based on the dielectric measurements and XPS results. For the 3Y-TZP ceramics that underwent the tetragonal to the monoclinic phase transition during the LTD treatment, the concentration of their oxygen vacancies decreased after LTD. In addition, the Ce-TZP/Al2O3 composites exhibited higher flexural strength and potential fracture toughness based on the BFS testing and strain vs electric field measurement results, indicating a great potential for use in fixed restorative dental applications. SIGNIFICANCE: This work suggested the stability of oxygen vacancies played a key role in the resistance to LTD. Optimizing the stability of the oxygen vacancies is key to the development of more reliable zirconia- based dental biomaterials with greater resistance to LTD.

Microstructure evolution and the deformation mechanism in nanocrystalline superior-deformed tantalum.

The temperature-controlled relationship between the mechanical properties and deformation mechanism of tantalum (Ta) enables the extension of its application potential in various areas of life, including energy and electronics industries. In this work, the microstructure and deformation behavior of nanocrystalline superior-deformed Ta have been investigated in a wide temperature range. The structural analysis revealed that the high-performance Ta consists of several different substructures, with an average size of about 20 nm. The tensile behavior of nanocrystalline Ta (NC-Ta) was analysed and simulated at various temperatures from 100 K to 1500 K by the molecular dynamics (MD) method. It is shown that with increasing average grain size, the elastic modulus of NC-Ta linearly increases, and the impact factor reaches a value close to 1.8. The critical grain size, as obtained from the Hall-Petch relationship, was found to be about 8.2 nm. For larger grains, the flow stress follows the Hall-Petch relationship, and the thermal behavior of twin bands determines the deformation process. On the other hand, when grains are smaller than the critical size, the relationship between the flow stress and structure transforms into the inverse Hall-Petch relationship, and the deformation mechanism is controlled by grain rotation, boundary sliding or atomic migration. The results of numerical simulations revealed that temperature significantly affects the critical grain size for the plastic deformation of NC-Ta. In addition, it is demonstrated that both the elastic modulus and dislocation density decrease with increasing temperature. These findings provide guidance for the design of polycrystalline tantalum materials with tailored mechanical properties for specific industrial applications such as heat exchangers and condensers in aerospace, bone substitutes in biomedicine, and surface acoustic wave filters or capacitors in electronics.

Origin of the switchable photocurrent direction in BiFeO3 thin films.

We report external bias driven switchable photocurrent (anodic and cathodic) in 2.3 eV indirect band gap perovskite (BiFeO3) photoactive thin films. Depending on the applied bias our BiFeO3 films exhibit photocurrents more usually found in p- or n-type semiconductor photoelectrodes. In order to understand the anomalous behaviour ambient photoemission spectroscopy and Kelvin-probe techniques have been used to determine the band structure of the BiFeO3. We found that the Fermi level (Ef) is at -4.96 eV (vs. vacuum) with a mid-gap at -4.93 eV (vs. vacuum). Our photochemically determined flat band potential (Efb) was found to be 0.3 V vs. NHE (-4.8 V vs. vacuum). These band positions indicate that Ef is close to mid-gap, and Efb is close to the equilibrium with the electrolyte enabling either cathodic or anodic band bending. We show an ability to control switching from n- to p-type behaviour through the application of external bias to the BiFeO3 thin film. This ability to control majority carrier dynamics at low applied bias opens a number of applications in novel optoelectronic switches, logic and energy conversion devices.

Achieving Ultrahigh Energy Storage Density of La and Ta Codoped AgNbO3 Ceramics by Optimizing the Field-Induced Phase Transitions.

Energy storage capacitors are extensively used in pulsed power devices because of fast charge/discharge rates and high power density. However, the low energy storage density and efficiency of dielectric capacitors limit their further commercialization in modern energy storage applications. Lead-free AgNbO3-based antiferroelectric (AFE) ceramics are considered to be one of the most promising environmentally friendly materials for dielectric capacitors because of their characteristic double polarization-electric field hysteresis loops with small remanent polarization and large maximum polarization. An enhancement of these characteristics allows achieving a synergistic improvement of both the energy storage density and efficiency of the antiferroelectric materials. This work reports on a feasible codoping strategy enabling the preparation of AgNbO3-based ceramics with high energy storage performance. An introduction of La3+ and Ta5+ ions into the AgNbO3 perovskite lattice was found to increase the structural stability of the antiferroelectric phase at the expense of a reduction of local polar regions, resulting in the shifting of the electric field-induced antiferroelectric-ferroelectric phase transition toward higher fields. An ultrahigh recoverable energy storage density of 6.73 J/cm3 and high energy storage efficiency of 74.1% are obtained for the Ag0.94La0.02Nb0.8Ta0.2O3 ceramic subjected to a unipolar electric field of 540 kV/cm. These values represent the best energy performance in reported lead-free ceramics so far. Hence, the La3+/Ta5+ codoping has been shown to be a good route to improve the energy storage properties of AgNbO3 ceramics.

Local Structure in α-BIMEVOXes (ME = Ge, Sn).

The BIMEVOXes are among the best oxide ion conductors at low and intermediate temperatures. Their high conductivity is associated with local defect structure. In this work, the local structures of two BIMEVOX compositions, Bi2V0.9Ge0.1O5.45 and Bi2V0.95Sn0.05O5.475, are examined using total neutron and X-ray scattering methods, with both compositions exhibiting the ordered α-phase at 25 °C and the disordered γ-phase at 700 °C. While the diffraction data for the α-phase do not allow for the polar (C2) and nonpolar (C2/m) structures to be readily distinguished, measurements of dielectric permittivity suggest the α-phase is weakly ferroelectric in character, consistent with calculations of spontaneous polarization based on a combination of density functional calculations and machine learning methodology. Reverse Monte Carlo (RMC) analysis of total scattering data reveals Ge preferentially adopts tetrahedral geometry at both temperatures, while Sn is found to predominantly adopt octahedral coordination in the α-phase and tetrahedral coordination in the γ-phase. In all cases, V polyhedra are found to consist of tetrahedral, pentacoordinate, and octahedral geometries, as also predicted by the crystallographic analysis and confirmed by 51V solid state NMR spectroscopy. Although similar long-range structures are observed at room temperature, the oxide ion vacancy distributions were found to be quite different between the two studied compositions, with a nonrandom deficiency in vacancy pairs in the second-nearest shell along the ⟨100⟩ tetragonal direction for BIGEVOX10, compared with a long-distance (>8.0 Å) ordering of equatorial vacancies for BISNVOX05. This is attributed to the differences in the preferred coordination geometries of the substituent cations in the two systems. Impedance spectroscopy measurements reveal both compositions show high conductivity in the order of 10-1 S cm-1 at 600 °C.

Enhancement of Thermoelectric Performance in Bi0.5Sb1.5Te3 Particulate Composites Including Ferroelectric BaTiO3 Nanodots.

An increasing number of studies have reported producing composite structures by combining thermoelectric and functional materials. However, combining energy filtering and ferroelectric polarization to enhance the dimensionless figure of merit thermoelectric ZT remains elusive. Here we report a composite that contains nanostructured BaTiO3 embedded in a Bi0.5Sb1.5Te3 matrix. We show that ferroelectric BaTiO3 particles are evenly composited with Bi0.5Sb1.5Te3 grains reducing the concentration of free charge carriers with increasing BaTiO3 content. Additionally, as a result of the energy-filtering effect and ferroelectric polarization, the Seebeck coefficient was improved by ∼10% with a ∼10% improvement in power factors. The BaTiO3 phase can effectively scatters phonons reducing lattice thermal conductivity κl (0.5 W m-1 K-1) and increasing ZT to 1.31 at 363 K in Bi0.5Sb1.5Te3 composites with 2 vol % BaTiO3 content giving an improvement of ∼25% over pure Bi0.5Sb1.5Te3. Our work indicates that the introduction of ferroelectric nanoparticles is an effective method for optimizing the ZT of Bi0.5Sb1.5Te3-based thermoelectric materials.

Terahertz Faraday Rotation of SrFe12O19 Hexaferrites Enhanced by Nb Doping.

The magneto-optical and dielectric behavior of M-type hexaferrites as permanent magnets in the THz band is essential for potential applications like microwave absorbers and antennas, while are rarely reported in recent years. In this work, single-phase SrFe12-xNbxO19 hexaferrite ceramics were prepared by the conventional solid-state sintering method. Temperature dependence of dielectric parameters was investigated here to determine the relationship between dielectric response and magnetic phase transition. The saturated magnetization increases by nearly 12%, while the coercive field decreases by 30% in the x = 0.03 composition compared to that of the x = 0.00 sample. Besides, the Nb substitution improves the magneto-optical behavior in the THz band by comparing the Faraday rotation parameter from 0.75 (x = 0.00) to 1.30 (x = 0.03). The changes in the magnetic properties are explained by a composition-driven increase of the net magnetic moment and enhanced ferromagnetic exchange coupling. The substitution of the donor dopant Nb on the Fe site is a feasible way to obtain multifunctional M-type hexaferrites as preferred candidates for permanent magnets, sensors, and other electronic devices.

Terahertz Characterization of Lead-Free Dielectrics for Different Applications.

In this spotlight on applications, we describe our recent progress on the terahertz (THz) characterization of linear and nonlinear dielectrics for broadening their applications in different electrical devices. We begin with a discussion on the behavior of dielectrics over a broadband of frequencies and describe the main characteristics of ferroelectrics, as they are an important category of nonlinear dielectrics. We then move on to look at the influence of point defects, porosities, and interfaces, including grain boundaries and domain walls, on the dielectric properties at THz frequencies. Based on our studies on linear dielectrics, we show that THz characterization is able to probe the effect of porosities, point defects, shear planes, and grain boundaries to improve dielectric properties for telecommunication applications. Further, we demonstrate that THz measurements on relaxor ferroelectrics can be successfully used to study the reversibility of the electric field-induced phase transitions, providing guidance for improving their energy storage efficiency in capacitors. Finally, we show that THz characterization can be used to characterize the effect of domain walls in ferroelectrics. In particular, our studies indicate that the dipoles located within domain walls provide a lower contribution to the permittivity at THz frequencies than the dipoles present in domains. The new findings could help develop a new memory device based on nondestructive reading operations using a THz beam.

Grain Size Effects in Mn-Modified 0.67BiFeO3-0.33BaTiO3 Ceramics.

Grain size can have significant effects on the properties of electroceramics for dielectric, piezoelectric, and ferroelectric applications. Here, we systematically investigate the effect of grain size on the structure and properties of Mn-modified 0.67BiFeO3-0.33BaTiO3 ceramics, an important lead-free piezoelectric ceramic that exhibits both a high piezoelectric coefficient and a high Curie point. Ceramics with average grain sizes ranging from 0.46 to 6.85 µm were prepared using conventional and spark plasma sintering. It was found that the morphotropic phase boundary compositions are composed of two polar structures, rhombohedral and tetragonal, with DC poling inducing an increase in the fraction of the rhombohedral phase. All ceramics show relaxor behavior and their freezing temperature moves to higher temperatures with increasing grain size, although their Burns temperature is independent of grain size. In fine-grained ceramics, which show pronounced relaxor behavior, significant grain size dependency is seen in dielectric, piezoelectric, and ferroelectric properties, which is attributed to the presence of single ferroelectric domains and high concentrations of polar nanoregions. In coarse-grained ceramics, a critical grain size of 2.83 µm yields the highest dielectric permittivity at room temperature, with the piezoelectric coefficient plateauing at this grain size, which can be attributed to the contribution of both polar nanoregions and high domain wall density.

Terahertz Reading of Ferroelectric Domain Wall Dielectric Switching.

Ferroelectric domain walls (DWs) are important nanoscale interfaces between two domains. It is widely accepted that ferroelectric domain walls work idly at terahertz (THz) frequencies, consequently discouraging efforts to engineer the domain walls to create new applications that utilize THz radiation. However, the present work clearly demonstrates the activity of domain walls at THz frequencies in a lead-free Aurivillius phase ferroelectric ceramic, Ca0.99Rb0.005Ce0.005Bi2Nb2O9, examined using THz-time-domain spectroscopy (THz-TDS). The dynamics of domain walls are different at kHz and THz frequencies. At low frequencies, domain walls work as a group to increase dielectric permittivity. At THz frequencies, the defective nature of domain walls serves to lower the overall dielectric permittivity. This is evidenced by higher dielectric permittivity in the THz band after poling, reflecting decreased domain wall density. An elastic vibrational model has also been used to verify that a single frustrated dipole in a domain wall represents a weaker contribution to the permittivity than its counterpart within a domain. The work represents a fundamental breakthrough in understanding the dielectric contributions of domain walls at THz frequencies. It also demonstrates that THz probing can be used to read domain wall dielectric switching.

High Thermoelectric Performance in SnTe Nanocomposites with All-Scale Hierarchical Structures.

SnTe has attracted considerable attention as an environmentally friendly thermoelectric material. The thermoelectric figure of merit ZT value is related to low thermal conductivity that can be successfully realized using fabrication of nanostructures. However, the practical realization of SnTe nanostructured composites is often limited by long reaction time, low yield, and aggregation of nanoparticles. Herein, a simple substitution reaction between Cu2Se and SnTe was adopted to realize Cu1.75Te-SnTe nanocomposites with unique all-scale hierarchical structures. On the atomic level, the substitution SeTe is introduced into the lattice via the reaction between Cu2Se and SnTe; on the nanoscopic level, Cu1.75Te nanoinclusions with 10 nm size are evenly distributed at the grain boundaries of SnTe with average grain size less than 1 µm; on the mesoscopic level, these SnTe grains stack up to larger particles (10-20 µm), which are further surrounded by Cu1.75Te grains with a predominant size of 1-2 µm. These hierarchical structures, together with additional SnTe stacking faults, can effectively scatter phonons with different wavelengths to reduce the lattice thermal conductivity. At 873 K, a thermal conductivity value of 0.49 W·m-1·K-1 was obtained in the SnTe nanocomposite sample with 0.057 Cu1.75Te molar content, which is 40% lower than that of the pristine SnTe. By using the same approach for scattering phonons across integrated length scales, a ZT value of 1.02 (∼80% enhancement, compared with that of the pristine SnTe) was achieved at 873 K for the sample of the SnTe nanocomposite with 0.034 Cu1.75Te molar content. This large increase in ZT values highlights the role of multiscale hierarchical architecture in controlling phonon scattering, offering a viable alternative to realize higher performance thermoelectric bulk materials.

Boosting the Thermoelectric Performance of Calcium Cobaltite Composites through Structural Defect Engineering.

Misfit-layered Ca3Co4O9 as a p-type semiconductor is difficult to commercialize because of its relatively poor performance. Here, Ca2.7-xLaxAg0.3Co4O9/Ag composites prepared by spark plasma sintering were systematically investigated in terms of La3+ dopant levels and nano-sized Ag compacts. Multiscale microstructures of stacking fault, dislocation, and oxygen vacancy-linked defects could be recognized as an effective strategy for tuning the transport of charge carriers and phonon scattering. An increasing concentration of charge carriers was caused by the introduction of nano-sized Ag particles at the grain boundary. The multiscale structural defects served as phonon scattering centers to reduce the thermal conductivity. Finally, the Ca2.61La0.09Ag0.3Co4O9/Ag sample exhibited a maximum ZT of 0.35 at 1073 K. The results suggest that the interplay of structural defects provides an impetus for a huge improvement in thermoelectric performance.

Solution-Processed Epitaxial Growth of Arbitrary Surface Nanopatterns on Hybrid Perovskite Monocrystalline Thin Films.

Semiconductor surface patterning at the nanometer scale is crucial for high-performance optical, electronic, and photovoltaic devices. To date, surface nanostructures on organic-inorganic single-crystal perovskites have been achieved mainly through destructive methods such as electron-beam lithography and focused ion beam milling. Here, we present a solution-based epitaxial growth method for creating nanopatterns on the surface of perovskite monocrystalline thin films. We show that high-quality monocrystalline arbitrary nanopatterns can form in solution with a low-cost simple setup. We also demonstrate controllable photoluminescence from nanopatterned perovskite surfaces by adjusting the nanopattern parameters. A seven-fold enhancement in photoluminescence intensity and a three-time reduction of the surface radiative recombination lifetime are observed at room temperature for nanopatterned MAPbBr3 monocrystalline thin films. Our findings are promising for the cost-effective fabrication of monocrystalline perovskite on-chip electronic and photonic circuits down to the nanometer scale with finely tunable optoelectronic properties.

The grain size effect on the properties of Aurivillius phase Bi3.15Nd0.85Ti3O12 ferroelectric ceramics.

Aurivillius phase, bismuth layer structured ferroelectric Bi(3.15)Nd(0.85)Ti(3)O(12) (BNdT) ceramics with average grain sizes from 90 nm and high densities (>97%) were fabricated by spark plasma sintering. Decreasing grain size produced a diffuse ferro-paraelectric phase transition and a decrease in the Curie point. Compared with BNdT ceramics with grain sizes of micrometre scale, nanograined BNdT ceramics exhibit a depression of the dielectric maximum at the Curie point, enhanced dielectric constant from room temperature to 350 degrees C and dramatically decreased losses. Although ferroelectric switching was greatly inhibited in nanograined ceramics, both ferroelectric and piezoelectric measurements still clearly showed that BNdT ceramics with 90 nm average grain sizes are ferroelectrically switchable. This is the first reported evidence that nanoscale Aurivillius phase ceramics are ferroelectrically active.

Ultrahigh ß-phase content poly(vinylidene fluoride) with relaxor-like ferroelectricity for high energy density capacitors.

Poly(vinylidene fluoride)-based dielectric materials are prospective candidates for high power density electric storage applications because of their ferroelectric nature, high dielectric breakdown strength and superior processability. However, obtaining a polar phase with relaxor-like behavior in poly(vinylidene fluoride), as required for high energy storage density, is a major challenge. To date, this has been achieved using complex and expensive synthesis of copolymers and terpolymers or via irradiation with high-energy electron-beam or γ-ray radiations. Herein, a facile process of pressing-and-folding is proposed to produce ß-poly(vinylidene fluoride) (ß-phase content: ~98%) with relaxor-like behavior observed in poly(vinylidene fluoride) with high molecular weight > 534 kg mol-1, without the need of any hazardous gases, solvents, electrical or chemical treatments. An ultra-high energy density (35 J cm-3) with a high efficiency (74%) is achieved in a pressed-and-folded poly(vinylidene fluoride) (670-700 kg mol-1), which is higher than that of other reported polymer-based dielectric capacitors to the best of our knowledge.